CN111584811A - Diaphragm, preparation method and lithium ion battery - Google Patents

Diaphragm, preparation method and lithium ion battery Download PDF

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Publication number
CN111584811A
CN111584811A CN202010557764.6A CN202010557764A CN111584811A CN 111584811 A CN111584811 A CN 111584811A CN 202010557764 A CN202010557764 A CN 202010557764A CN 111584811 A CN111584811 A CN 111584811A
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formula
separator
benzene ring
battery
preparation
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CN111584811B (en
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曹晨
李洋
陈超
李旭
王康平
彭祖玲
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China Aviation Lithium Battery Research Institute Co Ltd
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China Aviation Lithium Battery Research Institute 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • 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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

Providing a diaphragm comprising a structure shown in formula 1 and/or formula 2,
Figure DDA0002544931950000011
wherein R is-F, benzene ring, fluorine substituted benzene ring, cyano substituted benzene ring or C1‑8One or more of the perfluorocarbon chains of (a). Also provided are a method for preparing the separator and a lithium ion battery comprising the separator. The separator of the present invention has polymer electrolyte fixed to the separatorMechanical properties of the electrolyte. The lithium salts of the sulfonyl imides with high ionic conductivity are grafted on the diaphragm to limit the movement of anions, thereby reducing the concentration polarization in the battery. Amorphous PEO oligomer (polyethylene glycol methyl ether methacrylate) is selected as a lithium ion conducting chain segment, so that the motion capability of the chain segment is enhanced, and the conducting capability of lithium ions is improved.

Description

Diaphragm, preparation method and lithium ion battery
Technical Field
The invention belongs to the field of chemical power sources, and particularly relates to a diaphragm, a preparation method of the diaphragm and a lithium ion battery comprising the diaphragm.
Background
At present, a PEO-based solid polymer electrolyte is mostly adopted in a solid battery, and the PEO-based solid polymer electrolyte is a double-ion conductor (namely, anions and cations are transferred), but the anions do not participate in electrode reaction and are gathered on the surface of a positive electrode, so that concentration polarization is generated in the charging and discharging process of the battery, and the cycle life and the rate performance of the battery are reduced. And PEO has limited segment movement due to its high crystallinity and low room temperature ionic conductivity. In order to improve the ionic conductivity, an amorphous structure polymer with good segment flexibility is generally adopted, but the mechanical property is generally reduced, and a polymer electrolyte film which is independently supported cannot be easily prepared.
Disclosure of Invention
In order to overcome the defects, the invention provides a diaphragm, a preparation method thereof and a lithium ion battery comprising the diaphragm.
In one aspect of the present invention, there is provided a separator including a structure represented by formula 1 and/or formula 2,
Figure BDA0002544931940000011
wherein R is-F, -CF3Benzene ring, fluorine-substituted benzene ring, cyano-substituted benzene ring or C1-8One or more of the perfluorocarbon chains of (a).
In another aspect of the present invention, there is provided a method for preparing the above-mentioned separator, in which an initiator is dissolved in a solvent and a separator having a structure of formula 4 is immersed therein, followed by injecting a compound represented by formula 5 and a polymer represented by formula 6,
Figure BDA0002544931940000021
wherein R is-F, benzene ring, fluorine substituted benzene ring, cyano substituted benzene ring or C1-8One or more of the perfluorocarbon chains of (a).
The present invention also provides a method for preparing the above-mentioned separator, in which an initiator is dissolved in a solvent and a separator having a structure of formula 4 is immersed therein, followed by injecting a polymer represented by formula 6, compounds represented by formulae 7 and 8, and lithium hydroxide,
Figure BDA0002544931940000022
wherein R is-F, benzene ring, fluorine substituted benzene ring, cyano substituted benzene ring or C1-8One or more of the perfluorocarbon chains of (a).
In another aspect, the present invention provides a lithium ion battery comprising the above separator or the separator prepared by the above method.
The diaphragm of the invention fixes the polymer electrolyte on the diaphragm, thereby improving the mechanical property of the electrolyte. The lithium salts of the sulfonyl imides with high ionic conductivity are grafted on the diaphragm to limit the movement of anions, thereby reducing the concentration polarization in the battery. Amorphous PEO oligomer (polyethylene glycol methyl ether methacrylate) is selected as a lithium ion conducting chain segment, so that the motion capability of the chain segment is enhanced, and the conducting capability of lithium ions is improved.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The separator of the present invention includes the structure represented by formula 1 and/or formula 2,
Figure BDA0002544931940000031
wherein R is-F, benzene ring, fluorine substituted benzene ring, cyano substituted benzene ring or C1-8One kind of perfluorocarbon chain ofOr several of them. The invention fixes the polymer electrolyte on the diaphragm, and improves the mechanical property of the electrolyte. Further, since the lithium salts of the sulfoximines are fixed, the movement of anions is restricted, and the concentration polarization in the battery is reduced. The PEO chain segment is used as a lithium ion conducting chain segment to enhance the motion capability of the chain segment, thereby improving the lithium ion conducting capability.
In a preferred embodiment, in formula 1 or formula 2, x is 1 to 2000, y is 1 to 2000, and n is 2 to 30. If the values of x, y and n exceed the upper limit, the molecular weight is too high, which lowers the porosity of the separator and hinders the migration of lithium ions.
The content of the group represented by formula 3 in the separator may be up to 4mmol per gram of the separator, but it is of course possible to bond the group represented by formula 3 (relevant structure of LiTFSI) at any value between 0 and 4mmol per gram of the separator. Those skilled in the art can select an appropriate number of the structures to be formed on the separator according to the requirements of the actual battery, and also can select an appropriate number of the separators according to the lithium salt content and ionic conductivity required by the battery. For practical purposes, the content of groups of formula 3 in the membrane is preferably from 1 to 4mmol per gram of membrane. When the content of the group represented by formula 3 is less than 1mmol, the relevant structure of the LiTFSI immobilized by the separator is relatively small, and the separator has less anions capable of restricting movement, thereby contributing less to the reduction of concentration polarization inside the battery. Any value between 1-4mmol can be chosen by the skilled person according to the actual need, e.g. 1.5mmol, 2.0mmol, 2.5mmol, 3.0mmol, 3.5mmol etc. Preferably, the membrane is in-CH2-CH2O-group (EO segment) and Li+(contained in the group represented by formula 3) in a molar ratio of 1 to 30: 1.
Figure BDA0002544931940000041
diaphragm medium-CH2-CH2the-O-group is for conducting lithium ions, and the group represented by formula 3 may provide lithium ions. if-CH2-CH2Too small a proportion of-O-groups results in too many lithium ions not being conducted out quickly, resulting in a decrease in efficiency. If the ratio of the groups shown in Table 3 is too small, there is not enoughSufficient lithium ion conduction and reduced ionic conductivity. Thus, when the membrane is in-CH2-CH2The molar ratio of the-O-group to the group of formula 3 is 1 to 30: when 1, the performance of the battery is best improved. -CH2-CH2The molar ratio of the-O-group to the group of formula 3 is in the range of 1 to 30: a range of 1 is within the objectives of the present invention and any value within this range may be selected, for example 1: 1. 5: 1. 10: 1. 15: 1. 20: 1. 25: 1. 30: 1, etc.
The lithium ion battery using the separator does not need additional electrolyte or electrolyte solution because the polymer electrolyte on the separator is fixed on the separator. Of course, the object of the present invention can be achieved by using the above-described separator, additionally using an electrolyte or an electrolytic solution.
The structures of formula 1 and/or formula 2 in the membrane may be introduced in any manner.
In one embodiment, the lithium salt of the sulfonyl imide and the PEO segment may be grafted to the separator by dissolving an initiator in a solvent and immersing the separator having the structure of formula 4 therein, followed by injecting the compound of formula 5 and the polymer of formula 6.
Figure BDA0002544931940000042
Wherein R is-F, benzene ring, fluorine substituted benzene ring, cyano substituted benzene ring or C1-8One or more of the perfluorocarbon chains of (a).
Preferably, the compound represented by formula 5 is synthesized from a compound represented by formula 7 or 8 and lithium hydroxide:
Figure BDA0002544931940000051
in another embodiment, the initiator may be dissolved in a solvent and the separator having the structure of formula 4 may be immersed therein, followed by injecting the polymer of formula 6, the compounds of formulae 7 and 8, and lithium hydroxide,
Figure BDA0002544931940000052
wherein R is-F, benzene ring, fluorine substituted benzene ring, cyano substituted benzene ring or C1-8One or more of the perfluorocarbon chains of (a).
In a preferred embodiment, the separator comprising the structure of formula 4 is a cellulose separator.
In a preferred embodiment, the solvent is water or an organic solvent. When the solvent is water, the initiator is one or two of potassium persulfate and ammonium persulfate. When the solvent is an organic solvent, the initiator is one or two of azodiisobutyronitrile and benzoyl peroxide.
In the lithium ion battery using the separator, the positive electrode may be any suitable positive electrode material, such as lithium manganate, lithium cobaltate, lithium nickelate, ternary material, lithium iron phosphate, and the like. The negative electrode may be any suitable negative electrode material, such as carbon materials, silicon, carbon-silicon composites, lithium titanate, lithium metal, and the like.
Example 1
Preparation of the separator
The clean three-necked flask was placed in an ice bath and argon was introduced thereto for 30 minutes, and anhydrous acetonitrile was measured and poured therein. Then sequentially adding benzene sulfonamide, triethylamine, 4-dimethylamino pyridine and p-styrene sulfonyl chloride according to the amount of substances of 1:3:1:1 into a three-neck flask, stirring in an ice bath for half an hour, and then continuously stirring at room temperature for 24 hours. The reaction equation is shown in equation 1.
Figure BDA0002544931940000061
And after the reaction is finished, the solvent acetonitrile is evaporated out by a rotary evaporator, and after the evaporation is finished, the residue is dissolved in dichloromethane again. The dichloromethane solution was then transferred to a separatory funnel and washed with a 4% strength aqueous solution of sodium bicarbonate, then allowed to stand for a period of time, the dichloromethane phase was separated with a separatory funnel, and the water was discarded. Then the concentration of the mixture is 1 mol.L-1The dichloromethane phase separated is washed with hydrochloric acid solution and separated off with a separating funnelThe dichloromethane phase was separated with a separatory funnel and the aqueous phase was discarded. Finally, dichloromethane was removed by rotary evaporation and the product was dried in a vacuum oven at 40 ℃ for 12 hours to remove traces of dichloromethane. The product was then neutralized with lithium hydroxide in an amount of 1:1 to give a monomer (SSPSILIi).
Benzoyl Peroxide (BPO) was dissolved in acetonitrile and the cellulose membrane was immersed in it and stirred at 60 degrees for 30 minutes. SSPSILIi and methoxypolyethylene glycol methacrylate were then mixed as EO and Li+The molar ratio is 1:1 amount was poured into it and stirring was continued for 3 hours and the cellulose was fished out.
Figure BDA0002544931940000062
Preparation of positive plate
Lithium nickel cobalt manganese oxide (LiNi)0.5Co0.2Mn0.3O2) The conductive agent Super P and the adhesive PVDF are mixed with a solvent according to the weight ratio of 95:2:3 to form the anode slurry. And uniformly coating the obtained positive electrode slurry on an aluminum foil current collector, drying at 85 ℃, and obtaining a positive plate with the thickness of the positive electrode coating being 6 mu m after drying.
Preparation of negative plate
The artificial graphite, the binder Styrene Butadiene Rubber (SBR), the Super P and the thickener carboxymethylcellulose sodium are uniformly mixed according to the weight ratio of the artificial graphite to the Super P to CMC2200 to SBR to 96 to 2 to 1 to form the negative electrode slurry. And uniformly coating the negative electrode slurry on a copper foil current collector, and drying at 110 ℃ to obtain a negative electrode plate with the coating thickness of 6 mu m.
Assembled into a battery
And assembling the obtained positive plate, the diaphragm and the negative plate into a battery core, placing the battery core in a battery shell, and carrying out vacuum packaging, standing, formation, shaping and other procedures to form the battery.
Example 2
The membrane was prepared in substantially the same manner as in example 1, using SSPSILI and polyethylene glycol methyl ether methacrylate as EO and Li+The molar ratio is 4:1, may be used.
The preparation of the positive plate, the preparation of the negative plate, the preparation of the electrolyte and the assembly of the battery are the same as those in example 1. Finally, the battery is prepared.
Example 3
The membrane was prepared in substantially the same manner as in example 1, using SSPSILI and polyethylene glycol methyl ether methacrylate as EO and Li+The molar ratio is 8: 1, may be used.
The preparation of the positive plate, the preparation of the negative plate, the preparation of the electrolyte and the assembly of the battery are the same as those in example 1. Finally, the battery is prepared.
Example 4
The membrane was prepared in substantially the same manner as in example 1, using SSPSILI and polyethylene glycol methyl ether methacrylate as EO and Li+The molar ratio is 12: 1, may be used.
The preparation of the positive plate, the preparation of the negative plate, the preparation of the electrolyte and the assembly of the battery are the same as those in example 1. Finally, the battery is prepared.
Example 5
The membrane was prepared in substantially the same manner as in example 1, using SSPSILI and polyethylene glycol methyl ether methacrylate as EO and Li+The molar ratio is 16: 1, may be used.
The preparation of the positive plate, the preparation of the negative plate, the preparation of the electrolyte and the assembly of the battery are the same as those in example 1. Finally, the battery is prepared.
Example 6
The membrane was prepared in substantially the same manner as in example 1, using SSPSILI and polyethylene glycol methyl ether methacrylate as EO and Li+The molar ratio is 20: 1, may be used.
The preparation of the positive plate, the preparation of the negative plate, the preparation of the electrolyte and the assembly of the battery are the same as those in example 1. Finally, the battery is prepared.
Example 7
The membrane was prepared in substantially the same manner as in example 1, using SSPSILI and polyethylene glycol methyl ether methacrylate as EO and Li+The molar ratio is 24: 1, may be used.
The preparation of the positive plate, the preparation of the negative plate, the preparation of the electrolyte and the assembly of the battery are the same as those in example 1. Finally, the battery is prepared.
Example 8
The membrane was prepared in substantially the same manner as in example 1, using SSPSILI and polyethylene glycol methyl ether methacrylate as EO and Li+The molar ratio is 30: 1, may be used.
The preparation of the positive plate, the preparation of the negative plate, the preparation of the electrolyte and the assembly of the battery are the same as those in example 1. Finally, the battery is prepared.
Comparative example 1
The membrane was prepared in substantially the same manner as in example 1, using SSPSILI and polyethylene glycol methyl ether methacrylate as EO and Li+The molar ratio is 40: 1, may be used.
The preparation of the positive plate, the preparation of the negative plate, the preparation of the electrolyte and the assembly of the battery are the same as those in example 1. Finally, the battery is prepared.
Comparative example 2
The membrane was prepared in substantially the same manner as in example 1, using SSPSILI and polyethylene glycol methyl ether methacrylate as EO and Li+The molar ratio is 1: 2, may be used.
The preparation of the positive plate, the preparation of the negative plate, the preparation of the electrolyte and the assembly of the battery are the same as those in example 1. Finally, the battery is prepared.
Comparative example 3
LiTFSI and PEO as EO and Li+The molar ratio is 8: 1 in anhydrous acetonitrile, and preparing an electrolyte film by a tape casting method.
The preparation of the positive plate, the preparation of the negative plate, the preparation of the electrolyte and the assembly of the battery are the same as those in example 1. Finally, the battery is prepared.
Battery performance testing
Cycling at 25 ℃: the experiment is carried out in the environment of 25 ℃, constant-current and constant-voltage charging is carried out firstly, the constant-current and constant-voltage charging is carried out at 0.3 ℃ until the voltage reaches 4.3V, the current is cut off at 0.05C, then constant-current discharging is carried out, the constant-current discharging is carried out again, the discharging voltage is discharged at 0.3C until the voltage reaches 3V, the cycle is carried out for 500 times. The test results are shown in table 1.
TABLE 1
Figure BDA0002544931940000091
As can be seen from the data shown in table 1, the first discharge capacity and capacity retention after 500 charges and discharges of the batteries of examples 1 to 8 are higher than those of the batteries of comparative examples 1 to 2 and significantly higher than that of the battery of comparative example 3. This may indicate that the cycle performance of the battery may be improved and the lifespan of the battery may be increased using the separator including formula 1 and/or formula 2 according to the present invention. When EO segment and Li are present in the separator+In a molar ratio of 1-30: in the range of 1, the performance of the battery is improved to the greatest extent.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (10)

1. A diaphragm is characterized by comprising a structure shown in a formula 1 and/or a formula 2,
Figure FDA0002544931930000011
wherein R is-F, benzene ring, fluorine substituted benzene ring, cyano substituted benzene ring or C1-8One or more of the perfluorocarbon chains of (a).
2. The separator according to claim 1, wherein x-1-2000, y-1-2000, and n-2-30 in formula 1 or formula 2.
3. The membrane of claim 1, wherein the membrane is a cellulose membrane.
4. The membrane according to claim 1, wherein the content of the group of formula 3 per gram of membrane is 1 to 4mmol, preferably 1.5 to 3.5mmol, more preferably 2 to 3 mmol; in the membrane-CH2-CH2the-O-group with Li+In a molar ratio of 1 to 30: 1;
Figure FDA0002544931930000012
5. a method for preparing a separator, characterized in that an initiator is dissolved in a solvent and a separator having a structure of formula 4 is immersed therein, followed by injecting a compound represented by formula 5 and a polymer represented by formula 6,
Figure FDA0002544931930000021
wherein R is-F, benzene ring, fluorine substituted benzene ring, cyano substituted benzene ring or C1-8One or more of the perfluorocarbon chains of (a).
6. The method according to claim 5, wherein the compound represented by formula 5 is synthesized from a compound represented by formula 7 or 8 and lithium hydroxide:
Figure FDA0002544931930000022
7. a method for preparing a separator, characterized in that an initiator is dissolved in a solvent and a separator having a structure of formula 4 is immersed therein, followed by injecting a polymer represented by formula 6, compounds represented by formula 7 and formula 8, and lithium hydroxide,
Figure FDA0002544931930000023
wherein R is-F, benzene ring, fluorine substituted benzene ring, cyano substituted benzene ring or C1-8One or more of the perfluorocarbon chains of (a).
8. The production method according to claim 5 or 7, wherein the separator containing the structure of formula 4 is a cellulose separator.
9. The production method according to claim 8, wherein the solvent is water or an organic solvent;
when the solvent is water, the initiator is one or two of potassium persulfate and ammonium persulfate;
when the solvent is an organic solvent, the initiator is one or two of azodiisobutyronitrile and benzoyl peroxide.
10. A lithium ion battery comprising the separator according to any one of claims 1 to 4 or the separator produced by the production method according to any one of claims 5 to 9.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104681865A (en) * 2015-01-23 2015-06-03 清华大学深圳研究生院 All-solid state polymer electrolyte and application of electrolyte in battery

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104681865A (en) * 2015-01-23 2015-06-03 清华大学深圳研究生院 All-solid state polymer electrolyte and application of electrolyte in battery

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