CN105762408B - The preparation method of lithium-sulfur cell diaphragm self-supporting gel electrolyte - Google Patents
The preparation method of lithium-sulfur cell diaphragm self-supporting gel electrolyte Download PDFInfo
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- CN105762408B CN105762408B CN201410788369.3A CN201410788369A CN105762408B CN 105762408 B CN105762408 B CN 105762408B CN 201410788369 A CN201410788369 A CN 201410788369A CN 105762408 B CN105762408 B CN 105762408B
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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
The present invention relates to a kind of lithium-sulfur cell preparation methods of diaphragm self-supporting gel electrolyte, step includes: that 1, electrolysis causes the prepolymerization electrolyte with mobility: the solution of preparation is placed in two electrode systems, constant pressure after charging forms the prepolymerization electrolyte with mobility；2, it prepares the gel electrolyte of in-situ polymerization diaphragm support: electrolyte made of step 1 is poured into equipped in membrane vessel, sealing is stood at room temperature, forms the gel electrolyte of self-supporting on diaphragm.The present invention reflects the prepolymerization electrolyte with mobility using electrolysis polymerisation, is dipped in diaphragm, the gel-form solid polymer electrolyte of obtained diaphragm support；It does not need to be further processed, that is, may be directly applied in lithium-sulfur cell system, not only effectively improve the coulombic efficiency during lithium-sulfur cell circulating battery, and improve the specific capacity of battery, energy consumption has also utmostly been saved, has been reduced costs, the merchandized handling suitable for lithium-sulfur cell.
Description
Technical field
The invention belongs to lithium-sulfur cell technical fields, more particularly to a kind of lithium-sulfur cell diaphragm self-supporting gel electrolyte
The preparation method of matter.
Background technique
Lithium-sulfur cell has abundant raw material, valence due to very high theoretical energy density (- 2600Wh/kg)
Lattice are cheap, are easy the features such as preparation and are widely studied.But lithium-sulfur cell has more vulcanizations in charge and discharge process
Object (LixSy, such as Li2S8, Li2S6, Li2S4, Li2S3, Li2S2, Li2S it) generates, these polysulfides, which are soluble in electrolyte, to be made
Viability substance dissolves abjection from electrode, leads to the decaying of battery capacity appearance rapidly；Moreover, the polysulfide of dissolution can be
Diffusion mobility reacts to cathode, and with the lithium of cathode in electrolyte, to form a kind of redox shuttle effect
(shuttle), so the coulombic efficiency of lithium-sulfur cell is very low.
To improve coulombic efficiency, a large amount of lithium nitrate (LiNO is added in trial in the electrolytic solution3), LiNO3Degradation can be in lithium
Metal surface forms passivation layer, prevents polysulfide root (Sy 2-) reacted with lithium metal, the appearance of shuttle effect is prevented, to mention
Coulombic efficiency is risen.But LiNO3It is a kind of consumptive substance in lithium-sulfur cell system, once the LiNO in electrolyte3
After being exhausted, battery stops charge and discharge cycles immediately, therefore this method does not have implementation in lithium-sulfur cell system.
Summary of the invention
The present invention is to solve technical problem present in well-known technique and provide one kind and effectively improve lithium-sulfur cell battery and follow
Coulombic efficiency and specific capacity during ring, energy saving is low in cost, the lithium-sulfur cell suitable for lithium-sulfur cell merchandized handling
With the preparation method of diaphragm self-supporting gel electrolyte.
The present invention includes following technical solution:
The preparation method of lithium-sulfur cell diaphragm self-supporting gel electrolyte, its main feature is that: including following preparation step:
Step 1: electrolysis causes the prepolymerization electrolyte with mobility
(1) solvent is used as using 1,3- dioxolanes (DOL), using bis- (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI)
As lithium salts；Lithium salts is added in solvent, dissolution forms saturated solution；
(2) by step 1 (1) prepare solution be placed in two electrode systems, use battery test system by two electrodes with
0.01-1mA/cm2It is charged to 4.0-5.0V, then constant pressure 1-24h, forms the prepolymerization electrolyte with mobility；
Step 2: preparing the gel electrolyte of in-situ polymerization diaphragm support
The prepolymerization electrolyte with mobility is made in step 1 to pour into equipped in the membrane vessel cut, is sealed, room
Temperature is lower to stand 1-15 days, takes out diaphragm, forms the gel electrolyte of self-supporting on diaphragm, complete lithium-sulfur cell diaphragm of the present invention
The preparation process of self-supporting gel electrolyte.
The present invention can also use following technical measures:
The diaphragm is celgard diaphragm.
The present invention has the advantage that and good effect:
The present invention reflects the prepolymerization electrolyte with mobility using electrolysis polymerisation, and diaphragm is immersed in and is in
In the electrolyte of solution state, after being stored at room temperature, the auto polymerization reaction of solvent occurs in situ in the surface of diaphragm and hole, obtains
The gel-form solid polymer electrolyte of the diaphragm support arrived；It does not need to be further processed, that is, may be directly applied in lithium-sulfur cell system,
The coulombic efficiency during lithium-sulfur cell circulating battery is not only effectively improved, and improves the specific capacity of battery, also
Energy consumption has utmostly been saved, has been reduced costs, the merchandized handling suitable for lithium-sulfur cell.
Detailed description of the invention
Fig. 1 is the coulombic efficiency and currently known lithium for the lithium-sulfur cell diaphragm self-supporting gel electrolyte that the present invention makes
Sulphur battery coulombic efficiency comparison diagram.
Specific embodiment
Further to disclose invention, features and effects of the invention, especially exemplified by following instance, detailed description are as follows.
The preparation method of lithium-sulfur cell diaphragm self-supporting gel electrolyte, including following preparation step:
Step 1: electrolysis causes the prepolymerization electrolyte with mobility
(1) solvent is used as using 1,3- dioxolanes (DOL), using bis- (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI)
As lithium salts；Lithium salts is added in solvent, dissolution forms saturated solution；
(2) by step 1 (1) prepare solution be placed in two electrode systems, use battery test system by two electrodes with
0.01-1mA/cm2It is charged to 4.0-5.0V, then constant pressure 1-24h, forms the prepolymerization electrolyte with mobility；
Step 2: preparing the gel electrolyte of in-situ polymerization diaphragm support
The prepolymerization electrolyte with mobility is made in step 1 to pour into the celgard membrane vessel for being equipped with and cutting,
Sealing stands 1-15 days at room temperature, takes out celgard diaphragm, and the gel electrolyte of self-supporting is formed on celgard diaphragm, complete
At the lithium-sulfur cell of the present invention preparation process of diaphragm self-supporting gel electrolyte.
The electropolymerization gel electrolyte in situ and currently known electrolyte produced using the embodiment of the present invention 1 make phase respectively
With coulombic efficiency test is carried out under the lithium-sulfur cell room temperature of model, comparison diagram as shown in Figure 1 is formed, as can be seen from Figure 1, system of the present invention
The coulombic efficiency of battery is made much higher than currently known electrolyte for the coulombic efficiency that battery is made in the gel electrolyte of work.
Although the preferred embodiment of the present invention is described above, the invention is not limited to above-mentioned specific
Embodiment, the above mentioned embodiment is only schematical, is not restrictive, those skilled in the art
Under the inspiration of the present invention, without breaking away from the scope protected by the purposes and claims of the present invention, it can also make very
It is multi-form.Within these are all belonged to the scope of protection of the present invention.
Claims (1)
1. the lithium-sulfur cell preparation method of diaphragm self-supporting gel electrolyte, it is characterised in that: including following preparation step:
Step 1: electrolysis causes the prepolymerization electrolyte with mobility
(1) solvent is used as using 1,3- dioxolanes (DOL), using bis- (trimethyl fluoride sulfonyl) imine lithium (LiTFSI) conducts
Lithium salts；Lithium salts is added in solvent, dissolution forms saturated solution；
(2) solution that step 1 (1) is prepared is placed in two electrode systems, uses battery test system by two electrodes with 0.01-
1mA/cm2It is charged to 4.0-5.0V, then constant pressure 1-24h, forms the prepolymerization electrolyte with mobility；
Step 2: preparing the gel electrolyte of in-situ polymerization diaphragm support
The prepolymerization electrolyte with mobility is made in step 1 to pour into the celgard membrane vessel for being equipped with and cutting, it is close
Envelope stands 1-15 days at room temperature, takes out diaphragm, forms the gel electrolyte of self-supporting on diaphragm, complete lithium-sulfur cell diaphragm
The preparation process of self-supporting gel electrolyte.
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| Application Number | Priority Date | Filing Date | Title |
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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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| Application Number | Priority Date | Filing Date | Title |
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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 CN105762408A (en) | 2016-07-13 |
| CN105762408B true CN105762408B (en) | 2019-08-27 |
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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 |
-
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 |
|---|
| （"Polydioxolane Polymer Electrolyte";J.S.Foos et al;《Electrochemical Science And Technology》;19870731;第134卷(第7期);第1724页右栏倒数第2段至第1726页左栏第1段 * |
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| CN105762408A (en) | 2016-07-13 |
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