CN113366671A - Electrolyte solution and electrochemical device - Google Patents
Electrolyte solution and electrochemical device Download PDFInfo
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- CN113366671A CN113366671A CN201980090858.2A CN201980090858A CN113366671A CN 113366671 A CN113366671 A CN 113366671A CN 201980090858 A CN201980090858 A CN 201980090858A CN 113366671 A CN113366671 A CN 113366671A
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- electrolyte
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- electrochemical device
- negative electrode
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- 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
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 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
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 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
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- 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
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- 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
- H01M10/056—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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
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- 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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- 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
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Abstract
An aspect of the present invention provides an electrolyte solution containing: a compound represented by the following formula (1); and cyclic carbonates having carbon-carbon double bondsOr an ester. 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 or a sulfur 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.
Prior art documents
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 carbonates or esters having carbon-carbon double bonds.
[ 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 or a sulfur atom.]
According to one aspect, the electrolyte solution can improve cycle characteristics as a performance of an electrochemical device. In another aspect, the electrolytic solution can reduce the direct current resistance (discharge DCR) of the electrochemical device during discharge. In another aspect, the electrolyte solution can improve the capacity retention rate after the electrochemical device is stored at a high temperature. In another aspect, the electrolyte solution can suppress an increase in volume 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 an organic group containing a nitrogen atom. 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.]
R5May be an organic group containing a sulfur atom. R5May be a group represented by any one of the following formulae (3), (4) and (5).
[ in the formula (3), R8Represents an alkyl group and represents a bonding site.]
[ in the formula (4), R9Represents an alkyl group and represents a bonding site.]
[ in the formula (5), R10Represents an alkyl group and represents a bonding site.]
The cyclic carbonate may be vinylene carbonate.
The total of the content of the compound represented by formula (1) and the content of the cyclic carbonate or ester 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 electrolyte capable of improving the performance of an electrochemical device is 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.
FIG. 3 is a graph showing the results of the cycle test in examples and comparative examples.
FIG. 4 is a graph showing the measurement results of discharge DCR in examples and comparative examples.
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 electrolyte comprises: a compound represented by the following formula (1), a cyclic carbonate or ester having a carbon-carbon double bond (hereinafter, also simply referred to as "cyclic carbonate or ester"), 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 or a sulfur 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 fluorineAn atom.
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.
In one embodiment, R5Is an organic group containing a nitrogen atom, and is preferably a group represented by the following formula (2) from the viewpoint of further improving the performance of an electrochemical device.
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.
In another embodiment, R5Is an organic group containing a sulfur atom, and is preferably a group represented by any one of the following formulae (3), (4) and (5) from the viewpoint of further improving the performance of an electrochemical device.
In the formula (3), R8Represents an alkyl group. The alkyl group may be substituted with R as described above1～R3The alkyl groups represented are the same. Denotes the bonding site.
In the formula (4), R9Represents an alkyl group. The alkyl group may be substituted with R as described above1～R3The alkyl groups represented are the same. Denotes the bonding site.
In the formula (5), R10Represents an alkyl group. The alkyl group may be substituted with R as described above1～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.
A cyclic carbonate (cyclic carbonate) having a carbon-carbon double bond is a cyclic carbonate (cyclic carbonate ester) having a carbon-carbon double bond. In one embodiment, in the cyclic carbonate or ester, the two carbons that make up the ring may form a double bond. The cyclic carbonate may be, for example, vinylene carbonate, methyl vinylene carbonate, dimethyl vinylene carbonate (4, 5-dimethyl vinylene carbonate), ethyl vinylene carbonate (4, 5-diethyl vinylene carbonate), diethyl vinylene carbonate, or the like, and is preferably vinylene carbonate from the viewpoint of further improving the performance of the electrochemical device.
From the viewpoint of further improving the performance of the electrochemical device, the content of the cyclic carbonate or ester 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 is preferably 5 mass% or less, 3 mass% or less, or 2 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 content of the compound represented by formula (1) and the cyclic carbonate or ester is preferably 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.1 mass% or more, 0.5 mass% or more, or 1 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 electrolyte.
From the viewpoint of further improving 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 carbonate or ester (the content of the compound represented by formula (1)/the content of the cyclic carbonate or ester) 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, 3 or less, or 1 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 a compound represented by formula (1), a cyclic carbonate or ester having a carbon-carbon double bond, an electrolyte salt, and other materials than the nonaqueous solvent. Other materials may be, for example: a fluorine-containing cyclic carbonate or ester; a compound containing a nitrogen atom, a sulfur atom, or a nitrogen atom and a sulfur atom other than the compound represented by the formula (1); 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 or the like, and preferably 4-fluoro-1, 3-dioxolan-2-one (fluoroethylene carbonate; FEC). 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 sulfur atom-containing compound other than the compound represented by the formula (1) may be, for example: cyclic sulfonate compounds such as 1, 3-propane sultone and 1-propenyl-1, 3-sultone.
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 a compound represented by the above formula (1) and a cyclic carbonate or ester having a carbon-carbon double bond to an electrolytic solution. The present inventors speculate that the effects of the compound represented by formula (1) and the cyclic carbonate or ester having a carbon-carbon double bond in the electrolyte are as follows. That is, it is considered that the compound represented by the formula (1) and the cyclic carbonate or ester having a carbon-carbon double bond each act at a position where an 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 performance of the electrochemical device such as the nonaqueous electrolyte secondary battery 1 is improved. For example, in one aspect, the use of the electrolyte solution can improve the cycle characteristics of the electrochemical device. In another embodiment, the discharge DCR of the electrochemical device can be reduced by using the electrolyte solution. In another embodiment, the use of the electrolyte solution can improve the capacity retention rate after the electrochemical device is stored at high temperature. In another embodiment, the volume increase after the electrochemical device is stored at a high temperature can be suppressed.
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. The sequence of the 1 st to 4 th steps is arbitrary.
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 ]
To nickel cobalt lithium manganate (92 mass%) as a positive electrode active material, Acetylene Black (AB) (4 mass%) as a conductive agent and a binder (4 mass%) were added in this order and mixed. 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 2.8g/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 set to 98:1:1 of graphite, binder and thickener. 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 was added to the container,the container was heat-fused to prepare a lithium ion secondary battery for evaluation. As the electrolyte, LiPF containing 1mol/L was used6To a mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate, 1 mass% of a compound a represented by the following formula (6) and 1 mass% of vinylene carbonate (based on the total amount of the electrolyte) were added to obtain an electrolyte solution.
(example 2)
A lithium ion secondary battery was produced in the same manner as in example 1, except that in example 1, 0.3 mass% of compound B represented by the following formula (7) was added, based on the total amount of the electrolyte, instead of compound a.
(example 3)
A lithium ion secondary battery was produced in the same manner as in example 1, except that in example 1, 0.1 mass% of compound C represented by the following formula (8) was added, based on the total amount of the electrolyte, instead of compound a.
Comparative example 1
A lithium ion secondary battery was produced in the same manner as in example 1, except that compound a and vinylene carbonate 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.
[ first Charge and discharge ]
The lithium ion battery thus obtained was subjected to initial charge and discharge in the following manner. First, constant current charging was performed at a current value of 0.1C in an environment of 25 ℃ until the upper limit voltage became 4.2V, and then constant voltage charging was performed at 4.2V. 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 a final voltage of 2.7V. This charge-discharge cycle was repeated 3 times (the term "C" used as a unit of current value means "current value (a)/battery capacity (Ah)"). The discharge capacity at the 3 rd cycle was set as the capacity Q1 of the battery.
[ evaluation of cycle characteristics ]
After the initial charge and discharge, the cycle characteristics of each secondary battery were evaluated by a cycle test in which charge and discharge were repeated. In the charging mode, the secondary batteries of examples 1 to 3 and comparative examples 1 to 2 were subjected to constant current charging at a current value of 0.5C until the upper limit voltage was 4.2V, and then to constant voltage charging at 4.2V in an environment of 45 ℃. The charge termination condition was set to a current value of 0.05C. For the discharge, constant current discharge was performed at 0.5C until 2.7V, and the discharge capacity was determined. This series of charge and discharge was repeated 300 cycles, and the discharge capacity was measured for each charge and discharge. The relative value (discharge capacity maintenance rate (%)) of the discharge capacity at each cycle to the discharge capacity after the charge and discharge at the 1 st cycle was obtained. The results of the cycling test are shown in fig. 3. Fig. 3(a), 3(b), and 3(c) show the results of example 1, example 2, and example 3, respectively, and for comparison, the results of comparative example 1 and comparative example 2 are shown in all graphs of fig. 3(a) to 3 (c).
As a result, it is apparent that the discharge capacity maintenance rates at the 300 th cycle in examples 1 to 3 were 90%, 89%, and 89%, respectively, and were further improved as compared with the discharge capacity maintenance rates at the 300 th cycle (67% and 86%, respectively) in comparative example 1 and comparative example 2. The reason is considered to be: since the compound a, the compound B, or the compound C and vinylene carbonate form a stable film on the positive electrode or the negative electrode and decomposition of the electrolyte is suppressed by the film, the life of the secondary battery can be extended.
[ measurement of discharged DCR ]
For each secondary battery after the cycle test, the dc resistance at the time of discharge (discharge DCR) was measured in the following manner.
First, constant current charging at 0.2C was performed until the upper limit voltage was 4.2V, and then constant voltage charging was performed at 4.2V. The charge termination condition was set to a current value of 0.02C. Thereafter, constant current discharge was performed at a current value of 0.2C and a final voltage of 2.7V, and the current value at this time was I0.2CAnd the voltage change 10 seconds after the start of discharge is set to be delta V0.2C. Then, constant current charging was performed at 0.2C until the upper limit voltage became 4.2V, and then constant voltage charging was performed at 4.2V (the charging end condition was set to be a current value of 0.02C). Thereafter, after constant current discharge was performed at a current value of 0.5C with a terminal voltage of 2.7V, the current value at that time was set to I0.5CAnd the voltage change 10 seconds after the start of discharge is set to be delta V0.5C. The current value I of 1C was evaluated according to the same charge and discharge1CVoltage change Δ V10 seconds after the start of discharge1C. At the 3 plotted points (I) of the current value-voltage change0.2C,ΔV0.2C)、(I0.5C,ΔV0.5C)、(I1C,ΔV1C) An approximate straight line is drawn once using the least square method, and the slope thereof is set as the value of the discharge DCR. Fig. 4 shows the measurement results of the discharged DCR after 300 cycles.
As a result, it is clear that the discharge DCRs of examples 1 to 3 were 2.6 Ω, 2.5 Ω, and 2.5 Ω, respectively, and the resistance was further reduced as compared with the discharge DCRs of comparative examples 1 and 2 (4.9 Ω, and 4.0 Ω, respectively). The reason is considered to be: since the compound a, the compound B, or the compound C and vinylene carbonate form a stable coating on the positive electrode or the negative electrode, and excessive decomposition of the electrolyte is suppressed by the coating, an increase in the resistance of the secondary battery can be suppressed.
[ high temperature storage test ]
After the above-described initial charge and discharge, the secondary batteries of example 1 and comparative examples 1 to 2 were subjected to constant current charging at a current value of 0.1C in an environment of 25 ℃ until the upper limit voltage became 4.2V, and then to constant voltage charging at 4.2V. The charge termination condition was set to a current value of 0.01C. Then, these secondary batteries were stored in a thermostatic bath at 60 ℃ for 4 weeks.
[ measurement of volume increase rate ]
The volume of each of the secondary batteries of examples 1 and comparative examples 1 to 2 was measured using a densitometer (electronic densitometer MDS-300, manufactured by Alfa Mirage corporation) by the archimedes method. The volume increase rate was calculated from the volume before the high-temperature storage test (V1) and the volume of the secondary battery after being held at 25 ℃ for 30 minutes after the high-temperature storage test (V2) by the following equation.
Volume increase rate (%) ═ V2/V1X 100
As a result, the volume increase rate of example 1 was 105.5%, the volume increase rate of comparative example 1 was 107.1%, and the volume increase rate of comparative example 2 was 108.9%. The volume increase rate of the lithium ion secondary battery of comparative example 2, in which the electrolyte solution containing only vinylene carbonate was applied, was increased more than that of the lithium ion secondary battery of comparative example 1, in which the electrolyte solution containing neither compound a nor vinylene carbonate was applied. The reason is considered to be: in an environment of high temperature (60 ℃), vinylene carbonate decomposes to generate gas. On the other hand, the volume increase rate of the lithium-ion secondary battery of example 1 to which the electrolyte solution containing both the compound a and vinylene carbonate was applied was more reduced than that of the lithium-ion secondary batteries of comparative examples 1 and 2. The reason is considered to be: the compound a contributes to stabilization of an electrolyte containing vinylene carbonate and can suppress gas generation.
[ measurement of Capacity Retention ratio ]
After the secondary batteries of examples 1 and comparative examples 1 to 2 were stored in a thermostatic bath at 60 ℃ for 4 weeks, the batteries were taken out of the thermostatic bath, kept at 25 ℃ for 30 minutes, and then subjected to constant current discharge at a final voltage of 2.7V at a current value of 0.1C. The discharge capacity at this time was Q2. The capacity retention rate was calculated using Q1 and Q2 as described above and using the following formula.
Capacity retention rate (%) - (-) Q2/Q1X 100
As a result, the capacity maintenance ratio of example 1 was 92.9%, the capacity maintenance ratio of comparative example 1 was 90.7%, and the capacity maintenance ratio of comparative example 2 was 92.3%. The capacity retention rate of the lithium ion secondary battery of comparative example 2, in which the electrolyte solution containing only vinylene carbonate was applied, was better than that of the lithium ion battery of comparative example 1, in which the electrolyte solution containing neither compound a nor vinylene carbonate was applied. The reason is considered to be: the vinylene carbonate forms a stable film on the negative electrode, and the capacity retention rate is prevented from being reduced due to the decomposition of the electrolyte in a high-temperature (60 ℃) environment. In addition, the capacity retention rate of the lithium ion secondary battery of example 1, in which the electrolyte solution containing both compound a and vinylene carbonate was applied, was further improved as compared with the lithium ion secondary battery of comparative example 2, in which the electrolyte solution containing only vinylene carbonate was applied. The reason is considered to be: in addition to the vinylene carbonate forming a stable film on the negative electrode, compound a stabilizes the electrolyte and further suppresses the decomposition of the electrolyte.
As described above, the lithium ion secondary batteries of examples 1 to 3 using the electrolyte solution containing both the compound a and the cyclic carbonate or ester having a carbon-carbon double bond exhibited more excellent performance than the lithium ion secondary battery of comparative example 1 using the electrolyte solution not containing the cyclic carbonate or ester having a carbon-carbon double bond and the compound a, and the lithium ion secondary battery of comparative example 2 using the electrolyte solution containing the cyclic carbonate or ester having a carbon-carbon double bond and not containing the compound a.
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
cyclic carbonates or esters having carbon-carbon double bonds,
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 or a sulfur 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 any one of claims 1 to 3, wherein R is5Is an organic group containing a nitrogen atom.
5. The electrolyte of claim 4, 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.
6. The electrolyte of any one of claims 1 to 3, wherein R is5Is an organic group containing a sulfur atom.
7. The electrolyte of claim 6, wherein R5Is a group represented by any one of the following formulae (3), (4) or (5):
in the formula (3), R8Represents an alkyl group, represents a bonding site;
in the formula (4), R9Represents an alkyl group, represents a bonding site;
in the formula (5), R10Represents an alkyl group and represents a bonding site.
8. The electrolyte of any one of claims 1 to 7, wherein the cyclic carbonate is vinylene carbonate.
9. The electrolytic solution according to any one of claims 1 to 8, wherein the total of the content of the compound represented by formula (1) and the content of the cyclic carbonate or ester 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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