CN109449351A - A kind of lithium battery diaphragm and preparation method thereof - Google Patents
A kind of lithium battery diaphragm and preparation method thereof Download PDFInfo
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- CN109449351A CN109449351A CN201811384259.5A CN201811384259A CN109449351A CN 109449351 A CN109449351 A CN 109449351A CN 201811384259 A CN201811384259 A CN 201811384259A CN 109449351 A CN109449351 A CN 109449351A
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- lithium battery
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
-
- 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
-
- 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
Abstract
The invention discloses a kind of preparation methods of lithium battery diaphragm; first to dihydro -2; 4; 6- trioxy- -1; 3; 5- triazine -1,3 (2H, 4H)-dipropionic acid hydroxyl is protected; then with 2; polycondensation reaction occurs for bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2-, then is deprotected, and then carries out 3- (dimethylamino) ethyl acrylate graft modification to obtained condensation polymer; again with the nanometer calcium carbonate of surface modification, 2; two mercaptan of 7- naphthalene is uniformly mixed, and finally obtains polymer film, last drilling with heat setting process through molten squeeze.The lithium battery diaphragm disclosed by the invention being prepared by above-mentioned preparation method has higher lithium ion conductivity, superior weatherability, thermal stability and electrochemical stability, repeated charge keep height wellability and more preferably mechanical performance to electrolyte in the process.
Description
Technical field
The invention belongs to technical field of chemical power, are related to a kind of lithium cell component more particularly to a kind of lithium battery diaphragm
And preparation method thereof.
Background technique
It is increasingly reduced by the fossil resource of representative of petroleum, the automobile using petroleum as raw material offers convenience same to us
When worsening environment is also brought to us, the mankind are in the clean alternative energy source of searching done one's utmost.Lithium ion battery
Due to energy density height, have extended cycle life, be small in size, light weight the advantages that can use on electric car as clean energy resource.
Diaphragm is one of important composition component of lithium battery, its microcellular structure, physical property, chemical characteristic, hot property
Deng closely related with lithium battery performance, separation positive and negative electrode is played in lithium battery, prevents internal short-circuit of battery, allows electrolyte
Ion passes freely through, and completes the effect of charge discharge process.Its performance determines the interfacial structure of battery, internal resistance etc., directly
The characteristics such as capacity, cycle performance and the security performance for influencing battery are connect, the diaphragm haveing excellent performance is comprehensive to raising battery
It can play an important role, " the third electrode " of battery is known as by industry.
Currently, the lithium battery diaphragm of commercialization is mainly using polyethylene and polypropylene as the MIcroporous polyolefin film of material.So
And the fusing point of these conventional polyolefins diaphragms is lower, will appear contraction closed pore after heated, causes battery plus-negative plate contact short circuit, deposits
In potential security risk；In addition, polyolefins diaphragm itself is poor to electrolyte wetability, imbibition rate is not high, to influence
The cycle performance of battery.As the improvement to above-mentioned film, carried out currently, generalling use inorganic matter by matrix of polyolefin porous membrane
Coating is modified, but its compatibility always exists problem.
Chinese invention patent 201610743256.0 discloses a kind of septum for lithium ion battery, and it is sub- to prepare sulfonated polyether acyl first
The nano aluminium oxide of amine, surface chemical modification, later by sulfonated polyether acid imide, the nano aluminium oxide, poly- of surface chemical modification
Lysine and nanometer calcium carbonate are uniformly mixed by certain mass ratio, pass through pickling, ion exchange, ion after molten crowded and thermal finalization
In the nano aluminium oxide dispersion liquid of its surface coating surface chemical modification after body radiation, diaphragm finished product is made after processing.This hair
Bright method is simple and easy, lithium battery diaphragm ionic conductivity with higher obtained, good thermal stability, chemical stability
And electrochemical stability, repeated charge keep height wellability and excellent mechanical performance, but its table to electrolyte in the process
The nano aluminium oxide dispersion liquid and basement membrane compatibility of the surface chemical modification of face coating are bad, also influence lithium ion transport, and its
Weatherability needs to be further increased.
Therefore, develop a kind of while there is higher lithium ion conductivity, superior thermal stability, chemical stability,
Weatherability and electrochemical stability keep height wellability and more preferably mechanical performance to electrolyte during repeated charge
Lithium battery diaphragm accords with the demands of the market, and has extensive market value and application prospect.
Summary of the invention
In order to overcome the defects of the prior art, the present invention provides one kind and has more high-lithium ion conductivity, superior
Weatherability, thermal stability and electrochemical stability keep height wellability and more preferably to electrolyte during repeated charge
The lithium battery diaphragm of mechanical performance, while the preparation method of this kind of diaphragm being provided.
To achieve the above object of the invention, the technical solution adopted by the present invention is that,
A kind of preparation method of lithium battery diaphragm, includes the following steps:
I hydroxyl protection: -1,3 (2H, 4H)-dipropionic acid of dihydro -2,4,6- trioxy- -1,3,5- triazine is dissolved in N, N- bis-
Solution is formed in methylformamide, is stirred 10-20 minutes under ice-water bath, then imidazoles and trim,ethylchlorosilane are added thereto,
Continue stirring 2-3 hour, after reaction mixture is diluted with ethyl acetate, be washed with water 3-5 times, then with saturated common salt washing 3-5
It is secondary, it is finally removed water, is filtered with anhydrous magnesium sulfate, revolving removes solvent, obtains intermediate product；
The preparation of II condensation polymer: the bis- [4- (4- amino-benzene oxygen) of intermediate product, 2,2- that will be prepared by step I
Phenyl] hexafluoropropane, I-hydroxybenzotriazole, 4-dimethylaminopyridine be dissolved in high boiling solvent and form solution, then by solution
It is added in reaction kettle, with air in nitrogen or inert gas replacement kettle, sealing carries out for back flow reaction 3-4 hours in 150-170 DEG C
Then catalyst is added in amidation process thereto, be depressurized to 300-500Pa, and polycondensation reaction 10-12 is small at 260-270 DEG C
When, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, after the polymer of precipitation ethanol washing 4-6 times, then be placed in true
It dries at 80-90 DEG C of empty drying box to constant weight, obtains condensation polymer；
The deprotection of III hydroxyl: the condensation polymer being prepared by step II is dissolved in n,N-Dimethylformamide, then to
Methanaminium, N,N,N-trimethyl-, fluoride is wherein added, is stirred to react at 40-60 DEG C 2-3 hours, after be precipitated in water, the polymer of precipitation is used
After ethanol washing 4-6 times, then it is placed in dry at 80-90 DEG C of vacuum oven and obtains the condensation polymer with activity hydroxy to constant weight；
The preparation of IV chloro condensation polymer: the condensation polymer with activity hydroxy being prepared by step III is dissolved in N- first
In base pyrrolidones, then (±) -4- chlorostyrene epoxides and basic catalyst are added thereto, are stirred at 75-85 DEG C
Reaction 6-8 hours, after be precipitated in water, after the polymer of precipitation ethanol washing 3-5 times, then be placed in vacuum oven 80-
It dries at 90 DEG C to constant weight, obtains chloro condensation polymer；
V 3- (dimethylamino) ethyl acrylate modified condensation polymer: the chloro condensation polymer being prepared by step IV is molten
In n,N-Dimethylformamide, then 3- (dimethylamino) ethyl acrylate, sodium carbonate are added thereto, are stirred at 40-60 DEG C
Mix reaction 6-8 hours, after be precipitated in water, after the polymer of precipitation ethanol washing 3-5 times, then be placed in vacuum oven
It dries at 80-90 DEG C to constant weight, obtains 3- (dimethylamino) ethyl acrylate modified condensation polymer；
The preparation of VI polymer film: will by 3- (dimethylamino) ethyl acrylate modified condensation polymer made from step V,
The nanometer calcium carbonate of surface modification, 2,7- naphthalene, two mercaptan are uniformly mixed, and finally obtain polymer with heat setting process through molten squeeze
Film；
VII drilling: it is small that polymeric membrane made from step IV is immersed in 20-30 in the hydrochloric acid solution that mass fraction is 10-15%
When, after be rinsed with water film to eluent and be in neutrality, obtain lithium battery diaphragm.
Preferably, dihydro -2,4 described in step I, 6- trioxy- -1,3,5-triazines -1,3 (2H, 4H)-dipropionic acid, N, N-
Dimethylformamide, imidazoles, trim,ethylchlorosilane mass ratio be 2.51:(10-15): (0.3-0.5): 1.
Preferably, intermediate product described in step II, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane, 1- hydroxyl
Base benzotriazole, 4-dimethylaminopyridine, high boiling solvent, catalyst mass ratio be 1:1.36:(0.4-0.6): 0.3:
(10-15):0.5。
Preferably, the high boiling solvent is in dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
It is one or more of；The inert gas is selected from one of helium, neon, argon gas；The catalyst is selected from 2- furan boronic acid, three
One or more of (2,2,2- trifluoroethyl) borate, zinc chloride.
Preferably, condensation polymer described in step III, n,N-Dimethylformamide, Methanaminium, N,N,N-trimethyl-, fluoride mass ratio be (3-
5):(15-25):1。
Preferably, condensation polymer, the N-Methyl pyrrolidone, (±) -4- chlorobenzene second of activity hydroxy are had described in step IV
Alkene epoxides, basic catalyst mass ratio be (3-5): (10-15): 1:0.5；The basic catalyst be selected from sodium carbonate,
One or more of potassium carbonate, sodium hydroxide, potassium hydroxide.
Preferably, chloro condensation polymer described in step V, n,N-Dimethylformamide, 3- (dimethylamino) acrylic acid second
Ester, sodium carbonate mass ratio be (3-5): (10-15): 1:0.5.
Preferably, (dimethylamino) ethyl acrylate of 3- described in step VI modified condensation polymer, surface modification nano-sized carbon
Sour calcium, two mercaptan of 2,7- naphthalene mass ratio be 1:(0.1-0.2): 0.1.
Preferably, the molten extruding process temperature is 250-350 DEG C, and the temperature of heat setting process is 180-230 DEG C, when sizing
Between be 25-35min.
Preferably, the preparation method of the nanometer calcium carbonate of the surface modification includes the following steps: nanometer calcium carbonate point
Dissipate in ethyl alcohol, then thereto be added thiopurine methyltransferase methyldiethoxysilane, be stirred to react at 50-60 DEG C 4-6 hours, after from
The heart is placed at 60-70 DEG C of vacuum oven and dries 15-20 hours, obtains the nanometer calcium carbonate of surface modification；The nano-calcium carbonate
Calcium, ethyl alcohol, thiopurine methyltransferase methyldiethoxysilane mass ratio be (3-5): (10-15): 1.
Preferably, polymeric membrane described in step VII, hydrochloric acid solution mass ratio 1:(50-80).
A kind of lithium battery diaphragm is prepared using the preparation method of above-mentioned lithium battery diaphragm.
The beneficial effects of adopting the technical scheme are that
1) preparation method of lithium battery diaphragm provided by the invention, simple and easy, raw material is easy to get, and reaction condition is mild, right
Device dependence is not high, is suitble to large-scale production.
2) lithium battery diaphragm provided by the invention, the fusing point for overcoming conventional polyolefins lithium battery diaphragm is lower, after being heated
Will appear contraction closed pore, cause battery plus-negative plate contact short circuit, there are potential security risk, itself to electrolyte wetability compared with
Difference, imbibition rate is not high, to influence the defect of the cycle performance of battery, while having higher lithium ion conductivity, more excellent
Thermal stability, chemical stability, weatherability and electrochemical stability, keep height to soak electrolyte during repeated charge
Lubricant nature and more preferably mechanical performance.
3) lithium battery diaphragm provided by the invention, substrate use bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2,2-
With dihydro -2,4,6- trioxy- -1,3,5-triazines -1,3 (2H, 4H)-dipropionic acid polycondensation is made, and improves the comprehensive performance of film,
Especially triazines and the addition containing fluorine structure, so that its mechanical performance, weatherability, thermal stability, chemical stability have greatly
Width improves；3- (dimethylamino) ethyl acrylate is introduced on condensation polymer film side chain by modified, on the one hand, after introducing double bond is
Continuous crosslinking curing provides reaction site, and the amino in addition introduced, which reacts for mercapto with double bond, provides catalytic action, without in addition
Add catalyst；Importantly, the introducing by 3- (dimethylamino) ethyl acrylate has with preferable affinity
Height wellability is kept to electrolyte conducive to during film repeated charge, secondly in successive modified, is provided quaternized anti-
Site is answered, so that it can provide clear passage with positive electricity feature for positive electricity lithium ion, to improve lithium ion conductivity.
4) lithium battery diaphragm provided by the invention, it is modified by carrying out surface to nanometer calcium carbonate, so that it divides in film
Dissipate uniformly so that drilling is uniform, in addition, due to modified using thiopurine methyltransferase methyldiethoxysilane, thiopurine methyltransferase can with it is poly-
The unsaturated bond reaction on object side chain is closed, so that other small molecules will not be generated during drilling, to cause to lithium
The influence of battery diaphragm comprehensive performance and lithium battery performance.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention,
Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Present invention raw material as used in the following examples is purchased from shellfish (Shanghai) Biotechnology Co., Ltd that rubs.
Embodiment 1
A kind of preparation method of lithium battery diaphragm, includes the following steps:
I hydroxyl protection: -1,3 (2H, 4H)-dipropionic acid 2.51kg of dihydro -2,4,6- trioxy- -1,3,5- triazine is dissolved in
Solution is formed in n,N-Dimethylformamide 10kg, is stirred 10 minutes under ice-water bath, then imidazoles 0.3kg and three is added thereto
Methylchlorosilane 1kg, continue stirring 2 hours, after reaction mixture is diluted with ethyl acetate, be washed with water 3 times, then with saturation food
Salt is washed 3 times, is finally removed water with anhydrous magnesium sulfate, is filtered, and revolving removes solvent, obtains intermediate product；
The preparation of II condensation polymer: bis- [4- (the 4- aminobenzene oxygen of intermediate product 1kg, 2,2- that will be prepared by step I
Base) phenyl] hexafluoropropane 1.36kg, I-hydroxybenzotriazole 0.4kg, 4-dimethylaminopyridine 0.3kg be dissolved in dimethyl sulfoxide
Solution is formed in 10kg, then solution is added in reaction kettle, with air in nitrogen displacement kettle, sealing, in 150 DEG C of back flow reactions 3
Hour carries out amidation process, and 2- furan boronic acid 0.5kg is then added thereto, is depressurized to 300Pa, polycondensation is anti-at 260 DEG C
Answer 10 hours, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymer of precipitation with after ethanol washing 4 times, then set
It dries at 80 DEG C of vacuum oven to constant weight, obtains condensation polymer；
The deprotection of III hydroxyl: the condensation polymer 1.2kg being prepared by step II is dissolved in N,N-dimethylformamide 6kg
In, then thereto be added Methanaminium, N,N,N-trimethyl-, fluoride 0.4kg, be stirred to react at 40 DEG C 2 hours, after be precipitated in water, by precipitation
Polymer is with after ethanol washing 4 times, then is placed in dry at 80 DEG C of vacuum oven and obtains the polycondensation with activity hydroxy to constant weight
Object；
The preparation of IV chloro condensation polymer: the condensation polymer 1.2kg with activity hydroxy being prepared by step III is molten
In N-Methyl pyrrolidone 4kg, then (±) -4- chlorostyrene epoxides 0.4kg and sodium carbonate 0.2kg are added thereto,
Be stirred to react at 75 DEG C 6 hours, after be precipitated in water, by the polymer of precipitation with after ethanol washing 3 times, then to be placed in vacuum dry
It dries at 80 DEG C of dry case to constant weight, obtains chloro condensation polymer；
V 3- (dimethylamino) ethyl acrylate modified condensation polymer: the chloro condensation polymer that will be prepared by step IV
1.2kg is dissolved in n,N-Dimethylformamide 4kg, then 3- (dimethylamino) ethyl acrylate 0.4kg, sodium carbonate are added thereto
0.2kg is stirred to react 6 hours at 40 DEG C, after be precipitated in water, by the polymer of precipitation with after ethanol washing 3 times, then be placed in
It dries at 80 DEG C of vacuum oven to constant weight, obtains 3- (dimethylamino) ethyl acrylate modified condensation polymer；
The preparation of VI polymer film: will be by 3- (dimethylamino) ethyl acrylate modified condensation polymer made from step V
1kg, the nanometer calcium carbonate 0.1kg of surface modification, 2,7- naphthalene, two mercaptan 0.1kg are uniformly mixed, through molten crowded and heat setting process
It is final to obtain polymer film；The molten extruding process temperature is 250 DEG C, and the temperature of heat setting process is 180 DEG C, and setting time is
25min；
VII drilling: polymeric membrane 1kg made from step IV is immersed in 20 in the hydrochloric acid solution 50kg that mass fraction is 10%
Hour, after be rinsed with water film to eluent and be in neutrality, obtain lithium battery diaphragm.
The preparation method of the nanometer calcium carbonate of the surface modification includes the following steps: to disperse nanometer calcium carbonate 3kg in
In ethyl alcohol 10kg, then thereto be added thiopurine methyltransferase methyldiethoxysilane 1kg, be stirred to react at 50 DEG C 4 hours, after from
The heart is placed at 60 DEG C of vacuum oven and dries 15 hours, obtains the nanometer calcium carbonate of surface modification.
A kind of lithium battery diaphragm is prepared using the preparation method of above-mentioned lithium battery diaphragm.
Embodiment 2
A kind of preparation method of lithium battery diaphragm, includes the following steps:
I hydroxyl protection: -1,3 (2H, 4H)-dipropionic acid 2.51kg of dihydro -2,4,6- trioxy- -1,3,5- triazine is dissolved in
Form solution in n,N-Dimethylformamide 12kg, stirred 13 minutes under ice-water bath, then thereto be added imidazoles 0.35kg and
Trim,ethylchlorosilane 1kg, continue stirring 2.3 hours, after reaction mixture is diluted with ethyl acetate, be washed with water 4 times, then with satisfy
It washes 4 times with salt, is finally removed water with anhydrous magnesium sulfate, filtered, revolving removes solvent, obtains intermediate product；
The preparation of II condensation polymer: bis- [4- (the 4- aminobenzene oxygen of intermediate product 1kg, 2,2- that will be prepared by step I
Base) phenyl] hexafluoropropane 1.36kg, I-hydroxybenzotriazole 0.45kg, 4-dimethylaminopyridine 0.3kg be dissolved in N, N- dimethyl
Solution is formed in formamide 12kg, then solution is added in reaction kettle, and with air in helium replacement kettle, sealing flows back in 155 DEG C
3.3 hours progress amidation process are reacted, three (2,2,2- trifluoroethyl) borate 0.5kg are then added thereto, are depressurized to
350Pa, polycondensation reaction 10.5 hours at 263 DEG C, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymerization of precipitation
Object is with after ethanol washing 5 times, then is placed at 83 DEG C of vacuum oven and dries to constant weight, obtains condensation polymer；
The deprotection of III hydroxyl: the condensation polymer 1.5kg being prepared by step II is dissolved in N,N-dimethylformamide 7kg
In, then thereto be added Methanaminium, N,N,N-trimethyl-, fluoride 0.4kg, be stirred to react at 45 DEG C 2.3 hours, after be precipitated in water, will be precipitated
Polymer with after ethanol washing 5 times, then be placed in dry at 83 DEG C of vacuum oven and obtain the contracting with activity hydroxy to constant weight
Polymers；
The preparation of IV chloro condensation polymer: the condensation polymer 1.5kg with activity hydroxy being prepared by step III is molten
In N-Methyl pyrrolidone 4.5kg, then (±) -4- chlorostyrene epoxides 0.4kg and potassium carbonate are added thereto
0.2kg is stirred to react 6.5 hours at 78 DEG C, after be precipitated in water, by the polymer of precipitation with after ethanol washing 4 times, then set
It dries at 83 DEG C of vacuum oven to constant weight, obtains chloro condensation polymer；
V 3- (dimethylamino) ethyl acrylate modified condensation polymer: the chloro condensation polymer that will be prepared by step IV
1.5kg is dissolved in n,N-Dimethylformamide 4.5kg, then 3- (dimethylamino) ethyl acrylate 0.4kg, carbonic acid are added thereto
Sodium 0.2kg is stirred to react 6.5 hours at 45 DEG C, after be precipitated in water, by the polymer of precipitation with after ethanol washing 4 times, then
It is placed at 83 DEG C of vacuum oven and dries to constant weight, obtain 3- (dimethylamino) ethyl acrylate modified condensation polymer；
The preparation of VI polymer film: will be by 3- (dimethylamino) ethyl acrylate modified condensation polymer made from step V
1kg, the nanometer calcium carbonate 0.13kg of surface modification, 2,7- naphthalene, two mercaptan 0.1kg are uniformly mixed, through molten crowded and heat setting process
It is final to obtain polymer film；The molten extruding process temperature is 270 DEG C, and the temperature of heat setting process is 190 DEG C, and setting time is
27min；
VII drilling: polymeric membrane 1kg made from step IV is immersed in 23 in the hydrochloric acid solution 60kg that mass fraction is 12%
Hour, after be rinsed with water film to eluent and be in neutrality, obtain lithium battery diaphragm.
The preparation method of the nanometer calcium carbonate of the surface modification includes the following steps: to disperse nanometer calcium carbonate 3.5kg
In ethyl alcohol 12kg, then thiopurine methyltransferase methyldiethoxysilane 1kg is added thereto, is stirred to react at 53 DEG C 4.5 hours, after
Centrifugation, is placed at 63 DEG C of vacuum oven and dries 16 hours, obtain the nanometer calcium carbonate of surface modification.
A kind of lithium battery diaphragm is prepared using the preparation method of above-mentioned lithium battery diaphragm.
Embodiment 3
A kind of preparation method of lithium battery diaphragm, includes the following steps:
I hydroxyl protection: -1,3 (2H, 4H)-dipropionic acid 2.51kg of dihydro -2,4,6- trioxy- -1,3,5- triazine is dissolved in
Solution is formed in n,N-Dimethylformamide 13kg, is stirred 15 minutes under ice-water bath, then imidazoles 0.4kg and three is added thereto
Methylchlorosilane 1kg, continue stirring 2.5 hours, after reaction mixture is diluted with ethyl acetate, be washed with water 4 times, then be saturated
Salt is washed 4 times, is finally removed water with anhydrous magnesium sulfate, is filtered, and revolving removes solvent, obtains intermediate product；
The preparation of II condensation polymer: bis- [4- (the 4- aminobenzene oxygen of intermediate product 1kg, 2,2- that will be prepared by step I
Base) phenyl] hexafluoropropane 1.36kg, I-hydroxybenzotriazole 0.5kg, 4-dimethylaminopyridine 0.3kg be dissolved in N- methylpyrrole
Solution is formed in alkanone 13kg, then solution is added in reaction kettle, and with air in neon displacement kettle, sealing is anti-in 160 DEG C of reflux
3.5 hours progress amidation process are answered, zinc chloride is then added thereto, is depressurized to 400Pa, the polycondensation reaction 11 at 265 DEG C
Hour, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymer of precipitation with after ethanol washing 5 times, then be placed in true
It dries at 85 DEG C of empty drying box to constant weight, obtains condensation polymer；
The deprotection of III hydroxyl: the condensation polymer 1.7kg being prepared by step II is dissolved in N,N-dimethylformamide
In 8.5kg, then thereto be added Methanaminium, N,N,N-trimethyl-, fluoride 0.4kg, be stirred to react at 50 DEG C 2.5 hours, after be precipitated in water, will
The polymer of precipitation is with after ethanol washing 6 times, then is placed at 87 DEG C of vacuum oven and dries to constant weight, obtains with activity hydroxy
Condensation polymer；
The preparation of IV chloro condensation polymer: the condensation polymer 1.7kg with activity hydroxy being prepared by step III is molten
In N-Methyl pyrrolidone 5kg, then (±) -4- chlorostyrene epoxides 0.4kg and sodium hydroxide are added thereto
0.2kg is stirred to react 7 hours at 80 DEG C, after be precipitated in water, by the polymer of precipitation with after ethanol washing 4 times, then be placed in
It dries at 86 DEG C of vacuum oven to constant weight, obtains chloro condensation polymer；
V 3- (dimethylamino) ethyl acrylate modified condensation polymer: the chloro condensation polymer that will be prepared by step IV
1.7kg is dissolved in n,N-Dimethylformamide 5.2kg, then 3- (dimethylamino) ethyl acrylate 0.4kg, carbonic acid are added thereto
Sodium 0.2kg is stirred to react 7.1 hours at 52 DEG C, after be precipitated in water, by the polymer of precipitation with after ethanol washing 4 times, then
It is placed at 86 DEG C of vacuum oven and dries to constant weight, obtain 3- (dimethylamino) ethyl acrylate modified condensation polymer；
The preparation of VI polymer film: will be by 3- (dimethylamino) ethyl acrylate modified condensation polymer made from step V
1kg, the nanometer calcium carbonate 0.15kg of surface modification, 2,7- naphthalene, two mercaptan 0.1kg are uniformly mixed, through molten crowded and heat setting process
It is final to obtain polymer film；The molten extruding process temperature is 300 DEG C, and the temperature of heat setting process is 200 DEG C, and setting time is
30min。
VII drilling: polymeric membrane 1kg made from step IV is immersed in 26 in the hydrochloric acid solution 70kg that mass fraction is 13%
Hour, after be rinsed with water film to eluent and be in neutrality, obtain lithium battery diaphragm.
The preparation method of the nanometer calcium carbonate of the surface modification includes the following steps: to disperse nanometer calcium carbonate 4kg in
In ethyl alcohol 13.5kg, then thereto be added thiopurine methyltransferase methyldiethoxysilane 1kg, be stirred to react at 57 DEG C 5 hours, after from
The heart is placed at 66 DEG C of vacuum oven and dries 18 hours, obtains the nanometer calcium carbonate of surface modification.
A kind of lithium battery diaphragm is prepared using the preparation method of above-mentioned lithium battery diaphragm.
Embodiment 4
A kind of preparation method of lithium battery diaphragm, includes the following steps:
I hydroxyl protection: -1,3 (2H, 4H)-dipropionic acid 2.51kg of dihydro -2,4,6- trioxy- -1,3,5- triazine is dissolved in
Form solution in n,N-Dimethylformamide 14kg, stirred 18 minutes under ice-water bath, then thereto be added imidazoles 0.45kg and
Trim,ethylchlorosilane 1kg, continue stirring 2.8 hours, after reaction mixture is diluted with ethyl acetate, be washed with water 5 times, then with satisfy
It washes 4 times with salt, is finally removed water with anhydrous magnesium sulfate, filtered, revolving removes solvent, obtains intermediate product；
The preparation of II condensation polymer: bis- [4- (the 4- aminobenzene oxygen of intermediate product 1kg, 2,2- that will be prepared by step I
Base) phenyl] hexafluoropropane 1.36kg, I-hydroxybenzotriazole 0.55kg, 4-dimethylaminopyridine 0.3kg be dissolved in high boiling solvent
Solution is formed in 14.5kg, then solution is added in reaction kettle, with air in argon gas displacement kettle, sealing, in 165 DEG C of back flow reactions
Then catalyst 0.5kg is added thereto, is depressurized to 450Pa, the polycondensation reaction at 268 DEG C for 3.8 hours progress amidation process
11.5 hours, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, by the polymer of precipitation with after ethanol washing 6 times, then set
It dries at 88 DEG C of vacuum oven to constant weight, obtains condensation polymer；The high boiling solvent is dimethyl sulfoxide, N, N- dimethyl methyl
The mixture that amide, N-Methyl pyrrolidone 2:3:1 in mass ratio are mixed；The catalyst be 2- furan boronic acid, three (2,
2,2- trifluoroethyl) mixture that mixes of borate, zinc chloride 2:1:3 in mass ratio.
The deprotection of III hydroxyl: the condensation polymer 1.9kg being prepared by step II is dissolved in N,N-dimethylformamide
In 9.5kg, then thereto be added Methanaminium, N,N,N-trimethyl-, fluoride 0.4kg, be stirred to react at 55 DEG C 2.8 hours, after be precipitated in water, will
The polymer of precipitation is with after ethanol washing 6 times, then is placed at 89 DEG C of vacuum oven and dries to constant weight, obtains with activity hydroxy
Condensation polymer；
The preparation of IV chloro condensation polymer: the condensation polymer 1.9kg with activity hydroxy being prepared by step III is molten
In N-Methyl pyrrolidone 5.8kg, then (±) -4- chlorostyrene epoxides 0.4kg and basic catalyst are added thereto
0.2kg is stirred to react 7.8 hours at 84 DEG C, after be precipitated in water, by the polymer of precipitation with after ethanol washing 5 times, then set
It dries at 88 DEG C of vacuum oven to constant weight, obtains chloro condensation polymer；The basic catalyst is sodium carbonate, potassium carbonate, hydrogen
The mixture that sodium oxide molybdena, potassium hydroxide 2:1:2:3 in mass ratio are mixed；
V 3- (dimethylamino) ethyl acrylate modified condensation polymer: the chloro condensation polymer that will be prepared by step IV
1.9kg is dissolved in n,N-Dimethylformamide 5.8kg, then 3- (dimethylamino) ethyl acrylate 0.4kg, carbonic acid are added thereto
Sodium 0.2kg is stirred to react 7.8 hours at 58 DEG C, after be precipitated in water, by the polymer of precipitation with after ethanol washing 5 times, then
It is placed at 89 DEG C of vacuum oven and dries to constant weight, obtain 3- (dimethylamino) ethyl acrylate modified condensation polymer；
The preparation of VI polymer film: will be by 3- (dimethylamino) ethyl acrylate modified condensation polymer made from step V
1kg, the nanometer calcium carbonate 0.19kg of surface modification, 2,7- naphthalene, two mercaptan 0.1kg are uniformly mixed, through molten crowded and heat setting process
It is final to obtain polymer film；The molten extruding process temperature is 330 DEG C, and the temperature of heat setting process is 220 DEG C, and setting time is
33min；
VII drilling: polymeric membrane 1kg made from step IV is immersed in 28 in the hydrochloric acid solution 75kg that mass fraction is 14%
Hour, after be rinsed with water film to eluent and be in neutrality, obtain lithium battery diaphragm.
The preparation method of the nanometer calcium carbonate of the surface modification includes the following steps: to disperse nanometer calcium carbonate 4.8kg
In ethyl alcohol 14.5kg, then thiopurine methyltransferase methyldiethoxysilane 1kg is added thereto, is stirred to react at 58 DEG C 5.9 hours,
After be centrifuged, be placed at 69 DEG C of vacuum oven and dry 19.5 hours, obtain the nanometer calcium carbonate of surface modification.
A kind of lithium battery diaphragm is prepared using the preparation method of above-mentioned lithium battery diaphragm.
Embodiment 5
A kind of preparation method of lithium battery diaphragm, includes the following steps:
I hydroxyl protection: -1,3 (2H, 4H)-dipropionic acid 2.51kg of dihydro -2,4,6- trioxy- -1,3,5- triazine is dissolved in
Solution is formed in n,N-Dimethylformamide 15kg, is stirred 20 minutes under ice-water bath, then imidazoles 0.5kg and three is added thereto
Methylchlorosilane 1kg, continue stirring 3 hours, after reaction mixture is diluted with ethyl acetate, be washed with water 5 times, then with saturation food
Salt is washed 5 times, is finally removed water with anhydrous magnesium sulfate, is filtered, and revolving removes solvent, obtains intermediate product；
The preparation of II condensation polymer: bis- [4- (the 4- aminobenzene oxygen of intermediate product 1kg, 2,2- that will be prepared by step I
Base) phenyl] hexafluoropropane 1.36kg, I-hydroxybenzotriazole 0.6kg, 4-dimethylaminopyridine 0.3kg be dissolved in dimethyl sulfoxide
Solution is formed in 15kg, then solution is added in reaction kettle, with air in nitrogen displacement kettle, sealing, in 170 DEG C of back flow reactions 4
Hour carries out amidation process, and three (2,2,2- trifluoroethyl) borate 0.5kg are then added thereto, are depressurized to 500Pa,
Polycondensation reaction 12 hours at 270 DEG C, after be cooled to room temperature, be adjusted to normal pressure, be precipitated in water, the polymer of precipitation is washed with ethyl alcohol
It after washing 6 times, then is placed at 90 DEG C of vacuum oven and dries to constant weight, obtain condensation polymer；
The deprotection of III hydroxyl: the condensation polymer 2kg being prepared by step II is dissolved in N,N-dimethylformamide 10kg
In, then thereto be added Methanaminium, N,N,N-trimethyl-, fluoride 0.4kg, be stirred to react at 60 DEG C 3 hours, after be precipitated in water, by precipitation
Polymer is with after ethanol washing 6 times, then is placed in dry at 90 DEG C of vacuum oven and obtains the polycondensation with activity hydroxy to constant weight
Object；
The preparation of IV chloro condensation polymer: the condensation polymer 2kg with activity hydroxy being prepared by step III is dissolved in
In N-Methyl pyrrolidone 6kg, then (±) -4- chlorostyrene epoxides 0.4kg and potassium hydroxide 0.2kg are added thereto,
Be stirred to react at 85 DEG C 8 hours, after be precipitated in water, by the polymer of precipitation with after ethanol washing 5 times, then to be placed in vacuum dry
It dries at 90 DEG C of dry case to constant weight, obtains chloro condensation polymer；
V 3- (dimethylamino) ethyl acrylate modified condensation polymer: the chloro condensation polymer that will be prepared by step IV
2kg is dissolved in n,N-Dimethylformamide 6kg, then 3- (dimethylamino) ethyl acrylate 0.4kg, sodium carbonate are added thereto
0.2kg is stirred to react 8 hours at 60 DEG C, after be precipitated in water, by the polymer of precipitation with after ethanol washing 5 times, then be placed in
It dries at 90 DEG C of vacuum oven to constant weight, obtains 3- (dimethylamino) ethyl acrylate modified condensation polymer；The molten extruding process
Temperature is 350 DEG C, and the temperature of heat setting process is 230 DEG C, setting time 35min；
The preparation of VI polymer film: will be by 3- (dimethylamino) ethyl acrylate modified condensation polymer made from step V
1kg, the nanometer calcium carbonate 0.2kg of surface modification, 2,7- naphthalene, two mercaptan 0.1kg are uniformly mixed, through molten crowded and heat setting process
It is final to obtain polymer film；
VII drilling: polymeric membrane 1kg made from step IV is immersed in 30 in the hydrochloric acid solution 80kg that mass fraction is 15%
Hour, after be rinsed with water film to eluent and be in neutrality, obtain lithium battery diaphragm.
The preparation method of the nanometer calcium carbonate of the surface modification includes the following steps: to disperse nanometer calcium carbonate 5kg in
In ethyl alcohol 15kg, then thereto be added thiopurine methyltransferase methyldiethoxysilane 1kg, be stirred to react at 60 DEG C 6 hours, after from
The heart is placed at 70 DEG C of vacuum oven and dries 20 hours, obtains the nanometer calcium carbonate of surface modification.
A kind of lithium battery diaphragm is prepared using the preparation method of above-mentioned lithium battery diaphragm.
Comparative example
Commercially available lithium battery diaphragm, material PE are purchased from ZhongCai Science membrane material company.
Correlated performance test carried out to above-described embodiment 1-5 and the resulting lithium battery diaphragm of comparative example, test result and
Test method is shown in Table 1.Wherein, temperature tolerance is indicated (under the conditions of 120 DEG C, 1 hour) with shrinking percentage, Macmullin number (MacMullin
Number) ratio that refers to the resistance after diaphragm imbibition and bath resistance, reacted imbibition rate, the size of resistivity, be worth it is smaller more
It is good.1. Macmullin number test method: diaphragm being immersed in lithium hexafluorophosphate electrolyte solution 1 hour, room temperature (25 DEG C), taken out
Its resistance value is measured, the resistance value of the electrolyte of measurement is done into denominator, the resistance value of leaching electrolyte diaphragm does molecule, calculates its
Ratio；2. closed pore temperature test method: diaphragm being immersed in lithium hexafluorophosphate electrolyte solution, electrolyte is heated, according to different
Temperature, different resistance values release corresponding closed pore temperature (maximum value is closed completely).
Table 1
As it can be seen from table 1 lithium battery diaphragm disclosed by the embodiments of the present invention has more excellent temperature tolerance, it is higher
Being folded without breaking intensity and lithium ion conductivity.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. a kind of preparation method of lithium battery diaphragm, which comprises the steps of:
I hydroxyl protection: -1,3 (2H, 4H)-dipropionic acid of dihydro -2,4,6- trioxy- -1,3,5- triazine is dissolved in N, N- dimethyl
Solution is formed in formamide, is stirred 10-20 minutes under ice-water bath, then imidazoles and trim,ethylchlorosilane are added thereto, is continued
Stirring 2-3 hour, after reaction mixture is diluted with ethyl acetate, be washed with water 3-5 times, then with saturated common salt washing 3-5 times, most
It is removed water, is filtered with anhydrous magnesium sulfate afterwards, revolving removes solvent, obtains intermediate product；
The preparation of II condensation polymer: intermediate product, the 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] that will be prepared by step I
Hexafluoropropane, I-hydroxybenzotriazole, 4-dimethylaminopyridine, which are dissolved in high boiling solvent, forms solution, then solution is added instead
It answers in kettle, with air in nitrogen or inert gas replacement kettle, sealing, in the progress amidation in 3-4 hours of 150-170 DEG C of back flow reaction
Reaction, catalyst is then added thereto, is depressurized to 300-500Pa, rear cold polycondensation reaction 10-12 hours at 260-270 DEG C
But to room temperature, it is adjusted to normal pressure, is precipitated in water, after the polymer of precipitation ethanol washing 4-6 times, then be placed in vacuum oven
It dries at 80-90 DEG C to constant weight, obtains condensation polymer；
The deprotection of III hydroxyl: the condensation polymer being prepared by step II is dissolved in n,N-Dimethylformamide, then thereto
Be added Methanaminium, N,N,N-trimethyl-, fluoride, be stirred to react at 40-60 DEG C 2-3 hours, after be precipitated in water, by the polymer ethyl alcohol of precipitation
After washing 4-6 times, then it is placed in dry at 80-90 DEG C of vacuum oven and obtains the condensation polymer with activity hydroxy to constant weight；
The preparation of IV chloro condensation polymer: the condensation polymer with activity hydroxy being prepared by step III is dissolved in N- methyl pyrrole
In pyrrolidone, then (±) -4- chlorostyrene epoxides and basic catalyst are added thereto, are stirred to react at 75-85 DEG C
6-8 hours, after be precipitated in water, after the polymer of precipitation ethanol washing 3-5 times, then be placed in 80-90 DEG C of vacuum oven
Lower drying obtains chloro condensation polymer to constant weight；
V 3- (dimethylamino) ethyl acrylate modified condensation polymer: being dissolved in N for the chloro condensation polymer being prepared by step IV,
In dinethylformamide, then 3- (dimethylamino) ethyl acrylate, sodium carbonate are added thereto, are stirred at 40-60 DEG C anti-
Answer 6-8 hours, after be precipitated in water, after the polymer of precipitation ethanol washing 3-5 times, then be placed in vacuum oven 80-90
It dries at DEG C to constant weight, obtains 3- (dimethylamino) ethyl acrylate modified condensation polymer；
The preparation of VI polymer film: will be by 3- (dimethylamino) ethyl acrylate modified condensation polymer, surface made from step V
The nanometer calcium carbonate of modification, 2,7- naphthalene, two mercaptan are uniformly mixed, and finally obtain polymer film with heat setting process through molten squeeze；
VII drilling: polymeric membrane made from step IV is immersed in the hydrochloric acid solution that mass fraction is 10-15% 20-30 hours,
After be rinsed with water film to eluent and be in neutrality, obtain lithium battery diaphragm.
2. the preparation method of lithium battery diaphragm according to claim 1, which is characterized in that dihydro -2,4 described in step I,
The matter of -1,3 (2H, 4H)-dipropionic acid of 6- trioxy- -1,3,5- triazine, N,N-dimethylformamide, imidazoles, trim,ethylchlorosilane
Amount is than being 2.51:(10-15): (0.3-0.5): 1.
3. the preparation method of lithium battery diaphragm according to claim 1, which is characterized in that intermediate described in step II to produce
Object, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane, I-hydroxybenzotriazole, 4-dimethylaminopyridine, higher boiling
Solvent, catalyst mass ratio be 1:1.36:(0.4-0.6): 0.3:(10-15): 0.5.
4. the preparation method of lithium battery diaphragm according to claim 1, which is characterized in that the high boiling solvent is selected from two
One or more of first sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone；The inert gas is selected from helium, neon
One of gas, argon gas；The catalyst is in 2- furan boronic acid, three (2,2,2- trifluoroethyl) borates, zinc chloride
It is one or more of.
5. the preparation method of lithium battery diaphragm according to claim 1, which is characterized in that condensation polymer described in step III,
N,N-dimethylformamide, Methanaminium, N,N,N-trimethyl-, fluoride mass ratio be (3-5): (15-25): 1.
6. the preparation method of lithium battery diaphragm according to claim 1, which is characterized in that with active described in step IV
The condensation polymer of hydroxyl, N-Methyl pyrrolidone, (±) -4- chlorostyrene epoxides, basic catalyst mass ratio be (3-
5):(10-15):1:0.5；The basic catalyst be selected from one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or
It is several.
7. the preparation method of lithium battery diaphragm according to claim 1, which is characterized in that chloro polycondensation described in step V
Object, N,N-dimethylformamide, 3- (dimethylamino) ethyl acrylate, sodium carbonate mass ratio be (3-5): (10-15): 1:
0.5；(dimethylamino) ethyl acrylate of 3- described in step VI modified condensation polymer, the nanometer calcium carbonate of surface modification, 2,7- naphthalene
The mass ratio of two mercaptan of base is 1:(0.1-0.2): 0.1；The mass ratio 1:(50- of polymeric membrane described in step VII, hydrochloric acid solution
80)。
8. the preparation method of lithium battery diaphragm according to claim 1, which is characterized in that the molten extruding process temperature is
250-350 DEG C, the temperature of heat setting process is 180-230 DEG C, setting time 25-35min.
9. the preparation method of lithium battery diaphragm according to claim 1, which is characterized in that the nano-sized carbon of the surface modification
The preparation method of sour calcium includes the following steps: to disperse nanometer calcium carbonate in ethyl alcohol, then thiopurine methyltransferase methyl two is added thereto
Ethoxysilane is stirred to react 4-6 hours at 50-60 DEG C, rear to be centrifuged, and is placed at 60-70 DEG C of vacuum oven and is dried 15-20
Hour, obtain the nanometer calcium carbonate of surface modification；The nanometer calcium carbonate, ethyl alcohol, thiopurine methyltransferase methyldiethoxysilane matter
Amount is than being (3-5): (10-15): 1.
10. a kind of lithium battery diaphragm, it is characterised in that: use the system such as the described in any item lithium battery diaphragms of claim 1-9
Preparation Method is prepared.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110600758A (en) * | 2019-10-24 | 2019-12-20 | 湖南辰砾新材料有限公司 | Fuel cell diaphragm and preparation method thereof |
| CN112831130A (en) * | 2020-12-31 | 2021-05-25 | 苏州市新广益电子有限公司 | Poly 4-methyl-1-pentene microporous membrane and preparation method thereof |
| CN113224461A (en) * | 2021-03-30 | 2021-08-06 | 深圳供电局有限公司 | High-temperature-resistant lithium ion battery diaphragm and preparation method and application thereof |
| CN113577554A (en) * | 2021-07-05 | 2021-11-02 | 溥畅(杭州)智能科技有限公司 | Separated fiber-based galvanic cell and preparation method thereof |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110600758A (en) * | 2019-10-24 | 2019-12-20 | 湖南辰砾新材料有限公司 | Fuel cell diaphragm and preparation method thereof |
| CN112831130A (en) * | 2020-12-31 | 2021-05-25 | 苏州市新广益电子有限公司 | Poly 4-methyl-1-pentene microporous membrane and preparation method thereof |
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| CN113224461A (en) * | 2021-03-30 | 2021-08-06 | 深圳供电局有限公司 | High-temperature-resistant lithium ion battery diaphragm and preparation method and application thereof |
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