CN114614196A - Ceramic particle pore-forming aramid fiber coated lithium ion battery composite diaphragm and preparation method thereof - Google Patents
Ceramic particle pore-forming aramid fiber coated lithium ion battery composite diaphragm and preparation method thereof Download PDFInfo
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- CN114614196A CN114614196A CN202210320515.4A CN202210320515A CN114614196A CN 114614196 A CN114614196 A CN 114614196A CN 202210320515 A CN202210320515 A CN 202210320515A CN 114614196 A CN114614196 A CN 114614196A
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- aramid fiber
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- lithium ion
- ion battery
- composite diaphragm
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- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 43
- 239000002245 particle Substances 0.000 title claims abstract description 40
- 239000000919 ceramic Substances 0.000 title claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 46
- 238000000576 coating method Methods 0.000 claims abstract description 46
- 238000005530 etching Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 230000001112 coagulating effect Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 230000015271 coagulation Effects 0.000 claims abstract description 6
- 238000005345 coagulation Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000007711 solidification Methods 0.000 claims abstract description 3
- 230000008023 solidification Effects 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000004760 aramid Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 229920003235 aromatic polyamide Polymers 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007756 gravure coating Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000035699 permeability Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a lithium ion battery composite diaphragm coated with ceramic particle pore-forming aramid fiber and a preparation method thereof, wherein the preparation method of the composite diaphragm comprises the following steps: adding aramid fiber and ceramic particles into an oily solvent and uniformly mixing to obtain a coating material; coating a coating material on one side of a base film, and immersing the coated base film into a coagulating bath for coagulation; and after solidification, immersing the base film into an etching solution for etching treatment, forming a porous aramid fiber coating on the surface of the base film, and finally drying to obtain a target product. According to the invention, ceramic particles are introduced as a coating pore-forming agent, and the pore size distribution of the porous aramid fiber coating can be adjusted by adjusting the particle size of the ceramic particles, so that the process is simple; in addition, when the ceramic particles are not completely etched, the residual ceramic particles can also play a skeleton supporting role in the coating, so that the heat resistance of the composite diaphragm is further improved, and the composite diaphragm with excellent performance is prepared.
Description
Technical Field
The invention relates to the technical field of lithium ion diaphragm coating, in particular to a lithium ion battery composite diaphragm coated with ceramic particle pore-forming aramid fiber and a preparation method thereof.
Background
In the lithium ion battery, the diaphragm is one of four main materials, and the main function of the diaphragm is to realize the transportation and conduction of lithium ions in the battery; and meanwhile, the electronic conduction is isolated, so that the short circuit caused by the short circuit of the anode and the cathode of the battery is prevented. The performance of the diaphragm not only determines the interfacial structure, internal resistance, capacity, circulation and other electric properties of the battery, but also plays a vital role in influencing the safety performance of the battery. The battery is different in kind and the separator used is different. In lithium battery systems, since an electrolyte is an oily solvent system, a separator material having oil resistance is required, and a polyolefin porous film having high strength and being thinned is generally used. The lithium ion battery diaphragm has a complex structure, is pulled to drive the whole body, and has the following main technical parameters: thickness, porosity, air permeability, thermal shrinkage, tensile strength, puncture strength, elongation, pore size and distribution, closed cell rupture temperature, contact angle, and the like.
The lithium ion battery diaphragm is formed by stretching a high molecular polymer, the mechanical strength-tensile strength performance of the diaphragm is realized in the stretching process, and meanwhile, the lithium ion battery diaphragm inevitably has a heat shrinkage phenomenon in the stretching direction. Due to the characteristics, the battery is easy to cause short circuit and further cause thermal runaway due to the contraction of the diaphragm at high temperature; on the other hand, under the condition that the diaphragm is pierced, the heat release of the short circuit causes the increase of the damaged area of the diaphragm, and the thermal runaway risk of the diaphragm is further accelerated.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a lithium ion battery composite diaphragm coated with ceramic particle pore-forming aramid fibers and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a lithium ion battery composite diaphragm coated with ceramic particle pore-forming aramid fiber comprises the following steps:
adding aramid fiber and ceramic particles into an oily solvent and uniformly mixing to obtain a coating material; preferably, the aramid fiber is at least one of meta-aramid fiber and para-aramid fiber; the D50 of the ceramic particle is 100-3000 nm; the ceramic particles are made of silicon dioxide or aluminum oxide; the mass ratio of the ceramic particles to the aramid fibers is 0.1-5: 1; the oily solvent comprises at least one of NMP, DMAC and acetone.
Coating a coating material on one side of a base film, and immersing the coated base film into a coagulating bath for coagulation; preferably, the base film is made of PP, PE, PET or PI; wherein the porosity of the base film is 30 to 60%.
And after solidification, immersing the base film into etching solution for etching treatment, forming a porous aramid fiber coating on the surface of the base film, and finally drying to obtain a target product. Preferably, the etching solution is hydrofluoric acid with the mass fraction of 2-80 wt%; the temperature of the etching treatment is 10-50 ℃.
The invention also discloses a lithium ion battery composite diaphragm coated with the ceramic particle pore-forming aramid fiber, which is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
compared with the traditional ceramic diaphragm, the aramid fiber has the oxygen limiting index (LOI) of more than 28, is a permanent flame-retardant fiber, has good thermal stability, can be continuously used at 205 ℃, can still maintain higher strength at the high temperature of more than 205 ℃, cannot be melted or dripped at the high temperature, and starts to be carbonized at the temperature of more than 370 ℃. Based on the flame-retardant and heat-resistant characteristics of aramid fibers, the aramid fibers and ceramic particles are dispersed in an oily solvent (NMP, DMAC and the like), then the aramid fibers and the ceramic particles are coated on a traditional PE, PP and other base films, and finally a porous aramid fiber coating is formed on the surface of the base film after the ceramic particles are removed by etching, so that the composite diaphragm with excellent heat resistance is prepared. If ceramic particles are not added, the aramid fiber is directly dissolved in an oily solvent, and when the aramid fiber is coated on a base film, the pore structure of the base film is blocked, so that the transmission of lithium ions in the battery cell is seriously influenced. According to the invention, ceramic particles are introduced to serve as a coating pore-forming agent, so that the composite diaphragm can ensure the free passage of lithium ions in the battery cell. The pore size distribution of the porous aramid fiber coating can be adjusted by adjusting the particle size of the ceramic particles, and the process is simple; it is worth mentioning that when the ceramic particles are not completely etched, the rest ceramic particles can also play a skeleton supporting role in the coating, so that the heat resistance of the composite diaphragm is further improved.
Detailed Description
The present invention will be further described with reference to the following examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention. The following examples and comparative examples all used commercially available starting materials that were commercially available.
It should be noted that aramid stock solutions used in the following examples and comparative examples are meta-aramid and base films are wet-process double-drawn PE base films; they are all commercially available products, which are commercially available.
Example 1
Adding 1 part of aramid fiber stock solution and 1 part of silicon dioxide powder (D50 is 200nm) into an NMP solvent, blending the mixture in proportion to enable the solid content of the mixture to reach 20%, and mechanically stirring for 2 hours to enable the mixture to be uniformly mixed to obtain the coating material. Uniformly coating the coating material on one side of a 9-micron base film in a micro-gravure coating mode, controlling the coating thickness to be about 3 microns, immersing the coated diaphragm into a coagulating bath formed by mixing 80 wt% of NMP and water for coagulating for 1h, taking out the diaphragm, immersing the coagulated diaphragm into an HF (10 wt%) aqueous solution, extracting and etching an organic solvent and silicon dioxide in the diaphragm coating at 30 ℃ for 5h, and finally drying the extracted diaphragm at 60 ℃ to obtain a composite diaphragm which is marked as a sample 1.
Comparative example 1
Adding 1 part of aramid fiber stock solution into an NMP solvent, blending the proportion to enable the solid content of the mixed solution to reach 20%, and mechanically stirring for 2 hours to enable the mixed solution to be uniformly mixed to obtain the coating material. Uniformly coating the coating material on one side of a 9-micron base film in a micro-gravure coating mode, controlling the coating thickness to be about 3 microns, immersing the coated diaphragm into a coagulating bath formed by mixing 80 wt% of NMP and water, coagulating for 1 hour, taking out, immersing the coagulated diaphragm into water, extracting an organic solvent in the diaphragm coating at 30 ℃ for 5 hours, and finally drying the extracted diaphragm at 60 ℃ to obtain a composite diaphragm which is marked as a sample 2.
Comparative example 2
The difference between example 2 and example 1 is that: after the coated diaphragm was coagulated by a coagulation bath, it was directly dried without etching with an HF aqueous solution, and the sample obtained was recorded as sample 3.
Example 2
Adding 1 part of aramid fiber stock solution and 1 part of silicon dioxide powder (D50 is 200nm) into an NMP solvent, blending the mixture in proportion to enable the solid content of the mixture to reach 20%, and mechanically stirring for 2 hours to enable the mixture to be uniformly mixed to obtain the coating material. Uniformly coating the coating material on one side of a 9-micron base film in a micro-gravure coating mode, controlling the coating thickness to be about 3 microns, immersing the coated diaphragm into a coagulating bath formed by mixing 80 wt% of NMP and water, coagulating for 1 hour, taking out, immersing the coagulated diaphragm into an HF (10 wt%) aqueous solution, extracting and etching an organic solvent and silicon dioxide in the diaphragm coating at 30 ℃ for 1 hour, and finally drying the extracted diaphragm at 60 ℃ to obtain the meta-aramid coated diaphragm. Denoted as sample 4.
Example 3
Adding NMP solvent into 1 part of aramid fiber stock solution and 1 part of silicon dioxide powder (D50 is 400nm), blending the mixture according to the proportion to enable the solid content of the mixture to reach 20%, and mechanically stirring for 2 hours to enable the mixture to be uniformly mixed to obtain the coating material. Uniformly coating the coating material on one side of a 9-micron base film in a micro-gravure coating mode, controlling the coating thickness to be about 3 microns, immersing the coated diaphragm into a coagulation bath formed by mixing 80 wt% of NMP and water for coagulation for 1 hour, taking out the diaphragm, immersing the coagulated diaphragm into an HF aqueous solution (10 wt%), extracting at 30 ℃, etching an organic solvent and silicon dioxide in the diaphragm coating for 5 hours, and finally drying the extracted diaphragm at 60 ℃ to obtain the meta-aramid coated diaphragm. Denoted as sample 5.
Example 4
Adding 1 part of aramid fiber stock solution and 2 parts of silicon dioxide powder (D50 is 200nm) into an NMP solvent, blending the mixture in proportion to enable the solid content of the mixture to reach 20%, and mechanically stirring for 2 hours to enable the mixture to be uniformly mixed to obtain the coating material. Uniformly coating the coating material on one side of a 9-micron base film in a micro-gravure coating mode, controlling the coating thickness to be about 3 microns, immersing the coated diaphragm into a coagulating bath formed by mixing 80 wt% of NMP and water, coagulating for 1 hour, taking out, immersing the coagulated diaphragm into an HF (10 wt%) aqueous solution, extracting and etching an organic solvent and silicon dioxide in the diaphragm coating at 30 ℃ for 5 hours, and finally drying the extracted diaphragm at 60 ℃ to obtain the meta-aramid coated diaphragm. Denoted as sample 6.
Samples 1 to 6 obtained in each example and comparative example and the 9 μm base film used in example 1 were subjected to a heat shrinkage at 150 ℃ for 1 hour, a breakdown voltage by the national standard method, a pore size distribution by a water pressure instrument, and a liquid absorption for 1 hour (national standard electrolyte) respectively. As shown in table 1, the meta-aramid coated membrane has lower thermal shrinkage performance, smaller hot needle puncture loss area and higher breakdown voltage; compared with the sample 1, the sample 2 without the added silicon dioxide has a greatly increased air permeability value, and the aperture is only 10nm, which shows that the silicon dioxide plays a good pore-forming role; compared with sample 1, sample 3 does not undergo etching treatment of HF aqueous solution, and because silicon dioxide also generates some gaps through space occupation, but the gaps are fewer and far smaller than the etched diaphragm, the ventilation value is particularly obviously increased; in sample 4, the silica portion remained due to the short HF etching time, resulting in further improvement in the thermal shrinkage of sample 4, but the gas permeability value was increased, as compared with sample 1; in comparison with sample 1, sample 5, which adjusted silica D50 to 400nm, had a significantly larger average pore size; sample 6 had an increased silica fraction compared to sample 1, resulting in a significant increase in its imbibing properties.
TABLE 1 results of physical Properties measurements of various samples
Remarking: the air permeability values in the above table refer to the time required for 100ml of air to permeate the membrane.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of a lithium ion battery composite diaphragm coated with ceramic particle pore-forming aramid fiber is characterized by comprising the following steps of: the method comprises the following steps:
adding aramid fiber and ceramic particles into an oily solvent and uniformly mixing to obtain a coating material;
coating a coating material on one side of a base film, and immersing the coated base film into a coagulating bath for coagulation;
and after solidification, immersing the base film into an etching solution for etching treatment, forming a porous aramid fiber coating on the surface of the base film, and finally drying to obtain a target product.
2. The preparation method of the lithium ion battery composite diaphragm coated with the ceramic particle pore-forming aramid fiber according to claim 1, which is characterized by comprising the following steps of: the aramid fiber is at least one of meta-aramid fiber and para-aramid fiber.
3. The preparation method of the lithium ion battery composite diaphragm coated with the ceramic particle pore-forming aramid fiber according to claim 1, which is characterized by comprising the following steps of: the D50 of the ceramic particle is 100-3000 nm; the ceramic particles are made of silicon dioxide or aluminum oxide.
4. The preparation method of the lithium ion battery composite diaphragm coated with the ceramic particle pore-forming aramid fiber according to claim 1, which is characterized by comprising the following steps of: the mass ratio of the ceramic particles to the aramid fibers is 0.1-5: 1.
5. the preparation method of the lithium ion battery composite diaphragm coated with the ceramic particle pore-forming aramid fiber according to claim 1, which is characterized by comprising the following steps of: the oily solvent comprises at least one of NMP, DMAC and acetone.
6. The preparation method of the lithium ion battery composite diaphragm coated with the ceramic particle pore-forming aramid fiber according to claim 1, which is characterized by comprising the following steps of: the base film is made of PP, PE, PET or PI.
7. The preparation method of the lithium ion battery composite diaphragm coated with the ceramic particle pore-forming aramid fiber according to claim 1, which is characterized by comprising the following steps of: the porosity of the base film is 30-60%.
8. The preparation method of the lithium ion battery composite diaphragm coated with the ceramic particle pore-forming aramid fiber according to claim 1, which is characterized by comprising the following steps of: the etching solution is hydrofluoric acid with the mass fraction of 2-80 wt%.
9. The preparation method of the lithium ion battery composite diaphragm coated with the ceramic particle pore-forming aramid fiber according to claim 1, which is characterized by comprising the following steps of: the temperature of the etching treatment is 10-50 ℃.
10. The utility model provides a compound diaphragm of lithium ion battery of ceramic particle pore-forming aramid fiber coating which characterized in that: which is prepared by the preparation method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210320515.4A CN114614196A (en) | 2022-03-29 | 2022-03-29 | Ceramic particle pore-forming aramid fiber coated lithium ion battery composite diaphragm and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210320515.4A CN114614196A (en) | 2022-03-29 | 2022-03-29 | Ceramic particle pore-forming aramid fiber coated lithium ion battery composite diaphragm and preparation method thereof |
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| CN114614196A true CN114614196A (en) | 2022-06-10 |
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| CN202210320515.4A Pending CN114614196A (en) | 2022-03-29 | 2022-03-29 | Ceramic particle pore-forming aramid fiber coated lithium ion battery composite diaphragm and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181522A (en) * | 2018-07-17 | 2019-01-11 | 河北金力新能源科技股份有限公司 | Aramid fiber coating liquid, lithium ion battery separator and preparation method thereof |
| CN109509855A (en) * | 2018-04-04 | 2019-03-22 | 京工新能(北京)科技有限责任公司 | A kind of aramid fiber ceramic diaphragm and its preparation method and application |
| CN110556496A (en) * | 2019-09-17 | 2019-12-10 | 中国科学院青岛生物能源与过程研究所 | High-safety composite diaphragm with high-temperature self-closing function and preparation method thereof |
| CN111900305A (en) * | 2019-05-06 | 2020-11-06 | 湖南鑫和美新能源科技有限公司 | Battery diaphragm, preparation method thereof and battery prepared from battery diaphragm |
-
2022
- 2022-03-29 CN CN202210320515.4A patent/CN114614196A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109509855A (en) * | 2018-04-04 | 2019-03-22 | 京工新能(北京)科技有限责任公司 | A kind of aramid fiber ceramic diaphragm and its preparation method and application |
| CN109181522A (en) * | 2018-07-17 | 2019-01-11 | 河北金力新能源科技股份有限公司 | Aramid fiber coating liquid, lithium ion battery separator and preparation method thereof |
| CN111900305A (en) * | 2019-05-06 | 2020-11-06 | 湖南鑫和美新能源科技有限公司 | Battery diaphragm, preparation method thereof and battery prepared from battery diaphragm |
| CN110556496A (en) * | 2019-09-17 | 2019-12-10 | 中国科学院青岛生物能源与过程研究所 | High-safety composite diaphragm with high-temperature self-closing function and preparation method thereof |
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