CN116864806A - Application of arginine in lithium-sulfur battery electrolyte, electrolyte and lithium-sulfur battery - Google Patents
Application of arginine in lithium-sulfur battery electrolyte, electrolyte and lithium-sulfur battery Download PDFInfo
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- CN116864806A CN116864806A CN202310929238.1A CN202310929238A CN116864806A CN 116864806 A CN116864806 A CN 116864806A CN 202310929238 A CN202310929238 A CN 202310929238A CN 116864806 A CN116864806 A CN 116864806A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 136
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000004475 Arginine Substances 0.000 title claims abstract description 61
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 34
- 239000011593 sulfur Substances 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 33
- 230000000996 additive effect Effects 0.000 claims abstract description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 claims abstract description 5
- 239000013538 functional additive Substances 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 32
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 20
- 238000011068 loading method Methods 0.000 claims description 17
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 11
- 239000003273 ketjen black Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 7
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 125000006091 1,3-dioxolane group Chemical group 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- 239000011149 active material Substances 0.000 abstract description 9
- 238000004146 energy storage Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 abstract description 2
- 235000009697 arginine Nutrition 0.000 description 42
- 239000005077 polysulfide Substances 0.000 description 19
- 229920001021 polysulfide Polymers 0.000 description 19
- 150000008117 polysulfides Polymers 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 230000002829 reductive effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000011241 protective layer Substances 0.000 description 8
- 229910013553 LiNO Inorganic materials 0.000 description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
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- 238000004090 dissolution Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- 229910018091 Li 2 S Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000001484 arginines Chemical class 0.000 description 1
- 125000000637 arginyl group Chemical group N[C@@H](CCCNC(N)=N)C(=O)* 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- -1 phthalocyanine compound Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 239000002341 toxic gas Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
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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
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The application discloses an application of arginine in lithium sulfur battery electrolyte, the electrolyte and a lithium sulfur battery, and belongs to the technical field of lithium sulfur battery energy storage, so as to better solve the problems of active material loss and shuttle effect of the lithium sulfur battery and further improve the performance of the lithium sulfur battery. The application discloses an application of arginine in lithium sulfur battery electrolyte, wherein the arginine is used as a functional additive of the lithium sulfur battery electrolyte, the solvent of the electrolyte is an ether solvent, the lithium sulfur battery electrolyte containing the arginine additive comprises the ether solvent, lithium salt and arginine, and the lithium sulfur battery comprises the lithium sulfur battery electrolyte containing the arginine additive, a positive electrode material, a diaphragm and a negative electrode material. The application has the advantages of simple method, high sulfur load, less electrolyte consumption, good battery performance, safety, environmental protection and the like.
Description
Technical Field
The application relates to the technical field of lithium sulfur battery energy storage, in particular to application of arginine in lithium sulfur battery electrolyte, the electrolyte and a lithium sulfur battery.
Background
Lithium sulfur batteries are considered to be one of the most promising next generation energy storage secondary battery systems due to their high theoretical specific capacity (1675 mAh/g) and theoretical energy density (2600 Wh/kg), as well as the intrinsic advantages of sulfur (low cost, abundant reserves and environmental friendliness).
However, the current lithium sulfur battery has the following technical problems:
(1) In the discharging process, sulfur can generate high-concentration intermediate product lithium polysulfide which can be dissolved in conventional ether electrolyte, thereby causing active material loss and deteriorating the cycle performance of the battery.
(2) In the charging process, the soluble long-chain lithium polysulfide generated by the positive electrode can reciprocate between the positive electrode and the negative electrode under the action of concentration gradient force and electric field force, so that a shuttle effect is formed. This effect can corrode the lithium metal negative electrode, resulting in reduced battery efficiency and self-discharge behavior, and even in severe cases, can cause the battery to fail to charge to a cutoff voltage, affecting proper operation.
Thus, the massive dissolution loss of lithium polysulfide and the generation of shuttle effect lead to poor electrochemical performance of lithium sulfur batteries, which hinders commercial development and application of lithium sulfur batteries.
In order to solve the above problems, a great deal of research work is done by researchers, such as designing and synthesizing carbon materials with various nanostructures, conductive polymers, metal oxides/sulfides/nitrides, etc. as carrier materials or diaphragm coating materials for sulfur, and reducing the loss of lithium polysulfide by utilizing the physical or chemical adsorption effect of the carbon materials, conductive polymers, metal oxides/sulfides/nitrides, etc. on lithium polysulfide, thereby inhibiting the shuttle effect and achieving the purpose of improving the electrical performance of the battery. Compared with the complex and fine material structural design, the modification of the electrolyte is a strategy which is simpler and is beneficial to commercialization and popularization.
Patent CN112768766 discloses a method for improving the electrical properties of lithium sulfur batteries by adding a metal phthalocyanine compound additive to the electrolyte; patent CN108336405 discloses a method for improving the cycle stability of a battery by using a functional electrolyte additive 3-methyl-1, 4, 2-dioxazole-5-ketone; patent CN110993902 discloses a positive electrode additive ([ H) of positively charged organic small molecules 2 PBD] 2+ ·2[NO 3 ] - ) The shuttle effect is inhibited by utilizing the electrostatic adsorption effect of the lithium polysulfide and the lithium polysulfide, but the additive content is higher and is 5-10wt% of the total mass of the positive electrode, and the initial reversible specific capacity is lower, namely about 800mAh/g, so that the energy density of the battery is greatly reduced. The additive has the characteristics of high toxicity, complex synthesis or high usage amount and the like, and is not beneficial to popularization and application of lithium-sulfur batteries.
Therefore, based on the problems of the lithium-sulfur battery electrolyte in the aspect of additive improvement, it is necessary to develop an additive which has good action and effect, is low in cost and environment-friendly and has a small dosage.
Disclosure of Invention
The technical problems to be solved by the application are as follows: the lithium sulfur battery electrolyte is developed to better solve the problems of active material loss and shuttle effect of the lithium sulfur battery, thereby improving the performance of the lithium sulfur battery.
The application is realized by the following technical scheme:
the application of arginine in lithium sulfur battery electrolyte is that arginine is used as a functional additive of the lithium sulfur battery electrolyte, and the solvent of the electrolyte is an ether solvent.
The application preferably provides an electrolyte of a lithium sulfur battery containing an arginine additive, which comprises arginine and an ether solvent, wherein the addition amount of the arginine is 0.5-5 wt% of the total mass of the electrolyte of the lithium sulfur battery.
According to the application, arginine is directly applied to the electrolyte of the lithium sulfur battery, in the first-circle discharging process of the lithium sulfur battery, a precipitate which is insoluble in the electrolyte can be generated by utilizing the hydrogen bond effect between the amino group in the arginine and lithium polysulfide, and the precipitate is the arginine adsorbed with long-chain lithium polysulfide, meanwhile, the precipitate covers the surface of the positive electrode and can serve as a protective layer to reduce the dissolution of lithium polysulfide from the positive electrode side, so that the shuttle effect is reduced, the corrosion of the negative electrode of metal lithium is reduced, and the cycle life of the battery is remarkably prolonged; in addition, the protective layer also has the liquid-retaining capacity, so that the electrolyte infiltrated into the positive electrode material is fixed in the protective layer as much as possible, the loss of the electrolyte is reduced, the consumption of the electrolyte is reduced, and the energy density of the battery is improved. Moreover, the additive is environment-friendly and pollution-free, and the whole preparation method is simple and easy for large-scale production, and industrial popularization and application are easy to realize.
The application discloses a lithium sulfur battery electrolyte containing an arginine additive, which is characterized by further comprising an ether solvent and lithium salt, wherein the ether solvent is 1, 3-dioxolane and ethylene glycol dimethyl ether, and the volume ratio of the 1, 3-dioxolane to the ethylene glycol dimethyl ether is 1: (0.8-1.2).
The application discloses a lithium sulfur battery electrolyte containing an arginine additive, which is characterized in that lithium salt comprises one or two of lithium bistrifluoromethane sulfonyl imide and lithium nitrate, wherein the lithium bistrifluoromethane sulfonyl imide is chemically abbreviated as LiTFSI, and the lithium nitrate is chemically represented as LiNO 3 。
Preferably, the lithium salt is a mixture of lithium bistrifluoromethane sulfonyl imide and lithium nitrate, the molar concentration of the lithium bistrifluoromethane sulfonyl imide in the lithium sulfur battery electrolyte is 0.5-2.0 mol/L, and the mass concentration of the lithium nitrate in the lithium sulfur battery electrolyte is 1-5 wt%.
A preparation method of an electrolyte of a lithium sulfur battery containing an arginine additive is used for preparing the electrolyte of the lithium sulfur battery and comprises the following steps:
step 1: uniformly mixing 1, 3-dioxolane and ethylene glycol dimethyl ether according to a certain volume ratio (1) (0.8-1.2)), then adding a certain concentration of lithium salt, wherein the lithium salt is one or two of lithium bistrifluoromethane sulfonyl imide and lithium nitrate, and uniformly stirring to obtain a clear and transparent solution.
Step 2: adding arginine into the clear and transparent solution in the step 1, and strongly stirring for a certain time until the arginine is completely dissolved, thus obtaining the lithium-sulfur battery electrolyte containing the arginine additive.
A lithium-sulfur battery comprises a positive electrode material, a diaphragm, a negative electrode material, the electrolyte of the lithium-sulfur battery, and a sulfur carrying capacity of 1-8 mg/cm 2 The positive electrode material is Ketjen black/sulfur composite material, the diameter of a positive electrode plate is 8mm, and the diaphragm is Celgard-2400; the negative electrode material is a metal lithium sheet.
Preferably, the lithium metal sheet has a thickness of 50 to 100 μm and a diameter of 14 to 16mm.
Preferably, the diameter of Celgard-2400 is 18-20 mm, and the thickness is 23-27 μm.
The application has the following advantages and beneficial effects:
1. according to the application, low-cost, environment-friendly and nontoxic arginine is taken as an additive of the lithium sulfur battery electrolyte, and the arginine is dissolved in an ether solvent, so that on one hand, in the discharging process of the battery, the arginine and the soluble lithium polysulfide have hydrogen bond action to generate a precipitate which is insoluble in the electrolyte and covers the surface of the positive electrode, and the dissolution of the lithium polysulfide is blocked; on the other hand, the protective layer also has the liquid-retaining capacity, and the electrolyte infiltrated into the positive electrode material is fixed in the protective layer as much as possible, so that the loss of the electrolyte is reduced, the consumption of the electrolyte is reduced, the energy density of the battery is improved, and the electrochemical performance of the battery is improved.
2. The application improves the electrolyte and is matched with other substances and parameters, and the sulfur load of the lithium sulfur battery is 8.0mg/cm 2 When the initial surface capacity of the battery can reach 8.9mAh/cm 2 After 100 cycles, the capacity of the face remains 5.6mAh/cm 2 This number is higher than the current commercial lithium ion requirement for surface capacity (4 mAh/cm 2 ) At high sulfur loading, the electrolyte enables the battery to realize stable circulation; in addition, the lithium-sulfur battery also has good multiplying power performance, and the sulfur loading is 3.2mg/cm 2 At 1C of batteryThe reversible capacity is 650mAh/g under the multiplying power.
3. The technical scheme of using arginine as an electrolyte additive for the lithium-sulfur battery is simple and easy to operate, does not need to design and synthesize complex materials, does not generate pollution and toxic gas, accords with the environmental protection standard, does not involve high-temperature high-pressure reaction, is safe and controllable, and accords with the safety standard; in addition, the application has the characteristic of industrial application and has good commercial application prospect in the field of lithium-sulfur batteries.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. In the drawings:
FIG. 1 is a front-to-back comparative digital photograph of lithium polysulfide drop-wise added to a control electrolyte and an electrolyte of example 1; wherein, (a) is before dripping and (b) is after dripping.
Fig. 2 is a graph showing the cycling performance of lithium sulfur batteries in the example 1 electrolyte and the control electrolyte.
Fig. 3 is a lithium negative SEM of a lithium sulfur battery after 150 cycles in the electrolyte of example 1.
Fig. 4 is a lithium negative SEM of a lithium sulfur battery after 150 cycles in a control electrolyte.
Fig. 5 is a charge-discharge curve of a lithium sulfur battery in the electrolyte of example 1.
Fig. 6 is a charge-discharge curve of a lithium-sulfur battery in a control electrolyte.
Fig. 7 is the rate performance of lithium sulfur batteries in example 1 electrolyte and control electrolyte.
Fig. 8 is the electrical performance of a lithium sulfur battery in the electrolyte of example 1 at high sulfur surface loading and low electrolyte usage.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present application, the present application will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present application and the descriptions thereof are for illustrating the present application only and are not to be construed as limiting the present application.
Description: DOL represents 1, 3-dioxolane, DME represents ethylene glycol dimethyl ether, liTFSI represents lithium bistrifluoromethane sulfonyl imide, liNO 3 Representing lithium nitrate.
Preparation of a positive electrode material:
preparing a sulfur-carbon composite material by a hot melting method, specifically placing sulfur powder and ketjen black in a ball mill according to a mass ratio of 7:3, and ball milling for 6 hours to obtain an initial mixture of uniformly mixed sulfur and carbon; and placing the initial mixture in a reaction kettle, and then placing the reaction kettle in an oven at 155 ℃ for preserving heat for 12 hours to obtain the Keqin black/sulfur composite material.
Uniformly mixing the prepared ketjen black/sulfur composite material, super-p and LA133 according to the mass ratio of 8:1:1 to obtain slurry, coating the slurry on carbon-coated aluminum foil, preserving heat for 10 hours in a 70 ℃ oven, and drying to obtain the anode material. Finally, cutting the positive electrode material into small wafers with the diameter of 8mm by using a sheet punching machine for standby.
Preparation of electrolyte:
step 1:1, 3-dioxolane and ethylene glycol dimethyl ether are mixed according to a certain volume ratio of 1:1, then adding the lithium bistrifluoromethane sulfonyl imide and the lithium nitrate, and stirring uniformly until the solution is clear and transparent.
Step 2: adding arginine with a certain mass into the solution in the step 1, and then strongly stirring until the arginine is completely dissolved, wherein the solution is the lithium-sulfur battery electrolyte containing the arginine additive.
The use of arginine and LiNO in different mass contents was explored 3 And the effect of the ketjen black/sulfur composite positive electrode materials with different sulfur loadings on the electrochemical performance of the battery. Assembling a CR2032 button cell in a glove box filled with argon, wherein the anode is a metal lithium sheet with the diameter of 14 mm; the septum is Celgard2400 with a diameter of 19 mm; the positive electrode active material loading and the electrolyte composition are shown in Table 1, the concentration of lithium salt LiTFSI is 1.0mol/L, and the solvent is a mixed solution of DOL and DME in a volume ratio of 1:1. The assembled battery was activated 3 times at 0.05C and then cycled 100 times at 0.2C, see table 1 for specific information:
TABLE 1 arginines of different mass contentsAcid and LiNO 3 Influence of Ketjen black/sulfur composite positive electrode materials with different sulfur loadings on electrochemical performance of battery
As can be seen from the above table, in the technical scheme of the application, the mass ratio of arginine in the electrolyte is selected to be 1wt%, and LiNO 3 When the mass ratio in the electrolyte is 2wt%, the prepared lithium sulfur battery has better electrical performance. Thus, in the following examples, arginine was selected to be present in the electrolyte at a mass ratio of 1wt%, liNO 3 The mass ratio in the electrolyte was 2wt%.
Example 1
An electrolyte of a lithium sulfur battery containing an arginine additive comprises an ether solvent, lithium salt and the arginine additive; the ether solvent is a mixed solution of DOL and DME in a volume ratio of 1:1, and the lithium salt is LiTFSI and LiNO 3 LiTFSI concentration in the electrolyte is 1.0mol/L, liNO 3 The amount of the additive arginine in the electrolyte was 2wt% and the amount of the additive arginine in the electrolyte was 1wt%.
Step 1: stirring and mixing DOL and DME solvent uniformly according to a volume ratio of 1:1 in a glove box filled with argon, and then adding LiTFSI with a molar concentration of 1.0mol/L and LiNO with a mass concentration of 2wt% 3 The solution was stirred again until it was clear and transparent.
Step 2: and (2) adding arginine accounting for 1 weight percent of the total mass of the electrolyte into the clear and transparent solution obtained in the step (1) in a glove box filled with argon, and strongly stirring until the arginine is completely dissolved, so that the solution is clear and transparent, and the obtained solution is the electrolyte of the lithium-sulfur battery containing the arginine additive.
Control group
A matrix lithium sulfur electrolyte is provided as a comparative example. The solvent of the matrix lithium sulfur electrolyte is a mixed solution of DOL and DME in a volume ratio of 1:1, and the lithium salt is LiTFSI and LiNO 3 LiTFSI concentration in the electrolyte is 1.0mol/L, liNO 3 The amount in the electrolyte was 2wt% and the preparation was the same as in step 1 of example 1, except that arginine was not contained.
(1) Visual reaction experiments with lithium polysulfide were performed on the control electrolyte and the example 1 electrolyte:
specific operation of visual reaction experiment: preparation of 0.1mol/L Li in an argon-filled glove box 2 S 8 The solution, the solvent is a mixed solution of DOL and DME in a volume ratio of 1:1, is respectively dripped into the electrolyte of the control group and the electrolyte of the example 1, and is kept stand for 12 hours.
As shown in FIG. 1, the control electrolyte was observed to change from clear transparent to orange red, indicating Li 2 S 8 Is well dissolved in the electrolyte of the control group and does not react. In contrast, a pale yellow precipitate formed in the electrolyte of example 1 and the upper liquid turned slightly yellow only, indicating that the additive arginine could be combined with Li 2 S 8 The reaction occurs and the reaction product is insoluble in the electrolyte.
(2) Electrochemical performance verification was performed on lithium sulfur batteries prepared using the control electrolyte and the electrolyte of example 1:
and (3) battery assembly: CR2032 button cell was assembled in an argon-filled glove box using a control electrolyte and an example 1 electrolyte, respectively, with a positive electrode of ketjen black/sulfur composite, and an active material sulfur loading of 5.1mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The negative electrode is a metal lithium sheet with the diameter of 14 mm; the separator was Celgard2400 with a diameter of 19mm and a thickness of 24. Mu.m.
Electrochemical performance test: after the assembled lithium sulfur battery was left to stand at 25 ℃ for 12 hours, it was activated at 0.05C for 3 cycles between 1.7 and 2.8V, followed by recycling at 0.2C. As a result, as shown in FIG. 2, the initial reversible capacity of the lithium-sulfur battery using the electrolyte of example 1 after activation was 809mAh/g, the reversible capacity after 150 cycles was 667mAh/g, and the capacity retention was 82%. In clear contrast, the lithium sulfur battery using the control electrolyte had an initial reversible capacity of 807mAh/g after the completion of activation, but after 150 cycles, the reversible capacity was only 523mAh/g, with a capacity retention as low as 65%. This result shows that the electrolyte prepared in example 1 containing 1wt% arginine additive has excellent electrochemical properties in lithium sulfur batteries.
The lithium-sulfur battery using the control electrolyte and the electrolyte of example 1, respectively, was disassembled after 150 cycles, and subjected to field-generating scanning electron microscope test. The surface of the lithium anode using the electrolyte of example 1 was in a nodular structure with rounded edges as shown in fig. 3, while the morphology of the lithium anode using the electrolyte of the control group was fiber and needle-shaped as shown in fig. 4.
The comparative results show that the electrolyte prepared in example 1 containing 1wt% arginine additive can well inhibit the shuttle effect, thereby further reducing the corrosion degree of lithium polysulfide on the lithium metal negative electrode.
(3) Comparative tests were carried out on the self-discharge performance of lithium-sulfur batteries prepared using the control electrolyte and the electrolyte of example 1:
and (3) battery assembly: CR2032 button cell was assembled in an argon-filled glove box using a control electrolyte and an example 1 electrolyte, respectively, with a positive electrode of ketjen black/sulfur composite, and an active material sulfur loading of 6mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The negative electrode is a metal lithium sheet with the diameter of 14 mm; the septum was Celgard2400 with a diameter of 19 mm.
Electrochemical performance test: the assembled lithium sulfur battery was left to stand at 25 ℃ for 12 hours, activated between 1.7 and 2.8V for 3 cycles at 0.05C, and then cycled for 7 cycles at 0.1C. Then, when the battery was discharged to 2.1V at the 11 th turn, it was left to stand for 15 days, then discharged again to 1.7V at a rate of 0.1C, and finally the discharge specific capacity of the battery before and after the standing was compared.
As shown in fig. 5 and 6, the self-discharge rate of the lithium-sulfur battery using the electrolyte of example 1 was only 6.6% after standing for 15 days; and for the lithium sulfur battery using the electrolyte of the control group, the self-discharge rate is as high as 10.5% after the lithium sulfur battery is stood for 15 days; this result shows that the electrolyte prepared in example 1 containing 1wt% arginine additive can significantly inhibit the shuttle effect of lithium sulfur batteries.
(4) Comparative tests were performed on the rate performance of lithium sulfur batteries prepared using the control electrolyte and the electrolyte of example 1:
and (3) battery assembly: CR2032 button cell was assembled in an argon-filled glove box using a control electrolyte and an example 1 electrolyte, respectively, with a positive electrode of ketjen black/sulfur composite, and an active material sulfur loading of 3.2mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The negative electrode is a metal lithium sheet with the diameter of 14 mm; the septum was Celgard2400 with a diameter of 19 mm.
Electrochemical performance test: the assembled lithium sulfur battery was left to stand at 25 ℃ for 12 hours, activated for 3 cycles at a rate of 0.05C between 1.7 and 2.8V, then cycled for 5 cycles at 0.1C, 0.2C, 0.5C and 1C, respectively, and finally cycled for 150 cycles at a rate of 0.2C.
As a result, as shown in fig. 7, the lithium-sulfur battery using the electrolyte of example 1 had a specific discharge capacity of 650mAh/g at a large rate of 1C, and the specific discharge capacity remained at 740mAh/g after 150 cycles of rate adjustment to 0.2C; in contrast, the lithium sulfur battery using the control electrolyte has a specific discharge capacity of only 550mAh/g at a 1C rate, and the specific discharge capacity is reduced to 604mAh/g after 150 cycles of rate adjustment to 0.2C. The results show that the electrolyte containing 1wt% of arginine additive prepared in example 1 can significantly improve the specific discharge capacity of a lithium-sulfur battery under high current density, and can effectively inhibit shuttling of lithium polysulfide.
(5) The cycle performance of the lithium sulfur battery prepared by using the control group electrolyte and the electrolyte of the example 1 under the severe test conditions of high active substance surface loading and low electrolyte consumption is compared and tested:
and (3) battery assembly: CR2032 button cell was assembled in an argon-filled glove box using the electrolyte of example 1, the positive electrode was a Ketjen black/sulfur composite, and the active material sulfur loading was controlled at 8.0mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The negative electrode is a metal lithium sheet with the diameter of 14 mm; the septum is Celgard2400 with a diameter of 19 mm; the ratio of the amount of the electrolyte to the active material sulfur was 5. Mu.L/mg, and the ratio of the amount of the electrolyte to the active material sulfur was 22. Mu.L/mg under the other test conditions described above.
Electrochemical performance test: the assembled lithium sulfur battery was left to stand at 25 ℃ for 12 hours, activated 3 times between 1.7 and 2.8V at a rate of 0.05C, and then cycled at a rate of 0.1C.
As shown in FIG. 8, the initial surface capacity of the activated battery is as high as 8.9mAh/cm under the conditions of high sulfur loading and low electrolyte consumption 2 After 100 cycles, the capacity of the face remains 5.6mAh/cm 2 The value is still higher than the surface capacity (4 mAh/cm) 2 )。
Compared to most studies optimizing electrolytes to improve the electrical performance of lithium sulfur batteries, as in CN114678579, sulfur loading: 0.88-1.15 mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the In CN115360417, sulfur loading: 1.0mg/cm 2 Left and right; in CN115149104, sulfur loading: 0.7-1.1 mg/cm 2 The lithium sulfur battery assembled by using the electrolyte of the embodiment 1 has more severe test conditions and sulfur loading of up to 8.0mg/cm 2 The electrolyte dosage is only 5 mu L/mg, and the obtained data has reference value for the commercial application of the lithium-sulfur battery.
The reason why the electrolyte of example 1 can greatly improve the electrical performance of the lithium sulfur battery can be summarized as follows: the amino group in arginine can generate hydrogen bond action with lithium polysulfide, and can generate precipitate which is insoluble in electrolyte, and the precipitate is arginine adsorbed with long-chain lithium polysulfide. Meanwhile, the precipitate is covered on the surface of the positive electrode and can serve as a protective layer to reduce the dissolution of lithium polysulfide from the positive electrode side, so that the shuttle effect is reduced, the corrosion of a metal lithium negative electrode is reduced, and the cycle life of the battery is remarkably prolonged; in addition, the protective layer also has the liquid-retaining capacity, so that electrolyte infiltrated into pores of the positive electrode carbon material is fixed in the protective layer as much as possible, the loss of the electrolyte is reduced, the consumption of the electrolyte is reduced, and the energy density of the battery is improved.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the application, and is not meant to limit the scope of the application, but to limit the application to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the application are intended to be included within the scope of the application.
Claims (10)
1. The application of arginine in the lithium sulfur battery electrolyte is characterized in that arginine is used as a functional additive of the lithium sulfur battery electrolyte, and the solvent of the electrolyte is an ether solvent.
2. An electrolyte for lithium sulfur batteries containing an arginine additive comprising an ether solvent and the arginine of claim 1.
3. The lithium sulfur battery electrolyte containing the arginine additive according to claim 2, wherein the addition amount of the arginine is 0.5 to 5 weight percent of the total mass of the lithium sulfur battery electrolyte.
4. The electrolyte for a lithium sulfur battery containing an arginine additive according to claim 2 or 3, further comprising an ether solvent and a lithium salt.
5. The electrolyte of a lithium sulfur battery containing an arginine additive according to claim 4, wherein the ether solvent is 1, 3-dioxolane and ethylene glycol dimethyl ether, and the volume ratio of 1, 3-dioxolane to ethylene glycol dimethyl ether is 1: (0.8-1.2).
6. The arginine additive-containing lithium sulfur battery electrolyte of claim 4 wherein the lithium salt comprises one or a mixture of lithium bistrifluoromethane sulfonyl imide and lithium nitrate.
7. A method for preparing the lithium sulfur battery electrolyte containing arginine additive, which is used for preparing the lithium sulfur battery electrolyte according to any one of claims 2 to 6, comprising the following steps:
step 1: adding lithium salt into a solvent to be dissolved into clear transparent solution;
step 2: and (3) adding the arginine into the clear and transparent solution in the step (1), and mixing until the arginine is completely dissolved, thus obtaining the lithium-sulfur battery electrolyte containing the arginine additive.
8. A lithium-sulfur battery comprising a positive electrode material, a separator and a negative electrode material, and further comprising the lithium-sulfur battery electrolyte according to any one of claims 2 to 6 or the lithium-sulfur battery electrolyte prepared by the preparation method according to claim 7.
9. The lithium sulfur battery of claim 8 wherein the sulfur loading is 1 to 8mg/cm 2 。
10. The lithium sulfur battery of claim 8 or 9 wherein the positive electrode material is ketjen black/sulfur composite and the separator is Celgard-2400; the negative electrode material is a metal lithium sheet.
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| CN118507821A (en) * | 2024-05-20 | 2024-08-16 | 贵州轻工职业技术学院 | Gel electrolyte for lithium-sulfur battery and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012142101A (en) * | 2010-12-28 | 2012-07-26 | Toyota Central R&D Labs Inc | Lithium sulfur battery and method for manufacturing lithium sulfur battery |
| JP2019050135A (en) * | 2017-09-11 | 2019-03-28 | コニカミノルタ株式会社 | Nonaqueous electrolyte composition, and, nonaqueous electrolyte secondary battery |
| CN113394460A (en) * | 2021-06-24 | 2021-09-14 | 郑州大学 | Lithium-sulfur battery electrolyte containing benzenetrithiol additive and lithium-sulfur battery |
-
2023
- 2023-07-27 CN CN202310929238.1A patent/CN116864806A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012142101A (en) * | 2010-12-28 | 2012-07-26 | Toyota Central R&D Labs Inc | Lithium sulfur battery and method for manufacturing lithium sulfur battery |
| JP2019050135A (en) * | 2017-09-11 | 2019-03-28 | コニカミノルタ株式会社 | Nonaqueous electrolyte composition, and, nonaqueous electrolyte secondary battery |
| CN113394460A (en) * | 2021-06-24 | 2021-09-14 | 郑州大学 | Lithium-sulfur battery electrolyte containing benzenetrithiol additive and lithium-sulfur battery |
Non-Patent Citations (1)
| Title |
|---|
| 孙成: "铅酸蓄电池电解液添加剂发展概况", 电池, vol. 32, no. 01, 28 February 2002 (2002-02-28) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118507821A (en) * | 2024-05-20 | 2024-08-16 | 贵州轻工职业技术学院 | Gel electrolyte for lithium-sulfur battery and preparation method thereof |
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