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WO2018179167A1 - Matériau pour des batteries rechargeables au lithium-ion, matériau mixte d'électrode positive, électrode positive pour des batteries rechargeables au lithium-ion et batterie rechargeable au lithium-ion - Google Patents

Matériau pour des batteries rechargeables au lithium-ion, matériau mixte d'électrode positive, électrode positive pour des batteries rechargeables au lithium-ion et batterie rechargeable au lithium-ion Download PDF

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Publication number
WO2018179167A1
WO2018179167A1 PCT/JP2017/013010 JP2017013010W WO2018179167A1 WO 2018179167 A1 WO2018179167 A1 WO 2018179167A1 JP 2017013010 W JP2017013010 W JP 2017013010W WO 2018179167 A1 WO2018179167 A1 WO 2018179167A1
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Prior art keywords
lithium ion
ion secondary
positive electrode
aluminum silicate
secondary battery
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English (en)
Japanese (ja)
Inventor
馨 今野
紘揮 三國
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Resonac Corp
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Hitachi Chemical Co Ltd
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Priority to JP2019508449A priority Critical patent/JP6883230B2/ja
Priority to PCT/JP2017/013010 priority patent/WO2018179167A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Definitions

  • the present invention relates to a material for a lithium ion secondary battery, a positive electrode mixture, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery.
  • Lithium ion secondary batteries are high energy density secondary batteries, and are widely used as power sources for electronic devices such as notebook personal computers and portable information terminals such as smartphones by taking advantage of their characteristics. In recent years, especially with the enhancement of functionality of portable information terminals, development of lithium ion secondary batteries having excellent capacity retention after charge / discharge cycles has been strongly demanded.
  • the present invention has been made in view of the above circumstances, and is a material for a lithium ion secondary battery and a positive electrode composite material excellent in metal precipitation suppression ability, and a positive electrode for a lithium ion secondary battery produced using these materials and
  • An object is to provide a lithium ion secondary battery.
  • ⁇ 1> An aluminum silicate compound complex containing an aluminum silicate compound and carbon and having a total pore volume measured by a nitrogen adsorption method of 0.05 cm 3 / g or more, for a lithium ion secondary battery material. Is calculated by the following equation from ⁇ 2> and the peak area A of the oxidation point in the vicinity of 1490cm -1, which derived from pyridine adsorption IR spectrum of the aluminum silicate compound complex, the peak area B of the hydrogen bonds in the vicinity of 1446cm -1.
  • RA (%) A / B ⁇ 100 ⁇ 3>
  • the mass reduction rate between 350 ° C. and 850 ° C. measured by differential thermal-thermogravimetric analysis (TG-DTA) of the aluminum silicate compound composite is 0.5% to 30%.
  • TG-DTA differential thermal-thermogravimetric analysis
  • ⁇ 5> The volume average particle diameter measured by a laser diffraction particle size distribution analyzer of the aluminum silicate compound composite is 0.1 ⁇ m to 50 ⁇ m, according to any one of ⁇ 1> to ⁇ 4>.
  • ⁇ 6> The lithium according to any one of ⁇ 1> to ⁇ 5>, wherein an element molar ratio (Si / Al) of silicon to aluminum of the aluminum silicate compound composite is 1.5 to 3.0 Material for ion secondary battery.
  • ⁇ 7> A positive electrode mixture comprising the lithium ion secondary battery material according to any one of ⁇ 1> to ⁇ 6> and a positive electrode active material.
  • ⁇ 8> The positive electrode mixture according to ⁇ 7>, wherein the content of the lithium ion secondary battery material is 0.01% by mass to 10% by mass with respect to the total amount of the positive electrode mixture.
  • a positive electrode for a lithium ion secondary battery comprising the material for a lithium ion secondary battery according to any one of ⁇ 1> to ⁇ 6>.
  • a lithium ion secondary battery comprising the positive electrode for a lithium ion secondary battery according to ⁇ 9>.
  • the lithium ion secondary battery material and positive electrode compound material which are excellent in metal precipitation suppression capability, and the positive electrode and lithium ion secondary battery which are manufactured using these are provided.
  • the lithium ion secondary battery material of the present invention is excellent in the ability to suppress the precipitation of metal
  • the lithium ion secondary battery using the lithium ion secondary battery material of the present invention has a reduced capacity retention rate. There is a tendency.
  • the term “process” includes a process that is independent of other processes and includes the process if the purpose of the process is achieved even if it cannot be clearly distinguished from the other processes. It is.
  • numerical values indicated by using “to” include numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. Good. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the content rate or content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, the plurality of kinds present in the composition unless otherwise specified. It means the total content or content of substances.
  • the particle diameter of each component in the composition is a mixture of the plurality of types of particles present in the composition unless there is a specific indication when there are a plurality of types of particles corresponding to each component in the composition. Means the value of.
  • the term “layer” or “film” refers to a part of the region in addition to the case where the layer or the film is formed when the region where the layer or film exists is observed. It is also included when it is formed only.
  • the term “lamination” indicates that layers are stacked, and two or more layers may be combined, or two or more layers may be detachable.
  • the material for a lithium ion secondary battery of the present embodiment includes an aluminum silicate compound and a carbon, and an aluminum silicate compound composite having a total pore volume of 0.05 cm 3 / g or more measured by a nitrogen adsorption method Is the body.
  • the material for a lithium ion secondary battery according to the present embodiment is excellent in metal precipitation suppression ability. Therefore, in the lithium ion secondary battery manufactured using the lithium ion secondary battery material of the present embodiment, a decrease in capacity maintenance rate is suppressed. The reason is not necessarily clear, but the metal in the negative electrode or the like is absorbed by the aluminum silicate compound complex by adsorbing metal ions such as cobalt eluted from the positive electrode active material due to hydrogen fluoride generated in the electrolyte. It is presumed that the reprecipitation of ions is suppressed. In addition, it is estimated that elution of metal ions such as cobalt from the positive electrode active material is suppressed by adsorbing the hydrogen fluoride generated in the electrolytic solution to the aluminum silicate compound complex.
  • the total pore volume measured by the nitrogen adsorption method of the aluminum silicate compound composite is preferably 0.08 cm 3 / g or more.
  • the total pore volume measured by the nitrogen adsorption method of the aluminum silicate compound complex is measured from the nitrogen adsorption ability at 77K according to JIS Z 8830: 2001.
  • a nitrogen adsorption measuring apparatus for example, BELSORP-miniII manufactured by Nippon Bell Co., Ltd.
  • BELSORP-miniII manufactured by Nippon Bell Co., Ltd.
  • pretreatment for removing moisture by heating is first performed.
  • the measurement cell into which the measurement sample has been placed is kept under vacuum at 250 ° C. for 2 hours, and then naturally cooled to room temperature (25 ° C.) while maintaining the reduced pressure.
  • the evaluation temperature is 77K
  • the evaluation pressure range is measured as a relative pressure (equilibrium pressure with respect to saturated vapor pressure) of less than 1.
  • the total pore volume is determined from the amount of adsorption when the relative pressure is 0.990.
  • the state of the aluminum silicate compound and carbon (arrangement relationship, etc.) in the aluminum silicate compound composite is not particularly limited.
  • Carbon may be provided in a part or all of the aluminum silicate compound.
  • the aluminum silicate compound composite include those in which all or part of the surface of the particulate aluminum silicate compound is coated with carbon.
  • the presence or absence of carbon in the aluminum silicate compound complex can be confirmed by, for example, laser Raman spectroscopy measurement with an excitation wavelength of 532 nm.
  • Examples of the aluminum silicate compound in the aluminum silicate compound composite include allophane, kaolin, zeolite, saponite and imogolite which are aluminum silicates. Among these, from the viewpoint of improving the cycle characteristics, an amorphous aluminum silicate compound whose specific surface area can be easily adjusted is preferable.
  • the amorphous aluminum silicate compound is an aluminum silicate having an element molar ratio Si / Al in the range of 0.3 to 5.0.
  • the X-ray diffractometer for example, Geigerflex RAD-2X (manufactured by Rigaku Corporation) can be used. Specific measurement conditions are as follows. -Measurement condition- Divergence slit: 1 ° Scattering slit: 1 ° Receiving slit: 0.30mm X-ray output: 40 kV, 40 mA
  • the amorphous aluminum silicate compound may be synthesized or a commercially available product may be used.
  • a step of mixing a solution containing silicate ions and a solution containing aluminum ions to obtain a reaction product, and the reaction product in an aqueous medium in the presence of an acid A step of heat treatment, and may include other steps as necessary.
  • a washing step for performing desalting and solid separation at least after the heat treatment step, preferably both before and after the heat treatment step. It is preferable to have.
  • the method for providing carbon to the amorphous aluminum silicate compound is not particularly limited.
  • a method of coating an amorphous aluminum silicate compound with an organic compound (carbon precursor) that changes to a carbonaceous material by heat treatment and changing the carbon precursor to a carbonaceous material can be mentioned.
  • a wet method in which an amorphous aluminum silicate compound is added to a carbon precursor dissolved or dispersed in a solvent and then the solvent is removed by heating or the like.
  • examples thereof include a dry method in which a mixture obtained by mixing a carbon precursor and an amorphous aluminum silicate compound with solids is kneaded while applying a shearing force, and a gas phase method such as a CVD method. From the viewpoint of cost and production process reduction, a dry method or a gas phase method without using a solvent is preferable.
  • the type of carbon precursor is not particularly limited. Examples thereof include ethylene heavy end pitch, crude oil pitch, coal tar pitch, asphalt cracking pitch, pitch generated by thermal decomposition of polyvinyl chloride and the like, and synthetic pitch obtained by polymerizing naphthalene or the like in the presence of a super strong acid. Moreover, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, etc. can be used as a thermoplastic carbon precursor, and a phenol resin, a furan resin, etc. can be used as a thermosetting carbon precursor.
  • the heating conditions in this case are not particularly limited and can be determined in consideration of the carbonization rate of the carbon precursor. For example, it is preferable to heat in the range of 800 ° C. to 1300 ° C. in an inert atmosphere.
  • the heating temperature is 800 ° C. or higher, carbonization of the carbon precursor proceeds sufficiently, the specific surface area of the aluminum silicate compound composite does not become too large, and the initial irreversible capacity tends not to increase.
  • the heating temperature is 1300 ° C. or lower, the specific surface area does not become too small, and the resistance does not easily increase.
  • the inert atmosphere include nitrogen, argon, helium, and mixed gases thereof.
  • the element molar ratio of silicon to aluminum is preferably 1.0 to 5.0, and more preferably 1.5 to 3.0.
  • the Si / Al ratio of the aluminum silicate compound composite can be calculated from the values obtained for silicon and aluminum by conducting elemental analysis of the measurement sample. Elemental analysis can be performed by inductively coupled plasma (ICP) emission spectroscopy.
  • ICP inductively coupled plasma
  • the aluminum silicate compound complex preferably has a chlorine ratio (RCl) of 1% or less, more preferably 0.1% or less, and even more preferably less than 0.1%.
  • a chlorine ratio (RCl) is 1% or less, there is a tendency that a decrease in life due to deterioration (elution, film formation, etc.) of the positive electrode active material caused by a chlorine-derived compound (hydrogen chloride or the like) tends to be suppressed.
  • the chlorine ratio (RCl) is less than 0.1%, the expansion of the battery due to the gas generated by the reaction between chlorine and the electrolytic solution tends to be suppressed.
  • the chlorine ratio (RCl) means the ratio (%) of the Cl content to the total content of Al and Si in the aluminum silicate compound composite. Specifically, it is a value calculated by the following equation (1) from values obtained for each element by performing elemental analysis in the measurement sample. Elemental analysis can be measured using the same method and apparatus as the Si / Al ratio.
  • Aluminum silicate compound complex is calculated and the peak area A of the oxidation point in the vicinity of 1490cm -1, which derived from pyridine adsorption IR spectrum, the following equation from the peak area B of the hydrogen bonds in the vicinity of 1446cm -1 (2)
  • the oxidation point ratio (RA) is preferably less than 25%, and more preferably less than 20%.
  • RA (%) A / B ⁇ 100 (2)
  • the ratio (RA) of the oxidation point of the aluminum silicate compound complex is less than 25%, it becomes difficult to adsorb water, and the lifetime tends to be suppressed.
  • the oxidation point ratio (RA) is less than 20%, the expansion of the battery caused by the reaction between the functional group of the aluminum silicate compound complex and the electrolytic solution tends to be suppressed.
  • the oxidation point of the aluminum silicate compound complex can be measured from a pyridine adsorption IR spectrum obtained by infrared spectroscopy.
  • the pyridine adsorption IR spectrum can be obtained using, for example, a Fourier transform infrared spectrophotometer (for example, “Cary670” manufactured by Agilent Technologies).
  • the oxidation point of the aluminum silicate compound complex is measured as follows.
  • the cell filled with the sample is evacuated at 500 ° C. for 1 hour and then cooled to 30 ° C.
  • pyridine gas is introduced into the cell while being heated to 100 ° C., and is adsorbed for 5 minutes.
  • the physisorbed pyridine is removed by heating to 150 ° C. and exhausting for 60 minutes. Subsequently, it cools to 30 degreeC and measures an IR spectrum.
  • the peak area A of the oxidation point and the peak area B of the hydrogen bond are calculated by the following method, and the values calculated by the equation (2) using the calculated peak areas are the oxidation points.
  • the ratio (RA) is the ratio (RA).
  • a baseline is drawn with a straight line in the region of IR spectrum from 1485 cm ⁇ 1 to 1500 cm ⁇ 1 .
  • the maximum peak in the vicinity of 1490 cm ⁇ 1 is separated using a Gaussian function, and the area of the portion surrounded by the baseline is obtained.
  • (Calculation of hydrogen bond peak area B) Subtracting a baseline in a straight line from 1430 cm -1 of the IR spectrum in the region of 1460 cm -1.
  • the maximum peak near 1446 cm ⁇ 1 in the meantime is separated using a Gaussian function, and the area of the portion surrounded by the baseline is obtained.
  • the mass reduction rate between 350 ° C. and 850 ° C. measured using differential thermal-thermogravimetric analysis (TG-DTA) of the aluminum silicate compound composite is 0. 5% to 30% is preferable, 2% to 25% is more preferable, and 5% to 20% is still more preferable.
  • TG-DTA differential thermal-thermogravimetric analysis
  • the mass reduction rate of 350 ° C. to 850 ° C. of the aluminum silicate compound composite is the value obtained by the following formula (3).
  • Mass reduction rate (%) ⁇ (W1-W2) / W1 ⁇ ⁇ 100 (3)
  • W1 is the mass (g) of the measurement target after being heated from 25 ° C. to 350 ° C. at a rate of temperature increase of 10 ° C./min under a circulation of dry air and held at 350 ° C. for 20 minutes.
  • W2 is the mass (g) of the object to be measured after raising the temperature from 350 ° C. to 850 ° C. at a rate of temperature rise of 10 ° C./min under a circulation of dry air and holding at 850 ° C. for 20 minutes.
  • TG-DTA-6200 type manufactured by SII NanoTechnology Co., Ltd.
  • the volume average particle diameter (D50) measured by the laser diffraction particle size distribution analyzer is selected according to the desired size of the aluminum silicate compound composite, and 0 It is preferably 1 ⁇ m to 50 ⁇ m, more preferably 0.2 ⁇ m to 20 ⁇ m, and even more preferably 0.5 ⁇ m to 10 ⁇ m.
  • volume average particle diameter (D50) of the aluminum silicate compound composite is 0.1 ⁇ m or more, the viscosity of the positive electrode mixture does not become too high when a positive electrode is prepared using the positive electrode mixture described later, Tend to be well maintained.
  • the volume average particle diameter (D50) of the aluminum silicate compound composite is 50 ⁇ m or less, streaks tend not to be drawn when the positive electrode mixture is applied onto the current collector.
  • the volume average particle diameter (D50) of the aluminum silicate compound composite is preferably 0.5 ⁇ m or more from the viewpoint of cost reduction required for grinding, and from the viewpoint of the efficiency of adsorption of hydrogen fluoride and metal ions. It is preferable that it is 10 micrometers or less.
  • the volume average particle diameter (D50) of the aluminum silicate compound composite is measured using a laser diffraction method.
  • the measurement by the laser diffraction method can be performed using, for example, a laser diffraction particle size distribution measuring apparatus (SALD3000J, Shimadzu Corporation).
  • SALD3000J laser diffraction particle size distribution measuring apparatus
  • an aluminum silicate compound complex is dispersed in a dispersion medium such as water to prepare a dispersion, and a volume cumulative distribution curve is measured from the small diameter side from the small diameter side of this dispersion using a laser diffraction particle size distribution analyzer.
  • the particle diameter (D50) when the cumulative volume is 50% is determined as the volume average particle diameter.
  • the BET specific surface area of the aluminum silicate compound composite is preferably 80 m 2 / g or less, more preferably 40 m 2 / g or less, and 20 m 2 / g or less from the viewpoint of cycle characteristics and storage characteristics. More preferably it is.
  • the lower limit of the BET specific surface area is not particularly limited, but is preferably 1 m 2 / g or more and more preferably 2 m 2 / g or more from the viewpoint of improving the adsorption ability for hydrogen fluoride and metal ions. , even more preferably 3m 2 / g or more.
  • the BET specific surface area of the aluminum silicate compound composite is measured from the nitrogen adsorption capacity according to JIS Z 8830 (2001).
  • a nitrogen adsorption measuring device AUTOSORB-1, QUANTACHROME
  • AUTOSORB-1, QUANTACHROME nitrogen adsorption measuring device
  • a measurement cell charged with 0.05 g of a measurement sample is depressurized to 10 Pa or less with a vacuum pump and then heated at 110 ° C. After maintaining in this state for 3 hours or longer, the product is naturally cooled to room temperature (25 ° C.) while maintaining the reduced pressure state. After performing this pretreatment, the evaluation temperature is 77K, and the evaluation pressure range is measured as a relative pressure (equilibrium pressure with respect to saturated vapor pressure) of less than 1.
  • the positive electrode mixture of the present embodiment contains the lithium ion secondary battery material of the present embodiment and the positive electrode active material. In a lithium ion secondary battery having a positive electrode formed using the positive electrode mixture of the present embodiment, a decrease in capacity maintenance rate is suppressed.
  • the positive electrode mixture may include other materials such as a conductive material, a binder, a thickener, and a dispersion solvent as necessary. Details and preferred embodiments of the other materials are the same as those described for the lithium ion secondary battery described later.
  • the content of the lithium ion secondary battery material in the positive electrode mixture may be, for example, 0.01% by mass to 10% by mass with respect to the total amount of the positive electrode mixture, and 0.05% by mass to 5% by mass. It is preferable that Further, the mass ratio of the lithium ion secondary battery material and the positive electrode active material in the positive electrode mixture (lithium ion secondary battery material / positive electrode active material) may be, for example, 0.009 to 9.8, It is preferably 0.045 to 4.9.
  • the positive electrode for a lithium ion secondary battery of the present embodiment contains the material for a lithium ion secondary battery of the present embodiment.
  • the positive electrode for lithium ion secondary batteries can be manufactured by a well-known method using the positive electrode compound material of this embodiment, for example.
  • the lithium ion secondary battery of this embodiment is provided with the positive electrode for lithium ion secondary batteries of this embodiment.
  • the capacity maintenance rate is prevented from decreasing.
  • a lithium ion secondary battery has a positive electrode and a negative electrode, and a separator through which lithium ions can pass is usually disposed between the positive electrode and the negative electrode.
  • a charger When charging a lithium ion secondary battery, a charger is connected between the positive electrode and the negative electrode. At the time of charging, lithium ions inserted into the positive electrode active material of the positive electrode are desorbed and released into the electrolytic solution. The lithium ions released into the electrolytic solution move through the electrolytic solution, pass through the separator, and reach the negative electrode. The lithium ions that have reached the negative electrode are inserted into the negative electrode active material of the negative electrode.
  • charging / discharging is performed by inserting or desorbing lithium ions between the positive electrode active material and the negative electrode active material.
  • a configuration example of an actual lithium ion secondary battery will be described later (see, for example, FIG. 1).
  • the positive electrode, negative electrode, electrolytic solution, separator, and other components of the lithium ion secondary battery will be described.
  • the positive electrode includes the lithium ion secondary battery material of the present embodiment and a positive electrode active material.
  • the positive electrode has a current collector and a positive electrode mixture layer provided on both sides or one side of the current collector, and the positive electrode mixture layer is for the lithium ion secondary battery of the present embodiment.
  • the positive electrode mixture layer may include other materials such as a conductive material, a binder, a thickener, and a dispersion solvent as necessary.
  • the lithium-containing composite metal oxide or lithium-containing phosphate compound is a metal oxide or phosphate compound containing lithium and a metal other than lithium.
  • the metal other than lithium contained in the lithium-containing composite metal oxide or the lithium-containing phosphate compound may be only one kind or two or more kinds.
  • the lithium-containing composite metal oxide is preferably a metal oxide containing lithium and at least one transition metal selected from Co, Ni, and Mn.
  • part of the transition metal may be substituted with an element (heterogeneous element) different from the transition metal.
  • the different elements include Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B.
  • Mn, Al, Co, Ni, and the like At least one selected from the group consisting of Mg is preferred.
  • lithium-containing composite metal oxide examples include Li x CoO 2 , Li x NiO 2 , Li x MnO 2 , Li x Co y Ni 1-y O 2 , and Li x Co y M 1 1-y O z (Li In x Co y M 1 1-y O z , M 1 is at least one selected from the group consisting of Na, Mg, Sc, Y, Mn, Fe, Cu, Zn, Al, Cr, Pb, Sb, V, and B Li x Ni 1-y M 2 y O z (in Li x Ni 1-y M 2 y O z , M 2 is Na, Mg, Sc, Y, Mn, Fe, Cu, Represents at least one element selected from the group consisting of Zn, Al, Cr, Pb, Sb, V and B.), Li x Mn 2 O 4 and Li x Mn 2-y M 3 y O 4 (Li x In Mn 2-y M 3 y O 4 , M 3 is Na, M
  • x is in the range of 0 ⁇ x ⁇ 1.2
  • y is in the range of 0 to 0.9
  • z is in the range of 2.0 to 2.3.
  • the x value indicating the molar ratio of lithium increases or decreases due to charge / discharge.
  • lithium-containing phosphate compound examples include LiMPO 4 and Li 2 MPO 4 F (in the above formulas, M is Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, And at least one element selected from the group consisting of Pb, Sb, V and B.).
  • M is Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, And at least one element selected from the group consisting of Pb, Sb, V and B.
  • an olivine type lithium salt is preferable, and LiFePO 4 is more preferable.
  • the positive electrode active material may contain a compound other than the lithium-containing composite metal oxide or the lithium-containing phosphate compound.
  • examples of such compounds include chalcogen compounds and manganese dioxide.
  • examples of the chalcogen compound include titanium disulfide and molybdenum disulfide.
  • the positive electrode active material may be in the form of particles, and is preferably in a state of secondary particles formed by aggregation of primary particles.
  • the positive electrode active material is in the state of secondary particles, expansion and contraction of the positive electrode active material due to charge / discharge are alleviated compared to the case where the positive electrode active material is only primary particles, and positive electrode active due to stress caused by expansion and contraction is reduced. There is a tendency that deterioration such as destruction of a substance and cutting of a conductive path hardly occurs.
  • the shape is not particularly limited, and examples thereof include a lump shape, a polyhedron shape, a spherical shape, an elliptical spherical shape, a flake shape, a needle shape, and a column shape. Of these, spherical or elliptical spheres are preferred.
  • the shape of the positive electrode active material is spherical or elliptical, the degree of orientation of the positive electrode active material in the electrode is smaller than when the plate has a large aspect ratio, such as a plate shape, and the expansion of the electrode during charge / discharge Shrinkage tends to be suppressed.
  • the definition of the shape when the positive electrode active material is particulate the definition of the shape when the conductive material described later is particulate can be referred to.
  • the positive electrode active material is preferably in the form of secondary particles formed by aggregation of primary particles, and the shape of the secondary particles is preferably spherical or elliptical.
  • the volume average particle diameter (D50) measured with a laser diffraction particle size distribution analyzer of the positive electrode active material is not particularly limited.
  • the volume average particle diameter (D50) of the positive electrode active material may be 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, and more preferably 1 ⁇ m or more. Preferably, it is 3 ⁇ m or more.
  • the volume average particle diameter (D50) of the positive electrode active material may be 20 ⁇ m or less, preferably 18 ⁇ m or less, more preferably 16 ⁇ m or less, and more preferably 15 ⁇ m. More preferably, it is as follows.
  • the volume average particle diameter (D50) of the positive electrode active material means the volume average particle diameter (D50) of the secondary particles when the positive electrode active material is in the state of secondary particles.
  • the volume average particle diameter (D50) of the positive electrode active material is measured in the same manner as the volume average particle diameter (D50) of the lithium ion secondary battery material (aluminum silicate compound composite) of the present embodiment.
  • the average particle diameter of the primary particles forming the secondary particles is not particularly limited.
  • the average particle diameter of the primary particles may be 0.01 ⁇ m or more, preferably 0.05 ⁇ m or more, more preferably 0.08 ⁇ m or more, 0 More preferably, it is 1 ⁇ m or more.
  • the average particle size of the primary particles may be 3 ⁇ m or less, preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, and 0.6 ⁇ m or less. More preferably.
  • the average particle diameter of the primary particles when the positive electrode active material is in the state of secondary particles is, for example, scanning electron microscope / energy dispersive X-ray spectroscopy (SEM-EDX), transmission electron microscope / energy dispersive X It can be measured by line spectroscopy (TEM-EDX) or the like.
  • the BET specific surface area of the positive electrode active material is not particularly limited. From the viewpoint of improving battery performance, the BET specific surface area of the positive electrode active material is preferably 0.1 m 2 / g or more, more preferably 0.2 m 2 / g or more, and 0.3 m 2 / g. More preferably, it is the above. From the viewpoint of electrode formability, the BET specific surface area of the positive electrode active material is preferably 4.0 m 2 / g or less, more preferably 2.5 m 2 / g or less, and 1.5 m 2 / g or less. More preferably.
  • the BET specific surface area of the positive electrode active material is measured by the same method as the method for measuring the BET specific surface area of the aluminum silicate compound composite described above.
  • the positive electrode preferably contains a conductive material from the viewpoint of improving battery performance.
  • the conductive material include natural graphite, artificial graphite, graphite such as fibrous graphite, carbon black, and the like.
  • the carbon blacks acetylene black is preferable from the viewpoint of improving input / output characteristics.
  • the carbon black is preferably particles having an average particle diameter of 20 nm to 100 nm, and the average particle diameter is More preferred are particles of 30 nm to 80 nm, and even more preferred are particles having an average particle size of 40 nm to 60 nm.
  • the graphite When graphite is included as the conductive material, the graphite is preferably particles having an average particle diameter of 1 ⁇ m to 10 ⁇ m. Further, the graphite preferably has a carbon network plane interlayer (d002) in the X-ray wide angle diffraction method of 0.3354 nm to 0.337 nm.
  • d002 carbon network plane interlayer
  • the average particle diameter of the conductive material is an arithmetic average value of values measured for all particle images in the image taken with a scanning electron microscope taken at 200,000 times.
  • the shape is not particularly limited, and examples thereof include particles, flakes, spheres, columns, irregular shapes, and the like.
  • “particulate” is not an irregular shape but a shape having substantially the same dimensions (JIS Z2500: 2000).
  • the flake shape strip shape
  • JIS Z2500: 2000 is a plate-like shape (JIS Z2500: 2000) and is also referred to as a scaly shape because it is thin like a scale.
  • a scanning electron microscope is used. Analysis is performed from the observation results of the above, and particles having an aspect ratio (particle diameter a / average thickness t) in the range of 2 to 100 are formed into flakes.
  • the particle diameter a here is defined as the value of the square root of the area S when the flaky particles are viewed in plan.
  • Spherical means a shape almost similar to a sphere (see JIS Z2500: 2000). Further, the shape does not necessarily need to be spherical, and the ratio of the major axis (DL) to the minor axis (DS) of the particle (DL) / (DS) (sometimes referred to as spherical coefficient or sphericity) is 1. Those in the range of 0.0 to 1.2 are included in “spherical”. When the particles are spherical, the major axis (DL) is taken as the particle size. Examples of the columnar shape include a substantially circular column and a substantially polygonal column. When the particles are columnar, the height of the column is the particle size.
  • the content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and more preferably 0.5% by mass or more with respect to the total amount of the positive electrode mixture. More preferably.
  • the upper limit of the content of the conductive material is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less. When the content of the conductive material is within the above range, the battery capacity and input / output characteristics tend to be more excellent.
  • the positive electrode preferably includes a binder from the viewpoint of obtaining adhesion between the positive electrode mixture, the current collector, and the positive electrode active material.
  • the kind of binder is not particularly limited. Specific examples include resin polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, and nitrocellulose; SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), fluorine Rubbery polymers such as rubber, isoprene rubber, butadiene rubber, ethylene-propylene rubber; styrene / butadiene / styrene block copolymer or its hydrogenated product, EPDM (ethylene / propylene / diene terpolymer), styrene / Thermoplastic elastomeric polymers such as ethylene / butadiene / ethylene copolymers, styrene
  • the binder may be used alone or in combination of two or more. From the viewpoint of the stability of the positive electrode, it is preferable to use a fluorine-based polymer such as polyvinylidene fluoride (PVdF) or a polytetrafluoroethylene / vinylidene fluoride copolymer.
  • PVdF polyvinylidene fluoride
  • a binder having good solubility or dispersibility in the dispersion solvent contained in the positive electrode mixture it is preferable to select a binder having good solubility or dispersibility in the dispersion solvent contained in the positive electrode mixture.
  • the content is preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably 2% by mass with respect to the total amount of the positive electrode mixture. More preferably, it is the above.
  • the upper limit of the binder content is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and preferably 10% by mass or less. Particularly preferred.
  • a dispersion solvent When the positive electrode mixture is in a slurry state, a dispersion solvent may be included.
  • the dispersion solvent is not particularly limited as long as it can dissolve or disperse the material contained in the positive electrode mixture, and may be an aqueous solvent or an organic solvent.
  • the aqueous solvent include water, a mixed solvent of alcohol and water
  • the organic solvent include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, and acrylic.
  • a thickener may be included to adjust the viscosity.
  • the thickener is not particularly limited, and examples thereof include polymer compounds such as carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, and casein, and salts of these polymer compounds.
  • a thickener may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the content is not particularly limited. From the viewpoint of applicability of the positive electrode mixture, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and more preferably 0.5% by mass or more with respect to the total amount of the positive electrode mixture. More preferably. From the viewpoint of suppressing a decrease in battery capacity or an increase in resistance between the positive electrode active materials, the content of the thickener is preferably 5% by mass or less with respect to the total amount of the positive electrode mixture, and 3% by mass or less. More preferably, it is more preferably 2% by mass or less.
  • the material of the current collector is not particularly limited, and examples thereof include metal materials such as aluminum, stainless steel, nickel-plated steel, titanium, and tantalum, and carbonaceous materials such as carbon cloth and carbon paper. Of these, metal materials are preferable, and aluminum is more preferable.
  • the shape of the current collector is not particularly limited, and materials processed into various shapes can be used.
  • Examples of the shape when the current collector is a metal material include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punch metal, and foam metal.
  • Examples of the shape when the current collector is a carbonaceous material include a carbon plate, a carbon thin film, and a carbon cylinder. Among these, a metal thin film is preferable. The thin film may be mesh.
  • the thickness of the current collector is not particularly limited. From the viewpoint of obtaining sufficient strength as a current collector, the thickness of the current collector may be 1 ⁇ m or more, preferably 3 ⁇ m or more, and more preferably 5 ⁇ m or more. From the viewpoint of obtaining sufficient flexibility and workability, the thickness of the current collector may be 1 mm or less, preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • a method of forming a positive electrode mixture layer using a positive electrode mixture on a current collector a method of forming the positive electrode mixture into a sheet shape and press-bonding it to the current collector (dry method), a slurry-like positive electrode Examples thereof include a method (wet method) in which a composite material is applied to a current collector and dried.
  • the positive electrode mixture layer formed on the current collector is preferably consolidated by a hand press, a roller press or the like in order to improve the packing density of the positive electrode active material.
  • the density of the positive electrode mixture layer is preferably 3.0 g / cm 3 to 4.0 g / cm 3 .
  • the single-side coating amount on the current collector is preferably 100 g / m 2 to 300 g / m 2 .
  • Negative electrode contains a negative electrode active material.
  • the negative electrode includes a current collector and a negative electrode mixture layer provided on both sides or one side of the current collector, and the negative electrode mixture layer includes a negative electrode active material.
  • the negative electrode may include other materials such as a conductive material, a binder, a thickener, and a dispersion solvent as necessary.
  • the negative electrode active material is not particularly limited as long as it is a material that can occlude and release lithium ions.
  • carbonaceous materials, metal composite oxides, oxides or nitrides of Group 4 elements such as tin, germanium, and silicon, lithium alone, lithium alloys such as lithium aluminum alloys, and alloys with lithium such as Sn and Si Possible substances are listed. From the viewpoint of safety, at least one selected from the group consisting of a carbonaceous material and a metal composite oxide is preferable.
  • a negative electrode active material may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the negative electrode active material may be in the form of particles, for example.
  • carbonaceous materials include amorphous carbon materials, natural graphite, composite carbonaceous materials in which a film of amorphous carbon material is formed on natural graphite, artificial graphite (resin raw materials such as epoxy resins and phenol resins, or petroleum, And obtained by firing a pitch-based raw material obtained from coal or the like.
  • the metal composite oxide preferably contains one or both of titanium and lithium, and more preferably contains lithium.
  • carbonaceous materials have high conductivity and are particularly excellent in low temperature characteristics and cycle stability.
  • graphite is preferable from the viewpoint of increasing the capacity.
  • Graphite preferably has a carbon network plane interlayer (d002) of less than 0.34 nm in the X-ray wide angle diffraction method, more preferably 0.3354 nm or more and 0.337 nm or less.
  • a carbonaceous material that satisfies such conditions may be referred to as pseudo-anisotropic carbon.
  • the negative electrode mixture containing the negative electrode active material may further contain a conductive material.
  • a conductive material a highly conductive carbonaceous material such as graphitic carbon material, amorphous carbon material, activated carbon, or the like can be used. Specific examples include graphite (graphite) such as natural graphite and artificial graphite, carbon black such as acetylene black, and amorphous carbon material such as needle coke.
  • a conductive material may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the conductive material is a carbonaceous material having different properties from the carbonaceous material (first carbonaceous material) used as the negative electrode active material (The second carbonaceous material) is preferable.
  • the properties include 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. Exhibit one or more characteristics.
  • the content of the conductive material may be 1% by mass or more, preferably 2% by mass or more, and preferably 3% by mass or more with respect to the total amount of the negative electrode mixture. Is more preferable. From the viewpoint of suppressing an increase in initial irreversible capacity, the content of the conductive material may be 45% by mass or less, and preferably 40% by mass or less, with respect to the total amount of the negative electrode mixture.
  • the negative electrode mixture may contain a binder.
  • the binder is not particularly limited, and examples thereof include those exemplified as the binder that may be included in the positive electrode mixture.
  • a binder may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the binder is not particularly limited.
  • the content of the binder is preferably 0.1% by mass or more and 0.2% by mass or more with respect to the total amount of the negative electrode composite material. It is more preferable that the content is 0.5% by mass or more.
  • the content of the binder is 20% by mass or less with respect to the total amount of the negative electrode mixture. It is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 8% by mass or less.
  • the content of the binder is 0.1% by mass or more based on the total amount of the negative electrode mixture. It may be 0.2% by mass or more, and more preferably 0.5% by mass or more. Moreover, it may be 5 mass% or less with respect to the total amount of negative electrode compound materials, it is preferable that it is 3 mass% or less, and it is more preferable that it is 2 mass% or less.
  • SBR styrene-butadiene rubber
  • the content of the binder may be 1% by mass or more based on the total amount of the negative electrode mixture, and 2% by mass. Preferably, it is preferably 3% by mass or more. Moreover, it may be 15 mass% or less with respect to the total amount of negative electrode compound materials, it is preferable that it is 10 mass% or less, and it is more preferable that it is 8 mass% or less.
  • the negative electrode mixture may contain a thickener in order to adjust the viscosity.
  • the thickener is not particularly limited, and examples thereof include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof.
  • a thickener may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the content of the thickener may be 0.1% by mass or more, preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Is more preferable.
  • the content of the thickener may be 5% by mass or less, preferably 3% by mass or less, and preferably 2% by mass or less. It is more preferable that
  • the material of the current collector used for the negative electrode is not particularly limited, and examples thereof include metal materials such as copper, nickel, stainless steel, and nickel-plated steel. Among these, copper is preferable from the viewpoint of ease of processing and cost.
  • the shape of the current collector is not particularly limited, and materials processed into various shapes can be used. Specific examples include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punch metal, and foam metal. Among these, a metal thin film is preferable, and a copper foil is more preferable.
  • the copper foil includes a rolled copper foil formed by a rolling method and an electrolytic copper foil formed by an electrolytic method, both of which are suitably used as a current collector.
  • the thickness of the current collector is not particularly limited, but when the thickness is less than 25 ⁇ m, it is stronger to use a strong copper alloy (phosphor bronze, titanium copper, Corson alloy, Cu—Cr—Zr alloy, etc.) than pure copper. From the viewpoint of
  • a method for producing a negative electrode by using a negative electrode mixture and a current collector is not particularly formed.
  • it can be produced by forming a negative electrode mixture layer on a current collector using a negative electrode mixture in the same manner as the positive electrode described above.
  • Electrolytic Solution includes an electrolyte and a non-aqueous solvent that dissolves the electrolyte.
  • the electrolytic solution may contain an additive as necessary.
  • An electrolyte may be used individually by 1 type, or may be used in combination of 2 or more type.
  • electrolyte solution what contains a fluorine-containing electrolyte is preferable.
  • the electrolyte preferably contains a lithium salt, and more preferably contains lithium hexafluorophosphate (LiPF 6 ).
  • LiPF 6 lithium hexafluorophosphate
  • the electrolyte comprises a LiPF 6, even using only LiPF 6, it may be used in combination of a lithium salt other than LiPF 6.
  • the lithium salt other than LiPF 6, LiBF 4, LiAsF 6 , LiSbF 6 such as inorganic fluoride salts; inorganic chloride salts such as LiAlCl 4;; LiClO 4, LiBrO 4, perhalogenate of LiIO 4 such LiCF 3 Perfluoroalkane sulfonates such as SO 3 ; perfluoro such as LiN (CF 3 SO 2 ) 2 , LiN (CF 3 CF 2 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 9 ) Alkanesulfonylimide salt; Perfluoroalkanesulfonylmethide salt such as LiC (CF 3 SO 2 ) 3 ; Li [PF 5 (CF 2 CF 2 CF 3 )], Li [PF 4 (CF 2 CF 2 CF 3 ) 2 ], Li [PF 3 (CF 2 CF 2 CF 3 ) 3 ], Li [PF 5 (CF 2 CF 2 CF 3 CF 3
  • the content of LiPF 6 is preferably 10% by mass or more, and preferably 50% by mass or more of the entire lithium salt from the viewpoint of battery performance. More preferred.
  • the concentration of the electrolyte in the electrolytic solution is not particularly limited. From the viewpoint of sufficiently obtaining the electric conductivity of the electrolytic solution, it may be 0.5 mol / L or more, preferably 0.6 mol / L or more, and more preferably 0.7 mol / L or more. From the viewpoint of suppressing a decrease in electrical conductivity due to an increase in the viscosity of the electrolytic solution, it may be 2 mol / L or less, preferably 1.8 mol / L or less, and more preferably 1.7 mol / L or less. preferable.
  • the non-aqueous solvent is not particularly limited as long as it can be used as an electrolyte solvent for a lithium ion secondary battery.
  • Specific examples include cyclic carbonates, chain carbonates, chain esters, cyclic ethers, chain ethers and the like.
  • an alkylene group constituting the cyclic carbonate preferably has 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms.
  • Specific examples include ethylene carbonate, propylene carbonate, butylene carbonate, and the like. Of these, ethylene carbonate and propylene carbonate are preferable.
  • a dialkyl carbonate is preferable, and the number of carbon atoms of the two alkyl groups is preferably 1 to 5, and more preferably 1 to 4, respectively.
  • symmetrical chain carbonates such as dimethyl carbonate, diethyl carbonate, and di-n-propyl carbonate
  • asymmetric chain carbonates such as methyl ethyl carbonate, methyl-n-propyl carbonate, and ethyl-n-propyl carbonate Is mentioned.
  • dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate are preferable.
  • chain esters examples include methyl acetate, ethyl acetate, propyl acetate, and methyl propionate.
  • methyl acetate is preferable from the viewpoint of improving low temperature characteristics.
  • Examples of the cyclic ether include tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran and the like. Among these, tetrahydrofuran is preferable from the viewpoint of improving input / output characteristics.
  • chain ethers examples include dimethoxyethane and dimethoxymethane.
  • the non-aqueous solvent may be used alone or in combination of two or more.
  • Examples of the combination of two or more types include a combination of a high dielectric constant solvent such as cyclic carbonate and a low viscosity solvent such as chain carbonate and chain ester.
  • One of the preferable combinations is a combination mainly composed of a cyclic carbonate and a chain carbonate.
  • the total of the cyclic carbonate and the chain carbonate in the entire non-aqueous solvent may be 80% by volume or more, preferably 85% by volume or more, and more preferably 90% by volume or more.
  • the volume of the cyclic carbonate relative to the total of the cyclic carbonate and the chain carbonate may be 5% by volume or more, preferably 10% by volume or more, and more preferably 15% by volume or more.
  • the volume of the cyclic carbonate relative to the total of the cyclic carbonate and the chain carbonate may be 50% by volume or less, preferably 35% by volume or less, and more preferably 30% by volume or less.
  • cyclic carbonates and chain carbonates include ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate And methyl ethyl carbonate, ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate.
  • the additive is not particularly limited as long as it is an additive for a non-aqueous electrolyte solution of a lithium ion secondary battery.
  • other additives such as an overcharge preventing material, a negative electrode film forming material, a positive electrode protective material, and a high input / output material may be used depending on the required function.
  • the content of vinylene carbonate is preferably 0.3% by mass to 2.0% by mass with respect to the entire electrolytic solution.
  • the content of vinylene carbonate is 0.3% by mass or more, a coating film can be sufficiently formed on the negative electrode, and decomposition of the electrolytic solution tends to be suppressed.
  • the content of vinylene carbonate is 2.0% by mass or less, an increase in internal pressure at high temperatures and high voltages tends to be suppressed.
  • the content of vinylene carbonate is more preferably 0.5% by mass to 1.5% by mass with respect to the entire electrolytic solution.
  • Separator A separator is particularly suitable if it has ion permeability while electrically insulating between the positive electrode and the negative electrode, and has sufficient resistance to oxidation on the positive electrode side and reducibility on the negative electrode side. Not limited. Examples of the material (material) of the separator that satisfies such characteristics include resins, inorganic substances, and glass fibers.
  • the resin examples include olefin polymers, fluorine polymers, cellulose polymers, polyimide, nylon, and the like. Specifically, it is preferable to select from materials that are stable with respect to the non-aqueous electrolyte and have excellent liquid retention properties, and more preferable are porous sheets made of polyolefin such as polyethylene and polypropylene, and nonwoven fabrics.
  • Examples of the inorganic substance include oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate.
  • Examples of the separator using an inorganic material include a material in which a fiber-shaped or particle-shaped inorganic material is attached to a thin film-shaped substrate such as a nonwoven fabric, a woven fabric, or a microporous film.
  • a thin film-shaped substrate those having a pore diameter of 0.01 ⁇ m to 1 ⁇ m and a thickness of 5 ⁇ m to 50 ⁇ m are preferably used.
  • Another example includes a composite porous layer made of a fiber-shaped or particle-shaped inorganic substance using a binder such as a resin. Furthermore, what formed this composite porous layer in the surface of the positive electrode or the negative electrode is good also as a separator. For example, a composite porous layer in which alumina particles having a 90% particle size of less than 1 ⁇ m are bound using a fluororesin as a binder may be formed on the surface of the positive electrode to form a separator.
  • the lithium ion secondary battery may be provided with a cleavage valve as another component. By opening the cleavage valve, it is possible to suppress an increase in pressure inside the battery and to improve safety.
  • an inert gas for example, carbon dioxide
  • an inert gas for example, carbon dioxide
  • the cleavage valve can be opened quickly due to the generation of inert gas, and safety can be improved.
  • the material used for the above components include lithium carbonate and polyalkylene carbonate resin.
  • a laminate-type lithium ion secondary battery can be manufactured, for example, as follows. First, the positive electrode and the negative electrode are cut into squares, and tabs are welded to the respective electrodes to produce positive and negative electrode terminals. Next, a positive electrode, a separator (insulating layer), and a negative electrode are laminated in this order to produce a laminate, which is accommodated in a laminate pack, and the positive and negative electrode terminals are taken out of the laminate pack. Next, a non-aqueous electrolyte is poured into the laminate pack, and the opening of the laminate pack is sealed. Examples of the material of the laminate pack include aluminum.
  • the lithium ion secondary battery 1 has a bottomed cylindrical battery container 6 made of steel plated with nickel.
  • the battery container 6 accommodates an electrode group 5 produced by winding a belt-like positive electrode plate 2 and a negative electrode plate 3 with a separator 4 interposed therebetween.
  • the separator 4 may be a polyethylene porous sheet, for example, and may have a width of 58 mm and a thickness of 30 ⁇ m.
  • a ribbon-like positive electrode tab terminal made of aluminum and having one end fixed to the positive electrode plate 2 is led out.
  • the other end of the positive electrode tab terminal is disposed on the upper side of the electrode group 5 and is joined to the lower surface of a disk-shaped battery lid serving as a positive electrode external terminal by ultrasonic welding.
  • a negative electrode tab terminal made of copper and having one end fixed to the negative electrode plate 3 is led out on the lower end surface of the electrode group 5.
  • the other end of the negative electrode tab terminal is joined to the inner bottom of the battery container 6 by resistance welding. Therefore, the positive electrode tab terminal and the negative electrode tab terminal are respectively led to both end faces of the electrode group 5.
  • omitted illustration is given to the outer peripheral surface whole periphery of the electrode group 5.
  • the battery lid is caulked and fixed to the upper part of the battery container 6 via an insulating resin gasket. For this reason, the inside of the lithium ion secondary battery 1 is sealed. In addition, a non-aqueous electrolyte (not shown) is injected into the battery container 6.
  • the capacity ratio of the negative electrode to the positive electrode is preferably 1.03 to 1.8, and preferably 1.05 to 1.4 from the viewpoint of safety and energy density. It is more preferable.
  • the negative electrode capacity indicates [negative electrode discharge capacity]
  • the positive electrode capacity indicates [positive charge capacity of positive electrode minus negative electrode or positive electrode, whichever is greater, irreversible capacity].
  • the “negative electrode discharge capacity” is defined to be calculated by the charge / discharge device when the lithium ions inserted into the negative electrode active material are desorbed.
  • the “initial charge capacity of the positive electrode” is defined as that calculated by the charge / discharge device when lithium ions are desorbed from the positive electrode active material.
  • the capacity ratio between the negative electrode and the positive electrode can be calculated from, for example, “discharge capacity of the lithium ion secondary battery / discharge capacity of the negative electrode”.
  • the discharge capacity of the lithium ion battery is, for example, 4.4 V, 0.1 C to 0.5 C, 0.1 C to 0 after performing constant current and constant voltage (CCCV) charging with an end time of 2 to 15 hours. It can be measured under the conditions when a constant current (CC) is discharged to 2.5V at 5C.
  • the discharge capacity of the negative electrode was prepared by cutting a negative electrode having a measured discharge capacity of the lithium ion secondary battery into a predetermined area, using lithium metal as a counter electrode, and preparing a single electrode cell through a separator impregnated with an electrolyte.
  • the constant current (CC) was discharged to 1.5 V at 0.1 C to 0.5 C. It can be calculated by measuring the discharge capacity per predetermined area under the conditions of time and converting this to the total area when used as the negative electrode of the lithium ion battery.
  • the direction in which lithium ions are inserted into the negative electrode active material is defined as charging, and the direction in which the lithium ions inserted into the negative electrode active material are desorbed is defined as discharging.
  • C means “current value (A) / battery discharge capacity (Ah)”.
  • the aluminum silicate compound composite of this embodiment contains an aluminum silicate compound and carbon, and the total pore volume measured by the nitrogen adsorption method is 0.05 cm 3 / g or more.
  • the details and preferred aspects of the aluminum silicate compound composite of the present embodiment are the same as the details and preferred aspects of the aluminum silicate compound composite used as the material for the lithium ion secondary battery described above.
  • the aluminum silicate compound composite of the present embodiment is preferably used as a material for a lithium ion secondary battery, and is used as a material for a lithium ion secondary battery of a lithium ion secondary battery containing a fluorine-containing electrolyte in an electrolytic solution. It is more preferable.
  • the use of the aluminum silicate compound composite of the present embodiment is not limited to a material for a lithium ion secondary battery, and expresses an excellent adsorbing ability for metal ions, for example, for example, an air purification filter, It can be used as a component of water treatment materials, light absorption films, electromagnetic wave shielding films, organic solvents, non-aqueous solvent ion exchange filters, semiconductor encapsulants, and electronic materials.
  • the solution was then placed in a dryer and heated at 98 ° C. for 48 hours.
  • a 1 mol / L sodium hydroxide aqueous solution was added to the heated solution to adjust the pH to 9.
  • the salt in the solution was aggregated by adjusting the pH, the aggregate was precipitated by the same pressure filtration as described above, and then the supernatant was discharged to perform desalting.
  • the precipitate obtained after the desalting treatment was dried at 110 ° C. for 16 hours to collect the particle mass.
  • the recovered particle lump was pulverized with a jet mill to obtain a particulate aluminum silicate compound having a volume average particle diameter of about 3.5 ⁇ m.
  • the obtained aluminum silicate compound and polyvinyl alcohol powder (Wako Pure Chemical Industries, Ltd.) were mixed at a mass ratio of 100: 70 and fired (carbonized) at 1000 ° C. for 1 hour in a nitrogen atmosphere.
  • a particulate aluminum silicate compound composite comprising carbon derived from polyvinyl alcohol on an aluminum silicate compound was prepared.
  • Production Example 6 A particulate aluminum silicate compound composite was produced in the same manner as in Production Example 1 except that the firing conditions for carbonization were set at 900 ° C. for 1 hour.
  • Production Example 8 A particulate aluminum silicate compound composite was produced in the same manner as in Production Example 1 except that the aluminum silicate compound described in Production Example 1 and polyvinyl alcohol powder were mixed at a mass ratio of 100: 45.
  • a particulate aluminum silicate compound composite was produced in the same manner as in Production Example 1 except that the aluminum silicate compound described in Production Example 1 and polyvinyl alcohol powder were mixed at a mass ratio of 100: 100.
  • a particulate aluminum silicate compound having a volume average particle diameter of about 1.5 ⁇ m was obtained by pulverizing a particle lump of the aluminum silicate compound obtained in the same manner as in Production Example 1 with a jet mill.
  • a particulate aluminum silicate compound composite was prepared in the same manner as in Example 1 except that this aluminum silicate compound and polyvinyl alcohol powder were mixed at a mass ratio of 100: 70.
  • the desalting process of adding pure water to the precipitate after discharging the supernatant and returning to the volume before centrifugation was performed three times.
  • a gel-like precipitate obtained after the third desalting of the desalting treatment was dried at 60 ° C. for 16 hours to recover 30 g of a particle lump.
  • the particle lump was pulverized with a jet mill to produce a particulate aluminum silicate compound.
  • particulate aluminum silicate compound and polyvinyl alcohol powder (Wako Pure Chemical Industries, Ltd.) were mixed at a mass ratio of 100: 70 (aluminum oxide: polyvinyl alcohol powder), and 1 at 850 ° C. in a nitrogen atmosphere.
  • a particulate aluminum silicate compound composite in which carbon derived from polyvinyl alcohol was provided on an aluminum silicate compound was produced.
  • the Co solution before the addition of the aluminum silicate compound complex and the supernatant of the Co solution after standing were filtered using a filter having a pore size of 0.45 ⁇ m, and the Co ion concentration (ppm) was measured using an ICP emission spectrometer. ) Were measured respectively.
  • the difference between the Co ion concentration (500 ppm) of the Co solution at the initial stage (before addition of the aluminum silicate compound complex) and the Co ion concentration (ppm) of the supernatant after adsorption (after standing) was determined.
  • the Co adsorption capacity (mg / g) was calculated by multiplying the difference value by the amount of Co solution (5 g) and dividing by the mass (0.05 g) of the aluminum silicate compound complex.
  • FIG. 2 shows the relationship between the measurement results and the Si / Al ratio of the aluminum silicate compound composite.
  • the aluminum silicate compound composites obtained in Production Examples 1 to 5 and Production Example 13 were evaluated for hydrogen fluoride adsorption ability as follows. First, 1 mol / L of lithium hexafluorophosphate (LiPF 6 ) and 0.5% by mass of vinylene carbonate (VC) with respect to a mixed solvent of ethylene carbonate (EC): ethyl methyl carbonate (EMC) volume ratio 3: 7. A dissolved electrolyte solution (40 g) was prepared. Thereafter, an aluminum silicate compound composite (0.4 g) vacuum-dried at 120 ° C. for 10 hours was added to the electrolytic solution and stirred for 10 minutes, and then allowed to stand at room temperature for 3 hours.
  • LiPF 6 lithium hexafluorophosphate
  • VC vinylene carbonate
  • EMC ethyl methyl carbonate
  • the hydrogen fluoride concentration (ppm) was measured using ion chromatography (ICS-2000, manufactured by Thermo Fisher SCIENTIFIC). It was measured. The difference between the hydrogen fluoride concentration of the electrolyte solution at the initial stage (before addition of the aluminum silicate compound complex) and the hydrogen fluoride concentration (ppm) of the supernatant after adsorption (after standing) was determined. The hydrogen fluoride adsorption capacity (mg / g) was calculated by multiplying the difference value by the amount of the electrolytic solution (40 g) and dividing by the mass of the aluminum silicate compound complex (0.4 g). FIG. 3 shows the relationship between the measurement results and the Si / Al ratio of the aluminum silicate compound composite.
  • Example 1 [Production of positive electrode] Lithium cobaltate (94% by mass) as a positive electrode active material, fibrous graphite (1% by mass) and acetylene black (AB) (1% by mass) as conductive materials, and the aluminum silicate compound produced in Production Example 1 The composite (1% by mass) and polyvinylidene fluoride (PVDF) (3% by mass) as a binder were sequentially added and mixed. The composition of the mixture is shown in Table 1. The content of the conductive material in Table 1 is the total of fibrous graphite (1% by mass) and acetylene black (1% by mass).
  • a slurry-like positive electrode mixture was prepared by adding N-methyl-2-pyrrolidone (NMP) as a dispersion solvent to the above mixture and kneading.
  • NMP N-methyl-2-pyrrolidone
  • This positive electrode mixture was applied substantially uniformly and uniformly to an aluminum foil having a thickness of 20 ⁇ m, which is a current collector for the positive electrode. Then, the drying process was performed and it consolidated by the press to the predetermined density.
  • the density of the positive electrode mixture after drying was 3.6 g / cm 3, and the coating amount on one side of the positive electrode mixture after drying was 202 g / m 2 .
  • a positive electrode cut into a 13.5 cm 2 square is sandwiched between polyethylene porous sheets (trade name: Hypore, manufactured by Asahi Kasei Co., Ltd., thickness 30 ⁇ m, “Hypore” is a registered trademark), and further 14.3 cm.
  • a negative electrode cut into two squares was superposed to produce a laminate.
  • This laminate is placed in an aluminum laminate container (trade name: aluminum laminate film, manufactured by Dai Nippon Printing Co., Ltd.), 1 mL of electrolyte is added, the laminate container is heat-welded, and a lithium ion secondary battery for evaluation is prepared. Produced.
  • the electrolytic solution one obtained by adding 1% by mass of vinylene carbonate (VC) to a mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate containing 1 mol / L LiPF 6 with respect to the total amount of the mixed solution was used.
  • VC vinylene carbonate
  • Examples 2 to 11 instead of the aluminum silicate compound composite obtained in Production Example 1, the same procedure as in Example 1 was conducted except that the aluminum silicate compound composite obtained in Production Example shown in Table 1 was added to the positive electrode mixture. Thus, a lithium ion secondary battery for evaluation was produced.
  • Example 1 except that the ratio of lithium cobaltate as the positive electrode active material was 95% by mass, the aluminum silicate compound composite was not added, and the coating amount on one side of the positive electrode mixture was changed to 200 g / m 2. Thus, a lithium ion secondary battery for evaluation was produced.
  • the charge termination condition was a current value of 0.02C. Thereafter, constant current discharge with a final voltage of 2.5 V was performed at a current value of 0.2 C, and the capacity at the time of discharge was defined as the discharge capacity at a current value of 0.2 C. Next, a constant current charge of 0.2 C is performed up to the upper limit voltage of 4.4 V, and then a constant voltage charge is performed at 4.4 V (the charge termination condition is set to a current value of 0.02 C). A constant current discharge with a final voltage of 2.5 V was performed at a current value, and the capacity at the time of discharge was defined as the discharge capacity at a current value of 3C. Next, output characteristics were calculated by the following formula. The results are shown in Table 1.
  • Output characteristics (%) (discharge capacity at current value 3C / discharge capacity at current value 0.2C) ⁇ 100
  • Cycle characteristics (%) (discharge capacity after 200 cycles at current value 1C / discharge capacity after one cycle at current value 1C) ⁇ 100
  • High-temperature storage characteristics (battery expansion coefficient) were calculated as follows. After evaluating the output characteristics under the above conditions, the volume of the lithium ion secondary battery was measured with a high-precision electronic hydrometer (MDS-300, manufactured by Alpha Mirage Co., Ltd.). Thereafter, constant current charging was performed at 25 ° C. with a current value of 0.1 C up to an upper limit voltage of 4.4 V, and then constant voltage charging was performed at 4.4 V. The charge termination condition was a current value of 0.01C. In the charged state, the lithium ion secondary battery was left in a constant temperature bath at 80 ° C. for 48 hours, and a high temperature storage test was performed.
  • the lithium ion secondary battery was taken out from the thermostat, the volume after cooling to 25 ° C. was measured with a high-precision electronic hydrometer, and the expansion coefficient of the lithium ion secondary battery was calculated from the following formula. The results are shown in Table 1.
  • Battery expansion rate (%) (volume of lithium battery after high-temperature storage test / volume of lithium battery before high-temperature storage test) ⁇ 100
  • the lithium ion secondary batteries of Examples 1 to 11 manufactured using the aluminum silicate compound composite having a total pore volume of 0.05 cm 3 / g or more are aluminum silicate.
  • the lithium ion secondary battery of Comparative Example 1 manufactured without using the compound composite and the Comparative Examples 2 to 4 manufactured using the aluminum silicate compound composite having a total pore volume of less than 0.05 cm 3 / g As compared with the lithium ion secondary battery, the evaluation of the output characteristics and the cycle characteristics was good. Moreover, the precipitation of cobalt was also suppressed as compared with the lithium ion secondary battery of the comparative example. From these results, in the lithium ion secondary batteries of Examples 1 to 11, it was considered that the suppression of the precipitation of cobalt on the negative electrode was related to the suppression of the deterioration of the output characteristics and the cycle characteristics.
  • the reason why the precipitation of cobalt in the lithium ion secondary batteries of Examples 1 to 11 was suppressed was that cobalt ions eluted from the positive electrode active material due to hydrogen fluoride generated in the electrolyte were converted to aluminum silica. It is considered that the reprecipitation of cobalt ions was suppressed by the adsorption of the acid compound complex. Further, it is considered that elution of cobalt ions from the positive electrode active material was suppressed by adsorbing the hydrogen fluoride generated in the electrolytic solution to the aluminum silicate compound complex. From this, the aluminum silicate compound composite of this embodiment can be suitably used as an adsorbent such as metal ions and hydrogen fluoride, and is not particularly limited. For example, a lithium ion secondary battery It is preferably used for a positive electrode of a lithium ion secondary battery.
  • the lithium ion secondary batteries of the examples 1 to 10 were suppressed in expansion of the battery as compared with the lithium ion secondary battery of the example 11.
  • the reason for this is not necessarily clear, but since the oxidation point ratio (RA) of the aluminum silicate compound composite used in Examples 1 to 10 is lower than that in Example 11, gas generation due to reaction with the electrolytic solution is small, It is conceivable that gas such as carbon dioxide generated by the reaction between hydrogen fluoride and lithium carbonate on the electrode was less generated due to the adsorption of hydrogen fluoride in the electrolytic solution.
  • RA oxidation point ratio

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

La présente invention concerne un matériau pour des batteries rechargeables au lithium-ion, qui est un complexe de composé de silicate d'aluminium contenant un composé de silicate d'aluminium et du carbone et ayant un volume poreux total égal ou supérieur à 0,05 cm3/g, tel que mesuré par un procédé d'adsorption d'azote.
PCT/JP2017/013010 2017-03-29 2017-03-29 Matériau pour des batteries rechargeables au lithium-ion, matériau mixte d'électrode positive, électrode positive pour des batteries rechargeables au lithium-ion et batterie rechargeable au lithium-ion Ceased WO2018179167A1 (fr)

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JP2019508449A JP6883230B2 (ja) 2017-03-29 2017-03-29 リチウムイオン二次電池用材料、正極合材、リチウムイオン二次電池用正極及びリチウムイオン二次電池
PCT/JP2017/013010 WO2018179167A1 (fr) 2017-03-29 2017-03-29 Matériau pour des batteries rechargeables au lithium-ion, matériau mixte d'électrode positive, électrode positive pour des batteries rechargeables au lithium-ion et batterie rechargeable au lithium-ion

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009152197A (ja) * 2007-12-18 2009-07-09 Samsung Sdi Co Ltd カソード及びこれを採用したリチウム電池
JP2013062099A (ja) * 2011-09-13 2013-04-04 Hitachi Ltd リチウムイオン二次電池用電極およびリチウムイオン二次電池
WO2014200063A1 (fr) * 2013-06-12 2014-12-18 日立化成株式会社 Complexe de silicate d'aluminium, matériau conducteur, matériau conducteur pour un accumulateur à ion lithium, composition pour former une électrode négative pour accumulateur à ion lithium, composition pour former une électrode positive d'un accumulateur à ion lithium, électrode négative pour accumulateur à ion lithium, électrode positive pour accumulateur à ion lithium, et accumulateur à ion lithium
JP2015502627A (ja) * 2011-09-29 2015-01-22 ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ 再充電可能なリチウムイオン電池及び再充電可能なリチウムイオン電池へのガラス系材料の使用
WO2016098553A1 (fr) * 2014-12-17 2016-06-23 日立化成株式会社 Pile rechargeable au lithium-ion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009152197A (ja) * 2007-12-18 2009-07-09 Samsung Sdi Co Ltd カソード及びこれを採用したリチウム電池
JP2013062099A (ja) * 2011-09-13 2013-04-04 Hitachi Ltd リチウムイオン二次電池用電極およびリチウムイオン二次電池
JP2015502627A (ja) * 2011-09-29 2015-01-22 ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ 再充電可能なリチウムイオン電池及び再充電可能なリチウムイオン電池へのガラス系材料の使用
WO2014200063A1 (fr) * 2013-06-12 2014-12-18 日立化成株式会社 Complexe de silicate d'aluminium, matériau conducteur, matériau conducteur pour un accumulateur à ion lithium, composition pour former une électrode négative pour accumulateur à ion lithium, composition pour former une électrode positive d'un accumulateur à ion lithium, électrode négative pour accumulateur à ion lithium, électrode positive pour accumulateur à ion lithium, et accumulateur à ion lithium
WO2016098553A1 (fr) * 2014-12-17 2016-06-23 日立化成株式会社 Pile rechargeable au lithium-ion

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