CN101938010A - Manufacturing method of polymer lithium-ion power battery - Google Patents
Manufacturing method of polymer lithium-ion power battery Download PDFInfo
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- CN101938010A CN101938010A CN2009100325229A CN200910032522A CN101938010A CN 101938010 A CN101938010 A CN 101938010A CN 2009100325229 A CN2009100325229 A CN 2009100325229A CN 200910032522 A CN200910032522 A CN 200910032522A CN 101938010 A CN101938010 A CN 101938010A
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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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention discloses a manufacturing method of a polymer lithium-ion power battery. In the battery, an aluminum corrosion foil serves as a positive current collector; a copper foil serves as a negative current collector; a layer of positive conductive carbon slurry and a layer of negative conductive carbon slurry are pre-coated on two surfaces of the positive and negative current collectors respectively; positive and negative active slurries are coated on the positive and negative current collectors respectively; and after an electrolyte is poured into the battery, in-situ polymerization is initiated through electromagnetic induction heating. The manufacturing method is used for manufacturing the polymer lithium-ion power battery serving as a power battery of an electric vehicle, can increase the utilization rate of raw materials, reduce the cost of the battery, reduce the internal resistance between active substances and the current collectors, reduce the temperature rise of the battery, prolong the service life of the battery and improve the safety of the battery. Furthermore, the way of electromagnetic induction polymerization uniformly heats at a high speed, so that the performances and consistency of the battery are greatly improved.
Description
Technical field
The present invention relates to a kind of high power electrokinetic cell that is applied to electric automobile, be specifically related to high power polymer lithium-ion-power cell manufacture method.
Background technology
Current, global greenhouse gas emission total amount continues soaring, and in the CO2 emission, 25% from automobile.The pollution of motor vehicle emission has become the key factor of air pollution, and the pressure of reducing emission of carbon dioxide is with increasing.Greatly develop electric automobile, electricity consumption is the strategic measure that guarantees Chinese energy safety for oil.Lithium-ion-power cell is the electric automobile core component, and recent years, along with the raising of people's environmental consciousness and the support of national various preferential policies, lithium-ion-power cell has obtained development faster.According to the used electrolyte difference of lithium ion battery, lithium ion battery can be divided into liquid lithium ionic cell and polymer Li-ion battery two big classes.What liquid lithium ionic cell used is liquid electrolyte, and polymer Li-ion battery then replaces with solid polymer electrolyte, and this polymer can be " dry state ", also can be " colloidal state ".Also there is the shortcoming of the following aspects in the polymer Li-ion battery of using as power at present:
1, battery is when high power charging-discharging, and the heating phenomenon is serious, and this is because bigger than normal the causing of internal resistance of battery.With state-of-the art, the hybrid electrically Vehicular battery of a 8Ah, about internal resistance 3m Ω, with the 10C multiplying power discharging, the heat 19.2J that 1s produces.After discharge finished, the battery surface temperature was about 60～70 ℃, the battery of working under this temperature, life-span and fail safe meeting decrease to some degree.
2, battery utilization rate of raw materials in manufacturing process is not high, and rate of finished products is on the low side, causes the fringe cost height of battery.
3, the mode cost of polymerized in-situ is low, easily large-scale production, but the mode of heating during polymerization at present is to adopt the resistor oven heating, and the temperature distributing disproportionation in the baking oven greatly destroys the interface stability of the homogeneity of gel electrolyte and gel electrolyte and electrode slice, barrier film etc.
Summary of the invention
The technical problem to be solved in the present invention is the weak point that overcomes existing lithium battery manufacture method, and a kind of polymer lithium ion power cell manufacture method that can reduce battery manufacturing cost, raising battery serviceability, life-span and fail safe is provided.
Technical scheme of the present invention is: the polymer lithium ion power cell manufacture method is by slurry mixing, coating, rolling and cut, electric core making, encapsulation, fluid injection, heated polymerizable and change into, operation such as partial volume constitutes, improvements are in this manufacture method, adopt the aluminium etched foil as plus plate current-collecting body, the two sides of plus plate current-collecting body is the anodal conductive carbon layer slurry of spraying earlier, apply anodal active slurry again, the two sides of negative current collector is spraying negative pole conductive carbon layer slurry earlier, applies the negative electrode active slurry again; Electrolyte injects the back and adopts the intermediate frequency electromagnetic induction heating to cause polymerized in-situ; Above-mentioned anodal conductive carbon layer slurry consists of: conductive carbon material 10～49Wt%, anodal binding agent 1～10Wt%, anodal dispersant 50～89Wt%; Negative pole conductive carbon layer slurry consists of: conductive carbon material 10～49Wt%, negative pole binding agent 1～10Wt%, negative pole dispersant 50～89Wt%; Described conductive carbon material is one or more in acetylene black, superconduction carbon black, electrically conductive graphite, metallic fiber, gas-phase carbon fiber, the carbon CNT (carbon nano-tube); The temperature that above-mentioned intermediate frequency electromagnetic induction heating causes polymerized in-situ is 60～120 ℃, and the time is 1～24h.
Further scheme is: described aluminium etched foil thickness 20～60 μ m, corrosion depth 5～20 μ m; Described anodal binding agent adopts one or more in polyvinylidene fluoride, butadiene-styrene rubber, the sodium carboxymethylcellulose, and anodal dispersant adopts a kind of in deionized water, alcohol or the N-methyl pyrrolidone; Described negative pole binding agent adopts one or more in acrylate adhesive, the sodium carboxymethylcellulose, and the negative pole dispersant adopts deionized water; Electrolyte precursor consists of: lithium hexafluoro phosphate 12～15Wt%, dimethyl carbonate 4～15Wt%, methyl ethyl carbonate 35～50Wt%, ethylene carbonate 15～25Wt%, methyl methacrylate 3～10Wt%, butyl acrylate 1～5Wt%, polyvinylidene fluoride 1～5Wt%, TEG double methyl methacrylate 1～5Wt%, initator 0.01～2Wt%, so-called electrolyte precursor are meant the electrolyte before the heated polymerizable.
The present invention compares with existing manufacture method, and following good effect is arranged:
1, the product combination degree of positive electrode active materials and aluminium foil has bigger influence to the internal resistance of battery, traditional lithium ion cell positive collector all is the optical aluminum foil that adopts 20～40 μ m, plus plate current-collecting body adopts the aluminium etched foil among the present invention, and aluminium etched foil rough surface, active material is with it in conjunction with tightr, electrode slice cut or the process of stamping-out in the phenomenon of dry linting can not appear, improved raw-material utilance, reduced the battery cost.And because the use of aluminium etched foil, active material also reduces accordingly with the internal resistance that contacts of collector, and the rate charge-discharge performance of battery improves.
2, the conductivity of dynamic lithium battery both positive and negative polarity active material itself is not very high, the present invention sprays one deck conductive carbon coating earlier on collector, continue the coating process of operation down then, can effectively reduce the internal resistance that contacts between active material and the collector like this, temperature rise when reducing the battery multiplying power discharging improves battery life and fail safe.
3, methyl methacrylate vinegar and polyvinylidene fluoride blend can improve the mechanical performance of PMMA base polymer electrolyte system in the electrolyte, the gel electrolyte that is cross-linked to form with the TEG double methyl methacrylate can effectively suppress the formation of Li dendrite, and this is because the rigidity of a connection gel has increased the tightness degree that contacts with electrode.
4, at present conventional on-site polymerization mode of heating all is to adopt resistance heating, and heat all is that surface by battery is to inside battery in conductive process.After the battery surface temperature arrived polymeric reaction temperature, the polymer dielectric precursor began polymerization, and internal temperature of battery does not still reach.Because the difference of same battery local temperature can cause the inhomogeneous of electrolyte polymerization, and the molecular weight distribution broad of polymer, battery performance and consistency can not get guaranteeing.Cause the mode that polymerized in-situ adopts the intermediate frequency electromagnetic induction heating among the present invention, utilize electromagnetic field, make Copper Foil and aluminium foil heating at a high speed voluntarily itself at battery afflux liquid metal copper foil and the countless little eddy current of the inner generation of aluminium foil.There is not heat conducting process in this mode, homogeneous heating, and speed is fast, and can there be local difference in electrolyte in polymerization process, and the performance and the consistency of battery are greatly improved.
Embodiment
Further specify the present invention below by embodiment, production process is as follows among each embodiment:
Embodiment 1:
1, slurry mixes:
Anodal conductive carbon layer slurry is formed:
| Component | Content (Wt%) |
| Acetylene black | 10％ |
| The superconduction carbon black | 20％ |
| Polyvinylidene fluoride | 5％ |
| The N-methyl pyrrolidone | 65％ |
The order that feeds intake: add acetylene black and superconduction carbon black after polyvinylidene fluoride and N-methyl pyrrolidone stir.
Anodal active slurry solid constituent is formed:
| Component | Content (Wt%) |
| LiMn2O4 | 94％ |
| Acetylene black | 2.5％ |
| Electrically conductive graphite | 1％ |
| Polyvinylidene fluoride | 2.5％ |
The order that feeds intake: polyvinylidene fluoride and dispersant N-methyl pyrrolidone stir, and behind adding acetylene black and the electrically conductive graphite mixing, add LiMn2O4 at last.Solid content of slurry 52%, viscosity is controlled at 2500mPas.
Negative pole conductive carbon layer slurry is formed:
| Component | Content (Wt%) |
| The superconduction carbon black | 18％ |
| Electrically conductive graphite | 10％ |
| Acrylate adhesive (LA132) | 6％ |
| Deionized water | 66％ |
The order that feeds intake: LA132 and deionized water and stirring evenly back add superconduction carbon black and electrically conductive graphite.
The negative electrode active slurry solids becomes to be grouped into:
| Component | Content (Wt%) |
| Modified graphite | 90.5％ |
| Electrically conductive graphite | 4％ |
| Acrylate adhesive (LA132) | 4％ |
| Sodium carboxymethylcellulose | 1.5％ |
Feeding sequence: sodium carboxymethylcellulose, LA132 and deionized water and stirring are even, behind the adding electrically conductive graphite mixing, add modified graphite at last.Solid content of slurry 40%, viscosity is controlled at 2500mPas.
2, coating:
Plus plate current-collecting body adopts 40 μ m aluminium etched foils, sprays the anodal conductive carbon layer slurry of one deck in advance, the surface density 20g/m of dressing
2(two-sided), it is two-sided more anodal active slurry to be coated in uniformly the aluminium etched foil, dressing surface density 250g/m
2(not containing the conductive carbon intermediate layer).
Negative current collector adopts 8 μ m Copper Foils, sprays one deck negative pole conductive carbon layer slurry in advance, the surface density 30g/m of dressing
2(two-sided).It is two-sided then the negative electrode active slurry to be coated in uniformly Copper Foil, dressing surface density 130g/m
2(not containing the conductive carbon intermediate layer).
3, rolling and cutting: above-mentioned pole piece after rolling, is cut into the positive/negative plate of given size.
4, electric core is made: with the positive/negative plate that the cuts lug of burn-oning, bag membrane coil coiled electricity core.
5, encapsulation: electric core is packed in the aluminum plastic film, vacuumize, hot-press sealed is reserved liquid injection port.
6, fluid injection: inject the 48g gel electrolyte.The composition of electrolyte precursor (Wt%) is:
| Component | Content (Wt%) |
| Potassium Hexafluorophosphate | 13％ |
| Dimethyl carbonate | 10％ |
| Methyl ethyl carbonate | 40％ |
| Ethylene carbonate | 22％ |
| Methyl methacrylate | 5％ |
| Butyl acrylate | 4％ |
| Polyvinylidene fluoride | 2％ |
| The TEG double methyl methacrylate | 3.9％ |
| Initator | 0.1％ |
7, heated polymerizable: adopt the intermediate frequency electromagnetic induction heating to cause polymerized in-situ, 60 ℃ of temperature, heated polymerizable 8h.
8, change into, partial volume.
Embodiment 2
1, slurry mixes:
Anodal conductive carbon layer slurry is formed:
| Component | Content (Wt%) |
| Acetylene black | 18％ |
| The gas-phase carbon fiber | 8％ |
| Butadiene-styrene rubber | 4％ |
| Sodium carboxymethylcellulose | 1％ |
| Deionized water | 69％ |
The order that feeds intake: after butadiene-styrene rubber, sodium carboxymethylcellulose and deionized water and stirring are even, add gas-phase carbon fiber and acetylene black.
Anodal active slurry solid constituent is formed:
| Component | Content (Wt%) |
| LiFePO4 | 93％ |
| Acetylene black | 2.5％ |
| Electrically conductive graphite | 2％ |
| Polyvinylidene fluoride | 2.5％ |
The order that feeds intake: polyvinylidene fluoride and dispersant N-methyl pyrrolidone stir, and behind adding acetylene black and the electrically conductive graphite mixing, add LiFePO4 at last.Solid content of slurry 50%, viscosity is controlled at 2200mPas.
Negative pole conductive carbon layer slurry is formed:
| Component | Content (Wt%) |
| The superconduction carbon black | 15％ |
| Electrically conductive graphite | 12％ |
| Acrylate adhesive (LA132) | 6％ |
| Deionized water | 67％ |
The order that feeds intake: LA132 and deionized water and stirring evenly back add superconduction carbon black and electrically conductive graphite.
The negative electrode active slurry solids becomes to be grouped into:
| Component | Content (Wt%) |
| Modified graphite | 94％ |
| Superconduction carbon | 2％ |
| Acrylate adhesive (LA132) | 3.5％ |
| Sodium carboxymethylcellulose | 0.5％ |
Feeding sequence: sodium carboxymethylcellulose, LA132 and deionized water and stirring are even, behind the adding superconduction carbon mixing, add modified graphite at last.Solid content of slurry 40%, viscosity is controlled at 2300mPas.
2, coating:
Plus plate current-collecting body adopts 22 μ m aluminium etched foils, sprays the anodal conductive carbon layer slurry of one deck in advance, the surface density 22g/m of dressing
2(two-sided), it is two-sided more anodal active slurry to be coated in uniformly the aluminium etched foil, dressing surface density 240g/m
2(not containing the conductive carbon intermediate layer).
Negative current collector adopts 12 μ m Copper Foils, sprays one deck negative pole conductive carbon layer slurry in advance, the surface density 28g/m of dressing
2(two-sided).It is two-sided then the negative electrode active slurry to be coated in uniformly Copper Foil, dressing surface density 120g/m
2(not containing the conductive carbon intermediate layer).
3, rolling and cutting: after rolling, stamping-out becomes the positive/negative plate of given size with above-mentioned pole piece.
4, electric core is made: adopt the mode of Z type lamination, build up the electric core of specified volume.
5, encapsulation: electric core is packed in the aluminum plastic film, vacuumize, hot-press sealed is reserved liquid injection port.
6, fluid injection: inject the 48g gel electrolyte, electrolyte precursor is formed (Wt%) and is:
| Component | Content (Wt%) |
| Lithium hexafluoro phosphate | 13.5％ |
| Dimethyl carbonate | 12％ |
| Methyl ethyl carbonate | 39％ |
| Ethylene carbonate | 18％ |
| Methyl methacrylate | 6％ |
| Butyl acrylate | 4.5％ |
| Polyvinylidene fluoride | 2％ |
| The TEG double methyl methacrylate | 4.95％ |
| Initator | 0.05％ |
7, heated polymerizable: adopt the intermediate frequency electromagnetic induction heating to cause polymerized in-situ, 80 ℃ of temperature, heated polymerizable 1.5h.
8, change into, partial volume.
Embodiment 3
1, slurry mixes:
Anodal conductive carbon layer slurry is formed:
| Component | Content (Wt%) |
| CNT (carbon nano-tube) | 6％ |
| The superconduction carbon black | 11％ |
| Polyvinylidene fluoride | 4％ |
| The N-methyl pyrrolidone | 79％ |
The order that feeds intake: add CNT (carbon nano-tube) and superconduction carbon black after polyvinylidene fluoride and N-methyl pyrrolidone stir.
Anodal active slurry solid constituent is formed:
| Component | Content (Wt%) |
| LiMn2O4 | 94％ |
| Acetylene black | 2.5％ |
| Electrically conductive graphite | 1％ |
| Polyvinylidene fluoride | 2.5％ |
The order that feeds intake: polyvinylidene fluoride and dispersant N-methyl pyrrolidone stir, and behind adding acetylene black and the electrically conductive graphite mixing, add LiMn2O4 at last.Solid content of slurry 52%, viscosity is controlled at 2500mPas.
Negative pole conductive carbon layer slurry is formed:
| Component | Content (Wt%) |
| The superconduction carbon black | 14％ |
| LA132 | 6％ |
| Deionized water | 80％ |
The order that feeds intake: LA132 and deionized water and stirring evenly back add the superconduction carbon black.
The negative electrode active slurry solids becomes to be grouped into:
| Component | Content (Wt%) |
| Modified graphite | 90.5％ |
| Electrically conductive graphite | 4％ |
| LA132 | 4％ |
| Sodium carboxymethylcellulose | 1.5％ |
Feeding sequence: sodium carboxymethylcellulose, LA132 and dispersant water stir, and behind the adding electrically conductive graphite mixing, add modified graphite at last.Solid content of slurry 40%, viscosity is controlled at 2500mPas.
2, coating:
Plus plate current-collecting body adopts 60 μ m aluminium etched foils, sprays the anodal conductive carbon layer slurry of one deck in advance, the surface density 20g/m of dressing
2(two-sided), it is two-sided more anodal active slurry to be coated in uniformly the aluminium etched foil, dressing surface density 320g/m
2(not containing the conductive carbon intermediate layer).
Negative current collector adopts 8 μ m Copper Foils, sprays one deck negative pole conductive carbon layer slurry in advance, the surface density 30g/m of dressing
2(two-sided).It is two-sided then the negative electrode active slurry to be coated in uniformly Copper Foil, dressing surface density 150g/m
2(not containing the conductive carbon intermediate layer).
3, rolling and cutting: above-mentioned pole piece after rolling, is cut into the positive/negative plate of given size.
4, electric core is made: with the positive/negative plate that the cuts lug of burn-oning, bag membrane coil coiled electricity core.
5, encapsulation: electric core is packed in the aluminum plastic film, vacuumize, hot-press sealed is reserved liquid injection port.
6, fluid injection: inject the 48g gel electrolyte, electrolyte precursor is formed (Wt%) and is:
| Component | Content (Wt%) |
| Lithium hexafluoro phosphate | 13％ |
| Dimethyl carbonate | 10％ |
| Methyl ethyl carbonate | 40％ |
| Ethylene carbonate | 22％ |
| Methyl methacrylate | 5％ |
| Butyl acrylate | 4％ |
| Polyvinylidene fluoride | 2％ |
| The TEG double methyl methacrylate | 3.95％ |
| Initator | 0.05％ |
7, heated polymerizable: adopt the intermediate frequency electromagnetic induction heating to cause polymerized in-situ, 60 ℃ of temperature, heated polymerizable 24h.
8, change into, partial volume.
Claims (5)
1. polymer lithium ion power cell manufacture method, comprise that slurry mixes, collector is coated with, electrolyte injects and polymerization, it is characterized in that in this manufacture method, adopt the aluminium etched foil as plus plate current-collecting body, the two sides of plus plate current-collecting body is the anodal conductive carbon layer slurry of spraying earlier, apply anodal active slurry again, the two sides of negative current collector is spraying negative pole conductive carbon layer slurry earlier, applies the negative electrode active slurry again; Electrolyte injects the back and adopts the intermediate frequency electromagnetic induction heating to cause polymerized in-situ; Above-mentioned anodal conductive carbon layer slurry consists of: conductive carbon material 10～49Wt%, anodal binding agent 1～10Wt%, anodal dispersant 50～89Wt%; Negative pole conductive carbon layer slurry consists of: conductive carbon material 10～49Wt%, negative pole binding agent 1～10Wt%, negative pole dispersant 50～89Wt%; Described conductive carbon material is one or more in acetylene black, superconduction carbon black, electrically conductive graphite, metallic fiber, gas-phase carbon fiber, the carbon CNT (carbon nano-tube); The temperature that above-mentioned intermediate frequency electromagnetic induction heating causes polymerized in-situ is 60～120 ℃, and the time is 1～24h.
2. by the described polymer lithium ion power cell manufacture method of claim 1, it is characterized in that: described aluminium etched foil thickness 20～60 μ m, corrosion depth 5～20 μ m.
3. by the described polymer lithium ion power cell manufacture method of claim 1, it is characterized in that: described anodal binding agent adopts one or more in polyvinylidene fluoride, butadiene-styrene rubber, the sodium carboxymethylcellulose, and anodal dispersant adopts a kind of in deionized water, alcohol or the N-methyl pyrrolidone.
4. by the described polymer lithium ion power cell manufacture method of claim 1, it is characterized in that: described negative pole binding agent adopts one or more in acrylate adhesive, the sodium carboxymethylcellulose, and the negative pole dispersant adopts deionized water.
5. by the described polymer lithium ion power cell manufacture method of claim 1, it is characterized in that: electrolyte precursor consists of: lithium hexafluoro phosphate 12～15Wt%, dimethyl carbonate 4～15Wt%, methyl ethyl carbonate 35～50Wt%, ethylene carbonate 15～25Wt%, methyl methacrylate 3～10Wt%, butyl acrylate 1～5Wt%, polyvinylidene fluoride 1～5Wt%, TEG double methyl methacrylate 1～5Wt%, initator 0.01～2Wt%, so-called electrolyte precursor are meant the electrolyte before the heated polymerizable.
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| WO2012167407A1 (en) * | 2011-06-08 | 2012-12-13 | 江苏乐能电池股份有限公司 | Preparation process of nano-conductive carbon primer for precoating aluminum foil and coating method thereof |
| CN103131267A (en) * | 2011-11-24 | 2013-06-05 | 珠海银通新能源有限公司 | Lithium ion battery current collector precoating and preparation method thereof |
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