WO2020116580A1 - Electrolyte and electrochemical device - Google Patents
Electrolyte and electrochemical device Download PDFInfo
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- WO2020116580A1 WO2020116580A1 PCT/JP2019/047689 JP2019047689W WO2020116580A1 WO 2020116580 A1 WO2020116580 A1 WO 2020116580A1 JP 2019047689 W JP2019047689 W JP 2019047689W WO 2020116580 A1 WO2020116580 A1 WO 2020116580A1
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- compound
- electrolytic solution
- electrochemical device
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 37
- 150000001923 cyclic compounds Chemical class 0.000 claims abstract description 28
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 10
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- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 44
- -1 cyclic sulfonate compound Chemical class 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 125000004450 alkenylene group Chemical group 0.000 claims description 19
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- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 14
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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
- H01G11/64—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
-
- 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
Definitions
- the present invention relates to an electrolytic solution and an electrochemical device.
- Patent Document 1 discloses an electrolyte solution for a non-aqueous electrolyte battery containing a specific siloxane compound in order to improve cycle characteristics and internal resistance characteristics.
- the present invention aims to provide an electrolytic solution capable of improving the performance of an electrochemical device.
- One aspect of the present invention is an electrolytic solution containing a compound represented by the following formula (1) and a cyclic compound having no silicon atom and having a ring containing a sulfur atom.
- R 1 to R 3 each independently represent an alkyl group or a fluorine atom
- R 4 represents an alkylene group
- R 5 represents an organic group containing a sulfur atom.
- the electrolytic solution can suppress an increase in volume of the electrochemical device after the electrochemical device is stored at high temperature, as the performance of the electrochemical device. Further, according to this electrolytic solution, in another aspect, the cycle characteristics of the electrochemical device are improved (in particular, the capacity retention ratio after the cycle test is improved and the increase in the discharge DCR after the cycle test is suppressed). Planned. Further, according to this electrolytic solution, in another aspect, the discharge DCR after storing the electrochemical device at a high temperature can be reduced.
- At least one of R 1 to R 3 may be a fluorine atom.
- the number of silicon atoms in one molecule of the compound represented by formula (1) may be one.
- R 5 may be a group represented by the following formula (3), formula (4) or formula (5).
- R 8 represents an alkyl group, and * represents a bond.
- R 9 represents an alkyl group, and * represents a bond.
- R 10 represents an alkyl group, and * represents a bond.
- the cyclic compound may include a cyclic sulfonate compound.
- the cyclic sulfonic acid ester compound may include a compound represented by the following formula (X).
- a 1 represents 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 atom in the alkylene group and the alkenylene group is an alkyl group or a cycloalkyl group. It may be substituted with a group, an aryl group, or a fluoro group.
- the compound represented by the formula (X) may include at least one selected from the group consisting of 1,3-propane sultone and 1-propene-1,3-sultone.
- the cyclic compound may include at least one selected from the group consisting of the compound represented by the formula (Y) and the compound represented by the formula (Z).
- a 2 represents an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms
- the hydrogen atom in the alkylene group and the alkenylene group is an alkyl group, a cycloalkyl group or an aryl group. It may be substituted with a group.
- a 3 represents an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms
- the hydrogen atom in the alkylene group and the alkenylene group is an alkyl group, a cycloalkyl group or an aryl group. It may be substituted with a group.
- the sum of the content of the compound represented by the formula (1) and the content of the cyclic sulfonate compound may be 10% by mass or less based on the total amount of the electrolytic solution.
- Another aspect of the present invention is an electrochemical device including a positive electrode, a negative electrode, and the electrolytic solution.
- the negative electrode may contain a carbon material.
- the carbon material may contain graphite.
- the negative electrode may further contain a material containing at least one element selected from the group consisting of silicon and tin.
- the electrochemical device may be a non-aqueous electrolyte secondary battery or a capacitor.
- an electrolytic solution capable of improving the performance of an electrochemical device.
- FIG. 1 is a perspective view showing a non-aqueous electrolyte secondary battery as an electrochemical device according to an embodiment.
- FIG. 2 is an exploded perspective view showing an electrode group of the secondary battery shown in FIG. 1.
- FIG. 1 is a perspective view showing an electrochemical device according to one embodiment.
- the electrochemical device is a non-aqueous electrolyte secondary battery.
- the non-aqueous electrolyte secondary battery 1 includes an electrode group 2 including a positive electrode, a negative electrode, and a separator, and a bag-shaped battery exterior body 3 that houses the electrode group 2.
- a positive electrode current collecting tab 4 and a negative electrode current collecting tab 5 are provided on the positive electrode and the negative electrode, respectively.
- the positive electrode current collecting tab 4 and the negative electrode current collecting tab 5 project from the inside of the battery case 3 to the outside so that the positive electrode and the negative electrode can be electrically connected to the outside of the non-aqueous electrolyte secondary battery 1, respectively. ..
- the non-aqueous electrolyte secondary battery 1 may be a battery (coin type, cylindrical type, laminated type, etc.) having a shape other than the so-called “laminate type” as described above.
- the battery outer casing 3 may be a container formed of, for example, a laminated film.
- the laminated film may be, for example, a laminated film in which a resin film such as a polyethylene terephthalate (PET) film, a metal foil such as aluminum, copper and stainless steel, and a sealant layer such as polypropylene are laminated in this order.
- PET polyethylene terephthalate
- metal foil such as aluminum, copper and stainless steel
- a sealant layer such as polypropylene
- FIG. 2 is an exploded perspective view showing an embodiment of the electrode group 2 in the non-aqueous electrolyte secondary battery 1 shown in FIG.
- 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.
- the positive electrode current collector 9 is provided with the positive electrode current collector tab 4.
- the positive electrode current collector 9 is made of, for example, aluminum, titanium, stainless steel, nickel, baked carbon, conductive polymer, conductive glass, or the like.
- the positive electrode current collector 9 may be one in which the surface of aluminum, copper, or the like is treated with carbon, nickel, titanium, silver, or the like for the purpose of improving adhesiveness, conductivity, and oxidation resistance.
- the thickness of the positive electrode current collector 9 is, for example, 1 to 50 ⁇ m in terms of electrode strength and energy density.
- the positive electrode material 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 ⁇ m.
- the positive electrode active material may be, for example, lithium oxide.
- the positive electrode active material may be, for example, a lithium phosphate.
- the lithium phosphate include lithium manganese phosphate (LiMnPO 4 ), lithium iron phosphate (LiFePO 4 ), lithium cobalt phosphate (LiCoPO 4 ), and lithium vanadium phosphate (Li 3 V 2 (PO 4 ). 3 ).
- the content of the positive electrode active material may be 80% by mass or more, or 85% by mass or more, and 99% by 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, or carbon material such as graphite, graphene or carbon nanotube.
- the content of the conductive agent may be, for example, 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more, and 50% by mass or less, 30% by mass, based on the total amount of the positive electrode mixture layer. Or less, or 15% by mass or less.
- binder examples include resins such as polyethylene, polypropylene, polyethylene terephthalate, polymethylmethacrylate, polyimide, aromatic polyamide, cellulose and nitrocellulose; SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), fluororubber.
- resins such as polyethylene, polypropylene, polyethylene terephthalate, polymethylmethacrylate, polyimide, aromatic polyamide, cellulose and nitrocellulose
- SBR styrene-butadiene rubber
- NBR acrylonitrile-butadiene rubber
- fluororubber examples include fluororubber.
- a fluorine-containing resin a resin having a nitrile group-containing monomer as a monomer unit, a polymer composition having an alkali metal ion (for example, lithium ion) ion conductivity, and the like.
- the content of the binder may be, for example, 0.1% by mass or more, 1% by mass or more, or 1.5% by mass or more, based on the total amount of the positive electrode mixture layer, 30% by mass or less, 20% by mass. % Or less, or 10% by mass or less.
- the separator 7 is not particularly limited as long as it electrically insulates between the positive electrode 6 and the negative electrode 8 while allowing ions to pass therethrough and has resistance to the oxidizing property on the positive electrode 6 side and the reducing property on the negative electrode 8 side. Not done.
- Examples of the material (material) of the separator 7 include resins and inorganic materials.
- the separator 7 is preferably a porous sheet or a non-woven fabric formed of polyolefin such as polyethylene or polypropylene from the viewpoint of being stable with respect to the electrolytic solution and excellent in liquid retaining property.
- the inorganic substance examples include oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate.
- the separator 7 may be, for example, a thin film substrate such as a nonwoven fabric, a woven fabric, or a microporous film to which a fibrous or particulate inorganic substance is attached.
- 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, baked carbon, conductive polymer, conductive glass, aluminum-cadmium alloy, or the like.
- the negative electrode current collector 11 may be one in which the surface of copper, aluminum, or the like is 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 ⁇ m from the viewpoint of 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 absorb and release lithium ions.
- the negative electrode active material include carbon materials, metal composite oxides, oxides or nitrides of Group IV elements such as tin, germanium, and silicon, simple substances of lithium, lithium alloys such as lithium aluminum alloys, Sn, Si, and the like. And a metal capable of forming an alloy with lithium.
- the negative electrode active material is preferably at least one selected from the group consisting of carbon materials and metal composite oxides.
- the negative electrode active material may be one type of these alone or a mixture of two or more types.
- the shape of the negative electrode active material may be, for example, a particle shape.
- the carbon material amorphous carbon material, natural graphite, composite carbon material obtained by forming a film of amorphous carbon material on natural graphite, artificial graphite (resin raw material such as epoxy resin, phenol resin, or petroleum, coal, etc. Obtained by firing a pitch-based raw material obtained from the above).
- the metal composite oxide preferably contains one or both of titanium and lithium, and more preferably contains lithium.
- the negative electrode active materials carbon materials have high conductivity and are particularly excellent in low temperature characteristics and cycle stability.
- graphite is preferable from the viewpoint of high capacity.
- the carbon network plane layer (d002) in the X-ray wide-angle diffraction method is preferably less than 0.34 nm, and more preferably 0.3354 nm or more and 0.337 nm or less.
- a carbon material that satisfies such conditions may be referred to as pseudo-anisotropic carbon.
- the negative electrode active material may further contain a material containing at least one element selected from the group consisting of silicon and tin.
- the material containing at least one element selected from the group consisting of silicon and tin may be a simple substance of silicon or tin, or a compound containing at least one element selected from the group consisting of silicon and tin.
- the compound may be an alloy containing at least one element selected from the group consisting of silicon and tin. For example, in addition to silicon and tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver. , An alloy containing at least one selected from the group consisting of titanium, germanium, bismuth, antimony and chromium.
- the compound containing at least one element selected from the group consisting of silicon and tin may be an oxide, a nitride, or a carbide, and specifically, for example, silicon oxide such as SiO, SiO 2 , and LiSiO.
- silicon oxide such as SiO, SiO 2 , and LiSiO.
- a silicon nitride such as Si 3 N 4 or Si 2 N 2 O, a silicon carbide such as SiC, a tin oxide such as SnO, SnO 2 or LiSnO.
- the negative electrode 8 preferably contains a carbon material, more preferably graphite, and further preferably a carbon material, silicon and It contains a mixture with a material containing at least one element selected from the group consisting of tin, and particularly preferably contains a mixture of graphite and silicon oxide.
- the content of the carbon material (graphite) with respect to the material (silicon oxide) containing at least one element selected from the group consisting of silicon and tin in the mixture is 1% by mass or more based on the total amount of the mixture, or 3 It may be not less than 30% by mass and not more than 30% by mass.
- the content of the negative electrode active material may be 80% by mass or more, or 85% by mass or more, and 99% by 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 the binder and the content thereof in the positive electrode mixture layer described above.
- the negative electrode mixture layer 12 may contain a thickener to adjust the viscosity.
- the thickener is not particularly limited, but 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 one of these alone or a mixture of two or more thereof.
- the content thereof is not particularly limited.
- the content of the thickener may be 0.1% by mass or more, and preferably 0.2% by mass or more, based on the total amount of the negative electrode mixture layer, from the viewpoint of coatability of the negative electrode mixture layer. , And more preferably 0.5% by mass or more.
- the content of the thickener may be 5% by mass or less, preferably 3% by mass, 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. % Or less, and more preferably 2% by mass or less.
- the electrolytic solution in one embodiment, a compound represented by the following formula (1), a cyclic compound having no silicon atom and a ring containing a sulfur atom (hereinafter, also simply referred to as “cyclic compound”), It contains an electrolyte salt and a non-aqueous solvent.
- R 1 to R 3 each independently represent an alkyl group or a fluorine atom
- R 4 represents an alkylene group
- R 5 represents an organic group containing a sulfur atom.
- the alkyl group represented by R 1 to R 3 may have 1 or more carbon atoms and 3 or less carbon atoms.
- R 1 to R 3 may be a methyl group, an ethyl group, or a propyl group, and may be linear or branched.
- At least one of R 1 to R 3 is preferably a fluorine atom. May be any one of fluorine atom of R 1 ⁇ R 3, it may be any two of a fluorine atom of R 1 ⁇ R 3, all of R 1 ⁇ R 3 may be a fluorine atom.
- the carbon number of the alkylene group represented by R 4 may be 1 or more or 2 or more, and 5 or less or 4 or less.
- the alkylene group represented by R 4 may be a methylene group, an ethylene group, a propylene group, a butylene group, or a pentylene group, and may be linear or branched.
- the number of silicon atoms in one molecule of the compound represented by formula (1) is one. That is, in one embodiment, the organic group represented by R 5 does not include a silicon atom.
- R 5 is preferably a group represented by any of the following formula (3), formula (4) or formula (5).
- R 8 represents an alkyl group.
- the alkyl group may be the same as the alkyl group represented by R 1 to R 3 described above. * Indicates a bond.
- R 9 represents an alkyl group.
- the alkyl group may be the same as the alkyl group represented by R 1 to R 3 described above. * Indicates a bond.
- R 10 represents an alkyl group.
- the alkyl group may be the same as the alkyl group represented by R 1 to R 3 described above. * Indicates a bond.
- the content of the compound represented by the formula (1) is preferably 0.001% by mass or more and 0.005% by mass, based on the total amount of the electrolytic solution, from the viewpoint that the performance of the electrochemical device can be further improved. % Or more, 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more, 8 mass% or less, 5 mass% or less, 3 mass% or less, 2 mass% or less, or 1 mass. % Or less.
- a 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, at least one cyclic sulfonate compound (also referred to as a sultone compound).
- the cyclic sulfonate compound is a compound having a ring containing an —OSO 2 — group.
- the cyclic sulfonic acid ester compound has a ring containing one or two —OSO 2 — groups.
- the cyclic sulfonic acid ester compound having a ring containing one —OSO 2 — group may be, for example, a compound represented by the following formula (X).
- a 1 represents an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms
- the hydrogen atom in the alkylene group and the alkenylene group is an alkyl group, a cycloalkyl group or an aryl group. It may be substituted with a group or a fluoro group.
- the carbon number of the alkyl group may be, for example, 1 to 12.
- the cycloalkyl group may have, for example, 3 to 6 carbon atoms.
- the aryl group may have, for example, 6 to 12 carbon atoms.
- a 1 is preferably an alkylene group having 3 carbon atoms or an alkenylene group having 3 carbon atoms. That is, the cyclic sulfonate compound is preferably a compound represented by the following formula (X-1) or formula (X-2).
- R 11 to R 20 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a fluoro group.
- the carbon number of the alkyl group, cycloalkyl group and aryl group represented by R 11 to R 20 is the same as the carbon number of the alkyl group, cycloalkyl group and aryl group described for formula (X).
- R 11 to R 20 are preferably hydrogen atoms.
- 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, Monosulfonic acid esters such as 1-methyl-1,3-propane sultone, 3-methyl-1,3-propane sultone, 1-fluoro-1,3-propane sultone and 3-fluoro-1,3-propane sultone Is mentioned.
- 1,3-propane sultone (a compound in which all of R 11 to R 16 in the formula (X-1) are hydrogen atoms) or 1 from the viewpoint that the performance of the electrochemical device can be further improved.
- -Propene-1,3-sultone (a compound in which all of R 17 to R 20 in the formula (X-2) are hydrogen atoms) is preferable.
- the cyclic sulfonic acid ester compound having a ring containing two —OSO 2 — groups may be, for example, a compound represented by the following formula (X-3).
- B 1 and B 2 each independently represent an alkylene group having 1 to 5 carbon atoms or an alkenylene group having 1 to 5 carbon atoms
- the hydrogen atom in the alkylene group and the alkenylene group is an alkyl group, cycloalkyl It may be substituted with an alkyl group, an aryl group, or a fluoro group.
- B 1 and B 2 are preferably unsubstituted alkylene groups having 1 or 2 carbon atoms.
- Such cyclic sulfonic acid ester compound may be a disulfonic acid ester such as methylene methane disulfonic acid ester and ethylene methane disulfonic acid ester.
- the cyclic compound may include, for example, at least one selected from the group consisting of the compound represented by the formula (Y) and the compound represented by the formula (Z).
- a 2 and A 3 each independently represent an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms, and hydrogen in the alkylene group and the alkenylene group. Atoms may be substituted with alkyl, cycloalkyl or aryl groups.
- the carbon numbers of the alkyl group, cycloalkyl group and aryl group in A 2 and A 3 are the same as the carbon numbers of the alkyl group, cycloalkyl group and aryl group described for formula (X), respectively.
- Examples of the compound represented by the formula (Y) include sulfolane, 2-methylsulfolane, 3-methylsulfolane, 2-ethylsulfolane, 3-ethylsulfolane, 2,4-dimethylsulfolane, 2-phenylsulfolane and 3-phenylsulfolane. Examples thereof include phenylsulfolane, sulfolene, 3-methylsulfolene and the like.
- the compound represented by the formula (Y) is preferably sulfolane, from the viewpoint of further improving the performance of the electrochemical device.
- Examples of the compound represented by the formula (Z) include ethylene sulfite, propylene sulfite, butylene sulfite, vinylene sulfite, and phenylethylene sulfite.
- the compound represented by the formula (Z) is preferably ethylene sulfite, from the viewpoint that the performance of the electrochemical device can be further improved.
- the cyclic compound may contain at least one selected from the group consisting of a cyclic sulfonate compound, a compound represented by the formula (Y) and a compound represented by the formula (Z), and is represented by the formula (X).
- Compound represented by the formula (Y) and a compound represented by the formula (Z) may be included in the compound represented by the formula (X) and the formula (Z).
- the content of the cyclic compound is preferably 0.001 mass% or more, 0.005 mass% or more, 0.01 mass, based on the total amount of the electrolytic solution, from the viewpoint that the performance of the electrochemical device can be further improved. % 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.
- the total content of the compound represented by formula (1) and the content of the cyclic compound is preferably 0.001 based on the total amount of the electrolytic solution.
- % By mass 0.005% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 0.5% by mass or more, preferably 10% by mass or less, 7% by mass or less, 5% by mass % Or less, 3% by mass or less, or 2% by mass or less.
- the mass ratio of the content of the compound represented by the formula (1) to the content of the cyclic compound (content of the compound represented by the formula (1)/content of the cyclic compound) further improves the performance of the electrochemical device. From the viewpoint of being able to improve, it is preferably 0.01 or more, 0.05 or more, 0.1 or more, 0.2 or more, or 0.25 or more, and preferably 500 or less, 100 or less, It is 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 is, for example, LiPF 6 , LiBF 4 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , CF 3 SO 2 OLi, LiN(SO 2 F) 2 (Li[FSI], lithium bis. Fluorosulfonylimide), LiN(SO 2 CF 3 ) 2 (Li[TFSI], lithium bistrifluoromethanesulfonylimide), and at least one selected from the group consisting of LiN(SO 2 CF 2 CF 3 ) 2 Good.
- the lithium salt preferably contains LiPF 6 from the viewpoint of further excellent solubility in a solvent, charge/discharge characteristics of a secondary battery, output characteristics, cycle characteristics, and the like.
- the concentration of the electrolyte salt is preferably 0.5 mol/L or more, more preferably 0.7 mol/L or more, and further preferably 0.8 mol/L or more, based on the total amount of the non-aqueous solvent. Further, it is preferably 1.5 mol/L or less, more preferably 1.3 mol/L or less, still more preferably 1.2 mol/L or less.
- non-aqueous solvent examples include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ⁇ -butyl lactone, acetonitrile, 1,2-dimethoxyethane, dimethoxymethane, tetrahydrofuran, dioxolane, methylene chloride and methyl acetate. May be
- the non-aqueous solvent may be one of these alone or a mixture of two or more thereof, and preferably a mixture of two or more thereof.
- the electrolytic solution may further contain other materials other than the compound represented by the formula (1), the cyclic compound, the electrolyte salt and the non-aqueous solvent.
- Other materials include, for example, fluorine-containing cyclic carbonates, cyclic carbonates such as cyclic carbonates having a carbon-carbon double bond, compounds having a nitrogen atom, compounds represented by formula (1) and sulfur atoms other than cyclic compounds.
- the compound may have a cyclic carboxylic acid ester or the like.
- fluorine-containing cyclic carbonate examples include 4-fluoro-1,3-dioxolan-2-one (fluoroethylene carbonate; FEC), 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2. It may be trifluoroethylene carbonate, 1,1,2,2-tetrafluoroethylene carbonate, etc., preferably 4-fluoro-1,3-dioxolan-2-one (fluoroethylene carbonate; FEC).
- the cyclic carbonate having a carbon-carbon double bond may be vinylene carbonate, for example.
- the compound containing a nitrogen atom may be a nitrile compound such as succinonitrile.
- the present inventors applied the compound represented by the above formula (1) and the cyclic compound to an electrolytic solution to improve the performance of an electrochemical device. Revealed that can be made.
- the present inventors presume the action and effect of using the compound represented by formula (1) and the cyclic compound in the electrolytic solution as follows. That is, the compound represented by the formula (1) and the cyclic compound each act on the place where the effect is most likely to be exhibited in the lithium ion secondary battery, for example, stable film formation of the positive electrode or the negative electrode, or the electrolytic solution. Is considered to contribute to the stabilization of As a result, the performance of the electrochemical device such as the non-aqueous electrolyte secondary battery 1 is improved.
- the electrolytic solution of one embodiment as the performance of the electrochemical device, it is possible to suppress the volume increase after the electrochemical device is stored at a high temperature. Moreover, according to the electrolytic solution of one embodiment, the cycle characteristics of the electrochemical device are improved (in particular, the capacity retention ratio after the cycle test is improved and the increase in the discharge DCR after the cycle test is suppressed). Moreover, according to the electrolytic solution of one embodiment, it is possible to reduce the discharge DCR after the electrochemical device is stored at a high temperature.
- the manufacturing method of the non-aqueous electrolyte secondary battery 1 includes a first step of obtaining the positive electrode 6, a second step of obtaining the negative electrode 8, and a third step of accommodating the electrode group 2 in the battery outer casing 3. A fourth step of injecting the electrolytic solution into the battery exterior body 3.
- the material used for the positive electrode mixture layer 10 is dispersed in a dispersion medium using a kneader, a disperser or the like to obtain a positive electrode mixture in a slurry state, and then this positive electrode mixture is treated by a doctor blade method,
- the positive electrode current collector 9 is coated with a dipping method, a spray method, or the like, and then the dispersion medium is volatilized to obtain the positive electrode 6.
- a compression molding step using a roll press may be provided, if necessary.
- the positive electrode mixture layer 10 may be formed as a positive electrode mixture layer having a multi-layer structure by performing the above-described 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 second step may be the same as the above-mentioned first step, and the method of forming the negative electrode mixture layer 12 on the negative electrode current collector 11 may be the same method as the above-mentioned first step. ..
- the separator 7 is sandwiched between the produced positive electrode 6 and negative electrode 8 to form the electrode group 2.
- the electrode group 2 is housed in the battery case 3.
- the electrolytic solution is injected into the battery exterior body 3.
- the electrolytic solution can be prepared, for example, by first dissolving an electrolyte salt in a solvent and then dissolving other materials.
- the electrochemical device may be a capacitor.
- the capacitor may include an electrode group including a positive electrode, a negative electrode, and a separator, and a bag-shaped battery exterior body that houses the electrode group.
- the details of each component of the capacitor may be the same as those of the non-aqueous electrolyte secondary battery 1.
- Example 1 [Production of positive electrode] Acetylene black (AB) (4 mass %) as a conductive agent and a binder (4 mass %) were sequentially added to and mixed with lithium nickel cobalt manganate (92 mass %) as a positive electrode active material. 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 this positive electrode mixture was uniformly and uniformly applied to an aluminum foil having a thickness of 20 ⁇ m as a positive electrode current collector. After that, the dispersion medium was volatilized and then pressed to consolidate it to a density of 2.8 g/cm 3 to obtain a positive electrode.
- VC vinylene carbonate
- FEC fluoroethylene carbonate
- compound A represented by the following formula (6) 0.5% by mass
- 1,3-propanesultone 0.5% by mass
- Example 2 A lithium ion secondary battery was produced in the same manner as in Example 1 except that the amount of compound A added was changed to 2.0% by mass.
- Example 3 A lithium ion secondary battery was produced in the same manner as in Example 1, except that 0.3% by mass of the compound B represented by the following formula (7) was added in place of the compound A.
- Example 4 A lithium ion secondary battery was produced in the same manner as in Example 1 except that 0.1% by mass of the compound C represented by the following formula (8) was added in place of the compound A.
- Example 5 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.
- Example 6 A lithium ion secondary battery was produced in the same manner as in Example 1 except that methylene methane disulfonic acid ester (MMDS) was used instead of 1,3-propane sultone.
- MMDS methylene methane disulfonic acid ester
- Example 7 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.
- Example 1 A lithium ion secondary battery was produced in the same manner as in Example 1 except that the compound A and 1,3-propane sultone were not used.
- the direct current resistance (discharge DCR) during discharge was measured as follows. First, 0.2 C constant current charging was performed up to an upper limit voltage of 4.2 V, and then constant voltage charging was performed at 4.2 V. The charge termination condition was a current value of 0.02C. Then, constant current discharge with a final voltage of 2.7 V was performed at a current value of 0.2 C , the current value at this time was I 0.2 C , and the voltage change 10 seconds after the start of discharge was ⁇ V 0.2 C.
- constant current charging of 0.2 C was performed up to an upper limit voltage of 4.2 V, and then constant voltage charging was performed at 4.2 V (charging termination condition was a current value of 0.02 C), and then 0.
- Constant current discharge with a final voltage of 2.7 V was performed at a current value of 5 C , the current value at this time was I 0.5C , and the voltage change 10 seconds after the start of discharge was ⁇ V 0.5C .
- the current value of 1 C was evaluated as I 1C and the voltage change ⁇ V 1C 10 seconds after the start of discharge was evaluated after the same charge and discharge.
- the three-point plot of the current value-voltage change (I 0.2C , ⁇ V 0.2C ), (I 0.5C , ⁇ V 0.5C ), (I 1C , ⁇ V 1C ) is first-ordered using the least squares method. An approximate straight line was drawn, and the slope thereof was taken as the value DC1 of the discharge DCR.
- the lithium ion secondary batteries to which the electrolytic solutions of Examples 1 to 7 containing the compound represented by the formula (1) and the cyclic compound were applied were the compound represented by the formula (1) and the cyclic compound.
- the discharge DCR after the high temperature storage was performed was also measured.
- the discharge DCR of Example 1 was 1.70 ⁇
- the discharge DCR of Comparative Example 1 was 1.98 ⁇
- the discharge DCR of Comparative Example 2 was 1.79 ⁇ .
- the lithium-ion secondary battery of Comparative Example 2 to which an electrolytic solution containing 1,3-propane sultone and containing no compound A was applied was a comparative example to which an electrolytic solution containing neither compound A nor 1,3-propane sultone was applied.
- the discharge DCR after high temperature storage was reduced.
- 1,3-propane sultone formed a stable film on the positive electrode or the negative electrode.
- the lithium ion secondary battery of Example 1 to which the electrolytic solution containing both the compound A and 1,3-propane sultone was applied was stored at high temperature as compared with the lithium ion secondary batteries of Comparative Example 1 and Comparative Example 2.
- the latter discharge DCR was about 15% and about 5% good, respectively. It is considered that this is because Compound A contributed to the stabilization of the electrolytic solution in addition to the stable coating of 1,3-propane sultone on the positive electrode or the negative electrode.
- Non-aqueous electrolyte secondary battery electrochemical device
- 6 Positive electrode
- 7 Separator
- 8 Negative electrode
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Abstract
One aspect of the present invention is an electrolyte containing a compound represented by formula (1), and an cyclic compound not containing a silicon atom but having a ring which contains a sulfur atom. In formula (1), R1 to R3 independently represent an alkyl group or a fluorine atom, R4 represents an alkylene group, and R5 represents an organic group containing a sulfur atom.
Description
本発明は、電解液及び電気化学デバイスに関する。
The present invention relates to an electrolytic solution and an electrochemical device.
近年、携帯型電子機器、電気自動車等の普及により、リチウムイオン二次電池に代表される非水電解液二次電池、キャパシタ等の高性能な電気化学デバイスが必要とされている。電気化学デバイスの性能を向上させる手段としては、例えば、電解液に所定の添加剤を添加する方法が検討されている。特許文献１には、サイクル特性及び内部抵抗特性を改善するために、特定のシロキサン化合物を含有させた非水電解液電池用電解液が開示されている。
With the recent spread of portable electronic devices, electric vehicles, etc., high-performance electrochemical devices such as non-aqueous electrolyte secondary batteries represented by lithium-ion secondary batteries and capacitors are required. 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 solution for a non-aqueous electrolyte battery containing a specific siloxane compound in order to improve cycle characteristics and internal resistance characteristics.
本発明は、電気化学デバイスの性能を向上させることが可能な電解液を提供することを目的とする。
The present invention aims to provide an electrolytic solution capable of improving the performance of an electrochemical device.
本発明の一側面は、下記式（１）で表される化合物と、ケイ素原子を有さず、硫黄原子を含む環を有する環状化合物と、を含有する電解液である。
式（１）中、Ｒ１～Ｒ３は、それぞれ独立に、アルキル基又はフッ素原子を示し、Ｒ４はアルキレン基を示し、Ｒ５は、硫黄原子を含む有機基を示す。
One aspect of the present invention is an electrolytic solution containing a compound represented by the following formula (1) and a cyclic compound having no silicon atom and having a ring containing a sulfur atom.
In formula (1), R 1 to R 3 each independently represent an alkyl group or a fluorine atom, R 4 represents an alkylene group, and R 5 represents an organic group containing a sulfur atom.
この電解液によれば、一側面において、電気化学デバイスの性能として、電気化学デバイスを高温下で保存した後の体積増加を抑制することができる。また、この電解液によれば、他の一側面において、電気化学デバイスのサイクル特性の向上（特に、サイクル試験後の容量維持率の向上、及び、サイクル試験後の放電ＤＣＲの上昇の抑制）が図られる。また、この電解液によれば、他の一側面において、電気化学デバイスを高温下で保存した後の放電ＤＣＲを低減させることができる。
According to one aspect, the electrolytic solution can suppress an increase in volume of the electrochemical device after the electrochemical device is stored at high temperature, as the performance of the electrochemical device. Further, according to this electrolytic solution, in another aspect, the cycle characteristics of the electrochemical device are improved (in particular, the capacity retention ratio after the cycle test is improved and the increase in the discharge DCR after the cycle test is suppressed). Planned. Further, according to this electrolytic solution, in another aspect, the discharge DCR after storing the electrochemical device at a high temperature can be reduced.
Ｒ１～Ｒ３の少なくとも１つは、フッ素原子であってよい。式（１）で表される化合物１分子中のケイ素原子の数は、１個であってよい。
At least one of R 1 to R 3 may be a fluorine atom. The number of silicon atoms in one molecule of the compound represented by formula (1) may be one.
Ｒ５は、下記式（３）、式（４）又は式（５）のいずれかで表される基であってよい。
式（３）中、Ｒ８はアルキル基を示し、＊は結合手を示す。
式（４）中、Ｒ９はアルキル基を示し、＊は結合手を示す。
式（５）中、Ｒ１０はアルキル基を示し、＊は結合手を示す。
R 5 may be a group represented by the following formula (3), formula (4) or formula (5).
In formula (3), R 8 represents an alkyl group, and * represents a bond.
In formula (4), R 9 represents an alkyl group, and * represents a bond.
In formula (5), R 10 represents an alkyl group, and * represents a bond.
環状化合物は、環状スルホン酸エステル化合物を含んでよい。環状スルホン酸エステル化合物は、下記式（Ｘ）で表される化合物を含んでよい。
式（Ｘ）中、Ａ１は、炭素数３～５のアルキレン基又は炭素数３～５のアルケニレン基を含む基を表し、該アルキレン基及び該アルケニレン基における水素原子は、アルキル基、シクロアルキル基、アリール基、又はフルオロ基で置換されていてもよい。
The cyclic compound may include a cyclic sulfonate compound. The cyclic sulfonic acid ester compound may include a compound represented by the following formula (X).
In formula (X), A 1 represents 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 atom in the alkylene group and the alkenylene group is an alkyl group or a cycloalkyl group. It may be substituted with a group, an aryl group, or a fluoro group.
式（Ｘ）で表される化合物は、１，３－プロパンスルトン及び１－プロペン－１，３－スルトンからなる群より選ばれる少なくとも１種を含んでよい。
The compound represented by the formula (X) may include at least one selected from the group consisting of 1,3-propane sultone and 1-propene-1,3-sultone.
環状化合物は、式（Ｙ）で表される化合物及び式（Ｚ）で表される化合物からなる群より選ばれる少なくとも１種を含んでよい。
式（Ｙ）中、Ａ２は、炭素数３～５のアルキレン基又は炭素数３～５のアルケニレン基を表し、該アルキレン基及び該アルケニレン基における水素原子は、アルキル基、シクロアルキル基又はアリール基で置換されていてもよい。
式（Ｚ）中、Ａ３は、炭素数３～５のアルキレン基又は炭素数３～５のアルケニレン基を表し、該アルキレン基及び該アルケニレン基における水素原子は、アルキル基、シクロアルキル基又はアリール基で置換されていてもよい。
The cyclic compound may include at least one selected from the group consisting of the compound represented by the formula (Y) and the compound represented by the formula (Z).
In formula (Y), A 2 represents an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms, and the hydrogen atom in the alkylene group and the alkenylene group is an alkyl group, a cycloalkyl group or an aryl group. It may be substituted with a group.
In formula (Z), A 3 represents an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms, and the hydrogen atom in the alkylene group and the alkenylene group is an alkyl group, a cycloalkyl group or an aryl group. It may be substituted with a group.
式（１）で表される化合物の含有量及び環状スルホン酸エステル化合物の含有量の合計は、電解液全量を基準として１０質量％以下であってよい。
The sum of the content of the compound represented by the formula (1) and the content of the cyclic sulfonate compound may be 10% by mass or less based on the total amount of the electrolytic solution.
本発明の他の一側面は、正極と、負極と、上記電解液と、を備える電気化学デバイスである。
Another aspect of the present invention is an electrochemical device including a positive electrode, a negative electrode, and the electrolytic solution.
負極は、炭素材料を含有してよい。炭素材料は黒鉛を含有してよい。負極は、ケイ素及びスズからなる群より選ばれる少なくとも１種の元素を含む材料を更に含有してよい。
The negative electrode may contain a carbon material. The carbon material may contain graphite. The negative electrode may further contain a material containing at least one element selected from the group consisting of silicon and tin.
電気化学デバイスは、非水電解液二次電池又はキャパシタであってよい。
The electrochemical device may be a non-aqueous electrolyte secondary battery or a capacitor.
本発明によれば、電気化学デバイスの性能を向上させることが可能な電解液を提供することができる。
According to the present invention, it is possible to provide an electrolytic solution capable of improving the performance of an electrochemical device.
以下、図面を適宜参照しながら、本発明の実施形態について説明する。ただし、本発明は以下の実施形態に限定されるものではない。
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.
図１は、一実施形態に係る電気化学デバイスを示す斜視図である。本実施形態において、電気化学デバイスは非水電解液二次電池である。図１に示すように、非水電解液二次電池１は、正極、負極及びセパレータから構成される電極群２と、電極群２を収容する袋状の電池外装体３とを備えている。正極及び負極には、それぞれ正極集電タブ４及び負極集電タブ５が設けられている。正極集電タブ４及び負極集電タブ５は、それぞれ正極及び負極が非水電解液二次電池１の外部と電気的に接続可能なように、電池外装体３の内部から外部へ突き出している。電池外装体３内には、電解液（図示せず）が充填されている。非水電解液二次電池１は、上述したようないわゆる「ラミネート型」以外の形状の電池（コイン型、円筒型、積層型等）であってもよい。
FIG. 1 is a perspective view showing an electrochemical device according to one embodiment. In this embodiment, the electrochemical device is a non-aqueous electrolyte secondary battery. As shown in FIG. 1, the non-aqueous electrolyte secondary battery 1 includes an electrode group 2 including a positive electrode, a negative electrode, and a separator, and a bag-shaped battery exterior body 3 that houses the electrode group 2. A positive electrode current collecting tab 4 and a negative electrode current collecting tab 5 are provided on the positive electrode and the negative electrode, respectively. The positive electrode current collecting tab 4 and the negative electrode current collecting tab 5 project from the inside of the battery case 3 to the outside so that the positive electrode and the negative electrode can be electrically connected to the outside of the non-aqueous electrolyte secondary battery 1, respectively. .. An electrolyte solution (not shown) is filled in the battery exterior body 3. The non-aqueous electrolyte secondary battery 1 may be a battery (coin type, cylindrical type, laminated type, etc.) having a shape other than the so-called “laminate type” as described above.
電池外装体３は、例えばラミネートフィルムで形成された容器であってよい。ラミネートフィルムは、例えば、ポリエチレンテレフタレート（ＰＥＴ）フィルム等の樹脂フィルムと、アルミニウム、銅、ステンレス鋼等の金属箔と、ポリプロピレン等のシーラント層とがこの順で積層された積層フィルムであってよい。
The battery outer casing 3 may be a container formed of, for example, a laminated film. The laminated film may be, for example, a laminated film in which a resin film such as a polyethylene terephthalate (PET) film, a metal foil such as aluminum, copper and stainless steel, and a sealant layer such as polypropylene are laminated in this order.
図２は、図１に示した非水電解液二次電池１における電極群２の一実施形態を示す分解斜視図である。図２に示すように、電極群２は、正極６と、セパレータ７と、負極８とをこの順に備えている。正極６及び負極８は、正極合剤層１０側及び負極合剤層１２側の面がそれぞれセパレータ７と対向するように配置されている。
FIG. 2 is an exploded perspective view showing an embodiment of the electrode group 2 in the non-aqueous electrolyte secondary battery 1 shown in FIG. 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.
正極６は、正極集電体９と、正極集電体９上に設けられた正極合剤層１０とを備えている。正極集電体９には、正極集電タブ４が設けられている。
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. The positive electrode current collector 9 is provided with the positive electrode current collector tab 4.
正極集電体９は、例えば、アルミニウム、チタン、ステンレス、ニッケル、焼成炭素、導電性高分子、導電性ガラス等で形成されている。正極集電体９は、接着性、導電性及び耐酸化性向上の目的で、アルミニウム、銅等の表面にカーボン、ニッケル、チタン、銀等で処理が施されたものであってもよい。正極集電体９の厚さは、電極強度及びエネルギー密度の点から、例えば１～５０μｍである。
The positive electrode current collector 9 is made of, for example, aluminum, titanium, stainless steel, nickel, baked carbon, conductive polymer, conductive glass, or the like. The positive electrode current collector 9 may be one in which the surface of aluminum, copper, or the like is treated with carbon, nickel, titanium, silver, or the like for the purpose of improving adhesiveness, conductivity, and oxidation resistance. The thickness of the positive electrode current collector 9 is, for example, 1 to 50 μm in terms of electrode strength and energy density.
正極合剤層１０は、一実施形態において、正極活物質と、導電剤と、結着剤とを含有する。正極合剤層１０の厚さは、例えば２０～２００μｍである。
In one embodiment, the positive electrode material 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.
正極活物質は、例えばリチウム酸化物であってよい。リチウム酸化物としては、例えば、ＬｉｘＣｏＯ２、ＬｉｘＮｉＯ２、ＬｉｘＭｎＯ２、ＬｉｘＣｏｙＮｉ１－ｙＯ２、ＬｉｘＣｏｙＭ１－ｙＯｚ、ＬｉｘＮｉ１－ｙＭｙＯｚ、ＬｉｘＭｎ２Ｏ４及びＬｉｘＭｎ２－ｙＭｙＯ４（各式中、Ｍは、Ｎａ、Ｍｇ、Ｓｃ、Ｙ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ａｌ、Ｃｒ、Ｐｂ、Ｓｂ、Ｖ及びＢからなる群より選ばれる少なくとも１種の元素を示す（ただし、Ｍは、各式中の他の元素と異なる元素である）。ｘ＝０～１．２、ｙ＝０～０．９、ｚ＝２．０～２．３である。）が挙げられる。ＬｉｘＮｉ１－ｙＭｙＯｚで表されるリチウム酸化物は、ＬｉｘＮｉ１－（ｙ１＋ｙ２）Ｃｏｙ１Ｍｎｙ２Ｏｚ（ただし、ｘ及びｚは上述したものと同様であり、ｙ１＝０～０．９、ｙ２＝０～０．９であり、かつ、ｙ１＋ｙ２＝０～０．９である。）であってよく、例えばＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２、ＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２、ＬｉＮｉ０．６Ｃｏ０．２Ｍｎ０．２Ｏ２、ＬｉＮｉ０．８Ｃｏ０．１Ｍｎ０．１Ｏ２であってよい。ＬｉｘＮｉ１－ｙＭｙＯｚで表されるリチウム酸化物は、ＬｉｘＮｉ１－（ｙ３＋ｙ４）Ｃｏｙ３Ａｌｙ４Ｏｚ（ただし、ｘ及びｚは上述したものと同様であり、ｙ３＝０～０．９、ｙ４＝０～０．９であり、かつ、ｙ３＋ｙ４＝０～０．９である。）であってよく、例えばＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２であってもよい。
The positive electrode active material may be, for example, lithium oxide. Examples of the lithium oxide include Li x CoO 2 , Li x NiO 2 , Li x MnO 2 , Li x Co y Ni 1-y O 2 , Li x Co y M 1-y O z , and Li x Ni 1-. y M y O z , Li x Mn 2 O 4 and Li x Mn 2 -y M y O 4 (In each formula, M is Na, Mg, Sc, Y, Mn, Fe, Co, Cu, Zn, Al. , At least one element selected from the group consisting of Cr, Pb, Sb, V and B (provided that M is an element different from the other elements in each formula), x=0 to 1.2. , Y=0 to 0.9 and z=2.0 to 2.3). The lithium oxide represented by Li x Ni 1-y M y O z is Li x Ni 1-(y1+y2) Co y1 Mn y2 O z (where x and z are the same as those described above, and y1= 0 to 0.9, y2=0 to 0.9, and y1+y2=0 to 0.9), for example, LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2, may be LiNi 0.8 Co 0.1 Mn 0.1 O 2 . The lithium oxide represented by Li x Ni 1-y M y O z is Li x Ni 1-(y3+y4) Co y3 Al y4 O z (where x and z are the same as those described above, and y3= 0 to 0.9, y4=0 to 0.9, and y3+y4=0 to 0.9), for example, LiNi 0.8 Co 0.15 Al 0.05 O 2 . It may be.
正極活物質は、例えばリチウムのリン酸塩であってもよい。リチウムのリン酸塩としては、例えば、リン酸マンガンリチウム（ＬｉＭｎＰＯ４）、リン酸鉄リチウム（ＬｉＦｅＰＯ４）、リン酸コバルトリチウム（ＬｉＣｏＰＯ４）及びリン酸バナジウムリチウム（Ｌｉ３Ｖ２（ＰＯ４）３）が挙げられる。
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 3 V 2 (PO 4 ). 3 ).
正極活物質の含有量は、正極合剤層全量を基準として、８０質量％以上、又は８５質量％以上であってよく、９９質量％以下であってよい。
The content of the positive electrode active material may be 80% by mass or more, or 85% by mass or more, and 99% by mass or less, based on the total amount of the positive electrode mixture layer.
導電剤は、アセチレンブラック、ケッチェンブラック等のカーボンブラック、黒鉛、グラフェン、カーボンナノチューブなどの炭素材料であってよい。導電剤の含有量は、正極合剤層全量を基準として、例えば、０．０１質量％以上、０．１質量％以上、又は１質量％以上であってよく、５０質量％以下、３０質量％以下、又は１５質量％以下であってよい。
The conductive agent may be carbon black such as acetylene black or Ketjen black, or carbon material such as graphite, graphene or carbon nanotube. The content of the conductive agent may be, for example, 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more, and 50% by mass or less, 30% by mass, based on the total amount of the positive electrode mixture layer. Or less, or 15% by mass or less.
結着剤は、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリメチルメタクリレート、ポリイミド、芳香族ポリアミド、セルロース、ニトロセルロース等の樹脂；ＳＢＲ（スチレン－ブタジエンゴム）、ＮＢＲ（アクリロニトリル－ブタジエンゴム）、フッ素ゴム、イソプレンゴム、ブタジエンゴム、エチレン－プロピレンゴム等のゴム；スチレン・ブタジエン・スチレンブロック共重合体又はその水素添加物、ＥＰＤＭ（エチレン・プロピレン・ジエン三元共重合体）、スチレン・エチレン・ブタジエン・エチレン共重合体、スチレン・イソプレン・スチレンブロック共重合体又はその水素添加物等の熱可塑性エラストマー；シンジオタクチック－１、２－ポリブタジエン、ポリ酢酸ビニル、エチレン・酢酸ビニル共重合体、プロピレン・α－オレフィン共重合体等の軟質樹脂；ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン、フッ素化ポリフッ化ビニリデン、ポリテトラフルオロエチレン・エチレン共重合体、ポリテトラフルオロエチレン・フッ化ビニリデン共重合体等のフッ素含有樹脂；ニトリル基含有モノマーをモノマー単位として有する樹脂；アルカリ金属イオン（例えばリチウムイオン）のイオン伝導性を有する高分子組成物などが挙げられる。
Examples of the binder include resins such as polyethylene, polypropylene, polyethylene terephthalate, polymethylmethacrylate, polyimide, aromatic polyamide, cellulose and nitrocellulose; SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), fluororubber. , Isoprene rubber, butadiene rubber, ethylene-propylene rubber and the like; styrene/butadiene/styrene block copolymers or hydrogenated products thereof, EPDM (ethylene/propylene/diene terpolymer), styrene/ethylene/butadiene/ Thermoplastic elastomers such as ethylene copolymers, styrene/isoprene/styrene block copolymers or hydrogenated products thereof; syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene/vinyl acetate copolymers, propylene/α -Soft resin such as olefin copolymer; polyvinylidene fluoride (PVDF), polytetrafluoroethylene, fluorinated polyvinylidene fluoride, polytetrafluoroethylene/ethylene copolymer, polytetrafluoroethylene/vinylidene fluoride copolymer, etc. And a fluorine-containing resin, a resin having a nitrile group-containing monomer as a monomer unit, a polymer composition having an alkali metal ion (for example, lithium ion) ion conductivity, and the like.
結着剤の含有量は、正極合剤層全量を基準として、例えば、０．１質量％以上、１質量％以上、又は１．５質量％以上であってよく、３０質量％以下、２０質量％以下、又は１０質量％以下であってよい。
The content of the binder may be, for example, 0.1% by mass or more, 1% by mass or more, or 1.5% by mass or more, based on the total amount of the positive electrode mixture layer, 30% by mass or less, 20% by mass. % Or less, or 10% by mass or less.
セパレータ７は、正極６及び負極８間を電子的には絶縁する一方でイオンを透過させ、かつ、正極６側における酸化性及び負極８側における還元性に対する耐性を備えるものであれば、特に制限されない。このようなセパレータ７の材料（材質）としては、樹脂、無機物等が挙げられる。
The separator 7 is not particularly limited as long as it electrically insulates between the positive electrode 6 and the negative electrode 8 while allowing ions to pass therethrough and has resistance to the oxidizing property on the positive electrode 6 side and the reducing property on the negative electrode 8 side. Not done. Examples of the material (material) of the separator 7 include resins and inorganic materials.
樹脂としては、オレフィン系ポリマー、フッ素系ポリマー、セルロース系ポリマー、ポリイミド、ナイロン等が挙げられる。セパレータ７は、電解液に対して安定で、保液性に優れる観点から、好ましくは、ポリエチレン、ポリプロピレン等のポリオレフィンで形成された多孔質シート又は不織布である。
Examples of resins include olefin polymers, fluorine polymers, cellulosic polymers, polyimides and nylons. The separator 7 is preferably a porous sheet or a non-woven fabric formed of polyolefin such as polyethylene or polypropylene from the viewpoint of being stable with respect to the electrolytic solution and excellent in liquid retaining property.
無機物としては、アルミナ、二酸化珪素等の酸化物、窒化アルミニウム、窒化珪素等の窒化物、硫酸バリウム、硫酸カルシウム等の硫酸塩が挙げられる。セパレータ７は、例えば、不織布、織布、微多孔性フィルム等の薄膜状基材に、繊維状又は粒子状の無機物を付着させたセパレータであってよい。
Examples of the inorganic substance include oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate. The separator 7 may be, for example, a thin film substrate such as a nonwoven fabric, a woven fabric, or a microporous film to which a fibrous or particulate inorganic substance is attached.
負極８は、負極集電体１１と、負極集電体１１上に設けられた負極合剤層１２とを備えている。負極集電体１１には、負極集電タブ５が設けられている。
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.
負極集電体１１は、銅、ステンレス、ニッケル、アルミニウム、チタン、焼成炭素、導電性高分子、導電性ガラス、アルミニウム－カドミウム合金等で形成されている。負極集電体１１は、接着性、導電性、耐還元性向上の目的で、銅、アルミニウム等の表面にカーボン、ニッケル、チタン、銀等で処理が施されたものであってもよい。負極集電体１１の厚さは、電極強度及びエネルギー密度の点から、例えば１～５０μｍである。
The negative electrode current collector 11 is made of copper, stainless steel, nickel, aluminum, titanium, baked carbon, conductive polymer, conductive glass, aluminum-cadmium alloy, or the like. The negative electrode current collector 11 may be one in which the surface of copper, aluminum, or the like is 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 electrode strength and energy density.
負極合剤層１２は、例えば、負極活物質と、結着剤とを含有する。
The negative electrode mixture layer 12 contains, for example, a negative electrode active material and a binder.
負極活物質は、リチウムイオンを吸蔵及び放出可能な物質であれば特に制限されない。負極活物質としては、例えば、炭素材料、金属複合酸化物、錫、ゲルマニウム、ケイ素等の第四族元素の酸化物又は窒化物、リチウムの単体、リチウムアルミニウム合金等のリチウム合金、Ｓｎ、Ｓｉ等のリチウムと合金を形成可能な金属などが挙げられる。負極活物質は、安全性の観点からは、好ましくは炭素材料及び金属複合酸化物からなる群より選択される少なくとも１種である。負極活物質はこれらの１種単独又は２種以上の混合物であってよい。負極活物質の形状は、例えば、粒子状であってよい。
The negative electrode active material is not particularly limited as long as it can absorb and release lithium ions. Examples of the negative electrode active material include carbon materials, metal composite oxides, oxides or nitrides of Group IV elements such as tin, germanium, and silicon, simple substances of lithium, lithium alloys such as lithium aluminum alloys, Sn, Si, and the like. And a metal capable of forming an alloy with lithium. From the viewpoint of safety, the negative electrode active material is preferably at least one selected from the group consisting of carbon materials and metal composite oxides. The negative electrode active material may be one type of these alone or a mixture of two or more types. The shape of the negative electrode active material may be, for example, a particle shape.
炭素材料としては、非晶質炭素材料、天然黒鉛、天然黒鉛に非晶質炭素材料の被膜を形成した複合炭素材料、人造黒鉛（エポキシ樹脂、フェノール樹脂等の樹脂原料、又は、石油、石炭等から得られるピッチ系原料を焼成して得られるもの）などが挙げられる。金属複合酸化物は、高電流密度充放電特性の観点からは、好ましくはチタン及びリチウムのいずれか一方又は両方を含有し、より好ましくはリチウムを含有する。
As the carbon material, amorphous carbon material, natural graphite, composite carbon material obtained by forming a film of amorphous carbon material on natural graphite, artificial graphite (resin raw material such as epoxy resin, phenol resin, or petroleum, coal, etc. Obtained by firing a pitch-based raw material obtained from the above). From the viewpoint of high current density charge/discharge characteristics, the metal composite oxide preferably contains one or both of titanium and lithium, and more preferably contains lithium.
負極活物質の中でも炭素材料は、導電性が高く、低温特性及びサイクル安定性に特に優れている。炭素材料の中でも高容量化の観点からは、黒鉛が好ましい。黒鉛においては、好ましくはＸ線広角回折法における炭素網面層間（ｄ００２）が０．３４ｎｍ未満であり、より好ましくは０．３３５４ｎｍ以上０．３３７ｎｍ以下である。このような条件を満たす炭素材料を、擬似異方性炭素と称する場合がある。
Among the negative electrode active materials, carbon materials have high conductivity and are particularly excellent in low temperature characteristics and cycle stability. Among the carbon materials, graphite is preferable from the viewpoint of high capacity. In graphite, the carbon network plane layer (d002) in the X-ray wide-angle diffraction method is preferably less than 0.34 nm, and more preferably 0.3354 nm or more and 0.337 nm or less. A carbon material that satisfies such conditions may be referred to as pseudo-anisotropic carbon.
負極活物質には、ケイ素及びスズからなる群より選ばれる少なくとも１種の元素を含む材料が更に含まれていてもよい。ケイ素及びスズからなる群より選ばれる少なくとも１種の元素を含む材料は、ケイ素又はスズの単体、ケイ素及びスズからなる群より選ばれる少なくとも１種の元素を含む化合物であってよい。当該化合物は、ケイ素及びスズからなる群より選ばれる少なくとも１種の元素を含む合金であってよく、例えば、ケイ素及びスズの他に、ニッケル、銅、鉄、コバルト、マンガン、亜鉛、インジウム、銀、チタン、ゲルマニウム、ビスマス、アンチモン及びクロムからなる群より選ばれる少なくとも１種を含む合金である。ケイ素及びスズからなる群より選ばれる少なくとも１種の元素を含む化合物は、酸化物、窒化物、又は炭化物であってもよく、具体的には、例えば、ＳｉＯ、ＳｉＯ２、ＬｉＳｉＯ等のケイ素酸化物、Ｓｉ３Ｎ４、Ｓｉ２Ｎ２Ｏ等のケイ素窒化物、ＳｉＣ等のケイ素炭化物、ＳｎＯ、ＳｎＯ２、ＬｉＳｎＯ等のスズ酸化物などであってよい。
The negative electrode active material may further contain a material containing at least one element selected from the group consisting of silicon and tin. The material containing at least one element selected from the group consisting of silicon and tin may be a simple substance of silicon or tin, or a compound containing at least one element selected from the group consisting of silicon and tin. The compound may be an alloy containing at least one element selected from the group consisting of silicon and tin. For example, in addition to silicon and tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver. , An alloy containing at least one selected from the group consisting of titanium, germanium, bismuth, antimony and chromium. The compound containing at least one element selected from the group consisting of silicon and tin may be an oxide, a nitride, or a carbide, and specifically, for example, silicon oxide such as SiO, SiO 2 , and LiSiO. A silicon nitride such as Si 3 N 4 or Si 2 N 2 O, a silicon carbide such as SiC, a tin oxide such as SnO, SnO 2 or LiSnO.
負極８は、低温入力特性等の電気化学デバイスの性能を更に向上させる観点から、負極活物質として、好ましくは炭素材料を含み、より好ましくは黒鉛を含み、更に好ましくは、炭素材料と、ケイ素及びスズからなる群より選ばれる少なくとも１種の元素を含む材料との混合物を含み、特に好ましくは、黒鉛とケイ素酸化物との混合物を含む。当該混合物におけるケイ素及びスズからなる群より選ばれる少なくとも１種の元素を含む材料（ケイ素酸化物）に対する炭素材料（黒鉛）の含有量は、当該混合物全量を基準として、１質量％以上、又は３質量％以上であってよく、３０質量％以下であってよい。
From the viewpoint of further improving the performance of the electrochemical device such as low temperature input characteristics, the negative electrode 8 preferably contains a carbon material, more preferably graphite, and further preferably a carbon material, silicon and It contains a mixture with a material containing at least one element selected from the group consisting of tin, and particularly preferably contains a mixture of graphite and silicon oxide. The content of the carbon material (graphite) with respect to the material (silicon oxide) containing at least one element selected from the group consisting of silicon and tin in the mixture is 1% by mass or more based on the total amount of the mixture, or 3 It may be not less than 30% by mass and not more than 30% by mass.
負極活物質の含有量は、負極合剤層全量を基準として、８０質量％以上、又は８５質量％以上であってよく、９９質量％以下であってよい。
The content of the negative electrode active material may be 80% by mass or more, or 85% by mass or more, and 99% by mass or less, based on the total amount of the negative electrode mixture layer.
結着剤及びその含有量は、上述した正極合剤層における結着剤及びその含有量と同様であってよい。
The binder and the content thereof may be the same as the binder and the content thereof in the positive electrode mixture layer described above.
負極合剤層１２は、粘度を調節するために増粘剤を含有してもよい。増粘剤は、特に制限されないが、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、エチルセルロース、ポリビニルアルコール、酸化スターチ、リン酸化スターチ、カゼイン、これらの塩等であってよい。増粘剤は、これらの１種単独又は２種以上の混合物であってよい。
The negative electrode mixture layer 12 may contain a thickener to adjust the viscosity. The thickener is not particularly limited, but 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 one of these alone or a mixture of two or more thereof.
負極合剤層１２が増粘剤を含む場合、その含有量は特に制限されない。増粘剤の含有量は、負極合剤層の塗布性の観点からは、負極合剤層全量を基準として、０．１質量％以上であってよく、好ましくは０．２質量％以上であり、より好ましくは０．５質量％以上である。増粘剤の含有量は、電池容量の低下又は負極活物質間の抵抗の上昇を抑制する観点からは、負極合剤層全量を基準として、５質量％以下であってよく、好ましくは３質量％以下であり、より好ましくは２質量％以下である。
When the negative electrode mixture layer 12 contains a thickener, the content thereof is not particularly limited. The content of the thickener may be 0.1% by mass or more, and preferably 0.2% by mass or more, based on the total amount of the negative electrode mixture layer, from the viewpoint of coatability of the negative electrode mixture layer. , And more preferably 0.5% by mass or more. The content of the thickener may be 5% by mass or less, preferably 3% by mass, 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. % Or less, and more preferably 2% by mass or less.
電解液は、一実施形態において、下記式（１）で表される化合物と、ケイ素原子を有さず、硫黄原子を含む環を有する環状化合物（以下、単に「環状化合物」ともいう）と、電解質塩と、非水溶媒とを含有する。
式（１）中、Ｒ１～Ｒ３は、それぞれ独立に、アルキル基又はフッ素原子を示し、Ｒ４はアルキレン基を示し、Ｒ５は、硫黄原子を含む有機基を示す。
The electrolytic solution, in one embodiment, a compound represented by the following formula (1), a cyclic compound having no silicon atom and a ring containing a sulfur atom (hereinafter, also simply referred to as “cyclic compound”), It contains an electrolyte salt and a non-aqueous solvent.
In formula (1), R 1 to R 3 each independently represent an alkyl group or a fluorine atom, R 4 represents an alkylene group, and R 5 represents an organic group containing a sulfur atom.
Ｒ１～Ｒ３で表されるアルキル基の炭素数は、１以上であってよく、３以下であってよい。Ｒ１～Ｒ３は、メチル基、エチル基、又はプロピル基であってよく、直鎖状でも分岐状でもよい。Ｒ１～Ｒ３の少なくとも１つは、好ましくはフッ素原子である。Ｒ１～Ｒ３のいずれか１つがフッ素原子であってよく、Ｒ１～Ｒ３のいずれか２つがフッ素原子であってよく、Ｒ１～Ｒ３のすべてがフッ素原子であってよい。
The alkyl group represented by R 1 to R 3 may have 1 or more carbon atoms and 3 or less carbon atoms. R 1 to R 3 may be a methyl group, an ethyl group, or a propyl group, and may be linear or branched. At least one of R 1 to R 3 is preferably a fluorine atom. May be any one of fluorine atom of R 1 ~ R 3, it may be any two of a fluorine atom of R 1 ~ R 3, all of R 1 ~ R 3 may be a fluorine atom.
Ｒ４で表されるアルキレン基の炭素数は、１以上又は２以上であってよく、５以下又は４以下であってよい。Ｒ４で表されるアルキレン基は、メチレン基、エチレン基、プロピレン基、ブチレン基、又はペンチレン基であってよく、直鎖状でも分岐状でもよい。
The carbon number of the alkylene group represented by R 4 may be 1 or more or 2 or more, and 5 or less or 4 or less. The alkylene group represented by R 4 may be a methylene group, an ethylene group, a propylene group, a butylene group, or a pentylene group, and may be linear or branched.
一実施形態において、式（１）で表される化合物１分子中のケイ素原子の数は、１個である。すなわち、一実施形態において、Ｒ５で表される有機基は、ケイ素原子を含まない。
In one embodiment, the number of silicon atoms in one molecule of the compound represented by formula (1) is one. That is, in one embodiment, the organic group represented by R 5 does not include a silicon atom.
Ｒ５は、電気化学デバイスの性能を更に向上させることができる観点から、好ましくは、下記式（３）、式（４）又は式（５）のいずれかで表される基であってよい。
式（３）中、Ｒ８はアルキル基を示す。アルキル基は、上述したＲ１～Ｒ３で表されるアルキル基と同様であってよい。＊は結合手を示す。
式（４）中、Ｒ９はアルキル基を示す。アルキル基は、上述したＲ１～Ｒ３で表されるアルキル基と同様であってよい。＊は結合手を示す。
式（５）中、Ｒ１０はアルキル基を示す。アルキル基は、上述したＲ１～Ｒ３で表されるアルキル基と同様であってよい。＊は結合手を示す。
From the viewpoint of being able to further improve the performance of the electrochemical device, R 5 is preferably a group represented by any of the following formula (3), formula (4) or formula (5).
In formula (3), R 8 represents an alkyl group. The alkyl group may be the same as the alkyl group represented by R 1 to R 3 described above. * Indicates a bond.
In formula (4), R 9 represents an alkyl group. The alkyl group may be the same as the alkyl group represented by R 1 to R 3 described above. * Indicates a bond.
In formula (5), R 10 represents an alkyl group. The alkyl group may be the same as the alkyl group represented by R 1 to R 3 described above. * Indicates a bond.
式（１）で表される化合物の含有量は、電気化学デバイスの性能を更に向上させることができる観点から、電解液全量を基準として、好ましくは、０．００１質量％以上、０．００５質量％以上、０．０１質量％以上、０．０５質量％以上、又は０．１質量％以上であり、８質量％以下、５質量％以下、３質量％以下、２質量％以下、又は１質量％以下である。
The content of the compound represented by the formula (1) is preferably 0.001% by mass or more and 0.005% by mass, based on the total amount of the electrolytic solution, from the viewpoint that the performance of the electrochemical device can be further improved. % Or more, 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more, 8 mass% or less, 5 mass% or less, 3 mass% or less, 2 mass% or less, or 1 mass. % Or less.
環状化合物は、硫黄原子を含む環（複素環）を有する化合物である。なお、環状化合物は、上記式（１）で表される化合物以外の化合物である。言い換えれば、環状化合物は、ケイ素原子を有さない化合物である。
A 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.
環状化合物は、例えば、環状スルホン酸エステル化合物（スルトン化合物とも呼ばれる）の少なくとも１種を含んでいてよい。環状スルホン酸エステル化合物は、－ＯＳＯ２－基を含む環を有する化合物である。環状スルホン酸エステル化合物は、－ＯＳＯ２－基を１つ又は２つ含む環を有している。
The cyclic compound may include, for example, at least one cyclic sulfonate compound (also referred to as a sultone compound). The cyclic sulfonate compound is a compound having a ring containing an —OSO 2 — group. The cyclic sulfonic acid ester compound has a ring containing one or two —OSO 2 — groups.
－ＯＳＯ２－基を１つ含む環を有する環状スルホン酸エステル化合物は、例えば下記式（Ｘ）で表される化合物であってよい。
式（Ｘ）中、Ａ１は、炭素数３～５のアルキレン基又は炭素数３～５のアルケニレン基を表し、該アルキレン基及び該アルケニレン基における水素原子は、アルキル基、シクロアルキル基、アリール基、又はフルオロ基で置換されていてもよい。
The cyclic sulfonic acid ester compound having a ring containing one —OSO 2 — group may be, for example, a compound represented by the following formula (X).
In formula (X), A 1 represents an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms, and the hydrogen atom in the alkylene group and the alkenylene group is an alkyl group, a cycloalkyl group or an aryl group. It may be substituted with a group or a fluoro group.
上記アルキル基の炭素数は、例えば１～１２であってよい。上記シクロアルキル基の炭素数は、例えば３～６であってよい。上記アリール基の炭素数は、例えば６～１２であってよい。
The carbon number of the alkyl group may be, for example, 1 to 12. The cycloalkyl group may have, for example, 3 to 6 carbon atoms. The aryl group may have, for example, 6 to 12 carbon atoms.
Ａ１は、好ましくは、炭素数３のアルキレン基又は炭素数３のアルケニレン基である。すなわち、環状スルホン酸エステル化合物は、好ましくは、下記式（Ｘ－１）又は式（Ｘ－２）で表される化合物である。
A 1 is preferably an alkylene group having 3 carbon atoms or an alkenylene group having 3 carbon atoms. That is, the cyclic sulfonate compound is preferably a compound represented by the following formula (X-1) or formula (X-2).
式中、Ｒ１１～Ｒ２０は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基、又はフルオロ基を表す。Ｒ１１～Ｒ２０で表されるアルキル基、シクロアルキル基及びアリール基の炭素数は、式（Ｘ）について説明したアルキル基、シクロアルキル基及びアリール基の炭素数とそれぞれ同様である。Ｒ１１～Ｒ２０は、好ましくは水素原子である。
In the formula, R 11 to R 20 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a fluoro group. The carbon number of the alkyl group, cycloalkyl group and aryl group represented by R 11 to R 20 is the same as the carbon number of the alkyl group, cycloalkyl group and aryl group described for formula (X). R 11 to R 20 are preferably hydrogen atoms.
式（Ｘ）で表される環状スルホン酸エステル化合物としては、例えば、１，３－プロパンスルトン、１，４－ブタンスルトン、２，４－ブタンスルトン、１，３－プロペンスルトン、１，４－ブテンスルトン、１－メチル－１，３－プロパンスルトン、３－メチル－１，３－プロパンスルトン、１－フルオロ－１，３－プロパンスルトン、３－フルオロ－１，３－プロパンスルトン等のモノスルホン酸エステルなどが挙げられる。これらのうち、電気化学デバイスの性能を更に向上させることができる観点から、１，３－プロパンスルトン（式（Ｘ－１）において、Ｒ１１～Ｒ１６のすべてが水素原子である化合物）又は１－プロペン－１，３－スルトン（式（Ｘ－２）において、Ｒ１７～Ｒ２０のすべてが水素原子である化合物）が好ましい。
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, Monosulfonic acid esters such as 1-methyl-1,3-propane sultone, 3-methyl-1,3-propane sultone, 1-fluoro-1,3-propane sultone and 3-fluoro-1,3-propane sultone Is mentioned. Of these, 1,3-propane sultone (a compound in which all of R 11 to R 16 in the formula (X-1) are hydrogen atoms) or 1 from the viewpoint that the performance of the electrochemical device can be further improved. -Propene-1,3-sultone (a compound in which all of R 17 to R 20 in the formula (X-2) are hydrogen atoms) is preferable.
－ＯＳＯ２－基を２つ含む環を有する環状スルホン酸エステル化合物は、例えば下記式（Ｘ－３）で表される化合物であってよい。
式中、Ｂ１及びＢ２は、それぞれ独立に、炭素数１～５のアルキレン基又は炭素数１～５のアルケニレン基を表し、該アルキレン基及び該アルケニレン基における水素原子は、アルキル基、シクロアルキル基、アリール基、又はフルオロ基で置換されていてもよい。
The cyclic sulfonic acid ester compound having a ring containing two —OSO 2 — groups may be, for example, a compound represented by the following formula (X-3).
In the formula, B 1 and B 2 each independently represent an alkylene group having 1 to 5 carbon atoms or an alkenylene group having 1 to 5 carbon atoms, and the hydrogen atom in the alkylene group and the alkenylene group is an alkyl group, cycloalkyl It may be substituted with an alkyl group, an aryl group, or a fluoro group.
Ｂ１及びＢ２は、好ましくは、炭素数１又は２の無置換のアルキレン基である。このような環状スルホン酸エステル化合物は、メチレンメタンジスルホン酸エステル、エチレンメタンジスルホン酸エステル等のジスルホン酸エステルであってよい。
B 1 and B 2 are preferably unsubstituted alkylene groups having 1 or 2 carbon atoms. Such cyclic sulfonic acid ester compound may be a disulfonic acid ester such as methylene methane disulfonic acid ester and ethylene methane disulfonic acid ester.
環状化合物は、例えば、式（Ｙ）で表される化合物及び式（Ｚ）で表される化合物からなる群より選ばれる少なくとも１種を含んでいてもよい。
式（Ｙ），（Ｚ）中、Ａ２及びＡ３は、それぞれ独立に、炭素数３～５のアルキレン基又は炭素数３～５のアルケニレン基を表し、該アルキレン基及び該アルケニレン基における水素原子は、アルキル基、シクロアルキル基又はアリール基で置換されていてもよい。
The cyclic compound may include, for example, at least one selected from the group consisting of the compound represented by the formula (Y) and the compound represented by the formula (Z).
In formulas (Y) and (Z), A 2 and A 3 each independently represent an alkylene group having 3 to 5 carbon atoms or an alkenylene group having 3 to 5 carbon atoms, and hydrogen in the alkylene group and the alkenylene group. Atoms may be substituted with alkyl, cycloalkyl or aryl groups.
Ａ２及びＡ３におけるアルキル基、シクロアルキル基及びアリール基の炭素数は、式（Ｘ）について説明したアルキル基、シクロアルキル基及びアリール基の炭素数とそれぞれ同様である。
The carbon numbers of the alkyl group, cycloalkyl group and aryl group in A 2 and A 3 are the same as the carbon numbers of the alkyl group, cycloalkyl group and aryl group described for formula (X), respectively.
式（Ｙ）で表される化合物としては、例えば、スルホラン、２－メチルスルホラン、３－メチルスルホラン、２－エチルスルホラン、３－エチルスルホラン、２，４－ジメチルスルホラン、２－フェニルスルホラン、３－フェニルスルホラン、スルホレン、３－メチルスルホレン等が挙げられる。式（Ｙ）で表される化合物は、電気化学デバイスの性能を更に向上させることができる観点から、好ましくはスルホランである。
Examples of the compound represented by the formula (Y) include sulfolane, 2-methylsulfolane, 3-methylsulfolane, 2-ethylsulfolane, 3-ethylsulfolane, 2,4-dimethylsulfolane, 2-phenylsulfolane and 3-phenylsulfolane. Examples thereof include phenylsulfolane, sulfolene, 3-methylsulfolene and the like. The compound represented by the formula (Y) is preferably sulfolane, from the viewpoint of further improving the performance of the electrochemical device.
式（Ｚ）で表される化合物としては、例えば、エチレンサルファイト、プロピレンサルファイト、ブチレンサルファイト、ビニレンサルファイト、フェニルエチレンサルファイト等が挙げられる。式（Ｚ）で表される化合物は、電気化学デバイスの性能を更に向上させることができる観点から、好ましくはエチレンサルファイトである。
Examples of the compound represented by the formula (Z) include ethylene sulfite, propylene sulfite, butylene sulfite, vinylene sulfite, and phenylethylene sulfite. The compound represented by the formula (Z) is preferably ethylene sulfite, from the viewpoint that the performance of the electrochemical device can be further improved.
環状化合物は、環状スルホン酸エステル化合物、式（Ｙ）で表される化合物及び式（Ｚ）で表される化合物からなる群より選ばれる少なくとも１種を含んでもよく、式（Ｘ）で表される化合物、式（Ｙ）で表される化合物及び式（Ｚ）で表される化合物からなる群より選ばれる少なくとも１種を含んでもよく、式（Ｘ）で表される化合物及び式（Ｚ）で表される化合物からなる群より選ばれる少なくとも１種を含んでもよい。
The cyclic compound may contain at least one selected from the group consisting of a cyclic sulfonate compound, a compound represented by the formula (Y) and a compound represented by the formula (Z), and is represented by the formula (X). Compound represented by the formula (Y) and a compound represented by the formula (Z) may be included in the compound represented by the formula (X) and the formula (Z). At least one selected from the group consisting of compounds represented by
環状化合物の含有量は、電気化学デバイスの性能を更に向上させることができる観点から、電解液全量を基準として、好ましくは、０．００１質量％以上、０．００５質量％以上、０．０１質量％以上、０．０５質量％以上、又は０．１質量％以上であり、５質量％以下、３質量％以下、２質量％以下、又は１質量％以下である。
The content of the cyclic compound is preferably 0.001 mass% or more, 0.005 mass% or more, 0.01 mass, based on the total amount of the electrolytic solution, from the viewpoint that the performance of the electrochemical device can be further improved. % 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.
式（１）で表される化合物の含有量及び環状化合物の含有量の合計は、電気化学デバイスの性能を更に向上させることができる観点から、電解液全量を基準として、好ましくは、０．００１質量％以上、０．００５質量％以上、０．０１質量％以上、０．１質量％以上、又は０．５質量％以上であり、好ましくは、１０質量％以下、７質量％以下、５質量％以下、３質量％以下、又は２質量％以下である。
From the viewpoint that the performance of the electrochemical device can be further improved, the total content of the compound represented by formula (1) and the content of the cyclic compound is preferably 0.001 based on the total amount of the electrolytic solution. % By mass, 0.005% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 0.5% by mass or more, preferably 10% by mass or less, 7% by mass or less, 5% by mass % Or less, 3% by mass or less, or 2% by mass or less.
環状化合物の含有量に対する式（１）で表される化合物の含有量の質量比（式（１）で表される化合物の含有量／環状化合物の含有量）は、電気化学デバイスの性能を更に向上させることができる観点から、好ましくは、０．０１以上、０．０５以上、０．１以上、０．２以上、又は０．２５以上であり、また、好ましくは、５００以下、１００以下、５０以下、２０以下、１０以下、５以下、又は４以下である。
The mass ratio of the content of the compound represented by the formula (1) to the content of the cyclic compound (content of the compound represented by the formula (1)/content of the cyclic compound) further improves the performance of the electrochemical device. From the viewpoint of being able to improve, it is preferably 0.01 or more, 0.05 or more, 0.1 or more, 0.2 or more, or 0.25 or more, and preferably 500 or less, 100 or less, It is 50 or less, 20 or less, 10 or less, 5 or less, or 4 or less.
電解質塩は、例えばリチウム塩であってよい。リチウム塩は、例えば、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＢ（Ｃ６Ｈ５）４、ＬｉＣＨ３ＳＯ３、ＣＦ３ＳＯ２ＯＬｉ、ＬｉＮ（ＳＯ２Ｆ）２（Ｌｉ［ＦＳＩ］、リチウムビスフルオロスルホニルイミド）、ＬｉＮ（ＳＯ２ＣＦ３）２（Ｌｉ［ＴＦＳＩ］、リチウムビストリフルオロメタンスルホニルイミド）、及びＬｉＮ（ＳＯ２ＣＦ２ＣＦ３）２からなる群より選ばれる少なくとも１種であってよい。リチウム塩は、溶媒に対する溶解性、二次電池の充放電特性、出力特性、サイクル特性等に更に優れる観点から、好ましくはＬｉＰＦ６を含む。
The electrolyte salt may be, for example, a lithium salt. The lithium salt is, for example, LiPF 6 , LiBF 4 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , CF 3 SO 2 OLi, LiN(SO 2 F) 2 (Li[FSI], lithium bis. Fluorosulfonylimide), LiN(SO 2 CF 3 ) 2 (Li[TFSI], lithium bistrifluoromethanesulfonylimide), and at least one selected from the group consisting of LiN(SO 2 CF 2 CF 3 ) 2 Good. The lithium salt preferably contains LiPF 6 from the viewpoint of further excellent solubility in a solvent, charge/discharge characteristics of a secondary battery, output characteristics, cycle characteristics, and the like.
電解質塩の濃度は、充放電特性に優れる観点から、非水溶媒全量を基準として、好ましくは０．５ｍｏｌ／Ｌ以上、より好ましくは０．７ｍｏｌ／Ｌ以上、更に好ましくは０．８ｍｏｌ／Ｌ以上であり、また、好ましくは１．５ｍｏｌ／Ｌ以下、より好ましくは１．３ｍｏｌ／Ｌ以下、更に好ましくは１．２ｍｏｌ／Ｌ以下である。
From the viewpoint of excellent charge/discharge characteristics, the concentration of the electrolyte salt is preferably 0.5 mol/L or more, more preferably 0.7 mol/L or more, and further preferably 0.8 mol/L or more, based on the total amount of the non-aqueous solvent. Further, it is preferably 1.5 mol/L or less, more preferably 1.3 mol/L or less, still more preferably 1.2 mol/L or less.
非水溶媒は、例えば、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、γ－ブチルラクトン、アセトニトリル、１，２－ジメトキシエタン、ジメトキシメタン、テトラヒドロフラン、ジオキソラン、塩化メチレン、酢酸メチル等であってよい。非水溶媒は、これらの１種単独又は２種以上の混合物であってよく、好ましくは２種以上の混合物である。
Examples of the non-aqueous solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyl lactone, acetonitrile, 1,2-dimethoxyethane, dimethoxymethane, tetrahydrofuran, dioxolane, methylene chloride and methyl acetate. May be The non-aqueous solvent may be one of these alone or a mixture of two or more thereof, and preferably a mixture of two or more thereof.
電解液は、式（１）で表される化合物、環状化合物、電解質塩及び非水溶媒以外のその他の材料を更に含有してもよい。その他の材料は、例えば、フッ素含有環状カーボネート、炭素－炭素二重結合を有する環状カーボネート等の環状カーボネート、窒素原子を有する化合物、式（１）で表される化合物及び環状化合物以外の硫黄原子を有する化合物、環状カルボン酸エステル等であってよい。
The electrolytic solution may further contain other materials other than the compound represented by the formula (1), the cyclic compound, the electrolyte salt and the non-aqueous solvent. Other materials include, for example, fluorine-containing cyclic carbonates, cyclic carbonates such as cyclic carbonates having a carbon-carbon double bond, compounds having a nitrogen atom, compounds represented by formula (1) and sulfur atoms other than cyclic compounds. The compound may have a cyclic carboxylic acid ester or the like.
フッ素含有環状カーボネートは、例えば、４－フルオロ－１，３－ジオキソラン－２－オン（フルオロエチレンカーボネート；ＦＥＣ)、１，２－ジフルオロエチレンカーボネート、１，１－ジフルオロエチレンカーボネート、１，１，２－トリフルオロエチレンカーボネート、１，１，２，２－テトラフルオロエチレンカーボネート等であってよく、好ましくは、４－フルオロ－１，３－ジオキソラン－２－オン（フルオロエチレンカーボネート；ＦＥＣ）である。炭素－炭素二重結合を有する環状カーボネートは、例えばビニレンカーボネートであってよい。窒素原子を含有する化合物は、例えばスクシノニトリル等のニトリル化合物であってよい。
Examples of the fluorine-containing cyclic carbonate include 4-fluoro-1,3-dioxolan-2-one (fluoroethylene carbonate; FEC), 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2. It may be trifluoroethylene carbonate, 1,1,2,2-tetrafluoroethylene carbonate, etc., preferably 4-fluoro-1,3-dioxolan-2-one (fluoroethylene carbonate; FEC). The cyclic carbonate having a carbon-carbon double bond may be vinylene carbonate, for example. The compound containing a nitrogen atom may be a nitrile compound such as succinonitrile.
本発明者らは、様々な構造及び官能基を有する化合物を検討した結果、上述した式（１）で表される化合物及び環状化合物を電解液に適用することによって、電気化学デバイスの性能を向上させることができることを明らかにした。本発明者らは、式（１）で表される化合物及び環状化合物を電解液に用いることによる作用効果を以下のように推察している。すなわち、式（１）で表される化合物及び環状化合物が、それぞれリチウムイオン二次電池内において最も効果を発現しやすい場所に作用して、例えば、正極又は負極の安定な被膜形成、又は電解液の安定化に寄与すると考えられる。その結果、非水電解液二次電池１のような電気化学デバイスの性能が向上する。
As a result of examining compounds having various structures and functional groups, the present inventors applied the compound represented by the above formula (1) and the cyclic compound to an electrolytic solution to improve the performance of an electrochemical device. Revealed that can be made. The present inventors presume the action and effect of using the compound represented by formula (1) and the cyclic compound in the electrolytic solution as follows. That is, the compound represented by the formula (1) and the cyclic compound each act on the place where the effect is most likely to be exhibited in the lithium ion secondary battery, for example, stable film formation of the positive electrode or the negative electrode, or the electrolytic solution. Is considered to contribute to the stabilization of As a result, the performance of the electrochemical device such as the non-aqueous electrolyte secondary battery 1 is improved.
具体的には、一実施形態の電解液によれば、電気化学デバイスの性能として、電気化学デバイスを高温下で保存した後の体積増加を抑制することができる。また、一実施形態の電解液によれば、電気化学デバイスのサイクル特性の向上（特に、サイクル試験後の容量維持率の向上、及び、サイクル試験後の放電ＤＣＲの上昇の抑制）が図られる。また、一実施形態の電解液によれば、電気化学デバイスを高温下で保存した後の放電ＤＣＲを低減させることができる。
Specifically, according to the electrolytic solution of one embodiment, as the performance of the electrochemical device, it is possible to suppress the volume increase after the electrochemical device is stored at a high temperature. Moreover, according to the electrolytic solution of one embodiment, the cycle characteristics of the electrochemical device are improved (in particular, the capacity retention ratio after the cycle test is improved and the increase in the discharge DCR after the cycle test is suppressed). Moreover, according to the electrolytic solution of one embodiment, it is possible to reduce the discharge DCR after the electrochemical device is stored at a high temperature.
続いて、非水電解液二次電池１の製造方法を説明する。非水電解液二次電池１の製造方法は、正極６を得る第１の工程と、負極８を得る第２の工程と、電極群２を電池外装体３に収容する第３の工程と、電解液を電池外装体３に注液する第４の工程と、を備える。
Next, a method for manufacturing the non-aqueous electrolyte secondary battery 1 will be described. The manufacturing method of the non-aqueous electrolyte secondary battery 1 includes a first step of obtaining the positive electrode 6, a second step of obtaining the negative electrode 8, and a third step of accommodating the electrode group 2 in the battery outer casing 3. A fourth step of injecting the electrolytic solution into the battery exterior body 3.
第１の工程では、正極合剤層１０に用いる材料を混練機、分散機等を用いて分散媒に分散させてスラリー状の正極合剤を得た後、この正極合剤をドクターブレード法、ディッピング法、スプレー法等により正極集電体９上に塗布し、その後分散媒を揮発させることにより正極６を得る。分散媒を揮発させた後、必要に応じて、ロールプレスによる圧縮成型工程が設けられてもよい。正極合剤層１０は、上述した正極合剤の塗布から分散媒の揮発までの工程を複数回行うことにより、多層構造の正極合剤層として形成されてもよい。分散媒は、水、１－メチル－２－ピロリドン（以下、ＮＭＰともいう。）等であってよい。
In the first step, the material used for the positive electrode mixture layer 10 is dispersed in a dispersion medium using a kneader, a disperser or the like to obtain a positive electrode mixture in a slurry state, and then this positive electrode mixture is treated by a doctor blade method, The positive electrode current collector 9 is coated with a dipping method, a spray method, or the like, and then the dispersion medium is volatilized to obtain the positive electrode 6. After volatilizing the dispersion medium, a compression molding step using a roll press may be provided, if necessary. The positive electrode mixture layer 10 may be formed as a positive electrode mixture layer having a multi-layer structure by performing the above-described 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.
第２の工程は、上述した第１の工程と同様であってよく、負極集電体１１に負極合剤層１２を形成する方法は、上述した第１の工程と同様の方法であってよい。
The second step may be the same as the above-mentioned first step, and the method of forming the negative electrode mixture layer 12 on the negative electrode current collector 11 may be the same method as the above-mentioned first step. ..
第３の工程では、作製した正極６及び負極８の間にセパレータ７を挟み、電極群２を形成する。次いで、この電極群２を電池外装体３に収容する。
In the third step, the separator 7 is sandwiched between the produced positive electrode 6 and negative electrode 8 to form the electrode group 2. Next, the electrode group 2 is housed in the battery case 3.
第４の工程では、電解液を電池外装体３に注入する。電解液は、例えば、電解質塩をはじめに溶媒に溶解させてから、その他の材料を溶解させることにより調製することができる。
In the fourth step, the electrolytic solution is injected into the battery exterior body 3. The electrolytic solution can be prepared, for example, by first dissolving an electrolyte salt in a solvent and then dissolving other materials.
他の実施形態として、電気化学デバイスはキャパシタであってもよい。キャパシタは、上述した非水電解液二次電池１と同様に、正極、負極及びセパレータから構成される電極群と、電極群を収容する袋状の電池外装体とを備えていてよい。キャパシタにおける各構成要素の詳細は、非水電解液二次電池１と同様であってよい。
In another embodiment, the electrochemical device may be a capacitor. Like the above-described non-aqueous electrolyte secondary battery 1, the capacitor may include an electrode group including a positive electrode, a negative electrode, and a separator, and a bag-shaped battery exterior body that houses the electrode group. The details of each component of the capacitor may be the same as those of the non-aqueous electrolyte secondary battery 1.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
（実施例１）
［正極の作製］
正極活物質としてのニッケルコバルトマンガン酸リチウム（９２質量％）に、導電剤としてアセチレンブラック（ＡＢ）（４質量％）と、結着剤（４質量％）とを順次添加し、混合した。得られた混合物に対し、分散媒としてのＮＭＰを添加し、混練することによりスラリー状の正極合剤を調製した。この正極合剤を正極集電体としての厚さ２０μｍのアルミニウム箔に均等且つ均質に所定量塗布した。その後、分散媒を揮発させてから、プレスすることにより密度２．８ｇ／ｃｍ３まで圧密化して、正極を得た。 (Example 1)
[Production of positive electrode]
Acetylene black (AB) (4 mass %) as a conductive agent and a binder (4 mass %) were sequentially added to and mixed with lithium nickel cobalt manganate (92 mass %) as a positive electrode active material. 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 this positive electrode mixture was uniformly and uniformly applied to an aluminum foil having a thickness of 20 μm as a positive electrode current collector. After that, the dispersion medium was volatilized and then pressed to consolidate it to a density of 2.8 g/cm 3 to obtain a positive electrode.
［正極の作製］
正極活物質としてのニッケルコバルトマンガン酸リチウム（９２質量％）に、導電剤としてアセチレンブラック（ＡＢ）（４質量％）と、結着剤（４質量％）とを順次添加し、混合した。得られた混合物に対し、分散媒としてのＮＭＰを添加し、混練することによりスラリー状の正極合剤を調製した。この正極合剤を正極集電体としての厚さ２０μｍのアルミニウム箔に均等且つ均質に所定量塗布した。その後、分散媒を揮発させてから、プレスすることにより密度２．８ｇ／ｃｍ３まで圧密化して、正極を得た。 (Example 1)
[Production of positive electrode]
Acetylene black (AB) (4 mass %) as a conductive agent and a binder (4 mass %) were sequentially added to and mixed with lithium nickel cobalt manganate (92 mass %) as a positive electrode active material. 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 this positive electrode mixture was uniformly and uniformly applied to an aluminum foil having a thickness of 20 μm as a positive electrode current collector. After that, the dispersion medium was volatilized and then pressed to consolidate it to a density of 2.8 g/cm 3 to obtain a positive electrode.
［負極の作製］
黒鉛及びケイ素酸化物を含む負極活物質に、結着剤と、増粘剤としてのカルボキシメチルセルロースとを添加した。これらの質量比については、黒鉛：ケイ素酸化物：結着剤：増粘剤＝９２：５：１．５：１．５とした。得られた混合物に対し、分散媒としての水を添加し、混練することによりスラリー状の負極合剤を調製した。この負極合剤を負極集電体としての厚さ１０μｍの圧延銅箔に均等かつ均質に所定量塗布した。その後、分散媒を揮発させてから、プレスすることにより密度１．６ｇ／ｃｍ３まで圧密化して、負極を得た。 [Fabrication of negative electrode]
A binder and carboxymethyl cellulose as a thickener were added to a negative electrode active material containing graphite and silicon oxide. Regarding the mass ratio of these, graphite:silicon oxide:binder:thickener=92:5:1.5:1.5. Water as a dispersion medium was added to the obtained mixture, and the mixture was kneaded to prepare a slurry negative electrode mixture. A predetermined amount of this negative electrode mixture was uniformly and uniformly applied to a rolled copper foil having a thickness of 10 μm as a negative electrode current collector. After that, the dispersion medium was volatilized and then pressed to consolidate to a density of 1.6 g/cm 3 to obtain a negative electrode.
黒鉛及びケイ素酸化物を含む負極活物質に、結着剤と、増粘剤としてのカルボキシメチルセルロースとを添加した。これらの質量比については、黒鉛：ケイ素酸化物：結着剤：増粘剤＝９２：５：１．５：１．５とした。得られた混合物に対し、分散媒としての水を添加し、混練することによりスラリー状の負極合剤を調製した。この負極合剤を負極集電体としての厚さ１０μｍの圧延銅箔に均等かつ均質に所定量塗布した。その後、分散媒を揮発させてから、プレスすることにより密度１．６ｇ／ｃｍ３まで圧密化して、負極を得た。 [Fabrication of negative electrode]
A binder and carboxymethyl cellulose as a thickener were added to a negative electrode active material containing graphite and silicon oxide. Regarding the mass ratio of these, graphite:silicon oxide:binder:thickener=92:5:1.5:1.5. Water as a dispersion medium was added to the obtained mixture, and the mixture was kneaded to prepare a slurry negative electrode mixture. A predetermined amount of this negative electrode mixture was uniformly and uniformly applied to a rolled copper foil having a thickness of 10 μm as a negative electrode current collector. After that, the dispersion medium was volatilized and then pressed to consolidate to a density of 1.6 g/cm 3 to obtain a negative electrode.
［リチウムイオン二次電池の作製］
１３．５ｃｍ２の四角形に切断した正極電極を、セパレータであるポリエチレン製多孔質シート（商品名：ハイポア（登録商標）、旭化成株式会社製、厚さ３０μｍ）で挟み、更に１４．３ｃｍ２の四角形に切断した負極を重ね合わせて電極群を作製した。この電極群を、アルミニウム製のラミネートフィルム（商品名：アルミラミネートフィルム、大日本印刷株式会社製）で形成された容器（電池外装体）に収容した。次いで、容器の中に電解液を１ｍＬ添加し、容器を熱溶着させ、評価用のリチウムイオン二次電池を作製した。電解液としては、１ｍｏｌ／ＬのＬｉＰＦ６を含むエチレンカーボネート、ジメチルカーボネート及びエチルメチルカーボネートの混合溶液に、混合溶液全量に対して、ビニレンカーボネート（ＶＣ）１質量％、４－フルオロ－１，３－ジオキソラン－２－オン（フルオロエチレンカーボネート；ＦＥＣ）０．５質量％、下記式（６）で表される化合物Ａ ０．５質量％、及び１，３－プロパンスルトン０．５質量％（電解液全量基準）を添加したものを使用した。
[Preparation of lithium-ion secondary battery]
The positive electrode cut into a 13.5 cm 2 square was sandwiched by a polyethylene porous sheet (trade name: Hypore (registered trademark), manufactured by Asahi Kasei Co., Ltd., thickness: 30 μm), which is a separator, and further a 14.3 cm 2 square. The negative electrodes cut into pieces were stacked to prepare an electrode group. This electrode group was housed in a container (battery outer casing) formed of an aluminum laminate film (trade name: aluminum laminate film, manufactured by Dai Nippon Printing Co., Ltd.). Next, 1 mL of the electrolytic solution was added to the container, and the container was heat-welded to produce a lithium ion secondary battery for evaluation. As the electrolytic solution, a mixed solution of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate containing 1 mol/L of LiPF 6 , and 1% by mass of vinylene carbonate (VC) and 4-fluoro-1,3 with respect to the total amount of the mixed solution. -Dioxolan-2-one (fluoroethylene carbonate; FEC) 0.5% by mass, compound A represented by the following formula (6) 0.5% by mass, and 1,3-propanesultone 0.5% by mass (electrolysis The liquid added was used.
１３．５ｃｍ２の四角形に切断した正極電極を、セパレータであるポリエチレン製多孔質シート（商品名：ハイポア（登録商標）、旭化成株式会社製、厚さ３０μｍ）で挟み、更に１４．３ｃｍ２の四角形に切断した負極を重ね合わせて電極群を作製した。この電極群を、アルミニウム製のラミネートフィルム（商品名：アルミラミネートフィルム、大日本印刷株式会社製）で形成された容器（電池外装体）に収容した。次いで、容器の中に電解液を１ｍＬ添加し、容器を熱溶着させ、評価用のリチウムイオン二次電池を作製した。電解液としては、１ｍｏｌ／ＬのＬｉＰＦ６を含むエチレンカーボネート、ジメチルカーボネート及びエチルメチルカーボネートの混合溶液に、混合溶液全量に対して、ビニレンカーボネート（ＶＣ）１質量％、４－フルオロ－１，３－ジオキソラン－２－オン（フルオロエチレンカーボネート；ＦＥＣ）０．５質量％、下記式（６）で表される化合物Ａ ０．５質量％、及び１，３－プロパンスルトン０．５質量％（電解液全量基準）を添加したものを使用した。
The positive electrode cut into a 13.5 cm 2 square was sandwiched by a polyethylene porous sheet (trade name: Hypore (registered trademark), manufactured by Asahi Kasei Co., Ltd., thickness: 30 μm), which is a separator, and further a 14.3 cm 2 square. The negative electrodes cut into pieces were stacked to prepare an electrode group. This electrode group was housed in a container (battery outer casing) formed of an aluminum laminate film (trade name: aluminum laminate film, manufactured by Dai Nippon Printing Co., Ltd.). Next, 1 mL of the electrolytic solution was added to the container, and the container was heat-welded to produce a lithium ion secondary battery for evaluation. As the electrolytic solution, a mixed solution of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate containing 1 mol/L of LiPF 6 , and 1% by mass of vinylene carbonate (VC) and 4-fluoro-1,3 with respect to the total amount of the mixed solution. -Dioxolan-2-one (fluoroethylene carbonate; FEC) 0.5% by mass, compound A represented by the following formula (6) 0.5% by mass, and 1,3-propanesultone 0.5% by mass (electrolysis The liquid added was used.
（実施例２）
実施例１において、化合物Ａの添加量を２．０質量％に変更した以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。 (Example 2)
A lithium ion secondary battery was produced in the same manner as in Example 1 except that the amount of compound A added was changed to 2.0% by mass.
実施例１において、化合物Ａの添加量を２．０質量％に変更した以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。 (Example 2)
A lithium ion secondary battery was produced in the same manner as in Example 1 except that the amount of compound A added was changed to 2.0% by mass.
（実施例３）
実施例１において、化合物Ａの代わりに、下記式（７）で表される化合物Ｂを０．３質量％添加した以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。
(Example 3)
A lithium ion secondary battery was produced in the same manner as in Example 1, except that 0.3% by mass of the compound B represented by the following formula (7) was added in place of the compound A.
実施例１において、化合物Ａの代わりに、下記式（７）で表される化合物Ｂを０．３質量％添加した以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。
A lithium ion secondary battery was produced in the same manner as in Example 1, except that 0.3% by mass of the compound B represented by the following formula (7) was added in place of the compound A.
（実施例４）
実施例１において、化合物Ａの代わりに、下記式（８）で表される化合物Ｃを０．１質量％添加した以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。
(Example 4)
A lithium ion secondary battery was produced in the same manner as in Example 1 except that 0.1% by mass of the compound C represented by the following formula (8) was added in place of the compound A.
実施例１において、化合物Ａの代わりに、下記式（８）で表される化合物Ｃを０．１質量％添加した以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。
A lithium ion secondary battery was produced in the same manner as in Example 1 except that 0.1% by mass of the compound C represented by the following formula (8) was added in place of the compound A.
（実施例５）
実施例１において、１，３－プロパンスルトンの代わりに１，３－プロペンスルトンを使用した以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。 (Example 5)
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.
実施例１において、１，３－プロパンスルトンの代わりに１，３－プロペンスルトンを使用した以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。 (Example 5)
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.
（実施例６）
実施例１において、１，３－プロパンスルトンの代わりにメチレンメタンジスルホン酸エステル（ＭＭＤＳ）を使用した以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。 (Example 6)
A lithium ion secondary battery was produced in the same manner as in Example 1 except that methylene methane disulfonic acid ester (MMDS) was used instead of 1,3-propane sultone.
実施例１において、１，３－プロパンスルトンの代わりにメチレンメタンジスルホン酸エステル（ＭＭＤＳ）を使用した以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。 (Example 6)
A lithium ion secondary battery was produced in the same manner as in Example 1 except that methylene methane disulfonic acid ester (MMDS) was used instead of 1,3-propane sultone.
（実施例７）
実施例１において、１，３－プロパンスルトンの代わりにエチレンサルファイトを使用した以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。 (Example 7)
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.
実施例１において、１，３－プロパンスルトンの代わりにエチレンサルファイトを使用した以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。 (Example 7)
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.
（比較例１）
実施例１において、化合物Ａ及び１，３－プロパンスルトンを使用しなかった以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。 (Comparative Example 1)
A lithium ion secondary battery was produced in the same manner as in Example 1 except that the compound A and 1,3-propane sultone were not used.
実施例１において、化合物Ａ及び１，３－プロパンスルトンを使用しなかった以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。 (Comparative Example 1)
A lithium ion secondary battery was produced in the same manner as in Example 1 except that the compound A and 1,3-propane sultone were not used.
（比較例２）
実施例１において、化合物Ａを使用しなかった以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。 (Comparative example 2)
A lithium ion secondary battery was produced in the same manner as in Example 1 except that the compound A was not used.
実施例１において、化合物Ａを使用しなかった以外は、実施例１と同様にしてリチウムイオン二次電池を作製した。 (Comparative example 2)
A lithium ion secondary battery was produced in the same manner as in Example 1 except that the compound A was not used.
［高温保管特性の評価］
作製した各二次電池を、２５℃の環境下において０．１Ｃの電流値で定電流充電を上限電圧４．２Ｖまで行い、続いて４．２Ｖで定電圧充電を行った。充電終止条件は、電流値０．０１Ｃとした。その後、それらの二次電池を６０℃の恒温槽中で２週間保管した。
上記保管前の各二次電池の体積（Ｖ１）、及び、上記保管後に２５℃の環境下に３０分間静置した各二次電池の体積（Ｖ２）を、アルキメデス法に基づく比重計（電子比重計ＭＤＳ－３００、アルファミラージュ社製）により測定した。測定されたＶ１及びＶ２を用いて、体積変化率（％）＝Ｖ２／Ｖ１×１００を算出した。結果を表１に示す。 [Evaluation of high temperature storage characteristics]
Each of the manufactured secondary batteries was subjected to constant current charging at a current value of 0.1 C under an environment of 25° C. up to an upper limit voltage of 4.2 V, and then at 4.2 V. The charge termination condition was a current value of 0.01C. After that, these secondary batteries were stored for 2 weeks in a constant temperature bath at 60°C.
The volume (V1) of each rechargeable battery before storage and the volume (V2) of each rechargeable battery left standing for 30 minutes in an environment of 25°C after storage were measured by a densitometer (electronic specific gravity) based on the Archimedes method. MDS-300, manufactured by Alpha Mirage). A volume change rate (%)=V2/V1×100 was calculated using the measured V1 and V2. The results are shown in Table 1.
作製した各二次電池を、２５℃の環境下において０．１Ｃの電流値で定電流充電を上限電圧４．２Ｖまで行い、続いて４．２Ｖで定電圧充電を行った。充電終止条件は、電流値０．０１Ｃとした。その後、それらの二次電池を６０℃の恒温槽中で２週間保管した。
上記保管前の各二次電池の体積（Ｖ１）、及び、上記保管後に２５℃の環境下に３０分間静置した各二次電池の体積（Ｖ２）を、アルキメデス法に基づく比重計（電子比重計ＭＤＳ－３００、アルファミラージュ社製）により測定した。測定されたＶ１及びＶ２を用いて、体積変化率（％）＝Ｖ２／Ｖ１×１００を算出した。結果を表１に示す。 [Evaluation of high temperature storage characteristics]
Each of the manufactured secondary batteries was subjected to constant current charging at a current value of 0.1 C under an environment of 25° C. up to an upper limit voltage of 4.2 V, and then at 4.2 V. The charge termination condition was a current value of 0.01C. After that, these secondary batteries were stored for 2 weeks in a constant temperature bath at 60°C.
The volume (V1) of each rechargeable battery before storage and the volume (V2) of each rechargeable battery left standing for 30 minutes in an environment of 25°C after storage were measured by a densitometer (electronic specific gravity) based on the Archimedes method. MDS-300, manufactured by Alpha Mirage). A volume change rate (%)=V2/V1×100 was calculated using the measured V1 and V2. The results are shown in Table 1.
［サイクル特性の評価］
（初回充放電）
作製した各二次電池について、以下に示す方法で初回充放電を実施した。まず、２５℃の環境下において０．１Ｃの電流値で定電流充電を上限電圧４．２Ｖまで行い、続いて４．２Ｖで定電圧充電を行った。充電終止条件は、電流値０．０１Ｃとした。その後、０．１Ｃの電流値で終止電圧２．７Ｖの定電流放電を行った。この充放電サイクルを３回繰り返した。なお、電流値の単位として用いた「Ｃ」とは、「電流値（Ａ）／電池容量（Ａｈ）」を意味する（以下同様）。 [Evaluation of cycle characteristics]
(First charge/discharge)
Initial charging/discharging was implemented by the method shown below about each produced secondary battery. First, under a 25° C. environment, constant current charging was performed at a current value of 0.1 C up to an upper limit voltage of 4.2 V, and then constant voltage charging was performed at 4.2 V. The charge termination condition was a current value of 0.01C. After that, constant current discharge with a final voltage of 2.7 V was performed at a current value of 0.1 C. This charge/discharge cycle was repeated 3 times. Note that "C" used as a unit of current value means "current value (A)/battery capacity (Ah)" (the same applies hereinafter).
（初回充放電）
作製した各二次電池について、以下に示す方法で初回充放電を実施した。まず、２５℃の環境下において０．１Ｃの電流値で定電流充電を上限電圧４．２Ｖまで行い、続いて４．２Ｖで定電圧充電を行った。充電終止条件は、電流値０．０１Ｃとした。その後、０．１Ｃの電流値で終止電圧２．７Ｖの定電流放電を行った。この充放電サイクルを３回繰り返した。なお、電流値の単位として用いた「Ｃ」とは、「電流値（Ａ）／電池容量（Ａｈ）」を意味する（以下同様）。 [Evaluation of cycle characteristics]
(First charge/discharge)
Initial charging/discharging was implemented by the method shown below about each produced secondary battery. First, under a 25° C. environment, constant current charging was performed at a current value of 0.1 C up to an upper limit voltage of 4.2 V, and then constant voltage charging was performed at 4.2 V. The charge termination condition was a current value of 0.01C. After that, constant current discharge with a final voltage of 2.7 V was performed at a current value of 0.1 C. This charge/discharge cycle was repeated 3 times. Note that "C" used as a unit of current value means "current value (A)/battery capacity (Ah)" (the same applies hereinafter).
（放電ＤＣＲの測定）
初回充放電後の各二次電池について、放電時の直流抵抗（放電ＤＣＲ）を、以下のように測定した。
まず、０．２Ｃの定電流充電を上限電圧４．２Ｖまで行い、続いて４．２Ｖで定電圧充電を行った。充電終止条件は、電流値０．０２Ｃとした。その後、０．２Ｃの電流値で終止電圧２．７Ｖの定電流放電を行い、このときの電流値をＩ０．２Ｃ、放電開始１０秒後の電圧変化をΔＶ０．２Ｃとした。次に、０．２Ｃの定電流充電を上限電圧４．２Ｖまで行い、続いて４．２Ｖで定電圧充電を行った後（充電終止条件は、電流値０．０２Ｃとした。）、０．５Ｃの電流値で終止電圧２．７Ｖの定電流放電を行い、このときの電流値をＩ０．５Ｃ、放電開始１０秒後の電圧変化をΔＶ０．５Ｃとした。同様の充放電から１Ｃの電流値をＩ１Ｃ、放電開始１０秒後の電圧変化ΔＶ１Ｃを評価した。その電流値―電圧変化の３点のプロット（Ｉ０．２Ｃ、ΔＶ０．２Ｃ）、（Ｉ０．５Ｃ、ΔＶ０．５Ｃ）、（Ｉ１Ｃ、ΔＶ１Ｃ）に最小二乗法を用いて一次近似直線を引き、その傾きを放電ＤＣＲの値Ｒ１とした。 (Measurement of discharge DCR)
For each secondary battery after the initial charge/discharge, the direct current resistance (discharge DCR) during discharge was measured as follows.
First, 0.2 C constant current charging was performed up to an upper limit voltage of 4.2 V, and then constant voltage charging was performed at 4.2 V. The charge termination condition was a current value of 0.02C. Then, constant current discharge with a final voltage of 2.7 V was performed at a current value of 0.2 C , the current value at this time was I 0.2 C , and thevoltage change 10 seconds after the start of discharge was ΔV 0.2 C. Next, constant current charging of 0.2 C was performed up to an upper limit voltage of 4.2 V, and then constant voltage charging was performed at 4.2 V (charging termination condition was a current value of 0.02 C), and then 0. Constant current discharge with a final voltage of 2.7 V was performed at a current value of 5 C , the current value at this time was I 0.5C , and the voltage change 10 seconds after the start of discharge was ΔV 0.5C . The current value of 1 C was evaluated as I 1C and the voltage change ΔV 1C 10 seconds after the start of discharge was evaluated after the same charge and discharge. The three-point plot of the current value-voltage change (I 0.2C , ΔV 0.2C ), (I 0.5C , ΔV 0.5C ), (I 1C , ΔV 1C ) is first-ordered using the least squares method. An approximate straight line was drawn, and the slope thereof was taken as the value DC1 of the discharge DCR.
初回充放電後の各二次電池について、放電時の直流抵抗（放電ＤＣＲ）を、以下のように測定した。
まず、０．２Ｃの定電流充電を上限電圧４．２Ｖまで行い、続いて４．２Ｖで定電圧充電を行った。充電終止条件は、電流値０．０２Ｃとした。その後、０．２Ｃの電流値で終止電圧２．７Ｖの定電流放電を行い、このときの電流値をＩ０．２Ｃ、放電開始１０秒後の電圧変化をΔＶ０．２Ｃとした。次に、０．２Ｃの定電流充電を上限電圧４．２Ｖまで行い、続いて４．２Ｖで定電圧充電を行った後（充電終止条件は、電流値０．０２Ｃとした。）、０．５Ｃの電流値で終止電圧２．７Ｖの定電流放電を行い、このときの電流値をＩ０．５Ｃ、放電開始１０秒後の電圧変化をΔＶ０．５Ｃとした。同様の充放電から１Ｃの電流値をＩ１Ｃ、放電開始１０秒後の電圧変化ΔＶ１Ｃを評価した。その電流値―電圧変化の３点のプロット（Ｉ０．２Ｃ、ΔＶ０．２Ｃ）、（Ｉ０．５Ｃ、ΔＶ０．５Ｃ）、（Ｉ１Ｃ、ΔＶ１Ｃ）に最小二乗法を用いて一次近似直線を引き、その傾きを放電ＤＣＲの値Ｒ１とした。 (Measurement of discharge DCR)
For each secondary battery after the initial charge/discharge, the direct current resistance (discharge DCR) during discharge was measured as follows.
First, 0.2 C constant current charging was performed up to an upper limit voltage of 4.2 V, and then constant voltage charging was performed at 4.2 V. The charge termination condition was a current value of 0.02C. Then, constant current discharge with a final voltage of 2.7 V was performed at a current value of 0.2 C , the current value at this time was I 0.2 C , and the
（サイクル試験）
初回充放電後の各二次電池について、以下の充放電を繰り返すサイクル試験を実施した。充電パターンとしては、４５℃の環境下で、二次電池を０．５Ｃの電流値で定電流充電を上限電圧４．２Ｖまで行い、続いて４．２Ｖで定電圧充電を行った。充電終止条件は、電流値０．０５Ｃとした。放電については、１Ｃで定電流放電を２．７Ｖまで行い、放電容量を求めた。この一連の充放電を６３０サイクル繰り返した。１サイクル目の充放電後の放電容量Ｑ１と、６３０サイクル目の充放電後の放電容量Ｑ２とを用いて、放電容量維持率（％）＝Ｑ１／Ｑ２×１００を求めた。結果を表１に示す。
また、５００サイクル後の二次電池について、上記と同様に放電ＤＣＲの値Ｒ２を求めた。初回充放電後の放電ＤＣＲの値Ｒ１と、６３０サイクル目の充放電後の放電ＤＣＲの値Ｒ２とを用いて、放電ＤＣＲの上昇率（％）＝Ｒ２／Ｒ１×１００を求めた。結果を表１に示す。 (Cycle test)
With respect to each secondary battery after the initial charge/discharge, a cycle test for repeating the following charge/discharge was performed. Regarding the charging pattern, in a 45° C. environment, the secondary battery was subjected to constant current charging at a current value of 0.5 C up to an upper limit voltage of 4.2 V, and then at 4.2 V. The charge termination condition was a current value of 0.05C. Regarding discharge, constant-current discharge was performed up to 2.7 V at 1 C, and the discharge capacity was obtained. This series of charging/discharging was repeated for 630 cycles. Using the discharge capacity Q1 after charge/discharge in the first cycle and the discharge capacity Q2 after charge/discharge in the 630th cycle, the discharge capacity retention rate (%)=Q1/Q2×100 was determined. The results are shown in Table 1.
Further, the discharge DCR value R2 of the secondary battery after 500 cycles was obtained in the same manner as above. Using the value R1 of the discharge DCR after the first charge/discharge and the value R2 of the discharge DCR after the 630th cycle of charge/discharge, the increase rate (%) of the discharge DCR=R2/R1×100 was obtained. The results are shown in Table 1.
初回充放電後の各二次電池について、以下の充放電を繰り返すサイクル試験を実施した。充電パターンとしては、４５℃の環境下で、二次電池を０．５Ｃの電流値で定電流充電を上限電圧４．２Ｖまで行い、続いて４．２Ｖで定電圧充電を行った。充電終止条件は、電流値０．０５Ｃとした。放電については、１Ｃで定電流放電を２．７Ｖまで行い、放電容量を求めた。この一連の充放電を６３０サイクル繰り返した。１サイクル目の充放電後の放電容量Ｑ１と、６３０サイクル目の充放電後の放電容量Ｑ２とを用いて、放電容量維持率（％）＝Ｑ１／Ｑ２×１００を求めた。結果を表１に示す。
また、５００サイクル後の二次電池について、上記と同様に放電ＤＣＲの値Ｒ２を求めた。初回充放電後の放電ＤＣＲの値Ｒ１と、６３０サイクル目の充放電後の放電ＤＣＲの値Ｒ２とを用いて、放電ＤＣＲの上昇率（％）＝Ｒ２／Ｒ１×１００を求めた。結果を表１に示す。 (Cycle test)
With respect to each secondary battery after the initial charge/discharge, a cycle test for repeating the following charge/discharge was performed. Regarding the charging pattern, in a 45° C. environment, the secondary battery was subjected to constant current charging at a current value of 0.5 C up to an upper limit voltage of 4.2 V, and then at 4.2 V. The charge termination condition was a current value of 0.05C. Regarding discharge, constant-current discharge was performed up to 2.7 V at 1 C, and the discharge capacity was obtained. This series of charging/discharging was repeated for 630 cycles. Using the discharge capacity Q1 after charge/discharge in the first cycle and the discharge capacity Q2 after charge/discharge in the 630th cycle, the discharge capacity retention rate (%)=Q1/Q2×100 was determined. The results are shown in Table 1.
Further, the discharge DCR value R2 of the secondary battery after 500 cycles was obtained in the same manner as above. Using the value R1 of the discharge DCR after the first charge/discharge and the value R2 of the discharge DCR after the 630th cycle of charge/discharge, the increase rate (%) of the discharge DCR=R2/R1×100 was obtained. The results are shown in Table 1.
表１から分かるとおり、式（１）で表される化合物及び環状化合物を含有する実施例１～７の電解液を適用したリチウムイオン二次電池は、式（１）で表される化合物及び環状化合物の一方又は両方を含有しない電解液を適用した比較例１～２のリチウムイオン二次電池と比較して、高温保管特性に優れ（高温保管後の体積変化率が小さく）、サイクル特性にも優れている（サイクル試験後の容量維持率が高く、放電ＤＣＲの上昇を抑制できる）。これは、環状化合物が正極又は負極にて安定な被膜を形成したことに加えて、式（１）で表される化合物が、電解液の安定化に寄与したためと考えられる。
As can be seen from Table 1, the lithium ion secondary batteries to which the electrolytic solutions of Examples 1 to 7 containing the compound represented by the formula (1) and the cyclic compound were applied were the compound represented by the formula (1) and the cyclic compound. Excellent high-temperature storage characteristics (small volume change rate after high-temperature storage) and cycle characteristics as compared with the lithium-ion secondary batteries of Comparative Examples 1 and 2 to which one or both compounds are applied. Excellent (capacity retention rate after cycle test is high and increase in discharge DCR can be suppressed). It is considered that this is because the cyclic compound formed a stable film on the positive electrode or the negative electrode, and the compound represented by the formula (1) contributed to the stabilization of the electrolytic solution.
また、実施例１及び比較例１，２の二次電池については、上記高温保管を行った後の放電ＤＣＲも測定した。その結果、実施例１の放電ＤＣＲは１．７０Ω、比較例１の放電ＤＣＲは１．９８Ω、比較例２の放電ＤＣＲは１．７９Ωであった。１，３－プロパンスルトンを含み化合物Ａを含まない電解液を適用した比較例２のリチウムイオン二次電池は、化合物Ａ及び１，３－プロパンスルトンのどちらも含まない電解液を適用した比較例１のリチウムイオン二次電池と比較して、高温保管後の放電ＤＣＲが低下した。これは、１，３－プロパンスルトンが正極又は負極にて安定な被膜を形成したためと考えられる。また、化合物Ａ及び１，３－プロパンスルトンを両方含む電解液を適用した実施例１のリチウムイオン二次電池は、比較例１及び比較例２のリチウムイオン二次電池と比較して、高温保管後の放電ＤＣＲがそれぞれ約１５％及び約５％良好であった。これは、１，３－プロパンスルトンが正極又は負極にて安定な被膜を形成したことに加えて、化合物Ａが、電解液の安定化に寄与したためと考えられる。
Also, for the secondary batteries of Example 1 and Comparative Examples 1 and 2, the discharge DCR after the high temperature storage was performed was also measured. As a result, the discharge DCR of Example 1 was 1.70Ω, the discharge DCR of Comparative Example 1 was 1.98Ω, and the discharge DCR of Comparative Example 2 was 1.79Ω. The lithium-ion secondary battery of Comparative Example 2 to which an electrolytic solution containing 1,3-propane sultone and containing no compound A was applied was a comparative example to which an electrolytic solution containing neither compound A nor 1,3-propane sultone was applied. Compared with the lithium ion secondary battery of No. 1, the discharge DCR after high temperature storage was reduced. It is considered that this is because 1,3-propane sultone formed a stable film on the positive electrode or the negative electrode. In addition, the lithium ion secondary battery of Example 1 to which the electrolytic solution containing both the compound A and 1,3-propane sultone was applied was stored at high temperature as compared with the lithium ion secondary batteries of Comparative Example 1 and Comparative Example 2. The latter discharge DCR was about 15% and about 5% good, respectively. It is considered that this is because Compound A contributed to the stabilization of the electrolytic solution in addition to the stable coating of 1,3-propane sultone on the positive electrode or the negative electrode.
１…非水電解液二次電池（電気化学デバイス）、６…正極、７…セパレータ、８…負極。
1... Non-aqueous electrolyte secondary battery (electrochemical device), 6... Positive electrode, 7... Separator, 8... Negative electrode.
Claims (14)
- 下記式（１）で表される化合物と、
ケイ素原子を有さず、硫黄原子を含む環を有する環状化合物と、を含有する電解液。
An electrolyte solution containing a cyclic compound having no silicon atom and having a ring containing a sulfur atom.
- 前記Ｒ１～Ｒ３の少なくとも１つはフッ素原子である、請求項１に記載の電解液。 The electrolytic solution according to claim 1, wherein at least one of R 1 to R 3 is a fluorine atom.
- 前記式（１）で表される化合物１分子中のケイ素原子の数は１個である、請求項１又は２に記載の電解液。 The electrolytic solution according to claim 1 or 2, wherein the number of silicon atoms in one molecule of the compound represented by the formula (1) is one.
- 前記Ｒ５は、下記式（３）、式（４）又は式（５）のいずれかで表される基である、請求項１～３のいずれか一項に記載の電解液。
- 前記環状化合物は、環状スルホン酸エステル化合物を含む、請求項１～４のいずれか一項に記載の電解液。 The electrolytic solution according to any one of claims 1 to 4, wherein the cyclic compound contains a cyclic sulfonate compound.
- 前記環状スルホン酸エステル化合物は、下記式（Ｘ）で表される化合物を含む、請求項５に記載の電解液。
- 前記式（Ｘ）で表される化合物は、１，３－プロパンスルトン及び１－プロペン－１，３－スルトンからなる群より選ばれる少なくとも１種を含む、請求項６に記載の電解液。 The electrolytic solution according to claim 6, wherein the compound represented by the formula (X) contains at least one selected from the group consisting of 1,3-propane sultone and 1-propene-1,3-sultone.
- 前記環状化合物は、式（Ｙ）で表される化合物及び式（Ｚ）で表される化合物からなる群より選ばれる少なくとも１種を含む、請求項１～７のいずれか一項に記載の電解液。
- 前記式（１）で表される化合物の含有量及び前記環状化合物の含有量の合計は、前記電解液全量を基準として１０質量％以下である、請求項１～８のいずれか一項に記載の電解液。 The total content of the compound represented by the formula (1) and the content of the cyclic compound is 10% by mass or less based on the total amount of the electrolytic solution. Electrolyte.
- 正極と、負極と、請求項１～９のいずれか一項に記載の電解液と、を備える電気化学デバイス。 An electrochemical device comprising a positive electrode, a negative electrode, and the electrolytic solution according to any one of claims 1 to 9.
- 前記負極は炭素材料を含有する、請求項１０に記載の電気化学デバイス。 The electrochemical device according to claim 10, wherein the negative electrode contains a carbon material.
- 前記炭素材料は黒鉛を含有する、請求項１１に記載の電気化学デバイス。 The electrochemical device according to claim 11, wherein the carbon material contains graphite.
- 前記負極は、ケイ素及びスズからなる群より選ばれる少なくとも１種の元素を含む材料を更に含有する、請求項１１又は１２に記載の電気化学デバイス。 The electrochemical device according to claim 11 or 12, wherein the negative electrode further contains a material containing at least one element selected from the group consisting of silicon and tin.
- 前記電気化学デバイスは、非水電解液二次電池又はキャパシタである、請求項１０～１３のいずれか一項に記載の電気化学デバイス。 The electrochemical device according to any one of claims 10 to 13, wherein the electrochemical device is a non-aqueous electrolyte secondary battery or a capacitor.
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