CN110957514B - Strong-hydrophobicity ion exchange membrane and preparation method and application thereof - Google Patents
Strong-hydrophobicity ion exchange membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN110957514B CN110957514B CN201911226763.7A CN201911226763A CN110957514B CN 110957514 B CN110957514 B CN 110957514B CN 201911226763 A CN201911226763 A CN 201911226763A CN 110957514 B CN110957514 B CN 110957514B
- Authority
- CN
- China
- Prior art keywords
- ion exchange
- exchange membrane
- acid resin
- fumed silica
- prepared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Fuel Cell (AREA)
Abstract
The key point is that hydrophobic fumed silica is added into perfluorosulfonic acid resin solution through the action of siloxane stabilizer, and the ion exchange membrane is prepared through tape casting method. The effect is that the ion exchange membrane has strong apparent hydrophobicity, and water drops can freely roll on the surface of the membrane to show typical lotus leaf effect. By introducing the membrane with strong hydrophobicity into the all-vanadium redox flow battery system, the migration rate of water and vanadium ions passing through the ion exchange membrane can be greatly reduced, the coulombic efficiency of the battery is improved, and the swelling rate of the ion exchange membrane is reduced.
Description
Technical Field
The invention belongs to the field of polymer membrane materials, and particularly relates to a strong-hydrophobicity ion exchange membrane, a preparation method and application thereof.
Background
The ion exchange membrane is a key component of the all-vanadium redox flow battery system, and has the functions of isolating positive and negative electrolytes and conducting ions to enable the battery to form a complete closed loop. The ion exchange membranes used in the vanadium redox flow battery systems are mainly perfluorosulfonic acid ion exchange membranes, and the materials for producing the membranes are expensive, and the synthetic technology route is complicated, so that the cost is high, so that a large number of researchers try to recast the ion exchange membranes by treating broken waste membranes, leftover materials and used ion exchange membranes by certain means and then dissolving the treated waste membranes, leftover materials and used ion exchange membranes in specific solvents to prepare perfluorosulfonic acid resin solutions. Meanwhile, the perfluorosulfonic acid ion exchange membrane is not specially designed for an all-vanadium redox flow battery system, so that besides being high in price, the higher vanadium mobility and water mobility are also main disadvantages of the perfluorosulfonic acid ion exchange membrane. Therefore, the preparation of the ion exchange membrane with high vanadium resistance effect and low water mobility through the perfluorosulfonic acid resin solution becomes a main direction.
According to the invention, the hydrophobic fumed silica is introduced into the perfluorinated sulfonic acid resin ion exchange membrane system, so that the apparent hydrophobicity of the ion exchange membrane is greatly improved, the water mobility of the ion exchange membrane is greatly reduced, the membrane swelling rate is reduced, the vanadium blocking effect is excellent, and the coulomb efficiency of the battery is improved.
Disclosure of Invention
In order to make up the defects of the prior art, the invention provides a simple preparation method of the ion exchange membrane with strong hydrophobicity, and the ion exchange membrane prepared by the method has strong apparent hydrophobicity, so that the water mobility in the vanadium battery is reduced, the membrane swelling rate is reduced, the vanadium blocking effect is improved, and the coulombic efficiency of the battery is improved.
The technical scheme of the invention is as follows, the preparation method of the ion exchange membrane with strong hydrophobicity comprises the following steps:
(1) Dispersing hydrophobic fumed silica in a perfluorosulfonic acid resin solution, adding a certain amount of siloxane as a stabilizer, and strongly stirring until the system is completely transparent;
(2) Spreading the solution obtained in the step (1) on a horizontal glass plate, and preparing an ion exchange membrane by a tape casting method;
(3) And (3) soaking the ion exchange membrane in the step (2) in dilute sulfuric acid overnight, and then washing the ion exchange membrane with deionized water to obtain the strong-hydrophobicity ion exchange membrane.
The concentration of the perfluorinated sulfonic acid resin solution is 5-20wt%; the solvent of the perfluorinated sulfonic acid resin solution is dimethyl sulfoxide, N '-dimethylformamide, N' -dimethylOne of acetamides; the mass of the hydrophobic fumed silica is 2-8wt% of the content of the perfluorinated sulfonic acid resin in the perfluorinated sulfonic acid resin solution; the structure of the siloxane stabilizer is C n H 2n-1 -Si(OCH 3 ) 3 Or C n H 2n-1 -Si(OCH 2 CH 3 ) 3 Wherein n=2, 3 or 4, the mass ratio of the amount thereof to the hydrophobic fumed silica is (0.5 to 1.5): 1.
preferably, the hydrophobic fumed silica of the present invention is a HB-series hydrophobic fumed silica produced by Gibbs technology Co., ltd. In Guangzhou;
preferably, the HB-series hydrophobic fumed silica has a model number of HB-215.
Fumed silica is quite different from traditional silica and nanoparticles thereof, the traditional silica and nanoparticles thereof are only special in appearance and size, but the molecular structure of the silica is not changed; the fumed silica, particularly the hydrophobic fumed silica, is prepared by hydrolyzing chlorosilane in oxyhydrogen flame at high temperature (also called white carbon black) and connecting non-hydrolyzed methyl groups and other groups on the surface, and the hydrophilicity of the fumed silica can be greatly reduced.
The siloxane serving as a stabilizer can improve the solubility and stability of the hydrophobic fumed silica in the perfluorosulfonic acid resin solution, and is beneficial to forming a uniform solution.
The overnight soaking of the dilute sulfuric acid has the effect of fully hydrolyzing the residual siloxane on the surface of the membrane under the acidic condition, and the concentration of the siloxane is not particularly required.
It is another object of the present invention to protect the strongly hydrophobic ion exchange membrane prepared by the above method.
The third object of the invention is to protect the application of the ion exchange membrane with strong hydrophobicity prepared by the method in a flow battery.
The fourth purpose of the invention is to protect the application of the ion exchange membrane with strong hydrophobicity prepared by the method in the vanadium redox flow battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a novel method for preparing a strong-hydrophobicity ion exchange membrane by using a perfluorinated sulfonic acid resin solution, which has simple preparation process and low price of used auxiliary materials and is suitable for large-scale production;
(2) The ion exchange membrane with strong hydrophobicity prepared by the invention has strong apparent hydrophobicity, and water drops and sulfuric acid system vanadium electrolyte drops can freely roll on the surface of the membrane to show typical lotus leaf effect;
(3) The membrane with strong hydrophobicity is introduced into the all-vanadium redox flow battery system, so that the migration rate of water and vanadium ions passing through the ion exchange membrane can be greatly reduced, the coulombic efficiency of the battery is improved, and the swelling rate of the ion exchange membrane is reduced.
Detailed Description
The present invention is described in detail below by way of specific examples, but the scope of the present invention is not limited thereto. Unless otherwise specified, the experimental methods employed in the present invention are conventional, and the experimental equipment, materials, reagents, etc. used may be purchased from chemical companies or suppliers.
The instrument used for the contact angle test in the invention is an OCA50AF full-automatic optical contact angle tester manufactured by DataPhysics company of Germany, and in the test result, the larger the contact angle is, the better the apparent hydrophobicity is.
The swelling ratio (or the dimensional change rate) of the ion exchange membrane is tested by referring to the dimensional change rate test method in the energy industry standard NB/T42080-2016 ion conductive film test method for vanadium redox flow batteries of the people's republic of China.
All vanadium redox flow battery performance test conditions of ion exchange membrane: at a current density of 80mA/cm 2 Under the condition of charge and discharge experiment, charging to 1.55V, discharging to 1.00V, using graphite carbon felt produced by Beijing Jing Long carbon technology Co., ltd as reaction electrode, the effective working area of the electrode is 48cm 2 The positive and negative electrolyte is VO respectively 2+ /VO 2 + And V 2+ /V 3+ The battery operating temperature was 37 ℃.
The self-discharge time test of the battery is to disconnect an external liquid path from the battery when the battery is charged to 1.55V, and the battery voltage is reduced to 1.20V, because the self-discharge of the battery is mainly caused by the migration of vanadium ions through the ion membrane, the vanadium resistance of the ion exchange membrane can be judged through the self-discharge, namely, the longer the self-discharge time is, the better the vanadium resistance effect is.
Example 1
5g of hydrophobic fumed silica (HB-215) and 5g of vinyltriethoxysilane are dispersed in 1000g of dimethyl sulfoxide solution (concentration 10 wt%) of perfluorosulfonic acid resin, and the dispersion is carried out by a dispersing machine until the solution is in a uniform transparent system, so as to form a casting solution; then spreading the obtained casting film liquid on the surface of a smooth glass plate, and preparing an ion exchange film with the thickness of 50um by a tape casting method; and finally, soaking the prepared ion exchange membrane in 2mol/L dilute sulfuric acid overnight, taking out, and cleaning the surface with deionized water to prepare the ion exchange membrane with strong hydrophobicity.
In this example, the mass of the hydrophobic fumed silica is 5% of the mass of the perfluorosulfonic acid resin, and the mass ratio of the siloxane to the hydrophobic fumed silica is 1:1.
example 2
The concentration of the dimethyl sulfoxide solution of the perfluorosulfonic acid resin was changed from 10wt% to 5wt%, and the amounts of other substances were all in the same proportion as in example 1, to prepare a strongly hydrophobic ion exchange membrane having a thickness of 50. Mu.m.
Example 3
The concentration of the dimethyl sulfoxide solution of the perfluorosulfonic acid resin was changed from 10wt% to 20wt%, and the amounts of other substances were all in the same proportion as in example 1, to prepare a strongly hydrophobic ion exchange membrane having a thickness of 50. Mu.m.
Example 4
2g of hydrophobic fumed silica (HB-215) and 1g of vinyltriethoxysilane are dispersed in 1000g of dimethyl sulfoxide solution (concentration 10 wt%) of perfluorosulfonic acid resin, and the dispersion is carried out by a dispersing machine until the solution is in a uniform transparent system, so as to form a casting solution; then spreading the obtained casting film liquid on the surface of a smooth glass plate, and preparing an ion exchange film with the thickness of 50um by a tape casting method; and finally, soaking the prepared ion exchange membrane in 2mol/L dilute sulfuric acid overnight, taking out, and cleaning the surface with deionized water to prepare the ion exchange membrane with strong hydrophobicity.
In this example, the mass of the hydrophobic fumed silica was 2% of the mass of the perfluorosulfonic acid resin, and the mass ratio of the siloxane to the hydrophobic fumed silica was 0.5:1.
example 5
8g of hydrophobic fumed silica (HB-215) and 12g of vinyltriethoxysilane are dispersed in 1000g of dimethyl sulfoxide solution (concentration 10 wt%) of perfluorosulfonic acid resin, and the dispersion is carried out by a dispersing machine until the solution is in a uniform transparent system, so as to form a casting solution; then spreading the obtained casting film liquid on the surface of a smooth glass plate, and preparing an ion exchange film with the thickness of 50um by a tape casting method; and finally, soaking the prepared ion exchange membrane in 2mol/L dilute sulfuric acid overnight, taking out, and cleaning the surface with deionized water to prepare the ion exchange membrane with strong hydrophobicity.
In this example, the mass of the hydrophobic fumed silica was 8% of the mass of the perfluorosulfonic acid resin, and the mass ratio of the siloxane to the hydrophobic fumed silica was 1.5:1.
example 6
The procedure of example 1 was repeated except that the stabilizer was changed from vinyltriethoxysilane to isopropyltrimethoxysilane and the solvent of the perfluorosulfonic acid resin solution was changed from dimethyl sulfoxide to N, N' -dimethylformamide.
Example 7
The procedure of example 1 was repeated except that the stabilizer was changed from vinyltriethoxysilane to isobutyltriethoxysilane and the solvent of the perfluorosulfonic acid resin solution was changed from dimethyl sulfoxide to N, N' -dimethylacetamide.
Comparative example 1
Without adding hydrophobic fumed silica to the system, the other conditions were the same as in example 1, and a50 um ion exchange membrane was prepared.
TABLE 1 Performance data for ion exchange membranes prepared in examples 1-7 and comparative example 1
As can be seen from the data of examples and comparative examples in table 1, the contact angle of water drops on the ion exchange membrane incorporating the hydrophobic fumed silica is significantly improved, the swelling rate is significantly reduced, and the coulombic efficiency in the cell performance is significantly improved, the self-discharge time is significantly prolonged, which means that the introduction of the hydrophobic fumed silica significantly improves the hydrophobicity and vanadium resistance of the ion exchange membrane, and from examples 1,4,5, the more the amount of hydrophobic fumed silica incorporated in the perfluorosulfonic acid resin, the more remarkable the hydrophobic effect thereof. It can be seen from examples 1,2 and 3 that the hydrophobicity of the film surface is only related to the proportion of hydrophobic fumed silica incorporated in the film, and the properties are similar under the same proportion conditions; as can be seen from examples 1,6 and 7, similar effects can be achieved in membrane performance using different stabilizers when using perfluorosulfonic acid resin solutions of different solvents.
While the invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. The preparation method of the ion exchange membrane with strong hydrophobicity is characterized by comprising the following steps:
s1, dispersing hydrophobic fumed silica in a perfluorosulfonic acid resin solution, wherein the solvent of the perfluorosulfonic acid resin solution is one of dimethyl sulfoxide, N '-dimethylformamide and N, N' -dimethylacetamide, and the perfluorosulfonic acid resin solution is prepared from a perfluorosulfonic acid treeThe concentration of the fat solution is 5-20wt%, the mass of the hydrophobic fumed silica is 2-8wt% of the content of the perfluorinated sulfonic acid resin in the perfluorinated sulfonic acid resin solution, siloxane is added into the solution as a stabilizer, and the mass ratio of the siloxane to the hydrophobic fumed silica is (0.5-1.5): 1, the siloxane stabilizer has the structure C n H 2n-1 -Si(OCH 3 ) 3 Or C n H 2n-1 -Si(OCH 2 CH 3 ) 3 Wherein n=2, 3 or 4, stirring until the system is completely transparent to obtain a casting solution;
s2, the obtained casting film liquid is flatly paved on the surface of a smooth glass plate, and an ion exchange film is prepared by a tape casting method;
s3, soaking the prepared ion exchange membrane in dilute sulfuric acid overnight, and then washing with deionized water to obtain the ion exchange membrane with strong hydrophobicity.
2. A strongly hydrophobic ion exchange membrane prepared by the method of claim 1.
3. Use of the strongly hydrophobic ion exchange membrane of claim 2 in a flow battery.
4. The use of the strongly hydrophobic ion exchange membrane of claim 2 to improve the vanadium rejection in an all-vanadium flow battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911226763.7A CN110957514B (en) | 2019-12-04 | 2019-12-04 | Strong-hydrophobicity ion exchange membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911226763.7A CN110957514B (en) | 2019-12-04 | 2019-12-04 | Strong-hydrophobicity ion exchange membrane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110957514A CN110957514A (en) | 2020-04-03 |
| CN110957514B true CN110957514B (en) | 2023-04-25 |
Family
ID=69979707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911226763.7A Active CN110957514B (en) | 2019-12-04 | 2019-12-04 | Strong-hydrophobicity ion exchange membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110957514B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101773793A (en) * | 2009-12-07 | 2010-07-14 | 山东东岳神舟新材料有限公司 | SiO2/perfluorinated sulfonic resin compound proton exchange membrane and preparation method thereof |
| CN102437349A (en) * | 2011-12-10 | 2012-05-02 | 中国科学院金属研究所 | Ionic liquid reinforced membrane for all-vanadium redox flow battery and preparation method thereof |
| CN104332642A (en) * | 2014-09-09 | 2015-02-04 | 哈尔滨工业大学（威海） | Polytetrafluoroethylene-based ion exchange membrane for vanadium batteries, and its making method |
| CN110148770A (en) * | 2019-05-09 | 2019-08-20 | 朝阳华鼎储能技术有限公司 | A kind of structure regulating method of perfluorosulfonic acid proton exchange film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004075895A (en) * | 2002-08-20 | 2004-03-11 | Jsr Corp | Proton-conductive resin composition, its preparation process and proton-conductive film |
| KR101142235B1 (en) * | 2010-01-28 | 2012-05-24 | 금오공과대학교 산학협력단 | High molecular nano complexe membrane for DMFC, Membrane electrode assembly containg that, and Direct methanol fuel cell |
-
2019
- 2019-12-04 CN CN201911226763.7A patent/CN110957514B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101773793A (en) * | 2009-12-07 | 2010-07-14 | 山东东岳神舟新材料有限公司 | SiO2/perfluorinated sulfonic resin compound proton exchange membrane and preparation method thereof |
| CN102437349A (en) * | 2011-12-10 | 2012-05-02 | 中国科学院金属研究所 | Ionic liquid reinforced membrane for all-vanadium redox flow battery and preparation method thereof |
| CN104332642A (en) * | 2014-09-09 | 2015-02-04 | 哈尔滨工业大学（威海） | Polytetrafluoroethylene-based ion exchange membrane for vanadium batteries, and its making method |
| CN110148770A (en) * | 2019-05-09 | 2019-08-20 | 朝阳华鼎储能技术有限公司 | A kind of structure regulating method of perfluorosulfonic acid proton exchange film |
Non-Patent Citations (2)
| Title |
|---|
| "全钒氧化还原液流电池Nafion/SiO2复合膜的研究";柳东东等;《电化学》;20101130(第16卷第4期);第455-459页 * |
| Chi Hoon Park等."Nafion®nanocomposite membranes: Effect of fluorosurfactants on hydrophobic silica nanoparticle dispersion and direct methanol fuel cell performance".《Journal of Power Sources》.2009,第194卷第646-654页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110957514A (en) | 2020-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105789668A (en) | Preparation method of metal-organic framework material/polymer composite proton exchange membrane | |
| CN108365262A (en) | A kind of 3D networks hybrid inorganic-organic all solid state electrolyte and a kind of lithium secondary battery | |
| CN108976169B (en) | Imidazole ionic liquid and preparation method and application thereof | |
| CN108847498B (en) | Side chain type sulfonated polysulfone proton exchange membrane and preparation method thereof | |
| CN106887622A (en) | Fluorine-containing single ion conductor polymer dielectric and preparation method and application | |
| CN113437341B (en) | Amphoteric ion conduction membrane for flow battery and preparation method thereof | |
| CN102299353A (en) | Application of organic-inorganic composite membrane in acid electrolyte redox energy storage battery | |
| CN107317049A (en) | A kind of single ion conductive polymer electrolyte and its production and use | |
| Lou et al. | Highly efficient and low cost SPEEK/TiO2 nanocomposite membrane for vanadium redox flow battery | |
| Qian et al. | Synthesis and properties of anion exchange membranes with dense multi-cations and flexible side chains for water electrolysis | |
| KR100928718B1 (en) | Process for producing PEEK electrolyte membrane with uniform sulfuric acid group by organic solvent drying method | |
| Chen et al. | Polybenzimidazole and polyvinylpyrrolidone blend membranes for vanadium flow battery | |
| Ban et al. | Efficient and durable vanadium flow batteries enabled by high-performance fluorinated poly (aryl piperidinium) membranes | |
| CN106785031B (en) | A kind of preparation method of Pioloform, polyvinyl acetal base solid electrolyte | |
| CN108579472A (en) | A kind of separatory amphoteric ion membrane preparation method of biological medicine | |
| CN103319741B (en) | Preparation method of sulfonated polyimide/titanium dioxide composite proton conductive membrane | |
| CN108832178B (en) | Single ion polymer electrolyte and preparation method and application thereof | |
| Fang et al. | Hydrogen-bond-rich composite membrane with improved conductivity and selectivity for flow battery | |
| CN110957514B (en) | Strong-hydrophobicity ion exchange membrane and preparation method and application thereof | |
| CN113583243A (en) | Polymer electrolyte, preparation method of polymer electrolyte membrane and lithium ion battery | |
| CN107793564B (en) | Low-Tg polyether all-solid-state single-ion conductive polymer and preparation method thereof | |
| CN108461792B (en) | Composite alkaline polymer electrolyte membrane and preparation method and application thereof | |
| Ban et al. | Constructing high-performance fluoropoly (aryl piperidinium) ion exchange membranes via side-chain engineering for efficient vanadium flow batteries | |
| Cheng et al. | Polydopamine‐assisted in situ formation of dense aramid nanofibers layer on polyethylene separator for lithium‐ion battery | |
| CN115863923A (en) | Diaphragm and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |