CN110752407A - Lithium-sulfur battery electrolyte and lithium-sulfur battery - Google Patents
Lithium-sulfur battery electrolyte and lithium-sulfur battery Download PDFInfo
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- CN110752407A CN110752407A CN201810810845.5A CN201810810845A CN110752407A CN 110752407 A CN110752407 A CN 110752407A CN 201810810845 A CN201810810845 A CN 201810810845A CN 110752407 A CN110752407 A CN 110752407A
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- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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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
Abstract
The invention relates to a lithium-sulfur battery electrolyte, which comprises a lithium salt and an organic solvent, wherein the lithium salt comprises a lithium sulfate derivative shown as a general formula (1) and other lithium salts, and the general formula (1) is as follows:
Description
Technical Field
The invention belongs to the field of battery electrolyte materials, and particularly relates to a lithium-sulfur battery electrolyte and a lithium-sulfur battery.
Background
The lithium-sulfur battery is a lithium battery with elemental sulfur or a sulfur-containing material as a battery anode and metal lithium as a cathode. The theoretical discharge capacity of the lithium-sulfur battery can be calculated to be 1675mAh/g according to the electric quantity which can be provided by completely reducing the elemental sulfur of unit mass into the lithium sulfide, and the theoretical energy density is 2567 Wh/Kg.
However, the lithium sulfur battery has many problems in practical application, for example, the sulfur-containing material of the lithium sulfur battery can have a huge volume change during the charging and discharging processes, which will destroy the overall structure of the positive electrode plate, resulting in pulverization and falling off of the positive electrode material from the current collector during the circulation process. Meanwhile, polysulfide generated in the cycle generates a "shuttle effect", which causes a sharp drop in specific capacity and low coulombic efficiency, resulting in a decrease in cycle performance. More importantly, sulfur itself is nearly non-conductive, making conventional lithium sulfur batteries far from reaching their theoretical capacity.
The electrolyte is one of four main components of the lithium-sulfur battery and plays a key role in promoting the transmission of lithium ions. However, the organic solvent of the conventional lithium sulfur electrolyte merely maintains lithium ion transport although accounting for 90% of the total battery mass, and does not play a substantial role in further improving the capacity of the lithium sulfur battery. Meanwhile, in the circulation process of the lithium-sulfur battery with the traditional electrolyte, soluble polysulfide can shuttle between a positive electrode and a negative electrode, so that the basic problem of poor long-term circulation of the lithium-sulfur battery cannot be well solved.
Disclosure of Invention
The invention aims to provide a lithium-sulfur battery electrolyte and a lithium-sulfur battery, which can improve initial capacity and normal-temperature cycle performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
an object of the present invention is to provide an electrolyte for a lithium-sulfur battery comprising a lithium salt and an organic solvent, the lithium salt comprising a lithium sulfate derivative represented by the general formula (1) and other lithium salts,
the general formula (1) is as follows:
wherein L is an alkyl group having 1 to 12 carbon atoms which is substituted or unsubstituted with halogen, an alkoxy group having 2 to 12 carbon atoms which is substituted or unsubstituted with halogen, an aryl group having 6 to 12 carbon atoms which is substituted or unsubstituted with halogen, an alkenyl group having 2 to 7 carbon atoms which is substituted or unsubstituted with halogen, an alkynyl group having 3 to 8 carbon atoms which is substituted or unsubstituted with halogen, an organic group having 1 to 6 carbon atoms which contains sulfur atoms which is substituted or unsubstituted with halogen, an organic group having 4 to 10 carbon atoms which contains silicon atoms which is substituted or unsubstituted with halogen, an organic group having 2 to 7 carbon atoms which contains cyano groups which is substituted or unsubstituted with halogen, an organic group having 2 to 12 carbon atoms which contains phosphorus atoms which is substituted or unsubstituted with halogen, wherein the halogen substitution is fully or partially substituted;
the other lithium salt is one or more of lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perfluoroalkyl sulfonate and lithium perfluoroalkyl sulfonyl chloride;
the molar mass ratio of the lithium sulfate derivative represented by the general formula (1) to the other lithium salt is 1: 0.3-6.
Preferably, the lithium sulfate derivative represented by the general formula (1) is lithium methylsulfate, lithium ethylsulfate, lithium propylsulfate, lithium butylsulfate, lithium pentylsulfate, lithium hexylsulfate, lithium heptylsulfate, lithium octylsulfate, lithium isopropylsulfate, lithium sec-butylsulfate, lithium trifluoromethylsulfate, lithium 2,2, 2-trifluoroethylsulfate, lithium 2,2,3, 3-tetrafluoropropylsulfate, lithium 1,1,1,3,3, 3-hexafluoro-2-propylsulfate, lithium methoxyethylsulfate, lithium ethoxyethylsulfate, lithium methoxypropylsulfate, lithium phenylsulfate, lithium 4-methylphenylsulfate, lithium 4-fluorophenylsulfate, lithium perfluorophenylsulfate, lithium vinylsulfate, lithium allylsulfate, lithium propargylsulfate, lithium 1-oxo-1- (2-propynyloxy) propan-2-ylsulfonate, One or more of lithium 2- (trimethylsilyl) ethyl sulfate, lithium 2-cyanoethyl sulfate and lithium 1, 3-dicyanopropyl-2-yl sulfate.
Further preferably, the lithium sulfate derivative represented by the general formula (1) is one or more of lithium ethyl sulfate, lithium trifluoromethyl sulfate and lithium 2-cyanoethyl sulfate.
Preferably, the molar mass ratio of the lithium sulfate derivative represented by the general formula (1) to the other lithium salt is 1:1 to 3, more preferably 1:2 to 3, and still more preferably 1:2 to 2.5.
Preferably, the concentration of the lithium salt in the electrolyte is 0.1-5 mol/L, more preferably 0.5-2 mol/L, and still more preferably 0.8-1.5 mol/L.
Preferably, the organic solvent comprises a first solvent and a second solvent, wherein the first solvent is one or more of 1, 3-dioxolane, 1, 4-dioxane and 1, 1-dimethoxyethane, and the second solvent is one or more of ethylene glycol dimethyl ether and/or diethylene glycol dimethyl ether.
Further preferably, the volume ratio of the first solvent to the second solvent is 1: 0.5-1.5.
More preferably, the volume ratio of the first solvent to the second solvent is 1: 0.8-1.2.
Preferably, the electrolyte further comprises an additive accounting for 0.1-5% of the total mass of the electrolyte.
More preferably, the additive accounts for 1-3% of the total mass of the electrolyte.
Further preferably, the additive is anhydrous lithium nitrate.
The invention also provides a lithium-sulfur battery, which comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the electrolyte is the lithium-sulfur battery electrolyte.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention enables the lithium sulfate derivative to be on the lithium metal through improving the components of the electrolyteThe lithium polysulfide can reduce the dissolution of the active material of the positive electrode, and is oxidized into elemental sulfur to deposit on the surface of the positive electrode during charging, so as to make up the dissolution loss of the active material of the positive electrode, and simultaneously, the lithium polysulfide further reacts to generate Li2S and Li2O，Li2S and Li2O can be enriched on the surface of the lithium metal to form a protective film, the strength of an SEI film is enhanced, the generation of lithium dendrites is inhibited, and the initial capacity and the cycle life of the lithium-sulfur battery are improved.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Electrolyte solution: under the protection of argon, respectively measuring 1, 3-dioxolane (DOL, a first solvent) and ethylene glycol dimethyl ether (DME, a second solvent) with equal volumes in a glove box, and uniformly mixing; adding anhydrous lithium nitrate additive (LiNO) accounting for 2 wt% of the total mass of the electrolyte3)
Other components and amounts of the electrolyte are shown in table 1.
Pole piece: mixing 2g of acetylene black with 7g of sublimed sulfur powder, and performing ball milling for 6 hours at the rotating speed of 400rpm to obtain uniformly mixed powder MCMB/S; 4g of the ball-milled mixture MCMB/S and 0.5g of acetylene black were added to 0.1ml of NMP and stirred at 1000rpm for 2 hours at room temperature; then adding polyvinylidene fluoride binder (PVDF), and stirring at the speed of 1000r/min overnight to obtain prepared slurry;
uniformly coating the slurry on an aluminum foil, drying at 80 ℃ for 12 hours, cutting into pole pieces with the diameter of 12mm, and putting into a glove box for later use;
the prepared positive electrode, the prepared metallic lithium negative electrode, the prepared separator and the prepared electrolytes in the examples and the comparative examples are assembled into a button cell in a glove box.
The prepared battery is subjected to constant current charge and discharge test at room temperature on a Land battery tester, the cut-off voltage is 1.6-2.8V, the test current is 0.1C (150mA/g), the cycle number is 100 times, and the test results are shown in Table 1.
TABLE 1
Therefore, the electrolyte of the lithium-sulfur battery prepared by the method can greatly improve the capacity of the common lithium-sulfur battery and greatly improve the cycle performance of the lithium-sulfur battery, and the electrolyte of the lithium-sulfur battery has very outstanding performance in the aspects of improving the capacity of the lithium-sulfur battery and improving the cycle performance of the lithium-sulfur battery.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (9)
1. A lithium-sulfur battery electrolyte comprising a lithium salt and an organic solvent, characterized in that: the lithium salt comprises a lithium sulfate derivative shown as a general formula (1) and other lithium salts,
the general formula (1) is as follows:
wherein L is an alkyl group having 1 to 12 carbon atoms which is substituted or unsubstituted with halogen, an alkoxy group having 2 to 12 carbon atoms which is substituted or unsubstituted with halogen, an aryl group having 6 to 12 carbon atoms which is substituted or unsubstituted with halogen, an alkenyl group having 2 to 7 carbon atoms which is substituted or unsubstituted with halogen, an alkynyl group having 3 to 8 carbon atoms which is substituted or unsubstituted with halogen, an organic group having 1 to 6 carbon atoms which contains a sulfur atom which is substituted or unsubstituted with halogen, an organic group having 4 to 10 carbon atoms which contains a silicon atom which is substituted or unsubstituted with halogen, an organic group having 2 to 7 carbon atoms which contains a cyano group which is substituted or unsubstituted with halogen, an organic group having 2 to 1 carbon atoms which is substituted or unsubstituted with halogen2, wherein the halogen substitution is a full or partial substitution;
the other lithium salt is one or more of bis (trifluoromethane) sulfonyl imide lithium, lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perfluoroalkyl sulfonate and perfluoroalkyl sulfonic acid acyl methyl lithium;
the molar mass ratio of the lithium sulfate derivative represented by the general formula (1) to the other lithium salt is 1: 0.3-6.
2. The lithium sulfur battery electrolyte of claim 1 wherein: the lithium sulfate derivative represented by the general formula (1) is lithium methylsulfate, lithium ethylsulfate, lithium propylsulfate, lithium butylsulfate, lithium pentylsulfate, lithium hexylsulfate, lithium heptylsulfate, lithium octylsulfate, lithium isopropylsulfate, lithium sec-butylsulfate, lithium trifluoromethylsulfate, lithium 2,2, 2-trifluoroethylsulfate, lithium 2,2,3, 3-tetrafluoropropylsulfate, lithium 1,1,1,3,3, 3-hexafluoro-2-propylsulfate, lithium methoxyethylsulfate, lithium ethoxyethylsulfate, lithium methoxypropylsulfate, lithium phenylsulfate, lithium 4-methylphenylsulfate, lithium 4-fluorophenylsulfate, lithium perfluorophenylsulfate, lithium vinylsulfate, lithium allylsulfate, lithium propargylsulfate, lithium 1-oxo-1- (2-propynyloxy) propan-2-ylsulfonate, One or more of lithium 2- (trimethylsilyl) ethyl sulfate, lithium 2-cyanoethyl sulfate and lithium 1, 3-dicyanopropyl-2-yl sulfate.
3. The lithium sulfur battery electrolyte of claim 1 wherein: the molar mass ratio of the lithium sulfate derivative represented by the general formula (1) to the other lithium salt is 1: 1-3.
4. The lithium sulfur battery electrolyte of any one of claims 1 to 3, wherein: the concentration of the lithium salt in the electrolyte is 0.1-5 mol/L.
5. The lithium sulfur battery electrolyte of claim 1 wherein: the organic solvent comprises a first solvent and a second solvent, wherein the first solvent is one or more of 1, 3-dioxolane, 1, 4-dioxane and 1, 1-dimethoxyethane, and the second solvent is one or more of ethylene glycol dimethyl ether and/or diethylene glycol dimethyl ether.
6. The lithium sulfur battery electrolyte of claim 5 wherein: the volume ratio of the first solvent to the second solvent is 1: 0.5-1.5.
7. The lithium sulfur battery electrolyte of claim 1 wherein: the electrolyte also comprises an additive accounting for 0.1-5% of the total mass of the electrolyte.
8. The lithium sulfur battery electrolyte of claim 7 wherein: the additive is anhydrous lithium nitrate.
9. A lithium-sulfur battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that: the electrolyte is the lithium sulfur battery electrolyte as defined in any one of claims 1 to 8.
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Cited By (2)
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| CN111454182A (en) * | 2020-05-13 | 2020-07-28 | 杉杉新材料（衢州）有限公司 | Preparation method of lithium sulfate containing fluoroalkyl groups |
| CN112701354A (en) * | 2021-01-22 | 2021-04-23 | 广东邦普循环科技有限公司 | Electrolyte of lithium-sulfur battery and preparation method and application thereof |
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