WO2023058606A1 - 金属リチウム二次電池用電解液及び当該電解液を含む金属リチウム二次電池並びに金属リチウム二次電池用電解液の評価方法 - Google Patents

金属リチウム二次電池用電解液及び当該電解液を含む金属リチウム二次電池並びに金属リチウム二次電池用電解液の評価方法 Download PDF

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WO2023058606A1
WO2023058606A1 PCT/JP2022/036999 JP2022036999W WO2023058606A1 WO 2023058606 A1 WO2023058606 A1 WO 2023058606A1 JP 2022036999 W JP2022036999 W JP 2022036999W WO 2023058606 A1 WO2023058606 A1 WO 2023058606A1
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lithium
electrolytic solution
secondary battery
potential
dissolution
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French (fr)
Japanese (ja)
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淳夫 山田
裕貴 山田
晟齊 高
智宏 小武方
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University of Tokyo NUC
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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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/4166—Systems measuring a particular property of an electrolyte
    • G01N27/4168—Oxidation-reduction potential, e.g. for chlorination of water
    • 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
    • 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
    • H01M10/056—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
    • H01M10/056—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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4285—Testing apparatus
    • 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
    • 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

Definitions

  • the present invention relates to an electrolytic solution for a metallic lithium secondary battery and a metallic lithium secondary battery containing the electrolytic solution. Furthermore, it also relates to a method for evaluating an electrolyte for a metallic lithium secondary battery.
  • Lithium-ion batteries which have high energy density, are expected to spread on a large scale as large-scale storage batteries for electric vehicles and power storage applications, in addition to small portable devices such as mobile phones and laptop computers.
  • the distance that can be driven on a single charge (cruising distance) is shorter than that of existing gasoline-powered vehicles, so there is a need to significantly extend the cruising range.
  • secondary batteries with even higher capacities.
  • an object of the present invention is to provide a novel electrolyte material for a metallic lithium secondary battery that can achieve high reaction reversibility of a metallic lithium negative electrode.
  • the inventors of the present invention have found that the oxidation-reduction potential of ferrocene is used as a reference, and an electrolytic solution composition having a lithium deposition and dissolution potential within a predetermined range is used. It was newly found that the deposition and dissolution efficiency can be improved, and even in the case of a metallic lithium negative electrode, a highly efficient and high capacity metallic lithium secondary battery can be provided.
  • the present invention relates to an electrolytic solution for a metallic lithium secondary battery and a metallic lithium secondary battery containing the electrolytic solution, and more specifically, ⁇ 1>
  • the lithium salt includes lithium bis(trifluoromethanesulfonyl)imide (Li[N(CF 3 SO 2 ) 2 ]), lithium bis(perfluoroethylsulfonyl)imide (Li[N(C 2 F 5 SO 2 ) 2 ) or lithium bis(fluorosulfonyl)imide (Li
  • the present invention also relates to a method for evaluating an electrolytic solution for a metallic lithium secondary battery, more specifically, ⁇ 9>
  • a method for evaluating an electrolytic solution for a metallic lithium secondary battery comprising the step of preparing a test electrolytic solution containing a solvent and a lithium salt; adding 0.1 to 10 mmol/L of ferrocene to the test electrolytic solution. a step of performing an electrochemical measurement using the test electrolytic solution containing ferrocene and using lithium metal as a reference electrode to measure the oxidation-reduction potential of ferrocene; and a step of depositing lithium based on the oxidation-reduction potential of ferrocene.
  • An evaluation method comprising the step of calculating a dissolution potential (vs. Fc/Fc + ); ⁇ 10>
  • the present invention provides the evaluation method according to ⁇ 10> above, further comprising selecting an electrolytic solution having a lithium deposition and dissolution potential of ⁇ 3.35 V or higher (vs. Fc/Fc + ).
  • the electrolytic solution for a metallic lithium secondary battery of the present invention the reversibility of the reaction in the metallic lithium negative electrode can be greatly improved, thereby improving the deposition and dissolution efficiency of metallic lithium.
  • the evaluation method of the present invention makes it possible to evaluate and specify an electrolytic solution suitable for a metallic lithium secondary battery by a simple method.
  • FIG. 1 is a schematic diagram showing the relationship between the potential window (reductive decomposition potential) of the electrolytic solution and the lithium deposition and dissolution potential.
  • FIG. 2 is a graph showing an example of a current-potential curve (cyclic voltammogram) obtained by cyclic voltammetry (CV) measurement using lithium metal as a reference electrode.
  • FIG. 3 is a schematic diagram showing the shift of the lithium deposition and dissolution potential with reference to the oxidation-reduction potential of ferrocene.
  • FIG. 4 is a graph plotting the lithium deposition and dissolution potential (vs. Fc/Fc + ) and the coulombic efficiency (lithium deposition and dissolution efficiency) obtained in each electrolyte solution system of Examples.
  • Electrolyte solution of the present invention is suitable for a metallic lithium secondary battery, and is characterized by satisfying the following 1) and 2): 1) containing a solvent and a lithium salt; 2) Having a lithium deposition and dissolution potential of ⁇ 3.35 V or more (vs. Fc/Fc + ) based on the oxidation-reduction potential of ferrocene.
  • the definition of 2) above is based on ferrocene, whose reaction potential is constant regardless of the composition of the electrolyte, and the lithium deposition and dissolution potential closer to the oxidation-reduction potential of ferrocene, that is, the potential window of the electrolyte (reductive decomposition (Fig. 1).
  • the range of lithium deposition dissolution potential in the electrolytic solution of the present invention is -3.35V or more (vs. Fc/Fc + ), preferably -3.35 to -2.8V.
  • the deposition dissolution potential is a value measured in the range 20-35°C, typically a value measured at 25°C.
  • lithium metal negative electrodes have a problem of low utilization efficiency (coulombic efficiency), and it has been known that the deposition and dissolution reaction potential of lithium metal exists outside the potential window of the electrolyte.
  • the decomposition of the electrolyte solution has been kinetically suppressed by forming a protective film on the surface of the lithium metal using an electrolyte solution additive or the like.
  • such a conventional method has a problem that the surface protective coating is destroyed along with charging and discharging of the battery.
  • the present invention upshifts the reaction potential of lithium deposition and dissolution with respect to the oxidation-reduction potential of ferrocene, thereby forming a surface protective film in a milder reducing environment and It is characterized in that it has been found that a lithium deposition and dissolution reaction can occur and that the coulombic efficiency of lithium metal on the electrode surface can be improved. More specifically, as described above, the oxidation-reduction potential of ferrocene is used as a reference, and the lithium deposition and dissolution potential is ⁇ 3.35 V or higher (vs. Fc/Fc + ), thereby increasing the efficiency of the lithium deposition and dissolution reaction. A correlation of 80% or more was found. In the present invention, the lithium deposition and dissolution efficiency is preferably 85% or higher, more preferably 90% or higher.
  • the electrolytic solution of the present invention can significantly improve the reversible reactivity of the negative electrode of metallic lithium by having a lithium deposition and dissolution potential in such a range, and can exhibit excellent battery characteristics even in charge-discharge cycles.
  • a secondary battery can be provided.
  • the electrolytic solution of the present invention may have the above-described 1) and 2), and its specific composition is not necessarily limited. Describe typical examples of each component
  • solvent specified in 1) above can be a conventionally known solvent that can be used as an electrolyte for secondary batteries, and is not particularly limited. Typically, it is a non-aqueous solvent (organic solvent). Examples of such solvents include propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one.
  • PC propylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • ethyl methyl carbonate 4-trifluoromethyl-1,3-dioxolan-2-one.
  • DMM dimethoxymethane
  • DME 1,2-dimethoxyethane
  • DME 1,3-dimethoxypropane
  • pentafluoropropyl methyl ether 2, Ethers such as 2,3,3-tetrafluoropropyldifluoromethyl ether, 1,4-dioxane, tetrahydrofuran (THF), and 2-methyltetrahydrofuran
  • Esters such as methyl formate, methyl acetate, and ⁇ -butyrolactone
  • Acetonitrile, butyronitrile nitriles such as; amines such as triethylamine; amides such as N,N-dimethylformamide (DMF) and N,N-dimethylacetamide; carbamates such as 3-methyl-2-oxazolidone; sulfolane, dimethylsulfoxide (DMSO)
  • typical solvents include 1,2-dimethoxyethane (DME), hydrofluoroether (HFE), ethylene carbonate (EC), propylene carbonate (PC), fluorinated linear carbonate (FEMC), 1,4 - dioxane, sulfolane, toluene, diethylene glycol dimethyl ether (diglyme) can be used.
  • DME 1,2-dimethoxyethane
  • HFE hydrofluoroether
  • EC ethylene carbonate
  • PC propylene carbonate
  • FEMC fluorinated linear carbonate
  • 1,4 - dioxane 1,4 - dioxane
  • sulfolane 1,4 - dioxane
  • toluene diethylene glycol dimethyl ether
  • the electrolytic solution of the present invention contains a lithium salt, but a mixture of two or more lithium salts can also be used.
  • the anion constituting the lithium salt is preferably an anion containing one or more groups selected from the group consisting of a fluorosulfonyl group, a trifluoromethanesulfonyl group, and a perfluoroethanesulfonyl group.
  • bis(fluorosulfonyl)imide [N(FSO 2 ) 2 ] ⁇ ), (fluorosulfonyl)(trifluorosulfonyl)imide ([N(CF 3 SO 2 )(FSO 2 )] ⁇ ), bis(trifluoro romethanesulfonyl)imide ([N(CF 3 SO 2 ) 2 ] ⁇ ), bis(perfluoroethanesulfonyl)imide ([N(C 2 F 5 SO 2 ) 2 ] ⁇ ) or (perfluoroethanesulfonyl) (tri Fluoroethanemethanesulfonyl)imide ([N(C 2 F 5 SO 2 )(CF 3 SO 2 )] ⁇ ) is preferred.
  • lithium salt examples include lithium bis(fluorosulfonyl)imide (LiFSI), lithium (fluorosulfonyl)(trifluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(per fluoroethanesulfonyl)imide (LiBETI) or lithium(perfluoroethanesulfonyl)(trifluoroethanemethanesulfonyl)imide.
  • LiFSI lithium bis(fluorosulfonyl)amide
  • These salts are preferred because they have a weak cation-anion interaction and have high ion conductivity even at high concentrations.
  • the concentration of the lithium salt in the electrolytic solution can be within a range that enables reversible insertion/extraction reactions of lithium ions into the negative electrode carbon material, as long as precipitation of the lithium salt does not occur.
  • the molar ratio of the solvent to the lithium salt is preferably in the range of 1:20 to 1:0.5. If the concentration of the lithium salt is excessively low, the ionic conductivity is low, and if the concentration is excessively high, adverse effects such as increased viscosity may occur.
  • a supporting electrolyte known in the art can be included.
  • Such supporting electrolytes include, for example, LiPF 6 , LiBF 4 , LiClO 4 , LiNO 3 , LiCl, Li 2 SO 4 , Li 2 S, lithium difluoro(oxalato)borate (LiDFOB), and lithium bis(oxalato)borate ( LiBOB), etc. and any combination thereof.
  • the electrolytic solution of the present invention may contain other components as necessary for the purpose of improving its functions.
  • Other components include, for example, conventionally known overcharge inhibitors, dehydrating agents, deoxidizing agents, and property-improving aids for improving capacity retention properties and cycle properties after high-temperature storage.
  • overcharge inhibitors include aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether and dibenzofuran; partially fluorinated aromatic compounds such as biphenyl, o-cyclohexylfluorobenzene and p-cyclohexylfluorobenzene; fluorine-containing anisoles such as 2,4-difluoroanisole, 2,5-difluoroanisole and 2,6-difluoroaniol; compound.
  • the overcharge inhibitor may be used singly or in combination of two or more.
  • the content of the overcharge-preventing agent in the electrolytic solution is preferably 0.01 to 5% by mass.
  • the overcharge inhibitor in the electrolytic solution it becomes easier to suppress explosion and ignition of the secondary battery due to overcharge, and the secondary battery can be used more stably.
  • dehydrating agents examples include molecular sieves, mirabilite, magnesium sulfate, calcium hydride, sodium hydride, potassium hydride, and lithium aluminum hydride.
  • the solvent used in the electrolytic solution of the present invention may be dehydrated with the dehydrating agent and then rectified. Alternatively, a solvent that has been dehydrated with the dehydrating agent without being rectified may be used.
  • Examples of property-improving aids for improving capacity retention characteristics and cycle characteristics after high-temperature storage include succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, di Carboxylic anhydrides such as glycolic acid, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phenylsuccinic anhydride; ethylene sulfite, 1,3-propanesultone, 1,4-butanesultone, methanesulfonic acid including methyl, busulfan, sulfolane, sulfolene, dimethylsulfone, diphenylsulfone, methylphenylsulfone, dibutyl disulfide, dicyclohexyl disulfide, tetramethylthiuram monosulfide, N,N-dimethylmethanesul
  • the electrolyte contains a property-improving aid, the content of the property-improving aid in the electrolyte is preferably 0.01 to 5% by mass.
  • the metallic lithium secondary battery of the present invention comprises a positive electrode, a negative electrode, and the electrolyte solution described above.
  • the positive electrode and negative electrode in the secondary battery of the present invention are described below.
  • the negative electrode in the secondary battery of the present invention preferably contains an active material that accompanies deposition and dissolution reaction of lithium metal.
  • an active material that accompanies deposition and dissolution reaction of lithium metal.
  • alloys containing lithium include lithium aluminum alloys, lithium tin alloys, lithium lead alloys, and lithium silicon alloys.
  • metal nitrides containing lithium include lithium cobalt nitride, lithium iron nitride, lithium manganese nitride and the like.
  • Lithium titanate (Li 4 Ti 5 O 12 ) and lithium titanium niobate (TiNb 2 O 7 ) can also be used.
  • the negative electrode may contain only the negative electrode active material, and in addition to the negative electrode active material, contains at least one of a conductive material and a binder, and a negative electrode current collector as a negative electrode mixture. It may be in the form of being attached to.
  • the negative electrode active material is foil-shaped, the negative electrode can be made to contain only the negative electrode active material.
  • the negative electrode active material is powdery, the negative electrode can have the negative electrode active material and a binder.
  • a doctor blade method, a molding method using a compression press, or the like can be used as a method for forming the negative electrode using the powdery negative electrode active material.
  • Examples of conductive materials that can be used include carbon materials, conductive fibers such as metal fibers, metal powders such as copper, silver, nickel, and aluminum, and organic conductive materials such as polyphenylene derivatives.
  • Graphite, soft carbon, hard carbon, carbon black, ketjen black, acetylene black, graphite, activated carbon, carbon nanotube, carbon fiber, etc. can be used as the carbon material.
  • Mesoporous carbon obtained by firing a synthetic resin containing an aromatic ring, petroleum pitch, or the like can also be used.
  • binders include fluorine-based resins such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and ethylenetetrafluoroethylene (ETFE), carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR ), polyethylene, polypropylene and the like can be preferably used.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • ETFE ethylenetetrafluoroethylene
  • CMC carboxymethylcellulose
  • SBR styrene-butadiene rubber
  • polyethylene polypropylene and the like
  • a rod-shaped body, a plate-shaped body, a foil-shaped body, a mesh-shaped body, etc. mainly made of copper, nickel, aluminum, stainless steel, or the like can be used.
  • the positive electrode active material includes lithium cobaltate (LiCoO 2 ), lithium manganate (LiMnO 2 ), lithium manganese spinel (LiMn 2 O 4 ), lithium nickelate (LiNiO 2 ), etc., or one of these compositions.
  • the positive electrode may contain a conductive material and a binder.
  • the same materials as those for the negative electrode can be used.
  • the positive electrode current collector metal for example, copper, nickel, aluminum, stainless steel, etc. can be used.
  • the separator used in the secondary battery of the present invention is not particularly limited as long as it has a function of electrically separating the positive electrode layer and the negative electrode layer.
  • the separator used in the secondary battery of the present invention is not particularly limited as long as it has a function of electrically separating the positive electrode layer and the negative electrode layer.
  • PE polyethylene
  • PP polypropylene
  • polyester polyester
  • cellulose polyamide
  • other resin porous sheets and porous insulating materials
  • nonwoven fabrics such as nonwoven fabrics and glass fiber nonwoven fabrics.
  • (D) Shape of Battery The shape of the secondary battery of the present invention is not particularly limited as long as it can accommodate the positive electrode, the negative electrode, and the electrolytic solution. Laminate type etc. can be mentioned.
  • electrolytic solution and secondary battery of the present invention are suitable for use as a secondary battery, they are not excluded from being used as a primary battery.
  • the present invention also relates to a method for evaluating an electrolytic solution for a metallic lithium secondary battery, whereby an electrolytic solution suitable for a metallic lithium secondary battery is evaluated and specified by a simple method. can do.
  • the method for evaluating the electrolytic solution for a metallic lithium secondary battery of the present invention comprises: 1) preparing a test electrolyte containing a solvent and a lithium salt; 2) adding 0.1 to 10 mmol/L of ferrocene to the test electrolyte; 3) performing an electrochemical measurement using the test electrolyte containing ferrocene and using lithium metal as a reference electrode to measure the oxidation-reduction potential of ferrocene; and 4) lithium relative to the oxidation-reduction potential of ferrocene.
  • a step of calculating a deposition dissolution potential (vs. Fc/Fc + ) is included.
  • step 1 For the type of solvent and lithium salt in step 1), the ones explained above are applied as they are.
  • electrochemical measurement in step 3 typically, a cyclic voltammetry (CV) method can be used.
  • the evaluation table method of the present invention can further include the following step 5) after step 4). 5) A step of selecting an electrolytic solution having a lithium deposition dissolution potential of ⁇ 3.35 V or more (vs. Fc/Fc + ).
  • electrolyte solutions A and B with different compositions are prepared, CV measurement is performed using lithium metal as a reference electrode, and the results in Fig. 2 are obtained.
  • the lithium deposition and dissolution potentials of the electrolytes A and B are calculated to be ⁇ 3.38 V and ⁇ 3.18 V, respectively.
  • the lithium deposition and dissolution potential of electrolyte B is closer to the oxidation-reduction potential, that is, the lithium deposition and dissolution potential is closer to the potential window (reduction decomposition potential) of the electrolyte.
  • electrolytic solution B can cause film formation and lithium deposition and dissolution reactions in a milder reducing environment, and can improve coulombic efficiency.
  • Lithium deposition and dissolution potentials and their coulombic efficiencies were measured by cyclic voltammetry (CV) for various electrolyte systems according to the following procedure. All electrochemical measurements were performed at room temperature.
  • electrolytic solution system those having the compositions shown in Tables 1 and 2 below were used. These electrolytic solutions were prepared by dissolving lithium bis(fluorosulfonyl)imide (LiFSI: LiN(SO 2 F) 2 , manufactured by Nippon Shokubai Co., Ltd.) in a predetermined solvent in a glove box filled with Ar.
  • LiFSI lithium bis(fluorosulfonyl)imide
  • Cyclic voltammetry (CV) measurements were performed using a VMP3 potentiostat (BioLogic), the oxidation of Li metal in a three-electrode cell consisting of Pt as working electrode and Li metal as counter and reference electrodes. The reduction potential was evaluated with various electrolytes containing 1 mmol/L ferrocene (Fc: SigmaAldrich).
  • An electrochemical Li deposition and dissolution reaction test was performed using a half cell (Cu
  • Coin cell components stainless steel positive and negative cases, springs, spacers, polypropylene O-rings were commercially available from Hoshen.
  • Commercially available copper foils and lithium metal foils were used without treatment.
  • FIG. 4 shows the results of plotting the lithium deposition and dissolution potential (vs. Fc/Fc + ) and coulombic efficiency (lithium deposition and dissolution efficiency) obtained in each electrolyte solution system.
  • a clear correlation was found that the group of electrolyte solutions having a lithium deposition and dissolution potential of -3.35 V or higher had a lithium deposition and dissolution reaction efficiency of 90% or higher. That is, it was suggested that an electrolytic solution having a lithium deposition dissolution potential of ⁇ 3.35 V or more can improve the coulombic efficiency of lithium metal on the electrode surface and greatly improve the reversible reactivity of the metallic lithium negative electrode. This is believed to be due to the fact that a surface protective film can be formed and a lithium deposition and dissolution reaction can occur under a milder reducing environment.

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PCT/JP2022/036999 2021-10-05 2022-10-03 金属リチウム二次電池用電解液及び当該電解液を含む金属リチウム二次電池並びに金属リチウム二次電池用電解液の評価方法 Ceased WO2023058606A1 (ja)

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