CN105762408A - Preparation method of diaphragm self-supporting gel electrolyte used for lithium sulphur battery - Google Patents
Preparation method of diaphragm self-supporting gel electrolyte used for lithium sulphur battery Download PDFInfo
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- CN105762408A CN105762408A CN201410788369.3A CN201410788369A CN105762408A CN 105762408 A CN105762408 A CN 105762408A CN 201410788369 A CN201410788369 A CN 201410788369A CN 105762408 A CN105762408 A CN 105762408A
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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
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- 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
The present invention relates to a preparation method of a diaphragm self-supporting gel electrolyte used for a lithium sulphur battery, the method is as follows: 1, electrolytic initiation of a prepolymerization electrolyte solution having fluidity, to be more specific, a prepared solution is placed in a two-electrode system, and charged until a constant voltage is obtained to form the prepolymerization electrolyte solution having fluidity; and 2, preparation of an in-situ polymerization diaphragm-supported gel electrolyte, to be more specific, the prepolymerization electrolyte solution prepared in the step 1 is poured into a container equipped with a diaphragm, sealed, and allowed to stand at room temperature to form the self-supporting gel electrolyte on the diaphragm. The prepolymerization electrolyte solution having fluidity prepared by electrolytic initiation polymerization is immersed the diaphragm to obtain the diaphragm supported polymer gel electrolyte; the diaphragm self-supporting gel electrolyte can be directly used in a lithium sulphur battery system without further processing, coulombic efficiency in lithium-sulphur battery cyclic process can be effectively improved, the battery specific capacity is improved, energy consumption is saved to the greatest extent, cost is reduced, and the diaphragm self-supporting gel electrolyte is suitable for commercial production of lithium-sulphur batteries.
Description
Technical field
The invention belongs to lithium-sulfur cell technical field, the preparation method particularly relating to a kind of lithium-sulfur cell barrier film self-supporting gel electrolyte.
Background technology
Lithium-sulfur cell is owing to having very high theoretical energy density (-2600Wh/kg), and has the features such as abundant raw material, low price, easy preparation and studied widely.But, lithium-sulfur cell, in charge and discharge process, has polysulfide (LixSy, such as Li2S8, Li2S6, Li2S4, Li2S3, Li2S2, Li2S) generating, these polysulfides are soluble in electrolyte and active substance can be caused to dissolve from electrode, cause that decay rapidly occurs in battery capacity；And, the polysulfide of dissolving can to negative pole, and react with the lithium of negative pole in the electrolytic solution in diffusion mobility, shuttles back and forth effect (shuttle) thus forming a kind of oxidoreduction, so the coulombic efficiency of lithium-sulfur cell is non-normally low.
For improving coulombic efficiency, attempt adding substantial amounts of lithium nitrate (LiNO in the electrolytic solution3), LiNO3Degraded can lithium metal surface formed passivation layer, stop polysulfide root (Sy 2-) with the reaction of lithium metal, it is prevented that the appearance of shuttle effect, thus improving coulombic efficiency.But, LiNO3Lithium-sulfur cell system is a kind of consumptive material, once the LiNO in electrolyte3After being exhausted, battery stops charge and discharge cycles immediately, and therefore the method does not have implementation in lithium-sulfur cell system.
Summary of the invention
The present invention solves that the technical problem existed in known technology provides a kind of coulombic efficiency being effectively improved in lithium-sulfur cell circulating battery process and specific capacity, energy efficient, preparation method with low cost, that be suitable to the lithium-sulfur cell barrier film self-supporting gel electrolyte of lithium-sulfur cell merchandized handling.
The present invention includes following technical scheme:
The lithium-sulfur cell preparation method of barrier film self-supporting gel electrolyte, is characterized in: include following preparation process:
Step 1: electrolytic initiation has the prepolymerization electrolyte of mobility
(1) adopt 1,3-dioxolanes (DOL) as solvent, adopt double; two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI) as lithium salts；Lithium salts is joined in solvent, dissolve and form saturated solution；
(2) solution that step 1 (1) is prepared is placed in two electrode systems, adopts battery test system by two electrodes with 0.01-1mA/cm2It is charged to 4.0-5.0V, then constant voltage 1-24h, forms the prepolymerization electrolyte with mobility；
Step 2: prepare the gel electrolyte of in-situ polymerization diaphragm support
Step 1 is made the prepolymerization electrolyte with mobility and pours into equipped with in the membrane vessel cut, seal, left at room temperature 1-15 days, take out barrier film, barrier film is formed the gel electrolyte of self-supporting, completes the preparation process of lithium-sulfur cell barrier film self-supporting gel electrolyte of the present invention.
The present invention can also adopt following technical measures:
Described barrier film is celgard barrier film.
The present invention has the advantage that and good effect:
The present invention adopts electrolysis polymerisation to reflect the prepolymerization electrolyte with mobility, barrier film is immersed in the electrolyte being in solution state, after room temperature stands, auto polymerization reaction original position in the surface and hole of barrier film of solvent occurs, the gel-form solid polymer electrolyte of the diaphragm support obtained；Need not process further, namely may be directly applied in lithium-sulfur cell system, not only be effectively improved the coulombic efficiency in lithium-sulfur cell circulating battery process, and improve the specific capacity of battery, also at utmost save energy consumption, reduced cost, be suitable to the merchandized handling of lithium-sulfur cell.
Accompanying drawing explanation
Fig. 1 is the coulombic efficiency of the lithium-sulfur cell barrier film self-supporting gel electrolyte that the present invention makes and currently known lithium-sulfur cell coulombic efficiency comparison diagram.
Detailed description of the invention
For the summary of the invention of the present invention, feature and effect can be disclosed further, describe in detail as follows especially exemplified by following instance.
The lithium-sulfur cell preparation method of barrier film self-supporting gel electrolyte, including following preparation process:
Step 1: electrolytic initiation has the prepolymerization electrolyte of mobility
(1) adopt 1,3-dioxolanes (DOL) as solvent, adopt double; two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI) as lithium salts；Lithium salts is joined in solvent, dissolve and form saturated solution；
(2) solution that step 1 (1) is prepared is placed in two electrode systems, adopts battery test system by two electrodes with 0.01-1mA/cm2It is charged to 4.0-5.0V, then constant voltage 1-24h, forms the prepolymerization electrolyte with mobility；
Step 2: prepare the gel electrolyte of in-situ polymerization diaphragm support
Step 1 is made the prepolymerization electrolyte with mobility and pours into equipped with in the celgard membrane vessel cut, seal, left at room temperature 1-15 days, take out celgard barrier film, celgard barrier film is formed the gel electrolyte of self-supporting, completes the preparation process of lithium-sulfur cell barrier film self-supporting gel electrolyte of the present invention.
Adopt the original position electropolymerization gel electrolyte made of the embodiment of the present invention 1 and currently known electrolyte to make respectively and carry out coulombic efficiency test under the lithium-sulfur cell room temperature of same model, form comparison diagram as shown in Figure 1, as can be seen from Figure 1, the gel electrolyte that the present invention makes is made the coulombic efficiency of battery and is made the coulombic efficiency of battery far above currently known electrolyte.
Although above the preferred embodiments of the present invention being described; but the invention is not limited in above-mentioned detailed description of the invention; above-mentioned detailed description of the invention is merely schematic; it is not restrictive; those of ordinary skill in the art is under the enlightenment of the present invention; without departing under present inventive concept and scope of the claimed protection situation, it is also possible to make a lot of form.These belong within protection scope of the present invention.
Claims (2)
1. the lithium-sulfur cell preparation method of barrier film self-supporting gel electrolyte, it is characterised in that: include following preparation process:
Step 1: electrolytic initiation has the prepolymerization electrolyte of mobility
(1) adopt 1,3-dioxolanes (DOL) as solvent, adopt double; two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI) as lithium salts；Lithium salts is joined in solvent, dissolve and form saturated solution；
(2) solution that step 1 (1) is prepared is placed in two electrode systems, adopts battery test system by two electrodes with 0.01-1mA/cm2It is charged to 4.0-5.0V, then constant voltage 1-24h, forms the prepolymerization electrolyte with mobility；
Step 2: prepare the gel electrolyte of in-situ polymerization diaphragm support
Step 1 is made the prepolymerization electrolyte with mobility and pours into equipped with in the membrane vessel cut, seal, left at room temperature 1-15 days, take out barrier film, barrier film is formed the gel electrolyte of self-supporting, completes the preparation process of lithium-sulfur cell barrier film self-supporting gel electrolyte of the present invention.
2. the lithium-sulfur cell preparation method of barrier film self-supporting gel electrolyte according to claim 1, it is characterised in that: described barrier film is celgard barrier film.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410788369.3A CN105762408B (en) | 2014-12-17 | 2014-12-17 | The preparation method of lithium-sulfur cell diaphragm self-supporting gel electrolyte |
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| CN201410788369.3A CN105762408B (en) | 2014-12-17 | 2014-12-17 | The preparation method of lithium-sulfur cell diaphragm self-supporting gel electrolyte |
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| CN105762408A true CN105762408A (en) | 2016-07-13 |
| CN105762408B CN105762408B (en) | 2019-08-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116093426A (en) * | 2023-02-14 | 2023-05-09 | 武汉大学 | Electropolymerized gel electrolyte battery and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6537701B1 (en) * | 1998-09-03 | 2003-03-25 | Polyplus Battery Company, Inc. | Coated lithium electrodes |
| CN101983210A (en) * | 2008-04-28 | 2011-03-02 | 建筑研究和技术有限公司 | Method for initiating radical polymerizations |
| CN103258977A (en) * | 2013-04-23 | 2013-08-21 | 中南大学 | Method for preparing gel diaphragm cell by in-situ polymerization and prepared battery |
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2014
- 2014-12-17 CN CN201410788369.3A patent/CN105762408B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6537701B1 (en) * | 1998-09-03 | 2003-03-25 | Polyplus Battery Company, Inc. | Coated lithium electrodes |
| CN101983210A (en) * | 2008-04-28 | 2011-03-02 | 建筑研究和技术有限公司 | Method for initiating radical polymerizations |
| CN103258977A (en) * | 2013-04-23 | 2013-08-21 | 中南大学 | Method for preparing gel diaphragm cell by in-situ polymerization and prepared battery |
Non-Patent Citations (1)
| Title |
|---|
| J.S.FOOS ET AL: "（"Polydioxolane Polymer Electrolyte"", 《ELECTROCHEMICAL SCIENCE AND TECHNOLOGY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116093426A (en) * | 2023-02-14 | 2023-05-09 | 武汉大学 | Electropolymerized gel electrolyte battery and preparation method thereof |
| CN116093426B (en) * | 2023-02-14 | 2024-10-01 | 武汉大学 | Electropolymerized gel electrolyte battery and preparation method thereof |
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| CN105762408B (en) | 2019-08-27 |
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