CN107652430A - A kind of production method of the modified p-aramid fiber polymer dope of lithium ion battery plus-negative plate barrier film - Google Patents
A kind of production method of the modified p-aramid fiber polymer dope of lithium ion battery plus-negative plate barrier film Download PDFInfo
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- CN107652430A CN107652430A CN201710800004.1A CN201710800004A CN107652430A CN 107652430 A CN107652430 A CN 107652430A CN 201710800004 A CN201710800004 A CN 201710800004A CN 107652430 A CN107652430 A CN 107652430A
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- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
A kind of production method the present invention relates to lithium ion battery with both positive and negative polarity diagram modification p-aramid fiber polymer dope, modification by copolymerization is carried out to p-aramid fiber polymer by changing or introducing Third monomer.On the premise of the excellent physicochemical property of p-aramid fiber polymer is retained, make modified p-aramid fiber polymer that there is good mobility, beneficial to processing film forming；And modified p-aramid fiber Macroscopic single crystal is simple for process.Diaphragm for lithium ion battery made of the modification p-aramid fiber polymer dope prepared with the present invention, porosity is high, thermal shrinkage energy is good, while has higher ionic conductivity, good electrochemical stability, improves the safe application performance of battery.
Description
Technical field
The present invention relates to lithium ion battery and high polymer material production technical field, and in particular to a kind of lithium ion battery is used
The production method of both positive and negative polarity diagram modification p-aramid fiber polymer dope.
Background technology
As a kind of secondary energy sources of cleaning, lithium ion battery because with voltage is high, energy is big, memory-less effect, can be fast
The advantages that fast discharge and recharge, it is widely used in the fields such as portable type electronic product, electric automobile and energy-storage system, is current energy
The study hotspot of source domain.Lithium ion battery is mainly made up of both positive and negative polarity, barrier film, electrolyte.Its septation is in both positive and negative polarity material
Between material, because the film has the micropore of a large amount of tortuous insertions, ensure that electrolyte ion passes freely through to form charging and discharging circuit, when
When battery overcharges or temperature raises, barrier film is separated the both positive and negative polarity of battery by closed pore function, prevents short circuit.So as to reach
The conduction of barrier electric current, the effect for preventing battery overheat or even blast.The performance of barrier film determines internal resistance and the internal interface knot of battery
Structure, and then influence capacity, charge-discharge performance, cycle performance and the security performance of battery etc., therefore the quality of barrier film is to lithium ion
The combination property important of battery.
At present, commercial lithium-ion batteries barrier film is mainly polyolefin microporous film, such as Celgard companies of the U.S., Japan
The polyethylene films of the productions such as Asahi Kasei Corporation, polypropylene screen, polyethylene-polypropylene composite membrane etc..Polyolefin micropore barrier diaphragm has
The good advantage such as electrochemically stable performance and suitable mechanical strength, but there is also shortcomings：(1) electrolyte wetting property
Bad, liquid-keeping property is poor, limits the ionic conductivity of battery；(2) barrier film thermal stability is poor, when temperature is higher than 120 DEG C
Significant dimensional contraction occurs, is easily caused inside battery and short circuit occurs.These deficiencies limit lithium ion to a certain extent
The actual use of battery.Therefore, develop it is a kind of can be made ionic conductivity is high, thermal shrinkage can well and security performance is high
Diaphragm for lithium ion battery polymer is particularly important.
For aramid fiber, meta-aramid polymer is not easy because being dissolved in electrolyte as lithium ion battery separator material；
And p-aramid fiber polymer is preferential because turning into making lithium ion battery separator with the excellent physicochemical property such as solvent resistant, heat-resisting
The new material of consideration.But being undergone phase transition in the production process of p-aramid fiber polymer, final products exist in solid particulate form,
And the only a few strong protonic acid such as the concentrated sulfuric acid or benzene sulfonic acid is only only soluble in, post-production can not be carried out with the tape casting, this turns into contraposition
Aramid fiber polymeric compound materials application is in the biggest obstacle in lithium ion battery separator field.This patent methods described passes through modulation or introducing
Third monomer carries out modification by copolymerization to p-aramid fiber polymer, is retaining the premise of the excellent physicochemical property of p-aramid fiber polymer
Under so that modified p-aramid fiber polymer has good mobility, beneficial to processing film forming；And modified p-aramid fiber
Macroscopic single crystal is simple for process.
P-aramid fiber polymer：Undergone phase transition in the production process of p-aramid fiber polymer.In the twin-screw end reaction stage,
Twin-screw is used as reactor and extrusion equipment simultaneously.In this stage, pre-polymerization liquid is solid phase particles by liquid phase, gradually from pre-polymerization
Separate out in liquid, finally exist in solid particulate form.It is higher to equipment requirement and the reaction is successive reaction.
Modified p-aramid fiber polymer：The purpose for introducing Third monomer is to reduce the crystallinity of polymer, avoids polymerization anti-
Process is answered phase transformation occur.According to the response characteristic, using batch reactor：Kettle liner chuck, because being passed through medium in chuck
Difference and with heating and cooling abilities；Introduce compressed nitrogen reactive group is protected and transferred；Introduce vacuum tube
Deaeration processing is carried out to reacted stoste.Compared with p-aramid fiber polymer production before modified, the kettle is simultaneously as reaction
Kettle and deaeration kettle, simplify production technology, reduce requirement to equipment.
The content of the invention
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：
1) solution is prepared：Monomer A and monomer B are added in reactor, are pumped into solvent, be heated under nitrogen protection 30 DEG C~
80 DEG C, to dissolving, monomer A and monomer B total mol concentration is 0.30mol/L~0.60mol/L, monomer A and monomer B for stirring
Mol ratio is 1.00~2.33:1；
2) solution is cooled down：By step 1）Prepared solution is cooled to -15 DEG C~10 DEG C while stirring；
3) monomer C is added：Under -15 DEG C~10 DEG C, stirring condition, cool down in solution and add and monomer A, monomer B to step 2)
The monomer C of sum equimolar amounts；
4) lithium ion battery both positive and negative polarity diagram modification p-aramid fiber polymer dope is prepared：At -15 DEG C~10 DEG C, stirring condition
Under, 30min~45min is reacted, through deaeration, is cooled to room temperature, that is, obtains lithium ion battery both positive and negative polarity diagram modification contraposition virtue
Synthetic fibre polymer dope；
The monomer A is two kinds of p-phenylenediamine, one kind of adjacent chlorine p-phenylenediamine or arbitrary proportion；
The monomer B is two kinds of 3,4'- diaminodiphenyl ethers, one kind of 4,4'- diaminodiphenyl ethers or arbitrary proportion；
The monomer C is paraphthaloyl chloride；
The organic solvent is N,N-dimethylformamide（DMF）, DMAC N,N' dimethyl acetamide（DMAc）, 1-METHYLPYRROLIDONE
（NMP）In one kind or two kinds of arbitrary proportion.
Applied lithium ion battery is preferably power lithium-ion battery.
Step 4）Reaction temperature is -8 DEG C.
Invention has following advantageous effects：
1）According to the modification p-aramid fiber polymer dope of this patent methods described production, retaining, p-aramid fiber polymer is excellent
Physicochemical property on the premise of so that modified p-aramid fiber polymer has good mobility, beneficial to the tape casting process
Film forming；And modified p-aramid fiber Macroscopic single crystal is simple for process.
2）According to this patent methods described production modification p-aramid fiber polymer dope prepared by lithium ion battery every
Film, infiltrate in the electrolytic solution after film forming 72h without come off, pick up is up to 40%, it is believed that the membrane for polymer has excellent solvent resistant
Corrosivity, good interface stability and higher porosity；Transverse and longitudinal shrinkage factor is within 4%, and heat resistanceheat resistant shrinkage is good, simultaneously
Mechanical strength meets the requirement of cell assembling processes.
Embodiment
The specific embodiment of the present invention is given below.These specific embodiments are only used for being further discussed below the present invention, not
Limit the claims of the present patent application.The method or step that technical staff of the same trade or business is carried out to it are improved, and are equally fallen
Enter in the protection domain of this patent.
Embodiment 1
1) solution is prepared：By monomer A（Adjacent chlorine p-phenylenediamine）With monomer B（4,4'- diaminodiphenyl ethers）It is added in reactor,
Solvent DMF is pumped into, is heated to 40 DEG C under nitrogen protection, stirring to dissolving.Monomer A and monomer B total mol concentration is
0.4mol/L, monomer A and monomer B mol ratio are 1:1.5；
2) solution is cooled down：By step 1）Prepared solution is cooled to -2 DEG C while stirring；
3) monomer C is added：Under -2 DEG C, stirring condition, cool down to add in solution to step 2) and rubbed with monomer A, monomer B sums etc.
The monomer C of your amount（Paraphthaloyl chloride）；
4) lithium ion battery both positive and negative polarity diagram modification p-aramid fiber polymer dope is prepared：At -15 DEG C~10 DEG C, stirring condition
Under, react 40min.Through deaeration, room temperature is cooled to, that is, obtains lithium ion battery both positive and negative polarity diagram modification p-aramid fiber polymer
Stoste.
Embodiment 2
1) solution is prepared：By monomer A（P-phenylenediamine）With monomer B（3,4'- diaminodiphenyl ethers）It is added in reactor, is pumped into
Solvent NMP, 50 DEG C is heated under nitrogen protection, stirring to dissolving.Monomer A and monomer B total mol concentration is 0.50mol/
L, monomer A and monomer B mol ratio are 2:1；
2) solution is cooled down：By step 1）Prepared solution is cooled to -5 DEG C while stirring；
3) monomer C is added：Under -5 DEG C, stirring condition, cool down to add in solution to step 2) and rubbed with monomer A, monomer B sums etc.
The monomer C (paraphthaloyl chloride) of your amount；
4) lithium ion battery both positive and negative polarity diagram modification p-aramid fiber polymer dope is prepared：At -15 DEG C~10 DEG C, stirring condition
Under, react 35min.Through deaeration, room temperature is cooled to, that is, obtains lithium ion battery both positive and negative polarity diagram modification p-aramid fiber polymer
Stoste.
Embodiment 3
1) solution is prepared：Monomer A and monomer B are added in reactor, solvent is pumped into, is heated to 60 DEG C under nitrogen protection,
Stirring is extremely dissolved.Monomer A and monomer B total mol concentration is that 0.60mol/L, monomer A and monomer B mol ratio are 1:1.6；
2) solution is cooled down：By step 1）Prepared solution is cooled to -8 DEG C while stirring；
3) monomer C is added：Under -8 DEG C, stirring condition, cool down to add in solution to step 2) and rubbed with monomer A, monomer B sums etc.
The monomer C of your amount；
4) lithium ion battery both positive and negative polarity diagram modification p-aramid fiber polymer dope is prepared：At -15 DEG C~10 DEG C, stirring condition
Under, react 45min.Through deaeration, room temperature is cooled to, that is, obtains lithium ion battery both positive and negative polarity diagram modification p-aramid fiber polymer
Stoste；
It is 1 that the monomer A, which is p-phenylenediamine with adjacent chlorine p-phenylenediamine according to mol ratio,:1 composition；
It is 1 that the monomer B, which is 3,4'- diaminodiphenyl ethers with 4,4'- diaminodiphenyl ethers according to mol ratio,:1 composition；
The monomer C is paraphthaloyl chloride；
The solvent is DMF and DMAc according to volume ratio is 1:1 composition.
Embodiment 4
1) solution is prepared：Monomer A and monomer B are added in reactor, solvent is pumped into, is heated to 50 DEG C under nitrogen protection,
Stirring is extremely dissolved.Monomer A and monomer B total mol concentration is that 0.60mol/L, monomer A and monomer B mol ratio are 1:2.1；
2) solution is cooled down：By step 1）Prepared solution is cooled to -10 DEG C while stirring；
3) monomer C is added：Under -10 DEG C, stirring condition, addition and monomer A, monomer B sums etc. in solution are cooled down to step 2)
The monomer C of mole；
4) lithium ion battery both positive and negative polarity diagram modification p-aramid fiber polymer dope is prepared：At -15 DEG C~10 DEG C, stirring condition
Under, react 30min.Through deaeration, room temperature is cooled to, that is, obtains lithium ion battery both positive and negative polarity diagram modification p-aramid fiber polymer
Stoste；
It is 2 that the monomer A, which is p-phenylenediamine with adjacent chlorine p-phenylenediamine according to mol ratio,:1 composition；
It is 1 that the monomer B, which is 3,4'- diaminodiphenyl ethers with 4,4'- diaminodiphenyl ethers according to mol ratio,:2 composition；
The monomer C is paraphthaloyl chloride；
The solvent is DMF and DMAc according to volume ratio is 1:2 composition.
Embodiment 5
1) solution is prepared：Monomer A and monomer B are added in reactor, solvent is pumped into, is heated to 60 DEG C under nitrogen protection,
Stirring is extremely dissolved.Monomer A and monomer B total mol concentration is that 0.30mol/L, monomer A and monomer B mol ratio are 1:1；
2) solution is cooled down：By step 1）Prepared solution is cooled to 5 DEG C while stirring；
3) monomer C is added：Under 5 DEG C, stirring condition, cool down to add in solution to step 2) and rubbed with monomer A, monomer B sums etc.
The monomer C of your amount；
4) lithium ion battery both positive and negative polarity diagram modification p-aramid fiber polymer dope is prepared：At -15 DEG C~10 DEG C, stirring condition
Under, react 45min.Through deaeration, room temperature is cooled to, that is, obtains lithium ion battery both positive and negative polarity diagram modification p-aramid fiber polymer
Stoste；
It is 3 that the monomer A, which is p-phenylenediamine with adjacent chlorine p-phenylenediamine according to mol ratio,:1 composition；
It is 1 that the monomer B, which is 3,4'- diaminodiphenyl ethers with 4,4'- diaminodiphenyl ethers according to mol ratio,:3 composition；
The monomer C is paraphthaloyl chloride；
The solvent is DMF and DMAc according to volume ratio is 1:3 composition.
Beneficial effects of the present invention are further illustrated with reference to experiment and accompanying drawing：
1 experiment：
1.1 experiment places：Aramid fiber Technical Research Center analysis detection research department of country of Yantai Tayho Advanced Materials Co., Ltd.
1.2 experimental method：
5.2989g p-phenylenediamine, 4.2050g 3 are weighed, 4'- diaminodiphenyl ethers are placed in 250ml there-necked flask；
NMP of the 120ml water content less than 150ppm is taken to be transferred in above-mentioned 250ml there-necked flasks as solvent, be passed through nitrogen protection；
By above-mentioned system warming while stirring to 70 DEG C, until two kinds of monomers are completely dissolved.Then it is cooled to -8 DEG C of stable stirrings；
14.2967g paraphthaloyl chlorides are added into above-mentioned system, rotating speed is promoted to 300r/min, keeps 40min；
Reaction product is transferred in wide-mouth bottle after deaeration and sealed, is down to room temperature naturally, produces the modification that solid content is 6.8%
P-aramid fiber polymer dope.
1.3 experimental result：
After being film-made with above-mentioned polymer dope, infiltrate in the electrolytic solution 72h without come off, pick up is up to 40%, it is believed that the polymer every
Film has excellent solvent resistant corrosivity, good interface stability and higher porosity；Transverse and longitudinal shrinkage factor within 4%,
Heat resistanceheat resistant shrinkage is good while mechanical strength meets the requirements of cell assembling processes.
P-aramid fiber polymer before modified is particulate matter, can not be applied to subsequent machining technology.
Fig. 1 is present invention specific implementation schematic flow sheet.
Claims (3)
- A kind of 1. lithium ion battery production method of both positive and negative polarity diagram modification p-aramid fiber polymer dope, it is characterised in that：1) solution is prepared：Monomer A and monomer B are added in reactor, are pumped into solvent, be heated under nitrogen protection 30 DEG C~ 80 DEG C, to dissolving, monomer A and monomer B total mol concentration is 0.30mol/L~0.60mol/L, monomer A and monomer B for stirring Mol ratio is 1.00~2.33:1；2) solution is cooled down：By step 1）Prepared solution is cooled to -15 DEG C~10 DEG C while stirring；3) monomer C is added：Under -15 DEG C~10 DEG C, stirring condition, cool down in solution and add and monomer A, monomer B to step 2) The monomer C of sum equimolar amounts；4) lithium ion battery both positive and negative polarity diagram modification p-aramid fiber polymer dope is prepared：At -15 DEG C~10 DEG C, stirring condition Under, 30min~45min is reacted, through deaeration, is cooled to room temperature, that is, obtains lithium ion battery both positive and negative polarity diagram modification contraposition virtue Synthetic fibre polymer dope；The monomer A is two kinds of p-phenylenediamine, one kind of adjacent chlorine p-phenylenediamine or arbitrary proportion；The monomer B is two kinds of 3,4'- diaminodiphenyl ethers, one kind of 4,4'- diaminodiphenyl ethers or arbitrary proportion；The monomer C is paraphthaloyl chloride；The organic solvent is N,N-dimethylformamide（DMF）, DMAC N,N' dimethyl acetamide（DMAc）, 1-METHYLPYRROLIDONE （NMP）In one kind or two kinds of arbitrary proportion.
- 2. the lithium ion battery as claimed in claim 1 production method of both positive and negative polarity diagram modification p-aramid fiber polymer dope, It is characterized in that：Applied lithium ion battery is preferably power lithium-ion battery.
- 3. the lithium ion battery as claimed in claim 1 production method of both positive and negative polarity diagram modification p-aramid fiber polymer dope, It is characterized in that：Step 4）Reaction temperature is -8 DEG C.
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| CN201710800004.1A CN107652430A (en) | 2017-09-07 | 2017-09-07 | A kind of production method of the modified p-aramid fiber polymer dope of lithium ion battery plus-negative plate barrier film |
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| CN201710800004.1A CN107652430A (en) | 2017-09-07 | 2017-09-07 | A kind of production method of the modified p-aramid fiber polymer dope of lithium ion battery plus-negative plate barrier film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110499542A (en) * | 2019-09-27 | 2019-11-26 | 中芳特纤股份有限公司 | A kind of para-aramid fiber and preparation method thereof |
| CN110729437A (en) * | 2019-05-21 | 2020-01-24 | 清华大学 | Preparation method of para-aramid lithium ion battery diaphragm |
| CN112694610A (en) * | 2020-12-16 | 2021-04-23 | 烟台泰和新材料股份有限公司 | Modified para-aramid polymer liquid, coating slurry, lithium battery diaphragm and preparation method thereof |
| CN114316257A (en) * | 2021-12-17 | 2022-04-12 | 山东聚芳新材料股份有限公司 | Modified para-aramid stock solution and preparation method and application thereof |
| WO2023159790A1 (en) * | 2022-02-24 | 2023-08-31 | 中材锂膜有限公司 | Lithium ion battery composite separator and preparation method therefor |
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| US20130115837A1 (en) * | 2011-11-09 | 2013-05-09 | Dale S. Kitchen | Nanofiber nonwovens and nanofiber nonwoven composites containing roped fiber bundles |
| CN103469343A (en) * | 2013-09-13 | 2013-12-25 | 东华大学 | Method for improving interaction force among microfibers in aramid fiber |
| CN105723030A (en) * | 2013-09-06 | 2016-06-29 | 帝人芳纶有限公司 | Separator paper for electrochemical cells |
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2017
- 2017-09-07 CN CN201710800004.1A patent/CN107652430A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130115837A1 (en) * | 2011-11-09 | 2013-05-09 | Dale S. Kitchen | Nanofiber nonwovens and nanofiber nonwoven composites containing roped fiber bundles |
| CN105723030A (en) * | 2013-09-06 | 2016-06-29 | 帝人芳纶有限公司 | Separator paper for electrochemical cells |
| CN103469343A (en) * | 2013-09-13 | 2013-12-25 | 东华大学 | Method for improving interaction force among microfibers in aramid fiber |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110729437A (en) * | 2019-05-21 | 2020-01-24 | 清华大学 | Preparation method of para-aramid lithium ion battery diaphragm |
| CN110499542A (en) * | 2019-09-27 | 2019-11-26 | 中芳特纤股份有限公司 | A kind of para-aramid fiber and preparation method thereof |
| CN112694610A (en) * | 2020-12-16 | 2021-04-23 | 烟台泰和新材料股份有限公司 | Modified para-aramid polymer liquid, coating slurry, lithium battery diaphragm and preparation method thereof |
| CN114316257A (en) * | 2021-12-17 | 2022-04-12 | 山东聚芳新材料股份有限公司 | Modified para-aramid stock solution and preparation method and application thereof |
| CN114316257B (en) * | 2021-12-17 | 2023-12-01 | 山东聚芳新材料股份有限公司 | Modified para-aramid stock solution and preparation method and application thereof |
| WO2023159790A1 (en) * | 2022-02-24 | 2023-08-31 | 中材锂膜有限公司 | Lithium ion battery composite separator and preparation method therefor |
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Application publication date: 20180202 |