WO2014080871A1 - 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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- WO2014080871A1 WO2014080871A1 PCT/JP2013/081086 JP2013081086W WO2014080871A1 WO 2014080871 A1 WO2014080871 A1 WO 2014080871A1 JP 2013081086 W JP2013081086 W JP 2013081086W WO 2014080871 A1 WO2014080871 A1 WO 2014080871A1
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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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- 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
- 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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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- 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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- 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
- H01M2300/0037—Mixture of solvents
- H01M2300/0042—Four or more 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
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a lithium ion secondary battery.
- 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. Commonly used.
- the lithium ion secondary battery having such a positive electrode active material mainly uses a charge / discharge region of 4.2 V or less (hereinafter, a positive electrode having an operating potential of 4.2 V or less with respect to lithium metal is referred to as “4 V Sometimes referred to as “grade positive electrode”). Further, a carbon material such as graphite is used as the negative electrode active material.
- 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 to be a promising positive electrode material because it can improve the energy density by increasing the voltage.
- a positive electrode including a positive electrode active material (sometimes referred to as “5V class active material” or “5V class positive electrode active material”) exhibiting a high operating voltage of 4.5 V or higher with respect to lithium metal is referred to as a “5V class positive electrode. May also be described.
- a solvent having high oxidation resistance As a method for suppressing the oxidative decomposition of the electrolytic solution at the positive electrode at a high potential, it is conceivable to use a solvent having high oxidation resistance.
- a phosphoric acid ester containing fluorine as a halogen hereinafter referred to as a fluorinated phosphoric acid ester
- a fluorinated phosphoric acid ester contains 7 to 20% of the electrolytic solution solvent
- the electrolytic solution containing a chain ester or a cyclic ester has a withstand voltage. It is described that the solvent is high and has excellent self-extinguishing properties.
- Patent Document 2 discloses an electrolytic solution containing a fluorinated phosphate having a molecular chain terminal group structure of CF 2 H—, a cyclic carbonate having a carbon-carbon cage bond, and a cyclic compound having an S ⁇ O bond. It is described that the solvent is high and has excellent flame retardancy.
- the concentration of the fluorinated solvent in the electrolyte is as high as possible.
- increasing the concentration of the fluorinated solvent in the electrolytic solution lowers the ionic conductivity of the electrolytic solution, which makes it easier to obtain good charge / discharge characteristics at high temperatures, while charging / discharging characteristics at room temperature.
- the cycle characteristics at room temperature are deteriorated.
- a fluorinated solvent having high oxidation resistance may have reduced reduction resistance, and reductive decomposition at the negative electrode to form a high-resistance film is also a cause of deterioration in cycle characteristics at room temperature.
- One of the embodiments is as follows.
- R 1 and R 2 each independently represents a substituted or unsubstituted alkyl group.
- R 3 represents a substituted or unsubstituted alkylene group.
- the lithium ion secondary battery of this embodiment is A lithium ion secondary battery comprising a positive electrode and a nonaqueous electrolytic solution containing a nonaqueous electrolytic solvent,
- the positive electrode includes a positive electrode active material having an operating potential of 4.5 V or more with respect to lithium metal
- the non-aqueous electrolytic solvent is A fluorinated phosphate represented by the following formula (1); At least one selected from the group consisting of a sulfone compound represented by the following formula (2) and a sulfone compound represented by the following formula (3); Including 5% by volume or more of the sulfone compound is contained in the nonaqueous electrolytic solvent.
- R 1 , R 2 and R 3 each independently represents an alkyl group or a fluorinated alkyl group, and at least one of them is a fluorinated alkyl group
- R 1 and R 2 each independently represents a substituted or unsubstituted alkyl group
- R 3 represents a substituted or unsubstituted alkylene group.
- the non-aqueous electrolyte provided in the lithium ion secondary battery of the present embodiment includes a fluorinated phosphate ester represented by formula (1), a sulfone compound represented by formula (2), and a formula as a non-aqueous electrolyte solvent. And at least one selected from the group consisting of sulfone compounds represented by (3).
- the “nonaqueous electrolytic solvent” may be referred to as “nonaqueous solvent” or “solvent”.
- a fluorine-containing compound used as a nonaqueous electrolytic solvent may be referred to as “fluorinated solvent” or “fluorinated solvent”.
- the non-aqueous solvent includes a fluorinated phosphate ester represented by the following formula (1) (hereinafter sometimes simply referred to as “fluorinated phosphate ester”).
- R 1 , R 2 and R 3 each independently represents an alkyl group or a fluorinated alkyl group, and at least one of them is a fluorinated alkyl group).
- the fluorinated alkyl group is an alkyl group having at least one fluorine atom.
- R 1 , R 2 and R 3 each independently have 1 to 3 carbon atoms.
- At least one of R 1 , R 2 and R 3 is preferably a fluorinated alkyl group in which 50% or more of the hydrogen atoms of the corresponding unsubstituted alkyl group are substituted with fluorine atoms.
- all of R 1 , R 2 and R 3 are fluorinated alkyl groups, and 50% or more of the hydrogen atoms of the unsubstituted alkyl group to which R 1 , R 2 and R 3 correspond are substituted with fluorine atoms.
- the content of fluorine atoms is large, the voltage resistance is further improved, and even when a positive electrode active material that operates at a potential of 4.5 V or higher with respect to lithium is used, the deterioration of battery capacity after cycling is further reduced. Because it can.
- the ratio of the number of fluorine atoms to the total number of hydrogen atoms and fluorine atoms in the fluorinated alkyl group is more preferably 55% or more.
- Tris (2,2,2-trifluoroethyl) [Tris (2,2,2-trifluoroethyl) phosphate (TTFP)], tris (2,2,3,3-tetrafluoropropyl) phosphate [Tris (2,2 , 3,3-tetrafluoropropyl) phosphate], tris (3,3,3-trifluoropropyl) phosphate [Tris (3,3,3-trifluorofluoro) phosphate], Phosphate tris (2,2,3,3,3-pentafluoro-propyl) [Tris (2,2,3,3,3-pentafluoropropyl) phosphate] fluorinated alkyl phosphoric acid ester compounds and the like.
- Tris (2,2,2-trifluoroethyl) phosphate (TTFP) is preferable as the fluorinated phosphate compound. Fluorinated phosphates can be used alone or in combination of two or more.
- the content of the fluorinated phosphate is too much, the ionic conductivity decreases due to the increase in the viscosity of the electrolyte or the decrease in the dielectric constant, so that the internal resistance of the cell increases, and room temperature (about 20 ° C.) In some cases, the charge / discharge cycle characteristics of the battery deteriorate.
- the content of the fluorinated phosphate ester in the nonaqueous electrolytic solvent is preferably 5% by volume or more, preferably 10% by volume or more and 70% by volume or less, more preferably 10% by volume or more and 40% by volume or less, and more preferably 10% by volume or more.
- 30 volume% or less is more preferable, 13 volume% or more and 60 volume% or less are more preferable, and 16 volume% or more and 50 volume% or less are still more preferable.
- the nonaqueous electrolytic solvent is at least one selected from the group consisting of a sulfone compound represented by the following formula (2) and a sulfone compound represented by the following formula (3) (hereinafter simply referred to as “sulfone compound”). May be described.).
- R 1 and R 2 each independently represents a substituted or unsubstituted alkyl group.
- Examples of the sulfone compound represented by the formula (2) include ethyl methyl sulfone, ethyl isopropyl sulfone, ethyl isobutyl sulfone, dimethyl sulfone, and diethyl sulfone. Of these, dimethyl sulfone, ethyl methyl sulfone, ethyl isopropyl sulfone, and ethyl isobutyl sulfone are preferable, and dimethyl sulfone is more preferable.
- R 3 represents a substituted or unsubstituted alkylene group.
- the alkylene group preferably has 4 to 9 carbon atoms, and more preferably 4 to 6 carbon atoms.
- examples of the substituent include an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group), halogen atom (for example, chlorine atom, bromine atom, fluorine atom). Atom) and the like, and an alkyl group having 1 to 6 carbon atoms is more preferable.
- m is an integer of 1 to 6).
- m is an integer of 1 to 6, and preferably an integer of 1 to 3.
- Preferred examples of the cyclic sulfone compound represented by the formula (3) include tetramethylene sulfone (sulfolane), pentamethylene sulfone, hexamethylene sulfone and the like, and sulfolane is more preferable.
- Preferred examples of the cyclic sulfone compound having a substituent include 3-methylsulfolane and 2,4-dimethylsulfolane.
- the cyclic sulfone compound is excellent in oxidation resistance, gas generation in a high temperature cycle can be further suppressed. Since the chain sulfone compound has a low viscosity as a solvent, the room temperature cycle characteristics can be further improved.
- the sulfone compound is compatible with the fluorinated phosphate ester and has a relatively high dielectric constant, it has an advantage of being excellent in the dissolution / dissociation action of the lithium salt.
- the cycle characteristics at room temperature can be improved while suppressing gas generation at high temperature.
- cyclic carbonates such as ethylene carbonate (EC) and propylene carbonate (PC) have higher dielectric constants than sulfone compounds and are compatible with fluorinated phosphate esters. In the combination of only, room temperature cycle characteristics are low.
- the nonaqueous electrolytic solvent is described as a cyclic carbonate and / or a fluorinated ether represented by the formula (4) (hereinafter simply referred to as “fluorinated ether”) in addition to the fluorinated phosphate ester and the sulfone compound. More preferably).
- fluorinated ether represented by the formula (4)
- each compound will be described.
- the electrolytic solution preferably contains a cyclic carbonate as a nonaqueous electrolytic solvent.
- the cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC).
- a cyclic carbonate can be used individually by 1 type or in mixture of 2 or more types. Since EC and PC have a high dielectric constant and excellent electrolyte solubility, it is preferable that at least EC is contained, and further PC can be contained. Since PC has a high reactivity with the graphite negative electrode, if it is added in a large amount, gas generation at a high temperature may be increased or cycle characteristics may be deteriorated.
- the cyclic carbonate contained in the nonaqueous electrolytic solvent preferably contains EC and PC as main components (the total content of EC and PC is 80% by volume or more of the cyclic carbonate), and the volume ratio thereof.
- EC: PC 100: 0 to 40:60 is preferable
- EC: PC 100: 0 to 50:50 is more preferable.
- cyclic carbonate when it only describes as "cyclic carbonate", it shall differ from a fluorinated cyclic carbonate.
- the nonaqueous electrolytic solvent preferably contains a fluorinated ether represented by the following formula (4).
- the fluorinated ether represented by the formula (4) may be simply referred to as “fluorinated ether”.
- R 101 and R 102 each independently represents an alkyl group or a fluorinated alkyl group, and at least one of R 101 and R 102 is a fluorinated alkyl group).
- the total number of carbon atoms of R 101 and R 102 is preferably 10 or less.
- the alkyl group and the fluorinated alkyl group include linear or branched ones.
- the fluorinated ether is more preferably a compound represented by the following formula (4-2) from the viewpoint of voltage resistance and compatibility with other electrolytes.
- X 1- (CX 2 X 3 ) n -CH 2 O-CX 4 X 5 -CX 6 X 7 -X 8 (4-2) (In the formula (4-2), n is 1 to 7, and X 1 to X 8 are each independently a fluorine atom or a hydrogen atom, provided that at least one of X 1 to X 3 is a fluorine atom. And at least one of X 4 to X 8 is a fluorine atom).
- the fluorinated ether compound is more preferably represented by the following formula (4-3).
- n is 1, 2, 3 or 4.
- Y 1 to Y 8 are each independently a fluorine atom or a hydrogen atom. However, at least one of Y 1 to Y 4 is a fluorine atom, and at least one of Y 5 to Y 8 is a fluorine atom.
- n 2 or more, a plurality of Y 1 to Y 4 may be the same or different from each other.
- fluorinated ether examples include CF 3 OCH 3 , CF 3 OC 2 H 5 , F (CF 2 ) 2 OCH 3 , F (CF 2 ) 2 OC 2 H 5 , and CF 3 (CF 2 ).
- the content of the fluorinated ether compound represented by the formula (4) may be 0% by volume in the nonaqueous electrolytic solvent, preferably 20% by volume or more and 70% by volume or less, and 30% by volume or more and 60% by volume or less. It is preferably not more than volume%, more preferably not less than 40 volume% and not more than 60 volume%.
- the inclusion of fluorinated ethers has the advantage that the electrolytic solution has high oxidation resistance and low viscosity. On the other hand, because of its low dielectric constant, the dissociation property of the lithium salt is not sufficient, or with other non-aqueous solvents. The problem that compatibility is inferior may arise.
- the -OSO 2 -group may be in any direction.
- R 101 and R 102 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and n is 0, 1, 2, 3, or 4) .
- the cyclic sulfonate ester is preferably a cyclic disulfonate ester, and the cyclic disulfonate ester is preferably a compound represented by the following formula (5-2).
- R 201 to R 204 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and n is 1, 2, 3, or 4.
- n is 2 or more
- a plurality of R 203 may be the same or different from each other, and a plurality of R 204 may be the same or different from each other. .
- cyclic sulfonate ester examples include 1,3-propane sultone, 1,2-propane sultone, 1,4-butane sultone, 1,2-butane sultone, 1,3-butane sultone, 2,4-butane sultone, 1,3 -Monosulfonic acid esters such as pentane sultone (when X in formula (5) is a single bond), disulfonic acid esters such as methylenemethane disulfonic acid ester and ethylenemethane disulfonic acid ester (X in formula (5) is- OSO 2 - for group).
- 1,3-propane sultone (PS), 1,4-butane sultone (BS), and methylenemethane disulfonic acid ester (MMDS) are preferable from the viewpoints of film formation effect, availability, and cost.
- the cyclic disulfonic acid ester is characterized in that a good-quality film is easily formed on the negative electrode.
- the content of the cyclic sulfonic acid ester in the electrolytic solution is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and 0.2 to 3% by mass. Is more preferably 0.3 to 2% by mass. If the content is too low, the effect as a film cannot be obtained sufficiently. If the content is too high, the internal resistance may increase, or an excessive additive may react with the positive electrode to become a gas generation source.
- a compound containing N (SO 2 F) 2 anion (FSI anion) can be used as an additive of the electrolytic solution in the present embodiment.
- the FSI anion can form a film on both the negative electrode and the positive electrode.
- the FSI anion is generated when a compound containing the FSI anion is dissolved in the non-aqueous electrolyte.
- a salt of an FSI anion and an alkali metal is preferable, and examples thereof include LiFSI, NaFSI, and KFSI.
- LiFSI is more preferable because it also functions as an electrolyte of a lithium ion battery and can improve the ionic conductivity of the electrolytic solution.
- LiFSI is described as an example.
- a film of FSI anion is formed other than lithium salt, and is not limited to LiFSI.
- Fluorinated carbonate can be used as an additive for the electrolytic solution in the present embodiment.
- the fluorinated carbonate is a compound in which part or all of the hydrogen in the cyclic or chain carbonate is substituted with fluorine.
- the fluorinated carbonate can mainly form a film on the negative electrode.
- cyclic fluorinated carbonate easily forms a film on the negative electrode, and fluoroethylene carbonate and fluoropropylene carbonate are particularly preferable.
- the content of fluorinated carbonate in the nonaqueous electrolytic solution is preferably 5% by mass or less, preferably 3% by mass or less, and more preferably 0.1 to 3% by mass. Fluorinated carbonate tends to form a film on the negative electrode. When there is too much content of fluorinated carbonate, resistance may become large.
- the positive electrode in the present embodiment includes a positive electrode active material (5V class positive electrode 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 has a charge / discharge region at 4.5 V or higher with respect to lithium metal.
- a positive electrode including a positive electrode active material (5 V class positive electrode active material) having an operating potential of 4.5 V or higher with respect to lithium metal may be referred to as a “5 V class positive electrode”.
- the positive electrode active material contained in the 5V class positive electrode is preferably a lithium-containing composite oxide.
- the lithium-containing composite oxide 5V-class positive electrode active material 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, etc. Is mentioned.
- 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.
- Niobium electrode active material Although it does not restrict
- the negative electrode active material in addition to the carbon material, for example, a material that forms an alloy with Li, such as Si, Sn, and Al, a Si oxide, a Si composite oxide containing a metal element other than Si and Si, and a Sn oxide Sn composite oxides containing metal elements other than Sn and Sn, Li 4 Ti 5 O 12 , composite materials obtained by coating these materials with carbon, and the like can also be used.
- a negative electrode active material can be used individually by 1 type, and can also be used in combination of 2 or more type.
- a positive electrode active material layer is 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 (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 (binder), and a conductive support agent, for example.
- an aqueous binder in the production of the negative electrode.
- the water-based binder can reduce the binder concentration in the electrode mixture to 1 to 2% by mass, and is used together with an electrolytic solution using a fluorinated solvent that does not easily disturb the movement of lithium ions and easily decreases the ionic conductivity. Is more suitable.
- the CMC used in combination with the aqueous binder coats the negative electrode active material, thereby suppressing the reactivity between the fluorinated solvent and the negative electrode and improving the cycle characteristics.
- the concentration of the positive electrode binder is not particularly limited, but is preferably 1 to 10% by mass in the positive electrode mixture (in the total mass of the positive electrode active material forming the positive electrode active material layer, the positive electrode binder, and the conductive additive). 2-8% by mass is more preferred.
- 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 obtained, for example, by dispersing and kneading an active material, a binder (binder), and a conductive assistant in a solvent such as N-methyl-2-pyrrolidone (NMP) or water in a predetermined blending amount.
- NMP N-methyl-2-pyrrolidone
- the obtained slurry can be applied to a current collector to form an active material layer.
- the obtained electrode can be compressed to a suitable density by a method such as a roll press.
- 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 lithium ion secondary battery according to the present embodiment is not particularly limited.
- the lithium ion secondary battery has a configuration in which an electrode element in which a positive electrode and a negative electrode are opposed to each other and an electrolytic solution are included in an outer package. be able to.
- 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. By applying this negative electrode slurry on both sides of a 15 ⁇ m thick copper foil serving as a negative electrode current collector and drying at 125 ° C. for 10 minutes to evaporate NMP, a negative electrode active material layer is formed and further pressed. A negative electrode was produced. In addition, the weight of the negative electrode active material layer per unit area after drying was set to 0.013 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.
- the positive electrode slurry was applied to both surfaces of 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 producing a positive electrode.
- the weight of the positive electrode active material layer per unit area after drying was set to 0.035 g / cm 2 .
- Non-aqueous electrolyte EC, sulfolane (SL), and tris (2,2,2-trifluoroethyl phosphate) (hereinafter referred to as “FP1”) which is a fluorinated phosphate represented by O ⁇ P (OCH 2 CF 3 ) 3
- FP1 tris (2,2,2-trifluoroethyl phosphate
- non-aqueous solvent was prepared by mixing EC: SL: FP1 at a ratio of 30: 5: 65 (volume ratio). LiPF 6 was dissolved at a concentration of 1.0 mol / L as an electrolyte.
- the positive electrode and the negative electrode were cut into 1.5 cm ⁇ 3 cm.
- Four layers of the positive electrode and five layers of the negative electrode obtained were alternately stacked while sandwiching a polypropylene porous film as a separator.
- the ends of the positive electrode current collector not covered with the positive electrode active material and the negative electrode current collector not covered with the negative electrode active material are welded respectively, and further, the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are connected to the welded portion.
- Each was welded to obtain an electrode element having a planar laminated structure.
- the electrode element was wrapped with an aluminum laminate film as an outer package, and an electrolyte solution was injected therein, and then sealed while reducing the pressure to produce a secondary battery.
- Example 1 Comparative Example 1
- Table 1 shows the evaluation results of the battery characteristics of Comparative Examples 1-2 and Examples 1-5.
- Comparative Example 1 in which the solvent was cyclic carbonate (EC) and fluorinated phosphate ester (FP1), the cycle characteristics at 45 ° C. were good, but the capacity retention rate of the cycle characteristics at 20 ° C. was low.
- Comparative Example 2 where the solvent was composed of EC and a sulfone compound (SL), both characteristics at 20 ° C. and 45 ° C. were low.
- Examples 1 to 5 including EC, SL, and FP1 although the volume increase at 45 ° C. was slightly larger than that in Comparative Example 1, the capacity retention rate at 45 ° C. was good, and the capacity at 20 ° C.
- a secondary battery was fabricated and evaluated in the same manner as described above.
- a secondary battery was fabricated and evaluated in the same manner as described above.
- a secondary battery was prepared and evaluated in the same manner as in Example 1 except that.
- a secondary battery was prepared and evaluated in the same manner as in Example 1 except that.
- a secondary battery was prepared and evaluated in the same manner as in Example 1 except that.
- a secondary battery was prepared and evaluated in the same manner as in Example 1 except that.
- Table 2 shows the evaluation results of the battery characteristics of Comparative Examples 3 to 5 and Examples 6 to 9.
- Comparative Example 3 in which the nonaqueous electrolytic solvent was composed of EC and fluorinated ether (FE1), it was judged that the compatibility was low and a uniform solution could not be obtained, so that the evaluation was impossible.
- Comparative Example 4 in which the nonaqueous electrolytic solvent was composed of EC, fluorinated phosphate ester, and fluorinated ether, the characteristics at 45 ° C. were good, but the capacity retention rate at 20 ° C. cycle was low.
- Comparative Example 5 in which the nonaqueous electrolytic solvent is composed of EC, a sulfone compound (SL), and a fluorinated ether (FE1), the volume retention rate of the 20 ° C. cycle was relatively good, but the volume increase amount was slightly large. .
- Examples 6 to 9 including all of EC, sulfone compound (SL), fluorinated phosphate ester (FP1) and fluorinated ether (FE1) have high battery characteristics at 20 ° C. and 45 ° C., respectively, and temperature characteristics A battery with an excellent balance was obtained. Further, it was shown that the cyclic carbonate (EC) is more preferably 5 to 20% by volume, and the sulfone compound (SL) is more preferably 10 to 25% by volume.
- Table 3 shows the evaluation results of the battery characteristics of Examples 10 to 15. In both cases, the battery characteristics at 20 ° C. and 45 ° C. showed good values. It was suggested that the fluorinated phosphate ester (FP1) is more preferably 10 to 40% by volume in the nonaqueous electrolytic solvent, and further preferably 10 to 30% by volume. It was suggested that the fluorinated ether (FE1) is more preferably 30 to 60% by volume and more preferably 40 to 60% by volume in the nonaqueous electrolytic solvent.
- FP1 fluorinated phosphate ester
- FE1 fluorinated ether
- a secondary battery was prepared and evaluated in the same manner as in Example 1 except that the solvent was used.
- a secondary battery was produced in the same manner as in Example 1 and evaluated.
- a secondary battery was produced in the same manner as in Example 1 and evaluated.
- a secondary battery was produced in the same manner as in Example 1 and evaluated.
- Example 20 A secondary battery was prepared and evaluated in the same manner as in Example 12 except that 1% by mass of 1,3-propane sultone (PS) was added as an additive to the total electrolyte mass.
- PS 1,3-propane sultone
- Example 21 A secondary battery was produced and evaluated in the same manner as in Example 12 except that 1% by mass of methylenemethane disulfonic acid ester (MMDS) was added as an additive to the total electrolyte mass.
- MMDS methylenemethane disulfonic acid ester
- Example 22 A secondary battery was prepared and evaluated in the same manner as in Example 12 except that 1% by mass of LiFSI with respect to the total electrolyte mass was added as an additive.
- Example 23 A secondary battery was prepared and evaluated in the same manner as in Example 12 except that 1% by mass of monofluoroethylene carbonate (FEC) was added as an additive to the total electrolyte mass.
- FEC monofluoroethylene carbonate
- Example 24 A secondary battery was prepared and evaluated in the same manner as in Example 12 except that 0.5% by mass of PS and 0.5% by mass of MMDS were added as additives relative to the total electrolyte mass.
- Example 25 A secondary battery was produced and evaluated in the same manner as in Example 12 except that 0.5% by mass of PS and 0.5% by mass of LiFSI with respect to the total electrolyte mass were added as additives.
- Example 26 A secondary battery was prepared and evaluated in the same manner as in Example 12 except that 0.5% by mass of PS and 0.5% by mass of FEC were added as additives relative to the total electrolyte mass.
- Example 27 A secondary battery was prepared and evaluated in the same manner as in Example 12 except that 0.5% by mass of MMDS and 0.5% by mass of LiFSI were added as additives relative to the total electrolyte mass.
- Example 28 A secondary battery was produced and evaluated in the same manner as in Example 12 except that 0.5% by mass of MMDS and 0.5% by mass of FEC were added as additives relative to the total electrolyte mass.
- Example 29 A secondary battery was prepared and evaluated in the same manner as in Example 12 except that 0.5 mass% LiFSI and 0.5 mass% FEC were added as additives relative to the total electrolyte mass.
- Example 20 to 29 The evaluation results of the battery characteristics of Examples 20 to 29 are shown in Table 5. In any of Examples 20 to 29, the battery characteristics at 45 ° C. were higher than in Example 12. In any of Examples 20 to 29, the battery characteristics at 20 ° C. were good.
- the case of one type of additive the case of using cyclic disulfonic acid ester (MMDS) or LiFSI was particularly good.
- the addition of two types of additives tends to greatly improve the battery characteristics when added to one type.
- PS cyclic monosulfonate
- MMDS cyclic disulfonate
- PS or MMDS cyclic sulfonate
- PS cyclic sulfonic acid ester
- Example 30 A secondary battery was fabricated in the same manner as in Example 12, except that tris (2,2,3,3-tetrafluoropropyl) phosphate (FP2) was used instead of FP1 as the fluorinated phosphate ester. ,evaluated.
- FP2 tris (2,2,3,3-tetrafluoropropyl) phosphate
- Example 31 A secondary battery was prepared in the same manner as in Example 12, except that tris (2,2,3,3,3-pentafluoropropyl) phosphate (FP3) was used as the fluorinated phosphate ester instead of FP1. Prepared and evaluated.
- FP3 tris (2,2,3,3,3-pentafluoropropyl) phosphate
- Example 32 A secondary battery was prepared and evaluated in the same manner as in Example 12 except that CH 3 CH 2 O (CF 2 ) 4 F (FE2) was used as the fluorinated ether instead of FE1.
- Example 33 A secondary battery was prepared and evaluated in the same manner as in Example 12 except that CF 3 CHFCF 2 OCH 2 (CF 2 ) 2 F (FE3) was used as the fluorinated ether instead of FE1.
- Example 34 A secondary battery was prepared and evaluated in the same manner as in Example 12 except that dimethyl sulfone (DMS) was used instead of SL as the sulfone compound.
- DMS dimethyl sulfone
- Example 35 A secondary battery was prepared and evaluated in the same manner as in Example 12 except that ethyl methyl sulfone (EMS) was used instead of SL as the sulfone compound.
- EMS ethyl methyl sulfone
- Comparative Example 8 Comparative Example 4 except that LiCoPO 4 was used instead of LiNi 0.5 Mn 1.5 O 4 as the positive electrode active material, the upper limit voltage was 5.1 V, and the capacity retention rate after 100 cycles at 20 ° C. was evaluated. Secondary batteries were prepared and evaluated in the same manner.
- Example 12 Example 12 except that LiCoPO 4 was used instead of LiNi 0.5 Mn 1.5 O 4 as the positive electrode active material, the upper limit voltage was 5.1 V, and the capacity retention rate after 100 cycles at 20 ° C. was evaluated. Secondary batteries were prepared and evaluated in the same manner.
- Li (Li 0.15 Ni 0.2 Mn 0.65 ) O 2 was used instead of LiCoPO 4 as the positive electrode active material, the weight of the positive electrode active material layer per unit area was 0.025 g / cm 2 , and the upper limit A secondary battery was fabricated and evaluated in the same manner as in Comparative Example 8 except that the voltage was 4.7 V and the lower limit voltage was 2.5 V.
- Example 37 Li (Li 0.15 Ni 0.2 Mn 0.65 ) O 2 was used instead of LiCoPO 4 as the positive electrode active material, the weight of the positive electrode active material layer per unit area was 0.025 g / cm 2 , and the upper limit A secondary battery was prepared and evaluated in the same manner as in Example 36 except that the voltage was 4.7 V and the lower limit voltage was 2.5 V.
- Table 7 shows the capacity retention ratios after 100 cycles at 20 ° C. of Comparative Examples 8 and 9 and Examples 36 and 37.
- the positive electrode active material also contains both the sulfone compound (SL) and the fluorinated phosphate ester (FP1) in the olivine-type LiCoPO 4 or the layered structure Li (Li 0.15 Ni 0.2 Mn 0.65 ) O 2 . It was confirmed that the example had better 20 ° C. cycle characteristics. Therefore, it is considered that the present invention similarly shows an effect on the positive electrode having a high voltage of 4.5 V or more with respect to the Li metal regardless of the composition of the active material.
- SL sulfone compound
- FP1 fluorinated phosphate ester
- Example 38 SBR emulsions in which fine particles of styrene butadiene rubber (SBR) were emulsified and dispersed in water as a negative electrode binder and carboxymethyl cellulose sodium salt (CMC) as a thickener were prepared.
- the electrode slurry was prepared by dispersing and mixing with water so that the solid content ratio of graphite, SBR, and CMC was 97.5: 1.5: 1 (mass%), and applied to a current collector at 50 ° C.
- a secondary battery was prepared and evaluated in the same manner as in Example 12 except that the negative electrode obtained by drying at 100 ° C. for 10 minutes was used, and the negative electrode obtained by drying at 100 ° C. for 10 minutes was used.
- the 20 ° C. capacity retention rate was 90%
- the 45 ° C. capacity retention rate was 69%
- the 45 ° C. volume increase was 0.0932 cc.
- the battery characteristics of the aqueous binder were higher than those of Example 12 using PVDF as the negative electrode binder. The reason for this is that the binder concentration in the electrode can be lower than that of PVDF, so that lithium ions easily move, and the reaction between graphite and the by-product generated from the electrolyte and the positive electrode by coating CMC with graphite. It is conceivable that was suppressed.
- Example 39 (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. By applying this negative electrode slurry on both sides of a 15 ⁇ m thick copper foil serving as a negative electrode current collector and drying at 125 ° C. for 10 minutes to evaporate NMP, a negative electrode active material layer is formed and further pressed. A negative electrode was produced. In addition, the weight of the negative electrode active material layer per unit area after drying was set to 0.015 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.
- the positive electrode slurry was applied to both surfaces of 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 producing a positive electrode.
- the weight of the positive electrode active material layer per unit area after drying was set to 0.040 g / cm 2 .
- Non-aqueous electrolyte EC, PC (propylene carbonate), fluorinated ether FE1 represented by H (CF 2 ) 2 CH 2 OCF 2 CF 2 H, FP represented by O ⁇ P (OCH 2 CF 3 ) 3 ,
- a non-mixed mixture of a cyclic sulfone compound represented by C 4 H 8 SO 2 (sulfolane, SL) at a ratio of EC: PC: SL: FE1: FP 10: 10: 10: 40: 30 (volume ratio)
- An aqueous solvent was prepared. LiPF 6 was dissolved at a concentration of 0.8 mol / L as an electrolyte. In this electrolytic solution, 1 mass% of LiFSI as an additive was dissolved with respect to the total mass of the nonaqueous electrolytic solution to prepare a nonaqueous electrolytic solution.
- the positive electrode and the negative electrode were cut into 1.5 cm ⁇ 3 cm. Five layers of the obtained positive electrode and six layers of the negative electrode were alternately stacked while sandwiching a polypropylene porous film as a separator. The ends of the positive electrode current collector not covered with the positive electrode active material and the negative electrode current collector not covered with the negative electrode active material are welded respectively, and further, the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are connected to the welded portion. Each was welded to obtain an electrode element having a planar laminated structure. The electrode element was wrapped with an aluminum laminate film as an outer package, and an electrolyte solution was injected therein, and then sealed while reducing the pressure to produce a secondary battery.
- Example 40 A secondary battery was prepared and evaluated in the same manner as in Example 39 except that LiFSI was not added.
- Example 42 In place of the additive in Example 39, LiFSI was added in an amount of 0.5% by mass in the total mass of the non-aqueous electrolyte and MMDS was added in an amount of 0.5% by mass in the total mass of the non-aqueous electrolyte.
- a secondary battery was prepared and evaluated in the same manner as in Example 39.
- Example 50 A secondary battery was prepared and evaluated in the same manner as in Example 42 except that 1,3-propane sultone (PS) was used instead of MMDS as the cyclic sulfonate ester.
- PS 1,3-propane sultone
- Example 51 A secondary battery was prepared and evaluated in the same manner as in Example 42 except that 1,4-butane sultone (BS) was used instead of MMDS as the cyclic sulfonate ester.
- BS 1,4-butane sultone
- Table 10 shows the results of Examples 50 and 51.
Abstract
Description
前記正極は、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を含み、
前記非水電解溶媒は、
下記式(1)で表されるフッ素化リン酸エステルと、
下記式(2)で表されるスルホン化合物および下記式(3)で表されるスルホン化合物からなる群から選ばれる少なくとも1種と、
を含み、
前記スルホン化合物を非水電解溶媒中5体積%以上含むことを特徴とするリチウムイオン二次電池;
正極と、非水電解溶媒を含む非水電解液と、を備えるリチウムイオン二次電池であって、
前記正極は、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を含み、
前記非水電解溶媒は、
下記式(1)で表されるフッ素化リン酸エステルと、
下記式(2)で表されるスルホン化合物および下記式(3)で表されるスルホン化合物からなる群から選ばれる少なくとも1種と、
を含み、
前記スルホン化合物を非水電解溶媒中5体積%以上含む。
本実施形態のリチウムイオン二次電池が備える非水電解液は、非水電解溶媒として、式(1)で表されるフッ素化リン酸エステルと、式(2)で表されるスルホン化合物および式(3)で表されるスルホン化合物からなる群から選ばれる少なくとも1種と、を含む。なお、本明細書においては、「非水電解溶媒」のことを、「非水溶媒」、または「溶媒」と記載することもある。また、非水電解溶媒として用いられるフッ素を含有する化合物のことを、「フッ素化溶媒」または「フッ化溶媒」と記載することもある。
(式(4-1)中、n、mは、それぞれ独立に1~8である。X1~X6は、それぞれ独立に、フッ素原子または水素原子である。ただし、X1~X6の少なくとも1つはフッ素原子である。また、nが2以上のとき、複数個存在するX2およびX3は互いに独立であり、mが2以上のとき、複数個存在するX4およびX5は互いに独立である。)。
(式(4-2)中、nは1~7であり、X1~X8は、それぞれ独立に、フッ素原子または水素原子である。ただし、X1~X3の少なくとも1つはフッ素原子であり、X4~X8の少なくとも1つはフッ素原子である。)。
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(5V級正極活物質)を含む。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。なお、本明細書において、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(5V級正極活物質)を含む正極のことを「5V級正極」と記載することもある。
(式(6)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のうち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。黒鉛は人造黒鉛、天然黒鉛、非晶質炭素を被覆した黒鉛などを用いることができる。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(バインダー)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(バインダー)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。
本実施形態に係るリチウムイオン二次電池の構成は、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。
EC:エチレンカーボネート
PC:プロピレンカーボネート
DMC:ジメチルカーボネート
FE1:H(CF2)2CH2OCF2CF2H
FE2:CH3CH2O(CF2)4F
FE3:CF3CHFCF2OCH2(CF2)2F
FP1:O=P(OCH2CF3)3
FP2:リン酸トリス(2,2,3,3-テトラフルオロプロピル)
FP3:リン酸トリス(2,2,3,3,3―ペンタフルオロプロピル)
SL:C4H8SO2で表されるスルホラン
DMS:ジメチルスルホン
EMS:エチルメチルスルホン
(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の銅箔の両面に塗布して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0.013g/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のアルミニウム箔の両面に塗布後、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0.035g/cm2とした。
ECと、スルホラン(SL)と、O=P(OCH2CF3)3で表されるフッ素化リン酸エステルであるリン酸トリス(2,2,2-トリフルオロエチル)(以下、「FP1」と記載)とを、EC:SL:FP1=30:5:65(体積比)の比率で混合して非水溶媒を調製した。電解質として1.0mol/Lの濃度でLiPF6を溶解させた。
上記の正極と負極を1.5cm×3cmに切り出した。得られた正極の4層と負極の5層を、セパレータとしてのポリプロピレン多孔質フィルムを挟みつつ交互に重ねた。正極活物質に覆われていない正極集電体および負極活物質に覆われていない負極集電体の端部をそれぞれ溶接し、更にその溶接箇所にアルミニウム製の正極端子およびニッケル製の負極端子をそれぞれ溶接して、平面的な積層構造を有する電極素子を得た。上記電極素子を外装体としてのアルミニウムラミネートフィルムで包み、内部に電解液を注液した後、減圧しつつ封止することで二次電池を作製した。
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16mA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80mA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、20℃または45℃で250回繰り返した。初回放電容量に対する250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、初回充放電後と45℃250サイクル後のセル体積を求め、初回放電後と250サイクル後のセル体積の差から体積増加量(cc)を求めた。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。体積増加量は電池内部でのガス発生量を反映しており、小さいほど良い。なお、20℃サイクルではガス発生は非常に少ないため測定は行わなかった。
ECとSLとFP1とを、EC:SL:FP1=30:10:60(体積比)の比率で混合した非水溶媒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。
ECとSLとFP1とを、EC:SL:FP1=30:20:50(体積比)の比率で混合した非水溶媒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。
ECとSLとFP1とを、EC:SL:FP1=30:30:40(体積比)の比率で混合した非水溶媒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。
ECとSLとFP1とを、EC:SL:FP1=30:40:30(体積比)の比率で混合した非水溶媒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。
実施例1の非水溶媒に代えて、ECとFP1とをEC:FP1=30:70(体積比)の比率で混合した非水溶媒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。
実施例1の非水溶媒に代えて、ECとSLとをEC:SL=30:70(体積比)の比率で混合した非水溶媒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。
実施例1の非水溶媒に代えて、ECとH(CF2)2CH2OCF2CF2Hで表されるフッ素化エーテル(FE1)とを、EC:FE1=20:80(体積比)の比率で混合した非水溶媒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。
実施例1の非水溶媒に代えて、ECとFP1とFE1とを、EC:FP1:FE1=20:30:50(体積比)の比率で混合した非水溶媒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。
実施例1の非水溶媒に代えて、ECとSLとFE1とを、EC:SL:FE1=20:20:60(体積比)の比率で混合した非水溶媒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。
実施例1の非水溶媒に代えて、ECとSLとFP1とFE1とを、EC:SL:FP1:FE1=25:5:30:40(体積比)の比率で混合した非水溶媒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。
実施例1の非水溶媒に代えて、ECとSLとFP1とFE1とを、EC:SL:FP1:FE1=20:10:30:40(体積比)の比率で混合した非水溶媒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。
実施例1の非水溶媒に代えて、ECとSLとFP1とFE1とを、EC:SL:FP1:FE1=10:20:30:40(体積比)の比率で混合した非水溶媒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。
実施例1の非水溶媒に代えて、ECとSLとFP1とFE1とを、EC:SL:FP1:FE1=5:25:30:40(体積比)の比率で混合した非水溶媒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。
ECとSLとFP1とFE1とを、EC:SL:FP1:FE1=10:20:5:65(体積比)の比率で混合した非水溶媒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。
ECとSLとFP1とFE1とを、EC:SL:FP1:FE1=10:20:10:60(体積比)の比率で混合した非水溶媒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。
ECとSLとFP1とFE1とを、EC:SL:FP1:FE1=10:20:20:50(体積比)の比率で混合した非水溶媒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。
ECとSLとFP1とFE1とを、EC:SL:FP1:FE1=10:20:30:40(体積比)の比率で混合した非水溶媒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。
ECとSLとFP1とFE1とを、EC:SL:FP1:FE1=10:20:40:30(体積比)の比率で混合した非水溶媒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。
ECとSLとFP1とFE1とを、EC:SL:FP1:FE1=10:20:50:20(体積比)の比率で混合した非水溶媒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。
環状カーボネートとしてECとプロピレンカーボネート(PC)と、SLとFP1とFE1とを、EC:PC:SL:FP1:FE1=15:0:20:20:45(体積比)の比率で混合した非水溶媒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。
ECとPCとSLとFP1とFE1とを、EC:PC:SL:FP1:FE1=12:3:20:20:45(体積比)の比率で混合した非水溶媒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。
ECとPCとSLとFP1とFE1とを、EC:PC:SL:FP1:FE1=9:6:20:20:45(体積比)の比率で混合した非水溶媒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。
ECとPCとSLとFP1とFE1とを、EC:PC:SL:FP1:FE1=6:9:20:20:45(体積比)の比率で混合した非水溶媒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。
添加剤として、全電解液質量に対して1質量%の1,3-プロパンスルトン(PS)を加えた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
添加剤として、全電解液質量に対して1質量%のメチレンメタンジスルホン酸エステル(MMDS)を加えた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
添加剤として、全電解液質量に対して1質量%のLiFSIを加えた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
添加剤として、全電解液質量に対して1質量%のモノフルオロエチレンカーボネート(FEC)を加えた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
添加剤として、全電解液質量に対して0.5質量%のPSと0.5質量%のMMDSを加えた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
添加剤として、全電解液質量に対して0.5質量%のPSと0.5質量%のLiFSIを加えた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
添加剤として、全電解液質量に対して0.5質量%のPSと0.5質量%のFECを加えた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
添加剤として、全電解液質量に対して0.5質量%のMMDSと0.5質量%のLiFSIを加えた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
添加剤として、全電解液質量に対して0.5質量%のMMDSと0.5質量%のFECを加えた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
添加剤として、全電解液質量に対して0.5質量%のLiFSIと0.5質量%のFECを加えた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
非水電解溶媒として、環状カーボネートのECと鎖状カーボネートのジメチルカーボネート(DMC)とフッ素化リン酸エステル(FP1)とフッ素化エーテル(FE1)とを、EC:DMC:FP1:FE1=30:10:40:20(体積比)の比率で混合し、全電解液質量に対して0.67質量%のMMDSを加えた以外は、実施例1と同様の方法で二次電池を作製し、評価した。その結果、20℃容量維持率が90%、45℃容量維持率が63%、45℃体積増加量が0.302ccであり、20℃サイクル特性は高かったが、45℃サイクルの体積増加量が多かった。スルホン化合物を鎖状カーボネートに置き換えると、添加剤(環状ジスルホン酸エステル)を含んでいたとしても、ガス発生が顕著に増加することがわかった。このことから、溶媒としてスルホン化合物を含むことが好ましく、鎖状カーボネートは実質的に含まないことが好ましいことがわかった。
非水電解溶媒として、ECとFP1とFE1とを、EC:FP1:FE1=30:50:20(体積比)の比率で混合し、全電解液質量に対して3質量%のPSを加えた以外は、実施例1と同様の方法で二次電池を作製し、20℃サイクル特性を評価した。その結果、20℃容量維持率が35%と、環状スルホン酸エステル(PS)を3質量%添加しても、スルホン化合物を含んでいない場合は、20℃のサイクル特性が低かった。
フッ素化リン酸エステルとして、FP1に代えてリン酸トリス(2,2,3,3-テトラフルオロプロピル)(FP2)を用いた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
フッ素化リン酸エステルとして、FP1に変えてリン酸トリス(2,2,3,3,3―ペンタフルオロプロピル)(FP3)を用いた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
フッ素化エーテルとして、FE1に代えてCH3CH2O(CF2)4F(FE2)を用いた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
フッ素化エーテルとして、FE1に代えてCF3CHFCF2OCH2(CF2)2F(FE3)を用いた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
スルホン化合物として、SLに代えてジメチルスルホン(DMS)を用いた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
スルホン化合物として、SLに代えてエチルメチルスルホン(EMS)を用いた以外は、実施例12と同様の方法で二次電池を作製し、評価した。
正極活物質としてのLiNi0.5Mn1.5O4に代えてLiCoPO4を用い、上限電圧を5.1Vとし、20℃で100サイクル後の容量維持率を評価した以外は比較例4と同様の方法で二次電池を作製し、評価した。
正極活物質としてのLiNi0.5Mn1.5O4に代えてLiCoPO4を用い、上限電圧を5.1Vとし、20℃で100サイクル後の容量維持率を評価した以外は実施例12と同様の方法で二次電池を作製し、評価した。
正極活物質としてのLiCoPO4に代えてLi(Li0.15Ni0.2Mn0.65)O2を用い、単位面積当たりの正極活物質層の重量を0.025g/cm2とし、上限電圧を4.7V、下限電圧を2.5Vとした以外は比較例8と同様の方法で二次電池を作製し、評価した。
正極活物質としてのLiCoPO4に代えてLi(Li0.15Ni0.2Mn0.65)O2を用い、単位面積当たりの正極活物質層の重量を0.025g/cm2とし、上限電圧を4.7V、下限電圧を2.5Vとした以外は実施例36と同様の方法で二次電池を作製し、評価した。
負極バインダーとしてスチレンブタジエンゴム(SBR)の微粒子が水に乳化分散されたSBRエ系マルジョンと、増粘剤としてカルボキシメチルセルロースナトリウム塩(CMC)とを用意した。黒鉛とSBRとCMCの固形分比が、97.5:1.5:1(質量%)となるように、水とともに分散混合して電極スラリーを調整し、集電体に塗布して50℃で10分間乾燥させた後、100℃で10分乾燥させることによって得た負極を用いた以外は実施例12と同様の方法で二次電池を作製し、評価した。
EC:エチレンカーボネート
DMC:ジメチルカーボネート
FE1:H(CF2)2CH2OCF2CF2H
FE2:CH3CH2O(CF2)4F
FP:O=P(OCH2CF3)3
SL:C4H8SO2で表されるスルホラン
DMS:ジメチルスルホン
EMS:エチルメチルスルホン
EiPS:エチルイソプロピルスルホン
(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の銅箔の両面に塗布して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0.015g/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のアルミニウム箔の両面に塗布後、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0.040g/cm2とした。
ECと、PC(プロピレンカーボネート)と、H(CF2)2CH2OCF2CF2Hで表されるフッ素化エーテルFE1と、O=P(OCH2CF3)3で表されるFPと、C4H8SO2で表される環状スルホン化合物(スルホラン、SL)とを、EC:PC:SL:FE1:FP=10:10:10:40:30(体積比)の比率で混合した非水溶媒を調製した。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、添加剤としてLiFSIを、非水電解液の全質量に対し1質量%溶解させ、非水電解液を調製した。
上記の正極と負極を1.5cm×3cmに切り出した。得られた正極の5層と負極の6層を、セパレータとしてのポリプロピレン多孔質フィルムを挟みつつ交互に重ねた。正極活物質に覆われていない正極集電体および負極活物質に覆われていない負極集電体の端部をそれぞれ溶接し、更にその溶接箇所にアルミニウム製の正極端子およびニッケル製の負極端子をそれぞれ溶接して、平面的な積層構造を有する電極素子を得た。上記電極素子を外装体としてのアルミニウムラミネートフィルムで包み、内部に電解液を注液した後、減圧しつつ封止することで二次電池を作製した。
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16mA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80mA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、初回充放電後と300サイクル後のセル体積を求め、初回放電後に対する300サイクル後のセルの体積増加率(%)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。
LiFSIを添加しなかった以外は例39と同様の方法で二次電池を作製し、評価した。
例39のLiFSIに代えて、添加剤としてメチレンメタンジスルホン酸エステル(MMDS)を非水電解液の全質量中1質量%添加した以外は例39と同様の方法で二次電池を作製し、評価した。
例39の添加剤に代えて、添加剤として、LiFSIを非水電解液の全質量中0.5質量%とMMDSを非水電解液の全質量中0.5質量%とを添加した以外は実施例39と同様の方法で二次電池を作製し、評価した。
実施例42の非水溶媒に代えて、ECと、FE1と、FPと、SLとを、EC:SL:FE1:FP=10:20:40:30の体積比率で混合した非水溶媒を用いた以外は例42と同様の方法で二次電池を作製し、評価した。
フッ素化エーテルとして、FE1に代えて、CH3CH2O(CF2)4F(FE2)を用いた以外は例42と同様の方法で二次電池を作製し、評価した。
フッ素化エーテルとして、FE1に代えて、H(CF2)4CH2O(CF2)2Hを用いた以外は例42と同様の方法で二次電池を作製し、評価した。
フッ素化エーテルとして、FE1に代えて、CF3CHFCF2OCH2(CF2)2Fを用いた以外は例42と同様の方法で二次電池を作製し、評価した。
スルホン化合物として、SLに代えて、ジメチルスルホン(DMS)を用いた以外は例42と同様の方法で二次電池を作製し、評価した。
スルホン化合物として、SLに代えて、エチルメチルスルホン(EMS)を用いた以外は例42と同様の方法で二次電池を作製し、評価した。
スルホン化合物として、SLに代えて、エチルイソプロピルスルホン(EiPS)を用いた以外は例42と同様の方法で二次電池を作製し、評価した。
環状スルホン酸エステルとして、MMDSに代えて1,3―プロパンスルトン(PS)を用いた以外は例42と同様の方法で二次電池を作製し、評価した。
環状スルホン酸エステルとして、MMDSに代えて1,4-ブタンスルトン(BS)を用いた以外は例42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 (15)
- 正極と、非水電解溶媒を含む非水電解液と、を備えるリチウムイオン二次電池であって、
前記正極は、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を含み、
前記非水電解溶媒は、
下記式(1)で表されるフッ素化リン酸エステルと、
下記式(2)で表されるスルホン化合物および下記式(3)で表されるスルホン化合物からなる群から選ばれる少なくとも1種と、
を含み、
前記スルホン化合物を非水電解溶媒中5体積%以上含むことを特徴とするリチウムイオン二次電池;
- 前記非水電解溶媒は、さらに環状カーボネートを含むことを特徴とする請求項1又は2に記載のリチウムイオン二次電池。
- 前記非水電解溶媒において、前記環状カーボネート(CC)、前記スルホン化合物(SF)、前記フッ素化リン酸エステル(FP)、前記フッ素化エーテル(FE)の体積比率が、CC:SF:FP:FE=5~20:10~30:10~40:30~60(体積%)の範囲にあることを特徴とする請求項3に記載のリチウムイオン二次電池。
- 前記非水電解溶媒において、前記環状カーボネート(CC)、前記スルホン化合物(SF)、前記フッ素化リン酸エステル(FP)、前記フッ素化エーテル(FE)の体積比率が、CC:SF:FP:FE=5~15:15~25:10~30:40~60(体積%)の範囲にあることを特徴とする請求項3または4に記載のリチウムイオン二次電池。
- 前記スルホン化合物は、スルホランを含むことを特徴とする請求項1~5のいずれか一項に記載のリチウムイオン二次電池。
- 前記環状カーボネートは、エチレンカーボネート(EC)およびプロピレンカーボネート(PC)のうち少なくとも一方を含むことを特徴とする請求項3~6のいずれか一項に記載のリチウムイオン二次電池。
- 前記環状カーボネートにおいて、エチレンカーボネート(EC)およびプロピレンカーボネート(PC)の体積比率(体積%)が、EC:PC=100:0~50:50の範囲にあることを特徴とする請求項3~7のいずれか一項に記載のリチウムイオン二次電池。
- 前記非水電解液がさらに添加剤を含み、
前記添加剤が、環状モノスルホン酸エステル、環状ジスルホン酸エステル、N(SO2F)2アニオン(FSIアニオン)を含む化合物、およびフッ素化カーボネートから選ばれる少なくとも1種を含むことを特徴とする請求項1~8のいずれか一項に記載のリチウムイオン二次電池。 - 前記添加剤が、前記非水電解液の全質量に対して0.1~3質量%含まれることを特徴とする請求項9に記載のリチウムイオン二次電池。
- 前記添加剤が、1,3-プロパンスルトン、メチレンメタンジスルホン酸エステル、リチウムビス(フルオロスルホニル)イミド(LiFSI)、およびフルオロエチレンカーボネート(FEC)から選択される一種以上を含むことを特徴とする請求項9または10に記載のリチウムイオン二次電池。
- 前記添加剤が、環状モノスルホン酸エステル、環状ジスルホン酸エステル、N(SO2F)2アニオン(FSIアニオン)を含む化合物、およびフッ素化カーボネートから選ばれる2種以上の化合物を含むことを特徴とする請求項9~11のいずれか一項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(6)で表されることを特徴とする請求項1~12のいずれか一項に記載のリチウムイオン二次電池;
Lia(MxMn2-x-yAy)(O4-wZw) (6)
(式(6)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うちの少なくとも一種である。)。 - さらに負極を備え、
前記負極が、水系エマルジョンを用いた水系バインダーと、
カルボキシメチルセルロース(CMC)および/またはその誘導体とを含むことを特徴とする請求項1~13のいずれか一項に記載のリチウムイオン二次電池。 - 電極素子と電解液と外装体とを有するリチウムイオン二次電池の製造方法であって、
正極と、負極と、を対向配置して電極素子を作製する工程と、
前記電極素子と、非水電解溶媒を含む非水電解液とを外装体の中に封入する工程と、
を含み、
前記正極が、リチウムを吸蔵・放出することが可能で、リチウムに対して4.5V以上で動作する正極活物質を含み、
前記非水電解溶媒が、
式(1)で表されるフッ素化リン酸エステルと、
式(2)で表されるスルホン化合物および式(3)で表されるスルホン化合物からなる群から選ばれる少なくとも1種と、
を含み、前記スルホン化合物を非水電解溶媒中5体積%以上含むことを特徴とするリチウムイオン二次電池の製造方法;
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Also Published As
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JPWO2014080871A1 (ja) | 2017-01-05 |
CN104798245B (zh) | 2017-06-23 |
CN104798245A (zh) | 2015-07-22 |
EP2924796A4 (en) | 2016-05-18 |
JP6252486B2 (ja) | 2017-12-27 |
US10177413B2 (en) | 2019-01-08 |
US20150303521A1 (en) | 2015-10-22 |
EP2924796A1 (en) | 2015-09-30 |
EP2924796B1 (en) | 2018-04-18 |
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