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WO2006088021A1 - Equipement de test et son utilisation - Google Patents

Equipement de test et son utilisation Download PDF

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Publication number
WO2006088021A1
WO2006088021A1 PCT/JP2006/302541 JP2006302541W WO2006088021A1 WO 2006088021 A1 WO2006088021 A1 WO 2006088021A1 JP 2006302541 W JP2006302541 W JP 2006302541W WO 2006088021 A1 WO2006088021 A1 WO 2006088021A1
Authority
WO
WIPO (PCT)
Prior art keywords
booth
test
exhaust gas
aqueous electrolyte
safety
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/302541
Other languages
English (en)
Japanese (ja)
Inventor
Tomohiro Kawai
Yoshiaki Iizuka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Priority to JP2007503660A priority Critical patent/JP5050845B2/ja
Publication of WO2006088021A1 publication Critical patent/WO2006088021A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4285—Testing apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2066—Fluorine
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a test apparatus for conducting a safety test of a power storage and supply device, a safety evaluation method for a power supply device using the test apparatus, and a non-aqueous electrolyte secondary battery.
  • the power storage and supply devices as described above generally tend to require high capacity density and high power density, and it is desired to store and supply power at a larger current, and development is actively promoted.
  • the power storage and supply device When developing a power storage and supply device, in order to evaluate its safety, the power storage and supply device is operated by heating, short-circuiting, etc., and how the power storage and supply device is operated. To see if it behaves properly. For example, there is a heating evaluation test that heats the power storage and supply device and intentionally causes an explosion.
  • Non-patent document 1 Hosen Co., Ltd., product catalog, [online], [October 28, 2004 search], Internet ⁇ URL: http: z / www. Hohsen. Co. JpZjp, products / bat /23/index.html> Disclosure of the invention
  • exhaust gas may be generated due to the power storage and supply device power.
  • the power storage and supply device may be intentionally exploded to evaluate its safety. Sudden exhaust gas is generated
  • the conventional test apparatus including the test apparatus described in Non-Patent Document 1 is configured to simply discharge the exhaust gas as described above to the outside of the test apparatus.
  • the safety test as described above should be performed in a pressure relief system with the inside of the booth open to the outside.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a test apparatus capable of performing a safety test of an electric power storage and supply device while enabling treatment of exhaust gas. Another object of the present invention is to provide a secondary battery having high safety with less gas generation at the time of short circuit or destruction.
  • an exhaust gas treatment unit capable of treating exhaust gas in a test apparatus for performing a safety test of a power storage and supply device, and the exhaust gas
  • An exhaust gas holding unit that temporarily holds before entering the exhaust gas processing unit is provided, and the exhaust gas is sent to the exhaust gas processing unit slowly according to the processing capacity of the exhaust gas processing unit.
  • the booth is preferably configured to have a pressure resistance equal to or higher than the following booth pressure resistance A.
  • the test apparatus preferably includes an inert gas replacement unit that can replace the interior of the booth with an inert gas, and the booth is configured to have a pressure resistance equal to or higher than the following booth breakdown voltage A (claims). Section 2).
  • Booth pressure resistance A The amount of drug is calculated by multiplying the TNT dose equivalent to the total calorific value during heating of the power storage and supply device by the TNT yield, and the safety factor for the blast pressure determined by Hopkinson's third root rule. Applied pressure.
  • the booth is preferably configured to have a pressure resistance equal to or higher than the following booth pressure resistance B in the test apparatus.
  • the test apparatus includes an air replacement unit that can replace the inside of the booth with air, and the booth has a pressure resistance higher than the following booth breakdown voltage B. (Claim 3).
  • the initial pressure represents the booth internal pressure before the exhaust gas generation during the safety test
  • Tb represents the combustion flame temperature during the safety test
  • TO represents the ambient temperature inside the booth before the exhaust gas generation during the safety test. Represents.
  • the test apparatus includes a pressure reducing unit capable of reducing the pressure in the booth to 8 kPa or less (claim 4).
  • a pressure reducing unit capable of reducing the pressure in the booth to 8 kPa or less.
  • the test apparatus preferably includes a cooling section (cooling medium line) that lowers the temperature in the booth (Claim 5). This makes it possible to conduct safety tests at low temperatures.
  • the test apparatus includes an exhaust gas collecting unit that collects the exhaust gas.
  • the test apparatus includes a blast pressure sensor that measures a blast pressure of the explosion when an explosion of the power storage and supply device occurs (claim 8).
  • Another aspect of the present invention is to perform a safety test of the power supply device using the test apparatus (claims 1 to 8), and based on the test result, the safety of the power supply device.
  • the present invention resides in a method for evaluating the safety of a power supply device, characterized by performing the evaluation (claim 9).
  • the safety test in this safety evaluation method is preferably selected from nail penetration test, overcharge test, heating test, external short circuit test, drop test, crush test, overdischarge test, thermal shock test, vibration test ⁇ (Claim 10).
  • Another aspect of the present invention is a non-aqueous electrolyte secondary battery comprising a positive electrode and a negative electrode capable of occluding and releasing lithium ions, and a non-aqueous electrolyte solution.
  • the initial temperature of the atmosphere in the booth is 20 ⁇ 5 ° C.
  • the current is three times the current recommended by the manufacturer that manufactured the non-aqueous electrolyte secondary battery.
  • Another aspect of the present invention is a non-aqueous electrolyte secondary battery comprising a positive electrode and a negative electrode capable of occluding and releasing lithium ions, and a non-aqueous electrolyte solution.
  • the initial temperature of the atmosphere in the booth is 20 ⁇ 5 ° C.
  • the non-aqueous electrolyte secondary battery is measured in the process. It is preferable that the surface temperature of the non-aqueous electrolyte solution exceeds 50K or more than the ambient temperature in which the non-aqueous electrolyte secondary battery exists (claim 13).
  • these secondary batteries satisfy at least one property selected from the group forces consisting of the following (a), (b) and (c) (claim 14).
  • the non-aqueous electrolyte secondary battery includes an exterior, and the total electrode area of the positive electrode with respect to the surface area of the exterior is 20 times or more in area ratio.
  • the non-aqueous electrolyte secondary battery has a DC resistance component of 10 milliohms (m ⁇ ) or less.
  • test apparatus of the present invention it is possible to perform a safety test of an electric power storage and supply device while enabling treatment of exhaust gas. Further, according to the safety evaluation method for a power supply device of the present invention, it is possible to evaluate the safety of the power supply device using the test apparatus. In addition, according to the present invention, it is possible to provide a non-aqueous electrolyte secondary battery that has less gas generation and higher safety even when the battery is broken or an internal short circuit occurs.
  • FIG. 1 is a schematic block diagram showing a test apparatus as a first embodiment and a second embodiment of the present invention.
  • FIG. 2 Correlation diagram showing the relationship between reduced distance and blast pressure in Hopkinson's third-root rule.
  • Cooling line Cooling section
  • the electric power storage and supply device broadly means a device capable of storing or supplying electric power.
  • power storage and supply devices include primary batteries such as alkaline batteries and lithium batteries, lead acid batteries, nickel-cadmium batteries, nickel metal hydride batteries, and lithium ion batteries.
  • secondary batteries including water-based electrolyte secondary batteries, power generation batteries such as fuel cells, electrolytic capacitors, capacitors such as electric double layer capacitors, and the like.
  • the exhaust gas discharged from the power storage and supply device is mainly generated by the reaction, decomposition, or simply being released of the materials constituting the power storage and supply device.
  • vapor of organic solvent used in the electrolyte water vapor, hydrogen, carbon monoxide, carbon dioxide, hydrogen fluoride, Methane, ethane, ethylene, propane, propylene, oxygen, etc. can be generated as exhaust gas.
  • things that are not gas but should be treated like gas to disperse in the gas phase include electrolyte mist, fine fragments and dust from electrodes, current collectors, battery cans, etc.
  • Examples include solids (dust) generated as a result of thermal decomposition. All of these are preferably treated as exhaust gas.
  • the exhaust gas is generated mainly by the following mechanism.
  • the components are thermally decomposed, and the temperature of the power storage and supply device further increases due to the decomposition heat.
  • it becomes a so-called thermal runaway state in which exhaust gas generation due to thermal decomposition is accelerated.
  • thermal runaway state pyrolysis and reaction proceed rapidly, and the resulting exhaust gas generation rate is extremely fast.
  • the power storage and supply device is exposed to a high temperature as described above.
  • the power storage and supply device is not merely heated under the high temperature and heated as a whole.
  • a short circuit occurs inside the battery, and the energy of the discharge that the power storage and supply device itself has and the energy of the charger / discharger connected to the power storage and supply device are concentrated in the short circuit part and are locally generated by Joule heat. Can be very hot.
  • the power storage / supply device uses an electrolyte solution
  • the electrolyte solution is vaporized by heat, so that exhaust gas is also generated by the vaporization.
  • lithium Primary batteries and electric double layer capacitors usually use an organic solvent as an electrolyte, and the organic solvent is vaporized to become exhaust gas.
  • a nickel metal hydride battery uses an aqueous solvent as an electrolyte, and in this case, hydrogen is generated as exhaust gas.
  • the vapor pressure increases with temperature.
  • electrodes used in power storage and supply devices are generally made using powder, fine particles, or the like. Therefore, these powders, particles, and the like become powders when the power storage and supply device is broken or ruptured during the thermal decomposition reaction, and are dispersed in the gas phase to become gases.
  • test apparatus of the present invention is that it is possible to perform a safety test while processing exhaust gas generated as described above.
  • Specific examples of the safety test of such a power storage and supply device include a nail penetration test.
  • the nail penetration test is performed by attaching a nail to a pressing means such as a hydraulic press and moving the nail at a predetermined speed to insert the nail into a fixed power storage and supply device for testing. Inserting the nail causes an internal short circuit in the power storage and supply device.
  • power storage is provided when this internal short circuit occurs. Measure the voltage, surface temperature, electrolyte leakage, smoke, and damage level of the feeding device.
  • a specific example of the safety test is an overcharge test.
  • the overcharge test the power storage and supply device for the test is continuously charged beyond the normal charge capacity. This may cause abnormal heat generation in the power storage and supply device.
  • the overcharge test measure the voltage, current, surface temperature, electrolyte leakage, smoke, and damage of the power storage and supply device when this abnormal heat generation occurs.
  • the test conditions such as the charging current and the upper limit voltage can be set as appropriate.
  • a specific example of the safety test includes a heating test.
  • a heating test a power storage / supply device for testing is exposed to a high temperature using an oven, a hot plate, or the like to heat all or part of the power storage / supply device.
  • the voltage, surface temperature, electrolyte leakage, smoke generation, and degree of damage of the power storage and supply device during heating are measured.
  • test apparatus of the present invention includes, for example, an external short circuit test, a drop test, a crush test, an overdischarge test, a thermal shock test, Also includes vibration tests.
  • FIG. 1 is a block diagram schematically showing an outline of the test apparatus of the present embodiment.
  • the test apparatus of the present embodiment includes a booth 1, an exhaust gas treatment unit 2, an exhaust gas delivery line 3 as an exhaust gas delivery unit, an indoor gas replacement line 4, and a decompression label as a decompression unit.
  • IN 5 a coolant line 6 as a cooling unit, and an exhaust gas sampling line 7 as an exhaust gas sampling unit.
  • the direction of the exhaust gas and refrigerant flowing in the pipe is indicated by arrows.
  • the boot 1 may be formed by arbitrarily using a known pressure vessel, pressure door, or the like to enhance pressure resistance.
  • the booth 1 can also be configured to have a reinforced structure in which the surroundings of the booth 1 are reinforced with reinforcing steel concrete or the like.
  • Booth 1 should have high airtightness. Specifically, it is preferable to reduce the inside of Booth 1 to the design pressure and leave it for 30 minutes, so that there is no change in Booth 1. This prevents the atmosphere from entering the booth 1 and the exhaust gas in the booth 1 from leaking outside.
  • booth 1 is provided with a door for carrying test equipment and test samples into internal booth 1 and maintaining the test equipment.
  • the shape of the door is arbitrary.
  • booth 1 is box-shaped, one of the box-shaped side surfaces may be formed as a door.
  • the dimensions of the door are arbitrary as long as the test equipment can be taken in and out of booth 1 freely. Normally, the area of the door or equal to 0. lm 2 or more.
  • maintenance refers to inspection of test equipment, inspection of booth damage, inspection of wiring defects, inspection of piping defects, replacement of test equipment, repair of test equipment, cleaning of booth 1, etc. I mean.
  • a door (hereinafter referred to as "small door” as appropriate) may be provided in part of the door (hereinafter referred to as “large door” as appropriate).
  • Large doors as described above are usually heavy and difficult to open and close. During the safety test, it is preferable to quickly open and close the door in order to maintain hermeticity in Booth 1, but it takes time to open and close the door if the large door is heavy. In contrast, a small door is provided. In this way, small doors are generally easier to open and close than large doors, so they can be opened and closed quickly, and there is no loss of airtightness in booth 1.
  • the shape of the small door is arbitrary, and can be formed into an appropriate shape such as a rectangle or a circle.
  • the size of the small door is also arbitrary, the size of the power storage and supply device, and the booth through the small door. Appropriate dimensions can be set according to the size of parts to be taken in and out.
  • the area of the small door is usually 0.04 m 2 to 0.1 lm 2 .
  • test space provided in Booth 1 can be isolated from the outside and provided with airtightness, its shape and dimensions are not limited, depending on the test equipment and the purpose of the safety test. Can be set arbitrarily.
  • specific examples of the shape of the test space include a quadrangular prism shape, a cylindrical shape, and a spherical shape.
  • the volume in booth 1 is also an arbitrary force. Usually, it is 0.5m 3 or more and 10m 3 or less.
  • test equipment and wiring used for safety tests are usually installed.
  • appropriate types of equipment can be installed arbitrarily according to the type of safety test.
  • Specific examples of commonly used ones include test equipment such as heaters and nail penetration test presses, wiring for controlling them, and a power source for supplying power to them.
  • a heater it is preferable to use a heater that can be heated in a temperature range of 40 ° C to + 350 ° C.
  • observation equipment such as a CCD camera may be installed to observe and record the interior during the safety test.
  • a protective case made of SUS (stainless steel).
  • sensors used in the safety test it is preferable to install sensors used in the safety test in booth 1. There are no restrictions on the type of sensor, and any sensor that is appropriate for the purpose of the safety test can be selected. Can be used. For example, as shown in FIG. 1, a pressure sensor (blast pressure sensor) 11 may be provided in the booth 1. As a result, it is possible to measure the amount of exhaust gas generated by the safety test and the blast pressure when an explosion occurs during the safety test.
  • a pressure sensor blast pressure sensor
  • any pressure sensor can be used as long as the effects of the present invention are not impaired.
  • the pressure is usually set at a high frequency of 10 Hz or higher (i.e., at short measurement intervals). It is preferable to use a pressure sensor that can measure.
  • a strain gauge is installed to measure the strain, and the magnitude of the strain measured thereby From this, the pressure may be calculated.
  • examples of other sensors used include a temperature sensor.
  • a temperature sensor that can measure the ambient temperature in booth 1, the surface temperature of the power storage and supply device, the internal temperature, etc. can be used as appropriate according to the type and purpose of the safety test.
  • the temperature sensor is often used with a heater.
  • a position sensor for controlling the nail penetration position, nail penetration depth, and the like.
  • the exhaust gas generated from the power storage and supply device by the safety test is temporarily held before entering the exhaust gas treatment unit 2. That is, the normal exhaust gas treatment unit 2 has a predetermined limit in processing capacity (processing speed). In safety tests, exhaust gas generally exceeds the processing capacity, so if no measures are taken, exhaust gas treatment There is a risk that exhaust gas generated by the safety test in Part 2 cannot be completely processed. It is also conceivable to prepare an exhaust gas treatment unit 2 having a sufficiently large treatment capacity, but in this case, the equipment cost becomes very high.
  • the test apparatus of the present embodiment is provided with an exhaust gas delivery line 3 that can send exhaust gas to the exhaust gas treatment unit 2 at a speed corresponding to the exhaust gas treatment capability of the exhaust gas treatment unit 2. Temporarily keep the exhaust gas before Try to hold it.
  • the exhaust gas may be held anywhere as long as it is upstream of the exhaust gas treatment unit 2.
  • the exhaust gas holding unit 2 may be provided with a tank for holding the exhaust gas. Used to hold exhaust gas temporarily in booth 1.
  • booth 1 when booth 1 temporarily holds exhaust gas, how long the exhaust gas is held is arbitrary depending on the exhaust gas treatment capacity of exhaust gas treatment unit 2, but from booth 1 to exhaust gas treatment unit 2 It is desirable to keep the exhaust gas in accordance with the treatment capacity of the exhaust gas treatment unit 2 so that the exhaust gas treatment unit 2 does not exceed the processing capacity of the exhaust gas treatment unit 2. Specifically, it can be maintained usually for 20 minutes or longer, preferably for 1 hour or longer, more preferably for 3 hours or longer.
  • the pressure resistance of Booth 1 should be at least a pressure resistance that can maintain a hermeticity that allows gas replacement in the booth. This is because a large amount of exhaust gas may be generated depending on the conditions and types of the safety test, so it is desirable to provide booth 1 with sufficient pressure resistance to hold the exhaust gas.
  • the atmosphere in Booth 1 is an inert atmosphere. It is preferable to distinguish between a case where there is an air atmosphere and a case where there is an air atmosphere.
  • booth 1 has a pressure resistance enough to hold the exhaust gas, and includes a pressure sensor 11 in the booth 1. Since booth 1 has pressure resistance as described above, booth 1 can function as an exhaust gas holding unit in the test apparatus of the present embodiment.
  • the exhaust gas treatment unit 2 treats the exhaust gas generated in the safety test (hereinafter referred to as “detoxification treatment” as appropriate) and makes it harmless even if released outside the system.
  • the specific configuration is not limited, and any configuration can be used according to the type of exhaust gas to be generated.
  • the exhaust gas treatment unit 2 includes a fluorine adsorption tower 21, a water washing tower 22, an activated carbon treatment tank 23, a blower 24, and pipes 25, 26, 2 connecting the respective parts. It shall consist of seven.
  • the fluorine adsorption tower 21 is an adsorption tower filled with a fluoride adsorbent. By passing through the fluorine adsorption tower 21, the fluoride contained in the exhaust gas can be adsorbed on the fluoride adsorbent and removed. It ’s like that. Specific examples of the fluoride removed here include, for example, hydrogen fluoride. In order to remove fluoride, a scrubber using a sodium hydroxide aqueous solution as a cleaning solution can be used instead of (or in combination with) the fluorine adsorption tower 21.
  • the exhaust gas that has passed through the fluorine adsorption tower 21 is sent to the water washing tower 22 through the pipe 25.
  • the washing tower 22 is for washing the exhaust gas, and by passing through the washing tower 22, the solid phase component in the exhaust gas such as electrode material powder is washed away and the component easily dissolved in water, etc. It is possible to remove by melting.
  • the exhaust gas that has passed through the water washing tower 22 is sent to the activated carbon treatment tank 23 through the pipe 26.
  • the activated carbon treatment tank 23 is a container filled with activated carbon, and through the activated carbon treatment tank 23, an organic gas or the like can be adsorbed and removed by the activated carbon.
  • the exhaust gas that has passed through the activated carbon treatment tank 23 is sent to the blower 24 through the pipe 27.
  • the blower 24 is for releasing the sent exhaust gas out of the system.
  • the exhaust gas discharged from the blower 24 is processed in the fluorine adsorption tower 21, the water washing tower 22, and the activated carbon treatment tank 23! Therefore, the exhaust gas generated by the safety test can be prevented from harming the environment.
  • the exhaust gas treatment speed of the exhaust gas treatment unit 2 is not limited. Even if exhaust gas exceeding the limit of the processing speed is generated during the safety test, booth 1 can be used as an exhaust gas holding part V, and the exhaust gas can be temporarily held, so depending on the processing capacity of exhaust gas processing part 2. This is because the exhaust gas can be sent to the exhaust gas treatment unit 2 at a high speed.
  • the concentration of is usually 5% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less.
  • the harmful substances referred to here include, for example, fluorine-containing compounds, hydrocarbons, phosphorus-containing compounds, dusts, and the like.
  • the exhaust gas delivery line 3 is for sending exhaust gas from the booth 1 to the exhaust gas treatment unit 2 according to the processing capacity of the exhaust gas treatment unit 2. Specifically, the exhaust gas is sent from the booth 1 to the exhaust gas processing unit 2 while adjusting the flow rate of the exhaust gas so as not to exceed the limit of the processing speed of the exhaust gas processing unit 2.
  • the exhaust gas treatment line 3 includes a pipe 31 and an open / close valve 32.
  • the booth 1 and the fluorine adsorption tower 21 of the exhaust gas treatment unit 2 are connected by a pipe 31. If the on-off valve 32 is opened, the two communicate with each other to send the exhaust gas in the booth 1 to the fluorine adsorption tower 21. The above-mentioned delivery can be stopped by closing the on-off valve 32.
  • the suction of the blower 24 causes the pressure in the pipe 31 to be more negative than in the booth 1, so the pipe 31 sucks the gas in the booth 1. Therefore, the pressure in the booth 1 becomes lower than the external pressure of the test apparatus, and therefore, it is possible to prevent the gas in the booth 1 such as exhaust gas from leaking out of the test apparatus.
  • the exhaust gas delivery line 3 is provided with a flow rate adjusting means for adjusting the flow rate of the exhaust gas to be delivered according to the processing capacity of the exhaust gas treatment unit 2, so that the inflow exceeding the limit value of the exhaust gas treatment rate of the exhaust gas treatment unit 2 Make sure that the exhaust gas does not flow into the exhaust gas treatment section 2 at a speed.
  • the power to be adjusted is arbitrary.
  • the pipe 31 itself can function as a squeeze by setting the inner diameter of the pipe 31 to be equal to or less than a predetermined value and allowing only an exhaust gas having a flow rate corresponding to the treatment capacity of the exhaust gas treatment unit 2 to flow.
  • the inflow rate of the exhaust gas flowing into the exhaust gas treatment unit 2 is maintained so as not to exceed the limit of the exhaust gas treatment rate of the exhaust gas treatment unit 2, so that the exhaust gas that cannot be treated by the exhaust gas treatment unit 2 is rendered harmless. It can be prevented from being released outside the system without being released.
  • a throttle valve may be provided in addition to adjusting the diameter of the pipe 31.
  • the degree of restriction of the throttle valve is arbitrary, but it is preferable that the flow rate adjustment function of the throttle valve be within the range of the exhaust gas flow rate S and the exhaust gas treatment speed of the exhaust gas treatment unit 2. This also ensures that the exhaust gas flow rate does not exceed the limit of the processing capacity of the exhaust gas processing unit 2.
  • the amount of the exhaust gas sent from the exhaust gas sending unit 3 to the exhaust gas processing unit 2 per unit time is arbitrary as long as the processing capacity of the exhaust gas processing unit 2 is not exceeded.
  • the exhaust gas power exhaust gas is usually 90% or less, preferably 80% or less, more preferably 50% or less with respect to the limit value of the processing speed of the exhaust gas treatment unit 2. It is desirable to adjust the flow rate of the exhaust gas so that it flows into treatment 2.
  • a flow sensor and a safety valve that detect the flow rate of the exhaust gas are provided in the pipe 31, and the safety valve is closed or the flow path is restricted when the flow rate sensor detects an exhaust gas flow rate that exceeds the above range. I also like that.
  • some flow control means may be provided.
  • an on-off valve that repeatedly opens and closes every predetermined time is provided in the exhaust gas delivery line 3, and the flow rate of the exhaust gas is controlled by adjusting the ratio of the time that the on-off valve is open and closed.
  • an on-off valve that repeatedly opens and closes every predetermined time is provided in the exhaust gas delivery line 3, and the flow rate of the exhaust gas is controlled by adjusting the ratio of the time that the on-off valve is open and closed.
  • a gas cylinder 34 in which an inert gas such as nitrogen gas is stored is connected to the switching valve 33 by a pipe 35. Therefore, by switching the switching valve 33 and supplying an inert gas to the gas cylinder 3 4 force exhaust gas treatment unit 2, oxygen present in the system of the exhaust gas treatment unit 2 is expelled and exhaust gas treatment is performed when the exhaust gas is introduced. If the oxygen concentration in Part 2 is not within the explosion range!
  • the indoor gas replacement line 4 is for replacing the interior of the booth 1 with an inert gas.
  • the indoor gas replacement line 4 is configured by connecting a gas cylinder 41 storing an inert gas to the booth 1 through a pipe 43 having an on-off valve 42.
  • the on-off valve 42 is opened, the inert gas in the gas cylinder 41 is sent to the booth 1, and the atmosphere in the booth 1 can be replaced with the inert gas. That is, the inert gas replacement line 4 of the present embodiment functions as an inert gas replacement section!
  • the inside of the booth 1 is replaced with an inert gas because the exhaust gas discharged from the power storage and supply device is burned or exploded by oxygen in the air in the booth 1, and the composition of the exhaust gas. This is to prevent analysis from becoming impossible, or the booth 1 from being destroyed due to the internal pressure of the booth 1 exceeding that of the booth 1. Therefore, it is preferable to perform the replacement with the inert gas in the booth 1 when the composition of the exhaust gas is analyzed.
  • the decompression line 5 is for depressurizing the inside of the booth 1.
  • the vacuum pump 51, the pipe 52 connecting the vacuum pump 51 to the booth 1 and the exhaust gas delivery line 3, and the front and rear of the vacuum pump 51 of the pipe 52 That is, it has on-off valves 53 and 54 provided upstream and downstream, respectively. Therefore, by opening the on-off valves 53 and 54, the booth 1 and the vacuum pump 51 communicate with each other, the pressure inside the booth 1 is reduced, and the gas drawn from the booth 1 to the vacuum pump 51 passes through the exhaust gas delivery line 3. It will be sent to the exhaust gas treatment section 2 through.
  • decompression in booth 1 is performed because inert gas is supplied from gas cylinder 41 in a state where booth 1 is decompressed when the atmosphere in booth 1 is replaced by indoor gas replacement line 4. This is so that replacement can be performed efficiently by supplying. Even if exhaust gas remains in booth 1 when the atmosphere in booth 1 is replaced, the exhaust gas concentration in booth 1 can be reduced by reducing the pressure in booth 1 as described above. Therefore, even if the atmosphere and exhaust gas are mixed, the exhaust gas concentration can be prevented from entering the explosion range.
  • the depressurization line 5 effectively treats harmful gases and vapors containing fluoride. Therefore, the displacement can be controlled. That is, by adjusting the output of the vacuum pump 51 and the opening degree of the on-off valves 53 and 54, the amount of exhaust gas sent to the exhaust gas treatment unit 2 can be controlled using the vacuum pump 51.
  • the decompression line 5 can be used not only to decompress the interior of the booth 1 but also to send exhaust gas in the booth 1 to the exhaust gas treatment unit 2 through the decompression line 5.
  • the degree of decompression is arbitrary as long as the decompression can be performed more than the external pressure of the test apparatus (usually atmospheric pressure). Force It is usually preferable to be able to reduce the pressure to 8 kPa or less.
  • the pressure in the booth 1 can be reduced to 8 kPa or less using the pressure reducing line 5.
  • the cooling medium line 6 is a pipe through which the refrigerant flows, and the low-temperature refrigerant flows through the cooling medium line 6 so that the temperature in the booth 1 can be lowered. ! Any refrigerant can be used as long as the effect of the present invention is not significantly impaired.
  • a predetermined position in booth 1 may be cooled simply by lowering the ambient temperature of booth 1.
  • a cooling medium line 6 is provided so that the box or stand can be cooled, and power is stored in the box or stand. It is quite possible to install a supply device and perform a safety test. In the present embodiment, it is assumed that the coolant line 6 is installed so as to lower the ambient temperature in the booth 1.
  • the exhaust gas collection line 7 is for collecting exhaust gas generated by the safety test. In this exhaust gas collection line 7, exhaust gas is collected before it is processed in the exhaust gas treatment section 2, and by analyzing the separately collected exhaust gas, detailed prayer for the power storage and supply device becomes possible.
  • the exhaust gas collection line 7 includes a pipe 71 branched from the exhaust gas delivery line 3, and in this pipe 71, a sample container 72 for collecting the exhaust gas, and the exhaust gas to the exhaust gas delivery line 3 There are provided a vacuum pump 73 for extracting from the sample container 72 and open / close valves 74 and 75 provided before and after the sample container 72, respectively.
  • the sample container 72 is detachable from the pipe 71. Therefore, when collecting the exhaust gas, first, the on-off valve 74 upstream of the sample container 72 is closed, the downstream on-off valve 75 is opened, and the vacuum pump 73 is operated to decompress the inside of the sample container 72.
  • downstream open / close valve 75 is closed, and the upstream open / close valve 74 is opened, and the exhaust gas is taken into the sample container 72 from the exhaust gas delivery line 3.
  • the sample container 72 is filled with exhaust gas, so that the exhaust gas can be collected in the sample container 72.
  • the exhaust gas collected in this manner is appropriately subjected to analysis such as composition analysis, toxicity test, and flammability test.
  • analysis such as composition analysis, toxicity test, and flammability test.
  • analysis equipment used There is no limit to the method of analysis and the analysis equipment used, and analysis may be performed arbitrarily according to the purpose of the safety test.
  • the test apparatus of the present embodiment is configured as described above! Therefore, when using the above test apparatus, first, the power storage and supply device that is the subject of the safety test is installed in the booth 1. Install. Initially, the on-off valves 32, 42, 53, 54, 74, and 75 are closed, and the switching valve 33 communicates the booth 1 with the exhaust gas treatment unit 2.
  • the booth 1 door is closed, and the inside of the boot 1 is decompressed by the decompression line 5. Specifically, the on-off valves 53 and 54 are opened, and the vacuum pump 51 is operated to depressurize the booth 1. Normally, the pressure in booth 1 should be reduced to 20 kPa. Further, the pressure in the booth 1 may be detected by the pressure sensor 11. This depressurizes booth 1.
  • the above-described depressurization and atmosphere replacement in the booth 1 are usually performed twice or more, preferably six times or more.
  • the oxygen concentration in the booth 1 can be made sufficiently low (for example, 50 ppm or less), and the composition of the exhaust gas can be prevented from changing due to the reaction of the exhaust gas with the atmospheric gas.
  • the exhaust gas burns or explodes outside the power storage and supply device, the amount of heat generated inside the power storage and supply device may not be detected well, and safety tests may not be performed accurately. By suppressing combustion and explosion, the above soot can be eliminated.
  • the switching valve 33 is switched, and as described above, the inert gas is supplied from the gas cylinder 34 to the exhaust gas treatment unit 2, and is present in the system of the exhaust gas treatment unit 2. Expel the oxygen that you want.
  • the temperature in the booth 1 is adjusted using the coolant line 6 and the heater (not shown) in the booth 1. After adjustment, stop the temperature adjustment by the coolant line 6 or heater.
  • the on-off valves 32, 42, 53, 74 are closed and the booth 1 is sealed. Then, a safety test such as a nail penetration test is performed in Booth 1, and necessary data are measured using the test equipment and sensors in Booth 1. At this time, the power storage device supply exhaust gas is generated by the safety test.
  • the booth 1 is sealed.
  • the pressure sensor 11 detects the blast pressure when exhaust gas is generated and can also be used for analysis.
  • the exhaust gas is collected by the exhaust gas collection line 7. Specifically, as described above, the opening and closing valves 74 and 75 are alternately opened and closed to decompress the inside of the sample container 72, and the exhaust gas is collected in the sample container 72.
  • the sampled gas 72 can be removed from the collected exhaust gas, and the internal exhaust gas can be analyzed with an analytical instrument or the like.
  • open / close valves 74 and 75 are closed.
  • the on-off valve 32 is opened while adjusting the valve opening, and the switching valve 33 is switched so that the booth 1 and the exhaust gas treatment unit 2 communicate with each other to exhaust the exhaust gas in the booth 1.
  • the piping 31 is formed so as to function as a so-called squeeze, as described above, so that the exhaust gas delivery line 3 can adjust the flow rate of the exhaust gas delivered according to the processing capacity of the exhaust gas treatment unit 2, and the on-off valve 32 Since the exhaust gas also functions as a throttle valve, the exhaust gas can be temporarily held in the booth 1. Therefore, the exhaust gas that has flowed into the exhaust gas treatment unit 2 must be reliably detoxified. become.
  • an amount of exhaust gas that does not exceed the treatment capacity of the fluorine adsorption tower 21, the water washing tower 22 and the activated carbon treatment tank 23 is sent to the exhaust gas treatment section 2, and the fluorine adsorption tower 21, the water washing tower 22 and the activity It is treated in order in the charcoal treatment tank 23 and detoxified.
  • the detoxified exhaust gas is then discharged from the profile 24 to the outside of the system.
  • the safety test using the test apparatus of the present embodiment is performed.
  • the test apparatus of the present embodiment it is possible to perform a safety test of an electric power storage and supply device while enabling treatment of exhaust gas.
  • a safety test such as a nail penetration test, overcharge test, or heating test is performed on a power storage and supply device
  • a large amount of exhaust gas is generated suddenly. 3 is excluded
  • the exhaust gas is temporarily held before the exhaust gas flows into the exhaust gas processing unit 2, and the exhaust gas treatment is performed according to the processing capacity. Exhaust gas can flow into part 2. Therefore, the safety test can be performed safely without the possibility that exhaust gas exceeding the processing capacity flows into the exhaust gas treatment unit 2 and the exhaust gas cannot be detoxified.
  • power storage and supply devices that emit a large amount of exhaust gas such as large batteries, are likely to cause difficulties in exhaust gas treatment using conventional technology. Is big.
  • the test apparatus of the present embodiment is configured so that the booth 1 has pressure resistance, the exhaust gas can be reliably held in the booth 1. Furthermore, booth 1 has pressure resistance, so exhaust gas is suddenly generated when a safety test is performed in an inert gas atmosphere, and exhaust gas is temporarily held in booth 1. Even if the booth 1 is not damaged, the safety of the test can be further improved.
  • test apparatus of the present embodiment includes the pressure reducing line 5, the pressure in the booth 1 can be reduced when the gas in the booth 1 is replaced with another gas, and the gas can be replaced efficiently. It is also possible to perform a safety test under reduced pressure. Furthermore, since the test apparatus according to the present embodiment includes the cooling line 6 that lowers the temperature in the booth 1, the temperature can be adjusted appropriately, and a safety test can be performed at a low temperature. It becomes possible.
  • test apparatus of the present embodiment includes the exhaust gas collection line 7 for collecting the exhaust gas, various analyzes of the exhaust gas generated can be performed during the safety test.
  • test apparatus of the present embodiment includes the pressure sensor 11, it is possible to measure the blast pressure of an explosion that occurs due to the generation of exhaust gas during the safety test.
  • test apparatus is the same as the first embodiment except that the booth 1 has a pressure resistance higher than the booth pressure A.
  • the exhaust gas treatment unit 2 As for the test equipment, as shown in FIG. 1, the exhaust gas treatment unit 2, the exhaust gas delivery line 3, the indoor gas replacement line 4, the decompression line 5, the coolant line 6 and the exhaust gas collection line 7 are respectively shown. This is the same as in the first embodiment.
  • booth 1 is the same as the first embodiment except that the booth breakdown voltage is equal to or higher than booth breakdown voltage A.
  • the exhaust gas delivery line 3 sends exhaust gas according to the processing capacity of the exhaust gas treatment unit 2! As a result, the exhaust gas force S does not flow into the exhaust gas treatment unit 2 at an inflow rate that exceeds the limit value of the exhaust gas treatment rate of the exhaust gas treatment unit 2.
  • the safety test is performed in booth 1 as an inert atmosphere.
  • the booth 1 is configured to have a pressure resistance equal to or higher than the following booth pressure resistance A.
  • Booth pressure resistance A The amount of drug is calculated by multiplying the TNT dose equivalent to the total calorific value during heating of the power storage and supply device by the TNT yield, and the safety factor for the blast pressure determined by Hopkinson's third root rule. Applied pressure.
  • the relationship between the blast pressure using explosives as the source and the distance between the source and the power source is such that the correlation between the blast pressure and the conversion distance by Hopkinson's third root rule is wide as a scale rule. It consists of a range.
  • This Hopkinson's third-root rule indicates that the blast pressure of the explosion generated by the explosion is the same at the conversion distance, that is, “distance from the center of explosive divided by the third root of the explosive dose”.
  • TNT tritrotoluene
  • the Hopkinson's third root rule which is the scale rule based on the conversion distance using the TNT dose, as the source of power storage and supply. Estimate the strength of the blast pressure and calculate the pressure value multiplied by the safety factor.
  • the dose used to calculate the converted distance (hereinafter referred to as “converted dose” as appropriate) is the amount of heat equivalent to the amount of heat generated during a gas explosion compared to the amount of TNT generated during the explosion. Use the value multiplied by the yield.
  • the TNT yield is a measure of the intensity of explosion, and the TNT yield increases when soot gas that is easy to detonate is generated as exhaust gas. Therefore, when configuring a test device that can handle severe explosions that can occur in safety tests regardless of the type of exhaust gas, the TNT yield used to calculate the above-mentioned boot pressure resistance A is usually 0.01% or more. Preferably, it is 0.1% or more, more preferably 1% or more, and usually 20% or less, preferably 10 or less, more preferably 5% or less.
  • the specific method for obtaining the TNT yield is an arbitrary force.
  • the yield can be obtained by measuring the ratio of the measured value to the theoretical value as follows.
  • an experiment that actually pyrolyzes or explodes a power storage and supply device similar to the test sample (hereinafter referred to as “measurement experiment” as appropriate), measures the pressure of the test sample at a certain distance, and measures the pressure
  • TNT equivalent The mass of TNT explosive that generates the same pressure as the maximum value during explosion
  • the safety factor is a value representing the degree of certainty that Booth 1 is safe. The higher this value, the more securely Booth 1 is safer. This safety value is usually 1 or more, usually 2 or less, preferably 5 or less.
  • the booth breakdown voltage A can be obtained as follows. (1) For safety testing! The total amount of heat generated from the power storage and supply device is calculated and (2) Specify the TNT dose corresponding to the calorific value, and (3) multiply the TNT dose by the above TNT yield to calculate the converted dose. (4) Separately, the distance from booth 1's dimensional isoelectric power storage and supply device to the target site on the inner wall of booth 1 is obtained. (5) Then, the distance to the target part of the inner wall of Booth 1 from the electricity storage and supply device is divided by the third root of the converted dose to obtain the converted distance. (6) Further, identify the corresponding blast pressure from the conversion distance obtained as described above. (7) Finally, the booth pressure resistance A is calculated by multiplying the blast pressure by the safety factor.
  • the total calorific value generated from the power storage and supply device in the safety test is obtained.
  • literature values or assumed values may be used as the total heat generation amount, but in order to increase the reliability of the booth withstand voltage A, it is preferable to use experimental values of the total heat generation obtained experimentally. .
  • the capacity of the power storage and supply device used as the test device is preferably about 0.3 Ah (Ah) force and about 2 Ah. Since the dimensions of the power storage and supply device are not too small and not too large, the evaluation accuracy of the heat generation rate can be improved, and the safety can be enhanced.
  • the conditions of the heating test may be set arbitrarily according to the assumed safety test conditions.
  • heating is performed by raising the temperature from normal temperature to about 200 ° C to about 300 ° C, and the rate of temperature increase is usually set to lKZmin to 2KZmin.
  • the apparatus used for a heating is also arbitrary, normally an oven is used.
  • the test device is installed in the oven, and the surface temperature and the atmospheric temperature in the oven are measured while raising the temperature inside the oven also to room temperature.
  • any oven can be used.
  • an oven that can set the rate of temperature rise is preferred.
  • the time transitions of the temperature of the test device itself and the ambient temperature of the test device are measured.
  • the temperature of the test device itself either the surface temperature or the internal temperature may be adopted, and a temperature that is easy to measure can be adopted as appropriate.
  • the surface temperature is used as the temperature of the test device itself will be described, but the same can be done when the internal temperature is adopted as the temperature of the test device itself.
  • the heat generation rate of the test device is determined from the measured temperature transition, and the total heat generation from the test device is determined by integrating the heat generation rate with time.
  • the heat generation rate is calculated using the time change of the temperature of the test device itself obtained by the heating test, that is, here, the time change of the surface temperature of the test device. Specifically, first, the heat transfer coefficient of the measured test device is obtained using the surface temperature and ambient temperature of the test device. This heat transfer coefficient is a parameter that evaluates the heat exchange rate between the surface of the test device and the outside of the test device. This is the coefficient used to convert to degrees.
  • Equation 2 the heat transfer coefficient (U) can be obtained.
  • the value represented by each symbol is the same as in Equation 1 above.
  • the density of the test device used when calculating the heat transfer coefficient from Equation 2), the specific heat (Cp), the specific surface area (A), etc. are determined separately in advance.
  • Equation 2 The density, specific heat (Cp), specific surface area (A), etc. can be the same as those in Equation 2.
  • the “volume of the power storage and supply device” is the volume of the portion where heat is generated in the power storage and supply device.
  • the volume of the power storage and supply device (for example, cans and laminates) and excess The gap is not included! /.
  • the safety test in booth 1 is performed on the calorific value per unit volume obtained in the heating test.
  • the total amount of heat generated in the safety test by multiplying the volume of the power storage and supply device to be performed
  • the power capacity [J] of the power storage and supply device is usually 30% or more instead of performing the above heating test.
  • a value obtained by multiplying an appropriate coefficient value of 100% or less can be used as the total calorific value. For example, when a battery with a capacity of 10Ah and an average voltage of 3.7V is the subject of a safety test, its power capacity is
  • the value obtained by multiplying this by the coefficient value of 30% to 100% is regarded as the total heat generation amount of this battery, and the booth withstand voltage ⁇ is calculated even when performing the calculations (2) to (6) above. be able to.
  • the coefficient value multiplied by the power capacity may be obtained experimentally.
  • an assumed value or a document value may be used.
  • the total calorific value generated during the safety test is known, then the TNT dose corresponding to the total calorific value is identified. Since TNT's calorific value at the time of explosion is 2.6 ⁇ 10 9 Q [Zton], specifically, the total calorific value can be divided by 2.6 ⁇ 10 9 jZton. In the specific example of the above heating test, the total calorific value generated during the safety test is 1.3X10].
  • the TNT yield is then multiplied by the above-mentioned TNT yield to calculate the conversion dose to be applied to Hopkinson's third-root rule.
  • the TNT dosage corresponding to the total calorific value is 0.05 [kg]. Therefore, when the TNT yield is 5%, the equivalent dosage is
  • the power storage and supply device power in booth 1 The distance to the target part of the inner wall of booth 1 is obtained. This distance is used for later calculation of the converted distance. In the specific example of the heating test, this distance is 0.35 m.
  • the target part refers to a part to be provided with a pressure resistance higher than the booth pressure resistance A.
  • the power storage and supply device power is also calculated by dividing the distance to the target part of the inner wall of Booth 1 by the third root of the converted dose. Also, on the inner wall of Booth 1, the part with the smallest distance from the power storage and supply device receives the highest pressure, so the converted distance is obtained using the shortest distance between the power storage and supply device and the inner wall, It is preferable that the safety of the entire booth 1 be matched to the pressure resistance required for the part where the distance of the storage and supply device force is the smallest, since the safety of the test can be further increased. In the specific example of the heating test, the conversion distance is
  • the blast pressure corresponding to the conversion distance is specified.
  • the blast pressure on the vertical axis corresponding to the converted distance on the horizontal axis is identified using the correlation diagram shown in Fig. 2, which shows the relationship between the converted distance and the blast pressure in Hopkinson's third-root rule.
  • Fig. 2 shows the relationship between the converted distance and the blast pressure in Hopkinson's third-root rule.
  • the value 2 [KgfZcm 2 ] on the vertical axis corresponding to the converted distance 2.6 [m / kg ( 1/3) ] on the horizontal axis is Wind pressure.
  • the booth pressure A at the target site of Booth 1 is calculated by multiplying the above blast pressure by the safety factor. Therefore, when the safety factor is 1, the booth pressure resistance A of the target part in the specific example of the heating test is
  • booth 1 has at least a part of the wall, bottom, ceiling, etc. that make up booth 1, preferably the total strength of booth withstand pressure A or above. It is desirable to have a structure that can withstand the internal pressure up to the booth pressure A.
  • the booth 1 is provided with the pressure sensor 11, and the entire booth 1 is configured to have a pressure resistance and airtightness equal to or higher than the booth breakdown voltage A calculated as described above.
  • booth 1 since booth 1 has a pressure resistance higher than booth pressure A, booth 1 can function as an exhaust gas holding unit in the test apparatus of this embodiment.
  • test apparatus of the present embodiment is configured as described above, a safety test can be performed in the same manner as in the first embodiment.
  • the test apparatus of the present embodiment it is possible to perform a safety test of an electric power storage and supply device while enabling treatment of exhaust gas.
  • a safety test such as a nail penetration test, overcharge test, or heating test is performed on a power storage and supply device
  • a large amount of exhaust gas is generated abruptly.
  • 3 adjusts the flow rate of the exhaust gas sent according to the treatment capacity of the exhaust gas treatment unit 2, so it is temporarily held before the exhaust gas flows into the exhaust gas treatment unit 2 and then sent to the exhaust gas treatment unit 2 according to the treatment capacity.
  • Exhaust gas can be introduced. Therefore, the safety test can be performed safely without the possibility that exhaust gas exceeding the processing capacity flows into the exhaust gas treatment unit 2 and the exhaust gas cannot be detoxified.
  • test apparatus of the present embodiment is configured so that booth 1 has a pressure resistance higher than booth breakdown voltage A, the safety test is rapidly performed when the safety test is performed in an inert gas atmosphere. Even if gas is generated or the exhaust gas is temporarily held in booth 1, damage to booth 1 can be more reliably prevented, further improving test safety. That's right.
  • the test apparatus is configured such that the indoor gas replacement line replaces the inside of booth 1 with air, and the booth 1 has a pressure resistance higher than booth pressure B.
  • the rest is the same as in the first embodiment.
  • the exhaust gas treatment unit 2 As for the test apparatus, as shown in FIG. 1, the exhaust gas treatment unit 2, the exhaust gas delivery line 3, the decompression line 5, the coolant line 6 and the exhaust gas collection line 7 are the same as in the first embodiment.
  • booth 1 is the same as the first embodiment except that the booth breakdown voltage is equal to or higher than booth breakdown voltage B.
  • the exhaust gas delivery line 3 sends exhaust gas according to the processing capacity of the exhaust gas treatment unit 2!
  • the exhaust gas force S does not flow into the exhaust gas treatment unit 2 at an inflow rate that exceeds the limit value of the exhaust gas treatment rate of the exhaust gas treatment unit 2.
  • the booth 1 since the safety test is performed in the booth 1 in an air atmosphere, it is preferable that the booth 1 also has a pressure resistance corresponding to the safety test.
  • a safety test is performed in an air atmosphere! / ⁇ . If exhaust gas is generated in the safety test, it is considered that the combustible component of the exhaust gas burns in the air. However, the combustion flame temperature of the combustion usually does not exceed 2500K, which is the approximate value when a general organic combustible gas burns in air. Therefore, it occurs relative to the volume of booth 1. Therefore, the increase in the internal pressure of booth 1 due to the generation of exhaust gas is sufficiently small. That is, when a safety test is performed in an air atmosphere and the generated exhaust gas is combusted, the exhaust gas is generated after the exhaust gas is generated rather than the influence of the amount of exhaust gas generated by the power storage and supply device.
  • the initial pressure represents the internal pressure of booth 1 before exhaust gas generation during the safety test
  • Tb represents the combustion flame temperature during the safety test
  • TO represents the boot 1 before exhaust gas generation during the safety test.
  • the safety factor is the same value as described in the second embodiment, and Tb and TO are values at the absolute temperature.
  • the combustion flame temperature Tb is the ambient temperature during exhaust gas combustion
  • the measurement method is
  • the initial pressure is 0. IMPa and the ambient temperature TO in booth 1 before exhaust gas generation during the safety test is 25 ° C (298K).
  • the combustion flame temperature (2500K) during the test is Tb and the safety factor is 1, the booth pressure resistance B is
  • the blast pressure is calculated using Hopkinson's third-root rule, and the blast pressure is multiplied by the safety factor in the same manner as in the second embodiment, and the same is applied to booth 1. It may be possible to provide pressure resistance higher than the blast pressure.
  • the power storage and supply device is a battery
  • 10 times the mass of the electrolyte In the method for calculating the blast pressure described in the second embodiment, it can be used as the TNT dose corresponding to the total calorific value.
  • the mass of the electrolytic solution at this time conveniently, the 1Z3 volume of batteries, may be a value obtained by multiplying the density lOOOkgZm 3.
  • the TNT dose may be determined using TNT explosion heat value 2.6 X 10 9 j / ton. Specifically, the TNT dose can be calculated by dividing the combustion heat of the electrolyte by the TNT explosion heat value.
  • the TNT yield is the same as in the second embodiment. Further, an actual measurement value may be used as the TNT yield.
  • Booth 1 is required when the safety test is performed in an inert atmosphere as in the first and second embodiments and in an air atmosphere as in the third embodiment.
  • the pressure resistance is different for the following reasons.
  • oxygen used for decomposition or combustion reaction of combustible gas in the exhaust gas was originally present as oxygen in the power storage and supply device, or components were decomposed. It is only oxygen generated.
  • oxygen in the air is added to the above oxygen. Therefore, when performing safety tests in air, decomposition and combustion reactions progress more than when performing safety tests in an inert atmosphere, and as a result, the required pressure resistance differs. is there.
  • the booth 1 is configured to have a pressure resistance equal to or higher than the booth breakdown voltage B described above.
  • the indoor gas replacement line 4 is replaced with air instead of the inert gas used in the first embodiment. Therefore, the indoor gas replacement line 4 functions as an air replacement unit that can replace the interior of the booth 1 with air.In this way, the interior of the booth 1 is replaced with air, and the safety test is performed in an air atmosphere. By doing so, it is possible to evaluate the power storage and supply device in a state close to the actual use state. It is also possible to analyze how the exhaust gas burns and explodes due to factors external to the power storage and supply device.
  • the test apparatus of the present embodiment is configured as described above, when the safety test is prepared, the indoor gas replacement line 4 is used V and the inside of the booth 1 is replaced with air.
  • the safety test can be performed in the same manner as in the first embodiment.
  • booth 1 is configured to have a pressure resistance equal to or higher than booth breakdown voltage B, and thus exhaust gas is rapidly generated when the safety test is performed in an air atmosphere.
  • the exhaust gas is temporarily held in the booth 1, the booth 1 is not damaged, and the safety of the test can be further improved.
  • operations and effects similar to those of the first embodiment can be obtained.
  • test apparatus according to the present invention has been described above with reference to the embodiment.
  • the test apparatus according to the present invention is not limited to the above-described embodiment, and can be arbitrarily modified without departing from the gist of the present invention. can do.
  • the components described in the first, second, or third embodiment may be used in any combination.
  • the indoor gas replacement line 4 is provided with both a gas cylinder for supplying an inert gas and a gas cylinder for supplying air, and either the inert gas or the air is selectively replaced in the booth 1. You may comprise so that it can do. At this time, it is possible to replace the interior of booth 1 with an inert gas or air using a single indoor gas replacement line 4 using a switching valve or the like that may be provided with two or more indoor gas replacement lines 4. Also good.
  • the pressure resistance of Booth 1 is either the pressure resistance to be provided when performing a safety test in an inert atmosphere or the pressure resistance to be provided when performing a safety test in an air atmosphere. Therefore, it is desirable to have higher pressure resistance.
  • the interior of booth 1 is simply provided through a door provided in booth 1, without providing dedicated indoor gas replacement line 4. Try replacing the atmosphere.
  • a booth filled with a cooling medium may be installed in the booth 1 to cool the inside of the booth 1!
  • the exhaust gas collection line 7 is configured to extract the exhaust gas from the exhaust gas delivery line 3.
  • the exhaust gas collection line 7 may be configured to have a dedicated pipe directly connected to the booth 1.
  • the exhaust gas after passing through the exhaust gas collection line 7 may be returned to the exhaust gas delivery line 3 again.
  • the amount of exhaust gas released outside the system without being treated can be further reduced.
  • a safety valve, a pressure relief valve, etc. may be provided in booth 1 to further enhance safety.
  • the indoor gas replacement line 4 when the indoor gas replacement line 4 is not provided or when the atmosphere in the booth 1 is changed to an atmosphere of a gas other than an inert gas or air by the indoor gas replacement line 4, It may be possible to rub the booth withstand pressure A or booth withstand pressure B as described above.
  • the booth 1 when the exhaust gas generated by the safety test does not react with the gas present in the atmosphere in Booth 1, the booth 1 is used when the atmosphere in Booth 1 is changed to the air atmosphere by the indoor gas replacement line 4. 1 can be equipped with booth pressure resistance A.
  • the booth 1 may be provided with a booth pressure resistance B regardless of the atmosphere existing in the atmosphere in the booth 1 during the safety test. In this way, whether booth 1 is equipped with booth withstand voltage A or booth withstand voltage B can be arbitrarily set as appropriate.
  • the test apparatus of the present invention it is possible to perform a safety test of the power supply device and perform a safety evaluation of the power supply device based on the test result of the safety test.
  • a safety test of the power supply device there is no limit to the type of safety test, but for example, a nail penetration test, Overcharge test, heating test, external short circuit test, drop test, crush test, overdischarge test, thermal shock test, vibration test force
  • the selected test can be performed.
  • the content of the specific safety evaluation method is arbitrary, but based on the above, for example, "International certification for safety of lithium ion battery (small battery)” UL1642, "Battery industry association guidelines SBA G1101 This can be done in accordance with certification regulations such as “Lithium Secondary Battery Safety Evaluation Standard Guidelines”.
  • the test apparatus of the present invention since the test apparatus of the present invention has pressure resistance (sealing property), the gas generation amount and gas composition can be analyzed more accurately by using this. Therefore, using this analysis result, it is possible to design and produce a safe power supply device with less gas generation and the like even in the event of breakdown or internal short circuit.
  • Measurement items in various evaluation tests can be determined by various sensors installed in the booth.
  • the surface temperature of the power supply device and the gas temperature in the booth can be measured by a temperature sensor such as a thermocouple.
  • the amount of gas generated can be calculated by a gas equation of state.
  • the above equation of state is obtained from the change in the booth internal pressure before and after the safety test obtained by the pressure sensor and the gas temperature power in the booth obtained by the temperature sensor.
  • the component (composition) of the exhaust gas can be obtained by analyzing the gas collected from the exhaust gas collection line by a known analyzer or method such as gas chromatography or a mass spectrometer.
  • the visual behavior during the evaluation test can be captured.
  • a non-aqueous electrolyte secondary battery of the present invention has been developed using the above test apparatus and safety evaluation method, and includes a positive electrode and a negative electrode capable of occluding and releasing lithium ions, and a non-aqueous electrolyte. It is a non-aqueous electrolyte secondary battery.
  • the nonaqueous electrolyte secondary battery of the present invention satisfies the following condition (1) or condition (2), and preferably satisfies these conditions (1) and (2) at the same time. is there. Above all More preferably, it satisfies at least one of the conditions (3) and (4), and particularly preferably satisfies the conditions (3) and (4) at the same time.
  • Condition (1) is that when a non-aqueous electrolyte secondary battery of the present invention was subjected to an overcharge test under the following conditions using the above test apparatus, the change in the booth pressure before and after the test was 25 ° C. The following requirements are met.
  • C is a coefficient indicating the amount of gas generated during the test, and is preferably 100 times or less, more preferably 10 times or less, and more preferably 1 time or less.
  • the initial temperature of the atmosphere in the booth is 20 ⁇ 5 ° C.
  • the current is three times the current recommended by the manufacturer that manufactured the non-aqueous electrolyte secondary battery.
  • the initial temperature of the atmosphere in the booth in condition (i) may be measured at any position in the booth. However, the temperature is usually measured at a distance of 20 mm or more from the nonaqueous electrolyte secondary battery in the booth. Further, in condition (ii), whether or not the non-aqueous electrolyte secondary battery is completely discharged can be confirmed by checking that the battery voltage is lower than the lower limit voltage in the normal voltage range. On the other hand, the charge depth of 0% can be confirmed by the fact that the discharge capacity flowing when the battery voltage is maintained at the lower limit voltage in the normal voltage range for 30 minutes is 2% or less of the battery capacity.
  • condition (iii) indicates that charging is performed with a current having a current value that is three times the recommended current value.
  • the power is ideally charged to 250% of the charge capacity.Gas generation occurs before the charge amount reaches 250% of the charge capacity, and the charge capacity is 250%. If it does not reach the maximum, charge the battery up to the maximum chargeable amount, and measure the increase in booth internal pressure when the battery reaches the maximum charge.
  • the atmosphere in the booth is arbitrary, and either an inert gas or good air may be used. In some cases, other gases may be used.
  • the above overcharge test is a test for analyzing the behavior of the nonaqueous electrolyte secondary battery when the nonaqueous electrolyte secondary battery is excessively charged.
  • the above requirement is met if the non-aqueous electrolyte secondary battery is opened, ruptured or exploded in the non-aqueous electrolyte secondary battery during overcharge. This means that the amount of gas generated and the level of impact generated by the gas generation are small enough that they are not a practical problem.
  • the level of gas generated during overcharge and the level of impact generated by gas generation are complicatedly related to the type, amount, and arrangement of battery elements of the non-aqueous electrolyte secondary battery. Therefore, when trying to develop a non-aqueous electrolyte secondary battery with a low level of gas generation and a low level of impact caused by gas generation, it is actually necessary to use a non-aqueous electrolyte secondary battery. Overcharging the battery to cause gas generation and the analysis is repeated many times. Therefore, it can be expected that the development progresses better as the superior test equipment for performing the test is used, and the performance and function of the test equipment is developed using the test equipment. It is considered to be reflected in the secondary battery.
  • Condition (2) is that when a non-aqueous electrolyte secondary battery of the present invention was subjected to a nail penetration test using the above test equipment under the following conditions, the change in the booth pressure before and after the test was 25 ° C. The following requirements are met.
  • C is a coefficient indicating the amount of gas generated at the time of the test, and is preferably less than 100 times, more preferably less than 10 times, and more preferably less than 1 time.
  • the initial temperature of the atmosphere in the booth is 20 ⁇ 5 ° C.
  • a nail having a diameter of 2.5 mm to 5 mm is passed through the center of the non-aqueous electrolyte secondary battery in a direction perpendicular to the electrode surface, and left for 6 hours or more.
  • the initial temperature of the atmosphere in the booth in condition (i) may be measured at any position in the booth. However, the temperature is usually measured at a distance of 20 mm or more from the nonaqueous electrolyte secondary battery in the booth. In the condition (ii), the central part of the non-aqueous electrolyte secondary battery is within 10 mm around the center point of the electrode surface (positive electrode or negative electrode surface). Furthermore, there is no limit if the standing time is 6 hours or more, but usually it is 24 hours or less.
  • the nail penetration test described above may cause damage to the non-aqueous electrolyte secondary battery or non-aqueous electrolyte secondary battery. This is a test to analyze the behavior of the non-aqueous electrolyte secondary battery when a short circuit occurs due to impact or vibration from outside the pond. As a result of this nail penetration test, the above requirement is met if the non-aqueous electrolyte secondary battery is opened, ruptured or exploded in the non-aqueous electrolyte secondary battery when a short circuit occurs. This means that the amount of gas generated from the gas and the strength of the impact caused by the gas generation are small enough not to cause a practical problem.
  • Condition (3) is the surface temperature of the non-aqueous electrolyte secondary battery measured in the process when the non-aqueous electrolyte secondary battery of the present invention is subjected to a heating test under the following conditions using the above test apparatus. However, it does not exceed 50K above the ambient temperature at which the non-aqueous electrolyte secondary battery exists. Further, the surface temperature of the non-aqueous electrolyte secondary battery is preferably not more than 20K, more preferably not more than 10K, and more preferably not more than 5K. That is, the difference between the surface temperature and the ambient temperature of the non-aqueous electrolyte secondary battery is usually less than 50K, preferably less than 20K, more preferably less than 10K, and particularly preferably less than 5K.
  • the surface temperature of the non-aqueous electrolyte secondary battery in the test process is measured throughout the test.
  • the initial temperature of the atmosphere in the booth in condition (i) may be measured at any position in the booth. However, the temperature is usually measured at a distance of 20 mm or more from the non-aqueous electrolyte secondary battery in the booth.
  • the surface temperature of the non-aqueous electrolyte secondary battery can be measured with a thermocouple, a platinum resistance temperature detector, a thermistor, a radiation thermometer, or the like.
  • the pressure in the booth at the beginning of the test is usually preferably atmospheric pressure (0. IMPa).
  • the atmosphere in the booth is arbitrary, and either an inert gas or good air may be used. In some cases, other gases may be used.
  • the above heating test is a test for analyzing the degree of abnormal reaction at high temperature. As a result of this heating test, satisfying the above requirements means that the abnormal reaction at low temperatures and the generation of gas from the batteries are low even at high temperatures. Represent.
  • the degree of abnormal reaction during heating is also complicatedly related to the type, amount, and arrangement of the battery elements of the non-aqueous electrolyte secondary battery. Therefore, as in the case of the overcharge test and the nail clip test, when trying to develop a non-aqueous electrolyte secondary battery, a heating test is actually performed on the non-aqueous electrolyte secondary battery for analysis. Repeat what you do. At this time, a large amount of gas can also be generated in the non-aqueous electrolyte secondary battery power during the test process, so the test booth must be able to withstand the increase in booth internal pressure due to gas generation and be equipped with a treatment function for the generated gas. Is desirable. Therefore, it is considered that the performance and functions of the test equipment are also reflected in the non-aqueous electrolyte secondary battery developed using the test equipment.
  • the non-aqueous electrolyte secondary battery includes an exterior, and the total electrode area of the positive electrode with respect to the surface area of the exterior is 20 times or more in area ratio.
  • the non-aqueous electrolyte secondary battery has a DC resistance component of 10 milliohms (m ⁇ ) or less.
  • the non-aqueous electrolyte secondary battery has an outer package, and one battery is required to be stored in the outer package.
  • the electric capacity of the element is more than 3 amp hour (Ah).
  • the non-aqueous electrolyte secondary battery satisfying the above-mentioned property (a) has a large discharge capacity density, and is small compared to the discharge capacity. I like it.
  • a non-aqueous electrolyte secondary battery satisfying the property (b) is preferable because it has an advantage that a large current discharge can be performed because the battery internal resistance during charging and discharging is small.
  • the battery shape of the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, and examples thereof include a bottomed cylindrical shape, a bottomed square shape, a thin shape, a sheet shape, and a paper shape.
  • a different shape such as a horseshoe shape or a comb shape, taking into account the fit in the peripheral system arranged around the battery. Also good.
  • a rectangular shape having at least one relatively flat and large surface is preferable.
  • the largest surface area S (the product of the width and height of the outer dimensions excluding the terminal, unit m 2 ) is twice the thickness T (unit m)
  • the ratio 2SZT is preferably 100 or more, more preferably 200 or more.
  • the non-aqueous electrolyte secondary battery of the present invention includes a positive electrode and a negative electrode capable of occluding and releasing lithium ions, a non-aqueous electrolyte, a separator disposed between the positive electrode and the negative electrode, a current collecting terminal, and an outer case. At least composed. If necessary, protective elements may be mounted inside the battery and Z or outside the battery.
  • the positive electrode used for the non-aqueous electrolyte secondary battery of the present invention will be described below.
  • the positive electrode active material used for the positive electrode is described below.
  • the positive electrode active material is not particularly limited as long as it can electrochemically occlude / release lithium ions.
  • Substances containing lithium and at least one transition metal are preferred. Examples include lithium transition metal composite oxides and lithium-containing transition metal phosphate compounds.
  • lithium transition metal composite oxides include V, Ti, Cr, Mn, Fe, Co, Ni, and Cu.
  • lithium transition metal composite oxides such as LiCoO ⁇ ⁇ , LiNiO
  • Lithium nickel composite oxide such as 2 2 Lithium, LiMnO, LiMn O, Li MnO, etc.
  • transition metal atoms that are the main component of these complex metal oxides are Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga , Zr, Si and other metals substituted.
  • substituted one for example, LiNi Mn O, LiNi Co Al O, LiNi Co Mn O, LiMn Al
  • transition metals for lithium-containing transition metal phosphate compounds include V, Ti, Cr, Mn, Fe, Co, Ni, Cu, etc.
  • transition metals for lithium-containing transition metal phosphate compounds include V, Ti, Cr, Mn, Fe, Co, Ni, Cu, etc.
  • These surface-adhering substances are, for example, dissolved or suspended in a solvent and impregnated and dried in a positive electrode active material, or surface adhering substance precursor is dissolved or suspended in a solvent and impregnated in a positive electrode active material. After the addition, it can be attached to the surface of the positive electrode active material by a method of reacting by heating or the like, a method of adding to the positive electrode active material precursor and simultaneously firing it.
  • the amount of the surface adhering substance is, in terms of mass with respect to the positive electrode active material, preferably 0.1 ppm or more, more preferably 1 ppm or more, more preferably 10 ppm or more, and preferably 20% or less. More preferably, it is used at 10% or less, more preferably 5% or less.
  • the surface adhering substance can suppress the oxidation reaction of the non-aqueous electrolyte solution on the surface of the positive electrode active material and can improve the battery life. However, if the amount of the adhering quantity is too small, the effect cannot be fully expressed. If the amount is too large, the resistance may increase to inhibit the entry and exit of lithium ions.
  • the shape of the positive electrode active material particles is a block shape, a polyhedral shape, a spherical shape, an elliptical sphere as conventionally used. Shape, plate shape, needle shape, columnar shape, etc. are used, among which primary particles are aggregated to form secondary particles, and the shape of the secondary particles is preferably spherical or elliptical.
  • the active material in an electrode expands and contracts with the charge and discharge of an electrochemical element, so that the active material is easily damaged by the stress or the conductive path is broken. Therefore, it is preferable that the primary particles are aggregated to form secondary particles, rather than a single particle active material consisting of only primary particles, because the stress of expansion and contraction is relieved and deterioration is prevented.
  • spherical or oval spherical particles are less oriented when forming the electrode than plate-like equiaxed particles, so that there is less expansion and contraction of the electrode during charge and discharge. Even when mixed with a conductive agent, even though it is easy to mix evenly, it is preferable.
  • the tap density is measured by passing a sample having a mesh size of 300 ⁇ m, dropping the sample onto a 20 cm 3 taping cell to fill the cell volume, and then measuring a powder density measuring device (for example, Using a tap denser manufactured by Seisin Co., Ltd.), tapping with a stroke length of 10 mm is performed 1000 times, and the density obtained from the volume and the weight of the sample is defined as the tap density.
  • a powder density measuring device for example, Using a tap denser manufactured by Seisin Co., Ltd.
  • Particle diameter is usually 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, most preferably 3 ⁇ m or more, and the upper limit is usually 20 ⁇ m or less, preferably 18 ⁇ m or less More preferably, it is 16 / zm or less, most preferably 15 m or less. If the lower limit is not reached, a high bulk density product may not be obtained. If the upper limit is exceeded, it takes time to diffuse lithium in the particles, resulting in a decrease in battery performance or production of the positive electrode of the battery, that is, an active material. When a conductive agent or a binder is slurried with a solvent and applied in a thin film, a phenomenon such as streaking may occur.
  • two positive electrode active materials having different median diameters d are
  • the filling property at the time of producing the positive electrode can be further improved.
  • the median diameter d in the present invention is a known laser diffraction
  • the average primary particle size of the positive electrode active material is usually 0.01 ⁇ m or more, preferably 0.05 ⁇ m or more, and more Preferably it is 0.08 ⁇ m or more, most preferably 0.1 ⁇ m or more, and the upper limit is usually 3 ⁇ m or less, preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, and most preferably 0. 6 ⁇ m or less. If the above upper limit is exceeded, the powder filling properties that make it difficult to form spherical secondary particles are adversely affected, or the specific surface area is greatly reduced, so that the battery performance such as output characteristics is likely to deteriorate. There is. On the other hand, if the value is below the lower limit, a phenomenon such as inferior reversibility of charging / discharging due to the undeveloped crystal may occur.
  • the primary particle diameter is measured by observation using a scanning electron microscope (SEM). Specifically, in a photograph with a magnification of 10000 times, the longest value of the intercept by the left and right boundary lines of the primary particles with respect to the horizontal straight line is obtained for any 50 primary particles, and the average value is taken. Desired.
  • SEM scanning electron microscope
  • the BET specific surface area of the positive electrode active material is 0.2 m 2 Zg or more, preferably 0.3 m 2 Zg or more, more preferably 0.4 m 2 Zg or more, 4.0 m 2 Zg or less, preferably 2.5 m 2 Zg or less, more preferably 1.5 m 2 Zg or less. If the BET specific surface area force is smaller than this range, the battery performance will decrease, and if it is too large, the tap density will increase. May be easily reduced.
  • the BET specific surface area was measured with a surface area meter (for example, a fully automatic surface area measuring device manufactured by Okura Riken), preliminarily dried at 150 ° C for 30 minutes in a nitrogen stream, and then against the atmospheric pressure. This is defined as the value measured by the nitrogen adsorption BET one-point method using a nitrogen flow and gas flow method using a nitrogen and helium mixture gas that is precisely adjusted so that the relative pressure value of nitrogen is 0.3.
  • a surface area meter for example, a fully automatic surface area measuring device manufactured by Okura Riken
  • a general method is used as a manufacturing method of the inorganic compound.
  • various methods are conceivable for producing a spherical or elliptical active material.
  • transition metal raw materials such as transition metal nitrates and sulfates and, if necessary, raw materials of other elements such as water.
  • Dissolve in a solvent pulverize and disperse, adjust the pH while stirring to produce and recover a spherical precursor, dry it if necessary, and then use LiOH, Li CO,
  • Transition metal raw materials such as acid salts, hydroxides, oxides, and other raw material materials, if necessary, are dissolved in a solvent such as water, pulverized and dispersed, and then dried with a spray dryer or the like. Molded into spherical or ellipsoidal precursors with LiOH such as LiOH, Li CO, LiNO
  • transition metal source materials such as transition metal nitrates, sulfates, hydroxides and oxides
  • LiOH such as LiOH, Li CO and LiNO Source
  • the raw materials of other elements are dissolved or pulverized and dispersed in a solvent such as water, and then dried and molded with a spray dryer or the like to obtain a spherical or elliptical precursor, which is fired at a high temperature.
  • a solvent such as water
  • a spray dryer or the like examples thereof include a method for obtaining an active material.
  • the positive electrode is produced by forming a positive electrode active material layer containing positive electrode active material particles and a binder on a current collector.
  • Manufacture of the positive electrode using a positive electrode active material can be performed by a conventional method. That is, a positive electrode active material, a binder, and, if necessary, a sheet obtained by mixing a conductive material and a thickener, etc., in a dry manner, or a sheet that is pressure-bonded to the positive electrode current collector, or these materials as liquids Dissolve or disperse in a medium to form a slurry, which is applied to the positive electrode current collector and dried.
  • a positive electrode can be obtained by forming the positive electrode active material layer on the positive electrode active material layer.
  • the content of the positive electrode active material in the positive electrode active material layer is usually 10% by mass or more, preferably 30% by mass or more, and particularly preferably 50% by mass or more. Further, it is usually 99.9% by mass or less, preferably 99% by mass or less. If the content of the positive electrode active material in the positive electrode active material layer is low, the electric capacity may be insufficient. Conversely, if the content is too high, the strength of the positive electrode may be insufficient.
  • the positive electrode active material powder of the present invention may be used alone, or two or more of different compositions or different powder physical properties may be used in any combination and ratio.
  • a known conductive material can be arbitrarily used as the conductive material.
  • Specific examples include metal materials such as copper and nickel; black ships such as natural graphite and artificial black ships (graphite); carbon black such as acetylene black; and carbonaceous materials such as amorphous carbon such as needle coatus. I can get lost. These may be used alone or in combination of two or more in any combination and ratio.
  • the conductive material is usually at least 0.01 mass%, preferably at least 0.1 mass%, more preferably at least 1 mass%, and the upper limit is usually at most 50 mass%, It is preferably used so as to contain 30% by mass or less, more preferably 15% by mass or less. If the content is lower than this range, the conductivity may be insufficient. Conversely, if the content power is higher than this range, the battery capacity may decrease.
  • the binder used in the production of the positive electrode active material layer is not particularly limited.
  • any material that can be dissolved or dispersed in the liquid medium used in the production of the electrode may be used.
  • Ethylene butadiene.
  • Ethylene copolymer Thermoplastic elastomer-like polymer such as styrene 'isoprene' styrene block copolymer or hydrogenated product thereof; syndiotactic 1,2-polybutadiene, polyacetate butyl, ethylene 'butyl acetate copolymer, propylene' Soft resinous polymer such as a- olefin copolymer; poly (vinylidene fluoride) (PVdF), polytetrafluoroethylene, fluorinated poly (vinylidene fluoride), polytetrafluoroethylene 'ethylene copolymer And fluorine-based polymers such as polymer compositions having ion conductivity of alkali metal ions (particularly lithium ions). These substances may be used alone or in combination of two or more in any combination and ratio.
  • the ratio of the binder in the positive electrode active material layer is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and the upper limit is usually 80% by mass or less. It is preferably 60% by mass or less, more preferably 40% by mass or less, and most preferably 10% by mass or less. If the ratio of the binder is too low, the positive electrode active material cannot be sufficiently retained, and the mechanical strength of the positive electrode is insufficient, and battery performance such as cycle characteristics may be deteriorated. On the other hand, if it is too high, battery capacity and conductivity may be reduced.
  • the liquid medium for forming the slurry may be any kind of solvent that can dissolve or disperse the positive electrode active material, the conductive agent, the binder, and the thickener used as necessary. Either an aqueous solvent or an organic solvent may be used.
  • aqueous medium when used, it is preferable to make a slurry using a thickener and a latex such as styrene / butadiene rubber (SBR).
  • Thickeners are usually used to adjust the viscosity of the slurry.
  • the thickening agent is not particularly limited, and specific examples thereof include carboxy methenoresenorelose, methinoresenorelose, hydroxy methenoresenorelose, ethinoresenorelose, polybulu alcohol, oxidized starch, phosphorylated starch. , Casein and salts thereof. These may be used alone or in combination of two or more in any combination and ratio.
  • the ratio of the thickener to the active material is 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more.
  • the upper limit is usually 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less. Below this range, applicability may be significantly reduced. If it exceeds the upper limit, the proportion of the active material in the positive electrode active material layer may decrease, the battery capacity may decrease, and the resistance between the positive electrode active materials may increase.
  • the positive electrode active material layer obtained by coating and drying is preferably consolidated by a hand press, a roller press or the like in order to increase the packing density of the positive electrode active material.
  • the density of the positive electrode active material layer is preferably lgZcm 3 or more as a lower limit, more preferably 1.5 gZcm 3 , further preferably 2 gZcm 3 or more, and the upper limit is preferably 4 gZcm 3 or less, more preferably 3.5 gZcm 3 or less. More preferably, it is in the range of 3 gZcm 3 or less.
  • the permeability of the non-aqueous electrolyte to the vicinity of the current collector Z active material interface may decrease, and the charge / discharge characteristics at high current density may decrease.
  • the conductivity between the active materials may be reduced, and the battery resistance may be increased.
  • the thickness of the thin film is arbitrary, but usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and usually 1 mm or less, preferably 100 ⁇ m or less, more preferably 50 ⁇ m. It is as follows. If the thin film is thinner than this range, the strength required for the current collector may be insufficient. Conversely, the thin film may be handled with a thickness greater than this range, which may impair the performance.
  • the ratio of the thickness of the current collector to the positive electrode active material layer is not particularly limited, but (the thickness of the active material layer on one side immediately before non-aqueous electrolyte injection) Z (current collector thickness) is It is preferably 150 or less, particularly preferably 20 or less, more preferably 10 or less, and the lower limit is preferably 0.1 or more, particularly preferably 0.4 or more, more preferably 1 or more. is there. Above this range, the current collector may generate heat due to Joule heat during high current density charge / discharge. Below this range, the volume ratio of the current collector to the positive electrode active material may increase and the battery capacity may decrease.
  • the area of the positive electrode active material layer is preferably larger than the outer surface area of the battery outer case.
  • the total electrode area of the positive electrode with respect to the surface area of the external battery is preferably 20 times or more, more preferably 40 times or more.
  • the outer surface area of the outer case is the total area obtained by calculating the dimensional force of the vertical, horizontal, and thickness of the case part filled with the power generation element excluding the protruding part of the terminal in the case of a bottomed rectangular shape. . In the case of a bottomed cylindrical shape, it is a geometric surface area that approximates the case part filled with the power generation element excluding the protruding part of the terminal as a cylinder.
  • the total electrode area of the positive electrode is the geometric surface area of the positive electrode mixture layer facing the composite material layer containing the negative electrode active material, and in the structure in which the positive electrode mixture layer is formed on both sides via the current collector foil. , The sum of the areas where each surface is calculated separately.
  • the secondary battery 1 If the capacity of the battery element housed in the battery exterior (electric capacity when the battery is discharged to the fully charged state, the discharged state) is 3 Ah or more, the effect of improving the low-temperature discharge characteristics will increase. preferable. Therefore, the positive electrode plate is designed so that the discharge capacity is fully charged, usually 3 Ah or more, preferably 4 Ah or more, and usually 20 Ah or less, preferably lOAh or less. If it is less than 3 Ah, the voltage drop due to the electrode reaction resistance becomes large when taking out a large current, and the power efficiency may be deteriorated.
  • the negative electrode used for the non-aqueous electrolyte secondary battery of the present invention will be described below.
  • the negative electrode active material used for the negative electrode is described below.
  • the negative electrode active material is not particularly limited as long as it can electrochemically occlude and release lithium ions, metal oxides such as tin oxide and silicon oxide, and metal composite oxides. And lithium alloys such as simple lithium and lithium aluminum alloys, and metals that can form alloys with lithium such as Sn and Si. These may be used alone or in combination of two or more in any combination and ratio. Of these, carbonaceous materials or lithium complex oxides are preferably used in terms of safety.
  • the metal composite oxide is not particularly limited as long as it can occlude and release lithium. Force It contains titanium and Z or lithium as a constituent component so that high current density can be satisfied. Preferred in terms of discharge characteristics!
  • aromatic hydrocarbons such as caseena butylene, decacyclene, anthracene, phenanthrene, N-ring compounds such as phenazine atalidine, thiophene, bitiophene, etc.
  • S-ring compounds polyphenylenes such as biphenyl and terphenyl, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, insolubilized products of these, organic polymers such as nitrogen-containing polyacryl-tolyl, polypyrrole, Sulfur-containing polythiophene, organic polymers such as polystyrene, cellulose, lignin, mannan, polygalacturonic acid, chitosan, natural polymers such as polysaccharides such as saccharose, polyphenylene sulfide, polyphenylene oxide, etc.
  • Thermosetting resins such as thermoplastic resins, furfuryl alcohol resins, phenol-formaldehyde resins, and imide resins
  • thermoplastic resins furfuryl alcohol resins, phenol-formaldehyde resins, and imide resins
  • carbonized or carbonizable organic materials are benzene, toluene, xylene, quinoline, Solutions dissolved in low-molecular organic solvents such as n-hexane and their carbonization A carbonaceous material that has been heat-treated at least once in the range of 400-3200 ° C,
  • the ash content in the carbonaceous material may be 1% by mass or less, in particular 0.5% by mass or less, especially 0.1% by mass or less, and the lower limit is 1 ppm or more, based on the total mass of the carbonaceous material. preferable. If the above range is exceeded, battery performance degradation due to reaction with non-aqueous electrolyte during charge / discharge may not be negligible. Below this range, manufacturing may require significant time, energy and equipment to prevent contamination, which may increase costs.
  • the volume-based average particle size of carbonaceous material is the volume-based average particle size (median diameter) force obtained by the laser diffraction 'scattering method. Usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more More preferably, it is 7 ⁇ m or more.
  • the upper limit is usually 100 ⁇ m or less, preferably 50 m or less, more preferably 40 m or less, still more preferably 30 m or less, and particularly preferably 25 m or less. Below the above range, the irreversible capacity may increase, leading to loss of initial battery capacity. If the above range is exceeded, an electrode may be formed by coating, resulting in a non-uniform coating surface, which may be undesirable in the battery manufacturing process.
  • the Raman R value of the carbonaceous material measured using an argon ion laser Raman spectrum is usually 0.01 or more, preferably 0.03 or more, more preferably 0.10 or more, and the upper limit is 1.50 or less, preferably Is in the range of 1.2 or less, more preferably 1.0 or less, and still more preferably 0.50 or less. If the Raman R value is below this range, the crystallinity of the particle surface becomes too high, and there are cases where the number of sites where Li enters the interlayer increases with charge / discharge. In other words, chargeability may be reduced.
  • the negative electrode when the negative electrode is densified by applying it to the current collector and then pressing it, the crystals are likely to be oriented in a direction parallel to the electrode plate, which may lead to a decrease in load characteristics.
  • the crystallinity of the particle surface will decrease, the reactivity with the non-aqueous electrolyte will increase, and this may lead to a decrease in efficiency and an increase in gas generation.
  • the Raman half-value width of the near 1580 cm _1 of the carbonaceous material is not particularly limited, usually 10 cm _1 or more, preferably 15cm _ 1 or more, and as the upper limit, usually 100Cm- 1 or less, is preferred properly 80 cm _1 less More preferably, the range is 60 cm_1 or less, and still more preferably 40 cm_1 or less. If the Raman half width is less than this range, the crystallinity of the particle surface becomes too high, and there are cases where the number of sites where Li enters between layers decreases with charge and discharge. That is, charge acceptance may be reduced.
  • the negative electrode when the negative electrode is densified by applying it to the current collector and then pressing it, the crystals are likely to be oriented in a direction parallel to the electrode plate, which may lead to a decrease in load characteristics.
  • the crystallinity of the particle surface will decrease, the reactivity with the non-aqueous electrolyte will increase, and this may lead to a decrease in efficiency and an increase in gas generation.
  • the Raman R value of the carbonaceous material is defined as the Raman R value of the carbonaceous material.
  • the half-value width of peak P near 1580cm _ 1 of the obtained Raman spectrum was measured, and this was calculated as the Raman half-value of the carbonaceous material. Defined as width.
  • the specific surface area of the carbonaceous material was measured using the BET method is usually 0. lm 2 Zg above, rather preferably is 0. 7m 2 Zg or more, more preferably 1. 0 m 2 Zg or more, more preferably 1. 5 m 2 Zg or more.
  • the upper limit is usually 100 m 2 Zg or less, preferably 25 m 2 Zg or less, more preferably 15 m 2 Zg or less, still more preferably 10 m 2 Zg or less. If the value of the specific surface area is less than this range, the acceptability of lithium deteriorates during charging when it is used as a negative electrode material, and lithium is likely to precipitate on the electrode surface, which may reduce safety. On the other hand, if it exceeds this range, when used as a negative electrode material, the reactivity with the non-aqueous electrolyte increases, gas generation increases, and it may be difficult to obtain a favorable battery immediately.
  • the specific surface area according to the BET method is large after preliminarily drying the sample at 350 ° C for 15 minutes under a nitrogen flow using a surface area meter (for example, a fully automatic surface area measuring device manufactured by Okura Riken).
  • a surface area meter for example, a fully automatic surface area measuring device manufactured by Okura Riken.
  • the pore size distribution of the carbonaceous material is obtained by mercury porosimetry (mercury intrusion method).
  • the pore diameter is equivalent to 0.01 m or more and 1 m or less.
  • the amount of the contact surface between particles is not less than 0. OlmLZg, preferably not less than 0.05 mLZg, more preferably not less than 0.1 mLZg, and the upper limit is not more than 0.6 mLZg, preferably not more than 0.4 mLZg, more preferably 0.
  • the range is less than 3mLZg. Above this range In some cases, a large amount of binder may be required when the electrode plate is used. If it is lower than the range, the high current density charge / discharge characteristics may be deteriorated, and the expansion / contraction relaxation effect of the electrode during charge / discharge may not be obtained.
  • the total pore volume force corresponding to a pore diameter in the range of 0.01 ⁇ m to 100 m is preferably 0.1 mLZg or more, more preferably 0.25 mLZg or more, still more preferably 0.4 mLZg or more, and the upper limit.
  • 10 mLZg or less preferably 5 mLZg or less, more preferably 2 mLZg or less.
  • the average pore diameter is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, further preferably 0.5 ⁇ m or more, and the upper limit is 50 ⁇ m or less, preferably 20 It is in the range of ⁇ m or less, more preferably 10 m or less. Above this range, a large amount of binder may be required. If it is less, the high current density charge / discharge characteristics may deteriorate.
  • the average pore diameter is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, further preferably 0.5 ⁇ m or more, and the upper limit is 50 ⁇ m or less, preferably 20 It is in the range of ⁇ m or less, more preferably 10 m or less. Above this range, a large amount of binder may be required. If it is less, the high current density charge / discharge characteristics may deteriorate.
  • a mercury porosimeter (Autopore 9520: manufactured by Micrometrics) is used as an apparatus for mercury porosimetry. About 0.2 g of the sample is sealed in a cell for Noda, and pretreated by degassing for 10 minutes at room temperature under vacuum (50 mHg or less). Subsequently, the pressure is reduced to 4 psia (about 28 kPa), mercury is introduced, the pressure is increased stepwise from 4 psia (about 28 kPa) to 40000 psia (about 280 MPa), and then the pressure is reduced to 25 psia (about 170 kPa). The number of steps at the time of pressurization should be 80 points or more.
  • mercury intrusion is measured after an equilibration time of 10 seconds.
  • the mercury intrusion curve force obtained in this way is also used to calculate the pore size distribution using the Washburn equation.
  • the surface tension ( ⁇ ) of mercury is 485dyneZcm and the contact angle ( ⁇ ) is 140 °.
  • Circularity is used as the degree of sphericity of carbonaceous material, and its particle size is in the range of 3 to 40 m.
  • the circularity of the particles is preferably 0.1 or more, particularly preferably 0.5 or more, more preferably 0.8 or more, still more preferably 0.85 or more, and most preferably 0.9 or more. High circularity is preferable because high current density charge / discharge characteristics are improved.
  • the degree of circularity is defined by the following formula. When the degree of circularity is 1, it becomes a theoretical sphere.
  • the circularity value for example, a flow-type particle image analyzer (for example, FPIA manufactured by Sysmetas Industrial Co., Ltd.) was used, and about 0.2 g of a sample was added to polyoxyethylene (20) as a surfactant. dispersed in sorbitan monolaurate 0.2 mass 0/0 aqueous solution (about 50 mL), was irradiated for 1 minute ultrasound 28KH z at the output 60 W, specifies a detection range 0. 6 ⁇ 400 / ⁇ ⁇ Use the value measured for particles with a particle size in the range of 3-40 ⁇ m.
  • a flow-type particle image analyzer for example, FPIA manufactured by Sysmetas Industrial Co., Ltd.
  • the method for improving the circularity is not particularly limited, but a spheroidized sphere is preferred because the shape of the interparticle void when the electrode body is formed is preferable.
  • spheroidizing treatment include a method of mechanically bringing the particles into a spherical shape by applying a shearing force and a compressive force, and a mechanical / physical processing method in which a plurality of fine particles are granulated by the binder or the adhesive force of the particles themselves Etc.
  • True density of the carbonaceous material is usually 1. 4gZcm 3 or more, preferably 1. 6gZcm 3 or more, more preferably 1. 8gZcm 3 or more, more preferably 2. OgZcm 3 or more, the upper limit 2. 26gZcm 3 It is as follows. The upper limit is the theoretical value of graphite. Below this range, the crystallinity of the carbon is too low and the initial irreversible capacity may increase. In the present invention, the true density is defined by a value measured by a liquid phase substitution method (pitometer method) using butanol.
  • the tap density of the carbonaceous material is usually at least 0.1 lg / cm 3 , preferably at least 0.5 g / cm 3, more preferably at least 0.7 gZcm 3 , and particularly preferably at least lgZcm 3 .
  • the upper limit is preferably 2GZcm 3 or less, more preferably 1. 8gZcm 3 or less, particularly preferably 1. 6 g / cm 3 or less. If the tap density is below this range, it may not be possible to obtain a high-capacity battery in which the packing density is difficult to increase when used as a negative electrode.
  • the tap density is measured and defined by the same method as that described in the section of the positive electrode active material.
  • the orientation ratio is measured as follows by X-ray diffraction after molding the sample under pressure.
  • X-ray diffraction is measured by setting a molded product obtained by filling 0.47 g of a sample into a molding machine with a diameter of 17 mm and compressing it with 600 kgfZcm 2 so that it is flush with the surface of the sample holder for measurement. To do.
  • the X-ray diffraction measurement conditions here are as follows. “2 ⁇ ” indicates a diffraction angle.
  • the aspect ratio is theoretically 1 or more, and the upper limit is usually 10 or less, preferably 8 or less, more preferably 5 or less. If the upper limit is exceeded, streaking or a uniform coated surface may not be obtained during electrode plate deposition, and the high current density charge / discharge characteristics may deteriorate.
  • the aspect ratio is expressed as AZB, where the longest diameter A of the carbonaceous material particles when observed three-dimensionally and the shortest diameter B perpendicular to the carbonaceous material particles.
  • Observation of carbon particles Is performed with a scanning electron microscope capable of magnifying observation.
  • Sub-material mixture means that two or more carbonaceous materials having different properties are contained in the negative electrode and Z or the negative electrode active material.
  • the properties mentioned here are one or more of X-ray diffraction parameters, median diameter, aspect ratio, BET specific surface area, orientation ratio, Raman R value, tap density, true density, pore distribution, circularity, and ash content. The characteristics are shown.
  • V is not symmetrical with respect to the volume-based particle size distribution radians, or contains two or more carbonaceous materials having different Raman R values. And X-ray parameters are different.
  • carbonaceous materials such as graphite (graphite) such as natural graphite and artificial graphite, carbon black such as acetylene black, and amorphous carbon such as needle coatas are contained as a conductive agent.
  • the electrical resistance can be reduced.
  • the concentration of the carbonaceous material used as the conductive agent in the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass.
  • the upper limit is usually 45% by mass or less, preferably 40% by mass or less. Below this range, the effect of improving conductivity may be difficult to obtain. If exceeded, the initial irreversible capacity may increase.
  • the electrode may be manufactured by a conventional method. For example, it is formed by adding a binder, a solvent, and, if necessary, a thickener, a conductive material, a filler, etc. to a negative electrode active material to form a slurry, which is applied to a current collector, dried and then pressed. be able to.
  • the thickness of the negative electrode active material layer per side in the stage immediately before the non-aqueous electrolyte injection process of the battery is usually 15 m or more, preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, and the upper limit is It is 150 ⁇ m or less, preferably 120 m or less, more preferably 100 m or less.
  • the non-aqueous electrolyte solution hardly penetrates to the vicinity of the current collector interface, so the high current density charge / discharge characteristics are degraded. There is a case. Below this range, the volume ratio of the current collector to the negative electrode active material increases, and the battery capacity may decrease. Further, the negative electrode active material may be formed into a sheet electrode by roll molding, or may be formed into a pellet electrode by compression molding.
  • any known current collector can be used.
  • the current collector of the negative electrode include metal materials such as copper, nickel, stainless steel, nickel-plated steel, etc. Among these, copper is particularly preferable because of its ease of processing and cost.
  • the current collector is a metal material
  • examples of the shape of the current collector include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punch metal, and foam metal.
  • a metal thin film more preferably a copper foil, more preferably a rolled copper foil by a rolling method and an electrolytic copper foil by an electrolytic method, both of which can be used as a current collector.
  • a copper alloy phosphor bronze, titanium copper, Corson alloy, Cu—Cr—Zr alloy, etc.
  • the current collector made of copper foil produced by the rolling method has a small cylindrical battery that is resistant to cracking even if the negative electrode is rolled tightly or sharply, because the copper crystals are aligned in the rolling direction. Can be suitably used.
  • electrolytic copper foil for example, immerses a metal drum in a non-aqueous electrolyte solution in which copper ions are dissolved, and allows current to flow while rotating the copper drum, thereby depositing copper on the surface of the drum. It can be obtained by peeling off.
  • copper may be deposited on the surface of the rolled copper foil by an electrolytic method.
  • one or both surfaces of the copper foil may be subjected to a roughening treatment or a surface treatment (for example, a chromate treatment with a thickness of about several ⁇ ! To 1 ⁇ m, a base treatment such as Ti). .
  • the average surface roughness (Ra) of the negative electrode active material thin film forming surface of the current collector substrate defined by the method described in JISB0601—1994 is not particularly limited, but is usually 0.05 ⁇ m or more, preferably ⁇ or 0 Above, particularly preferably ⁇ is 0.15 / zm or more, usually 1.5 / zm or less, preferably 1.3 m or less, particularly preferably 1. O / zm or less.
  • the upper limit of the average surface roughness (Ra) is not particularly limited, but those with an average surface roughness (Ra) exceeding 1.5 m are generally available as foils of practical thickness as batteries. Since it is difficult, a length of 1.5 m or less is preferable.
  • the tensile strength of the current collector substrate is not particularly limited, but is usually lOONZmm 2 or more, preferably 250 NZmm 2 or more, more preferably 400 NZmm 2 or more, and particularly preferably 500 NZ mm 2 or more.
  • Tensile strength is the maximum tensile force required for a specimen to break, divided by the cross-sectional area of the specimen.
  • the tensile strength in the present invention is measured by the same apparatus and method as the elongation percentage. If the current collector substrate has a high tensile strength, the negative electrode active material thin film can be prevented from expanding due to charging and discharging, and cracking of the current collector substrate can be suppressed, and good cycle characteristics can be obtained. Can do.
  • the 0.2% resistance of the current collector substrate is not particularly limited, but is usually 30 NZmm 2 or more, preferably 150 NZmm 2 or more, and particularly preferably 300 NZmm 2 or more.
  • 0.2% proof stress is the amount of load necessary to give a plastic (permanent) strain of 0.2%, and even if it is unloaded after applying this amount of load, it deforms by 0.2%. It means that 0.2% resistance is measured with the same equipment and method as elongation. 0.
  • a current collector substrate having a high 2% proof stress can suppress plastic deformation of the current collector substrate due to expansion and contraction of the negative electrode active material thin film accompanying charging and discharging, and obtain good cycle characteristics. Can do.
  • the thickness ratio between the current collector and the negative electrode active material layer is not particularly limited, but (non-aqueous electrolyte injection)
  • the thickness of the negative electrode active material layer on one side immediately before) Z is preferably 150 or less, particularly preferably 20 or less, more preferably 10 or less, and the lower limit is 0.1 or more
  • Particularly preferred is a range of 0.4 or more, more preferably 1 or more. Above this range, the current collector may generate heat due to Joule heat during high current density charge / discharge. Below this range, the volume ratio of the current collector to the negative electrode active material may increase and the battery capacity may decrease.
  • the binder for binding the negative electrode active material is not particularly limited as long as it is a material that is stable with respect to the non-aqueous electrolyte solution and the solvent used in manufacturing the electrode.
  • any solvent can be used as long as it can dissolve or disperse the negative electrode active material, the binder, and the thickener and conductive agent used as necessary.
  • Either an aqueous solvent or an organic solvent may be used without particular limitation. Examples of aqueous solvents include water, alcohol, etc.
  • organic solvents examples include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylethylketone, cyclohexanone, methyl acetate, acrylic Methyl acid, Jettiltriamine, N-N-dimethylaminopropylamine, Tetrahydrofuran (THF), Toluene, Acetone, Jetyl ether, Dimethylacetamide, Hexamethylphosphalamide, Dimethylsulfoxide, Benzene, Xylene Quinoline, pyridine, methylnaphthalene, hexane and the like.
  • NMP N-methylpyrrolidone
  • dimethylformamide dimethylacetamide
  • methylethylketone cyclohexanone
  • methyl acetate acrylic Methyl acid
  • Jettiltriamine N-N-dimethylaminopropylamine
  • THF Tetrahydrofuran
  • a dispersant or the like is added to the thickener, and the mixture is slurried using a latex such as SBR.
  • a dispersant or the like is added to the thickener, and the mixture is slurried using a latex such as SBR.
  • the ratio of the binder to the negative electrode active material is preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, more preferably 0.6% by mass or more. Usually, it is 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 8% by mass or less. If the amount exceeds this range, the binder ratio in which the binder amount does not contribute to the battery capacity increases, and the battery capacity may be reduced. On the other hand, if it is lower, the strength of the negative electrode may be reduced.
  • the ratio of the noder to the negative electrode active material is 0.1% by mass or more, preferably 0.5% by mass or more.
  • the upper limit is usually 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less.
  • the ratio to the negative electrode active material is 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass.
  • the upper limit is 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less. It is a circle.
  • the electrode plate orientation ratio is preferably 0.001 or more, particularly preferably 0.005 or more, more preferably 0.01 or more, and the upper limit is a theoretical value of 0.67 or less. Below this range, the high-density charge / discharge characteristics may deteriorate.
  • the measurement of the electrode plate orientation ratio is as follows.
  • the negative electrode active material orientation ratio of the electrode is measured by X-ray diffraction.
  • the specific method is not particularly limited, but the standard method is to fit the (110) and (004) diffraction peaks of carbon by X-ray diffraction using asymmetric Pearson VII as the profile function. Further peak separation is performed, and the integrated intensities of the (110) diffraction and (004) diffraction peaks are calculated. From the obtained integrated intensity, a ratio represented by (110) diffraction integrated intensity Z (004) diffraction integrated intensity is calculated and defined as the negative electrode active material orientation ratio of the electrode.
  • Electrode is fixed to glass plate with double-sided tape of 0.1mm thickness
  • the resistance of the negative electrode when the discharge state force is charged to 60% of the nominal capacity preferably 100 ⁇ or less, particularly preferably 50 ⁇ or less, more preferably 20 ⁇ or less, and the Z or double layer capacity is IX 10 _6 F
  • the above is particularly preferably 1 ⁇ 10_5 F, more preferably 1 ⁇ 10_4 F. Within this range, the output characteristics are good and preferable.
  • the resistance and double layer capacity of the negative electrode are measured by the following procedure.
  • the non-aqueous electrolyte secondary battery to be measured is charged at a current value that can be charged in a nominal capacity of 5 hours, then charged and discharged for 20 minutes, and then the nominal capacity is discharged in an hour.
  • the non-aqueous electrolyte secondary battery is quickly disassembled and taken out without the negative electrode being discharged or short-circuited, and if it is a double-sided coated electrode, the negative electrode active material on one side is peeled off without damaging the negative electrode active material on the other side. Then, punch out two negative electrodes to 12.5mm ⁇ and face each other through the separator so that the surface of the negative electrode active material is not displaced. 60 ⁇ L of the non-aqueous electrolyte used in the battery was dropped and adhered between the separator and both negative electrodes, and kept in contact with the outside air! Execute the AC impedance method. Measurement is temperature
  • the area of the negative electrode plate is not particularly limited, but is designed to be slightly larger than the opposing positive electrode plate so that the positive electrode plate does not protrude outside the negative electrode plate force. From the viewpoint of suppressing the cycle life after repeated charge and discharge and the deterioration due to high temperature storage, it is preferable to make the area as close to the positive electrode as possible, since the ratio of electrodes that work more uniformly and effectively is increased and the characteristics are improved. In particular, the design of this electrode area is important when used at high currents.
  • the thickness of the negative electrode plate is designed according to the positive electrode plate used, and is not particularly limited. However, the thickness of the composite layer obtained by subtracting the thickness of the metal foil of the core is usually 15 m or more
  • the upper limit is 150 ⁇ m or less, preferably 120 ⁇ m or less, more preferably 100 ⁇ m or less.
  • the lithium salt is not particularly limited as long as it is known to be used as an electrolyte of a non-aqueous electrolyte solution for a non-aqueous electrolyte secondary battery, and examples thereof include the following.
  • Inorganic fluoride salts such as LiPF, LiBF, LiAsF, LiSbF; LiCIO, LiBrO, LilO
  • Perhalogenates such as 6 4 6 6 4 4 4; inorganic chloride salts such as LiAlCl.
  • Perfluoroalkane sulfonates such as LiCF SO; LiN (CF SO), LiN (CF C
  • Perfluoroalkane sulfonimide salts such as F SO) and LiN (CF SO) (C F SO)
  • Perfluoroalkane sulfolmethide salt such as LiC (CF SO); Li [PF (CF CF C
  • Fluoro such as Li [PF (CF CF CF CF)], Li [PF (CF CF CF CF)]
  • Lithium difunoleoleoxalate borate lithium bis (oxalato) borate, etc.
  • LiPF, LiBF, etc. are preferred when comprehensively judging the solubility in non-aqueous solvents, the charge / discharge characteristics of secondary batteries, output characteristics, cycle characteristics, etc.
  • the concentration of the lithium salt in the nonaqueous electrolytic solution is not particularly limited, but is usually 0.3 mol / L or more, preferably 0.6 molZL or more, and more preferably 0.7 molZL or more.
  • the upper limit is usually 2 molZL or less, preferably 1.8 molZL or less, more preferably 1.7 molZL or less. If the concentration is too low, the electrical conductivity of the non-aqueous electrolyte may be insufficient. On the other hand, if the concentration is too high, the electrical conductivity may decrease due to an increase in viscosity. Battery performance may be reduced.
  • the non-aqueous electrolyte preferably contains a fluorine-containing lithium salt as the lithium salt.
  • the concentration of the fluorine-containing lithium salt in the nonaqueous electrolytic solution is not particularly limited, but is preferably 0.5 molZL or more, particularly preferably 0.7 molZL or more. Further, the upper limit is preferably 2 molZL or less, and 1.7 molZL or less is particularly preferable. If the concentration is too low, the electrical conductivity of the non-aqueous electrolyte may be insufficient.On the other hand, if the concentration is too high, the electrical conductivity will decrease due to an increase in viscosity, resulting in a non-aqueous electrolyte secondary solution. Battery performance may be reduced.
  • One lithium salt may be used alone, or two or more lithium salts may be used in any combination and ratio.
  • a preferred example of using two or more lithium salts in combination is LiPF.
  • the amount is not less than 20% by mass and not more than 20% by mass, and more preferably not less than 0.1% by mass and not more than 5% by mass.
  • Another preferred example is the combined use of an inorganic fluoride salt and a perfluoroalkanesulfonilimide salt.
  • the proportion of the inorganic fluoride salt in the total of both is 70% by mass or more, It is particularly preferably 99% by mass or less, more preferably 80% by mass or more and 98% by mass or less.
  • the combined use of both has the effect of suppressing deterioration due to high temperature storage.
  • non-aqueous solvent it can be appropriately selected from those conventionally proposed as solvents for non-aqueous electrolyte solutions. For example, the following are mentioned.
  • the number of carbon atoms of the alkylene group constituting the cyclic carbonate is particularly preferably 2-6. 2-4. Specific examples include ethylene carbonate, propylene carbonate, butylene carbonate and the like. Of these, ethylene carbonate and propylene carbonate are preferred.
  • cyclic ester examples include ⁇ -petit-mouth rataton, ⁇ -valerolataton, and the like.
  • chain ester examples include methyl acetate, ethyl acetate, propyl acetate, methyl propionate and the like.
  • cyclic ether examples include tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran and the like.
  • chain ether examples include dimethoxyethane and dimethoxymethane.
  • sulfur-containing organic solvent examples include sulfolane and jetyl sulfone.
  • One preferred combination of the non-aqueous solvents is a combination mainly composed of cyclic carbonates and chain carbonates.
  • the total power of the cyclic carbonates and the chain force-bonates in the nonaqueous solvent is 85% by volume or more, preferably 90% by volume or more, more preferably 95% by volume or more.
  • the capacity of the cyclic carbonates relative to the total of the cyclic carbonates and the chain carbonates is 5% or more, preferably 10% or more, more preferably 15% or more, and usually 50% or less, preferably 35%. Below, more preferably 30% or less, and still more preferably 25% or less. It is particularly preferred that the above preferred volume range of the total amount of carbonates in the whole non-aqueous solvent and the preferred range of cyclic carbonates relative to cyclic and chain carbonates are combined.
  • Preferred examples of the combination of cyclic carbonates and chain carbonates include ethylene carbonate and dimethyl carbonate, ethylene carbonate and jetyl carbonate, ethylene carbonate and ethino retino carbonate, ethylene carbonate and dimethyl carbonate. And ethylene carbonate, dimethyl carbonate, ethinoremethinole carbonate, ethylene carbonate, jetino carbonate, ethylmethyl carbonate, ethylene carbonate, dimethyl carbonate, jetyl carbonate, ethylmethyl carbonate, etc. It is done.
  • a combination in which propylene carbonate is further combined with the combination of these ethylene carbonates and chain carbonates is also a preferable combination.
  • the volume ratio of ethylene carbonate to propylene carbonate is preferably 99: 1 to 40:60 S, particularly preferably 95: 5 to 50:50.
  • those containing asymmetric chain carbonates are more preferred, especially ethylene carbonate and dimethyl carbonate and ethylmethyl carbonate, ethylene strength -bonate, jetinole carbonate and ethinolemethinole.
  • Carbonate, ethylene carbonate, dimethylolate carbonate, jetinole carbonate, and ethinoremethinole carbonate, which contain ethylene carbonate, symmetric chain carbonates, and asymmetric chain carbonates, have cycle characteristics and large current discharge characteristics. Is preferable because the balance of Of these, it is preferable that the asymmetric chain carbonate is ethylmethyl carbonate.
  • the alkyl group constituting the dialkyl carbonate preferably has 1 to 2 carbon atoms!
  • non-aqueous solvent examples include a chain ester.
  • methyl acetate and ethyl acetate are particularly preferred chain esters from the viewpoint of improving the low-temperature characteristics of a battery that contains a chain ester in a mixed solvent of cyclic carbonates and chain carbonates.
  • the capacity of the chain ester in the non-aqueous solvent is usually 5% or more, preferably 8% or more, more preferably 15% or more, usually 50% or less, preferably 35% or less, more preferably 30% or less, More preferably, it is 25% or less.
  • Examples of other preferable non-aqueous solvents include ethylene carbonate, propylene carbonate, ⁇
  • the amount of gamma petit rataton in the non-aqueous solvent is 60% by volume or more, or the total force of ethylene carbonate and 0-petit lataton in the non-aqueous solvent is 80% by volume or more, preferably 90% by volume.
  • the volume ratio of ethylene carbonate and ⁇ -butyrolacton is 5: 95-45: 55, or the total power of ethylene carbonate and propylene carbonate in the non-aqueous solvent is 80% by volume or more.
  • the volume ratio is preferably 90% by volume or more and the volume ratio of ethylene carbonate to propylene carbonate is 30:70 to 60:40, the balance between cycle characteristics and large current discharge characteristics is generally improved.
  • the non-aqueous electrolyte solution in the non-aqueous electrolyte secondary battery of the present invention further includes a cyclic siloxane compound represented by the general formula (1), a fluorosilane compound represented by the general formula (2), and a general formula (3).
  • a cyclic siloxane compound represented by the general formula (1) a fluorosilane compound represented by the general formula (2)
  • a general formula (3) a general formula (3).
  • One or more compounds selected from the group consisting of a compound represented by the formula, a compound having an S—F bond in the molecule, nitrate, nitrite, monofluorophosphate, difluorophosphate, acetate and propionate may be contained in any amount as required.
  • R 1 and R 2 may be the same or different from each other] 2 represents an organic group, and n represents an integer of 3 to 10. ]
  • R 3 to R 5 represent the same or different organic group having 1 to 12 carbon atoms, X represents an integer of 1 to 3, p, q and Each r represents an integer from 0 to 3, l ⁇ p + q + r ⁇ 3. ]
  • the non-aqueous electrolyte containing at least one lithium salt and the above-mentioned specific compound in the non-aqueous solvent (mixed solvent) is a cycle characteristic and a high-temperature storage characteristic (particularly, a battery produced using this). , Remaining capacity after high temperature storage and high load discharge capacity) and gas generation suppression bar I like lance because it improves!
  • these specific compounds can suppress side reactions with the electrolytic solution and the like by adsorbing on the surface of the positive electrode active material or the surface of the metal material.
  • gas generation can be suppressed, and generation of gas at the time of battery breakdown or internal short circuit can be suppressed.
  • R 1 and R 2 in the cyclic siloxane compound represented by the general formula (1) are organic groups having 1 to 12 carbon atoms which may be the same or different from each other.
  • R 1 and R 2 include
  • Chain alkyl groups such as methyl group, ethyl group, n propyl group, isopropyl group, butyl group, isobutyl group, se c butyl group and t butyl group; cyclic alkyl groups such as cyclohexyl group and norbornyl group; 1 Alkyl group such as probe group, aryl group, butyl group, 1, 3 butagel group; alkyl group such as etulyl group, propylene group, and butyl group
  • a halogen group such as a trifluoromethyl group; an alkyl group having a saturated heterocyclic group such as a 3-pyrrolidinopropyl group; an alkyl substituent, an aryl group such as a phenyl group; Groups: aralkyl groups such as a phenylmethyl group and a phenylethyl group; a trialkylsilyl group such as a trimethylsilyl group; a trialkylsiloxy group such as a trimethylsiloxy group;
  • organic compounds having 1 to 6 carbon atoms are more likely to exhibit characteristics when they have fewer carbon atoms.
  • Groups are preferred.
  • the alkell group acts on the non-aqueous electrolyte and the coating on the electrode surface to improve the input / output characteristics, and the allyl group captures radicals generated in the battery during charge and discharge to improve overall battery performance. This is preferable. Therefore, as R 1 and R 2 , a methyl group, a vinyl group or a phenyl group is particularly preferable.
  • n is preferably an integer of 3 to 6 representing an integer of 3 to 10, and particularly preferably 3 or 4.
  • Examples of the cyclic siloxane compound represented by the general formula (1) include hexamethylcyclotrisiloxane, hexahexylcyclotrisiloxane, hexaphenylcyclotrisiloxane,
  • 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane and other cyclotrisiloxanes 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane and other cyclotrisiloxanes, otamethylcyclotetrasiloxane and other cyclotetrasiloxanes, decamethylcyclopentasiloxane and other cyclopentasiloxanes Can be mentioned. Of these, cyclotrisioxane is particularly preferred.
  • R 3 to R 5 in the fluorosilane compound represented by the general formula (2) are organic groups having 1 to 12 carbon atoms which may be the same as or different from each other.
  • R 3 to R 5 include a chain alkyl group, a cyclic alkyl group, an alkenyl group, an alkyl group, a halogenated alkyl group mentioned as examples of R 1 and R 2 in the general formula (1),
  • an aryl group such as an alkyl group having a saturated heterocyclic group, a phenyl group that may have an alkyl group, an aralkyl group, a trialkylsilyl group, a trialkylsiloxy group, an ethoxycarbolethyl group, etc.
  • Carbonyl group carboxy group such as acetoxy group, acetooxymethyl group, trifluoroacetoxy group; oxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, aroxy group; amino group such as allylamino group; A benzyl group etc. can be mentioned.
  • the fluorosilane compound represented by the general formula (2) volatilizes when the boiling point is low, so that it may be difficult to add a predetermined amount to the non-aqueous electrolyte.
  • the battery even after inclusion in a non-aqueous electrolyte, there is a possibility that the battery will generate heat due to charge and discharge and may volatilize under conditions that cause the external environment to become hot. Accordingly, those having a boiling point of 50 ° C. or higher at 1 atm are preferable, and those having a boiling point of 60 ° C. or higher are particularly preferable.
  • R 6 to R 8 in the compound represented by the general formula (3) are organic groups having 1 to 12 carbon atoms which may be the same as or different from each other.
  • R 6 to R 8 include chain alkyl groups, cyclic alkyl groups, alkyl groups, alkyl groups, halogenated alkyl groups mentioned as examples of R 3 to R 5 in the general formula (2), An alkyl group having a saturated heterocyclic group, an aryl group such as a phenyl group which may have an alkyl group, an aralkyl group, a trialkylsilyl group, a trialkylsiloxy group, a carboxylic group, a carboxyl group, an oxy group, An amino group, a benzyl group, etc. can be mentioned similarly.
  • a in the compound represented by the general formula (3) is not particularly limited as long as A is a group that also constitutes H, C, N, 0, F, S, Si, and Z or P force.
  • C, S, Si or P is preferable as the element directly bonded to the oxygen atom in the general formula (3).
  • Examples of the existence form of these atoms include a chain alkyl group, a cyclic alkyl group, an alkyl group, an alkyl group, and a halo group. Those contained in a genated alkyl group, a carbonyl group, a sulfol group, a trialkylsilyl group, a phosphoryl group, a phosphier group and the like are preferable.
  • Examples of the compound represented by the general formula (3) include hexamethyldisiloxane, 1,3 dimethyltetramethyldisiloxane, hexaethyldisiloxane, and otamethyltrisiloxane.
  • Siloxane compounds alkoxysilanes such as methoxytrimethylsilane and ethoxytrimethylsilane; peracids such as bis (trimethylsilyl) peroxide; trimethylsilyl acetate, triethylsilyl acetate, trimethylsilyl propionate, trimethylsilyl methacrylate, trifluoroacetic acid Carboxylic acid esters such as trimethylsilyl; sulfonic acid esters such as trimethylsilyl methanesulfonate, trimethylsilyl ethanesulfonate, triethylsilyl methanesulfonate, and trimethylsilyl fluoromethanesulfonate; bis (trimethylsilyl) (1) Sulfate esters such as sulfate; Phosphoric acid esters such as tris (trimethylsiloxy) boron; Phosphoric acid or phosphite esters such as tris (trimethylsily
  • siloxane compounds sulfonic acid esters, and sulfate esters are preferred. Sulfonic acid esters are particularly preferred.
  • bis (trimethylsilyl) sulfate is preferred as the sulfonic acid ester in which hexamethyldisiloxane is preferred, and as the sulfate ester in which trimethylsilyl methanesulfonate is preferred.
  • the compound having an S—F bond in the molecule is not particularly limited, but sulfofluorides and fluorosulfonic acid esters are preferable.
  • methanesulfur fluoride methane bis (s
  • NI 12 (wherein each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms), quaternary ammonia, and the like.
  • the organic group having 1 to 12 carbon atoms of R 9 to R 12 may be substituted with a halogen atom, or may be substituted with an alkyl group or a halogen atom !, may! /, Cycloalkyl.
  • R 9 to R 12 an aryl group optionally substituted with a halogen atom, a nitrogen atom-containing heterocyclic group, and the like.
  • R 9 to R 12 a hydrogen atom, an alkyl group, a cycloalkyl group, a nitrogen atom-containing heterocyclic group, and the like are preferable.
  • Specific compounds that is, cyclic siloxane compounds represented by general formula (1), fluorosilane compounds represented by general formula (2), compounds represented by general formula (3), intramolecular
  • any compound having an S—F bond, nitrate, nitrite, monofluorophosphate, difluorophosphate, acetate or propionate may be used alone, or two or more compounds may be used. You may use together in a combination and a ratio.
  • one kind may be used alone, or two or more kinds of compounds may be used in any combination and ratio.
  • the ratio of these specific compounds in the non-aqueous electrolyte is generally a total of lOppm or more (0.001% by mass or more) with respect to the total non-aqueous electrolyte, preferably 0.01 mass % Or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more.
  • the upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and still more preferably 3% by mass or less. If the concentration of the specific compound is too low, it may be difficult to obtain the effect of maintaining the output characteristics and the effect of suppressing gas generation even after long-term use, while if the concentration is too high, the charge / discharge efficiency may be reduced. May invite.
  • the non-aqueous electrolyte solution in the non-aqueous electrolyte secondary battery of the present invention can further contain other compounds as required in an arbitrary amount within a range not impairing the effects of the present invention.
  • other compounds specifically, for example,
  • overcharge prevention agents biphenyl, alkyl biphenyl, terfal, tarfal partially hydride, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenol.
  • Aromatic compounds such as ether and dibenzofuran are preferred. These may be used alone or in combination of two or more in any combination and ratio. However, when two or more kinds are used in combination, it is particularly preferable to use cyclohexylbenzene or terfal (or a partially hydrogenated product thereof) together with t-butylbenzene or t-amylbenzene.
  • the negative electrode film-forming agent carbonate, butylethylene carbonate, fluoroethylene carbonate, succinic anhydride, and maleic anhydride are preferable. These can be used alone. Two or more can be used in any combination and ratio.
  • the positive electrode protective agent ethylene sulfite, propylene sulfite, propane sultone, butane sultone, methyl methanesulfonate, and busulfan are preferable. These may be used alone or in combination of two or more in any combination and ratio. Further, the combined use of a negative electrode film forming agent and a positive electrode protective agent, and the combined use of an overcharge inhibitor, a negative electrode film forming agent, and a positive electrode protective agent are particularly preferred.
  • the separator has a predetermined mechanical strength that electrically insulates both electrodes, has a high ion permeability, and has resistance to acidity on the side in contact with the positive electrode and reduction on the negative electrode side. If so, it is not particularly limited.
  • a material of the separator having such required characteristics for example, a resin, an inorganic material, a glass fiber, or the like is used.
  • the above-mentioned resins include polyolefin polymers, fluorine polymers, cellulose polymers, polymers Riimide, nylon or the like is used.
  • oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate are used. Things are used.
  • a thin film shape such as a nonwoven fabric, a woven fabric, or a microporous film is used. In the thin film shape, those having a pore diameter of 0.01 to 1; ⁇ ⁇ and a thickness force of 50 m are preferably used.
  • a separator formed by forming a composite porous layer containing inorganic particles on the positive electrode and the surface layer of Z or negative electrode using a resin binder is used.
  • the separator may be integrally formed as an electrode group together with the positive electrode and the negative electrode.
  • the electrode group for example, a layered structure in which the above-described positive electrode plate and negative electrode plate are interposed via the above-described separator, and the above-described positive electrode plate and negative electrode plate are interposed via the above-described separator. Any one having a spirally wound structure may be used.
  • the ratio of the electrode group volume to the battery internal volume (hereinafter referred to as electrode group occupancy ratio) is usually 40% or more, preferably 50% or more, and usually 90% or less, preferably 80% or less. . If the electrode group occupancy is less than 40%, the battery capacity is small, and if it is 90% or more, the battery expands due to the high temperature of the battery with less void space, and the vapor pressure of the liquid component of the electrolyte is high. As a result, the internal pressure rises, and the characteristics such as repeated charge / discharge performance and high-temperature storage of the battery may be deteriorated. Furthermore, the gas release valve that releases the internal pressure may be activated.
  • the non-aqueous electrolyte secondary battery of the present invention preferably includes a current collecting terminal as appropriate.
  • the current collecting terminal is a terminal used to construct a current collecting structure that reduces the resistance of the wiring part and the joint part. In order to more effectively realize the above-described improvement of the low-temperature discharge characteristics by the non-aqueous electrolyte solution. It is suitable for use. By forming such a current collecting structure, the wiring part The effect of using the non-aqueous electrolyte is particularly good when the internal resistance of the part or the joint is reduced.
  • a current collecting structure of a type formed by bundling the metal core portions of each electrode layer and welding them to the current collecting terminal is preferably used. It is done. For example, when the area of one electrode increases, the internal resistance increases. Therefore, it is also preferable to reduce the resistance by providing a plurality of current collecting terminals in the electrode. Furthermore, for example, in the case where the electrode group has the winding structure described above, the internal resistance can be lowered by providing a plurality of lead structures on the positive electrode and the negative electrode, respectively, and bundling the current collector terminals.
  • the internal resistance can be minimized.
  • the impedance measured by the 10 kHz AC method (hereinafter abbreviated as “DC resistance component”) be 10 milliohms (m ⁇ ) or less. It is more preferred that the component is 5 milliohms (m ⁇ ) or less. If the DC resistance component is 0.1 milliohm or less, the high output characteristics will be improved, but the proportion of the current collector structure (current collector terminal, etc.) used will increase and the battery capacity may decrease.
  • the non-aqueous electrolyte described above is effective in reducing the reaction resistance related to lithium insertion / extraction with respect to the electrode active material, which is a factor that can realize good low-temperature discharge characteristics.
  • a battery with a normal DC resistance greater than 10 milliohms ( ⁇ ) may be blocked by DC resistance, and the effect of reducing reaction resistance may not be 100% reflected in the low-temperature discharge characteristics.
  • ⁇ milliohms
  • the material of the outer case is not particularly limited as long as it is a substance that is stable with respect to the nonaqueous electrolyte used. Specific examples include nickel-plated steel sheets, stainless steel, aluminum or aluminum alloys, magnesium alloys and other products, or products of resin and aluminum foil. A layer film (laminate film) is used. From the viewpoint of light weight, an aluminum or aluminum alloy metal or a laminate film is preferably used.
  • the metal is welded to each other by laser welding, resistance welding, or ultrasonic welding to form a sealed hermetically sealed structure, or the metal through a resin gasket There is a structure using a force structure.
  • Examples of the outer case using the laminate film include those having a sealed and sealed structure by heat-sealing the resin layers.
  • a resin different from the resin used for the laminate film may be interposed between the resin layers.
  • the resin having a polar group as the intervening resin is a polar group. Modified sebaceous oil into which is introduced is preferably used.
  • PTC Pressure Temperature Coefficient
  • thermal fuse thermistor
  • thermistor whose resistance increases when abnormal heat generation or excessive current flows, current flowing in the circuit due to sudden rise in internal pressure or internal temperature of the battery when abnormal heat generation occurs
  • a valve that cuts off current can be used.
  • a protective element that does not work under normal use at a high current.
  • the method for producing the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, and can be performed by any method.
  • it can be manufactured by the following method. That is, the positive electrode and the negative electrode are alternately arranged, and are stacked or wound so that the separator is sandwiched between the electrodes. At this time, the positive electrode active material surface is faced so as not to deviate from the negative electrode active material surface.
  • the uncoated portions of the positive electrode and the negative electrode are bundled together and connected together with, for example, spot welding etc. together with a metal piece to be a current collecting terminal to produce a current collecting tab to form an electrode group.
  • a battery exterior material for example, a sheet in which a polypropylene film, an aluminum foil, a nylon film, and the like are laminated in this order is used, and an exterior case is formed so that the polypropylene film comes on the inner surface side.
  • the above-mentioned electrode group is the unsealed part of the current collector terminal S cup end Enclose it in an outer case so that it comes out, and inject a non-aqueous electrolyte solution to fully penetrate the electrode.
  • the upper end of the cup is heat-sealed under reduced pressure and sealed to produce a non-aqueous electrolyte secondary battery.
  • the 2MPa box-type stainless steel pressure-resistant sealed container was used as a booth for conducting safety tests, and overcharge tests were performed on various batteries.
  • This booth is equipped with a supply pipe that can replace the inside of the booth with air, a nitrogen supply pipe that can replace the inside of the booth with nitrogen, and a vacuum pipe that can decompress the inside of the booth.
  • a supply pipe that can replace the inside of the booth with air
  • a nitrogen supply pipe that can replace the inside of the booth with nitrogen
  • a vacuum pipe that can decompress the inside of the booth.
  • Each pipe is equipped with a knob in the immediate vicinity of the booth to maintain the pressure resistance and airtightness of the booth body.
  • the booth is equipped with a blast pressure sensor to measure the pressure inside the booth. Also, the booth is equipped with a charging / discharging cable connected to an external charger / discharger. It is possible to charge and discharge the battery inside.
  • a K-type thermocouple for measuring the temperature inside the booth is introduced from outside the booth, and the temperature inside the booth can be measured.
  • the voltage of the battery to be measured was set to 3 V, which is the lower limit voltage in normal use of the battery, by discharging or charging it. Subsequently, a charge / discharge cable was connected to the positive electrode terminal and the negative electrode terminal of this battery, and then installed in the booth. After the booth was sealed, the inside of the booth was replaced with nitrogen, and it was confirmed that the internal pressure of the booth after replacement was 0.1 lMPa (l atmospheric pressure). Subsequently, it was confirmed that the temperature inside the booth was 25 ° C.
  • the battery was charged at a current of 18 amps until the charge capacity reached 15 amps hour.
  • the booth is turned on when the temperature inside the booth reaches 25 ° C. The pressure in the chamber was measured.
  • the c value could be calculated using the following formula.
  • This booth is equipped with supply piping that can replace the interior of the booth with air, nitrogen supply piping that can replace the interior of the booth with nitrogen, and vacuum piping that can depressurize the interior of the booth.
  • supply piping that can replace the interior of the booth with air
  • nitrogen supply piping that can replace the interior of the booth with nitrogen
  • vacuum piping that can depressurize the interior of the booth.
  • Each pipe is equipped with a valve in the immediate vicinity of the booth, so that the pressure and airtightness of the booth body can be maintained.
  • the booth is equipped with a blast pressure sensor and can measure the pressure inside the booth. Also, a hydraulic press is installed inside the booth, and this press can also be operated from outside the booth. Can do.
  • a K-type thermocouple for measuring the temperature inside the booth is installed inside the booth from outside the booth so that the temperature inside the booth can be measured.
  • the voltage of the battery to be measured was set to 4. IV, the upper limit voltage during normal use of the battery, by discharging or charging it.
  • a stainless steel nail with an outer diameter of 2.5 mm was attached to the tip of the movable part of the hydraulic press.
  • the battery was installed in the booth at a position where this nail penetrated perpendicularly to this surface at the intersection of the 120 x 110 mm surface of the battery.
  • the inside of the booth was replaced with nitrogen, and it was confirmed that the booth internal pressure after replacement was 0.1 lMPa (l atmosphere). Subsequently, it was confirmed that the temperature in the booth was 25 ° C.
  • a 1000mm wide, 800mm deep, 1000mm high, 450mm internal volume, 450 liters internal pressure, 0.2MPa box-type stainless steel pressure-resistant sealed container as a booth for conducting safety tests and heating tests on various batteries was done.
  • This booth is equipped with supply piping that can replace the interior of the booth with air, nitrogen supply piping that can replace the interior of the booth with nitrogen, and vacuum piping that can depressurize the interior of the booth.
  • Each pipe is equipped with a valve in the immediate vicinity of the booth to maintain the pressure resistance and airtightness of the booth body.
  • a K-type thermocouple for measuring the temperature inside the booth and the battery surface temperature is introduced from outside the booth, and the temperature inside the booth and the battery surface temperature can be measured.
  • a box oven for heating the battery is installed inside the booth.
  • the voltage of the battery to be measured was set to 4. IV, which is the upper limit voltage during normal use of the battery, by discharging or charging it. Subsequently, a K-type thermocouple was installed at the intersection of the diagonal lines of the 120 X I 10 mm surface of the battery so that the battery surface temperature could be measured.
  • the battery was placed in a battery heating oven installed in the booth. After the booth was sealed, the inside of the booth was replaced with nitrogen. Subsequently, it was confirmed that the temperature in the booth was 25 ° C, and then the ambient temperature of the battery in the oven was raised to 150 ° C in 1KZ. After reaching 150 ° C, it was left in that state for 10 minutes, and the oven was allowed to cool to room temperature. Through this test, the transition of the battery surface temperature could be measured.
  • LiNiO lithium nickelate
  • Tylene black 5% by weight and polyvinylidene fluoride (PVdF) 5% by weight as a binder were mixed in an N-methylpyrrolidone solvent to form a slurry.
  • the resulting slurry was 15 m It is applied to both sides of aluminum foil, dried, rolled to a thickness of 80 m with a press machine, cut into a shape with an uncoated part with a width of 100 mm, a length of 100 mm and a width of 30 mm as the size of the active material layer. It was.
  • the obtained slurry was applied to both sides of a 10 m copper foil, dried, rolled to 75 m with a press machine, and the active material layer had an uncoated part with a width of 104 mm, a length of 104 mm and a width of 30 mm. It cut out into the shape and set it as the negative electrode.
  • Lithium hexafluorophosphate fully dried at a concentration of ImolZL in a mixture of ethylene carbonate (EC), dimethyl carbonate (DMC) and ethylmethyl carbonate (EMC) (volume ratio 3: 3: 4) in a dry argon atmosphere (LiPF 4) was dissolved. Furthermore,
  • the Jifuruororin acid lithium salt (LiPO F) were contained so that 0.3 mass 0/0.
  • the rated discharge capacity of this battery is about 6 amp hours (Ah), and the DC resistance component measured by the 10kHz AC method is about 5 milliohms (m ⁇ ).
  • the ratio of the total electrode area of the positive electrode to the sum of the outer surface areas of the batteries is 20.6.
  • the discharge capacity was defined as the initial capacity.
  • Example 4 After the charge / discharge cycle prepared in Example 4 above, a new battery was subjected to initial charge / discharge for 5 cycles at 25 ° C., and then used as a battery for safety testing. An overcharge test is performed on this battery under the same conditions as described above for the overcharge test.
  • the C value calculated from the change in booth pressure before and after the test is 10 or less.
  • Example 4 After the charge / discharge cycle prepared in Example 4 above, a new battery was subjected to initial charge / discharge for 5 cycles at 25 ° C., and this was used as a battery for safety testing. A nail penetration test is performed on this battery under the same conditions as described above for the nail penetration test.
  • the C value for calculating the changing force of the booth pressure before and after the test is 10 or less.
  • Example 4 After the charge / discharge cycle prepared in Example 4 above, a new battery was subjected to initial charge / discharge for 5 cycles at 25 ° C., and this was used as a battery for safety testing. This battery is subjected to a heating test under the same conditions as described in the heating test described above, and the maximum value of the battery surface temperature throughout the heating test is measured. Throughout this test, the maximum battery surface temperature does not exceed 155 ° C.

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Abstract

L’invention concerne un équipement de test réalisant des tests de sécurité sur un dispositif de stockage et d’alimentation en énergie tout en traitant le gaz d’échappement, comprenant une cabine pour réaliser des tests de sécurité du dispositif de stockage et d’alimentation en énergie, une section de traitement du gaz d’échappement généré par le dispositif de stockage et d’alimentation en énergie, et une section de fourniture de gaz d’échappement de la cabine vers la section de traitement de gaz d’échappement selon la capacité de la section de traitement de gaz d’échappement.
PCT/JP2006/302541 2005-02-15 2006-02-14 Equipement de test et son utilisation Ceased WO2006088021A1 (fr)

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