CN113794033A - Diaphragm suitable for solid-state flexible chloride ion battery and preparation method - Google Patents
Diaphragm suitable for solid-state flexible chloride ion battery and preparation method Download PDFInfo
- Publication number
- CN113794033A CN113794033A CN202111049413.5A CN202111049413A CN113794033A CN 113794033 A CN113794033 A CN 113794033A CN 202111049413 A CN202111049413 A CN 202111049413A CN 113794033 A CN113794033 A CN 113794033A
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- China
- Prior art keywords
- polyvinyl alcohol
- solid
- ion battery
- diaphragm
- chloride
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 35
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 35
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- 238000005452 bending Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- 230000002335 preservative effect Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
Abstract
The invention provides a diaphragm suitable for a solid-state flexible chloride ion battery and a preparation method thereof, belonging to the field of batteries. The method comprises the following specific steps: putting polyvinyl alcohol into water, and stirring at high temperature until the polyvinyl alcohol is completely dissolved to form a polyvinyl alcohol solution. Adding tetramethylammonium chloride into the dissolved polyvinyl alcohol solution, and uniformly stirring while maintaining the dissolved polyvinyl alcohol to obtain a mixed solution. Stopping heating, pouring the obtained mixed solution into a glass mold, and naturally cooling to form a film. The invention is based on a polyvinyl alcohol high-temperature cooling film forming technology, and the diaphragm is based on a water system solvent, thereby being safe and environment-friendly. Meanwhile, the polyvinyl alcohol is low in price, the diaphragm is simple in manufacturing process, the cost of the battery is reduced, and large-scale popularization is facilitated.
Description
Technical Field
The invention relates to the field of batteries, and provides a flexible solid diaphragm suitable for a chloride ion battery.
Background
The chlorine ion battery is one of green power batteries, and the theoretical volume energy density of the battery is high (2500Wh L)-1) Low cost and good safety. Since seawater, minerals, salt lakes, etc. contain abundant chlorine resources, the chloride ion battery is also considered to be a chlorine ion batteryIs a potential "next generation" electrochemical storage device. Traditional chlorine ion battery is because there is the problem that anodal active material dissolves, and battery cycle life is poor, and meanwhile, traditional rigidity battery is compared to flexible battery and has great advantage, therefore the present market is higher to flexible battery's call, along with consumer electronics products such as cell-phone, wearable equipment develop to the direction of flexibilization gradually, the demand of market to flexible battery increases gradually.
In view of the above situation, we propose a novel chloride ion battery based on the adsorption of carbon materials to chloride ions, synthesize a flexible solid-state diaphragm and assemble the flexible chloride ion battery.
Disclosure of Invention
In order to solve the above problems, the present invention provides a flexible solid separator suitable for a chloride ion battery. The invention adopts a polyvinyl alcohol high-temperature cooling film-forming technology and tetramethylammonium chloride as an electrolyte solute to synthesize the stable, safe and good-performance flexible solid diaphragm.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a diaphragm suitable for a solid-state flexible chloride ion battery comprises the following steps:
(1) putting polyvinyl alcohol into water, and stirring at high temperature until the polyvinyl alcohol is completely dissolved to form a polyvinyl alcohol solution.
(2) Adding tetramethylammonium chloride into the dissolved polyvinyl alcohol solution, and uniformly stirring while maintaining the dissolved polyvinyl alcohol to obtain a mixed solution.
Further, the concentration of the tetramethylammonium chloride in the mixed solution is 2.5-7.5mol/L, preferably 5 mol/L. The mass ratio of the tetramethylammonium chloride to the polyvinyl alcohol in the mixed solution is 5.48:1-16.44: 1.
(3) Stopping heating, pouring the mixed liquid obtained in the step (2) into a glass mold, and naturally cooling to form a film.
The invention has the beneficial effects that: the invention is based on a polyvinyl alcohol high-temperature cooling film forming technology, and the diaphragm is based on a water system solvent, thereby being safe and environment-friendly. Meanwhile, the polyvinyl alcohol is low in price, the diaphragm is simple in manufacturing process, the cost of the battery is reduced, and large-scale popularization is facilitated. The flexible solid diaphragm is used for assembling the flexible chlorine ion battery, the battery is bent, folded, charged and discharged within the range of 0-180 degrees, the performance is stable, no mechanical damage exists, 20 LED bulbs (rated voltage: 1.8V) can be lightened by the battery through actual tests, and the flexible solid diaphragm has actual application value.
Drawings
FIG. 1 is a flow chart of the fabrication of a flexible solid diaphragm.
In fig. 2, (a) shows a charge/discharge curve of the battery at different bending angles, (b) is 0 °, (c) is 30 °, (d) is 60 °, (e) is 90 °, (f) is 120 °, (g) is 150 °, (h) is 180 °, and (i) shows a synthetic flexible solid electrolyte.
FIG. 3 is a graph of the bending of a battery at different angles and a picture of an illuminated Led bulb; (a) 0 °, (b) 30 °, (c) 60 °, (d) 90 °, (e) 120 °, (f) 150 °, (g) 180 °, (h) a picture in which the battery lights the Led bulb at a bending angle of 0 ° and (i) a picture in which the battery lights the Led bulb at a bending angle of 180 °.
Detailed Description
The present invention is further explained below.
The invention adopts a polyvinyl alcohol high-temperature cooling technology and tetramethylammonium chloride as an electrolyte. The high-temperature cooling film-forming process of the polyvinyl alcohol is simple to operate, the cost of the raw materials is low, the cost of the battery is greatly reduced, and the popularization and the application of the battery are facilitated. Meanwhile, the discovery that the film formed by the tetramethylammonium chloride and the polyvinyl alcohol has higher stability, because the reagent with water absorption and the polyvinyl alcohol can not form a film after being cooled at room temperature, and the tetramethylammonium chloride has water absorption and good film forming effect after being cooled shows that the tetramethylammonium chloride and the polyvinyl alcohol can reach new phase balance after being dissolved at high temperature, and the discovery provides important information for the research of the flexible chloride ion battery. The synthetic flow chart of the flexible solid diaphragm is shown in the attached figure 1, and the synthetic flexible solid diaphragm has the advantages of strong toughness, high conductivity, safety and environmental protection. Using the flexible membrane we assembled a flexible chloride ion battery, as shown in FIG. 2, performance tests were performed at 0-180 degree bends and angles. Meanwhile, as shown in fig. 3, the battery is tested in practical application under different bending angles, and the battery can light 20 LED bulbs under different bending angles.
Example 1
Adding 1g of polyvinyl alcohol into 20ml of deionized water, placing the mixture into a beaker, then transferring the beaker onto a constant-temperature magnetic heating stirrer through a preservative film sealing port, stirring at constant temperature of 100 ℃ until the polyvinyl alcohol is completely dissolved, then weighing 5.48g of tetramethylammonium chloride, placing the tetramethylammonium chloride into the solution, stirring for 20min to completely dissolve the tetramethylammonium chloride, preparing 2.5 mol/L electrolyte, turning off heating, and transferring the liquid into a glass culture dish to cool and form a film.
Example 2
Adding 1g of polyvinyl alcohol into 20ml of deionized water, placing the mixture into a beaker, then transferring the beaker onto a constant-temperature magnetic heating stirrer through a preservative film sealing port, stirring at a constant temperature of 100 ℃ until the polyvinyl alcohol is completely dissolved, then weighing 10.96g of tetramethylammonium chloride, placing the tetramethylammonium chloride into the solution, stirring for 20min to completely dissolve the tetramethylammonium chloride, preparing 5mol/L electrolyte, turning off heating, transferring the liquid into a glass culture dish, and cooling to form a film.
Example 3
Adding 1g of polyvinyl alcohol into 20ml of deionized water, placing the mixture into a beaker, then transferring the beaker onto a constant-temperature magnetic heating stirrer through a preservative film sealing port, stirring at a constant temperature of 100 ℃ until the polyvinyl alcohol is completely dissolved, then weighing 16.44g of tetramethylammonium chloride, placing the tetramethylammonium chloride into the solution, stirring for 20min to completely dissolve the tetramethylammonium chloride, preparing 7.5mol/L electrolyte, turning off heating, and transferring the liquid into a glass culture dish to cool and form a film.
Comparative example 1
Adding 1g of polyvinyl alcohol into 20ml of deionized water, placing the mixture into a beaker, sealing the beaker by using a preservative film, transferring the beaker onto a constant-temperature magnetic heating stirrer, stirring the mixture at a constant temperature of 100 ℃ until the polyvinyl alcohol is completely dissolved, weighing 5.349g of ammonium chloride, placing the ammonium chloride into the solution, stirring the ammonium chloride for 20min to completely dissolve the ammonium chloride, preparing 5mol/L electrolyte, turning off heating, transferring the liquid into a glass culture dish, and cooling the solution to form a film. It was found that the solvent became ammonium chloride and that a large amount of white ammonium chloride powder precipitated after the solution was cooled, and the separator became very brittle and did not form a flexible separator. This means that not all reagents will form a flexible membrane in this way.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (5)
1. A preparation method of a diaphragm suitable for a solid-state flexible chloride ion battery is characterized by comprising the following steps:
(1) putting polyvinyl alcohol into water, and stirring at high temperature until the polyvinyl alcohol is completely dissolved to form a polyvinyl alcohol solution;
(2) adding tetramethylammonium chloride into the dissolved polyvinyl alcohol solution, and uniformly stirring the solution while maintaining the dissolved polyvinyl alcohol to obtain a mixed solution;
(3) stopping heating, pouring the mixed liquid obtained in the step (2) into a glass mold, and naturally cooling to form a film.
2. The method of claim 1, wherein the mixed solution contains tetramethylammonium chloride at a concentration of 2.5-7.5 mol/L.
3. The method of claim 2, wherein the mixed solution contains tetramethylammonium chloride at a concentration of 5 mol/L.
4. The method for preparing the diaphragm suitable for the solid-state flexible chloride ion battery according to claim 1, 2 or 3, wherein the mass ratio of the tetramethylammonium chloride to the polyvinyl alcohol in the mixed solution is 5.48:1-16.44: 1.
5. A separator suitable for use in a solid-state flexible chloride ion battery, wherein said flexible solid-state separator is prepared by the method of any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111049413.5A CN113794033B (en) | 2021-09-08 | 2021-09-08 | Diaphragm suitable for solid-state flexible chloride ion battery and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111049413.5A CN113794033B (en) | 2021-09-08 | 2021-09-08 | Diaphragm suitable for solid-state flexible chloride ion battery and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113794033A true CN113794033A (en) | 2021-12-14 |
| CN113794033B CN113794033B (en) | 2022-05-10 |
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| Application Number | Title | Priority Date | Filing Date |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193821A (en) * | 1998-02-18 | 1998-09-23 | 中国科学院化学研究所 | Solid electrolyte and preparation and uses thereof |
| CN103333466A (en) * | 2013-06-20 | 2013-10-02 | 天津市凯华绝缘材料有限公司 | High-flexibility epoxy resin with interpenetrating network structure and synthetic method thereof |
| CN104513508A (en) * | 2013-09-30 | 2015-04-15 | 青岛德圣泰建筑安装工程有限公司 | Wear-resistant curable coating for walls |
| CN110099950A (en) * | 2016-12-07 | 2019-08-06 | 赛鹏科技有限公司 | Micro-structure ionic conduction composite material and application thereof |
-
2021
- 2021-09-08 CN CN202111049413.5A patent/CN113794033B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193821A (en) * | 1998-02-18 | 1998-09-23 | 中国科学院化学研究所 | Solid electrolyte and preparation and uses thereof |
| CN103333466A (en) * | 2013-06-20 | 2013-10-02 | 天津市凯华绝缘材料有限公司 | High-flexibility epoxy resin with interpenetrating network structure and synthetic method thereof |
| CN104513508A (en) * | 2013-09-30 | 2015-04-15 | 青岛德圣泰建筑安装工程有限公司 | Wear-resistant curable coating for walls |
| CN110099950A (en) * | 2016-12-07 | 2019-08-06 | 赛鹏科技有限公司 | Micro-structure ionic conduction composite material and application thereof |
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| Publication number | Publication date |
|---|---|
| CN113794033B (en) | 2022-05-10 |
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Effective date of registration: 20240516 Address after: 116011 No.106, Building 57A-1, Tongqing Street, Xigang District, Dalian City, Liaoning Province Patentee after: Dalian Xingyuan Liquid Flow Battery Co.,Ltd. Country or region after: China Address before: 116024 No. 2 Ling Road, Ganjingzi District, Liaoning, Dalian Patentee before: DALIAN University OF TECHNOLOGY Country or region before: China |