CN113396500A - Electrolyte solution and electrochemical device - Google Patents
Electrolyte solution and electrochemical device Download PDFInfo
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- CN113396500A CN113396500A CN201980091226.8A CN201980091226A CN113396500A CN 113396500 A CN113396500 A CN 113396500A CN 201980091226 A CN201980091226 A CN 201980091226A CN 113396500 A CN113396500 A CN 113396500A
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- 150000001875 compounds Chemical class 0.000 claims abstract description 63
- 150000001923 cyclic compounds Chemical class 0.000 claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
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- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 15
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- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
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- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 6
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
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- 239000007788 liquid Substances 0.000 description 1
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
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- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 125000002560 nitrile group Chemical group 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
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Images
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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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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- Secondary Cells (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
An aspect of the present invention is an electrolytic solution containing: a compound represented by the following formula (1); and cyclic compounds having a ring containing a sulfur atom. In the formula (1), R1～R3Each independently represents an alkyl group or a fluorine atom, R4Represents an alkylene group, R5Represents an organic group containing a nitrogen atom.
Description
Technical Field
The invention relates to an electrolyte and an electrochemical device.
Background
In recent years, due to the spread of portable electronic devices, electric vehicles, and the like, high-performance electrochemical devices such as nonaqueous electrolyte secondary batteries typified by lithium ion secondary batteries, capacitors, and the like have been regarded as essential. As a means for improving the performance of an electrochemical device, for example, a method of adding a predetermined additive to an electrolytic solution has been studied. Patent document 1 discloses an electrolyte for a nonaqueous electrolyte battery containing a specific siloxane compound in order to improve cycle characteristics and internal resistance characteristics.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2015-005329
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to provide an electrolyte capable of improving the performance of an electrochemical device.
Means for solving the technical problem
An aspect of the present invention is an electrolytic solution containing: a compound represented by the following formula (1); and cyclic compounds having a ring containing a sulfur atom.
In the formula (1), R1～R3Each independently represents an alkyl group or a fluorine atom, R4Represents an alkylene group, R5Represents an organic group containing a nitrogen atom.
According to one aspect, the electrolyte solution can suppress a voltage drop after the electrochemical device is stored at a high temperature as a performance of the electrochemical device. In another aspect, the electrolyte solution can suppress an increase in volume of the electrochemical device after the electrochemical device is stored at a high temperature. In another aspect, the electrolyte solution can improve the capacity retention rate of the electrochemical device after the electrochemical device is stored at a high temperature. In another aspect, the electrolyte solution can improve the capacity recovery rate of the electrochemical device after storage at a high temperature.
R1～R3At least 1 of which may be a fluorine atom. The number of silicon atoms in one molecule of the compound represented by formula (1) may be 1.
R5May be a group represented by the following formula (2).
In the formula (2), R6And R7Each independently represents a hydrogen atom or an alkyl group, and represents a bonding site.
The cyclic compound may comprise a cyclic sulfonate compound. The cyclic sulfonate compound may include a compound represented by the following formula (X).
In the formula (X), A1The compound is a group containing an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms, and the hydrogen atoms in the alkylene group and the alkenylene group may be substituted with an alkyl group, a cycloalkyl group, an aryl group or a fluoro group.
The compound represented by formula (X) may include at least 1 selected from the group consisting of 1, 3-propane sultone and 1-propene-1, 3-sultone.
The cyclic compound may include at least 1 selected from the group consisting of a compound represented by formula (Y) and a compound represented by formula (Z).
In the formula (Y), A2Represents an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms, wherein hydrogen atoms in the alkylene group and the alkenylene group may be substituted with an alkyl group, a cycloalkyl group or an aryl group.
In the formula (Z), A3Represents an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms, wherein hydrogen atoms in the alkylene group and the alkenylene group may be substituted with an alkyl group, a cycloalkyl group or an aryl group.
The total of the content of the compound represented by formula (1) and the content of the cyclic sulfonate compound may be 10% by mass or less based on the total amount of the electrolyte.
Another embodiment of the present invention is an electrochemical device including: a positive electrode, a negative electrode and the electrolyte.
The negative electrode may contain a carbon material. The carbon material may contain graphite. The anode may further contain a material containing at least 1 element selected from the group consisting of silicon and tin.
The electrochemical device may be a nonaqueous electrolyte secondary battery or a capacitor.
Effects of the invention
According to the present invention, an electrolytic solution capable of improving the performance of an electrochemical device can be provided.
Drawings
Fig. 1 is a perspective view showing a nonaqueous electrolyte secondary battery as an electrochemical device according to an embodiment.
Fig. 2 is an exploded perspective view illustrating an electrode group of the secondary battery shown in fig. 1.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings as appropriate. However, the present invention is not limited to the following embodiments.
Fig. 1 is a perspective view showing an electrochemical device according to an embodiment. In the present embodiment, the electrochemical device is a nonaqueous electrolyte secondary battery. As shown in fig. 1, a nonaqueous electrolyte secondary battery 1 includes: an electrode group 2 composed of a positive electrode, a negative electrode, and a separator; and a pouch-shaped battery exterior body 3 that houses the electrode group 2. A positive electrode collector tab 4 and a negative electrode collector tab 5 are provided on the positive electrode and the negative electrode, respectively. The positive electrode current collector tab 4 and the negative electrode current collector tab 5 protrude from the inside to the outside of the battery exterior package 3 so that the positive electrode and the negative electrode can be electrically connected to the outside of the nonaqueous electrolyte secondary battery 1. The battery exterior body 3 is filled with an electrolyte (not shown). The nonaqueous electrolyte secondary battery 1 may be a battery (coin type, cylindrical type, laminated type, etc.) having a shape other than the so-called "laminated type" as described above.
The battery exterior package 3 may be a container formed of a laminate film, for example. The laminate film may be, for example, a laminate film in which a resin film such as a polyethylene terephthalate (PET) film, a metal foil such as aluminum, copper, stainless steel, or the like, and a sealant layer such as polypropylene are sequentially laminated.
Fig. 2 is an exploded perspective view showing an embodiment of the electrode group 2 in the nonaqueous electrolyte secondary battery 1 shown in fig. 1. As shown in fig. 2, the electrode group 2 includes a positive electrode 6, a separator 7, and a negative electrode 8 in this order. The positive electrode 6 and the negative electrode 8 are arranged such that the surfaces on the positive electrode mixture layer 10 side and the negative electrode mixture layer 12 side face the separator 7, respectively.
The positive electrode 6 includes a positive electrode current collector 9 and a positive electrode mixture layer 10 provided on the positive electrode current collector 9. A positive electrode collector tab 4 is provided on the positive electrode collector 9.
The positive electrode current collector 9 is made of, for example, aluminum, titanium, stainless steel, nickel, calcined carbon, a conductive polymer, conductive glass, or the like. The positive electrode current collector 9 may be treated with carbon, nickel, titanium, silver, or the like on the surface of aluminum, copper, or the like for the purpose of improving adhesion, conductivity, and oxidation resistance. The thickness of the positive electrode current collector 9 is, for example, 1 to 50 μm from the viewpoint of the electrode strength and energy density.
In one embodiment, the positive electrode mixture layer 10 contains a positive electrode active material, a conductive agent, and a binder. The thickness of the positive electrode mixture layer 10 is, for example, 20 to 200 μm.
The positive electrode active material may be, for example, lithium oxide. Examples of lithium oxides include: lixCoO2、LixNiO2、LixMnO2、LixCoyNi1-yO2、LixCoyM1-yOz、LixNi1-yMyOz、LixMn2O4And LixMn2-yMyO4(wherein M represents at least 1 element selected from the group consisting of Na, Mg, Sc, Y, Mn, Fe, Co, Cu, Zn, Al, Cr, Pb, Sb, V and B (wherein M is an element different from the other elements in the formulae). x is 0 to 1.2, Y is 0 to 0.9, and z is 2.0 to 2.3.). From LixNi1-yMyOzThe lithium oxide represented may be LixNi1-(y1+y2)Coy1Mny2Oz(wherein x and z are the same as above, y1 is 0 to 0.9, y2 is 0 to 0.9, and y1+ y2 is 0 to 0.9.), for example, LiNi may be used1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2. From LixNi1-yMyOzThe lithium oxide represented may be LixNi1-(y3+y4)Coy3Aly4Oz(wherein x and z are the same as above, y3 is 0 to 0.9, y4 is 0 to 0.9, and y3+ y4 is 0 to 0.9.), for example, LiNi may be used0.8Co0.15Al0.05O2。
The positive electrode active material may be, for example, a lithium phosphate. Examples of the lithium phosphate include lithium manganese phosphate (LiMnPO)4) Lithium iron phosphate (LiFePO)4) Lithium cobalt phosphate (LiCoPO)4) And lithium vanadium phosphate (Li)3V2(PO4)3)。
The content of the positive electrode active material may be 80 mass% or more or 85 mass% or more, and may be 99 mass% or less, based on the total amount of the positive electrode mixture layer.
The conductive agent may be carbon black such as acetylene black or Ketjen black (Ketjen black), or a carbon material such as graphite, graphene, or carbon nanotubes. The content of the conductive agent may be, for example, 0.01 mass% or more, 0.1 mass% or more, or 1 mass% or more, and may be 50 mass% or less, 30 mass% or less, or 15 mass% or less, based on the total amount of the positive electrode mixture layer.
Examples of binders include: resins such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, and nitrocellulose; rubbers such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), fluororubber, isoprene rubber, butadiene rubber, and ethylene-propylene rubber; thermoplastic elastomers such as styrene-butadiene-styrene block copolymers or hydrogenated products thereof, EPDM (ethylene-propylene-diene terpolymer), styrene-ethylene-butadiene-ethylene copolymers, styrene-isoprene-styrene block copolymers or hydrogenated products thereof; soft resins such as syndiotactic-1, 2-polybutadiene, polyvinyl acetate, ethylene-vinyl acetate copolymers and propylene- α -olefin copolymers; fluorine-containing resins such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene, fluorinated polyvinylidene fluoride, polytetrafluoroethylene-ethylene copolymer, and polytetrafluoroethylene-vinylidene fluoride copolymer; a resin having a nitrile group-containing monomer as a monomer unit; and a polymer composition having ion conductivity of an alkali metal ion (for example, lithium ion).
The content of the binder may be, for example, 0.1 mass% or more, 1 mass% or more, or 1.5 mass% or more, and may be 30 mass% or less, 20 mass% or less, or 10 mass% or less, based on the total amount of the positive electrode material layer.
The separator 7 is not particularly limited as long as it can electrically insulate the positive electrode 6 and the negative electrode 8 from each other, can transmit ions, and has oxidation resistance on the positive electrode 6 side and reduction resistance on the negative electrode 8 side. Examples of the material (material) of the separator 7 include resins and inorganic substances.
Examples of the resin include olefin polymers, fluorine polymers, cellulose polymers, polyimides, and nylons. From the viewpoint of stability to an electrolytic solution and excellent liquid retention, the separator 7 is preferably a porous sheet or nonwoven fabric formed of polyolefin such as polyethylene or polypropylene.
Examples of the inorganic substance include oxides such as alumina and silica, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate. The separator 7 may be a separator in which a fibrous or particulate inorganic substance is attached to a film-like base material such as a nonwoven fabric, a woven fabric, or a microporous film.
The negative electrode 8 includes a negative electrode current collector 11 and a negative electrode mixture layer 12 provided on the negative electrode current collector 11. The negative electrode current collector 11 is provided with a negative electrode current collector tab 5.
The negative electrode current collector 11 is made of copper, stainless steel, nickel, aluminum, titanium, calcined carbon, a conductive polymer, conductive glass, an aluminum-cadmium alloy, or the like. The negative electrode current collector 11 may be surface-treated with carbon, nickel, titanium, silver, or the like for the purpose of improving adhesion, conductivity, and reduction resistance. The thickness of the negative electrode current collector 11 is, for example, 1 to 50 μm from the viewpoint of the electrode strength and energy density.
The negative electrode mixture layer 12 contains, for example, a negative electrode active material and a binder.
The negative electrode active material is not particularly limited as long as it can intercalate and deintercalate lithium ions. Examples of the negative electrode active material include: a carbon material; a metal composite oxide; oxides or nitrides of group iv elements such as tin, germanium, and silicon; the simple substance of lithium; lithium alloys such as lithium aluminum alloys; sn, Si, and other metals capable of forming an alloy with lithium. From the viewpoint of safety, the negative electrode active material is preferably at least 1 selected from the group consisting of carbon materials and metal composite oxides. The negative electrode active material may be a mixture of 1 or 2 or more of these alone. The negative electrode active material may be in the form of particles, for example.
Examples of the carbon material include an amorphous carbon material, natural graphite, a composite carbon material in which a coating film of an amorphous carbon material is formed on natural graphite, and artificial graphite (graphite obtained by calcining a resin raw material such as an epoxy resin or a phenol resin or a pitch-based raw material obtained from petroleum or coal). The metal composite oxide preferably contains either or both of titanium and lithium, and more preferably contains lithium, from the viewpoint of high current density charge-discharge characteristics.
Among the negative electrode active materials, the carbon material has high conductivity and is particularly excellent in low-temperature characteristics and cycle stability. Among carbon materials, graphite is preferable from the viewpoint of high capacity. In graphite, the carbon network interlayer (d002) in the X-ray wide angle diffraction method is preferably less than 0.34nm, more preferably 0.3354nm or more and 0.337nm or less. A carbon material satisfying such conditions is sometimes referred to as pseudo anisotropic carbon.
The negative electrode active material may further contain a material containing at least 1 element selected from the group consisting of silicon and tin. The material containing at least 1 element selected from the group consisting of silicon and tin may be a simple substance of silicon or tin, a compound containing at least 1 element selected from the group consisting of silicon and tin. The compound may be an alloy containing at least 1 element selected from the group consisting of silicon and tin, for example, an alloy containing at least 1 element selected from the group consisting of nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, and chromium in addition to silicon and tin. The compound containing at least 1 element selected from the group consisting of silicon and tin may be an oxide, nitride or carbide, and specifically, for example, SiO or SiO2Silicon oxides such as LiSiO; si3N4、Si2N2Silicon nitride such as O; silicon carbide such as SiC; SnO, SnO2And tin oxides such as LiSnO.
The negative electrode 8 preferably contains a carbon material, more preferably graphite, further preferably a mixture containing a carbon material and a material containing at least 1 element selected from the group consisting of silicon and tin, and particularly preferably a mixture containing graphite and silicon oxide, as a negative electrode active material, from the viewpoint of further improving the performance of an electrochemical device such as low-temperature input characteristics. The content of the carbon material (graphite) relative to the material (silicon oxide) containing at least 1 element selected from the group consisting of silicon and tin in the mixture may be 1 mass% or more or 3 mass% or more, and may be 30 mass% or less, based on the total amount of the mixture.
The content of the negative electrode active material may be 80 mass% or more or 85 mass% or more, and may be 99 mass% or less, based on the total amount of the negative electrode mixture layer.
The binder and the content thereof may be the same as those of the binder and the content thereof in the positive electrode binder layer described above.
The negative electrode mixture layer 12 may contain a thickener in order to adjust the viscosity. The thickener is not particularly limited, and may be carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, salts thereof, or the like. The thickener may be a mixture of 1 or 2 or more of these alone.
When the negative electrode mixture layer 12 contains a thickener, the content thereof is not particularly limited. From the viewpoint of coating properties of the negative electrode mixture layer, the content of the thickener may be 0.1 mass% or more, preferably 0.2 mass% or more, and more preferably 0.5 mass% or more, based on the total amount of the negative electrode mixture layer. The content of the thickener may be 5 mass% or less, preferably 3 mass% or less, and more preferably 2 mass% or less, based on the total amount of the negative electrode mixture layer, from the viewpoint of suppressing a decrease in battery capacity or an increase in resistance between the negative electrode active materials.
In one embodiment, the electrolytic solution contains a compound represented by the following formula (1), a cyclic compound having a ring containing a sulfur atom (hereinafter, also simply referred to as "cyclic compound"), an electrolyte salt, and a nonaqueous solvent.
In the formula (1), R1～R3Each independently represents an alkyl group or a fluorine atom, R4Represents an alkylene group, R5Represents an organic group containing a nitrogen atom.
From R1～R3The number of carbon atoms of the alkyl group represented may be 1 or more and 3 or less. R1～R3The alkyl group may be a methyl group, an ethyl group or a propyl group, and may be linear or branched. Preferably R1～R3At least 1 of which is a fluorine atom. R1～R3Any of which may be a fluorine atom, R1～R3Any two of (A) may be fluorine atoms, R1～R3All may be fluorine atoms.
From R4The number of carbon atoms of the alkylene group represented may be 1 or more or 2 or more, and may be 5 or less or 4 or less. From R4The alkylene group may be a methylene group, an ethylene group, a propylene group, a butylene group or a pentylene group, and may be a straight chain or a branched chain.
In one embodiment, the number of silicon atoms in one molecule of the compound represented by formula (1) is 1. That is, in one embodiment, R is substituted with5The organic groups represented do not contain silicon atoms.
From the viewpoint of being able to further improve the performance of the electrochemical device, R5Preferred is a group represented by the following formula (2).
In the formula (2), R6And R7Each independently represents a hydrogen atom or an alkyl group. From R6Or R7The alkyl group represented by R may be substituted with the above-mentioned group1～R3The alkyl groups represented are the same. Denotes the bonding site.
From the viewpoint of further improving the performance of the electrochemical device, the content of the compound represented by formula (1) is preferably 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more, and 8 mass% or less, 5 mass% or less, 3 mass% or less, 2 mass% or less, or 1 mass% or less, based on the total amount of the electrolyte.
The cyclic compound is a compound having a ring (heterocycle) containing a sulfur atom. The cyclic compound is a compound other than the compound represented by the above formula (1). In other words, the cyclic compound is a compound having no silicon atom.
The cyclic compound may include, for example, among cyclic sulfonate compounds (also referred to as sultone compounds)At least 1. The cyclic sulfonate compound is a compound having a structure containing-OSO2-cyclic compounds of the group. The cyclic sulfonate compound has a structure containing 1 or 2-OSO2-a ring of radicals.
Having a structure comprising 1-OSO2The cyclic sulfonate compound of the ring of the-group may be, for example, a compound represented by the following formula (X).
In the formula (X), A1The compound is a group containing an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms, and the hydrogen atoms in the alkylene group and the alkenylene group may be substituted with an alkyl group, a cycloalkyl group, an aryl group or a fluoro group.
The number of carbon atoms of the alkyl group may be, for example, 1 to 12. The cycloalkyl group may have 3 to 6 carbon atoms, for example. The number of carbon atoms of the aryl group may be, for example, 6 to 12.
A1An alkylene group having 3 carbon atoms or an alkenylene group having 3 carbon atoms is preferable. That is, the cyclic sulfonic acid ester compound is preferably a compound represented by the following formula (X-1) or formula (X-2).
In the formula, R11～R20Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a fluoro group. From R11～R20The number of carbon atoms of the alkyl group, the cycloalkyl group and the aryl group is the same as the number of carbon atoms of the alkyl group, the cycloalkyl group and the aryl group described for the formula (X). R11～R20Preferably a hydrogen atom.
Examples of the cyclic sulfonate compound represented by the formula (X) include: 1, 3-propane sultone, 1, 4-butane sultone, 2, 4-butane sultone, 1, 3-propene sultone, 1, 4-butene sultone, 1-methyl-1, 3-propane sultone, 3-methyl-1, 3-propane sultone, 1-fluoro-1, 3-propane sultone, 3-fluoro-1, 3-propane sultone, and the likeMonosulfonate esters, and the like. Of these, 1, 3-propane sultone (in the formula (X-1), R is preferable from the viewpoint of further improving the performance of the electrochemical device11～R16All hydrogen atoms) or 1-propene-1, 3-sultone (in the formula (X-2), R17～R20Compounds all of which are hydrogen atoms).
Having a structure comprising 2-OSO2The cyclic sulfonate compound of the ring of the-group may be, for example, a compound represented by the following formula (X-3).
In the formula, B1And B2Each independently represents an alkylene group having 1 to 5 carbon atoms or an alkenylene group having 1 to 5 carbon atoms, and hydrogen atoms in the alkylene group and the alkenylene group may be substituted by an alkyl group, a cycloalkyl group, an aryl group or a fluoro group.
B1And B2An unsubstituted alkylene group having 1 or 2 carbon atoms is preferable. Such cyclic sulfonate compounds may be disulfonates such as methylene methanedisulfonate and ethylene methanedisulfonate.
The cyclic compound may include, for example, at least 1 selected from the group consisting of a compound represented by formula (Y) and a compound represented by formula (Z).
In the formulae (Y), (Z), A2And A3Each independently represents an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms, and hydrogen atoms in the alkylene group and the alkenylene group may be substituted with an alkyl group, a cycloalkyl group or an aryl group.
A2And A3The number of carbon atoms of the alkyl group, the cycloalkyl group and the aryl group in (b) is the same as the number of carbon atoms of the alkyl group, the cycloalkyl group and the aryl group described for the formula (X).
As the compound represented by the formula (Y), for example: sulfolane, 2-methylsulfolane, 3-methylsulfolane, 2-ethylsulfolane, 3-ethylsulfolane, 2, 4-dimethylsulfolane, 2-phenylsulfolane, 3-phenylsulfolane, sulfolene (sulfolene), 3-methylsulfolene sulfone, etc. The compound represented by the formula (Y) is preferably sulfolane from the viewpoint of being able to further enhance the performance of the electrochemical device.
As the compound represented by the formula (Z), for example: ethylene sulfite, propylene sulfite, butylene sulfite, vinylene sulfite, phenylethylene sulfite, and the like. The compound represented by formula (Z) is preferably ethylene sulfite from the viewpoint of being able to further improve the performance of the electrochemical device.
The cyclic compound may include at least 1 selected from the group consisting of a cyclic sulfonate compound, a compound represented by formula (Y), and a compound represented by formula (Z), may include at least 1 selected from the group consisting of a compound represented by formula (X), a compound represented by formula (Y), and a compound represented by formula (Z), and may include at least 1 selected from the group consisting of a compound represented by formula (X) and a compound represented by formula (Z).
From the viewpoint of further improving the performance of the electrochemical device, the content of the cyclic compound is preferably 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more, and 5 mass% or less, 3 mass% or less, 2 mass% or less, or 1 mass% or less, based on the total amount of the electrolyte.
From the viewpoint of further improving the performance of the electrochemical device, the total of the content of the compound represented by formula (1) and the content of the cyclic compound is preferably 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.1 mass% or more, or 0.5 mass% or more, and preferably 10 mass% or less, 7 mass% or less, 5 mass% or less, 3 mass% or less, or 2 mass% or less, based on the total amount of the electrolytic solution.
From the viewpoint of being able to further improve the performance of the electrochemical device, the mass ratio of the content of the compound represented by formula (1) to the content of the cyclic compound (content of the compound represented by formula (1)/content of the cyclic compound) is preferably 0.01 or more, 0.05 or more, 0.1 or more, 0.2 or more, or 0.25 or more, and is preferably 500 or less, 100 or less, 50 or less, 20 or less, 10 or less, 5 or less, or 4 or less.
The electrolyte salt may be, for example, a lithium salt. The lithium salt may be selected from, for example, LiPF6、LiBF4、LiClO4、LiB(C6H5)4、LiCH3SO3、CF3SO2OLi、LiN(SO2F)2(Li[FSI]Lithium bis (fluorosulfonylimide), LiN (SO)2CF3)2(Li[TFSI]Lithium bistrifluoromethanesulfonimide) and LiN (SO)2CF2CF3)2At least 1 of the group consisting of. The lithium salt preferably contains LiPF from the viewpoint of further excellent solubility in a solvent, charge/discharge characteristics of a secondary battery, output characteristics, cycle characteristics, and the like6。
The concentration of the electrolyte salt is preferably 0.5mol/L or more, more preferably 0.7mol/L or more, and even more preferably 0.8mol/L or more, and is preferably 1.5mol/L or less, more preferably 1.3mol/L or less, and even more preferably 1.2mol/L or less, based on the total amount of the nonaqueous solvent, from the viewpoint of excellent charge and discharge characteristics.
The nonaqueous solvent may be, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, γ -butyrolactone, acetonitrile, 1, 2-dimethoxyethane, dimethoxymethane, tetrahydrofuran, dioxolane (dioxolane), methylene chloride, methyl acetate, or the like. The nonaqueous solvent may be a mixture of 1 or 2 or more kinds among these alone, and preferably a mixture of 2 or more kinds among these.
The electrolytic solution may further contain other materials than the compound represented by formula (1), the cyclic compound, the electrolyte salt, and the nonaqueous solvent. Other materials may be, for example: cyclic carbonates such as fluorine-containing cyclic carbonates and cyclic carbonates having a carbon-carbon double bond; a compound having a nitrogen atom other than the compound represented by the formula (1); a compound having a sulfur atom other than the cyclic compound; cyclic carboxylic acid esters, and the like.
The fluorine-containing cyclic carbonate may be, for example: 4-fluoro-1, 3-dioxolan-2-one (fluoroethylene carbonate; FEC), 1, 2-difluoroethylene carbonate, 1, 2-trifluoroethylene carbonate, 1,2, 2-tetrafluoroethylene carbonate and the like, and preferably 4-fluoro-1, 3-dioxolan-2-one (fluoroethylene carbonate; FEC). The cyclic carbonate having a carbon-carbon double bond may be, for example, vinylene carbonate. The compound containing a nitrogen atom other than the compound represented by the formula (1) may be a nitrile compound such as succinonitrile (succinonitril).
The present inventors have studied compounds having various structures and functional groups, and as a result, have found that the performance of an electrochemical device can be improved by applying the compound represented by the above formula (1) and a cyclic compound to an electrolytic solution. The present inventors speculate that the action and effect of using the compound represented by the formula (1) and the cyclic compound in the electrolyte solution are as follows. That is, it is considered that the compound represented by the formula (1) and the cyclic compound each act at a position where the effect is most likely to be exhibited in the lithium ion secondary battery, and contribute to, for example, formation of a stable film on the positive electrode or the negative electrode or stabilization of the electrolyte solution. As a result, the nonaqueous electrolyte secondary battery 1 is obtained.
Specifically, according to the electrolyte solution of one embodiment, as the performance of the electrochemical device, the voltage drop after the electrochemical device is stored at a high temperature can be suppressed. Further, according to the electrolyte solution of one embodiment, an increase in volume of the electrochemical device after storage at a high temperature can be suppressed. Further, according to the electrolyte solution of one embodiment, the capacity retention rate of the electrochemical device after storage at a high temperature can be improved. In addition, according to the electrolyte solution of one embodiment, the capacity recovery rate of the electrochemical device after storage at a high temperature can be improved.
Next, a method for manufacturing the nonaqueous electrolyte secondary battery 1 will be described. The method for manufacturing the nonaqueous electrolyte secondary battery 1 includes: step 1, obtaining a positive electrode 6; step 2, obtaining a negative electrode 8; a 3 rd step of housing the electrode group 2 in the battery exterior body 3; and a 4 th step of injecting the electrolyte solution into the battery exterior body 3.
In the step 1, the material for the positive electrode mixture layer 10 is dispersed in a dispersion medium using a kneader, a disperser, or the like to obtain a slurry-like positive electrode mixture, and then the positive electrode mixture is applied to the positive electrode current collector 9 by a doctor blade (doctor blade) method, an immersion method, a spraying method, or the like, and the dispersion medium is evaporated to obtain the positive electrode 6. After the dispersion medium is volatilized, a compression molding step using a roll press may be provided as necessary. The positive electrode mixture layer 10 can be formed into a multilayer structure by performing the steps from the application of the positive electrode mixture to the volatilization of the dispersion medium a plurality of times. The dispersion medium may be water, 1-methyl-2-pyrrolidone (hereinafter, also referred to as NMP), or the like.
The 2 nd step may be the same as the 1 st step, and the method of forming the negative electrode mixture layer 12 on the negative electrode current collector 11 may be the same as the 1 st step.
In the 3 rd step, the separator 7 is sandwiched between the manufactured positive electrode 6 and negative electrode 8 to form the electrode group 2. Next, the electrode group 2 is housed in the battery exterior body 3.
In the 4 th step, the electrolytic solution is injected into the battery exterior body 3. The electrolytic solution can be prepared, for example, by dissolving an electrolyte salt in a solvent and then dissolving other materials.
As another embodiment, the electrochemical device may be a capacitor. The capacitor may include, in the same manner as the nonaqueous electrolyte secondary battery 1: an electrode group composed of a positive electrode, a negative electrode and a separator; and a bag-shaped battery outer package body for accommodating the electrode group. The details of each constituent element in the capacitor may be the same as those of the nonaqueous electrolyte secondary battery 1.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
(example 1)
[ production of Positive electrode ]
In lithium cobaltate (95 mass%) as a positive electrode active materialFibrous graphite (1 mass%) as a conductive agent, Acetylene Black (AB) (1 mass%) and a binder (3 mass%) were added and mixed in this order. NMP as a dispersion medium was added to the obtained mixture, and the mixture was kneaded to prepare a slurry-like positive electrode mixture. A predetermined amount of the positive electrode mixture was uniformly and homogeneously applied to an aluminum foil having a thickness of 20 μm as a positive electrode current collector. Thereafter, the dispersion medium was volatilized, and densification was conducted by pressurization until the density became 3.6g/cm3Thus, a positive electrode was obtained.
[ production of negative electrode ]
A binder and carboxymethyl cellulose as a thickener are added to graphite as a negative electrode active material. The mass ratio of these is 98:1:1, where the negative electrode active material, binder and thickener are used. Water as a dispersion medium was added to the obtained mixture, and the mixture was kneaded to prepare a slurry-like negative electrode mixture. A predetermined amount of the negative electrode mixture was uniformly and homogeneously applied to a rolled copper foil having a thickness of 10 μm as a negative electrode current collector. Thereafter, the dispersion medium was volatilized, and densification was conducted by pressurization to a density of 1.6g/cm3Thus, a negative electrode was obtained.
[ production of lithium ion Secondary Battery ]
A polyethylene porous sheet (trade name: Hipore (registered trademark) with a thickness of 30 μm, manufactured by Asahi Kasei Co., Ltd.) as a separator was sandwiched between two sheets and cut into pieces of 13.5cm2Further stacked with a square positive electrode cut to 14.3cm2The negative electrode of (2) is formed into an electrode group. The electrode group was housed in a container (battery exterior body) formed of an aluminum laminate film (trade name: aluminum laminate film, manufactured by japan printing corporation, japan). Next, 1mL of the electrolyte solution was added to a container, and the container was heat-welded to prepare a lithium ion secondary battery for evaluation. As the electrolyte, LiPF containing 1mol/L was used6To the mixed solution of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, 1 mass% of Vinylene Carbonate (VC), 0.5 mass% of 4-fluoro-1, 3-dioxolan-2-one (fluoroethylene carbonate; FEC) and 0.5 mass% of the total amount of the mixed solution were addedAn electrolyte solution obtained from a compound A represented by the following formula (6) and 0.5 mass% of 1, 3-propane sultone (based on the total amount of the electrolyte solution).
(example 2)
A lithium ion secondary battery was produced in the same manner as in example 1, except that 1, 3-propene sultone was used instead of 1, 3-propane sultone in example 1.
(example 3)
A lithium ion secondary battery was fabricated in the same manner as in example 1, except that Methylene Methanedisulfonate (MMDS) was used instead of 1, 3-propane sultone in example 1.
(example 4)
A lithium ion secondary battery was produced in the same manner as in example 1, except that ethylene sulfite was used instead of 1, 3-propane sultone in example 1.
Comparative example 1
A lithium ion secondary battery was produced in the same manner as in example 1, except that compound a and 1, 3-propane sultone were not used in example 1.
Comparative example 2
A lithium ion secondary battery was produced in the same manner as in example 1, except that compound a was not used in example 1.
[ evaluation of high temperature storage Properties ]
(first Charge and discharge)
Each of the secondary batteries thus produced was subjected to initial charge and discharge by the following method. First, constant current charging was performed at a current value of 0.1C until the upper limit voltage became 4.45V in an environment of 25 ℃, and then constant voltage charging was performed at 4.45V. The charge termination condition was set to a current value of 0.01C. Thereafter, constant current discharge was performed at a current value of 0.1C with an end voltage of 2.5V. This charge-discharge cycle was repeated 3 times. The discharge capacity at the 3 rd cycle was set as the capacity Q1 of the secondary battery. The "C" used as a unit of the current value means "current value (a)/battery capacity (Ah)" (the same applies hereinafter).
(high temperature storage)
Each of the secondary batteries thus produced was subjected to constant-current charging at a current value of 0.1C to an upper limit voltage of 4.45V in an environment of 25 ℃, and then to constant-voltage charging at 4.45V. The charge termination condition was set to a current value of 0.01C. Thereafter, these secondary batteries were kept in a constant temperature bath at 80 ℃ for 4 hours.
(measurement of Voltage after high temperature storage)
After the secondary batteries stored at a high temperature were left standing at 25 ℃ for 30 minutes, the voltage of each secondary battery was measured. The results are shown in Table 1.
(measurement of volume Change Rate)
The volume of each secondary battery before high-temperature storage (V1) and the volume of each secondary battery after standing at 25 ℃ for 30 minutes after high-temperature storage (V2) were measured using a densitometer (electronic densitometer MDS-300, manufactured by Alfa Mirage corporation) based on the archimedes method. Using the measured V1 and V2, the volume change rate (%) was calculated as V2/V1 × 100. The results are shown in Table 1.
(cycle test)
After each secondary battery stored at a high temperature was left standing at 25 ℃ for 30 minutes, constant current discharge was performed at a current value of 0.1C so as to terminate the voltage at 2.5V. The discharge capacity at this time was Q2. Then, constant current charging was performed at a current value of 0.1C until the upper limit voltage became 4.45V, and then constant voltage charging was performed at 4.45V. The charge termination condition was set to a current value of 0.01C. Thereafter, constant current discharge was performed at a current value of 0.1C with an end voltage of 2.5V. The discharge capacity at this time was Q3. The capacity maintenance rate and the capacity recovery rate were calculated by the following equations using Q1, Q2, and Q3. The results are shown in Table 1.
Capacity retention rate (%) - (-) Q2/Q1X 100
Capacity recovery rate (%) - (-) - (-) Q3/Q1X 100
[ Table 1]
As is apparent from table 1, the lithium ion secondary batteries using the electrolytes of examples 1 to 4 containing the compound represented by formula (1) and the cyclic compound are superior in high-temperature storage characteristics (the voltage drop and the volume change rate after high-temperature storage are small, and the capacity retention rate and the capacity recovery rate after high-temperature storage are high) to the lithium ion batteries of comparative examples 1 to 2 using the electrolytes containing neither or both of the compound represented by formula (1) and the cyclic compound. The reason is considered to be: in addition to the cyclic compound forming a stable coating on the positive electrode or the negative electrode, the compound represented by formula (1) also contributes to stabilization of the electrolytic solution.
Description of the symbols
1-nonaqueous electrolyte secondary battery (electrochemical device), 6-positive electrode, 7-separator, 8-negative electrode.
Claims (14)
1. An electrolyte, comprising:
a compound represented by the following formula (1); and
a cyclic compound having a ring containing a sulfur atom,
in the formula (1), R1～R3Each independently represents an alkyl group or a fluorine atom, R4Represents an alkylene group, R5Represents an organic group containing a nitrogen atom.
2. The electrolyte of claim 1, wherein R1～R3At least 1 of which is a fluorine atom.
3. The electrolytic solution according to claim 1 or 2, wherein the number of silicon atoms in one molecule of the compound represented by formula (1) is 1.
4. The electrolyte of claim 3, wherein R5Is a group represented by the following formula (2):
in the formula (2), R6And R7Each independently represents a hydrogen atom or an alkyl group, and represents a bonding site.
5. The electrolyte of any one of claims 1 to 4, wherein the cyclic compound comprises a cyclic sulfonate compound.
6. The electrolyte of claim 5, wherein the cyclic sulfonate compound comprises a compound represented by the following formula (X):
in the formula (X), A1The compound is a group containing an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms, and the hydrogen atoms in the alkylene group and the alkenylene group may be substituted with an alkyl group, a cycloalkyl group, an aryl group or a fluoro group.
7. The electrolyte solution according to claim 6, wherein the compound represented by formula (X) contains at least 1 selected from the group consisting of 1, 3-propane sultone and 1-propene-1, 3-sultone.
8. The electrolyte solution according to any one of claims 1 to 7, wherein the cyclic compound contains at least 1 selected from the group consisting of a compound represented by formula (Y) and a compound represented by formula (Z):
in the formula (Y), A2Represents an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms, wherein hydrogen atoms in the alkylene group and the alkenylene group may be substituted with an alkyl group, a cycloalkyl group or an aryl group;
in the formula (Z), A3Represents an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms, wherein hydrogen atoms in the alkylene group and the alkenylene group may be substituted with an alkyl group, a cycloalkyl group or an aryl group.
9. The electrolytic solution according to any one of claims 1 to 8, wherein a total of the content of the compound represented by formula (1) and the content of the cyclic compound is 10% by mass or less based on the total amount of the electrolytic solution.
10. An electrochemical device, comprising: a positive electrode, a negative electrode and the electrolyte according to any one of claims 1 to 9.
11. The electrochemical device of claim 10, wherein the negative electrode comprises a carbon material.
12. The electrochemical device according to claim 11, wherein the carbon material contains graphite.
13. The electrochemical device according to claim 11 or 12, wherein the negative electrode further contains a material containing at least 1 element selected from the group consisting of silicon and tin.
14. The electrochemical device according to any one of claims 10 to 13, wherein the electrochemical device is a nonaqueous electrolyte secondary battery or a capacitor.
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| KR20210096213A (en) | 2021-08-04 |
| TWI830831B (en) | 2024-02-01 |
| WO2020116580A1 (en) | 2020-06-11 |
| TWI835942B (en) | 2024-03-21 |
| JPWO2020116582A1 (en) | 2021-10-21 |
| WO2020116582A1 (en) | 2020-06-11 |
| KR20210096214A (en) | 2021-08-04 |
| TW202032844A (en) | 2020-09-01 |
| TW202032847A (en) | 2020-09-01 |
| CN113396496A (en) | 2021-09-14 |
| JP7415947B2 (en) | 2024-01-17 |
| JP7415946B2 (en) | 2024-01-17 |
| JPWO2020116580A1 (en) | 2021-10-21 |
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