WO2014007026A1 - 二次電池 - Google Patents
二次電池 Download PDFInfo
- Publication number
- WO2014007026A1 WO2014007026A1 PCT/JP2013/066007 JP2013066007W WO2014007026A1 WO 2014007026 A1 WO2014007026 A1 WO 2014007026A1 JP 2013066007 W JP2013066007 W JP 2013066007W WO 2014007026 A1 WO2014007026 A1 WO 2014007026A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- carbon atoms
- secondary battery
- negative electrode
- substituted
- Prior art date
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 43
- 125000003118 aryl group Chemical group 0.000 claims abstract description 43
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 30
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 7
- 125000003302 alkenyloxy group Chemical group 0.000 claims abstract description 7
- 125000005133 alkynyloxy group Chemical group 0.000 claims abstract description 7
- 125000000000 cycloalkoxy group Chemical group 0.000 claims abstract description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 98
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 63
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 62
- 229910052710 silicon Inorganic materials 0.000 claims description 47
- 239000010703 silicon Substances 0.000 claims description 46
- 125000001424 substituent group Chemical group 0.000 claims description 44
- 239000007773 negative electrode material Substances 0.000 claims description 43
- 239000008151 electrolyte solution Substances 0.000 claims description 41
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 26
- 239000003575 carbonaceous material Substances 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 20
- 125000002947 alkylene group Chemical group 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 150000002367 halogens Chemical class 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- 239000005001 laminate film Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000005248 alkyl aryloxy group Chemical group 0.000 claims description 6
- 125000002431 aminoalkoxy group Chemical group 0.000 claims description 6
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000005159 cyanoalkoxy group Chemical group 0.000 claims description 6
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 239000003125 aqueous solvent Substances 0.000 abstract description 5
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- -1 acetylenedicarboxylic acid ester Chemical class 0.000 description 88
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 43
- 239000002245 particle Substances 0.000 description 31
- 239000010410 layer Substances 0.000 description 24
- 229910052731 fluorine Inorganic materials 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 17
- 239000011737 fluorine Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 14
- 125000004093 cyano group Chemical group *C#N 0.000 description 14
- 239000010408 film Substances 0.000 description 14
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- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 238000006467 substitution reaction Methods 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000011883 electrode binding agent Substances 0.000 description 9
- IMAKHNTVDGLIRY-UHFFFAOYSA-N methyl prop-2-ynoate Chemical compound COC(=O)C#C IMAKHNTVDGLIRY-UHFFFAOYSA-N 0.000 description 9
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 125000001153 fluoro group Chemical group F* 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
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- 239000010439 graphite Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
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- 239000005977 Ethylene Substances 0.000 description 4
- 239000004962 Polyamide-imide Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- MLTWWHUPECYSBZ-UHFFFAOYSA-N ethene-1,1,2-triol Chemical group OC=C(O)O MLTWWHUPECYSBZ-UHFFFAOYSA-N 0.000 description 4
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
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- 239000002033 PVDF binder Substances 0.000 description 3
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- 229910003002 lithium salt Inorganic materials 0.000 description 3
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
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- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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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
- 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
-
- 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
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- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a secondary battery, particularly a lithium ion secondary battery.
- Non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries have already been put to practical use as batteries for notebook computers and mobile phones due to their advantages such as high energy density, low self-discharge, and excellent long-term reliability. Yes.
- electronic devices have been enhanced in functionality and used in electric vehicles, and the development of secondary batteries with higher energy density has been demanded.
- a chemical reaction or decomposition of the electrolyte layer may occur on the electrode surface of the positive electrode and / or the negative electrode.
- problems such as deterioration of storage characteristics of the battery at high temperature, deterioration of cycle characteristics of the secondary battery, and generation of gas due to decomposition products.
- a compound having a protective film generating function is added to the electrolytic solution contained in the electrolyte layer.
- a protective function that intentionally promotes the decomposition of the compound added to the electrolyte solution on the negative electrode active material surface during initial charging and prevents the decomposition of the new electrolyte layer.
- a film that is, SEI (Solid Electrolyte Interface) is formed. And by forming this protective film, it is reported that the chemical reaction and decomposition of the electrolyte layer on the electrode surface in the negative electrode are appropriately suppressed, and as a result, there is an effect of maintaining the battery performance of the secondary battery. ing.
- protective film forming additives include oxygen-containing aliphatic compounds having an alkynyl group and / or alkynylene group (Patent Document 1), acetylenedicarboxylic acid ester (Patent Document 2), dimethyl 2,4-hexadiynedioate, and vinylene carbonate. And / or utilizing 1,3-propane sultone (Patent Document 3), LiBF 4 and acetylenedicarboxylic acid diester (Patent Document 4) is disclosed.
- the capacity may be significantly reduced along with the charge / discharge cycle.
- the secondary battery when the battery is charged and discharged in a high temperature environment, the secondary battery may swell, and deterioration of cycle characteristics may be a problem.
- an object of the present invention is to provide a secondary battery having excellent cycle characteristics under a high temperature environment.
- a first embodiment of the present invention is a secondary battery having an electrode element in which a positive electrode and a negative electrode are arranged to face each other and an electrolyte solution, wherein the negative electrode active material is a metal that can be alloyed with lithium, and / or A carbonyl compound represented by the following formula (1), which contains a metal oxide capable of inserting and extracting lithium ions, and wherein the electrolyte is a non-aqueous electrolyte in which an electrolyte salt is dissolved in a non-aqueous solvent.
- the present invention relates to a secondary battery comprising:
- two R 1 s may be the same or different, and each independently of one another, a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a substituted or unsubstituted aromatic group, Group, the following formula (2):
- R 21 represents an alkylene group having 1 to 6 carbon atoms
- R 22 represents a hydrocarbon group having 1 to 12 carbon atoms
- n represents an integer of 1 to 10.
- R 21 represents an alkylene group having 1 to 6 carbon atoms
- R 22 represents a hydrocarbon group having 1 to 12 carbon atoms
- n represents an integer of 1 to 10
- the second embodiment of the present invention relates to an assembled battery having a plurality of secondary batteries according to the first embodiment of the present invention.
- the third embodiment of the present invention relates to a vehicle on which the secondary battery of the first embodiment of the present invention or the assembled battery of the second embodiment of the present invention is mounted as a motor driving power source.
- the carbonyl compound represented by the general formula (1) is reduced on the negative electrode surface during the charging process, and is deposited on the negative electrode surface to form a film (electrode protective film).
- the carbonyl compound represented by the general formula (1) has a higher reactivity than carbonate or the like used as an electrolyte solvent, and forms a film by reductive decomposition on the negative electrode surface first. Decomposition can be suppressed.
- the formed product has high lithium ion conductivity, it does not cause a decrease in charge / discharge rate (a decrease in charge / discharge rate characteristics).
- the film formed of the carbonyl compound represented by the general formula (1) partially forms a polymer (organic polymer), a strong film is formed. That is, the film formed of the carbonyl compound represented by the general formula (1) has high lithium ion conductivity, and is a strong material that does not collapse with charge / discharge of the active material.
- Negative electrode As the negative electrode, for example, a negative electrode active material formed by binding a negative electrode current collector with a negative electrode binder and providing a negative electrode active material layer on the current collector can be used. .
- the negative electrode active material layer is formed by, for example, applying a coating liquid obtained by slurrying a negative electrode active material, a binder, and various auxiliary agents as necessary with a solvent to a current collector, and then drying. Can be manufactured.
- the negative electrode active material in the present embodiment includes a metal that can be alloyed with lithium and / or a metal oxide that can occlude and release lithium ions.
- metals that can be alloyed with lithium examples include Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, and alloys of two or more thereof. Is mentioned. Two or more of these metals or alloys may be used in combination. These metals or alloys may contain one or more non-metallic elements.
- silicon single silicon is preferable.
- Examples of the metal oxide that can occlude and release lithium ions include silicon oxide, aluminum oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, and composites thereof. Two or more of these metal oxides may be used in combination. In addition, one or more elements selected from nitrogen, boron and sulfur may be added to the metal oxide, for example, 0.1 to 5% by mass. Silicon oxide (silicon oxide) is preferable as the metal oxide capable of inserting and extracting lithium ions of the negative electrode active material.
- the negative electrode active material in the present embodiment preferably contains silicon (silicon) and / or silicon oxide (silicon oxide).
- the silicon oxide is not particularly limited, but is represented by, for example, SiOx (0 ⁇ x ⁇ 2).
- the silicon oxide may contain Li, and the silicon oxide containing Li is represented by, for example, SiLiyOz (y> 0, 2> z> 0).
- the silicon oxide may contain a trace amount of a metal element or a nonmetal element.
- the silicon oxide can contain, for example, 0.1 to 5% by mass of one or more elements selected from nitrogen, boron and sulfur. By containing a trace amount of a metal element or a nonmetal element, the electrical conductivity of the silicon oxide can be improved. Further, the silicon oxide may be crystalline or amorphous.
- the negative electrode active material preferably contains a carbon material capable of inserting and extracting lithium ions in addition to silicon and / or silicon oxide.
- the carbon material can also be contained in a composite state with silicon or silicon oxide. Similar to silicon oxide, the carbon material has the role of relaxing expansion and contraction due to repeated charge and discharge of the negative electrode active material itself and ensuring conduction between silicon as the negative electrode active material. Therefore, better cycle characteristics can be obtained by the coexistence of silicon, silicon oxide, and carbon material.
- the carbon material graphite, amorphous carbon, diamond-like carbon, carbon nanotube, or a composite thereof can be used.
- graphite with high crystallinity has high electrical conductivity, and is excellent in adhesion to a current collector made of a metal such as copper and voltage flatness.
- amorphous carbon having low crystallinity has a relatively small volume expansion, it has a high effect of relaxing the volume expansion of the entire negative electrode, and deterioration due to non-uniformity such as crystal grain boundaries and defects hardly occurs.
- the content of the carbon material in the negative electrode active material is preferably 2% by mass or more and 50% by mass or less, and more preferably 2% by mass or more and 30% by mass or less.
- Examples of a method for producing a negative electrode active material containing silicon and silicon oxide include a method in which simple silicon and silicon oxide are mixed and sintered under high temperature and reduced pressure. Furthermore, in addition to the method for producing the negative electrode active material, it can be combined with carbon. For example, a method of introducing a mixed sintered product of simple silicon and silicon oxide into a gas atmosphere of an organic compound in a high temperature non-oxygen atmosphere, and a mixed sintered product of simple silicon and silicon oxide in a high temperature non-oxygen atmosphere By a method of mixing a carbon precursor resin, a coating layer made of carbon can be formed around the core of simple silicon and silicon oxide. Thereby, the suppression of volume expansion with respect to charging / discharging and the further improvement effect of cycling characteristics are acquired.
- silicon is used as the negative electrode active material in the present embodiment, it is preferably made of a composite containing silicon, silicon oxide and carbon material (hereinafter also referred to as Si / SiO / C composite).
- the silicon oxide having an amorphous structure can suppress the volume expansion of a carbon material or silicon which is another negative electrode active material. Although this mechanism is not clear, it is presumed that the formation of a film on the interface between the carbon material and the electrolytic solution has some influence due to the amorphous structure of silicon oxide.
- the amorphous structure is considered to have relatively few elements due to non-uniformity such as crystal grain boundaries and defects. Note that it can be confirmed by X-ray diffraction measurement (general XRD measurement) that all or part of silicon oxide has an amorphous structure. Specifically, when silicon oxide does not have an amorphous structure, a peak peculiar to silicon oxide is observed, but when all or part of silicon oxide has an amorphous structure, silicon oxide is observed. A unique peak is observed as a broad peak.
- the Si / SiO / C composite it is preferable that all or part of silicon is dispersed in silicon oxide.
- silicon oxide By dispersing at least a part of silicon in silicon oxide, volume expansion as a whole of the negative electrode can be further suppressed, and decomposition of the electrolytic solution can also be suppressed.
- all or part of silicon is dispersed in the silicon oxide because transmission electron microscope observation (general TEM observation) and energy dispersive X-ray spectroscopy measurement (general EDX measurement). It can confirm by using together. Specifically, the cross section of the sample is observed, the oxygen concentration of the silicon portion dispersed in the silicon oxide is measured, and it can be confirmed that the sample is not an oxide.
- the Si / SiO / C composite for example, all or part of silicon oxide has an amorphous structure, and all or part of silicon is dispersed in silicon oxide.
- a Si / SiO / C composite can be produced, for example, by a method disclosed in Japanese Patent Application Laid-Open No. 2004-47404. That is, the Si / SiO / C composite can be obtained, for example, by performing a CVD process on silicon oxide in an atmosphere containing an organic gas such as methane gas.
- the Si / SiO / C composite obtained by such a method has a form in which the surface of particles made of silicon oxide containing silicon is coated with carbon. Silicon is nanoclustered in silicon oxide.
- the ratio of silicon, silicon oxide and carbon material is not particularly limited.
- Silicon is preferably 5% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 50% by mass or less with respect to the Si / SiO / C composite.
- the silicon oxide is preferably 5% by mass or more and 90% by mass or less, and more preferably 40% by mass or more and 70% by mass or less with respect to the Si / SiO / C composite.
- the carbon material is preferably 2% by mass or more and 50% by mass or less, and more preferably 2% by mass or more and 30% by mass or less with respect to the Si / SiO / C composite.
- the Si / SiO / C composite can be composed of a mixture of simple silicon, silicon oxide and carbon material, and can also be produced by mixing simple silicon, silicon oxide and carbon material by mechanical milling. it can.
- the Si / SiO / C composite can be obtained by mixing particulate silicon, silicon oxide and carbon materials.
- the average particle diameter of simple silicon can be made smaller than the average particle diameter of the carbon material and the average particle diameter of the silicon oxide.
- single silicon having a large volume change during charge / discharge has a relatively small particle size, and carbon materials and silicon oxides having a small volume change have a relatively large particle size. Is more effectively suppressed.
- lithium is occluded and released in the order of large-diameter particles, small-diameter particles, and large-diameter particles during the charge / discharge process. This also suppresses the occurrence of residual stress and residual strain. Is done.
- the average particle size of the single silicon can be, for example, 20 ⁇ m or less, and is preferably 15 ⁇ m or less.
- the average particle diameter of silicon oxide is preferably 1/2 or less of the average particle diameter of the carbon material, and the average particle diameter of simple silicon is 1/2 or less of the average particle diameter of silicon oxide. preferable. Furthermore, it is more preferable that the average particle diameter of the silicon oxide is 1/2 or less of the average particle diameter of the carbon material, and the average particle diameter of the simple silicon is 1/2 or less of the average particle diameter of the silicon oxide. . By controlling the average particle diameter in such a range, the effect of relaxing the volume expansion can be obtained more effectively, and a secondary battery excellent in the balance between energy density, cycle life and efficiency can be obtained.
- the average particle diameter of silicon oxide is 1 ⁇ 2 or less of the average particle diameter of graphite, and the average particle diameter of simple silicon is 1 ⁇ 2 or less of the average particle diameter of silicon oxide.
- the average particle diameter of the single silicon can be, for example, 20 ⁇ m or less, and is preferably 15 ⁇ m or less.
- the negative electrode active material a material obtained by treating the surface of the above-mentioned Si / SiO / C composite with a silane coupling agent may be used.
- the binder for the negative electrode is not particularly limited.
- polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer Rubber, polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamideimide and the like can be used.
- polyimide, polyamideimide, polyacrylic acid (including lithium salt, sodium salt and potassium salt neutralized with alkali), carboxymethylcellulose (lithium salt neutralized with alkali) due to its strong binding properties , Sodium salts and potassium salts) are preferred.
- the amount of the binder for the negative electrode to be used is preferably 5 to 25 parts by mass with respect to 100 parts by mass of the negative electrode active material from the viewpoints of “sufficient binding force” and “high energy” which are in a trade-off relationship. .
- the material for the current collector of the negative electrode a known material can be arbitrarily used, but for example, a metal material such as copper, nickel, SUS or the like is used. Among these, copper is particularly preferable from the viewpoint of ease of processing and cost.
- the current collector is preferably subjected to a roughening treatment in advance.
- the shape of the current collector is also arbitrary, and examples thereof include a foil shape, a flat plate shape, and a mesh shape. Also, a perforated current collector such as expanded metal or punching metal can be used.
- the preferable thickness and shape when using a thin film as the current collector are also arbitrary.
- the negative electrode can be produced by forming a negative electrode active material layer containing a negative electrode active material and a negative electrode binder on a negative electrode current collector.
- the method for forming the negative electrode active material layer include a doctor blade method, a die coater method, a CVD method, and a sputtering method.
- a thin film of aluminum, nickel, or an alloy thereof may be formed by a method such as vapor deposition or sputtering to form a negative electrode current collector.
- the positive electrode is formed, for example, by binding a positive electrode active material so as to cover the positive electrode current collector with a positive electrode binder.
- lithium manganate having a layered structure such as LiMnO 2 , Li x Mn 2 O 4 (0 ⁇ x ⁇ 2) or lithium manganate having a spinel structure; LiCoO 2 , LiNiO 2 or a transition metal thereof Lithium transition metal oxides in which a specific transition metal such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 does not exceed half the lithium transition metal oxides; In which Li is made excessive in comparison with the stoichiometric composition.
- a positive electrode active material can be used individually by 1 type or in combination of 2 or more types.
- the same negative electrode binder can be used.
- polyvinylidene fluoride is preferable from the viewpoint of versatility and low cost.
- the amount of the positive electrode binder used is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material from the viewpoints of “sufficient binding force” and “higher energy” which are in a trade-off relationship. .
- the positive electrode current collector the same as the negative electrode current collector can be used.
- a conductive auxiliary material may be added to the positive electrode active material layer containing the positive electrode active material for the purpose of reducing impedance.
- the conductive auxiliary material include carbonaceous fine particles such as graphite, carbon black, and acetylene black.
- Electrolytic Solution is a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent. And the electrolyte solution in this embodiment contains the carbonyl compound shown by following formula (1).
- two R 1 s may be the same or different, and each independently of one another, a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a substituted or unsubstituted aromatic group, Group, the following formula (2):
- R 21 represents an alkylene group having 1 to 6 carbon atoms
- R 22 represents a hydrocarbon group having 1 to 12 carbon atoms
- n represents an integer of 1 to 10.
- R 21 represents an alkylene group having 1 to 6 carbon atoms
- R 22 represents a hydrocarbon group having 1 to 12 carbon atoms
- n represents an integer of 1 to 10
- R 1 is an unsubstituted alkyl group, it may be a linear alkyl group or a branched alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, Examples include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, n-hexyl and the like.
- R 1 is an alkyl group having a substituent
- the alkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms. It is.
- —NR 11 R 12 halogen and —CN are preferable.
- R 11 and R 12 are each independently H or an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, preferably at least one of R 11 and R 12 , more preferably both are It is an alkyl group.
- the number of carbon atoms in R 11 and R 12 are not included in the number of carbon atoms in the alkyl group, include the carbon number of R 11 and R 12, it is also preferable that the above-mentioned number of carbon atoms.
- halogen of the substituent examples include fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine, bromine, more preferably fluorine and chlorine, and particularly preferably fluorine.
- the number of halogen substitutions is not limited, and the position of substitution is not particularly limited, but at least at the terminal of the alkyl group is preferably 1 substitution, preferably 2 or 3 substitution.
- the substitution position is not particularly limited, but it is preferably substituted at the end of the alkyl group.
- alkyl group whose substituent is —NR 11 R 12, that is, an aminoalkyl group include, for example, N, N-diethylaminobutyl, N, N-diethylaminopropyl, N, N-diethylaminoethyl, N, N— Examples include diethylaminomethyl, N, N-dimethylaminobutyl, N, N-dimethylaminopropyl, N, N-dimethylaminoethyl, N, N-dimethylaminomethyl, N-methylaminomethyl and the like.
- alkyl group in which the substituent is halogen that is, a haloalkyl group
- a fluoroalkyl group for example, —CF 2 CF 3 , —CF 2 CF 2 H, —CFHCF 3 , —CH 2 CF 3 , —CHFCF 2 H, — CH 2 CF 2 H, —CH 2 CFH 2 , —CH 2 CH 2 CF 3 , —CH 2 CFHCF 3 , —CH 2 CF 2 CF 3 , —CH 2 CH 2 CH 2 CF 3 etc.
- chloroalkyl group examples thereof include chlorobutyl, chloropropyl, chloroethyl, chloromethyl), bromoalkyl groups (for example, bromobutyl, bromopropyl, bromoethyl, bromomethyl) and the like.
- alkyl group whose substituent is —CN, ie, a cyanoalkyl group examples include cyanoethyl, cyanopropyl, cyanobutyl, cyanopentyl, cyanohexyl and the like.
- R 1 is a cycloalkyl group
- a cycloalkyl group having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms is preferred, and specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. .
- R 1 is an alkenyl group
- an alkenyl group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms is preferable, and examples thereof include vinyl, 1-propenyl, 2-propenyl, 2-butenyl and the like. .
- R 1 is an alkynyl group
- an alkynyl group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms is preferable, and examples thereof include acetylenyl, 1-propynyl, 2-propynyl, and 2-butynyl. .
- R 1 is a substituted or unsubstituted aromatic group, for example, it is preferably an aryl group, an arylalkyl group, or an alkylaryl group, preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. Is an aromatic group.
- the aromatic group may be unsubstituted or may have a substituent.
- the aromatic group has a substituent, it has a halogen such as —CN, fluorine and chlorine (particularly preferred is fluorine) on the aromatic ring as the substituent. It is preferable.
- a halogen such as a cyano group or fluor
- R 21 is an alkylene group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, more preferably ethylene or propylene, particularly preferably ethylene;
- R 22 is an alkyl group having 1 to 12 carbon atoms, preferably 1 to 7 carbon atoms, or an aryl group having 6 to 12 carbon atoms, particularly preferably a linear alkyl group having 1 to 7 carbon atoms;
- n is an integer of 1 to 10, preferably 1 to 4.
- the alkylene structure of R 21 may be bonded at any position such as propane-1,2-diyl, propane-1,3-diyl and the like.
- R 1 is an unsubstituted alkoxy group, it may be a linear alkoxy group or a branched alkoxy group, preferably an alkoxy group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. Methoxy, ethoxy, propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, n-hexoxy group and the like. In addition, an alkoxy group having 7 to 12 carbon atoms may be preferable.
- R 1 is an alkoxy group having a substituent
- the alkoxy group having a substituent when expressed as -O-R 2b, is preferred
- R 2b is an "alkyl group having a substituent" of the aforementioned . That is, the alkoxy group having a substituent is preferably an alkoxy group having 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.
- the substituent —NR 11 R 12 , halogen and —CN are preferable.
- R 11 and R 12 are each independently H or an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, preferably at least one of R 11 and R 12 , more preferably both are It is an alkyl group.
- the number of carbon atoms in R 11 and R 12 are not included in the number of carbon atoms in the alkoxy groups, include a number of carbon atoms in R 11 and R 12, it is also preferable that the above-mentioned number of carbon atoms.
- halogen of the substituent examples include fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine, bromine, more preferably fluorine and chlorine, and particularly preferably fluorine.
- the number of halogen substitutions is not limited, and the position of substitution is not particularly limited, but at least at the terminal of the alkyl group is preferably 1 substitution, preferably 2 or 3 substitution.
- the substitution position is not particularly limited, but it is preferably substituted at the end of the alkyl group.
- alkoxy group in which the substituent is —NR 11 R 12 that is, an aminoalkoxy group
- an aminoalkoxy group include, for example, N, N-diethylaminobutoxy, N, N-diethylaminopropoxy, N, N-diethylaminoethoxy, N, N— Examples include diethylaminomethoxy, N, N-dimethylaminobutoxy, N, N-dimethylaminopropoxy, N, N-dimethylaminoethoxy, N, N-dimethylaminomethoxy and the like.
- alkoxy group in which the substituent is halogen that is, a haloalkoxy group
- a fluoroalkoxy group for example, —OCF 2 CF 3 , —OCF 2 CF 2 H, —OCHFCF 3 , —OCH 2 CF 3 , —OCHFCF 2 H, —OCH 2 CF 2 H, —OCH 2 CFH 2 , —OCH 2 CH 2 CF 3 , —OCH 2 CFHCF 3 , —OCH 2 CF 2 CF 3 , —OCH 2 CH 2 CH 2 CF 3 etc.), chloroalkoxy group (For example, chlorobutoxy, chloropropoxy, chloroethoxy, chloromethoxy), bromoalkoxy groups (for example, bromobutoxy, bromopropoxy, bromoethoxy, bromomethoxy) and the like can be mentioned.
- alkoxy group whose substituent is —CN that is, a cyanoalkoxy group
- examples of the alkoxy group whose substituent is —CN include cyanoethoxy, cyanopropoxy, cyanobutoxy, cyanopentoxy, cyanohexoxy and the like.
- R 1 is a cycloalkyloxy group
- a cycloalkyloxy group having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms is preferable, and specifically, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyl Oxy and the like can be mentioned.
- R 1 is an alkenyloxy group
- an alkenyloxy group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms is preferable, and examples thereof include vinyloxy, 1-propenyloxy, 2-propenyloxy, 2-butenyloxy and the like. Can be mentioned.
- R 1 is an alkynyloxy group
- an alkynyloxy group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms is preferable.
- acetylenyloxy, 1-propynyloxy, 2-propynyloxy, 2- Butynyloxy and the like can be mentioned.
- R 1 is a substituted or unsubstituted aromatic oxy group, it is preferably, for example, an aryloxy group, an arylalkoxy group, or an alkylaryloxy group, preferably 6 to 18 carbon atoms, more preferably a carbon number 6 to 12 aromatic oxy groups.
- the aromatic oxy group may be unsubstituted or may have a substituent.
- a halogen such as —CN, fluorine and chlorine (especially fluorine is preferred), etc., is substituted on the aromatic ring. It is preferable to have.
- a halogen such as a cyano group or fluor
- R 21 is an alkylene group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, more preferably ethylene or propylene, particularly preferably ethylene;
- R 22 is an alkyl group having 1 to 12 carbon atoms, preferably 1 to 7 carbon atoms, or an aryl group having 6 to 12 carbon atoms, particularly preferably a linear alkyl group having 1 to 7 carbon atoms;
- n is an integer of 1 to 10, preferably 1 to 4.
- the alkylene structure of R 21 may be bonded at any position such as propane-1,2-diyl, propane-1,3-diyl and the like.
- two R 1 in the formula (1) are each independently of each other, An unsubstituted alkoxy group having 1 to 12 carbon atoms; From a fluoroalkoxy group, an aminoalkoxy group having a substituent —NR 11 R 12 (wherein R 11 and R 12 independently represent H or an alkyl group having 1 to 6 carbon atoms), and a cyanoalkoxy group
- a substituted or unsubstituted aromatic oxy group selected from the group consisting of an aryloxy group, an arylalkyloxy group and an alkylaryloxy group, optionally having —CN or halogen on the aromatic ring as a substituent; and
- R 21 represents an alkylene group having 1 to 6 carbon atoms
- R 22 represents a hydrocarbon group having 1 to 12 carbon atoms
- n represents an integer of 1 to 10.
- the compound which is group chosen from the oxyalkyleneoxy group represented by these is preferable.
- the carbonyl compound of the formula (1) is preferably a compound represented by the following formula (3).
- R 3 and R 4 are each an unsubstituted alkoxy group, an alkoxy group having a substituent, a substituted or unsubstituted fragrance, wherein R 3 O— and R 4 O— are each shown as the preferred R 1 above.
- R 1 represents a group oxy group or an oxyalkyleneoxy group. More preferred of these groups are as described above for each group.
- Examples of carbonyl compounds used in the present invention include the following compounds.
- the carbonyl compound used in the present invention can be synthesized by a coupling reaction such as a Gracer reaction (or Gracer coupling reaction), an Ellington coupling reaction, a Hay coupling reaction or the like using acetylene and copper.
- a coupling reaction such as a Gracer reaction (or Gracer coupling reaction), an Ellington coupling reaction, a Hay coupling reaction or the like using acetylene and copper.
- R has the same meaning as R 1 in formula (1).
- the catalyst copper monovalent copper such as copper (I) chloride, copper (I) bromide, copper (I) iodide, and divalent copper such as copper acetate (II) can be used.
- nitrogen-based ligands such as bipyridyl, phenanthroline, tetramethylethylenediamine (TMEDA), triphenylphosphine, tri (t-butylphosphine), tricyclohexylphosphine, diphenylphosphinoethane (dppe) , Phosphorus-based ligands such as diphenylphosphinopropane (dppp) and diphenylphosphinobutane (dppb) can be used.
- solvent in addition to common organic solvents such as tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, chloroform, dichloromethane and dichloroethane, basic solvents such as pyridine and triethylamine can be used.
- the content of the carbonyl compound of the formula (1) in the electrolytic solution is, for example, 0.01 to 10% by mass, preferably 0.1% by mass or more, and preferably 4% by mass. % Or less, more preferably 2% by mass or less.
- the electrolytic solution used in the present embodiment is a non-aqueous electrolytic solution that is stable at the battery operating potential, and an electrolyte salt (supporting salt) is dissolved in the non-aqueous solvent.
- non-aqueous solvent examples include propylene carbonate (PC), ethylene carbonate (EC), fluoroethylene carbonate (FEC), t-difluoroethylene carbonate (t-DFEC), butylene carbonate (BC), and vinylene carbonate (VC).
- PC propylene carbonate
- EC ethylene carbonate
- FEC fluoroethylene carbonate
- t-DFEC t-difluoroethylene carbonate
- BC butylene carbonate
- Cyclic carbonates such as vinyl ethylene carbonate (VEC); chain carbonates such as allyl methyl carbonate (AMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dipropyl carbonate (DPC) Propylene carbonate derivatives; Aliphatic carboxylic acid esters such as methyl formate, methyl acetate, and ethyl propionate; Cyclic esters such as ⁇ -butyrolactone (GBL), etc. Solvents.
- a non-aqueous solvent can be used individually by 1 type or in combination of 2 or more types.
- sulfur-containing cyclic compounds such as sulfolane, fluorinated sulfolane, propane sultone, propene sultone, and the like can also be used.
- the electrolytic solution preferably further contains a fluorinated ether compound.
- the fluorinated ether compound has a high affinity with an alloy-based negative electrode such as silicon or tin, and when added to the electrolytic solution, the cycle characteristics (particularly capacity retention rate) of the secondary battery are improved.
- the fluorinated ether compound is a fluorinated chain ether compound having a structure in which a part of hydrogen of the non-fluorinated chain ether compound is substituted with fluorine, and a part of hydrogen of the non-fluorinated cyclic ether compound is substituted with fluorine. It may be a fluorinated cyclic ether compound having a structure.
- Non-fluorinated chain ether compounds include, for example, dimethyl ether, methyl ethyl ether, diethyl ether, methyl propyl ether, ethyl propyl ether, dipropyl ether, methyl butyl ether, ethyl butyl ether, propyl butyl ether, dibutyl ether, methyl pentyl ether, ethyl Non-fluorinated chain monoether compounds such as pentyl ether, propyl pentyl ether, butyl pentyl ether, dipentyl ether; 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), ethoxymethoxyethane (EME) ), 1,2-dipropoxyethane, propoxyethoxyethane, propoxymethoxyethane, 1,2-dibutoxyethane, butoxypropoxyethane, butoxyethoxy Ethane,
- Non-fluorinated cyclic ether compounds include, for example, ethylene oxide, propylene oxide, oxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, tetrahydropyran, 2-methyltetrahydropyran, 3-methyltetrahydropyran, 4-methyltetrahydropyran.
- Non-fluorinated cyclic monoether compounds such as 1,3-dioxolane, 2-methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,4-dioxane, 2-methyl-1,4- Dioxane, 1,3-dioxane, 2-methyl-1,3-dioxane, 4-methyl-1,3-dioxane, 5-methyl-1,3-dioxane, 2,4-dimethyl-1,3-dioxane, Non-fluorinated rings such as 4-ethyl-1,3-dioxane Diether compounds.
- the fluorinated chain ether compound is preferably a compound represented by the following formula (7).
- R a and R b each independently represent an alkyl group or a fluorine-substituted alkyl group, and at least one of R a and R b is a fluorine-substituted alkyl group.
- the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8, more preferably 1 to 6, and more preferably 1 to 4. Particularly preferred.
- the alkyl group includes a linear, branched, or cyclic group, but is preferably a linear group.
- At least one of R a and R b is a fluorine-substituted alkyl group.
- the fluorine-substituted alkyl group represents a substituted alkyl group having a structure in which at least one hydrogen atom of the unsubstituted alkyl group is substituted with a fluorine atom.
- the fluorine-substituted alkyl group is preferably linear.
- R a and R b are each independently preferably a fluorine-substituted alkyl group having 1 to 6 carbon atoms, and more preferably a fluorine-substituted alkyl group having 1 to 4 carbon atoms.
- the fluorinated chain ether compound is more preferably represented by the following formula (8) from the viewpoint of stability.
- n is 1, 2, 3 or 4
- X 1 to X 8 are each independently a fluorine atom or a hydrogen atom.
- at least one of X 1 to X 4 is a fluorine atom
- at least one of X 5 to X 8 is a fluorine atom.
- X 1 to X 4 may be independent for each n.
- the atomic ratio of fluorine atoms to hydrogen atoms is preferably 1 or more. That is, it is preferable that (total number of fluorine atoms) / (total number of hydrogen atoms) ⁇ 1.
- the fluorinated chain ether compound is more preferably represented by the following formula (9) from the viewpoint of stability.
- n 1 or 2.
- chain fluorinated ether compound examples include CF 3 OCH 3 , CF 3 OC 2 H 6 , F (CF 2 ) 2 OCH 3 , F (CF 2 ) 2 OC 2 H 5 , and F (CF 2 ) 3 OCH.
- the content of the fluorinated chain ether compound in the electrolytic solution is, for example, 1 to 70% by mass.
- the content of the fluorinated chain ether compound in the electrolytic solution is preferably 2 to 60% by mass, more preferably 3 to 55% by mass, and further preferably 4 to 50% by mass. preferable.
- strand-shaped ether compound is 50 mass% or less, dissociation of Li ion in a support salt occurs easily and the electroconductivity of electrolyte solution improves.
- strand-shaped ether compound is 1 mass% or more, it is thought that it becomes easy to suppress reductive decomposition on the negative electrode of electrolyte solution.
- electrolyte salt (supporting salt) contained in the electrolytic solution is not particularly limited to, LiPF 6, LiAsF 6, LiAlCl 4, LiClO 4, LiBF 4, LiSbF 6, LiCF 3 SO 3 , lithium salts such as LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 and the like.
- the supporting salt can be used alone or in combination of two or more.
- concentration of the supporting salt is not particularly limited, and is, for example, 0.01 mol / L to 3 mol / L.
- the separator is not particularly limited, and a porous film such as polypropylene or polyethylene or a nonwoven fabric can be used. Moreover, what laminated
- Exterior Body is not particularly limited, and for example, a laminate film can be used.
- the laminate film can be appropriately selected as long as it is stable to the electrolytic solution and has a sufficient water vapor barrier property.
- As the exterior body of the laminate film for example, a laminate film made of aluminum, silica, alumina-coated polypropylene, polyethylene, or the like can be used.
- an aluminum laminate film is preferable from the viewpoint of suppressing volume expansion.
- the distortion of the electrode element becomes very large when gas is generated, compared to a secondary battery using a metal can as the exterior body. This is because the laminate film is more easily deformed by the internal pressure of the secondary battery than the metal can. Furthermore, when sealing a secondary battery using a laminate film as an exterior body, the internal pressure of the battery is usually lower than the atmospheric pressure, so there is no extra space inside, and if gas is generated, it is immediately It may lead to battery volume changes and electrode element deformation.
- the secondary battery according to this embodiment can overcome the above problem. As a result, it is possible to provide a laminate-type lithium ion secondary battery that is inexpensive and has excellent flexibility in designing the cell capacity by changing the number of layers.
- a structure in which a metal thin film layer and a heat-fusible resin layer are laminated can be mentioned.
- a protective layer made of a film of polyester such as polyethylene terephthalate or nylon is further laminated on the surface of the metal thin film layer opposite to the heat fusion resin layer. The structure which was made is mentioned.
- the battery element is surrounded with the heat-fusible resin layer facing each other.
- the metal thin film layer for example, a foil of Al, Ti, Ti alloy, Fe, stainless steel, Mg alloy or the like having a thickness of 10 to 100 ⁇ m is used.
- the resin used for the heat-fusible resin layer is not particularly limited as long as it can be heat-sealed.
- An ionomer resin bonded between molecules is used as the heat-fusible resin layer.
- the thickness of the heat-fusible resin layer is preferably 10 to 200 ⁇ m, more preferably 30 to 100 ⁇ m.
- the configuration of the secondary battery is not particularly limited.
- a laminated laminate type 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, can do.
- FIG. 1 is a schematic cross-sectional view showing a structure of an electrode element included in a laminated laminate type secondary battery.
- This electrode element is formed by alternately stacking a plurality of positive electrodes c and a plurality of negative electrodes a having a planar structure with a separator b interposed therebetween.
- the positive electrode current collector e of each positive electrode c is welded to and electrically connected to each other at an end portion not covered with the positive electrode active material, and a positive electrode terminal f is welded to the welded portion.
- the negative electrode current collector d of each negative electrode a is welded and electrically connected to each other at an end portion not covered with the negative electrode active material, and a negative electrode terminal g is welded to the welded portion.
- the electrode element having such a planar laminated structure does not have a portion with a small R (a region close to the winding core of the wound structure), the electrode element associated with charge / discharge is compared with an electrode element having a wound structure.
- an electrode element having a wound structure since the electrode is curved, the structure is easily distorted when a volume change occurs.
- a negative electrode active material having a large volume change due to charge / discharge such as silicon oxide
- a secondary battery using an electrode element having a wound structure has a large capacity reduction due to charge / discharge.
- the electrode element having a planar laminated structure has a problem that when the gas is generated between the electrodes, the generated gas tends to stay between the electrodes. This is because, in the case of an electrode element having a wound structure, the distance between the electrodes is difficult to widen because tension is applied to the electrodes, whereas in the case of an electrode element having a laminated structure, the distance between the electrodes is widened. This is because it is easy. This problem is particularly noticeable when the outer package is an aluminum laminate film.
- the above problem can be solved by including the carbonyl compound represented by the general formula (1) in the electrolytic solution, and a laminated laminate type lithium ion secondary battery using a high energy type negative electrode. Even in the secondary battery, long-life driving is possible.
- the secondary battery according to one embodiment of the present invention includes a laminated laminate type two battery having an electrode element in which a positive electrode and a negative electrode are arranged to face each other, an electrolytic solution, and an outer package containing the electrode element and the electrolytic solution.
- the negative electrode includes a negative electrode active material including a metal capable of being alloyed with lithium and at least one metal oxide capable of inserting and extracting lithium ions, and the negative electrode active material is a binder for a negative electrode. It is bound to the negative electrode current collector by an agent, and the electrolytic solution contains a carbonyl compound represented by the general formula (1). However, the carbonyl compound represented by the general formula (1) is also effective in a secondary battery using an electrode element having a wound structure.
- Example 1 A simple silicon having an average particle diameter of 5 ⁇ m as silicon and graphite having an average particle diameter of 30 ⁇ m as a carbon material are weighed at a mass ratio of 90:10 and mixed by so-called mechanical milling for 24 hours to obtain a negative electrode active material. Obtained.
- 3 layers of the obtained positive electrode and 4 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 that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
- the carbonyl compound was mixed at 2% by mass to obtain an electrolytic solution.
- the electrode element was wrapped with an aluminum laminate film as an outer package, the electrolyte was poured into the interior, and then sealed while reducing the pressure to 0.1 atm to produce a secondary battery.
- Examples 2 to 5 A secondary battery was fabricated in the same manner as in Example 1, except that the compounds represented by the above formulas (107), (111), (132), and (134) were used as the carbonyl compounds.
- Example 6 A secondary battery was prepared in the same manner as in Example 1 except that polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Pyromax (registered trademark)) was used instead of polyimide as a negative electrode binder. Produced.
- PAI polyamideimide
- Pyromax registered trademark
- Example 7 A secondary battery was fabricated in the same manner as in Example 6, except that the compounds represented by the above formulas (107), (111), (132), and (134) were used as the carbonyl compounds.
- Example 11 A single silicon having an average particle diameter of 5 ⁇ m as silicon, an amorphous silicon oxide (SiO x , 0 ⁇ x ⁇ 2) having an average particle diameter of 13 ⁇ m as a silicon compound, and graphite having an average particle diameter of 30 ⁇ m as a carbon material. , 29:61:10, and they were mixed by so-called mechanical milling for 24 hours to obtain a negative electrode active material composed of a Si / SiO / C composite. In this negative electrode active material, simple silicon was dispersed in silicon oxide (SiO x , 0 ⁇ x ⁇ 2).
- a secondary battery was fabricated in the same manner as in Example 1.
- Example 12 A secondary battery was fabricated in the same manner as in Example 11, except that the compounds represented by the above formulas (107), (111), (132), and (134) were used as the carbonyl compounds.
- Example 16 A secondary battery was prepared in the same manner as in Example 11 except that polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Pyromax (registered trademark)) was used instead of polyimide as the binder for the negative electrode. Produced.
- PAI polyamideimide
- Pyromax trade name: Pyromax (registered trademark)
- Example 17 to 20 A secondary battery was fabricated in the same manner as in Example 16, except that the compounds represented by the above formulas (107), (111), (132), and (134) were used as the carbonyl compounds.
- a secondary battery was fabricated in the same manner as described above.
- a secondary battery was fabricated in the same manner as described above.
- a secondary battery was fabricated in the same manner as described above.
- a secondary battery was fabricated in the same manner as described above.
- the secondary battery was subjected to a test in which charging / discharging was repeated 50 times in a voltage range of 2.5 V to 4.1 V in a thermostat kept at 60 ° C. Then, (discharge capacity at the 50th cycle) / (discharge capacity at the 5th cycle) (unit:%) was calculated as the maintenance rate. Further, (battery volume at the 50th cycle) / (battery volume before the cycle) (unit:%) was calculated as the swelling rate. The results are shown in Table 1.
- the maintenance rate was determined to be “ ⁇ ” at 50% or more, “ ⁇ ” at 25% or more and less than 50%, and “X” at less than 25%.
- the swelling rate was judged as “ ⁇ ” when less than 10%, “ ⁇ ” when 10% or more but less than 20%, and “x” when 20% or more.
- a secondary battery having an electrode element in which a positive electrode and a negative electrode are arranged to face each other, and an electrolyte solution
- the negative electrode active material includes a metal that can be alloyed with lithium and / or a metal oxide that can occlude and release lithium ions
- a secondary battery wherein the electrolytic solution is a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent, and contains a carbonyl compound represented by the following formula (1).
- two R 1 s may be the same or different, and each independently of one another, a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a substituted or unsubstituted aromatic group, Group, the following formula (2):
- R 21 represents an alkylene group having 1 to 6 carbon atoms
- R 22 represents a hydrocarbon group having 1 to 12 carbon atoms
- n represents an integer of 1 to 10.
- R 21 represents an alkylene group having 1 to 6 carbon atoms
- R 22 represents a hydrocarbon group having 1 to 12 carbon atoms
- n represents an integer of 1 to 10
- two R 1 s are independently of each other, An unsubstituted alkyl group having 1 to 12 carbon atoms; From a fluoroalkyl group, an aminoalkyl group having a substituent —NR 11 R 12 (wherein R 11 and R 12 independently represent H or an alkyl group having 1 to 6 carbon atoms), and a cyanoalkyl group
- R 21 represents an alkylene group having 1 to 6 carbon atoms
- R 22 represents a hydrocarbon group having 1 to 12 carbon atoms
- n represents an integer of 1 to 10
- two R 1 s are independently of each other, An unsubstituted alkoxy group having 1 to 12 carbon atoms; From a fluoroalkoxy group, an aminoalkoxy group having a substituent —NR 11 R 12 (wherein R 11 and R 12 independently represent H or an alkyl group having 1 to 6 carbon atoms), and a cyanoalkoxy group
- a substituted or unsubstituted aromatic oxy group selected from the group consisting of an aryloxy group, an arylalkyloxy group and an alkylaryloxy group, optionally having —CN or halogen on the aromatic ring as a substituent; and
- the secondary battery according to Item 5 wherein the negative electrode active material is a silicon / silicon oxide / carbon composite containing silicon, silicon oxide, and a carbon material. 7).
- Item 7. The secondary battery according to any one of Items 1 to 6, further comprising an outer package enclosing the electrode element and the electrolytic solution, wherein the outer package is a laminate film. 8).
- Item 8. The secondary battery according to Item 7, wherein the secondary battery is a laminated laminate type having an electrode element in which the negative electrode and the positive electrode are laminated via a separator. 9.
- An assembled battery comprising a plurality of the secondary batteries according to any one of items 1 to 8. 10.
- a vehicle in which the secondary battery according to any one of Items 1 to 8 or the assembled battery according to Item 9 is mounted as a motor driving power source.
- This embodiment can be used in, for example, all industrial fields that require a power source and industrial fields related to the transport, storage, and supply of electrical energy.
- power supplies for mobile devices such as mobile phones and notebook computers
- power supplies for transportation and transportation media such as trains, satellites, and submarines, including electric vehicles such as electric cars, hybrid cars, electric bikes, and electric assist bicycles
- a backup power source such as a UPS
- a power storage facility for storing power generated by solar power generation, wind power generation, etc .
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Abstract
Description
で表されるオキシアルキレン基、置換または無置換のアルコキシ基、シクロアルキルオキシ基、アルケニルオキシ基、アルキニルオキシ基、置換または無置換の芳香族オキシ基、または下記式(2b):
負極は、例えば負極活物質が負極用結着剤によって負極集電体に結着されてなり、集電体上に負極活物質層を設けて構成されたものを用いることができる。負極活物質層は、例えば、負極活物質と、結着剤と、必要に応じて各種の助剤等とを、溶媒でスラリー化してなる塗布液を、集電体に塗布し、乾燥することにより製造することができる。
正極は、例えば、正極活物質が正極用結着剤によって正極集電体を覆うように結着されてなる。
本実施形態における電解液は、非水溶媒中に電解質塩が溶解している非水電解液である。そして、本実施形態における電解液は、下記式(1)で示されるカルボニル化合物を含有する。
で表されるオキシアルキレン基、置換または無置換のアルコキシ基、シクロアルキルオキシ基、アルケニルオキシ基、アルキニルオキシ基、置換または無置換の芳香族オキシ基、または下記式(2b):
R21は、炭素数1~6、好ましくは炭素数2~4のアルキレン基であり、より好ましくはエチレンまたはプロピレン、特に好ましくはエチレンであり;
R22は、炭素数1~12、好ましくは炭素数1~7のアルキル基、または炭素数6~12のアリール基であり、特に好ましくは炭素数1~7の直鎖アルキル基であり;
nは、1~10、好ましくは1~4の整数である。
R21は、炭素数1~6、好ましくは炭素数2~4のアルキレン基であり、より好ましくはエチレンまたはプロピレン、特に好ましくはエチレンであり;
R22は、炭素数1~12、好ましくは炭素数1~7のアルキル基、または炭素数6~12のアリール基であり、特に好ましくは炭素数1~7の直鎖アルキル基であり;
nは、1~10、好ましくは1~4の整数である。
炭素数1~12の無置換のアルコキシ基;
フルオロアルコキシ基、置換基-NR11R12を有するアミノアルコキシ基(但し、R11およびR12は、互いに独立に、Hまたは炭素数1~6のアルキル基を示す。)、およびシアノアルコキシ基からなる群より選ばれる置換基を有するアルコキシ基;
置換基として芳香環上に、-CNまたはハロゲンを有していてもよい、アリールオキシ基、アリールアルキルオキシ基およびアルキルアリールオキシ基からなる群より選ばれる置換または無置換の芳香族オキシ基;および
下記式(2b):
セパレータとしては、特に制限されるものではないが、ポリプロピレン、ポリエチレン等の多孔質フィルムや不織布を用いることができる。また、セパレータとしては、それらを積層したものを用いることもできる。
外装体としては、特に制限されるものではないが、例えば、ラミネートフィルムを用いることができる。ラミネートフィルムとしては、電解液に安定でかつ十分な水蒸気バリア性を持つものであれば、適宜選択することができる。ラミネートフィルムの外装体としては、例えば、アルミニウム、シリカ、アルミナをコーティングしたポリプロピレン、ポリエチレン等のラミネートフィルムを用いることができる。特に、体積膨張を抑制する観点から、アルミニウムラミネートフィルムが好ましい。
二次電池の構成は、特に制限されるものではないが、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積層ラミネート型とすることができる。
以下に示す合成スキーム(10)に従い、上記式(101)で表されるカルボニル化合物の合成を行った。
1H NMR(ppm) 3.65(6H,s)
以下に示す合成スキーム(11)に従い、合成例1と同様の方法で、プロピオール酸メチルの代わりに、プロピオール酸メチルと等モル量のプロピオール酸トリフルオロエチルを用いること以外はほぼ同様の操作を行うことで、上記式(107)の化合物を収率47%で得た。
1H NMR(ppm) 4.70(4H,q)
以下に示す合成スキーム(12)に従い、合成例1と同様の方法で、プロピオール酸メチルの代わりに、プロピオール酸メチルと等モル量のプロピオール酸シアノメチルを用いること以外はほぼ同様の操作を行うことで、上記式(111)の化合物を収率64%で得た。
1H NMR(ppm) 5.30(4H,s)
以下に示す合成スキーム(13)に従い、合成例1と同様の方法で、プロピオール酸メチルの代わりに、プロピオール酸メチルと等モル量のプロピオール酸メチルトリオキシエチルを用いること以外はほぼ同様の操作を行うことで、上記式(118)の化合物を収率62%で得た。
1H NMR(ppm) 3.23(6H,s)、3.56(16H,m)、3.68(4H,m)、4.35(4H,m)
以下に示す合成スキーム(14)に従い、合成例1と同様の方法で、プロピオール酸メチルの代わりに、プロピオール酸メチルと等モル量のプロピオール酸エチルトリオキシエチルを用いること以外はほぼ同様の操作を行うことで、上記式(119)の化合物を収率46%で得た。
1H NMR(ppm) 1.17(6H,t)、3.39(4H,s)、3.56(16H,m)、3.68(4H,m)、4.35(4H,m)
シリコンとしての平均粒径5μmの単体ケイ素と炭素材料としての平均粒径30μmの黒鉛とを、90:10の質量比で計量し、それらをいわゆるメカニカルミリングで24時間混合して、負極活物質を得た。この負極活物質(平均粒径D50=5μm)と、負極用結着剤としてのポリイミド(PI、宇部興産株式会社製、商品名:UワニスA)とを、85:15の質量比で計量し、それらをn-メチルピロリドンと混合して、負極スラリーを得た。そして、負極スラリーを厚さ10μmの銅箔に塗布した後に乾燥し、さらに窒素雰囲気300℃の熱処理を行うことで、負極を作製した。
カルボニル化合物としてそれぞれ上記式(107)、(111)、(132)、(134)で表される化合物を用いたこと以外は、実施例1と同様にして二次電池を作製した。
負極用結着剤としてのポリイミドの代わりにポリアミドイミド(PAI、東洋紡績株式会社製、商品名:パイロマックス(登録商標))を用いたこと以外は、実施例1と同様にして二次電池を作製した。
カルボニル化合物としてそれぞれ上記式(107)、(111)、(132)、(134)で表される化合物を用いたこと以外は、実施例6と同様にして二次電池を作製した。
シリコンとしての平均粒径5μmの単体ケイ素と、シリコン化合物としての平均粒径13μmの非晶質酸化シリコン(SiOx、0<x≦2)と、炭素材料としての平均粒径30μmの黒鉛とを、29:61:10の質量比で計量し、それらをいわゆるメカニカルミリングで24時間混合して、Si/SiO/C複合体からなる負極活物質を得た。なお、この負極活物質において、単体ケイ素は、酸化シリコン(SiOx、0<x≦2)中に分散していた。
カルボニル化合物としてそれぞれ上記式(107)、(111)、(132)、(134)で表される化合物を用いたこと以外は、実施例11と同様にして二次電池を作製した。
負極用結着剤としてのポリイミドの代わりにポリアミドイミド(PAI、東洋紡績株式会社製、商品名:パイロマックス(登録商標))を用いたこと以外は、実施例11と同様にして二次電池を作製した。
カルボニル化合物としてそれぞれ上記式(107)、(111)、(132)、(134)で表される化合物を用いたこと以外は、実施例16と同様にして二次電池を作製した。
EC/DEC=30/70(体積比)からなるカーボネート系非水電解溶媒に支持塩としてのLiPF6を1mol/Lの濃度で溶解させた液を電解液として用いたこと以外は、実施例1と同様にして二次電池を作製した。
EC/DEC=30/70(体積比)からなるカーボネート系非水電解溶媒に支持塩としてのLiPF6を1mol/Lの濃度で溶解させた液を電解液として用いたこと以外は、実施例6と同様にして二次電池を作製した。
EC/DEC=30/70(体積比)からなるカーボネート系非水電解溶媒に支持塩としてのLiPF6を1mol/Lの濃度で溶解させた液を電解液として用いたこと以外は、実施例11と同様にして二次電池を作製した。
EC/DEC=30/70(体積比)からなるカーボネート系非水電解溶媒に支持塩としてのLiPF6を1mol/Lの濃度で溶解させた液を電解液として用いたこと以外は、実施例16と同様にして二次電池を作製した。
実施例1~20および比較例1~4で作製した二次電池について、高温環境下におけるサイクル特性を評価した。
本出願の開示事項は次のとおりにまとめられる。
1. 正極および負極が対向配置された電極素子と、電解液とを有する二次電池であって、
前記負極活物質が、リチウムと合金可能な金属、および/または、リチウムイオンを吸蔵、放出し得る金属酸化物を含み、
前記電解液が、非水溶媒中に電解質塩が溶解されている非水電解液であって、下記式(1)で示されるカルボニル化合物を含有することを特徴とする二次電池。
で表されるオキシアルキレン基、置換または無置換のアルコキシ基、シクロアルキルオキシ基、アルケニルオキシ基、アルキニルオキシ基、置換または無置換の芳香族オキシ基、または下記式(2b):
で表されるオキシアルキレンオキシ基を表す。)
2. 前記式(1)中の2つのR1が、それぞれ互いに独立に、
炭素数1~12の無置換のアルキル基;
フルオロアルキル基、置換基-NR11R12を有するアミノアルキル基(但し、R11およびR12は、互いに独立に、Hまたは炭素数1~6のアルキル基を示す。)、およびシアノアルキル基からなる群より選ばれる置換基を有するアルキル基;
置換基として芳香環上に、-CNまたはハロゲンを有していてもよい、アリール基、アリールアルキル基およびアルキルアリール基からなる群より選ばれる置換または無置換の芳香族基;
下記式(2):
で表されるオキシアルキレン基;
炭素数1~12の無置換のアルコキシ基;
フルオロアルコキシ基、置換基-NR11R12を有するアミノアルコキシ基(但し、R11およびR12は、互いに独立に、Hまたは炭素数1~6のアルキル基を示す。)、およびシアノアルコキシ基からなる群より選ばれる置換基を有するアルコキシ基;
置換基として芳香環上に、-CNまたはハロゲンを有していてもよい、アリールオキシ基、アリールアルキルオキシ基およびアルキルアリールオキシ基からなる群より選ばれる置換または無置換の芳香族オキシ基;および
下記式(2b):
で表されるオキシアルキレンオキシ基から選ばれる基であることを特徴とする前記項1記載の二次電池。
3. 前記式(1)中の2つのR1が、それぞれ互いに独立に、
炭素数1~12の無置換のアルコキシ基;
フルオロアルコキシ基、置換基-NR11R12を有するアミノアルコキシ基(但し、R11およびR12は、互いに独立に、Hまたは炭素数1~6のアルキル基を示す。)、およびシアノアルコキシ基からなる群より選ばれる置換基を有するアルコキシ基;
置換基として芳香環上に、-CNまたはハロゲンを有していてもよい、アリールオキシ基、アリールアルキルオキシ基およびアルキルアリールオキシ基からなる群より選ばれる置換または無置換の芳香族オキシ基;および
下記式(2b):
で表されるオキシアルキレンオキシ基から選ばれる基であることを特徴とする前記項2記載の二次電池。
4. 前記式(1)で示されるカルボニル化合物の非水電解液中における含有量が、0.1~2wt%の範囲であることを特徴とする前記項1~3のいずれか1項に記載の二次電池。
5. 前記負極活物質が、ケイ素および/またはケイ素酸化物を含むことを特徴とする前記項1~4のいずれか1項に記載の二次電池。
6. 前記負極活物質が、ケイ素、ケイ素酸化物及び炭素材料を含むケイ素/ケイ素酸化物/炭素複合体であることを特徴とする前記項5に記載の二次電池。
7. 前記電極素子と前記電解液とを内包する外装体を備え、前記外装体がラミネートフィルムであることを特徴とする前記項1~6のいずれか1項に記載の二次電池。
8. 前記負極と前記正極がセパレータを介して積層配置された電極素子を有する積層ラミネート型であることを特徴とする前記項7に記載の二次電池。
9. 前記項1~8のいずれか1項に記載の二次電池を複数個有する組電池。
10. 前記項1~8のいずれか1項に記載の二次電池、または前記項9に記載の組電池がモータ駆動用電源として搭載されている車両。
b セパレータ
c 正極
d 負極集電体
e 正極集電体
f 正極端子
g 負極端子
Claims (10)
- 正極および負極が対向配置された電極素子と、電解液とを有する二次電池であって、
前記負極活物質が、リチウムと合金可能な金属、および/または、リチウムイオンを吸蔵、放出し得る金属酸化物を含み、
前記電解液が、非水溶媒中に電解質塩が溶解されている非水電解液であって、下記式(1)で示されるカルボニル化合物を含有することを特徴とする二次電池。
で表されるオキシアルキレン基、置換または無置換のアルコキシ基、シクロアルキルオキシ基、アルケニルオキシ基、アルキニルオキシ基、置換または無置換の芳香族オキシ基、または下記式(2b):
で表されるオキシアルキレンオキシ基を表す。) - 前記式(1)中の2つのR1が、それぞれ互いに独立に、
炭素数1~12の無置換のアルキル基;
フルオロアルキル基、置換基-NR11R12を有するアミノアルキル基(但し、R11およびR12は、互いに独立に、Hまたは炭素数1~6のアルキル基を示す。)、およびシアノアルキル基からなる群より選ばれる置換基を有するアルキル基;
置換基として芳香環上に、-CNまたはハロゲンを有していてもよい、アリール基、アリールアルキル基およびアルキルアリール基からなる群より選ばれる置換または無置換の芳香族基;
下記式(2):
で表されるオキシアルキレン基;
炭素数1~12の無置換のアルコキシ基;
フルオロアルコキシ基、置換基-NR11R12を有するアミノアルコキシ基(但し、R11およびR12は、互いに独立に、Hまたは炭素数1~6のアルキル基を示す。)、およびシアノアルコキシ基からなる群より選ばれる置換基を有するアルコキシ基;
置換基として芳香環上に、-CNまたはハロゲンを有していてもよい、アリールオキシ基、アリールアルキルオキシ基およびアルキルアリールオキシ基からなる群より選ばれる置換または無置換の芳香族オキシ基;および
下記式(2b):
で表されるオキシアルキレンオキシ基から選ばれる基であることを特徴とする請求項1記載の二次電池。 - 前記式(1)中の2つのR1が、それぞれ互いに独立に、
炭素数1~12の無置換のアルコキシ基;
フルオロアルコキシ基、置換基-NR11R12を有するアミノアルコキシ基(但し、R11およびR12は、互いに独立に、Hまたは炭素数1~6のアルキル基を示す。)、およびシアノアルコキシ基からなる群より選ばれる置換基を有するアルコキシ基;
置換基として芳香環上に、-CNまたはハロゲンを有していてもよい、アリールオキシ基、アリールアルキルオキシ基およびアルキルアリールオキシ基からなる群より選ばれる置換または無置換の芳香族オキシ基;および
下記式(2b):
で表されるオキシアルキレンオキシ基から選ばれる基であることを特徴とする請求項2記載の二次電池。 - 前記式(1)で示されるカルボニル化合物の非水電解液中における含有量が、0.1~2wt%の範囲であることを特徴とする請求項1~3のいずれか1項に記載の二次電池。
- 前記負極活物質が、ケイ素および/またはケイ素酸化物を含むことを特徴とする請求項1~4のいずれか1項に記載の二次電池。
- 前記負極活物質が、ケイ素、ケイ素酸化物及び炭素材料を含むケイ素/ケイ素酸化物/炭素複合体であることを特徴とする請求項5に記載の二次電池。
- 前記電極素子と前記電解液とを内包する外装体を備え、前記外装体がラミネートフィルムであることを特徴とする請求項1~6のいずれか1項に記載の二次電池。
- 前記負極と前記正極がセパレータを介して積層配置された電極素子を有する積層ラミネート型であることを特徴とする請求項7に記載の二次電池。
- 請求項1~8のいずれか1項に記載の二次電池を複数個有する組電池。
- 請求項1~8のいずれか1項に記載の二次電池、または請求項9に記載の組電池がモータ駆動用電源として搭載されている車両。
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US20210226196A1 (en) * | 2017-12-07 | 2021-07-22 | Enevate Corporation | Methods of forming electrochemical cells |
JP2019033102A (ja) * | 2018-12-03 | 2019-02-28 | 日立化成株式会社 | リチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極及びリチウムイオン二次電池 |
Also Published As
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US20150194703A1 (en) | 2015-07-09 |
US9666904B2 (en) | 2017-05-30 |
JPWO2014007026A1 (ja) | 2016-06-02 |
JP6225903B2 (ja) | 2017-11-08 |
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