WO2013183769A1 - リチウムイオン二次電池 - Google Patents
リチウムイオン二次電池 Download PDFInfo
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- WO2013183769A1 WO2013183769A1 PCT/JP2013/065863 JP2013065863W WO2013183769A1 WO 2013183769 A1 WO2013183769 A1 WO 2013183769A1 JP 2013065863 W JP2013065863 W JP 2013065863W WO 2013183769 A1 WO2013183769 A1 WO 2013183769A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0034—Fluorinated solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a non-aqueous electrolyte and a lithium ion secondary battery using the same.
- lithium ion secondary batteries Since lithium ion secondary batteries have a small volume, a large mass capacity density, and a high voltage can be taken out, they are widely used as power sources for small devices. For example, it is used as a power source for mobile devices such as mobile phones and notebook computers. Also, in recent years, in addition to small mobile device applications, large secondary devices that require a long life with a large capacity, such as electric vehicles (EV) and power storage fields, are being considered due to consideration for environmental issues and increased awareness of energy conservation. Application to batteries is expected.
- EV electric vehicles
- a positive electrode active material based on LiMO 2 having a layered structure (M is at least one of Co, Ni, and Mn) or LiMn 2 O 4 having a spinel structure is used. It is used. Further, a carbon material such as graphite is used as the negative electrode active material.
- a battery voltage mainly uses a charge / discharge region of 4.2 V or less.
- a material obtained by substituting a part of Mn of LiMn 2 O 4 with Ni or the like shows a high charge / discharge region of 4.5 to 4.8 V with respect to lithium metal.
- spinel compounds such as LiNi 0.5 Mn 1.5 O 4 are not redox of conventional Mn 3+ and Mn 4+ , but Mn exists in the state of Mn 4+ and redox of Ni 2+ and Ni 4+ Therefore, a high operating voltage of 4.5 V or higher is shown.
- Such a material is called a 5V class active material and is expected as a promising positive electrode material because it can improve the energy density by increasing the voltage.
- an SEI film is formed on the surface of an active material by adding an additive to an electrolytic solution.
- This SEI film is an electronic insulator, but is believed to have lithium ion conductivity, and functions to prevent the reaction between the active material and the electrolytic solution.
- Many of these additives form a film on the negative electrode.
- the additive for forming a film on the negative electrode has not obtained a sufficient effect on gas generation.
- Patent Documents 1 to 3 a technique for improving battery performance by coating the surface of a positive electrode or a positive electrode active material with a conductive polymer typified by polyaniline by electrolytic oxidation or chemical oxidation is disclosed.
- Patent Documents 1 to 3 there is no specific description of additives that are effective in suppressing gas generation of 5V class active materials.
- An object of the present invention is to provide an electrolytic solution effective for reducing the amount of gas generated in a charge / discharge cycle of a lithium ion secondary battery, preferably a lithium ion secondary battery using a 5V class positive electrode.
- the present invention relates to a nonaqueous electrolytic solution containing at least one aniline derivative represented by the following formula (1) and a nonaqueous solvent.
- Each of the substituents R 1 to R 5 is independently a hydrogen atom, a halogen atom, an alkyl group, a vinyl group, an alkoxy group, a halogenated alkyl group, a halogenated vinyl group, or a halogenated alkoxy group,
- the alkyl group, alkoxy group, halogenated alkyl group, and halogenated alkoxy group each have 1 or 2 carbon atoms.
- the total number of halogen atoms is 5 or less, and Of the substituents R 1 to R 5 , the number of substituents other than a hydrogen atom and a halogen atom is 1 or 2.
- the decomposition reaction of the non-aqueous electrolyte is suppressed, and the high temperature Gas generation in the charge / discharge cycle can be reduced.
- Non-aqueous electrolytic solution of this embodiment contains at least one aniline derivative represented by the following formula (1) and a nonaqueous solvent.
- Each of the substituents R 1 to R 5 is independently a hydrogen atom, a halogen atom, an alkyl group, a vinyl group, an alkoxy group, a halogenated alkyl group, a halogenated vinyl group, or a halogenated alkoxy group,
- the alkyl group, alkoxy group, halogenated alkyl group, and halogenated alkoxy group each have 1 or 2 carbon atoms.
- the total number of halogen atoms is 5 or less, and Of the substituents R 1 to R 5 , the number of substituents other than a hydrogen atom and a halogen atom is 1 or 2.
- the nonaqueous electrolytic solution of the present embodiment contains an aniline derivative represented by the formula (1), so that the decomposition reaction of the nonaqueous electrolytic solution is suppressed and gas generation in a high-temperature charge / discharge cycle can be reduced.
- the aniline derivative represented by the formula (1) forms a high-quality film on the surface of the positive electrode active material by oxidative polymerization, so that the decomposition reaction of the electrolytic solution is suppressed and gas generation in the high-temperature charge / discharge cycle is reduced. This is thought to be possible.
- the nonaqueous electrolytic solution of the present embodiment can exert its effect more effectively in a secondary battery including a 5V-grade positive electrode active material that has a large problem of gas generation in the electrode.
- aniline derivative represented by the formula (1) may be simply referred to as “aniline derivative”.
- the substituent of the aniline derivative represented by the formula (1) refers to any substituent selected from R 1 to R 5 and does not include the —NH 2 group.
- each of the substituents R 1 to R 5 is independently a hydrogen atom, a halogen atom, an alkyl group, a vinyl group, an alkoxy group, a halogenated alkyl group, a halogenated vinyl group, or a halogenated alkoxy group. is there.
- examples of the halogen atom as a substituent include fluorine, chlorine, and bromine, and fluorine is preferable.
- the carbon number of the alkyl group and the alkoxy group is 1 or 2, respectively.
- the number of carbon atoms is 3 or more, film formation may be hindered by steric hindrance effects and the like.
- the alkyl group include a methyl group and an ethyl group
- examples of the alkoxy group include a methoxy group and an ethoxy group.
- a halogenated alkyl group, a halogenated vinyl group, and a halogenated alkoxy group each have a substitution in which part or all of the hydrogens of the alkyl group, vinyl group, and alkoxy group are substituted with a halogen atom.
- the halogenated alkyl group and the halogenated alkoxy group each have 1 or 2 carbon atoms. When the number of carbon atoms is 3 or more, film formation may be hindered due to a steric hindrance effect.
- Examples of the halogen atom in the halogenated alkyl group, the halogenated vinyl group, and the halogenated alkoxy group include fluorine, chlorine, and bromine, and fluorine is preferable. It can be expected that the stability of the positive electrode film against oxidation is improved by including fluorine in a part of the substituent.
- Examples of the halogenated alkyl group include —CF 3 , —CHF 2 , —CH 2 F, —CF 2 CF 3 , —CH 2 CF 3 , —CH 2 CHF 2 and the like.
- Examples of the vinyl halide group include —CH ⁇ CF 2 and —CH ⁇ CHF.
- Examples of the halogenated alkoxy group include —OCF 3 , —OCH 2 F and the like.
- the total number of halogen atoms is 5 or less.
- the total number of halogen atoms means the sum of the number of halogen atoms as substituents and the number of halogen atoms as part of substituents.
- the number of halogen atoms contained in the aniline derivative is 6 or more, the oxidative polymerization reaction of the aniline derivative is difficult to occur and the film formation tends to be hindered.
- the number of substituents other than hydrogen atoms and halogen atoms in the aniline derivative that is, the number of substituents containing carbon atoms is 1 or 2.
- a nonaqueous electrolytic solution using unsubstituted aniline that is, aniline in which R 1 to R 5 are all hydrogen atoms in formula (1)
- polyaniline is known as a conductive polymer, and since the electronic conductivity of the polyaniline film formed on the positive electrode is high, the electronic insulation required for SEI is likely to be impaired.
- side reactions are likely to occur and gas is likely to be generated.
- the number of substituents containing carbon atoms is too large, the polymerization reaction is hindered by the steric hindrance effect and the like, and it is considered that a film is hardly formed.
- the total number of carbons contained in the substituents R 1 to R 5 is preferably 1 or 2.
- the total number of carbons contained in all substituents is 3 or more, film formation may be easily inhibited due to steric hindrance effects or the like.
- the aniline derivative is not particularly limited, but preferably includes at least one selected from trifluoromethylaniline, methoxyaniline, and methylaniline.
- aniline derivative in the present embodiment is shown below, but is not limited thereto.
- aniline derivatives may be used alone or in combination of two or more.
- the content of the aniline derivative in the electrolytic solution is preferably 0.1% by mass or more and 1% by mass or less with respect to the total mass of the nonaqueous electrolytic solution.
- the content of the aniline derivative is too small, a film is not sufficiently formed on the positive electrode, and the effect of suppressing the decomposition reaction with the electrolytic solution is reduced.
- the content of the aniline derivative is too large, the amount of gas generated may increase due to a side reaction of the aniline derivative remaining without being used for film formation during the charge / discharge cycle.
- the nonaqueous solvent contained in the nonaqueous electrolytic solution of the present embodiment is not particularly limited, and examples thereof include cyclic carbonates, chain carbonates, aliphatic carboxylic acid esters, ⁇ -lactones, cyclic ethers, and chain forms. At least one organic solvent selected from ethers can be used.
- Examples of the cyclic carbonate include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and derivatives thereof (including fluorinated products).
- chain carbonate examples include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dipropyl carbonate (DPC), and derivatives thereof (including fluorinated products).
- Examples of the aliphatic carboxylic acid ester include methyl formate, methyl acetate, ethyl propionate, and derivatives thereof (including fluorinated products).
- Examples of ⁇ -lactone include ⁇ -butyrolactone and its derivatives (including fluorinated products).
- examples of the cyclic ether include tetrahydrofuran, 2-methyltetrahydrofuran and derivatives thereof (including fluorinated products).
- examples of the chain ether include 1,2-ethoxyethane (DEE), ethoxymethoxyethane (EME), diethyl ether, and derivatives thereof (including fluorinated compounds). These can be used individually by 1 type or in mixture of 2 or more types.
- non-aqueous solvents include, for example, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, dioxolane, acetonitrile, propyl nitrile, nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, dioxolane derivatives , Sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, anisole, N-methylpyrrolidone, and derivatives thereof (including fluorinated products) Can also be used.
- the fluorine-containing solvent refers to a solvent composed of a compound containing a fluorine atom.
- the fluorine-containing solvent has high oxidation resistance, decomposition of the solvent on the positive electrode can be suppressed.
- the electrolytic solution contains a fluorine-containing solvent, the effect of reducing gas generation by adding the aniline derivative can be further enhanced.
- the fluorine-containing solvent has high oxidation resistance, so that decomposition products derived from the solvent are difficult to deposit on the surface of the positive electrode, and as a result, the quality of the positive electrode film formed by the aniline derivative is improved Possible possibility.
- the fluorine-containing solvent preferably contains at least one selected from a fluorinated ether compound and a fluorinated phosphate ester compound from the viewpoints of solubility of lithium salt, compatibility with a carbonate solvent, battery performance, and the like.
- the fluorinated ether compound is not particularly limited, for example, CF 3 OCH 3, CF 3 OC 2 H 5, F (CF 2) 2 OCH 3, F (CF 2) 2 OC 2 H 5, CF 3 (CF 2) CH 2 O (CF 2 ) CF 3, F (CF 2) 3 OCH 3, F (CF 2) 3 OC 2 H 5, F (CF 2) 4 OCH 3, F (CF 2) 4 OC 2 H 5 , F (CF 2 ) 5 OCH 3 , F (CF 2 ) 5 OC 2 H 5 , F (CF 2 ) 8 OCH 3 , F (CF 2 ) 8 OC 2 H 5 , F (CF 2 ) 9 OCH 3 CF 3 CH 2 OCH 3 , CF 3 CH 2 OCHF 2 , CF 3 CF 2 CH 2 OCH 3 , CF 3 CF 2 CH 2 OCHF 2 , CF 3 CF 2 CH 2 O (CF 2 ) 2 H, CF 3 CF 2 CH 2 O ( F 2) 2 F, HCF 2 CH 2 OCH 3, (
- Tris (trifluoromethyl) phosphate Tris (pentafluoroethyl) phosphate, Tris (2,2,2-trifluoroethyl) phosphate (TTFP), Tris (2, 2, 3) , 3-tetrafluoropropyl) phosphate, Tris (3,3,3-trifluoropropyl) phosphate, Tris (2,2,3,3,3-pentafluoropropyl) phosphate, and the like.
- Tris (2,2,2-trifluoroethyl) phosphate (TTFP) is preferable as the fluorinated phosphate compound.
- the fluorinated phosphate ester compounds can be used singly or in combination of two or more.
- the content of the fluorine-containing solvent is not particularly limited, but is preferably 30% by volume or more and 90% by volume or less, and 40% by volume or more and 85% by volume with respect to the total volume of the nonaqueous solvent. More preferably, it is 50 volume% or more and 80 volume% or less.
- nonaqueous electrolytic solution of the present embodiment it is preferable that an electrolyte composed of a lithium salt is dissolved in a nonaqueous solvent.
- lithium salt is not particularly limited, for example, lithium imide salt, LiPF 6, LiAsF 6, LiAlCl 4, LiClO 4, LiBF 4, LiSbF 6 and the like. Among these, LiPF 6 and LiBF 4 are preferable.
- the lithium imide salt for example, LiN (C k F 2k + 1 SO 2) (C m F 2m + 1 SO 2) (k and m are each independently 1 or 2).
- a lithium salt can be used individually by 1 type, and can also be used in combination of 2 or more type.
- the concentration of the lithium salt in the electrolytic solution is preferably 0.5 to 1.5 mol / L. By setting the concentration of the lithium salt within this range, it is easy to adjust the density, viscosity, electrical conductivity, and the like to an appropriate range.
- an additive (excluding the aniline derivative represented by the above formula (1)) may be added to the non-aqueous electrolyte in order to form a high-quality SEI film on the negative electrode surface.
- the SEI film functions to suppress the reactivity with the electrolytic solution, or to smooth the desolvation reaction accompanying the insertion / desorption of lithium ions to prevent structural deterioration of the active material.
- examples of such additives include propane sultone, vinylene carbonate, and cyclic disulfonic acid esters.
- the addition amount of the additive in the non-aqueous electrolyte is preferably 0.2% by mass to 5% by mass with respect to the total mass of the non-aqueous electrolyte.
- the positive electrode in the present embodiment preferably includes a positive electrode active material (hereinafter sometimes referred to as “5 V class active material”) having an operating potential of 4.5 V or higher with respect to lithium metal. That is, the positive electrode active material used in the present embodiment preferably has a charge / discharge region at 4.5 V or higher with respect to lithium metal.
- a positive electrode active material hereinafter sometimes referred to as “5 V class active material” having an operating potential of 4.5 V or higher with respect to lithium metal. That is, the positive electrode active material used in the present embodiment preferably has a charge / discharge region at 4.5 V or higher with respect to lithium metal.
- the 5V class active material is preferably a lithium-containing composite oxide.
- Examples of the 5V class active material of the lithium-containing composite oxide include spinel-type lithium manganese composite oxide, olivine-type lithium manganese-containing composite oxide, reverse spinel-type lithium manganese-containing composite oxide, Li 2 MnO 3 -based solid solution, and the like. Can be mentioned.
- lithium manganese composite oxide represented by the following formula (2).
- M includes only Ni or one or more of Co and Fe containing Ni as a main component.
- A is more preferably one or more of B, Mg, Al, and Ti.
- Z is more preferably F. Such a substitution element serves to stabilize the crystal structure and suppress the deterioration of the active material.
- the average particle diameter (D 50 ) of the positive electrode active material is preferably 1 to 50 ⁇ m, and more preferably 5 to 25 ⁇ m.
- the average particle diameter (D 50 ) of the positive electrode active material can be measured by a laser diffraction scattering method (microtrack method).
- the 5V class active material is a positive electrode active material other than the above formula (2) as long as it is a positive electrode active material having a charge / discharge region of 4.5 V (vs. Li / Li + ) or more with respect to lithium metal. It doesn't matter. It is considered that the quality and stability of the film formed on the surface of the positive electrode active material are dominated by the potential and are not directly influenced by the composition of the active material.
- Li x MPO 4 F y (0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1, M is at least one of Co and Ni).
- Si-containing composite oxide represented by Li x MSiO 4 (0 ⁇ x ⁇ 2, M: at least one of Mn, Fe and Co); Li x [Li a M b Mn 1-ab ] O 2 (0 ⁇ x ⁇ 1, 0.02 ⁇ a ⁇ 0.3, 0.1 ⁇ b ⁇ 0.7, M is at least Ni, Co, Fe and Cr
- One type of positive electrode active material may be used alone, or two or more types may be used in combination.
- the positive electrode active material may include a 4V class positive electrode active material such as lithium cobalt oxide.
- Negative electrode active material Although it does not restrict
- a negative electrode active material can be used individually by 1 type, and can also be used in combination of 2 or more type.
- the positive electrode has, for example, a positive electrode active material layer formed on at least one surface of a positive electrode current collector.
- a positive electrode active material layer is comprised by the positive electrode active material which is a main material, a binder, and a conductive support agent, for example.
- the negative electrode has, for example, a negative electrode active material layer formed on at least one surface of a negative electrode current collector.
- a negative electrode active material layer is comprised by the negative electrode active material which is a main material, a binder, and a conductive support agent, for example.
- binder used in the positive electrode examples include polyvinylidene fluoride (PVDF) and acrylic polymers.
- binder used in the negative electrode examples include styrene butadiene rubber (SBR) and the like in addition to the above.
- SBR styrene butadiene rubber
- a thickener such as carboxymethyl cellulose (CMC) can also be used.
- carbon materials such as carbon black, granular graphite, flake graphite, and carbon fiber can be used for both the positive electrode and the negative electrode.
- carbon black having low crystallinity for the positive electrode.
- positive electrode current collector for example, aluminum, stainless steel, nickel, titanium, or an alloy thereof can be used.
- negative electrode current collector for example, copper, stainless steel, nickel, titanium, or an alloy thereof can be used.
- the electrode is prepared by dispersing and kneading an active material, a binder, and a conductive aid in a solvent such as N-methyl-2-pyrrolidone (NMP) in a predetermined blending amount. It can be obtained by applying to an electric body to form an active material layer. The obtained electrode can be compressed to a suitable density by a method such as a roll press.
- NMP N-methyl-2-pyrrolidone
- the separator is not particularly limited, and for example, a porous film made of a polyolefin such as polypropylene or polyethylene, a fluororesin, an inorganic separator made of cellulose, glass, or the like can be used.
- the exterior body for example, coin-shaped, rectangular, cylindrical, etc. cans and laminate exterior bodies can be used. From the viewpoint of reducing the weight and improving the battery energy density, synthetic resin and metal A laminate outer package using a flexible film made of a laminate with a foil is preferred. Since the laminate type battery is excellent in heat dissipation, it is suitable as an in-vehicle battery such as an electric vehicle.
- an aluminum laminate film, a SUS laminate film, a laminate film made of silica-coated polypropylene, polyethylene, or the like can be used as the outer package.
- an aluminum laminate film from the viewpoint of suppressing volume expansion and cost.
- the configuration of the secondary battery according to the present embodiment is not particularly limited, and for example, an electrode element in which a positive electrode and a negative electrode are opposed to each other and an electrolytic solution may be included in an exterior body. it can.
- the shape of the secondary battery is not particularly limited, and examples thereof include a cylindrical shape, a flat wound rectangular shape, a laminated rectangular shape, a coin shape, a flat wound laminated shape, and a laminated laminated shape.
- FIG. 1 shows a laminated secondary battery as an example of the secondary battery according to this embodiment.
- the secondary battery shown in FIG. 1 includes a positive electrode composed of a positive electrode active material layer 1 including a positive electrode active material and a positive electrode binder, and a positive electrode current collector 3, and a negative electrode active material layer 2 including a negative electrode active material capable of occluding and releasing lithium. And the negative electrode current collector 4 is sandwiched between the separator 5.
- the positive electrode current collector 3 is connected to the positive electrode tab 8, and the negative electrode current collector 4 is connected to the negative electrode tab 7.
- a laminated outer package 6 is used as the outer package, and the inside of the secondary battery is filled with the nonaqueous electrolytic solution according to the present embodiment.
- a positive electrode tab and a negative electrode tab are connected to the positive electrode for a secondary battery and the negative electrode according to this embodiment via a positive electrode current collector and a negative electrode current collector, respectively.
- the positive electrode and the negative electrode are arranged opposite to each other with the separator interposed therebetween, and an electrode laminate is produced in which the positive electrode and the negative electrode are laminated.
- the electrode laminate is accommodated in an exterior body and immersed in an electrolytic solution.
- a secondary battery is manufactured by sealing the exterior body so that a part of the positive electrode tab and the negative electrode tab protrudes to the outside.
- Example 1 (Preparation of negative electrode) Natural graphite powder (average particle size (D 50 ): 20 ⁇ m, specific surface area: 1 m 2 / g) as a negative electrode active material and PVDF as a binder are uniformly dispersed in NMP at a mass ratio of 95: 5 Thus, a negative electrode slurry was produced. After coating this negative electrode slurry on a copper foil having a thickness of 15 ⁇ m to be a negative electrode current collector, the negative electrode active material layer is formed by drying at 125 ° C. for 10 minutes to evaporate NMP, and further pressing to form a negative electrode Was made. In addition, the weight of the negative electrode active material layer per unit area after drying was set to 0.008 g / cm 2 .
- LiNi 0.5 Mn 1.5 O 4 powder (average particle diameter (D 50 ): 10 ⁇ m, specific surface area: 0.5 m 2 / g) as a positive electrode active material was prepared.
- a positive electrode active material, PVDF as a binder, and carbon black as a conductive additive were uniformly dispersed in NMP at a mass ratio of 93: 4: 3 to prepare a positive electrode slurry.
- This positive electrode slurry was applied on a 20 ⁇ m thick aluminum foil serving as a positive electrode current collector, and then dried at 125 ° C. for 10 minutes to evaporate NMP, thereby preparing a positive electrode.
- the weight of the positive electrode active material layer per unit area after drying was set to 0.018 g / cm 2 .
- Non-aqueous electrolyte EC, DMC, and fluorinated ether (FE) represented by H (CF 2 ) 2 CH 2 OCF 2 CF 2 H as a fluorine-containing solvent
- EC: DMC: FE 40: 20: 40 (volume)
- the non-aqueous solvent was prepared by mixing at a ratio of (ratio).
- the concentration of the fluorine-containing solvent at this time is 40% by volume with respect to the total volume of the nonaqueous solvent.
- LiPF 6 was dissolved as an electrolyte at a concentration of 0.8 mol / L.
- the above-mentioned 2,5-dimethoxyaniline was dissolved as an aniline derivative in an amount of 0.5% by mass based on the total mass of the nonaqueous electrolytic solution to prepare a nonaqueous electrolytic solution.
- the positive electrode and the negative electrode produced as described above were cut into 5 cm ⁇ 6.0 cm, respectively. Of these, a side of 5 cm ⁇ 1 cm is a portion where an electrode active material layer is not formed to connect the tab (uncoated portion), and a portion where the electrode active material layer is formed is 5 cm ⁇ 5 cm.
- a positive electrode tab made of aluminum having a width of 5 mm, a length of 3 cm, and a thickness of 0.1 mm was ultrasonically welded to the uncoated portion of the positive electrode with a length of 1 cm. Also, a nickel negative electrode tab having the same size as the positive electrode tab was ultrasonically welded to the uncoated portion of the negative electrode.
- the negative electrode and the positive electrode were placed on both sides of a 6 cm ⁇ 6 cm separator made of polyethylene and polypropylene so that the electrode active material layer overlapped with the separator therebetween to obtain an electrode laminate.
- Three sides of the two 7 cm ⁇ 10 cm aluminum laminate films except one of the long sides were bonded to each other with a width of 5 mm by thermal fusion to produce a bag-shaped laminate outer package.
- the electrode laminate was inserted so as to be a distance of 1 cm from one short side of the laminate outer package. After injecting 0.2 g of the non-aqueous electrolyte solution and impregnating it with a vacuum, a laminated battery was produced by sealing the opening with a width of 5 mm by thermal fusion under reduced pressure.
- Example 2 A secondary battery was prepared and evaluated in the same manner as in Example 1 except that the aforementioned 2-methoxyaniline was used as the aniline derivative.
- Example 3 A secondary battery was prepared and evaluated in the same manner as in Example 1 except that the above-mentioned 2-methylaniline was used as the aniline derivative.
- Example 4 A secondary battery was prepared and evaluated in the same manner as in Example 1 except that the above-mentioned 2-trifluoromethylaniline was used as the aniline derivative.
- Table 1 shows the evaluation results of Examples 1 to 4 and Comparative Examples 1 to 5.
- Any of the aniline derivatives used in Examples 1 to 4 is a kind of the compound represented by the formula (1). Compared with the result of Comparative Example 1 in which no aniline derivative was added, it was confirmed that the volume change amount was reduced in Examples 1 to 4. This is presumably because the aniline derivative represented by the formula (1) formed a high-quality film on the surface of the 5V class active material and suppressed decomposition of the electrolytic solution under high voltage and high temperature.
- Comparative Examples 2 to 5 aniline or an aniline derivative not included in the compound represented by the formula (1) was used. In these Comparative Examples 2 to 5, the effect of reducing gas generation was not recognized. Further, compared to Comparative Example 1 in which no aniline derivative was added, unsubstituted aniline (Comparative Example 2), pentafluoroaniline in which 5 hydrogen atoms of the benzene ring were substituted with fluorine atoms (Comparative Example 3), substitution 2,3,5-trimethylaniline (Comparative Example 5) containing three methyl groups as a group had a large cycle deterioration and less than 300 cycles, the capacity retention rate was 20% or less, and the volume change was as large as 5 times or more. 2,5-bis (trifluoromethyl) aniline (Comparative Example 4) containing two trifluoromethyl groups was almost the same as Comparative Example 1.
- Example 5 A secondary battery was produced and evaluated in the same manner as in Example 4 except that the amount of 2-trifluoromethylaniline (2TFMA) added to the electrolyte was 0.05% by mass in the total mass of the electrolyte. .
- Example 6 A secondary battery was prepared and evaluated in the same manner as in Example 4 except that the amount of 2TFMA added was 0.1 mass% in the total mass of the electrolyte.
- Example 7 A secondary battery was prepared and evaluated in the same manner as in Example 4 except that the amount of 2TFMA added was 0.3% by mass in the total mass of the electrolytic solution.
- Example 8 A secondary battery was prepared and evaluated in the same manner as in Example 4 except that the amount of 2TFMA added was 1.0 mass% in the total mass of the electrolytic solution.
- Example 9 A secondary battery was prepared and evaluated in the same manner as in Example 4 except that the amount of 2TFMA added was 1.5% by mass in the total mass of the electrolytic solution.
- Table 2 shows the evaluation results of Examples 5 to 9. When the addition amount of 2TFMA is 0.1% by mass or more and 1% by mass or less in the total mass of the electrolytic solution, it is found that the volume change amount is smaller and more preferable.
- Example 10 A secondary battery was produced and evaluated in the same manner as in Comparative Example 6 except that 2 TFMA was dissolved in the non-aqueous electrolyte at 0.5 mass% with respect to the total mass of the non-aqueous electrolyte.
- Example 11 A secondary battery was fabricated and evaluated in the same manner as in Comparative Example 7 except that a non-aqueous electrolyte solution in which 0.5% by mass of 2TFMA was dissolved in the non-aqueous electrolyte solution was used with respect to the total mass of the non-aqueous electrolyte solution. .
- Table 3 shows the evaluation results of Comparative Examples 6 and 7 and Examples 10 and 11.
- concentration of the fluorine-containing solvent was 50% by volume with respect to the total volume of the nonaqueous solvent
- the volume change decreased by 44% from 0.018 to 0.01 cc / mAh by the addition of 2TFMA.
- concentration of the fluorine-containing solvent was 60% by volume with respect to the total volume of the non-aqueous solvent
- the volume change decreased by 49% from 0.0085 to 0.0043 cc / mAh by the addition of 2TFMA.
- the fluorine-containing solvent concentration was 40% by volume with respect to the total volume of the nonaqueous solvent, but the volume change amount was 0.03 to 0.02 cc / mAh by the addition of 2TFMA. And 33% decrease. From this result, the volumetric change amount, that is, the effect of suppressing gas generation is further improved by using a nonaqueous electrolytic solution having a fluorine-containing solvent concentration of 50% by volume or more and the aniline derivative represented by the formula (1). I found it big.
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Abstract
Description
置換基R1~R5は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、ビニル基、アルコキシ基、ハロゲン化アルキル基、ハロゲン化ビニル基、またはハロゲン化アルコキシ基であり、
前記アルキル基、アルコキシ基、ハロゲン化アルキル基、およびハロゲン化アルコキシ基の炭素数は、それぞれ1または2である。
置換基R1~R5のうち、水素原子およびハロゲン原子以外の置換基の数は1または2である。)
本実施形態の非水電解液は、下式(1)で表されるアニリン誘導体の少なくとも一種と、非水溶媒とを含む。
置換基R1~R5は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、ビニル基、アルコキシ基、ハロゲン化アルキル基、ハロゲン化ビニル基、またはハロゲン化アルコキシ基であり、
前記アルキル基、アルコキシ基、ハロゲン化アルキル基、およびハロゲン化アルコキシ基の炭素数は、それぞれ、1または2である。
置換基R1~R5のうち、水素原子およびハロゲン原子以外の置換基の数は1または2である。)
本実施形態における正極は、リチウム金属に対して4.5V以上に動作電位を有する正極活物質(以下、「5V級活物質」と記載することもある)を含むことが好ましい。すなわち、本実施形態で用いる正極活物質は、リチウム金属に対して4.5V以上に充放電領域を有することが好ましい。
(式(2)中、0.4≦x≦1.2、0≦y、x+y<2、0≦a≦1.2、0≦w≦1であり、Mは、Co、Ni、Fe、CrおよびCuからなる群から選択される少なくとも一種であり、Aは、Li、B、Na、Mg、Al、Ti、Si、KおよびCaからなる群から選択される少なくとも一種であり、Zは、FおよびClの少なくとも一種である。)。
負極活物質としては、特に制限されるものではないが、例えば、黒鉛や非晶質炭素等の炭素材料を用いることができる。負極活物質としては、エネルギー密度の観点から、黒鉛を用いることが好ましい。また、負極活物質として、炭素材料以外にも、例えば、Si、Sn、Al等のLiと合金を形成する材料、Si酸化物、SiとSi以外の他金属元素を含むSi複合酸化物、Sn酸化物、SnとSn以外の他金属元素を含むSn複合酸化物、Li4Ti5O12、これらの材料にカーボンを被覆した複合材料等を用いることもできる。負極活物質は、1種を単独で用いることができ、2種以上を組み合わせて用いることもできる。
正極は、例えば、正極集電体の少なくとも一方の面に正極活物質層が形成されてなる。正極活物質層は、例えば、主材である正極活物質と、結着剤と、導電助剤とによって構成される。負極は、例えば、負極集電体の少なくとも一方の面に負極活物質層が形成されてなる。負極活物質層は、例えば、主材である負極活物質と、結着剤と、導電助剤とによって構成される。
セパレータとしては、特に限定されるものではないが、例えば、ポリプロピレン、ポリエチレン等のポリオレフィンやフッ素樹脂等からなる多孔性フィルム、セルロースやガラスなどからなる無機セパレータ等を用いることができる。
外装体としては、例えば、コイン型、角型、円筒型等の缶や、ラミネート外装体を用いることができるが、軽量化が可能であり電池エネルギー密度の向上を図る観点から、合成樹脂と金属箔との積層体からなる可撓性フィルムを用いたラミネート外装体が好ましい。ラミネート型電池は、放熱性にも優れているため、電気自動車などの車載用電池として好適である。
本実施形態に係る二次電池の構成は、特に制限されるものではなく、例えば、正極および負極が対向配置された電極素子と、電解液とが外装体に内包されている構成とすることができる。二次電池の形状は、特に制限されるものではないが、例えば、円筒型、扁平捲回角型、積層角型、コイン型、扁平捲回ラミネート型、又は積層ラミネート型が挙げられる。
本実施形態に係る二次電池の製造方法は特に限定されないが、例えば、以下に示す方法が挙げられる。本実施形態に係る二次電池用正極および前記負極にそれぞれ正極集電体及び負極集電体を介して正極タブ、負極タブを接続する。前記正極と前記負極とを前記セパレータを挟んで対向配置させ、積層させた電極積層体を作製する。該電極積層体を外装体内に収容し、電解液に浸す。正極タブ、負極タブの一部を外部に突出するようにして外装体を封止することで、二次電池を作製する。
(負極の作製)
負極活物質としての天然黒鉛粉末(平均粒径(D50):20μm、比表面積:1m2/g)と、結着剤としてのPVDFとを、質量比95:5でNMP中に均一に分散させて、負極スラリーを作製した。この負極スラリーを負極集電体となる厚み15μmの銅箔上に塗布後、125℃にて10分間乾燥させてNMPを蒸発させることにより、負極活物質層を形成し、さらにプレスすることによって負極を作製した。なお、乾燥後の単位面積当たりの負極活物質層の重量を0.008g/cm2とした。
正極活物質としてのLiNi0.5Mn1.5O4粉末(平均粒径(D50):10μm、比表面積:0.5m2/g)を用意した。正極活物質と、結着剤としてのPVDFと、導電助剤としてのカーボンブラックとを、質量比93:4:3でNMP中に均一に分散させて、正極スラリーを作製した。この正極スラリーを正極集電体となる厚み20μmのアルミニウム箔上に塗布後、125℃にて10分間乾燥させてNMPを蒸発させることにより、正極を作製した。なお、乾燥後の単位面積当たりの正極活物質層の重量を0.018g/cm2とした。
ECと、DMCと、フッ素含有溶媒としてのH(CF2)2CH2OCF2CF2Hで表されるフッ素化エーテル(FE)とを、EC:DMC:FE=40:20:40(体積比)の比率で混合して非水溶媒を調製した。このときのフッ素含有溶媒の濃度は非水溶媒全体積に対して40体積%である。この非水溶媒に、電解質として0.8mol/Lの濃度でLiPF6を溶解させた。この電解溶液に、アニリン誘導体として前記の2,5-ジメトキシアニリンを、非水電解液の全質量に対し0.5質量%溶解させ、非水電解液を調整した。
上記のように作製した正極および負極を各々5cm×6.0cmに切り出した。このうち、一辺5cm×1cmはタブを接続するために電極活物質層を形成していない部分(未塗布部)であって、電極活物質層が形成された部分は5cm×5cmである。幅5mm×長さ3cm×厚み0.1mmのアルミニウム製の正極タブを、正極の未塗布部に長さ1cmで超音波溶接した。また、正極タブと同サイズのニッケル製の負極タブを、負極の未塗布部に超音波溶接した。6cm×6cmのポリエチレンおよびポリプロピレンからなるセパレータの両面に上記負極と正極を電極活物質層がセパレータを隔てて重なるように配置して、電極積層体を得た。2枚の7cm×10cmのアルミニウムラミネートフィルムの長辺の一方を除いて三辺を熱融着により幅5mmで接着して、袋状のラミネート外装体を作製した。ラミネート外装体の一方の短辺より1cmの距離となるように上記電極積層体を挿入した。上記非水電解液を0.2g注液して真空含浸させた後、減圧下にて開口部を熱融着により幅5mmで封止することで、ラミネート型電池を作製した。
上記のように作製したラミネート型電池を、20℃にて5時間率(0.2C)相当の12mAの定電流で4.75Vまで充電した後、合計で8時間の4.75V定電圧充電を行ってから、1時間率(1C)相当の60mAで3.0Vまで定電流放電した。
初回充放電が終了したラミネート型電池を、1Cで4.75Vまで充電した後、合計で2.5時間の4.75V定電圧充電を行ってから、1Cで3.0Vまで定電流放電するという充放電サイクルを、45℃で300回繰り返した。初回放電容量に対する300サイクル後の放電容量の比率を容量維持率(%)として算出した。また、サイクル後のセル体積から初回充放電後のセル体積を差し引いて体積変化量(cc)を求め、体積変化量(cc)を初回放電容量(mAh)で除して得られる電池容量で規格化した体積変化量(cc/mAh)を算出した。体積は水中と空気中での重量差からアルキメデス法を用いて測定した。
アニリン誘導体として前記の2-メトキシアニリンを用いた以外は実施例1と同様の方法で二次電池を作製し、評価した。
アニリン誘導体として前記の2-メチルアニリンを用いた以外は実施例1と同様の方法で二次電池を作製し、評価した。
アニリン誘導体として前記の2-トリフルオロメチルアニリンを用いた以外は実施例1と同様の方法で二次電池を作製し、評価した。
アニリン誘導体を添加しなかった点以外は実施例1と同様の方法で二次電池を作製し、評価した。
2,5-ジメトキシアニリンに代えて、下記の無置換のアニリンを用いた以外は実施例1と同様の方法で二次電池を作製し、評価した。
2,5-ジメトキシアニリンに代えて、下記のペンタフルオロアニリンを用いた以外は実施例1と同様の方法で二次電池を作製し、評価した。
2,5-ジメトキシアニリンに代えて下記の2,5-ビス(トリフルオロメチル)アニリンを用いた以外は実施例1と同様の方法で二次電池を作製し、評価した。
2,5-ジメトキシアニリンに代えて下記の2,3,5-トリメチルアニリンを用いた以外は実施例1と同様の方法で二次電池を作製し、評価した。
2-トリフルオロメチルアニリン(2TFMA)の電解液への添加量を、電解液全質量中、0.05質量%とした以外は実施例4と同様の方法で二次電池を作製し、評価した。
2TFMAの添加量を、電解液全質量中、0.1質量%とした以外は実施例4と同様の方法で二次電池を作製し、評価した。
2TFMAの添加量を、電解液全質量中、0.3質量%とした以外は実施例4と同様の方法で二次電池を作製し、評価した。
2TFMAの添加量を、電解液全質量中、1.0質量%とした以外は実施例4と同様の方法で二次電池を作製し、評価した。
2TFMAの添加量を、電解液全質量中、1.5質量%とした以外は実施例4と同様の方法で二次電池を作製し、評価した。
ECと、DMCと、フッ素含有溶媒としてのH(CF2)2CH2OCF2CF2Hで表されるフッ素化エーテル(FE)と、O=P(OCH2CF3)3で表されるフッ素化リン酸エステル(FP)とを、EC:DMC:FE:FP=35:15:25:25(体積比)の比率で混合して非水溶媒を調製した。このときのフッ素含有溶媒の濃度は、非水溶媒全体積に対して50体積%である。この非水溶媒に、電解質として0.8mol/Lの濃度でLiPF6を溶解させた。この非水電解液を用いた以外は比較例1と同様の方法で二次電池を作製し、評価した。
非水電解液に2TFMAを、非水電解液全質量に対し0.5質量%溶解させた以外は比較例6と同様の方法で二次電池を作製し、評価した。
ECと、DMCと、フッ素含有溶媒としてのH(CF2)2CH2OCF2CF2Hで表されるフッ素化エーテル(FE)と、O=P(OCH2CF3)3で表されるフッ素化リン酸エステル(FP)とを、EC:DMC:FE:FP=30:10:20:40(体積比)の比率で混合して非水溶媒を調製した。このときのフッ素含有溶媒の濃度は、非水溶媒全体積に対して60体積%である。この非水溶媒に、電解質として0.8mol/Lの濃度でLiPF6を溶解させた。この非水電解液を用いた以外は比較例1と同様の方法で二次電池を作製し、評価した。
非水電解液に2TFMAを、非水電解液全質量に対し0.5質量%溶解させた非水電解液を用いた以外は比較例7と同様の方法で二次電池を作製し、評価した。
2 負極活物質層
3 正極集電体
4 負極集電体
5 セパレータ
6 ラミネート外装体
7 負極タブ
8 正極タブ
Claims (12)
- 前記式(1)中、置換基R1~R5に含まれる炭素の総数が1または2であることを特徴とする請求項1に記載の非水電解液。
- 前記式(1)で表されるアニリン誘導体に含まれるハロゲン原子は、フッ素であることを特徴とする請求項1または2に記載の非水電解液。
- 前記式(1)で表されるアニリン誘導体は、トリフルオロメチルアニリン、メトキシアニリン、および、メチルアニリンから選ばれる少なくとも一種であることを特徴とする請求項1~3のいずれか1項に記載の非水電解液。
- 前記式(1)で表されるアニリン誘導体の含有量は、非水電解液の全質量中、0.1質量%以上1質量%以下であることを特徴とする請求項1~4のいずれか1項に記載の非水電解液。
- 前記非水溶媒は、フッ素含有溶媒を含むことを特徴とする請求項1~5のいずれか1項に記載の非水電解液。
- 前記フッ素含有溶媒の含有量は、非水溶媒の全体積に対し、50体積%以上であることを特徴とする請求項6に記載の非水電解液。
- 前記フッ素含有溶媒は、フッ素化エーテル化合物およびフッ素化リン酸エステル化合物から選ばれる少なくとも一種を含むことを特徴とする請求項6または7に記載の非水電解液。
- 請求項1~8のいずれか1項に記載の非水電解液を有するリチウムイオン二次電池。
- さらに、リチウム金属に対して4.5V以上に動作電位を有する正極活物質を含む正極を有する、請求項9に記載のリチウムイオン二次電池。
- 前記正極活物質が、下記式(2)で表される請求項10に記載のリチウムイオン二次電池;
Lia(MxMn2-x-yAy)(O4-wZw) (2)
(式(2)中、0.4≦x≦1.2、0≦y、x+y<2、0≦a≦1.2、0≦w≦1であり、Mは、Co、Ni、Fe、CrおよびCuからなる群から選択される少なくとも一種であり、Aは、Li、B、Na、Mg、Al、Ti、Si、KおよびCaからなる群から選択される少なくとも一種であり、Zは、FおよびClの少なくとも一種である。)。
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