CN108598556A - A kind of high temperature modification polymer Li-ion battery and preparation method thereof - Google Patents

A kind of high temperature modification polymer Li-ion battery and preparation method thereof Download PDF

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CN108598556A
CN108598556A CN201810485668.8A CN201810485668A CN108598556A CN 108598556 A CN108598556 A CN 108598556A CN 201810485668 A CN201810485668 A CN 201810485668A CN 108598556 A CN108598556 A CN 108598556A
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ion battery
lithium
electrolyte
temperature modification
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CN108598556B (en
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朱传钦
周显茂
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Guangdong Weiduli New Energy Co Ltd
CHONGQING ZIJIAN ELECTRONICS CO LTD
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CHONGQING ZIJIAN ELECTRONICS CO LTD
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

A kind of high temperature modification polymer Li-ion battery of the present invention and preparation method thereof.The lithium ion battery includes mainly positive plate, negative plate, porous isolating membrane and electrolyte；The positive plate includes：Cobalt acid lithium, Kynoar, carbon nanotube, carbon black；The negative plate includes：Artificial graphite, carboxycellulose sodium, butadiene-styrene rubber and carbon black；The porous isolating membrane is mixed painting diaphragm；The electrolyte is made of lithium salts, carbonate mixture and additive.Cobalt acid lithium and artificial graphite have the characteristics that D10 is larger and specific surface area is smaller, are conducive to weaken side reaction under hot conditions and occur, stablize battery performance；Isolation film applies diaphragm using ceramics/Kynoar is mixed, is conducive to the thermal stability of battery molding and battery；Additive composition used in electrolyte has the function of anode, cathode film formation protection, and dosage is relatively low, advantageously reduces battery impedance, is conducive to cycle performance.

Description

A kind of high temperature modification polymer Li-ion battery and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, it is related to a kind of high temperature modification polymer Li-ion battery and its preparation side Method.
Background technology
Lithium ion battery is widely used in automobile, storage due to the advantages that its is environmental-friendly, energy density is high, good cycle The fields such as energy, number.Polymer Li-ion battery energy density is with respect to liquid lithium ionic cell higher, and battery appearance can root It is especially welcome in digital domain according to needing to customize.Performance is difficult to protect existing polymer Li-ion battery under high temperature environment Card usually only meets under 60 DEG C of environment and ensures cycle life in storage and 45 DEG C of environment.And stored under 85 DEG C of environment, battery is difficult With regular picture, or even there is gas and rise phenomenon, cycle life is also short under 60 DEG C of environment.This cannot meet for high temperature area and The demand of the equipment of hot environment.
Invention content
The object of the present invention is to provide a kind of high temperature modification lithium ion battery and preparation method thereof, the polymer Li-ion batteries After 85 DEG C of hot environments are stored, battery performance keeps normal；Under room temperature and 60 DEG C of hot environments, battery cycle life is good.
Technical solution of the present invention is as follows.
A kind of high temperature modification polymer Li-ion battery, the lithium ion battery include mainly positive plate, negative plate, porous isolation Film and electrolyte；
The positive plate divides the percentages to include by quality：Cobalt acid lithium 94~97%, Kynoar (PVDF) 1~2%： Carbon nanotube (CNT) 1~2%：Carbon black (SP) 1~2%；
The negative plate divides the percentages to include by quality：Artificial graphite 90~96%, carboxycellulose sodium (CMC) 1.5 ~2%, butadiene-styrene rubber (SBR) 1.5~2.5%, carbon black (SP) 1~2%；
The porous isolating membrane is mixed painting diaphragm；
The electrolyte is made of lithium salts, carbonate mixture and additive.
A kind of high temperature modification polymer Li-ion battery according to claim 1, it is characterised in that：The positive plate Cobalt acid lithium D10 is 10~14 μm, and specific surface area is：0.2~0.3m2/g.A kind of high temperature modification polymerization according to claim 1 Object lithium ion battery, it is characterised in that：The artificial graphite D10 of the negative plate is 13~17 μm, and specific surface area is：0.6~ 1.0m2/g.A kind of high temperature modification polymer Li-ion battery according to claim 1, it is characterised in that：The porous isolation Film applies diaphragm to be mixed, and basement membrane is polyethylene porous membrane, and basement membrane thickness is 9~16 μm, and mixed coating is alundum (Al2O3) and gathers inclined The mixture of vinyl fluoride forms, and coating layer thickness is 3 μm, and coating corresponds to positive pole-face.
Further, the lithium salts of the electrolyte is LiPF6, and the content of lithium salts is 1.0~1.2mol/L；
The mass ratio of the carbonate mixture each component is ethylene carbonate (EC)：Propene carbonate (PC)：Carbonic acid Diethylester (DEC)：Ethyl methyl carbonate (EMC)：Dimethyl carbonate (DMC)=30~45：5~20：30~45：0~15：0~15； The carbonate mixture accounts for the 75%~85% of electrolyte gross mass；
The additive level accounts for the 1%~9% of electrolyte gross mass, and the mass ratio of various additives is：Fluoro carbon Vinyl acetate (FEC)：Vinylene carbonate (VC)：1,3- propane sultone (PS), succinonitrile (AN)：Adiponitrile (ADN)=1 ~3：1~3：0.2~1：0~1：0~1.
Further, the lithium ion battery passes through：It prepares positive plate, prepare negative plate-welding electrode ear-winding-assembly-baking Polymer Li-ion battery is made in roasting-fluid injection-high temperature ageing-- two envelopes of chemical conversion-molding-partial volume process.
Further, the positive plate is obtained by three steps；
First step example cobalt acid lithium in mass ratio：Kynoar (PVDF)：Carbon nanotube (CNT)：Carbon black (SP)=94~ 97%：1~2%：1~2%:1~2% weighs material requested, and anode sizing agent is obtained by blender batch mixing；
First step slurry is coated on using coating machine in aluminum foil current collector by second step, coated face density≤42mg/cm2,
Third walks, using walking pole piece, roll-in density≤4.0g/cm in roll squeezer roll-in3。
Further, the negative plate is obtained by two steps；
First step example artificial graphite in mass ratio：Carboxycellulose sodium (CMC)：Butadiene-styrene rubber (SBR)：Carbon black (SP)=90 ~96%：1.5~2%：1.5~2.5%:1~2% weighs material requested, and negative electrode slurry is obtained by blender batch mixing；
First step slurry is coated on using coating machine in copper foil current collector by second step, coated face density≤21mg/cm2；
Third step uses and walks pole piece, roll-in density≤1.5g/cm in roll squeezer roll-in3。
Further, the temperature parameter of the high temperature ageing process is 40~50 DEG C, and ageing time is 36~48 hours.
Compared with prior art, advantage of the invention is that：
1. cobalt acid lithium and artificial graphite have the characteristics that D10 is larger and specific surface area is smaller, be conducive to weaken hot conditions Lower side reaction occurs, and stablizes battery performance；
2. isolation film applies diaphragm using ceramics/Kynoar is mixed, be conducive to the thermal stability of battery molding and battery；
3. the carbonic ester composition used in electrolyte has the characteristics that boiling point is high, infiltration is good, is conducive to high-temperature stability and follows Ring performance；
4. the additive composition used in electrolyte has the function of anode, cathode film formation protection, and dosage is relatively low, favorably In reducing battery impedance, be conducive to cycle performance；
5. positive plate and cathode slice prescription are reasonable, the internal resistance of cell is advantageously reduced, cycle performance is conducive to；And surface density It is moderate with compacted density, be conducive to electrolyte and fully infiltrate pole piece, is conducive to cycle performance；
6. high temperature ageing temperature and time, which is conducive to electrolyte, fully infiltrates pole piece, be conducive to cycle performance.
8. the polymer Li-ion battery of the present invention, after 85 DEG C of hot environments are stored, battery performance keeps normal；Normal Under mild 60 DEG C of hot environments, battery cycle life is good.
Specific implementation mode
The present invention is described in further details with reference to specific embodiment.Following embodiment helps to understand this hair It is bright, but therefore do not limit the present invention among the embodiment described range.
In following embodiments, a kind of high temperature modification polymer Li-ion battery, mainly include positive plate, negative plate, it is porous every Film and organic electrolyte.The positive plate mainly contains cobalt acid lithium；The negative plate mainly contains artificial graphite；The isolation film Diaphragm is applied for ceramics/Kynoar is mixed；The electrolyte is made of lithium salts, carbonate mixture and various additives.This hair For bright polymer Li-ion battery after 85 DEG C of hot environments are stored, battery performance keeps normal；In room temperature and 60 DEG C of high temperature rings Under border, battery cycle life is good.
Embodiment 1
The cobalt acid lithium D10 of the positive plate is 11 μm, and specific surface area is：0.2m2/g
The artificial graphite D10 of the negative plate is 13 μm, and specific surface area is：0.9m2/g。
The basement membrane of the isolation film is polyethylene porous membrane, and basement membrane thickness is 12 μm, and mixed coating is alundum (Al2O3) and gathers The mixture of vinylidene, the two mass ratio are 1:1 composition, coating layer thickness is 3 μm, and coating corresponds to positive pole-face.
The lithium salts of the electrolyte is LiPF6, and the content of lithium salts is 1.0mol/L；
The mass ratio of the carbonate mixture each component is ethylene carbonate (EC)：Propene carbonate (PC)：Carbonic acid Diethylester (DEC)：Ethyl methyl carbonate (EMC)=40：15：30：15；
The additive level accounts for the 5.5% of electrolyte gross mass, and the mass ratio of various additives is fluoro carbonic acid second Enester (FEC)：Vinylene carbonate (VC)：1,3- propane sultone (PS), succinonitrile (AN)：Adiponitrile (ADN)=3：1： 0.5：0.5：0.5.
The lithium ion battery passes through：It prepares positive plate, prepare negative plate-welding electrode ear-winding-assembly-baking-fluid injection- Polymer Li-ion battery is made in high temperature ageing-- two envelopes of chemical conversion-molding-partial volume process.
Wherein, positive plate is obtained by following three steps；
First step example cobalt acid lithium in mass ratio：Kynoar (PVDF)：Carbon nanotube (CNT)：Carbon black (SP)=96：2： 1：1 weighs material requested, and anode sizing agent is obtained by blender batch mixing；
First step slurry is coated in aluminum foil current collector by second step, coated face density 40mg/cm2,
Third walks, using walking pole piece, roll-in density 4.0g/cm in roll squeezer roll-in3。
Negative plate is obtained by following three steps；
First step example artificial graphite in mass ratio：Carboxycellulose sodium (CMC)：Butadiene-styrene rubber (SBR)：Carbon black (SP)= 95：1.7：2:1.3 weigh material requested, and negative electrode slurry is obtained by blender batch mixing；
First step slurry is coated in copper foil current collector by second step, coated face density 18mg/cm2,
Third walks, and using pole piece is walked in roll squeezer roll-in, roll-in density is 1.5g/cm3。
The temperature parameter of the high temperature ageing process is 40~50 DEG C, and ageing time is 36~48 hours.
Embodiment 2
The cobalt acid lithium D10 of the positive plate is 11 μm, and specific surface area is：0.2m2/g；
The artificial graphite D10 of the negative plate is 13 μm, and specific surface area is：0.9m2/g。
The basement membrane of the isolation film is polyethylene porous membrane, and basement membrane thickness is 12 μm, and mixed coating is alundum (Al2O3) and gathers The mixture of vinylidene forms, and coating layer thickness is 3 μm, and coating corresponds to positive pole-face.
The lithium salts of the electrolyte is LiPF6, and the content of lithium salts is 1.0mol/L；
The mass ratio of the carbonate mixture each component is ethylene carbonate (EC)：Propene carbonate (PC)：Carbonic acid Diethylester (DEC)：Ethyl methyl carbonate (EMC)=40：15：30：15；The carbonate mixture accounts for electrolyte gross mass 81.5%.
The additive level accounts for the 5.5% of electrolyte gross mass, and the mass ratio of various additives is fluoro carbonic acid second Enester (FEC)：Vinylene carbonate (VC)：1,3- propane sultone (PS), succinonitrile (AN)：Adiponitrile (ADN)=3：1： 0.5：0.5：0.5.
The lithium ion battery passes through：It prepares positive plate, prepare negative plate-welding electrode ear-winding-assembly-baking-fluid injection- Polymer Li-ion battery is made in the processes such as high temperature ageing-- two envelopes of chemical conversion-molding-partial volume.
Wherein, positive plate is obtained by following three steps；
First step example cobalt acid lithium in mass ratio：Kynoar (PVDF)：Carbon nanotube (CNT)：Carbon black (SP)=96：2： 1：1 weighs material requested, and anode sizing agent is obtained by blender batch mixing；
First step slurry is coated in aluminum foil current collector by second step, coated face density 42mg/cm2,
Third walks, using walking pole piece, roll-in density 4.0g/cm in roll squeezer roll-in3。
Negative plate is obtained by following three steps；
First step example artificial graphite in mass ratio：Carboxycellulose sodium (CMC)：Butadiene-styrene rubber (SBR)：Carbon black (SP)= 95：1.7：2:1.3 weigh material requested, and negative electrode slurry is obtained by blender batch mixing；
First step slurry is coated in copper foil current collector by second step, coated face density 19mg/cm2,
Third walks, using walking pole piece, roll-in density 1.5g/cm in roll squeezer roll-in3。
The temperature parameter of the high temperature ageing process is 40~50 DEG C, and ageing time is 36~48 hours.
Embodiment 3
The cobalt acid lithium D10 of the positive plate is 11 μm, and specific surface area is：0.2m2/g；
The artificial graphite D10 of the negative plate is 13 μm, and specific surface area is：0.9m2/g。
The basement membrane of the isolation film is polyethylene porous membrane, and basement membrane thickness is 12 μm, and mixed coating is alundum (Al2O3) and gathers The mixture of vinylidene forms, and coating layer thickness is 3 μm, and coating corresponds to positive pole-face.
The lithium salts of the electrolyte is LiPF6, and the content of lithium salts is 1.0mol/L；
The mass ratio of the carbonate mixture each component is ethylene carbonate (EC)：Propene carbonate (PC)：Carbonic acid Diethylester (DEC)：Ethyl methyl carbonate (EMC)=40：15：30：15；
The additive level accounts for the 6.5% of electrolyte gross mass, and the mass ratio of various additives is fluoro carbonic acid second Enester (FEC)：Vinylene carbonate (VC)：1,3- propane sultone (PS), succinonitrile (AN)：Adiponitrile (ADN)=3：1： 0.5：1：1.
The lithium ion battery passes through：It prepares positive plate, prepare negative plate-welding electrode ear-winding-assembly-baking-fluid injection- Polymer Li-ion battery is made in the processes such as high temperature ageing-- two envelopes of chemical conversion-molding-partial volume.
Wherein, positive plate is obtained by following three steps；
First step example cobalt acid lithium in mass ratio：Kynoar (PVDF)：Carbon nanotube (CNT)：Carbon black (SP)=96：2： 1：1 weighs material requested, and anode sizing agent is obtained by blender batch mixing；
First step slurry is coated in aluminum foil current collector by second step, coated face density 42mg/cm2,
Third walks, using walking pole piece, roll-in density 4.0g/cm in roll squeezer roll-in3。
Negative plate is obtained by following three steps：
First step example artificial graphite in mass ratio：Carboxycellulose sodium (CMC)：Butadiene-styrene rubber (SBR)：Carbon black (SP)= 95：1.7：2:1.3 weigh material requested, and negative electrode slurry is obtained by blender batch mixing；
First step slurry is coated in copper foil current collector by second step, coated face density 19mg/cm2,
Third walks, using walking pole piece, roll-in density 1.5g/cm in roll squeezer roll-in3。
The temperature parameter of the high temperature ageing process is 40~50 DEG C, and ageing time is 36~48 hours.
Polymer Li-ion battery prepared by embodiment 1,2,3 is tested for the property：(1) 85 DEG C of high temperature storage test：25 Under ± 5 DEG C of environment then battery is placed in 85 DEG C of environment by 1C electric currents by the fully charged 4.2V of battery, is stored 24 hours, and electricity is taken out Pond measures thickness and the internal resistance variation of battery；After being placed 2 hours under 25 ± 5 DEG C of environment, 0.2C current discharge 3.0V measure electricity Pond residual capacity, then 0.5C chargings 4.2V, 0.2C electric discharge 3.0V, test restore capacity.It is obtained by performance calculating before and after storage Obtain the data such as cell thickness change rate.
(2) 60 DEG C of high temperature circulation tests：Battery is put into 60 DEG C of environment, 0.5C fully charged 4.2V, 0.5C electric discharge 3.0V, Charge-discharge cycle 500 times observes the capacity retention ratio, thickness change and internal resistance change rate of battery.
Table 1 is 85 DEG C of high temperature storage test results
Table 2 is 60 DEG C of high temperature circulation test results
Table 1
Table 2
As known from Table 1,85 DEG C of high temperature of all embodiments store the equal OK of test performance, and cell thickness change rate is less than 8%, Capacity retention ratio is 80% or more, and capacity restoration rate is 85% or more；The performance ratio embodiment 1 of embodiment 2 is poor, because of positive plate Bigger with the surface density of negative plate, electrolyte infiltrates that pole piece is more difficult, and battery impedance is bigger, so performance is more after high temperature storage Difference；Embodiment 3 is smaller than 2 property thickness change of embodiment, and capacity retention ratio and recovery rate higher illustrate additive A N, ADN content all When being increased to 1%, anode is better protected, and battery impedance also increases without deterioration property, and battery overall performance compares AN, ADN Content is more stable when being all 0.5%.
As known from Table 2,60 DEG C of equal OK of high temperature circulation test performance of all embodiments, cell thickness change rate are less than 8%, Capacity retention ratio is more than 80% normal line 80% or more；Capacity retention ratio sequence is that 3 ＞ embodiments of embodiment, 1 ＞ is implemented The sequence of example 2, thickness growth rate is 2 ＞ embodiments of embodiment, 1 ＞ embodiments 3, and the sequence of internal resistance change rate is 2 ＞ of embodiment real Apply 1 ＞ embodiments 3 of example.This illustrates that the surface density of positive plate and negative plate is unfavorable for more greatly battery high-temperature cycle performance；Additive When AN, ADN content are all increased to 1%, when compared to AN, ADN content being all 0.5%, high temperature cyclic performance is more preferable！
After the warm environment storage of 85 DEG C of polymer Li-ion battery of the present invention, battery performance keeps normal；In room temperature and 60 Under DEG C hot environment, battery cycle life is good.
Embodiment described above is not intended to limit the invention, all spirit in the present invention for specifically describing the present invention With within principle made by any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention.

Claims (9)

1. a kind of high temperature modification polymer Li-ion battery, it is characterised in that：The lithium ion battery includes mainly positive plate, cathode Piece, porous isolating membrane and electrolyte；
The positive plate divides the percentages to include by quality：Cobalt acid lithium 94~97%, Kynoar (PVDF) 1~2%, carbon are received Mitron (CNT) 1~2% and carbon black (SP) 1~2%；
The negative plate divides the percentages to include by quality：Artificial graphite 90~96%, carboxycellulose sodium (CMC) 1.5~ 2%, butadiene-styrene rubber (SBR) 1.5~2.5% and carbon black (SP) 1~2%；
The porous isolating membrane is mixed painting diaphragm；
The electrolyte is made of lithium salts, carbonate mixture and additive.
2. a kind of high temperature modification polymer Li-ion battery according to claim 1, it is characterised in that：The cobalt of the positive plate Sour lithium D10 is 10~14 μm, and specific surface area is：0.2~0.3m2/g.
3. a kind of high temperature modification polymer Li-ion battery according to claim 1, it is characterised in that：The people of the negative plate It is 13~17 μm to make graphite D10, and specific surface area is：0.6~1.0m2/g.
4. a kind of high temperature modification polymer Li-ion battery according to claim 1, it is characterised in that：The porous isolating membrane Diaphragm is applied to be mixed, basement membrane is polyethylene porous membrane, and basement membrane thickness is 9~16 μm, and mixed coating is alundum (Al2O3) and poly- inclined fluorine The mixture of ethylene forms, and coating layer thickness is 3 μm, and coating corresponds to positive pole-face.
5. a kind of high temperature modification polymer Li-ion battery according to claim 1, it is characterised in that：The lithium of the electrolyte Salt is LiPF6, and the content of lithium salts is 1.0~1.2mol/L；
The mass ratio of the carbonate mixture each component is ethylene carbonate (EC)：Propene carbonate (PC)：Carbonic acid diethyl Ester (DEC)：Ethyl methyl carbonate (EMC)：Dimethyl carbonate (DMC)=30~45：5~20：30~45：0~15：0~15；It is described Carbonate mixture accounts for the 75%~85% of electrolyte gross mass；
The additive level accounts for the 1%~9% of electrolyte gross mass, and the mass ratio of various additives is：Fluoro carbonic acid second Enester (FEC)：Vinylene carbonate (VC)：1,3- propane sultone (PS), succinonitrile (AN)：Adiponitrile (ADN)=1~3： 1~3：0.2~1：0~1：0~1.
6. the preparation method of high temperature modification polymer Li-ion battery described in claim 1, it is characterised in that：The lithium-ion electric Pond passes through：Prepare positive plate, prepare negative plate-welding electrode ear-winding-assembly-baking-fluid injection-- two envelope of high temperature ageing-chemical conversion-at Polymer Li-ion battery is made in type-partial volume process.
7. the preparation method of the high temperature modification polymer Li-ion battery described in claim 6, it is characterised in that：The positive plate is logical Three steps are crossed to obtain；
First step example cobalt acid lithium in mass ratio：Kynoar (PVDF)：Carbon nanotube (CNT)：Carbon black (SP)=94~97%： 1~2%：1~2%:1~2% weighs material requested, and anode sizing agent is obtained by blender batch mixing；
First step slurry is coated on using coating machine in aluminum foil current collector by second step, coated face density≤42mg/cm2,
Third walks, using walking pole piece, roll-in density≤4.0g/cm in roll squeezer roll-in3。
8. a kind of preparation method of high temperature modification polymer Li-ion battery according to claim 7, it is characterised in that：It is described Negative plate is obtained by two steps；
First step example artificial graphite in mass ratio：Carboxycellulose sodium (CMC)：Butadiene-styrene rubber (SBR)：Carbon black (SP)=90~ 96%：1.5~2%：1.5~2.5%:1~2% weighs material requested, and negative electrode slurry is obtained by blender batch mixing；
First step slurry is coated on using coating machine in copper foil current collector by second step, coated face density≤21mg/cm2；
Third step uses and walks pole piece, roll-in density≤1.5g/cm in roll squeezer roll-in3。
9. a kind of preparation method of high temperature modification polymer Li-ion battery according to claim 7, it is characterised in that：It is described The temperature parameter of high temperature ageing process is 40~50 DEG C, and ageing time is 36~48 hours.
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