CN108258317B - Lithium-sulfur battery - Google Patents

Lithium-sulfur battery Download PDF

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CN108258317B
CN108258317B CN201810021831.5A CN201810021831A CN108258317B CN 108258317 B CN108258317 B CN 108258317B CN 201810021831 A CN201810021831 A CN 201810021831A CN 108258317 B CN108258317 B CN 108258317B
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lithium
sulfur
equal
electrolyte
sulfur battery
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CN108258317A (en
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任齐都
王传水
熊鲲
王冰桐
施苏萍
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Jiangsu Guotai Super Power New Materials Co ltd
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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
    • 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
    • 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
    • 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 provides a lithium-sulfur battery, which comprises a positive electrode, a negative electrode and electrolyte, wherein the positive electrode comprises a sulfur-containing material, the negative electrode comprises a lithium-containing material, the electrolyte comprises a lithium salt and an organic solvent, the lithium salt comprises lithium fluorophosphate shown in a formula I, and the formula I: LiPRxFyWherein R is oxygen or oxalate, x and y are integers, x is more than or equal to 1 and less than or equal to 4, y is more than or equal to 1 and less than or equal to 4, and x + y is less than or equal to 5. According to the invention, by adopting the lithium fluorophosphate shown in the formula I and matching with an organic solvent and the like, the SEI film performance on the surface of the electrode of the lithium-sulfur battery can be effectively improved, so that the capacity percentage and the temperature characteristic of the lithium-sulfur battery can be greatly improved, and the cycle life and the storage life of the lithium battery can be favorably prolonged.

Description

Lithium-sulfur battery
Technical Field
The invention belongs to the technical field of chemical materials, and relates to a lithium-sulfur battery.
Background
The lithium-sulfur battery is a high-capacity secondary green chemical power source which is paid much attention and invested in much research in recent years, and the good electrochemical performance of the lithium-sulfur battery initially shows the potential application in future pure electric vehicles.
The lithium-sulfur secondary battery which takes elemental sulfur as the active ingredient of the positive electrode, an organic nonaqueous solution system containing lithium salt as the electrolyte and metallic lithium as the negative electrode has many advantages. According to the final reduction of the reaction product Li2S, the theoretical specific capacity of elemental sulfur is 1675mAh/g, the theoretical specific capacity of metal lithium is 3860mAh/g, the theoretical energy density of a Li/S redox pair is as high as 2600Wh/kg, and the lithium ion battery has quite attractive application prospect in the aspect of high-specific-energy batteries.
However, elemental sulfur has its inherent disadvantage as a battery material, namely the reduction product LixS (x is less than or equal to 2) is easily dissolved in the electrolyte and is diffused to the negative electrode Li to react with the electrolyte. Not only can self-discharge be caused; and will be at Li potentialThe electrode surface is deposited with a layer of insulation which deteriorates the cell performance, especially the capacity fade. Furthermore, elemental sulfur or sulfides act as electronic insulators and greatly affect the performance of the battery. In addition, the reliability problem of the lithium metal negative electrode has not been solved at all, and thus, the lithium sulfur battery has not been applied to a large scale so far.
In order to improve the performance of sulfur-containing positive electrodes, researchers have made efforts from various perspectives. Through many years of research and practice, a common electrolyte currently used in lithium sulfur batteries is 1M LiFSI (LiN (SO)2F)2) DME (1, 2-dimethoxyethane) + DOL (1, 3-dioxolane) plus LiNO3And (3) an additive. In the electrolyte, lithium dendrite is easily generated on a metal lithium cathode, the lithium cycle efficiency is mostly lower than 98%, the shuttle reaction of polysulfide ions exists in the elemental sulfur composite cathode, and in the carbonate electrolyte, the lithium dendrite precipitation and the low cycle efficiency of the lithium cathode greatly influence the cycle life of the battery.
Therefore, the development of the electrolyte with simple preparation process, excellent film-forming performance and capability of preventing lithium dendrite precipitation, particularly the electrolyte which can be stably used at low temperature and high temperature, has very important significance for improving the performance, safety and cycle life of the lithium-sulfur battery.
Disclosure of Invention
The invention aims to provide a lithium-sulfur battery which can greatly improve the capacity percentage and the temperature characteristic of the lithium-sulfur battery and is beneficial to improving the cycle life and the storage life of the lithium battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
a lithium-sulfur battery comprises a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises a sulfur-containing material, the negative electrode comprises a lithium-containing material, the electrolyte comprises a lithium salt and an organic solvent, the lithium salt comprises lithium fluorophosphate shown in a formula I, and the formula I: LiPRxFyWherein R is oxygen or oxalate, x and y are integers, x is more than or equal to 1 and less than or equal to 4, y is more than or equal to 1 and less than or equal to 4, and x + y is less than or equal to 5.
Preferably, the fluorophosphoric acid of formula ILithium is LiPO2F2、LiP(C2O4)2F2、LiP(C2O4)F4One or more of them.
Preferably, the concentration of the lithium fluorophosphate represented by the formula I in the electrolyte is 0.001-2 mol/L, and more preferably 0.01-1 mol/L.
Preferably, the lithium salt further comprises other lithium salts selected from LiN (SO)2F)2、LiBr、LiI、LiBF4、LiPF6、LiAsF6、LiClO4、LiSO3CF3、LiC2O4BC2O4、LiF2BC2O4、LiN(CF3SO2)2One or more of them.
Further preferably, the concentration of the other lithium salt in the electrolyte is 0.001-2 mol/L, and more preferably 0.1-1 mol/L.
Preferably, the electrolyte further comprises a functional additive, wherein the functional additive is one or more selected from lithium nitrate, biphenyl, vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, propylene sulfite, butylene sulfite, 1, 3-propane sultone, 1, 4-butane sultone, 1, 3- (1-propylene) sultone, ethylene sulfite, ethylene sulfate, cyclohexylbenzene, tert-butyl benzene, tert-amyl benzene and succinonitrile.
More preferably, the feeding mass of the functional additive is 0.001-5% of the total mass of the electrolyte.
Preferably, the organic solvent is an ether organic solvent and/or a carbonate organic solvent, and the ether organic solvent is one or more selected from tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane and diglyme; the carbonate organic solvent is a cyclic carbonate compound and/or a chain carbonate compound; the cyclic carbonate compound is one or more selected from ethylene carbonate, propylene carbonate, gamma-butyrolactone and butylene carbonate; the chain carbonate compound is one or more of carbonic ester derivatives synthesized by dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, straight chain or branched chain aliphatic monoalcohol with 3-8 carbon atoms and carbonic acid.
More preferably, the organic solvent is a mixed solvent of DME (1, 2-dimethoxyethane) and DOL (1, 3-dioxolane) in a volume ratio of 1: 0.5-2.0.
Preferably, the sulfur-containing material is one or more of elemental sulfur, a sulfur-carbon composite material and an organic sulfur-containing material.
Preferably, the lithium-containing material is one or more of metallic lithium, surface-treated metallic lithium and lithium-containing alloy material.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, by adopting the lithium fluorophosphate shown in the formula I and matching with an organic solvent and the like, the SEI film performance on the surface of the electrode of the lithium-sulfur battery can be effectively improved, so that the capacity percentage and the temperature characteristic of the lithium-sulfur battery can be greatly improved, and the cycle life and the storage life of the lithium battery can be favorably prolonged.
Detailed Description
The following examples are intended to illustrate several embodiments of the present invention, but are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Preparation of lithium-sulfur battery: preparation of a sulfur positive electrode: dispersing 55 wt.% of sublimed sulfur, 35 wt.% of Super-P conductive carbon black and 10 wt.% of polyvinylidene fluoride (PVDF) in N-methylpyrrolidone (NMP) solvent, stirring for 12 hours until the slurry is uniformly mixed, coating the slurry on an aluminum current collector coated with a carbon layer, and drying at 60 ℃ for 12 hours to obtain a positive electrode active sulfur content of 1.5mg/cm2(ii) a The negative electrode was a lithium plate with a thickness of 50 μm. Assembling the above components in a layered structure of positive electrode/separator/negative electrode, and adding electrolysisSealing after the liquid is filled. After standing for 12h, charging and discharging the battery at 0.2C and 1.5-2.8V, investigating the capacity retention rate of the battery after 100 cycles, and testing the capacity retention rate and the capacity recovery rate of the battery at 0.2C after storing for 15 days at 60 ℃.
The invention lists the component compositions of 1-14 fluorine-containing lithium fluorophosphate electrolytes, and the test data of the capacity retention rate, the capacity retention rate after high-temperature storage and the capacity recovery rate after the lithium-sulfur battery prepared from each electrolyte is cycled for 100 times at normal temperature in a table form, which is detailed in table 1:
TABLE 1
Figure BDA0001543781000000031
Figure BDA0001543781000000041
Figure BDA0001543781000000051
Note: LiTFSI in Table 1 is LiN (CF)3SO2)2(ii) a LiFSI is LiN (SO)2F)2(ii) a DME is 1, 2-dimethoxyethane; DOL is 1, 3-dioxolane.
From the above examples, especially in comparison with comparative examples, it can be seen that: after the lithium-sulfur battery electrolyte provided by the invention is applied to a lithium-sulfur battery, the battery performance is obviously improved, which is mainly based on that fluorine-containing lithium phosphate has good solubility and stability in an electrolyte system, a stable SEI film can be formed on the surface of a sulfur anode, and the improvement of the cycle life and the high-temperature performance of the battery is facilitated.
The present invention includes but is not limited to the above embodiments, and those skilled in the art can convert more embodiments within the claims of the present invention.

Claims (5)

1. A lithium-sulfur battery comprises a positive electrode, a negative electrode and an electrolyteA liquid characterized by: the positive electrode comprises a sulfur-containing material, the negative electrode comprises a lithium-containing material, the electrolyte comprises a lithium salt and an organic solvent, the lithium salt comprises lithium fluorophosphate shown in a formula I, and the formula I is as follows: LiPRxFyWherein R is oxygen or oxalate, x and y are integers, x is more than or equal to 1 and less than or equal to 4, y is more than or equal to 1 and less than or equal to 4, and x + y is less than or equal to 5; the lithium fluorophosphate shown as the formula I is LiPO2F2、LiP(C2O4)2F2、LiP(C2O4)F4One or more of the above; the concentration of the lithium fluorophosphate shown in the formula I in the electrolyte is 0.01-1 mol/L; the lithium salt also comprises other lithium salts, and the other lithium salts are selected from LiN (SO)2F)2、LiBr、LiI、LiBF4、LiPF6、LiAsF6、LiClO4、LiSO3CF3、LiC2O4BC2O4、LiF2BC2O4、LiN(CF3SO2)2One or more of the above; the concentration of the other lithium salt in the electrolyte is 0.1-1 mol/L; the organic solvent is an ether organic solvent, and the ether organic solvent is one or more selected from tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane and diglyme.
2. The lithium sulfur battery of claim 1, wherein: the electrolyte also comprises a functional additive, wherein the functional additive is one or more selected from lithium nitrate, biphenyl, vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, propylene sulfite, butylene sulfite, 1, 3-propane sultone, 1, 4-butane sultone, 1, 3- (1-propylene) sultone, ethylene sulfite, ethylene sulfate, cyclohexylbenzene, tert-butyl benzene, tert-amyl benzene and succinonitrile.
3. The lithium sulfur battery of claim 2, wherein: the feeding mass of the functional additive is 0.001-5% of the total mass of the electrolyte.
4. The lithium sulfur battery of claim 1, wherein: the sulfur-containing material is one or more of elemental sulfur, a sulfur-carbon composite material and an organic sulfur-containing material.
5. The lithium sulfur battery of claim 1, wherein: the lithium-containing material is one or more of metal lithium, surface-treated metal lithium and lithium-containing alloy materials.
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CN108987803B (en) * 2018-07-17 2020-06-09 四川华昆能源有限责任公司 Lithium metal negative electrode film-forming electrolyte for lithium-sulfur battery and additive thereof
CN109216769A (en) * 2018-11-02 2019-01-15 珠海光宇电池有限公司 A kind of lithium metal battery electrolyte and lithium metal battery and lithium-sulfur cell
CN110061292B (en) * 2019-03-28 2021-04-09 合肥国轩高科动力能源有限公司 Low-temperature electrolyte and lithium battery using same
CN111710907A (en) * 2020-06-12 2020-09-25 南方科技大学 Metal sulfur battery electrolyte and metal sulfur battery comprising same
CN114956020A (en) * 2022-05-18 2022-08-30 武汉理工大学 Li 3 Preparation method of P crystal powder and Li 3 P crystal powder and application thereof

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