CN1971998A - Dynamic type polymer lithium ion power supply and its manufacturing process - Google Patents
Dynamic type polymer lithium ion power supply and its manufacturing process Download PDFInfo
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- CN1971998A CN1971998A CNA2005101013315A CN200510101331A CN1971998A CN 1971998 A CN1971998 A CN 1971998A CN A2005101013315 A CNA2005101013315 A CN A2005101013315A CN 200510101331 A CN200510101331 A CN 200510101331A CN 1971998 A CN1971998 A CN 1971998A
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- 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
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- 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
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Abstract
This invention relates to one series of new materials and process, which solve the current problems of safety, reliability and according of current lithium battery to improve productivity efficiency and to lower product cost. The technique dynamic polymer lithium ion power has output capacity at 1000 with energy intensity as 130 w/ kg and power intensity as 950 w/kg.
Description
Technical field
Patent of the present invention relates to a kind of design and production technology of dynamic type polymer lithium ion power supply.In order to realize three high requests of product high-energy, high power and high security, in power supply design of the present invention and producing, use a series of new materials and new technology, for example large-capacity high power polymer lithium-ion battery monomer integrated drive generator technology, multi-functional applying filler in power supply thermal management, high duty metal shell and plastic end cover as power supply external packing etc., solved the ubiquitous fail safe of lithium-ion-power cell, reliability and consistency problem preferably, improved production efficiency and rate of finished products simultaneously, reduced product cost.The dynamic type polymer lithium ion power supply that uses this technology to produce can be used for various large-capacity high-power mobile devices, for example electric bicycle, battery-operated motor cycle, electric automobile, electronic yacht, satellite communication machine, drone, rocket launcher, submarine communication power supply and military equipment power supply or the like.
Background technology
In all energy, electric energy is to clean most, environmental protection, use most convenient and the highest energy form of transformation efficiency.Therefore, store electrical energy expeditiously, using in various occasions then is the common requirements of modern society.Particularly under the background of environmental pollution that is on the rise and depleted day by day petroleum resources, development and development electric motor car or hybrid vehicle have become the industry that various countries, the world today first develop.Serious environmental harm has been caused because of industrial waste gas and vehicle exhaust in the whole world: the urban air quality descends, and the air of pollution causes lung, respiratory tract, heart, skin and other human organ pathology.In the air pollution composition 63% is from motor vehicle exhaust emission: per 1000 automobiles give off 3000 kilograms of carbon monoxide CO and carbon dioxide CO every day
2, 150 kilograms of oxynitrides NO
x, 400 kg of carbon hydrogen compounds, 70 kilograms of noxious substances such as lead, phenol and dust.A large amount of noxious substances that the fuel-engined vehicle exhaust emissions goes out continue and worsen long-rangely existent environment of people, directly the health of harmful to human.
In addition, the scholarly forecast data according to UNEP's announcement in 2000 show: industrial waste gas and vehicle exhaust have caused global greenhouse effect.Greenhouse effect are quickening the speed that global temperatures rises, and the speed that this century, global temperatures rose will be increased to every century-old 5～7 degree from every century-old 0.2 degree of eighties of last century.The global temperatures rising can cause many catastrophic effects, and first south, fossil ice island, the two poles of the earth, north and high mountain ice and snow layer melt the inflow ocean, make sea-level rise, and the city, seashore on many island and land will be submerged; It two is that the temperature difference between the hot and cold air-flow strengthens, and extreme climate increases, and typhoon or whirlwind destructive power are strengthened, and wind-force may increase to the strongest 20 grades from the strongest 12 grades, and Super Typhoon can bring a large amount of rainwater and cause the frequent floods in coastal area and disaster caused by a windstorm destroys; It three is opposite with the floods and the disaster caused by a windstorm of coastal area, and in hinterland arid aggravation, the rivers cutout phase prolongs, even annual dry, reservoir exhaustion, desertification of land aggravation, the desert area enlarges rapidly, thereby has greatly reduced the human existence space, and environment and resource are all by heavy damage.In recent years, natural calamities such as frequent in the world superpower hurricane that occurs and typhoon caused disaster caused by a windstorm and floods to cause the loss of property and the injury of human life, the verified environment and the ruined order of severity of resource.
The fuel consume of Shuai Jie petroleum resources and increase day by day is another aspect of problem day by day, and the petroleum reserves in the whole world was only enough exploited 50 years, yet the world oil consumption is with annual 20% speed sustainable growth.Oil crisis will cause each side heated volatiles such as economy, politics, military affairs, society and life.Electrification is the optimal selections that solve environmental pollution and oil crisis as the power of the various vehicles.Therefore, cleaning such as electric power bicycle, electric power motorcycle, Electric power car and the electric power aircraft vehicles are paid much attention to and are greatly developed by world developed country.Electrokinetic cell is the core component of electric motor car.In various high-power drives pond, large-scale lithium-ion-power cell is first-selected best power source source.
Because superior more many than plumbic acid and Ni-MH battery on the technical performance, for example, high-energy-density and memory-less effect, lithium-ion-power cell are causing increasing attention.But there are four deadly defects in the lithium-ion-power cell that prior art is produced.First poor stability.As everyone knows, the electrolyte of lithium-ion-power cell is liquid.Because the flash-point of liquid organic electrolyte is lower, poor stability, decomposes, catching fire easily.In battery charge and discharge process, the defective of inside battery or outside improper use can make battery overheated, emit a large amount of heats, and liquid organic electrolyte at first decomposes and burns, and produce high interior pressure and cause battery to catch fire even explode.The existing repeatedly report of incident of burning and blast to the electric vehicle lithium-ion-power cell in use takes place in medium both domestic and external.It two is that reliability is low.In order to solve the safety issue that exists in the lithium-ion-power cell, prior art is to use small handsets polymer Li-ion battery technology, amplifies the size of battery how much simply, prepares large-scale lithium-ion-power cell.The shell of small handsets polymer Li-ion battery uses aluminum-plastic composite membrane as flexible packing material, though have light and safe characteristics for compact battery, but for large-sized battery, the flexible package shell is damaged in production, transportation and use easily, also can influence the fail safe and the reliability of battery.It three is that consistency is poor.The electric vehicle electrokinetic cell must be used by a plurality of cell series connection, to increase output voltage, reaches the high-power of electric motor car requirement.Though, in battery pack production and assembling process, can adopt the method for many index sorting to cell, matched combined satisfies conforming requirement.But, in the battery use, owing to making vibrations extraneous in electrode slice expansion, the vehicle ' process and battery electrolyte inside, repeated charge decomposes reasons such as gasification, spacing between the positive and negative electrode sheet in the liquid lithium ion electrokinetic cell can change, and cause the internal resistance of cell to change, cause battery consistency to degenerate, make the technical performance and the security performance variation of battery pack.It four is expensive.The production difficulty of high capacity lithium ion battery is big, the spillage of material height, and product qualified rate is low, product integrated cost height.Compare with Ni-MH battery with plumbic acid, the price of the lithium-ion-power cell that prior art is produced is 2～4 times of lead-acid battery, and is higher by 10～30% than the price of Ni-MH battery.Above-mentioned defective hinders and has limited the application and the development of lithium-ion-power cell.
Summary of the invention
In order to overcome above-mentioned four major problem, in patent of the present invention, provide the method for designing and the production technology thereof of the polymer lithium ion power supply of a kind of high-energy, high power and high security.The technical characterstic of patent of the present invention is to adopt gelinite preparation of electrolyte battery cell, assembled battery structural design, multi-functional applying filler in power supply thermal management and metal/plastic assembled battery shell etc., overcome above-mentioned battery security, reliability and conforming shortcoming, the power polymer lithium ion battery of preparing can long-time safe discharge work under 3～20C multiplying power.
Technology contents of the present invention has two aspects:
First aspect, the know-why that patent of the present invention is solved above-mentioned safety issue describes.
The reason of the security of lithium-ion-power cell difference that prior art is produced is complicated.A large amount of cell safety test datas be the analysis showed that, battery catch fire the reason of blast be since battery under abnormality (battery in or external short circuit, electric current impulse electricity or the temperature that is subjected to transfiniting of transfiniting toast), produce the abnormal chemical reactions and the evolution of heat between the battery material, cause the unusual and rising hastily of internal temperature of battery; Battery is overheated to impel abnormal chemical reactions aggravation between the material conversely, when inside battery heat and accumulation of pressure to a certain degree the time, the blast of catching fire promptly appears in battery.Wherein the main abnormal chemical reaction has following three:
1, the negative terminal surface diaphragm destroys
There is one deck insulating protective film on the battery cathode surface, and the protection negative pole does not react with electrolyte.But this diaphragm instability in the time of 90～120 ℃, can be decomposed with the electrolyte reaction, emits heat and gas simultaneously.Make battery continue to heat up and boost.After the insulation protection film destroy of negative terminal surface, electrolyte directly and lithiated carbon (the Li in the negative pole
xC
6) and binding agent (PVDF) react, send more heat.
2, electrolyte decomposition
Electrolyte is made up of lithium salts and organic solvent.Inflammable, the easy decomposition of organic solvent, flash-point is low.About 100 ℃, electrolyte begins to decompose, and discharges a large amount of gases and heat energy, quickens battery intensification and interior pressure and increases.
3, anodal over oxidation
About 200 ℃ and under the state of oxidation, the exothermic decomposition of positive active material own, and emit oxygen; Positive active material reacts with electrolyte simultaneously, discharges more gas and heat energy, finally causes the battery blast of catching fire.
In sum, the various dangerous phenomenons of lithium-ion-power cell all directly and electrolyte and battery is overheated links together.In other words, electrolyte abnormal response and battery are overheated is the key problem of security of lithium-ion-power cell.In order to solve large-scale security of lithium-ion-power cell problem, what at first will do is, eliminates electrolyte from battery, the substitute is the gelinite polymer dielectric.Opposite with electrolyte, the flash-point of gelinite polymer is higher, and chemism is low, stability better, decomposes and volatilization are few, how therefore battery become safety.
Secondly, avoid battery overheated, promptly resolve the reduction of heat and the heat dissipation problem of battery.As everyone knows; pertinent regulations according to international battery industry; in order to use lithium ion battery safely; must on battery, equip Circuit management system (abbreviating fulgurite system or baffle as); equalizing charge and anti-overcharge electricity when promptly charging, and the anti-overdischarge of when discharge, anti-short circuit and anti-overcurrent.But many people have ignored the another one aspect, and promptly except using the fulgurite system, lithium ion battery also must use thermal management (abbreviating hot-pipe system as) simultaneously.The working temperature upper limit of lithium ion battery is 60 ℃, and as mentioned above, battery is overheated also to be one of key problem of security of lithium-ion-power cell.A kind of hot-pipe system of lithium-ion-power cell is provided in patent of the present invention, has solved the reduction of heat and the heat dissipation problem of battery effectively.Detailed content is in joint explanation down.
Second aspect, multi-functional applying filler is in the power supply thermal management.
The lithium-ion-power cell that prior art is produced is not all considered hot-pipe system, and the heat that battery produces when work only relies on the contact nature heat radiation of battery case and air.For small size and small-capacity cells, because the battery caloric value is few, battery can satisfy the heat radiation requirement by shell with contacting of air.But for large volume and high capacity cell, not only cell itself sends a large amount of heat energy, and, during power supply that tens, tens batteries are formed, the heat energy of generation converges effect, makes battery can't arrive cooling and the purpose of dispelling the heat by the contact nature heat radiation of shell and air.Long-term battery of under superheat state, working, light then damage the technical characteristic of battery, for example, capacity attenuation is too fast, and internal resistance increases, consistency variation, cycle life minimizing; Heavy then produce the cell safety accident.In addition, when unusual condition takes place (short circuit of battery inside/outside portion, transfinite electric current impulse electricity or the temperature that is subjected to transfiniting baking), the inside battery heat increases that to overrun be to cause the battery blast principal element of catching fire.For example, the inside battery heat rises rapidly, breaks through 135 ℃ of the safe closed pore temperatures of mode separation strapping rapidly, and battery will cause the blast of catching fire because of crossing thermal runaway; Otherwise, in the short circuit of generation battery inside/outside portion, when transfiniting electric current impulse electricity or the temperature that is subjected to transfiniting baking, if can control the inside battery heat slowly rises, near 135 ℃ of temperature, there is the enough time to produce safe closed pore effect for mode separation strapping, close the lithium ion passage between the positive and negative electrode, internal resistance increases to infinity, and battery has become safety because of inefficacy.
A kind of hot-pipe system of lithium ion power power supply is provided in patent of the present invention, can solves reduction of heat and the heat dissipation problem of battery when operate as normal effectively, and when the battery unusual condition, realize the purpose that control inside battery heat slowly rises.The power supply hot-pipe system is made up of following elements:
1, the monomer-polymer lithium ion battery of slim design
Big capacity power source is formed in parallel by the monomer-polymer lithium ion battery of some slim designs.The capacity of cell is less than 20 ampere-hours.Each cell all uses the colloidal polymer electrolyte, and cell thickness is less than 8 millimeters, and width and length are big as far as possible, makes the distance of inside battery heat energy arrival battery aluminum-plastic composite membrane shell short, rapid heat dissipation.
2, metal shell and plastic end cover
In order to protect polymer Li-ion battery, avoid being worn, shake and impact, and for the ease of the battery heat radiation, power supply peripheric surface shell uses rigid metallic material, for example aluminium and steel, perhaps alloy material.End cap uses plastics, for example polyethylene, polypropylene, polyvinyl chloride and polyester up and down.Being connected of plastic end cover and peripheric surface metal shell is that metal shell embeds in the plastic end cover up and down, fixes with self-tapping screw then.Under extremity, plastic end cover can play the effect of explosion-proof valve up and down.Adopt the structure of metal shell and plastic end cover to prepare outer casing of power supply, except the advantage of secure context, the advantage of conveniently producing and reducing cost in addition.
3, multi-functional decalescence and heat filling
Between slim monomer-polymer lithium ion battery, and all leave the slit between battery and metal shell, its gap size is 0.05～16 millimeter.In the slit, insert multi-functional decalescence and Heat Conduction Material.Select a kind of independent use or multiple mixing to use in the compound that this material can be given an example from below: paraffin, high density polyethylene (HDPE) paraffin, stearic acid, alkane, ester, alcoholic compound.Paraffin is made of high-molecular hydrocarbons, and its chemical general formula is C
nH
2n+2, carbon number n=17～36 in the formula, n is big more, and melting point of paraffin wax is high more, and its fusing point is continuous adjustable at 52～70 ℃.Relative density is 0.86～0.94, and molecular weight is about 240～450.The chemism of paraffin is lower, is neutral, and chemical property is stable, does not have an effect with bronsted lowry acids and bases bronsted lowry solution under usual conditions.Paraffin is being not easy to decompose carbonization below 140 ℃; And have certain intensity and good plasticity, not easy to crack.Paraffin has bigger conductive coefficient～0.348W/ (mK), and when undergoing phase transition, heat absorption can reach 150kJ/kg～250kJ/kg.
Use decalescence such as paraffin and Heat Conduction Material to form the power supply hot-pipe system, can arrive following purpose as the battery filler:
(1), battery promotes the fail safe of power supply by being absorbed heat and dispel the heat
Paraffin is present best heat absorption and heat sink material, and its fusing point is at 52～70 ℃, 60 ℃ of the working temperature upper limits of corresponding lithium ion battery.If appearring in battery, abnormality (for example inside/outside portion short circuit, the electric current impulse electricity transfinites) cause temperature to rise; when arriving melting point of paraffin wax; paraffin is liquid by solid state transformation, absorbs a large amount of heat energy in its solid-liquid phase change process, and the protection battery avoids overheated or the control internal temperature slowly rises.Paraffin under the fused solution not only itself continue heat absorption, and its conductive coefficient is very high, can be rapidly with the thermal energy transfer of each battery to shell, distribute by metal shell, arrive heat absorption and heat radiation thus, the purpose that the battery heat is regulated and control.When the abnormality of battery finished, temperature fell after rise, and melt paraffin is crystallization more slowly, change into by liquid state solid-state, in order to use next time.The solid-liquid phase change of paraffin absorbs the heat energy process, is completely reversibility, and can moving in circles, it is unlimited to use.Secondly, the density of paraffin is 0.86～0.94, and is also lighter than water.In power supply, use paraffin can significantly not gain in weight as the battery thermal system.Its three, the chemism of paraffin is low and chemical property is stable, is inert substance, uses paraffin can not bring new security risk as the battery thermal system in power supply.
(2) by cell being separated the fail safe that promotes whole power supply
In the high capacity lithium ion battery, battery material total amount thousands of grams that weigh.To the analysis of cell safety problem as seen, most of materials in the battery comprise that negative pole, electrolyte and positive pole all may participate in abnormal chemical reactions from last joint, cause the battery blast of catching fire.A large amount of lithium ion battery security test datas of accumulation at present show that the monomer capacity detects by country and international safety standard easily less than the lithium ion battery of 40 ampere-hours; The monomer capacity is difficult to detect by country and international safety standard greater than the lithium ion battery of 40 ampere-hours.In the present invention, separate by multi-functional decalescence and heat filling between each cell, the capacity of all cells is less than 20 ampere-hours, and the combustible material that comprises in the cell is limited on the one hand, can not cause security incident during abnormality that cell occurs; The heat that produces during the single battery abnormal chemical reactions can be absorbed by filler rapidly on the other hand, avoids feeding through to other battery.Use multi-functional decalescence and heat filling small-capacity cells to be separated the fail safe that can significantly promote big capacity power source.
(3) protection monomer-polymer lithium ion battery and aluminum-plastic composite membrane shell are to strengthen power supply reliability
The metallic shell lithium-ion battery uses laser machine welding shell, and weld seam has rigidity and intensity, and is solid and reliable.Different with the metal-back battery, polymer Li-ion battery uses plastic-aluminum combined film as the flexible package shell, and flexible package shell seam is to rely on plastic-aluminum combined film inner layer CPP film to connect by hot melt.The CPP film thickness has only 0.03mm, the intensity difference that hot melt connects, and reliability is low.Particularly under the complex environment road conditions condition of external vibrations, mechanical shock and cold and hot tension force, the aluminum-plastic composite membrane flexible package shell of polymer Li-ion battery is damaged easily, and may ftracture in the hot melt junction, cause battery failure.
In patent of the present invention, use paraffin to wrap up each battery case, help the fixedly hot melt connection seam of aluminum-plastic composite membrane flexible package shell on the one hand, prevent its cracking; Two aspects can absorb external shock power and vibration energy, reduce and avoid the destruction of external force to polymer Li-ion battery and aluminum-plastic composite membrane flexible package shell; The rapid influence that changes battery of ambient temperature can be slowed down in three aspects.In a word, use decalescence such as paraffin and Heat Conduction Material can strengthen the reliability of power supply as the battery filler.
(4) control monomer-polymer lithium ion battery expansion deformation maintaining coherency
Lithium-ion-power cell generally all adopts stacked in order to realize the output of big capacity and high power: by tens in addition hundreds of align that negative electrode plate folder mode separation strapping is stacked to constitute battery.Under the environment of liquid electrolyte, these electrode slices are loose, occur the volumetric expansion distortion repeatedly during impulse electricity at battery easily, cause the battery performance decay, the consistency variation.Polymer Li-ion battery in patent of the present invention uses colloidal electrolyte, and positive and negative electrode sheet and mode separation strapping are bonded together by colloidal electrolyte, and the distortion of inert substance as filler constraint electrode slice arranged between the thin battery.Therefore, the volumetric expansion of battery when impulse electricity repeatedly is effectively controlled, and the consistency of battery strengthens.
In order to bring into play the characteristic of multi-functional decalescence and heat filling better, can in paraffin, add various additives, for example silicon dioxide SiO
2Powder and titanium dioxide TiO
2Powder.The characteristics of these pressed powders are lightweight, high-strength, high stability, and they are joined in the paraffin, can increase the intensity and the thermal stability of paraffin.Silicon dioxide SiO
2Powder and titanium dioxide TiO
2The specific area of powder is 0.2～1000 meters squared per gram, and the addition in paraffin is 0～30%.High density polyethylene (HDPE) paraffin is that paraffin is sneaked in the parent phase of high density polyethylene (HDPE) mutually as son, forms porous carrier by high density polyethylene (HDPE), and paraffin fuses in the hole of high density polyethylene (HDPE) formation.Paraffin is 10～60% in the combined amount of high density polyethylene (HDPE).Other organic compound, for example stearic acid, alkane, ester, alcoholic compound have the characteristic similar to paraffin, also can use separately as decalescence and heat filling, perhaps with paraffin, high density polyethylene (HDPE) and silicon dioxide SiO
2Powder and titanium dioxide TiO
2Powder preparation becomes solid solution or mixture to use.
In sum, the characteristics of patent process of the present invention are:
1, uses production technology provided by the invention to prepare dynamic type polymer lithium ion power supply, solved fail safe, reliability and the consistency problem of power supply preferably;
2, be resolved owing to safety issue, adopt production technology provided by the invention, according to customer demand, be combined into the power supply of various capacity outputs by the monomer-polymer lithium ion battery, the power supply output capacity can be up to 1000 ampere-hours, energy density can reach 130 watt-hour/kilograms, and power density can reach 950 watts/kilogram.
3, can reduce the product integrated cost.The capacity of power-type lithium ion battery is up to tens even the hundreds of ampere-hour, and the error of any one link in the production process all might cause waste product, causes material and artificial loss.According to method provided by the invention, the preparation capacity is combined into cell the big capacity power source of customer demand then less than the cell of 20 ampere-hours, and the difficulty of producing the low capacity cell on the one hand is low, the rate of finished products height; Even occur waste product on the other hand, material and artificial loss reduce significantly.Therefore, the integrated cost of product reduces significantly.
By structure and each element of reference accompanying drawing and detailed description dynamic type polymer lithium ion power supply of the present invention, characteristics of the present invention and advantage can be described more clearly.Wherein:
Fig. 1 is that dynamic type polymer lithium ion power supply provided by the invention is faced generalized section.In dynamic type polymer lithium ion power supply 10, slim colloidal electrolytic polymer lithium-ion battery monomer 11 is arranged, metal shell 12, CPP lug sealing-in adhesive tape 13, lug electrode slice 14, electrode column piece 15, assembling spinning stop pin 16, electrode column nut 17, electrode column gasket seal 18, last plastic end cover and metal shell attachment screw 19, last plastic end cover 20, multi-functional decalescence and heat filling 22, following plastic end cover 23.
Fig. 2 is a dynamic type polymer lithium ion power supply side-looking generalized section provided by the invention.Wherein 11 is the slim polymer Li-ion battery monomers of colloidal electrolyte, the 14th, the lug electrode slice, the 15th, the electrode column piece, the 18th, the electrode column gasket seal, the 19th, last plastic end cover and metal shell attachment screw, the 20th, last plastic end cover, the 22nd, multi-functional decalescence and heat filling, the 23rd, following plastic end cover.
Describe following preferred embodiment in detail, will understand superiority of the present invention better.
Example 1
(1) preparation of negative electrode:
(1.1) the poly-inclined to one side vinylidene fluoride of 1560 grams is dissolved in the N-first and gives a tongue-lashing and cough up the alkane diketone, at first add 20 gram oxalic acid, add 500 gram acetylene blacks then, add 22000 gram graphite powders at last for-2-.Through high-speed stirred evenly, vacuum or leave standstill degasification after make the cathode size of pulpous state.
(1.2) film:, cathode size is coated in equably on positive and negative two surfaces of Copper Foil of 16 micron thickness according to the battery product designing requirement.Give a tongue-lashing and cough up the alkane diketone for-2-120 ℃ of down dry N-first of desolvating of removing, the THICKNESS CONTROL of electrode band is at 160 ± 10 microns.
(1.3) roll-in: cathode pole piece is pressed onto the thickness of appointment at the certain pressure lower roll, the porosity of control pole piece film density and pole piece film.The THICKNESS CONTROL of electrode band after roll-in is at 110 ± 5 microns.
(1.4) film-making: the size according to the battery product design becomes chopper type with negative electrode band cutting: the Copper Foil of hilt for not filming, as the afflux utmost point, area is 30 * 10mm
2Kitchen knife is an electrode slice, and area is 156 * 266mm
2
(2) preparation of positive electrode:
(2.1) slurrying: the poly-inclined to one side vinylidene fluoride of 4000 grams is dissolved in the N-first gives a tongue-lashing and cough up the alkane diketone, add 2530 gram acetylene blacks then, add 50000 gram lithium manganese oxides at last for-2-.Through high-speed stirred evenly, vacuum or leave standstill degasification after make the anode sizing agent of pulpous state.
(2.2) film: according to the battery product designing requirement, the slurry of making is coated in equably positive and negative two surfaces of 25 micron thickness aluminum metallic foil, give a tongue-lashing and cough up the alkane diketone for-2-120 ℃ of down dry N-first of desolvating of removing, the THICKNESS CONTROL of electrode band is at 180 ± 10 microns.
(2.3) roll-in: anode pole piece is pressed onto the thickness of appointment at the certain pressure lower roll, controls the porosity of pole piece film density and pole piece film.The THICKNESS CONTROL of electrode band after roll-in is at 125 ± 5 microns.
(2.4) film-making: the size according to the battery product design becomes chopper type with positive electrode band cutting: the aluminium foil of hilt for not filming, as the afflux utmost point, area is 30 * 10mm
2Kitchen knife is an electrode slice, and area is 150 * 260mm
2
(3) barrier film: compound PE-PP membrane paper is cut into the size that battery product designs, make mode separation strapping.
(4) stacked battery core: with positive, negative electrode plate and thickness is that 25 microns, width are that the PE-PP membrane band of 270mm is folded in proper order by negative electrode plate/diaphragm/electrode film/diaphragm/negative electrode plate, builds up 6.5 * 160 * 270mm
3Battery.74 layers on 36 layers of the total positive plates of battery, 37 layers of negative electrode plates and PE-PP membrane band.Use the aluminium pole ears and the nickel lug that have sealed the CPP adhesive tape in advance to be welded on the positive and negative electrode lead-in wire hilt.The design capacity of cell core is 20 ampere-hours.
(5) assembling: in the above-mentioned battery for preparing is packed aluminum-plastic composite membrane into, use heat sealing machine to carry out closedtop and side seal, reserve bottom sides as liquid injection port.
(6) monomer, initator and the preparation of electrolyte mixed liquor: monomer is EDIA (Ethyleneglycol diacrylate), ethylene glycol dimethacrylate (Ethylene glycoldimethacrylate) and vinyl pyrrole quinoline (vinyl pyrrolidone) ternary mixed system, and ratio is 1: 1: 1; Initator is selected azodiisobutyronitrile (Diisopropyl peroxydi) etc. for use.The proportioning of monomer and initator is 1000: 4.The concentration of monomer in electrolyte is 5%.Electrolyte is made up of electrolytic salt and organic solvent.Electrolytic salt can be selected lithium hexafluoro phosphate LiPF for use
6Organic solvent can be selected ethylene carbonate EC, methyl ethyl carbonate fat EMC and carbonic acid diethyl ester DEC ternary system for use, and mixed proportion is 1: 1: 1.The concentration of electrolytic salt in organic solvent is every liter 1.2 gram molecule.
(7) fluid injection:, annotate in the battery the monomer for preparing in advance, initator and electrolyte mixed liquor quantity 70 grams by the battery product design.Then, sealing fluid injection limit.
(8) on-the-spot thermal polymerization chemical reaction: under the 100 ℃ of heating and the 0.5 MPa condition of pressurizeing, through 1600 seconds, high molecular polymerization and gelation reaction can take place in the low molecular monomer, initator and the electrolyte mixed liquor that are injected in the battery, be transformed into normal colloidal state polymer electrolyte, positive and negative electrode and barrier film are closely bonded together, make battery form a integral body with self bulk strength and rigidity.
(9) change into and place: with special-purpose battery charging and discharging equipment the finished product battery being charged at a slow speed changes into; form diaphragm at negative electrode surface. after placing several weeks then, remake discharge test, each battery is all detected; filter out qualified finished product battery, the power supply that is made into to be installed.To this operation, slim colloidal electrolytic polymer lithium-ion battery monomer preparation is finished.
(10) power supply assembling: at first, be that the aluminium shell that 5 millimeters following plastic end cover and thickness are 2 millimeters assembles, 10 slim colloidal electrolytic polymer lithium-ion battery monomers are immersed respectively in the melt paraffin liquid, lift out then with thickness.Every battery surface all applies last layer paraffin, and thickness is about 0.5 millimeter.Secondly, with these 10 batteries aluminum hull of packing into, pour into melt paraffin liquid at the gap location of battery and aluminum hull, the height of paraffin sizing is as the criterion for 3 millimeters for flooding the CPP film.Other process also has immersion, cast, casting, injection and spray etc.The 3rd step connected positive negative battery sheet respectively with the positive and negative electrode post, will go up the plastic end cover fit on, installed and fixed screw and electrode column nut.In the 4th step, the power supply that assembling finishes is tested.The power supply produced of method thus, its discharge capacity is 200 ampere-hours.
Example 2
(1) preparation of negative electrode:
(1.1) the poly-inclined to one side vinylidene fluoride of 1560 grams is dissolved in the N-first and gives a tongue-lashing and cough up the alkane diketone, at first add 20 gram oxalic acid, add 500 gram acetylene blacks then, add 35000 gram amorphous tin lithium composite xoide SnLi at last for-2-
ρP
B
χO
ψThrough high-speed stirred evenly, vacuum or leave standstill degasification after make the cathode size of pulpous state.
(1.2) film:, cathode size is coated in equably on positive and negative two surfaces of Copper Foil of 16 micron thickness according to the battery product designing requirement.Give a tongue-lashing and cough up the alkane diketone for-2-120 ℃ of down dry N-first of desolvating of removing, the THICKNESS CONTROL of electrode band is at 150 ± 10 microns.
(1.3) roll-in: cathode pole piece is pressed onto the thickness of appointment at the certain pressure lower roll, the porosity of control pole piece film density and pole piece film.The THICKNESS CONTROL of electrode band after roll-in is at 100 ± 5 microns.
(1.4) film-making: according to the size of battery product design, it is 266 * 1050mm that negative electrode band cutting is become area
2The stripe shape electrode slice.0.1 millimeter of thickness of spot welding and 10 millimeters nickel down-leads of width on the initial copper-clad surface of not filming then.
(2) preparation of positive electrode:
(2.1) slurrying: the poly-inclined to one side vinylidene fluoride of 3650 grams is dissolved in the N-first gives a tongue-lashing and cough up the alkane diketone, add 2530 gram acetylene blacks then, add 25000 gram lithium and cobalt oxides and 25000 gram lithium manganese oxides at last for-2-.Through high-speed stirred evenly, vacuum or leave standstill degasification after make the anode sizing agent of pulpous state.
(2.2) film: according to the battery product designing requirement, the slurry of making is coated in equably positive and negative two surfaces of 25 micron thickness aluminum metallic foil, give a tongue-lashing and cough up the alkane diketone for-2-120 ℃ of down dry N-first of desolvating of removing, the THICKNESS CONTROL of electrode band is at 170 ± 10 microns.
(2.3) roll-in: anode pole piece is pressed onto the thickness of appointment at the certain pressure lower roll, controls the porosity of pole piece film density and pole piece film.The THICKNESS CONTROL of electrode band after roll-in is at 115 ± 5 microns.
(2.4) film-making: according to the size of battery product design, positive electrode band cutting is in strip: area is 260 * 1040mm
20.1 millimeter of thickness of spot welding and 10 millimeters aluminum leads of width on the initial copper-clad surface of not filming then.
(3) barrier film: compound PE-PP membrane paper is cut into the size that battery product designs, make mode separation strapping.
(4) coiled battery core: with the positive and negative electrode band, the PE-PP membrane band that accompanies thickness in the middle of it and be 25 microns, width and be 270mm is put in order in proper order by negative electrode band/mode separation strapping/positive electrode band/mode separation strapping, align electrode band, mode separation strapping, the cross arrangement of negative electrode band with three, be wound into 6 * 160 * 270mm with one heart
3Battery.It is that the thickness of aluminium pole ears is 0.1 millimeter on 30 millimeters the aluminium pole ears that three aluminum leads are welded on the prior CPP of heat-sealing adhesive tape, width side by side; It is that the thickness of nickel lug is 0.1 millimeter on 30 millimeters the nickel lug that three nickel down-leads are welded on the prior CPP of heat-sealing adhesive tape, width side by side.The design capacity of cell core is 18 ampere-hours.
(5) assembling: in the above-mentioned battery for preparing is packed aluminum-plastic composite membrane into, use heat sealing machine to carry out closedtop and side seal, reserve bottom sides as liquid injection port.
(6) monomer, initator and the preparation of electrolyte mixed liquor: monomer is methyl methacrylate (Methylmethacrylate) and ethylene glycol dimethacrylate (Ethylene glycol dimethacrylate) binary mixture, and ratio is 1: 1; Initator is selected azodiisobutyronitrile (Diisopropylperoxydi) etc. for use.The proportioning of monomer and initator is 1000: 3.The concentration of monomer in electrolyte is 6%.Electrolyte is made up of electrolytic salt and organic solvent.Electrolytic salt can be selected lithium hexafluoro phosphate LiPF for use
6Organic solvent can be selected ethylene carbonate EC, methyl ethyl carbonate fat EMC and carbonic acid diethyl ester DEC ternary system for use, and mixed proportion is 1: 1: 1.The concentration of electrolytic salt in organic solvent is every liter 1.2 gram molecule.
(7) fluid injection:, annotate in the battery the monomer for preparing in advance, initator and electrolyte mixed liquor quantity 65 grams by the battery product design.Then, sealing fluid injection limit.
(8) on-the-spot thermal polymerization chemical reaction: under the 90 ℃ of heating and the 0.5 MPa condition of pressurizeing, through 2000 seconds, high molecular polymerization and gelation reaction can take place in the low molecular monomer, initator and the electrolyte mixed liquor that are injected in the battery, be transformed into normal colloidal state polymer electrolyte, positive and negative electrode and barrier film are closely bonded together, make battery form a integral body with self bulk strength and rigidity.
(9) change into and place: with special-purpose battery charging and discharging equipment the finished product battery being charged at a slow speed changes into; form diaphragm at negative electrode surface. after placing several weeks then, remake discharge test, each battery is all detected; filter out qualified finished product battery, the power supply that is made into to be installed.To this operation, slim colloidal electrolytic polymer lithium-ion battery monomer preparation is finished.
(10) power supply assembling: at first, configuration stearic acid and silicon dioxide SiO
2The powder additive mixed molten liquid.Stearic acid has many kinds, for example, and glycerine stearic acid (Sterin acid) and arachidic acid (Arachidicacid).With specific area is the silicon dioxide SiO of 10 meters squared per gram
2Powder joins the glycerine stearic acid as additive, and addition is 10%, is prepared into mixed fillers, and melt temperature is 70 ℃.Secondly, be that the aluminium shell that 5 millimeters following plastic end cover and thickness are 2 millimeters assembles with thickness.In the 3rd step, 6 slim colloidal electrolytic polymer lithium-ion battery monomers are immersed respectively in the melting mixing filler.Then, battery is lifted out from mixed molten liquid.Every battery surface all applies the last layer mixed fillers, and thickness is about 0.5 millimeter.The 4th step with these 6 batteries aluminum hull of packing into, poured into the melting mixing liquation at the gap location of battery and aluminum hull, and the height of mixed fillers is as the criterion for 3 millimeters for flooding the CPP film.The 5th step connected positive negative battery sheet respectively with the positive and negative electrode post, will go up the plastic end cover fit on, installed and fixed screw and electrode column nut.At last, the power supply that assembling is finished is tested.The power supply produced of method thus, its discharge capacity is 108 ampere-hours.
Claims (10)
1. dynamic type polymer lithium ion power supply is characterized in that:
(1) a plurality of slim Colloid Electrolytic Polymer Lithium Ion Battery monomers combination in parallel;
(2) multi-functional decalescence and heat filling constitute the power supply thermal management;
(3) metal shell and plastic end cover are as outer casing of power supply.
2. monomer-polymer lithium ion battery according to claim 1 mainly is made of as five kinds of elements of battery flexible package shell positive electrode, negative electrode, barrier film, colloidal polymer electrolyte and aluminum-plastic composite membrane between positive and negative electrode.
3. described gel polymer electrolyte is present between positive electrode and the barrier film and on the surface of each element between negative electrode and the barrier film, positive and negative electrode and barrier film is bonded together securely, forms a rigid unitary.
4. dynamic type polymer lithium ion power supply according to claim 1 between slim monomer-polymer lithium ion battery, and all leaves the slit between battery and metal shell, its gap size is 0.05～16 millimeter.In the slit, insert multi-functional decalescence and Heat Conduction Material.
5. in the dynamic type polymer lithium ion power supply according to claim 1, use multi-functional decalescence and heat filling to constitute the power supply thermal management.Select a kind of independent use or multiple mixing to use in the compound that this filler can be given an example from below: paraffin, high density polyethylene (HDPE) paraffin, stearic acid, alkane, ester, alcoholic compound.
6. multi-functional decalescence according to claim 5 and heat conduction paraffin sizing, its chemical general formula are C
nH
2n+2, carbon number n=17～36 in the formula, its fusing point 52～70 ℃ continuous adjustable, relative density is 0.86～0.94, molecular weight is about 240～450.
7. multi-functional decalescence according to claim 5 and heat filling, can with silicon dioxide SiO
2Powder and titanium dioxide TiO
2Powder additive mixes use.Silicon dioxide SiO
2Powder and titanium dioxide TiO
2The specific area of powder is 0.2～1000 meters squared per gram, and the addition of additive is 0～30%.
8. paraffin according to claim 5 fuses in the hole of high density polyethylene (HDPE), constitutes high density polyethylene (HDPE) paraffin.Paraffin is 10～60% in the combined amount of high density polyethylene (HDPE).
9. in the dynamic type polymer lithium ion power supply according to claim 1, adopt the process of immersion, cast, casting, injection and spray, with multi-functional decalescence with heat filling is introduced between the slim monomer-polymer lithium ion battery and in the slit between battery and the metal shell.
10. dynamic type polymer lithium ion power supply according to claim 1 uses metal shell and plastic end cover as outer casing of power supply.Metal shell adopts aluminium and stainless steel; Plastic end cover adopts polyethylene, polypropylene, polyvinyl chloride and polyester.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005101013315A CN1971998A (en) | 2005-11-21 | 2005-11-21 | Dynamic type polymer lithium ion power supply and its manufacturing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005101013315A CN1971998A (en) | 2005-11-21 | 2005-11-21 | Dynamic type polymer lithium ion power supply and its manufacturing process |
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| CN1971998A true CN1971998A (en) | 2007-05-30 |
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| CNA2005101013315A Pending CN1971998A (en) | 2005-11-21 | 2005-11-21 | Dynamic type polymer lithium ion power supply and its manufacturing process |
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