CN112740459A - Electrolyte solution and electrochemical device - Google Patents
Electrolyte solution and electrochemical device Download PDFInfo
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- CN112740459A CN112740459A CN201980062244.3A CN201980062244A CN112740459A CN 112740459 A CN112740459 A CN 112740459A CN 201980062244 A CN201980062244 A CN 201980062244A CN 112740459 A CN112740459 A CN 112740459A
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- fluorine
- negative electrode
- electrochemical device
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- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 54
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- 239000011737 fluorine Substances 0.000 claims abstract description 46
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
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- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
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- 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
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- H—ELECTRICITY
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- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- 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
- H01G11/22—Electrodes
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- H01G11/42—Powders or particles, e.g. composition thereof
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- H01—ELECTRIC ELEMENTS
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- 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
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- H01M10/052—Li-accumulators
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- 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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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Abstract
As one mode, the present invention providesDisclosed is an electrolyte solution containing a compound represented by the following formula (1) and a fluorine-containing cyclic carbonate or ester. In the formula (1), R1～R3Each independently represents an alkyl group or a fluorine atom, R4Represents an alkylene group, R5Represents an organic group containing a sulfur atom.
Description
Technical Field
The invention relates to an electrolyte and an electrochemical device.
Background
In recent years, due to the spread of portable electronic devices, electric vehicles, and the like, high-performance electrochemical devices such as nonaqueous electrolyte secondary batteries typified by lithium ion secondary batteries, capacitors, and the like have been regarded as essential. As a means for improving the performance of an electrochemical device, for example, a method of adding a predetermined additive to an electrolytic solution has been studied. Patent document 1 discloses an electrolyte for a nonaqueous electrolyte battery containing a specific siloxane compound in order to improve cycle characteristics and internal resistance characteristics.
Prior art documents
Patent document
Patent document 1: japanese laid-open patent publication No. 2015-005329
Disclosure of Invention
Technical problem to be solved by the invention
In order to apply an electrochemical device to an in-vehicle application, it is important to improve heat resistance at high temperatures. As an index of the heat resistance of the electrochemical device, for example, the expansion of the electrochemical device after storage at high temperature is suppressed. Alternatively, it is also possible to cite that various performance degradations of the following electrochemical devices are suppressed: the degree of capacity reduction after high-temperature storage, the degree of increase in Direct Current Resistance (DCR) at the time of discharge, and the like. Since the electrochemical device is problematic in terms of safety if it swells and breaks during storage at high temperatures, it is important to suppress the swelling of the electrochemical device.
Accordingly, an object of the present invention is to provide an electrolytic solution capable of suppressing expansion of an electrochemical device even at high temperatures. Further, an object of the present invention is to provide an electrochemical device in which expansion is suppressed even at high temperatures.
Means for solving the technical problem
The present inventors have found that when an electrolyte solution contains a specific compound containing a silicon atom and a sulfur atom and a fluorine-containing cyclic carbonate (fluorine-containing cyclic carbonate), swelling of an electrochemical device can be suppressed more remarkably than when each compound is contained alone.
The present inventors have also found that when these compounds are contained in an electrolyte solution, the capacity of an electrochemical device after storage at high temperatures can be suppressed from decreasing, and the increase in DCR during discharge can be suppressed.
As a 1 st aspect, the present invention provides an electrolytic solution containing a compound represented by the following formula (1) and a fluorine-containing cyclic carbonate or ester.
[ in the formula (1), R1～R3Each independently represents an alkyl group or a fluorine atom, R4Represents an alkylene group, R5Represents an organic group containing a sulfur atom.]
In embodiment 1, the number of silicon atoms in one molecule of the compound represented by formula (1) is preferably 1.
R5Preferably, the group is represented by any one of the following formulae (2), (3) or (4).
[ in the formula (2), R6Represents an alkyl group and represents a bonding site.]
[ in the formula (3), R7Represents an alkyl group and represents a bonding site.]
[ in the formula (4), R8Represents an alkyl group and represents a bonding site.]
Preferably R1～R3At least one of which is a fluorine atom.
The fluorine-containing cyclic carbonate or ester is preferably 4-fluoro-1, 3-dioxolan-2-one.
The total of the content of the compound represented by formula (1) and the content of the fluorine-containing cyclic carbonate or ester is preferably 10% by mass or less based on the total amount of the electrolyte.
As a second aspect, the present invention provides an electrochemical device comprising: a positive electrode, a negative electrode and the electrolyte.
In embodiment 2, the negative electrode preferably contains a carbon material. The carbon material preferably contains graphite. The anode preferably further contains a material containing at least 1 element selected from the group consisting of silicon and tin.
The electrochemical device is preferably a nonaqueous electrolyte secondary battery or a capacitor.
Effects of the invention
According to the present invention, it is possible to provide an electrolytic solution that can suppress expansion of an electrochemical device even at high temperatures. Further, according to the present invention, it is possible to provide an electrochemical device in which swelling is suppressed even at high temperatures.
Drawings
Fig. 1 is a perspective view showing a nonaqueous electrolyte secondary battery as an electrochemical device according to an embodiment.
Fig. 2 is an exploded perspective view illustrating an electrode group of the secondary battery shown in fig. 1.
FIG. 3 is a graph showing the measurement results of the volume increase rate in examples and comparative examples.
Fig. 4 is a graph showing the measurement results of the capacity retention ratios in the examples and comparative examples.
FIG. 5 is a graph showing the measurement results of discharge DCR in examples and comparative examples.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings as appropriate. However, the present invention is not limited to the following embodiments.
Fig. 1 is a perspective view showing an electrochemical device according to an embodiment. In the present embodiment, the electrochemical device is a nonaqueous electrolyte secondary battery. As shown in fig. 1, a nonaqueous electrolyte secondary battery 1 includes: an electrode group 2 composed of a positive electrode, a negative electrode, and a separator; and a pouch-shaped battery exterior body 3 that houses the electrode group 2. A positive electrode collector tab 4 and a negative electrode collector tab 5 are provided on the positive electrode and the negative electrode, respectively. The positive electrode current collector tab 4 and the negative electrode current collector tab 5 protrude from the inside to the outside of the battery exterior package 3 so that the positive electrode and the negative electrode can be electrically connected to the outside of the nonaqueous electrolyte secondary battery 1. The battery exterior body 3 is filled with an electrolyte (not shown). The nonaqueous electrolyte secondary battery 1 may be a battery (coin type, cylindrical type, laminated type, etc.) having a shape other than the so-called "laminated type" as described above.
The battery exterior package 3 may be a container formed of a laminate film, for example. The laminate film may be, for example, a laminate film in which a resin film such as a polyethylene terephthalate (PET) film, a metal foil such as aluminum, copper, stainless steel, or the like, and a sealant layer such as polypropylene are sequentially laminated.
Fig. 2 is an exploded perspective view showing an embodiment of the electrode group 2 in the nonaqueous electrolyte secondary battery 1 shown in fig. 1. As shown in fig. 2, the electrode group 2 includes a positive electrode 6, a separator 7, and a negative electrode 8 in this order. The positive electrode 6 and the negative electrode 8 are arranged such that the surfaces on the positive electrode mixture layer 10 side and the negative electrode mixture layer 12 side face the separator 7, respectively.
The positive electrode 6 includes a positive electrode current collector 9 and a positive electrode mixture layer 10 provided on the positive electrode current collector 9. A positive electrode collector tab 4 is provided on the positive electrode collector 9.
The positive electrode current collector 9 can be formed using, for example, aluminum, titanium, stainless steel, nickel, calcined carbon, a conductive polymer, conductive glass, or the like. The positive electrode current collector 9 may be formed by treating the surface of aluminum, copper, or the like 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 from the viewpoint of the electrode strength and energy density.
In one embodiment, the positive electrode mixture layer 10 contains a positive electrode active material, a conductive agent, and a binder. The thickness of the positive electrode mixture layer 10 is, for example, 20 to 200 μm.
The positive electrode active material may be, for example, lithium oxide. Examples of lithium oxides include: lixCoO2、LixNiO2、LixMnO2、LixCoyNi1-yO2、LixCoyM1-yOz、LixNi1-yMyOz、LixMn2O4And LixMn2-yMyO4(wherein M represents at least 1 element selected from the group consisting of Na, Mg, Sc, Y, Mn, Fe, Co, Cu, Zn, Al, Cr, Pb, Sb, V and B (wherein M is an element different from the other elements in the formulae). x is 0 to 1.2, Y is 0 to 0.9, and z is 2.0 to 2.3). From LixNi1-yMyOzThe lithium oxide represented may be LixNi1-(y1+y2)Coy1Mny2Oz(wherein x and z are the same as above, y1 is 0 to 0.9, y2 is 0 to 0.9, and y1+ y2 is 0 to 0.9), for example, LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2. From LixNi1-yMyOzThe lithium oxide represented may be LixNi1-(y3+y4)Coy3Aly4Oz(wherein x and z are the same as above, y3 is 0 to 0.9, y4 is 0 to 0.9, and y3+ y4 is 0 to 0.9), for example, LiNi0.8Co0.15Al0.05O2。
The positive electrode active material may be, for example, a lithium phosphate. Examples of the lithium phosphate include lithium manganese phosphate (LiMnPO)4) Lithium iron phosphate (LiFePO)4) Lithium cobalt phosphate (LiCoPO)4) And lithium vanadium phosphate (Li)3V2(PO4)3)。
The content of the positive electrode active material may be 80 mass% or more or 85 mass% or more, and may be 99 mass% or less, based on the total amount of the positive electrode mixture layer.
The conductive agent may be carbon black such as acetylene black or Ketjen black (Ketjen black), or a carbon material such as graphite, graphene, or carbon nanotubes. The content of the conductive agent may be, for example, 0.01 mass% or more, 0.1 mass% or more, or 1 mass% or more, and may be 50 mass% or less, 30 mass% or less, or 15 mass% or less, based on the total amount of the positive electrode mixture layer.
Examples of binders include: resins such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, and nitrocellulose; rubbers such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), fluororubber, isoprene rubber, butadiene rubber, and ethylene-propylene rubber; thermoplastic elastomers such as styrene-butadiene-styrene block copolymers or hydrogenated products thereof, EPDM (ethylene-propylene-diene terpolymer), styrene-ethylene-butadiene-ethylene copolymers, styrene-isoprene-styrene block copolymers or hydrogenated products thereof; soft resins such as syndiotactic-1, 2-polybutadiene, polyvinyl acetate, ethylene-vinyl acetate copolymers and propylene- α -olefin copolymers; fluorine-containing resins such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene, fluorinated polyvinylidene fluoride, polytetrafluoroethylene-ethylene copolymer, and polytetrafluoroethylene-vinylidene fluoride copolymer; a resin having a nitrile group-containing monomer as a monomer unit; and a polymer composition having ion conductivity of an alkali metal ion (for example, lithium ion).
The content of the binder may be, for example, 0.1 mass% or more, 1 mass% or more, or 1.5 mass% or more, and may be 30 mass% or less, 20 mass% or less, or 10 mass% or less, based on the total amount of the positive electrode material layer.
The separator 7 is not particularly limited as long as it can electrically insulate the positive electrode 6 and the negative electrode 8 from each other, can transmit ions, and has oxidation resistance on the positive electrode 6 side and reduction resistance on the negative electrode 8 side. Examples of the material (material) of the separator 7 include resins and inorganic substances.
Examples of the resin include olefin polymers, fluorine polymers, cellulose polymers, polyimides, and nylons. The separator 7 is preferably a porous sheet or nonwoven fabric made of polyolefin such as polyethylene or polypropylene, from the viewpoint of stability to an electrolytic solution and excellent liquid retention.
Examples of the inorganic substance include oxides such as alumina and silica, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate. The separator 7 may be a separator in which a fibrous or particulate inorganic substance is attached to a film-like base material such as a nonwoven fabric, a woven fabric, or a microporous film.
The negative electrode 8 includes a negative electrode current collector 11 and a negative electrode mixture layer 12 provided on the negative electrode current collector 11. The negative electrode current collector 11 is provided with a negative electrode current collector tab 5.
The negative electrode current collector 11 can be formed using, for example, copper, stainless steel, nickel, aluminum, titanium, calcined carbon, a conductive polymer, conductive glass, an aluminum-cadmium alloy, or the like. The negative electrode current collector 11 may be formed by treating the surface of copper, aluminum, or the like with carbon, nickel, titanium, silver, or the like for the purpose of improving adhesion, conductivity, and reduction resistance. The thickness of the negative electrode current collector 11 is, for example, 1 to 50 μm from the viewpoint of the electrode strength and energy density.
The negative electrode mixture layer 12 contains, for example, a negative electrode active material and a binder.
The negative electrode active material is not particularly limited as long as it can intercalate and deintercalate lithium ions. Examples of the negative electrode active material include: a carbon material; a metal composite oxide; oxides or nitrides of group iv elements such as tin, germanium, and silicon; the simple substance of lithium; lithium alloys such as lithium aluminum alloys; sn, Si, and other metals capable of forming an alloy with lithium. The negative electrode active material is preferably at least 1 selected from the group consisting of carbon materials and metal composite oxides from the viewpoint of safety. The negative electrode active material may be a mixture of 1 or 2 or more of these alone. The negative electrode active material may be in the form of particles, for example.
Examples of the carbon material include an amorphous carbon material, natural graphite, a composite carbon material in which a coating film of an amorphous carbon material is formed on natural graphite, and artificial graphite (obtained by calcining a resin raw material such as an epoxy resin or a phenol resin or a pitch-based raw material obtained from petroleum or coal). The metal composite oxide preferably contains one or both of titanium and lithium, and more preferably contains lithium, from the viewpoint of high current density charge/discharge characteristics.
The negative electrode active material may further contain a material containing at least 1 element selected from the group consisting of silicon and tin. The material containing at least 1 element selected from the group consisting of silicon and tin may be a simple substance of silicon or tin, a compound containing at least 1 element selected from the group consisting of silicon and tin. The compound may be an alloy containing at least 1 element selected from the group consisting of silicon and tin, for example, an alloy containing at least 1 element selected from the group consisting of nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, and chromium in addition to silicon and tin. The compound containing at least 1 element selected from the group consisting of silicon and tin may be an oxide, nitride or carbide, and specifically, for example, SiO or SiO2Silicon oxides such as LiSiO; si3N4、Si2N2Silicon nitride such as O; silicon carbide such as SiC; SnO, SnO2And tin oxides such as LiSnO.
The negative electrode mixture layer 12 preferably contains a carbon material, more preferably contains graphite, further preferably contains a mixture of a carbon material and a material containing at least 1 element selected from the group consisting of silicon and tin, and particularly preferably contains a mixture of graphite and silicon oxide, as the negative electrode active material, from the viewpoint of further improving the performance of the electrochemical device such as cycle characteristics. In the mixture, the content of the material (silicon oxide) containing at least 1 element selected from the group consisting of silicon and tin may be 1 mass% or more or 3 mass% or more, and may be 30 mass% or less, based on the total amount of the mixture.
The content of the negative electrode active material may be 80 mass% or more or 85 mass% or more, and may be 99 mass% or less, based on the total amount of the negative electrode mixture layer.
The binder and the content thereof may be the same as those of the binder and the content thereof in the positive electrode binder layer described above.
The negative electrode mixture layer 12 may further contain a thickener in order to adjust the viscosity. The thickener is not particularly limited, and may be carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, salts thereof, or the like. The thickener may be a mixture of 1 or 2 or more of these alone.
When the negative electrode mixture layer 12 contains a thickener, the content thereof is not particularly limited. The content of the thickener may be 0.1 mass% or more, preferably 0.2 mass% or more, and more preferably 0.5 mass% or more, based on the total amount of the negative electrode mixture layer, from the viewpoint of coatability of the negative electrode mixture layer. The content of the thickener may be 5 mass% or less, preferably 3 mass% or less, and more preferably 2 mass% or less, based on the total amount of the negative electrode mixture layer, from the viewpoint of suppressing a decrease in battery capacity or an increase in resistance between the negative electrode active materials.
In one embodiment, the electrolytic solution contains a compound represented by the following formula (1), a fluorine-containing cyclic carbonate or ester, an electrolyte salt, and a nonaqueous solvent.
In the formula (1), R1～R3Each independently represents an alkyl group or a fluorine atom, R4Represents an alkylene group, R5Represents an organic group containing a sulfur atom.
From R1～R3The number of carbon atoms of the alkyl group represented may be 1 or more and 3 or less. R1～R3The alkyl group may be a methyl group, an ethyl group or a propyl group, and may be linear or branched. Preferably R1～R3At least one of which is a fluorine atom.
From R4The number of carbon atoms of the alkylene group represented may be 1 or more or 2 or more, and may be 5 or less or 4 or less. From R4The alkylene group may be a methylene group, an ethylene group, a propylene group, a butylene group or a pentylene group, and may be a straight chain or a branched chain.
From the viewpoint of further suppressing the expansion of the electrochemical device and making it easy to suppress the decrease in capacity at high temperature and the increase in DCR at the time of discharge, in one embodiment, R5May be a group represented by the following formula (2).
In the formula (2), R6Represents an alkyl group. The alkyl group may be substituted with the above-mentioned group R1～R3The alkyl groups represented are the same. Denotes the bonding site.
From the viewpoint of further suppressing the expansion of the electrochemical device and making it easy to suppress the decrease in capacity at high temperature and the increase in DCR at the time of discharge, in another embodiment, R5May be a group represented by the following formula (3).
In the formula (3), R7Represents an alkyl group. The alkyl group may be substituted with the above-mentioned group R1～R3The alkyl groups represented are the same. Denotes the bonding site.
From the viewpoint of further suppressing the expansion of the electrochemical device and making it easy to suppress the decrease in capacity at high temperature and the increase in DCR at the time of discharge, in another embodiment, R5May be a group represented by the following formula (4).
In the formula (4), R8Represents an alkyl group. The alkyl group may beAnd the above-mentioned group consisting of R1～R3The alkyl groups represented are the same. Denotes the bonding site.
In one embodiment, the number of silicon atoms in one molecule of the compound represented by formula (1) is 1. That is, in one embodiment, R is substituted with5The organic groups represented do not contain silicon atoms.
From the viewpoint of further suppressing the expansion of the electrochemical device and also making it easy to suppress the decrease in capacity at high temperatures and the increase in DCR at the time of discharge, the content of the compound represented by formula (1) is preferably 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more, and 8 mass% or less, 5 mass% or less, 3 mass% or less, 2 mass% or less, or 1 mass% or less, based on the total amount of the electrolytic solution.
The fluorine-containing cyclic carbonate or ester is a cyclic carbonate containing a fluorine atom in the molecule. In one embodiment, the fluorine-containing cyclic carbonate is a cyclic carbonate containing a fluorine group. The fluorine-containing cyclic carbonate or ester is not particularly limited as long as it is a cyclic carbonate containing a fluorine group, and examples thereof include 4-fluoro-1, 3-dioxolan-2-one (fluoroethylene carbonate; FEC), 1, 2-difluoroethylene carbonate, 1, 2-trifluoroethylene carbonate, and 1,1,2, 2-tetrafluoroethylene carbonate. The fluorine-containing cyclic carbonate or ester is preferably 4-fluoro-1, 3-dioxolan-2-one (fluoroethylene carbonate; FEC) from the viewpoint of suppressing side reactions when a stable coating film is formed on the negative electrode.
From the viewpoint of further suppressing the expansion of the electrochemical device and also making it easy to suppress the decrease in capacity at high temperatures and the increase in DCR at the time of discharge, the content of the fluorine-containing cyclic carbonate or ester is preferably 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more, and 5 mass% or less, 3 mass% or less, 2 mass% or less, or 1 mass% or less, based on the total amount of the electrolytic solution.
From the viewpoint of further suppressing the expansion of the electrochemical device and also making it easy to suppress the decrease in capacity at high temperatures and the increase in DCR at the time of discharge, the total of the content of the compound represented by formula (1) and the content of the fluorine-containing cyclic carbonate or ester is preferably 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.1 mass% or more, or 0.5 mass% or more, and preferably 10 mass% or less, 7 mass% or less, 5 mass% or less, 3 mass% or less, 2 mass% or less, or 1.5 mass% or less, based on the total amount of the electrolytic solution. From the same viewpoint, the total of the content of the compound represented by the formula (1) and the content of the fluorine-containing cyclic carbonate or ester is based on the total amount of the electrolyte solution, preferably 0.001 to 10% by mass, 0.001 to 7% by mass, 0.001 to 5% by mass, 0.001 to 3% by mass, 0.001 to 2% by mass, 0.001 to 1.5% by mass, 0.005 to 10% by mass, 0.005 to 7% by mass, 0.005 to 5% by mass, 0.005 to 3% by mass, 0.005 to 2% by mass, 0.005 to 1.5% by mass, 0.01 to 10% by mass, 0.01 to 7% by mass, 0.01 to 5% by mass, 0.01 to 3% by mass, 0.01 to 2% by mass, 0.01 to 1.5% by mass, 0.1 to 10% by mass, 0.1 to 7% by mass, 0.1 to 5% by mass, 0.1 to 3% by mass, 0.1 to 2% by mass, 0.1 to 1.5% by mass, 0.5 to 10% by mass, 0.5 to 7% by mass, 0.5 to 3% by mass, 0.5 to 2% by mass, or 0.5 to 1.5% by mass.
From the viewpoint of further suppressing the expansion of the electrochemical device and also making it easy to suppress the decrease in capacity at high temperatures and the increase in DCR at the time of discharge, the mass ratio of the content of the compound represented by formula (1) to the content of the fluorine-containing cyclic carbonate or ester (content of the compound represented by formula (1)/content of the fluorine-containing cyclic carbonate or ester) is 0.01 or more, 0.05 or more, or 0.1 or more, and is preferably 100 or less, 50 or less, or 20 or less.
The electrolyte salt may be, for example, a lithium salt. The lithium salt may be selected from, for example, LiPF6、LiBF4、LiClO4、LiB(C6H5)4、LiCH3SO3、CF3SO2OLi、LiN(SO2F)2(Li[FSI]Lithium bis (fluorosulfonylimide), LiN (SO)2CF3)2(Li[TFSI]Lithium bistrifluoromethanesulfonimide), and LiN (SO)2CF2CF3)2At least 1 of the group consisting of. The lithium salt preferably contains LiPF from the viewpoint of further excellent solubility in a solvent, charge/discharge characteristics of a secondary battery, output characteristics, cycle characteristics, and the like6。
The concentration of the electrolyte salt is preferably 0.5mol/L or more, more preferably 0.7mol/L or more, and even more preferably 0.8mol/L or more, and is preferably 1.5mol/L or less, more preferably 1.3mol/L or less, and even more preferably 1.2mol/L or less, based on the total amount of the nonaqueous solvent, from the viewpoint of excellent charge and discharge characteristics.
The nonaqueous solvent may be, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, γ -butyrolactone, acetonitrile, 1, 2-dimethoxyethane, dimethoxymethane, tetrahydrofuran, dioxolane (dioxolane), methylene chloride, methyl acetate, or the like. The nonaqueous solvent may be a mixture of 1 or 2 or more kinds among these alone, and preferably a mixture of 2 or more kinds among these.
The electrolytic solution may further contain other materials than the compound represented by formula (1) and the fluorine-containing cyclic carbonate, the electrolyte salt, and the nonaqueous solvent. The other material may be, for example, a cyclic carbonate or ester having a carbon-carbon double bond, or a heterocyclic compound containing nitrogen, sulfur, or nitrogen and sulfur, a cyclic carboxylate, or the like other than the above-described compounds. The other material may be a compound having an unsaturated bond in the molecule other than the above-described compounds.
The cyclic carbonate or ester having a carbon-carbon double bond is a cyclic carbonate having a carbon-carbon double bond. In one embodiment, the 2 carbons comprising the ring in the cyclic carbonate or ester may form a double bond. The cyclic carbonate may be vinylene carbonate, methyl vinylene carbonate, dimethyl vinylene carbonate (4, 5-dimethyl vinylene carbonate), ethyl vinylene carbonate (4, 5-diethyl vinylene carbonate), diethyl vinylene carbonate, or the like, and is preferably vinylene carbonate from the viewpoint of improving the performance of the electrochemical device.
The present inventors have studied compounds having various structures and functional groups, and as a result, have found that by applying the compound represented by the above formula (1) and a fluorine-containing cyclic carbonate or ester to an electrolytic solution, expansion of an electrochemical device at high temperatures can be suppressed more than in the case where each compound is applied alone. In particular, the present inventors have found that, although swelling of an electrochemical device cannot be suppressed when a fluorine-containing cyclic carbonate or ester is used alone in an electrolytic solution, swelling of the electrochemical device can be significantly suppressed when used in combination with a compound represented by formula (1). The present inventors speculate that the action and effect of using the compound represented by formula (1) and the fluorine-containing cyclic carbonate or ester in the electrolyte are as follows. That is, it is considered that the compound a and the fluorine-containing cyclic carbonate or ester each act at a place where the effect is most likely to be exhibited in the lithium ion secondary battery, and contribute to, for example, formation of a stable film of the positive electrode or the negative electrode or stabilization of the electrolyte solution. Alternatively, it is considered that the electrolytic solution is stabilized by the interaction between the compound represented by the formula (1) and the fluorine-containing cyclic carbonate or ester, and the generation of gas due to the decomposition of the electrolyte salt can be suppressed. As a result, the expansion of the electrochemical device such as the nonaqueous electrolyte secondary battery 1 at high temperatures can be suppressed.
The compound represented by formula (1) can form a stable coating on the positive electrode or the negative electrode. This can suppress a decrease in output characteristics caused by deposition of the decomposition product of the electrolyte on the positive electrode or the negative electrode. By stabilizing the electrolytic solution with the compound represented by formula (1), it is possible to suppress a decrease in capacity and an increase in resistance (including an increase in direct current resistance (discharge DCR) at the time of discharge) due to decomposition of the electrolyte salt even at high temperatures. This effect is further remarkable by using the compound represented by formula (1) and the fluorine-containing cyclic carbonate or ester in combination.
Next, a method for manufacturing the nonaqueous electrolyte secondary battery 1 will be described. The method for manufacturing the nonaqueous electrolyte secondary battery 1 includes: step 1, obtaining a positive electrode 6; step 2, obtaining a negative electrode 8; a 3 rd step of housing the electrode group 2 in the battery exterior body 3; and a 4 th step of injecting the electrolyte solution into the battery exterior body 3.
In the step 1, the material for the positive electrode mixture layer 10 is dispersed in a dispersion medium using a kneader, a disperser, or the like to obtain a slurry-like positive electrode mixture, and then the positive electrode mixture is applied to the positive electrode current collector 9 by a doctor blade (doctor blade) method, an immersion method, a spraying method, or the like, and the dispersion medium is evaporated to obtain the positive electrode 6. After the dispersion medium is volatilized, a compression molding step using a roll press may be provided as necessary. The positive electrode mixture layer 10 can be formed into a multilayer structure by performing the steps from the application of the positive electrode mixture to the volatilization of the dispersion medium a plurality of times. The dispersion medium may be water, 1-methyl-2-pyrrolidone (hereinafter, also referred to as NMP), or the like.
The 2 nd step may be the same as the 1 st step, and the method of forming the negative electrode mixture layer 12 on the negative electrode current collector 11 may be the same as the 1 st step.
In the 3 rd step, the separator 7 is sandwiched between the manufactured positive electrode 6 and negative electrode 8 to form the electrode group 2. Next, the electrode group 2 is housed in the battery exterior body 3.
In the 4 th step, the electrolytic solution is injected into the battery exterior body 3. The electrolytic solution can be prepared, for example, by dissolving an electrolyte salt in a nonaqueous solvent and then dissolving other materials.
As another embodiment, the electrochemical device may be a capacitor. The capacitor may include, as in the nonaqueous electrolyte secondary battery 1, the following: an electrode group composed of a positive electrode, a negative electrode and a separator; and a bag-shaped battery outer package body for accommodating the electrode group. The details of each constituent element in the capacitor may be the same as those of the nonaqueous electrolyte secondary battery 1.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
(example 1)
[ production of Positive electrode ]
Fibrous graphite (1 mass%) and Acetylene Black (AB) (1 mass%) as a conductive agent were added to lithium cobaltate (95 mass%) as a positive electrode active material in this orderWt%) and a binder (3 wt%) were mixed. NMP as a dispersion medium was added to the obtained mixture, and the mixture was kneaded to prepare a slurry-like positive electrode mixture. A predetermined amount of the positive electrode mixture was uniformly and homogeneously applied to an aluminum foil having a thickness of 20 μm as a positive electrode current collector. Thereafter, the dispersion medium was volatilized, and densification was conducted by pressurization until the density reached 3.6g/cm3Thereby obtaining a positive electrode.
[ production of negative electrode ]
A binder and carboxymethyl cellulose as a thickener are added to graphite as a negative electrode active material. The mass ratio of these is 98:1:1, where the negative electrode active material, binder and thickener are used. Water as a dispersion medium was added to the obtained mixture, and the mixture was kneaded to prepare a slurry-like negative electrode mixture. A predetermined amount of the negative electrode mixture was uniformly and homogeneously applied to a rolled copper foil having a thickness of 10 μm as a negative electrode current collector. Thereafter, the dispersion medium was volatilized, and densification was conducted by pressurization until the density reached 1.6g/cm3And a negative electrode is obtained.
[ production of lithium ion Secondary Battery ]
A polyethylene porous sheet (product name: Hipore (registered trademark) manufactured by Asahi Kasei corporation, thickness: 30 μm) as a separator was sandwiched between two sheets and cut into pieces of 13.5cm2And a square positive electrode further cut to 14.3cm2The square negative electrodes are overlapped to form an electrode group. The electrode group was housed in a container (battery exterior body) formed of an aluminum laminated film (trade name aluminum laminated film, manufactured by japan printing corporation). Next, 1mL of the electrolyte solution was added to a container, and the container was heat-welded to prepare a lithium ion secondary battery for evaluation. As the electrolyte, LiPF containing 1mol/L was used6To the mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate, 1 mass% of Vinylene Carbonate (VC), 0.5 mass% of compound A represented by the following formula (5) and 0.5 mass% of 4-fluoro-1, 3-dioxolan-2-one (fluoroethylene carbonate; FEC) (total electrolyte solution) were added based on the total amount of the mixed solutionQuantitative basis) was prepared.
(example 2)
A lithium ion secondary battery was produced in the same manner as in example 1, except that 0.8 mass% of compound a and 0.2 mass% of FEC (based on the total amount of the electrolyte solution) were added to example 1.
(example 3)
A lithium ion secondary battery was produced in the same manner as in example 1, except that 0.2 mass% of compound a and 0.8 mass% of FEC (based on the total amount of the electrolyte solution) were added to example 1.
(example 4)
A lithium ion secondary battery was produced in the same manner as in example 1, except that 0.5 mass% of compound B represented by the following formula (6) and 1.0 mass% of FEC (based on the total amount of the electrolyte solution) were added in example 1.
(example 5)
A lithium ion secondary battery was produced in the same manner as in example 1, except that 0.1 mass% of compound C represented by the following formula (7) and 1.0 mass% of FEC (based on the total amount of the electrolyte solution) were added in example 1.
Comparative example 1
A lithium ion secondary battery was produced in the same manner as in example 1, except that compound a and FEC were not used in example 1.
Comparative example 2
A lithium ion secondary battery was produced in the same manner as in example 1, except that compound a was not used in example 1 and 1.0 mass% of FEC was added.
(reference example 1)
A lithium ion secondary battery was produced in the same manner as in example 1, except that compound a was added in an amount of 1.0 mass% without FEC in example 1.
[ first Charge and discharge ]
The lithium ion battery thus produced was subjected to initial charge and discharge by the following method. First, constant current charging was performed at a current value of 0.1C until the upper limit voltage became 4.45V in an environment of 25 ℃ and then constant voltage charging was performed at 4.45V. The charge termination condition was set to a current value of 0.01C. Thereafter, constant current discharge was performed at a current value of 0.1C with an end voltage of 2.5V. This charge-discharge cycle was repeated 3 times (the "C" used as a unit of current value is "current value (a)/battery capacity (Ah)"). The discharge capacity at the 3 rd cycle was set as the capacity Q1 of the battery.
[ high temperature storage test ]
The secondary batteries of examples 1 to 5, comparative examples 1 to 2, and reference example 1 were subjected to constant current charging at a current value of 0.1C until the upper limit voltage was 4.45V, and then to constant voltage charging at 4.45V in an environment of 25 ℃. The charge termination condition was set to a current value of 0.01C. Thereafter, these secondary batteries were kept in a constant temperature bath at 80 ℃ for 4 hours.
[ measurement of volume increase rate ]
The volumes of the secondary batteries of examples 1 to 5, comparative examples 1 to 2, and reference example 1 were measured by a densitometer (electronic densitometer MDS-300, manufactured by Alfa Mirage corporation) by the archimedes method. The volume increase rate was calculated from the volume before the high-temperature storage test (V1) and the volume of the secondary battery after being held at 25 ℃ for 30 minutes after the high-temperature storage test (V2) by the following formula. The results are shown in FIG. 3.
Volume increase rate V2/V1
As shown in fig. 3, the lithium ion secondary battery of comparative example 1, in which the electrolyte solution containing neither compound a nor the fluorine-containing cyclic carbonate or ester was used, was compared with the lithium ion secondary battery containing fluorine-containing cyclic carbonThe lithium ion secondary battery of comparative example 2 in which the electrolyte of the acid salt or ester had a large volume increase rate. The reason is considered to be that: the fluorine-containing cyclic carbonate or ester is subjected to oxidative decomposition under a high-voltage (about 4.45V) and high-temperature (80 ℃) environment to generate gas; alternatively, the decomposition product thereof reacts with the electrolyte component to generate a gas. On the other hand, the lithium ion secondary batteries of examples 1 to 5 using the electrolyte solution containing both the compound a and the fluorine-containing cyclic carbonate or ester were found to have a significantly reduced volume increase rate and an effect of suppressing the swelling of the lithium ion secondary battery due to the generation of gas, as compared with the lithium ion secondary batteries of comparative examples 1 to 2 and reference example 1. Although the mechanism of this decrease in the volume increase rate is not completely understood, it is considered that the reason is: since a stable coating is formed on the positive electrode or the negative electrode by the interaction between the compound a and the fluorine-containing cyclic carbonate or ester, the electrolytic solution or LiPF is suppressed6And (5) decomposing. Alternatively, the reason is considered to be that: by interaction of compound A with cyclic carbonate or ester containing fluorine, electrolyte or LiPF6Is stabilized to suppress the electrolytic solution or LiPF6And (5) decomposing.
[ measurement of Capacity Retention ratio ]
The secondary batteries of examples 1 to 5 and comparative examples 1 to 2, which had been kept in a constant temperature bath at 80 ℃ for 4 hours, were taken out of the constant temperature bath, and after being kept at 25 ℃ for 30 minutes, constant current discharge was performed at a current value of 0.1C with an end voltage of 2.5V. The discharge capacity at this time was Q2. The capacity retention rate was calculated using the above Q1 and Q2 and using the following formula. The results are shown in FIG. 4.
Capacity retention rate (%) - (-) Q2/Q1X 100
As shown in fig. 4, the capacity retention rate of the lithium ion secondary battery of comparative example 2, which applied the electrolyte solution containing the fluorine-containing cyclic carbonate or ester and not containing the compound a, was slightly better than that of the lithium ion secondary battery of comparative example 1, which applied the electrolyte solution not containing either the compound a or the fluorine-containing cyclic carbonate or ester. It is considered that the lithium ion of comparative example 1 is because the fluorine-containing cyclic carbonate or ester or the compound a forms a stable film on the positive electrode or the negative electrode and inhibits the decomposition of the electrolytic solutionThe capacity retention rate of the secondary battery is improved. On the other hand, the lithium ion secondary batteries of examples 1 to 5 using the electrolyte solution containing both the compound a and the fluorine-containing cyclic carbonate or ester were further superior in capacity retention rate to the lithium ion secondary batteries of comparative examples 1 to 2. Although the mechanism of this improvement in the capacity retention rate is not completely understood, it is considered that the reason is: the compound a and the fluorine-containing cyclic carbonate or ester each act at a place where the effect is most likely to be exhibited in the lithium ion secondary battery, and contribute to, for example, formation of a stable film of the positive electrode or the negative electrode or stabilization of the electrolyte solution. Alternatively, the reason is considered to be that: the interaction of the compound A and the fluorine-containing cyclic carbonate or ester can inhibit the electrolyte or LiPF6Decomposition, etc.
[ measurement of discharged DCR ]
The dc resistance at the time of discharge (discharge DCR) of the secondary battery after the high-temperature storage test was measured in the following manner.
First, constant current charging at 0.2C was performed until the upper limit voltage was 4.45V, and then constant voltage charging was performed at 4.45V. The charge termination condition was set to a current value of 0.02C. Thereafter, constant current discharge was performed at a current value of 0.2C and a final voltage of 2.5V, and the current value at this time was I0.2CThe voltage change 10 seconds after the start of discharge was set to Δ V0.2C. Then, after constant current charging at 0.2C to an upper limit voltage of 4.45V and constant voltage charging at 4.45V (the charging end condition is set to a current value of 0.02C), constant current discharging at an end voltage of 2.5V is performed at a current value of 0.5C, and the current value at this time is set to I0.5CThe voltage change 10 seconds after the start of discharge was set to Δ V0.5C. The current value of 1C was evaluated as I according to the same charge and discharge1CThe voltage change 10 seconds after the start of discharge was evaluated as Δ V1C. Plotting (I) of the three points of the current value-voltage variation0.2C、ΔV0.2C)、(I0.5C、ΔV0.5C)、(I1C、ΔV1C) An approximate straight line is drawn once using the least square method, and the slope thereof is set as the value of the discharge DCR. The results are shown in FIG. 5.
As shown in fig. 5, the discharge DCR of the lithium-ion secondary battery of comparative example 2, which applied the electrolyte solution containing the fluorine-containing cyclic carbonate or ester and not containing the compound a, was slightly decreased compared to the lithium-ion secondary battery of comparative example 1, which applied the electrolyte solution not containing either the compound a or the fluorine-containing cyclic carbonate or ester. It is considered that the discharge DCR of comparative example 1 is slightly decreased because the fluorine-containing cyclic carbonate or ester forms a stable film on the positive electrode or the negative electrode. On the other hand, the lithium ion secondary batteries of examples 1 to 5 using the electrolyte solution containing both the compound a and the fluorine-containing cyclic carbonate or ester exhibited better (lower) discharge DCR than the lithium ion secondary batteries of comparative examples 1 to 2. Although the mechanism of the discharge DCR in the lithium ion secondary batteries of examples 1 to 5 is not completely understood, it is considered that the reason is: the interaction between the compound A and the fluorine-containing cyclic carbonate or ester forms a stable coating film having good ionic conductivity on the positive electrode or the negative electrode, or the interaction between the compound A and the fluorine-containing cyclic carbonate or ester forms LiPF6Is stabilized to thereby suppress LiPF6And decomposed to cause a decrease in the concentration of the Li carrier.
Description of the symbols
1-nonaqueous electrolyte secondary battery (electrochemical device), 6-positive electrode, 7-separator, 8-negative electrode.
Claims (11)
1. An electrolyte solution containing a compound represented by the following formula (1) and a fluorine-containing cyclic carbonate or ester,
in the formula (1), R1～R3Each independently represents an alkyl group or a fluorine atom, R4Represents an alkylene group, R5Represents an organic group containing a sulfur atom.
2. The electrolytic solution according to claim 1, wherein the number of silicon atoms in one molecule of the compound represented by formula (1) is 1.
3. The electrolyte of claim 1 or 2, wherein R is5Is a group represented by any one of the following formulae (2), (3) or (4):
in the formula (2), R6Represents an alkyl group, represents a bonding site;
in the formula (3), R7Represents an alkyl group, represents a bonding site;
in the formula (4), R8Represents an alkyl group and represents a bonding site.
4. The electrolyte of any one of claims 1 to 3, wherein R is1～R3At least one of which is a fluorine atom.
5. The electrolyte of any one of claims 1 to 4, wherein the fluorine-containing cyclic carbonate or ester is 4-fluoro-1, 3-dioxolan-2-one.
6. The electrolytic solution according to any one of claims 1 to 5, wherein the total of the content of the compound represented by the formula (1) and the content of the fluorine-containing cyclic carbonate or ester is 10% by mass or less based on the total amount of the electrolytic solution.
7. An electrochemical device, comprising: a positive electrode, a negative electrode and the electrolyte according to any one of claims 1 to 6.
8. The electrochemical device according to claim 7, wherein the negative electrode contains a carbon material.
9. The electrochemical device according to claim 8, wherein the carbon material contains graphite.
10. The electrochemical device according to claim 8 or 9, wherein the negative electrode further contains a material containing at least 1 element selected from the group consisting of silicon and tin.
11. The electrochemical device according to any one of claims 7 to 10, wherein the electrochemical device is a nonaqueous electrolyte secondary battery or a capacitor.
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| PCT/JP2019/029543 WO2020027003A1 (en) | 2018-07-31 | 2019-07-26 | Electrolyte and electrochemical device |
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| US20130250485A1 (en) * | 2011-06-09 | 2013-09-26 | Wildcat Discovery Technologies, Inc. | Materials for electrolytes and methods for use |
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| JP2016189327A (en) * | 2015-03-27 | 2016-11-04 | 旭化成株式会社 | Additive of electrolyte for nonaqueous power storage device |
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- 2019-07-26 JP JP2020533508A patent/JPWO2020027003A1/en active Pending
- 2019-07-26 KR KR1020217005823A patent/KR20210033042A/en not_active Application Discontinuation
- 2019-07-26 CN CN201980062244.3A patent/CN112740459A/en active Pending
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| JP2008288112A (en) * | 2007-05-18 | 2008-11-27 | Sony Corp | Nonaqueous electrolytic secondary battery |
| WO2009113545A1 (en) * | 2008-03-13 | 2009-09-17 | 宇部興産株式会社 | Non-aqueous electrolyte for a lithium battery, lithium battery wherein said electrolyte is used, and hydroxy-acid derivative for use in said electrolyte |
| CN101971409A (en) * | 2008-03-13 | 2011-02-09 | 宇部兴产株式会社 | Non-aqueous electrolyte for a lithium battery, lithium battery wherein said electrolyte is used, and hydroxy-acid derivative for use in said electrolyte |
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| KR20210033042A (en) | 2021-03-25 |
| JPWO2020027003A1 (en) | 2021-08-10 |
| WO2020027003A1 (en) | 2020-02-06 |
| TW202017241A (en) | 2020-05-01 |
| TWI825137B (en) | 2023-12-11 |
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