WO2013058235A1 - 非水電解液及びそれを用いた蓄電デバイス - Google Patents
非水電解液及びそれを用いた蓄電デバイス Download PDFInfo
- Publication number
- WO2013058235A1 WO2013058235A1 PCT/JP2012/076690 JP2012076690W WO2013058235A1 WO 2013058235 A1 WO2013058235 A1 WO 2013058235A1 JP 2012076690 W JP2012076690 W JP 2012076690W WO 2013058235 A1 WO2013058235 A1 WO 2013058235A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbonate
- lithium
- aqueous electrolyte
- chain
- dione
- Prior art date
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 59
- 238000003860 storage Methods 0.000 title claims abstract description 53
- -1 cyclic acid anhydride Chemical class 0.000 claims abstract description 73
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 50
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims abstract description 42
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 30
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims abstract description 8
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 70
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 65
- 239000008151 electrolyte solution Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 230000005611 electricity Effects 0.000 claims description 15
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 150000005678 chain carbonates Chemical class 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 5
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 5
- 229910012258 LiPO Inorganic materials 0.000 claims description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims description 5
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- QLTWDRPUZFBSDC-UHFFFAOYSA-N 3-prop-2-ynyloxolane-2,5-dione Chemical compound O=C1CC(CC#C)C(=O)O1 QLTWDRPUZFBSDC-UHFFFAOYSA-N 0.000 claims description 4
- 229910013131 LiN Inorganic materials 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- WUMMIJWEUDHZCL-UHFFFAOYSA-N 3-prop-2-enyloxolane-2,5-dione Chemical compound C=CCC1CC(=O)OC1=O WUMMIJWEUDHZCL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- RCIJMMSZBQEWKW-UHFFFAOYSA-N methyl propan-2-yl carbonate Chemical compound COC(=O)OC(C)C RCIJMMSZBQEWKW-UHFFFAOYSA-N 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- ANPMHDUGFOMMJJ-UHFFFAOYSA-N 3-(2-methylprop-2-enyl)oxolane-2,5-dione Chemical compound CC(=C)CC1CC(=O)OC1=O ANPMHDUGFOMMJJ-UHFFFAOYSA-N 0.000 claims description 2
- FWBMVXOCTXTBAD-UHFFFAOYSA-N butyl methyl carbonate Chemical compound CCCCOC(=O)OC FWBMVXOCTXTBAD-UHFFFAOYSA-N 0.000 claims description 2
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- 150000003606 tin compounds Chemical class 0.000 claims description 2
- MCSBDMFGKYZBTA-UHFFFAOYSA-N 4-fluoro-1,3-dioxolane Chemical compound FC1COCO1 MCSBDMFGKYZBTA-UHFFFAOYSA-N 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- FOLJHXWWJYUOJV-UHFFFAOYSA-N 4-ethynyl-1,3-dioxolan-2-one Chemical compound O=C1OCC(C#C)O1 FOLJHXWWJYUOJV-UHFFFAOYSA-N 0.000 abstract description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 abstract description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- 230000000694 effects Effects 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 229910003002 lithium salt Inorganic materials 0.000 description 14
- 159000000002 lithium salts Chemical class 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
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- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 4
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- 229920003026 Acene Polymers 0.000 description 1
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- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
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- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- 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
- H01M10/0568—Liquid materials characterised by the solutes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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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
- 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
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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
- 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
- Y02E60/13—Energy storage using capacitors
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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 nonaqueous electrolytic solution capable of improving electrochemical characteristics in a wide temperature range and an electricity storage device using the same.
- power storage devices particularly lithium secondary batteries
- small electronic devices such as mobile phones and notebook computers, electric vehicles, and power storage. Since these electronic devices and automobiles may be used in a wide temperature range such as a high temperature in midsummer or a low temperature of extremely cold, it is required to improve electrochemical characteristics in a wide range of temperatures. In particular, in order to prevent global warming, there is an urgent need to reduce CO 2 emissions.
- environmentally friendly vehicles equipped with power storage devices consisting of power storage devices such as lithium secondary batteries and capacitors
- HEV hybrid electric vehicles
- PHEV plug-in hybrid electric vehicles
- BEV battery electric vehicles
- lithium secondary battery Due to the long travel distance of automobiles, automobiles may be used in areas with a wide temperature range from extremely hot areas in the tropics to extremely cold areas. Therefore, in particular, these in-vehicle power storage devices are required not to deteriorate in electrochemical characteristics even when used in a wide temperature range from high temperature to low temperature.
- the term lithium secondary battery is used as a concept including a so-called lithium ion secondary battery.
- the lithium secondary battery is mainly composed of a positive electrode and a negative electrode containing a material capable of occluding and releasing lithium, a non-aqueous electrolyte composed of a lithium salt and a non-aqueous solvent, and the non-aqueous solvent includes ethylene carbonate (EC), Carbonates such as propylene carbonate (PC) are used.
- EC ethylene carbonate
- PC propylene carbonate
- metal lithium metal compounds that can occlude and release lithium (metal simple substance, oxide, alloy with lithium, etc.) and carbon materials are known, and in particular, lithium can be occluded and released.
- Lithium secondary batteries using carbon materials such as coke, artificial graphite and natural graphite have been widely put into practical use.
- a lithium secondary battery using a highly crystallized carbon material such as natural graphite or artificial graphite as a negative electrode material is a decomposition product generated by reductive decomposition of a solvent in a non-aqueous electrolyte on the negative electrode surface during charging. It has been found that the gas interferes with the desired electrochemical reaction of the battery, resulting in poor cycle characteristics. Moreover, when the decomposition product of the nonaqueous solvent accumulates, it becomes impossible to smoothly occlude and release lithium into the negative electrode, and the electrochemical characteristics in a wide temperature range are liable to deteriorate.
- lithium secondary batteries using lithium metal, alloys thereof, simple metals such as tin or silicon, and oxides as negative electrode materials have high initial capacities, but fine powders progress during the cycle.
- reductive decomposition of a non-aqueous solvent occurs at an accelerated rate, and battery performance such as battery capacity and cycle characteristics is greatly reduced.
- these anode materials are finely powdered or decomposition products of non-aqueous solvents accumulate, it becomes impossible to smoothly occlude and release lithium into the anode, and the electrochemical characteristics in a wide temperature range are likely to deteriorate. .
- a lithium secondary battery using, for example, LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiFePO 4, or the like as the positive electrode has a non-aqueous solvent in a non-aqueous electrolyte charged and a positive electrode material and a non-aqueous electrolyte. It has been found that degradation products and gases generated by partial oxidative decomposition locally at the interface of the battery inhibit the desired electrochemical reaction of the battery, resulting in degradation of electrochemical characteristics over a wide temperature range. Yes.
- the battery performance has been deteriorated due to the movement of lithium ions or the expansion of the battery due to the decomposition product or gas when the non-aqueous electrolyte is decomposed on the positive electrode or the negative electrode.
- electronic devices equipped with lithium secondary batteries are becoming more and more multifunctional and power consumption is increasing.
- the capacity of lithium secondary batteries has been increasing, and the volume occupied by non-aqueous electrolyte in the battery has become smaller, such as increasing the electrode density and reducing the useless space volume in the battery. . Therefore, the electrochemical characteristics in a wide temperature range are likely to be deteriorated by a slight decomposition of the nonaqueous electrolytic solution.
- Patent Document 1 proposes a nonaqueous electrolytic solution to which a specific unsaturated cyclic acid anhydride is added, and discloses that cycle characteristics are improved.
- Patent Document 2 proposes a nonaqueous electrolytic solution containing a carboxylic acid anhydride organic compound obtained by reacting maleic anhydride with 1-pentene, and discloses that it has excellent storage characteristics.
- Patent Document 3 proposes a non-aqueous electrolyte containing a mixture of maleic anhydride and N-methylsuccinimide, which discloses improving the charge storage characteristics.
- An object of the present invention is to provide a nonaqueous electrolytic solution capable of improving electrochemical characteristics in a wide temperature range and an electricity storage device using the same.
- the present inventors have examined in detail the performance of the above-described prior art non-aqueous electrolyte.
- the non-aqueous electrolyte of the above-mentioned patent document cannot be said to be sufficiently satisfactory for the problem of improving electrochemical characteristics in a wide temperature range such as low temperature discharge characteristics after high temperature storage. It was a fact.
- the inventors of the present invention have made extensive studies to solve the above problems, and in a non-aqueous solvent, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 4-fluoro-1 , 3-dioxolan-2-one, trans or cis-4,5-difluoro-1,3-dioxolan-2-one, vinylene carbonate, vinylethylene carbonate, and 4-ethynyl-1,3-dioxolan-2-one And a specific cyclic acid anhydride to which a side chain having 3 or more carbon atoms having a double bond or a triple bond at the end is bonded in the non-aqueous electrolyte solution.
- the inventors have found that the electrochemical characteristics in a wide temperature range, in particular, the electrochemical characteristics of a lithium battery can be improved, and the present invention has been completed.
- the present invention provides the following (1) to (2).
- the nonaqueous solvent is ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 4-fluoro-1, From 3-dioxolan-2-one, trans or cis-4,5-difluoro-1,3-dioxolan-2-one, vinylene carbonate, vinyl ethylene carbonate, and 4-ethynyl-1,3-dioxolan-2-one Cyclic ring containing two or more kinds of cyclic carbonates selected, and further having a side chain having 3 or more carbon atoms bonded to the terminal with a double bond or triple bond represented by the following general formula (I) in the non-aqueous electrolyte A non-aqueous electrolyte containing 0.01 to 10% by mass of an acid anhydride.
- R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, or an alkyl group in which at least one hydrogen atom having 1 to 6 carbon atoms may be substituted with halogen.
- R 3 represents A straight-chain or branched alkenyl group having 2 to 4 carbon atoms having a double bond at the terminal, or a straight-chain or branched alkynyl group having 2 to 4 carbon atoms having a triple bond at the terminal.
- An electricity storage device including a non-aqueous electrolyte in which an electrolyte salt is dissolved in a positive electrode, a negative electrode, and a non-aqueous solvent, wherein the non-aqueous electrolyte is the non-aqueous electrolyte described in (1) above.
- non-aqueous electrolyte capable of improving electrochemical characteristics in a wide temperature range, particularly low-temperature discharge characteristics after high-temperature storage, and a storage device such as a lithium battery using the non-aqueous electrolyte.
- the non-aqueous electrolyte of the present invention is a non-aqueous electrolyte in which an electrolyte salt is dissolved in a non-aqueous solvent, and ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate is contained in the non-aqueous solvent.
- the reason why the nonaqueous electrolytic solution of the present invention can greatly improve electrochemical characteristics in a wide temperature range such as low temperature discharge characteristics after high temperature storage is not necessarily clear, but is considered as follows.
- the cyclic acid anhydride represented by the general formula (I) contained in the non-aqueous electrolyte of the present invention undergoes reductive decomposition on the negative electrode during the initial charge, and forms a dense and highly heat-resistant film to store at high temperature. The effect of suppressing the subsequent capacity drop can be obtained.
- the coating derived from the cyclic acid anhydride represented by the general formula (I) has a double bond or a triple bond at the end of the side chain, it tends to have high resistance, and the low-temperature characteristics after high-temperature storage deteriorates. There was a problem that it was easy.
- cyclic carbonates selected from dioxolane-2-one, vinylene carbonate, vinylethylene carbonate, and 4-ethynyl-1,3-dioxolan-2-one are cyclic acids represented by the above general formula (I)
- the decomposition product of two or more different cyclic carbonates and the decomposition product of the cyclic acid anhydride represented by the general formula (I) are combined and incorporated as a coating component.
- cyclic carbonates in addition to ethylene carbonate, cyclic carbonate having a methyl group at the 4-position of ethylene carbonate, that is, propylene carbonate, cyclic carbonate having a carbon-carbon double bond or carbon-carbon triple bond, that is, It has been found that the above effect is further enhanced by including one or more selected from vinylene carbonate, vinyl ethylene carbonate, and 4-ethynyl-1,3-dioxolan-2-one.
- the cyclic acid anhydride contained in the nonaqueous electrolytic solution of the present invention is represented by the following general formula (I).
- R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, or an alkyl group in which at least one hydrogen atom having 1 to 6 carbon atoms may be substituted with halogen.
- R 3 represents A straight-chain or branched alkenyl group having 2 to 4 carbon atoms having a double bond at the terminal, or a straight-chain or branched alkynyl group having 2 to 4 carbon atoms having a triple bond at the terminal.
- R 1 and R 2 in the general formula (I) include hydrogen atom, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, n-propyl group, n-butyl group, and n-pentyl group.
- N-hexyl group, iso-propyl group, sec-butyl group, tert-butyl group, trifluoromethyl group, 2,2,2-trifluoroethyl, etc. are preferably raised.
- R 1 and R 2 in the general formula (I) are more preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, still more preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group, Preferably they are a hydrogen atom, a fluorine atom, or a methyl group.
- R 3 in the general formula (I) examples include vinyl group (ethenyl group), allyl group (2-propenyl group), isopropenyl group (1-methylethenyl group), 3-buten-1-yl group, Preferable examples include 1-propen-2-yl group, 2-methyl-2-propen-1-yl group, ethynyl group, 2-propyn-1-yl group, and 3-butyn-1-yl group.
- R 3 in the general formula (I) is more preferably a linear or branched alkenyl group having 2 to 3 carbon atoms having a double bond at the terminal, or a linear or branched carbon number having a triple bond at the terminal.
- alkynyl groups more preferably a vinyl group, isopropenyl group, ethynyl group, 2-propyn-1-yl group, or 3-butyn-1-yl group, and particularly preferably a vinyl group, A propenyl group or an ethynyl group.
- cyclic acid anhydride represented by the general formula (I) include compounds having the following structural formulas 1 to 43.
- the structural formula 1 (3-allyldihydrofuran-2,5-dione), the structural formula 2 (3- (3-methylallyl) dihydrofuran-2, 5-dione), structural formula 13 (3- (3,3-dimethylallyl) dihydrofuran-2,5-dione), structural formula 21 (3- (2-methylallyl) dihydrofuran-2,5-dione), Structural formula 22 (3- (2,3-dimethylallyl) dihydrofuran-2,5-dione), structural formula 26 (3- (2,3,3-trimethylallyl) dihydrofuran-2,5-dione), Structural formula 31 (3- (2-propyn-1-yl) dihydrofuran-2,5-dione), structural formula 32 (3- (1-methyl-2-propyn-1-yl) dihydrofuran-2,5 -Dione) and structural formula 36 (3- (1, -Dimethyl-2-propy
- the content of the cyclic acid anhydride represented by the general formula (I) contained in the non-aqueous electrolyte is 0.001 to 10% by mass in the non-aqueous electrolyte. is there.
- the content is 10% by mass or less, there is little possibility that a coating film is excessively formed on the electrode and the low-temperature characteristics are deteriorated.
- the content is 0.001% by mass or more, the coating film is sufficiently formed and stored at high temperature. The effect of improving the characteristics is increased.
- the content is preferably 0.05% by mass or more, and more preferably 0.2% by mass or more in the nonaqueous electrolytic solution.
- the upper limit is preferably 8% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less.
- non-aqueous electrolyte of the present invention by combining the following non-aqueous solvent, electrolyte salt, and other additives, electrochemical characteristics in a wide temperature range such as low-temperature discharge characteristics after high-temperature storage are synergistic. It exhibits a unique effect of improving.
- Nonaqueous solvent examples of the nonaqueous solvent used in the nonaqueous electrolytic solution of the present invention include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, and 4-fluoro-1,3.
- EC ethylene carbonate
- PC propylene carbonate
- 1,2-butylene carbonate 1,2-butylene carbonate
- 2,3-butylene carbonate 1,2-butylene carbonate
- FEC -Dioxolan-2-one
- DFEC cis-4,5-difluoro-1,3-dioxolan-2-one
- VC vinylene carbonate
- VEC ethylene carbonate
- EEC 4-ethynyl-1,3-dioxolan-2-one
- the non-aqueous solvent preferably contains only the cyclic carbonate or both the cyclic carbonate and the chain ester.
- chain ester is used as a concept including chain carbonate and chain carboxylic acid ester. It is preferable to include two or more cyclic carbonates as the cyclic carbonate because the low temperature characteristics after high temperature storage are improved.
- VC vinylene carbonate
- VC vinylene carbonate
- VC vinylene carbonate
- VEC vinyl ethylene carbonate
- EEC 4-ethynyl-1,3-dioxolan-2-one
- the cyclic carbonate having a methyl group at the 4-position of ethylene carbonate is preferably 1% by volume or more, more preferably 4% by volume or more, and further preferably 8% by volume or more with respect to the total volume of the nonaqueous solvent.
- the upper limit is preferably 50% by volume or less, more preferably 40% by volume or less, and further preferably 30% by volume or less, the coating during further high-temperature storage without impairing the Li ion permeability at low temperatures. This is preferable because the stability can be increased.
- the content of the cyclic carbonate having a carbon-carbon double bond is preferably 0.07% by volume or more, more preferably 0.2% by volume or more, based on the total volume of the nonaqueous solvent. More preferably, it is 0.7% by volume or more, and the upper limit thereof is preferably 7% by volume or less, more preferably 4% by volume or less, and further preferably 2.5% by volume or less. This is preferable because the stability of the film during high temperature storage can be further increased without impairing the properties.
- these cyclic carbonates are used in combination of two or more, the electrochemical characteristics in a wide temperature range are improved, and it is more preferable to use a combination of three or more.
- Preferred combinations of these cyclic carbonates include EC and PC, EC and VC, PC and VC, VC and FEC, EC and FEC, PC and FEC, FEC and DFEC, EC and DFEC, PC and DFEC, VC and DFEC , VC and EEC, EC and EEC, VEC and DFEC, EC and PC and VC, EC and PC and FEC, EC and VC and FEC, EC and VC and VEC, EC and VC and EEC, EC and VC and EEC, EC and PC and EEC, EC And EEC and FEC, PC and VC and FEC, EC and VC and DFEC, PC and VC and DFEC, EC and PC and VC and DFEC, EC and PC and VC and
- an asymmetric chain carbonate selected from methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate, and ethyl propyl carbonate, dimethyl carbonate (DMC), diethyl Symmetrical chain carbonates selected from carbonate (DEC), dipropyl carbonate, and dibutyl carbonate, and pivalate esters such as methyl pivalate (MPV), ethyl pivalate, propyl pivalate, methyl propionate, ethyl propionate, acetic acid
- MEC methyl ethyl carbonate
- MPC methyl propyl carbonate
- MIPC methyl isopropyl carbonate
- DMC dimethyl carbonate
- DEC diethyl Symmetrical chain carbonates
- DEC dipropyl carbonate
- dibutyl carbonate dibutyl carbonate
- pivalate esters such as
- chain esters one or more symmetrical chain carbonates selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, and dibutyl carbonate are preferable, and diethyl carbonate (DEC) is more preferable. preferable.
- chain esters When chain esters are used, it is more preferable to use a combination of two or more.
- a pivalic acid ester which is a tertiary carboxylic acid ester is contained in the chain ester, a cyclic acid in which a side chain having 3 or more carbon atoms having a double bond or a triple bond at the end of the present invention is bonded.
- an unpredictable effect of improving the lithium ion permeability is exhibited without excessively densifying the film, and in a wide temperature range. It is preferable because electrochemical characteristics can be further improved, and it is particularly preferable that methyl pivalate is contained.
- the content of the chain ester is not particularly limited, but it is preferably in the range of 30 to 90% by volume, more preferably in the range of 60 to 80% by volume with respect to the total volume of the nonaqueous solvent. If the content is 30% by volume or more, the effect of lowering the viscosity of the non-aqueous electrolyte is sufficiently obtained, and if it is 90% by volume or less, the electrical conductivity of the non-aqueous electrolyte is sufficiently increased, and in a wide temperature range. The above-mentioned range is preferable since the electrochemical characteristics of the above are improved.
- the volume ratio of the pivalic acid ester in the chain ester is preferably 5% by volume or more, more preferably 15% by volume or more, and still more preferably 55% by volume or more.
- 100 volume% or less is preferable, 95 volume% or less is more preferable, and 85 volume% or less is still more preferable. The above case is preferable because electrochemical characteristics in a wider temperature range are improved.
- the ratio between the cyclic carbonate and the chain ester is preferably 10:90 to 70:30, and 15:85 to 50:30 in terms of the cyclic carbonate: chain ester (volume ratio) from the viewpoint of improving electrochemical characteristics in a wide temperature range. 50 is more preferable, and 20:80 to 45:55 is still more preferable.
- lactones that are non-aqueous solvents include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -angelica lactone, etc.
- ethers include tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 1,3- Examples include cyclic ethers such as dioxane (DOX) and 1,4-dioxane, chain ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane. , Dimethylformamide, and the like.
- Preferred examples of the sulfone include sulfolane.
- the above non-aqueous solvents are usually used as a mixture in order to achieve appropriate physical properties.
- the combination includes, for example, a combination of a cyclic carbonate and a chain carbonate, a combination of a cyclic carbonate and a chain carboxylic acid ester, a combination of a cyclic carbonate, a chain carbonate and a lactone, and a combination of a cyclic carbonate, a chain carbonate and an ether.
- a combination, a combination of a cyclic carbonate, a chain carbonate, and a chain carboxylate, and the like are preferable.
- additives include trimethyl phosphate, tributyl phosphate, and trioctyl phosphate, ethyl 2- (diethoxyphosphoryl) acetate, 2-propynyl 2- (diethoxyphosphoryl) acetate, ethyl 2- (di-) Phosphate esters such as ethoxyphosphoryl) -2-fluoroacetate and 2- (diethoxyphosphoryl) -2,2-difluoroacetate, isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate and octamethylene diisocyanate, 1,3-propane sultone 1,3-butane sultone, 2,4-butane sultone, 1,4-butane sultone, 2,2-dioxide-1,2-oxa
- additives include cyclohexylbenzene, fluorocyclohexylbenzene compounds (1-fluoro-2-cyclohexylbenzene, 1-fluoro-3-cyclohexylbenzene, 1-fluoro-4-cyclohexylbenzene), tert- Aromatic compounds having a branched alkyl group such as butylbenzene, tert-amylbenzene, 1-fluoro-4-tert-butylbenzene, 1-fluoro-4-tert-alkylbenzene, biphenyl, terphenyl (o-, m -, P-isomer), diphenyl ether, fluorobenzene, difluorobenzene (o-, m-, p-isomer), anisole, 2,4-difluoroanisole, terphenyl hydride (1,2-dicyclohexylbenzene, 2 -Phenylbicy
- Examples of the aromatic compound having a fluorine atom, a tert-alkyl group, or both tert-alkyl groups include fluorocyclohexylbenzene compounds (1-fluoro-2-cyclohexylbenzene, 1-fluoro-3-cyclohexylbenzene, 1-fluoro -4-cyclohexylbenzene), fluorobenzene, difluorobenzene (o-, m-, p-isomer), 2,4-difluoroanisole, tert-butylbenzene, tert-amylbenzene, 1-fluoro-4-tert-butyl Preferred examples include benzene and 1-fluoro-4-tert-alkylbenzene.
- benzene is preferred, and one selected from fluorobenzene, difluorobenzene (o-, m-, p-isomer), tert-amylbenzene, and 1-fluoro-4-tert-butylbenzene
- two or more are more preferable, and aromatic compounds having a fluorine atom and a tert-alkyl group, such as 1-fluoro-4-tert-butylbenzene and 1-fluoro-4-tert-alkylbenzene, are particularly preferable.
- the content of the aromatic compound having a fluorine atom, a tert-alkyl group, or both is preferably 0.1 to 15% by mass in the non-aqueous electrolyte. In this range, the coating film is sufficiently formed without becoming too thick, and the effect of improving the electrochemical characteristics over a wide temperature range is enhanced.
- the content is more preferably 0.5% by mass or more in the nonaqueous electrolytic solution, further preferably 1% by mass or more, and the upper limit is more preferably 13% by mass or less.
- a side chain having 3 or more carbon atoms having a double bond or a triple bond at the terminal of the present invention is bonded.
- Examples of phosphoric acid ester compounds include ethyl 2- (diethoxyphosphoryl) acetate, 2-propynyl 2- (diethoxyphosphoryl) acetate, ethyl 2- (diethoxyphosphoryl) -2-fluoroacetate, 2- (diethoxyphosphoryl) -2,2-difluoroacetate is preferred, among which 2-propynyl 2- (diethoxyphosphoryl) acetate, ethyl 2- (diethoxyphosphoryl) -2-fluoroacetate, 2- (diethoxyphosphoryl) -2 , 2-difluoroacetate is preferred.
- isocyanate examples include diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and octamethylene diisocyanate. Among them, hexamethylene diisocyanate is preferable.
- sultone compounds include 1,3-propane sultone, 2,4-butane sultone, 2,2-dioxide-1,2-oxathiolan-4-yl acetate, 5,5-dimethyl-1,2-oxathiolan-4-one 2,2-dioxide is preferred, among which 1,3-propane sultone, 2,2-dioxide-1,2-oxathiolan-4-yl acetate, 5,5-dimethyl-1,2-oxathiolane-4 -On 2,2-dioxide is preferred.
- sulfonic acid esters examples include 2-propynyl methanesulfonate, butyne-1,4-diyl dimethanesulfonate, pentane-1,5-diyl dimethanesulfonate, butane-2,3-diyl dimethanesulfonate, and methylenemethane disulfonate. And pentafluorophenyl methanesulfonate and methylenemethane disulfonate are preferable.
- nitriles include acetonitrile, propionitrile, succinonitrile, glutaronitrile, adiponitrile, and pimelonitrile. Pimeonitrile is more preferable, and adiponitrile and pimelonitrile are more preferable.
- the content of one or more selected from phosphate ester compounds, isocyanates, sultone compounds, sulfonate esters, and nitriles is preferably 0.01 to 5% by mass in the non-aqueous electrolyte. In this range, the coating film is sufficiently formed without becoming too thick, and the effect of improving the electrochemical characteristics over a wide temperature range is enhanced.
- the content is more preferably 0.05% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.3% by mass or more in the non-aqueous electrolyte, and the upper limit is 3% by mass or less. More preferred is 2% by mass or less.
- the content of other additives is preferably 0.05% by mass or more, and more preferably 0.2% by mass or more in the nonaqueous electrolytic solution from the viewpoint of improving electrochemical characteristics in a wide temperature range.
- the upper limit is preferably 8% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less.
- Electrolyte salt Preferred examples of the electrolyte salt used in the present invention include the following lithium salts and onium salts.
- lithium salt examples include inorganic lithium salts such as LiPF 6 , LiPO 2 F 2 , Li 2 PO 3 F, LiBF 4 , LiClO 4 , LiSO 3 F, LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2.
- the concentration of the lithium salt is usually preferably 0.3 M or more, more preferably 0.7 M or more, and further preferably 1.1 M or more with respect to the non-aqueous solvent.
- the upper limit is preferably 2.5M or less, more preferably 2.0M or less, and still more preferably 1.6M or less.
- suitable combinations of these lithium salts include LiPF 6 , and LiPO 2 F 2 , LiBF 4 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 F) 2 , and difluorobis [oxalate- O, O ′] It is preferable that one or more lithium salts selected from lithium phosphate are contained in the non-aqueous electrolyte.
- the proportion of lithium salt other than LiPF 6 in the non-aqueous solvent is 0.001M or more, the effect of improving electrochemical characteristics at high temperature is easily exhibited, and when it is 0.5M or less, electrochemical characteristics at high temperature. This is preferable because there is little concern that the effect of improving the resistance will decrease. More preferably, it is 0.01M or more, More preferably, it is 0.03M or more, Most preferably, it is 0.04M or more. The upper limit is more preferably 0.4M or less, and still more preferably 0.2M or less.
- onium salt As an onium salt, the various salts which combined the onium cation and anion shown below are mentioned suitably.
- Specific examples of onium cations include tetramethylammonium cation, ethyltrimethylammonium cation, diethyldimethylammonium cation, triethylmethylammonium cation, tetraethylammonium cation, N, N-dimethylpyrrolidinium cation, N-ethyl-N-methylpyrrole.
- N, N-diethylpyrrolidinium cation Dinium cation, N, N-diethylpyrrolidinium cation, spiro- (N, N ′)-bipyrrolidinium cation, N, N′-dimethylimidazolinium cation, N-ethyl-N′-methylimidazoli
- Preferable examples include nium cation, N, N′-diethylimidazolinium cation, N, N′-dimethylimidazolium cation, N-ethyl-N′-methylimidazolium cation, and N, N′-diethylimidazolium cation.
- anions include PF 6 anion, BF 4 anion, ClO 4 anion, AsF 6 anion, CF 3 SO 3 anion, N (CF 3 SO 2 ) 2 anion, N (C 2 F 5 SO 2 ) 2 anion. Etc. are preferable.
- electrolyte salts can be used singly or in combination of two or more.
- the non-aqueous electrolyte of the present invention is represented, for example, by the general formula (I) with respect to the non-aqueous electrolyte obtained by mixing the non-aqueous solvent and adding the electrolyte salt thereto. It can be obtained by adding a cyclic acid anhydride. At this time, it is preferable that the compound added to the non-aqueous solvent and the non-aqueous electrolyte to be used is one that is purified in advance and has as few impurities as possible within a range that does not significantly reduce the productivity.
- the non-aqueous electrolyte of the present invention can be used in the following first to fourth power storage devices, and as the non-aqueous electrolyte, not only a liquid but also a gelled one can be used. Furthermore, the non-aqueous electrolyte of the present invention can be used for a solid polymer electrolyte. In particular, it is preferably used for the first electricity storage device (that is, for a lithium battery) or the fourth electricity storage device (that is, for a lithium ion capacitor) that uses a lithium salt as an electrolyte salt, and is used for a lithium battery. More preferably, it is most suitable for use as a lithium secondary battery.
- the lithium battery of the present invention is a generic term for a lithium primary battery and a lithium secondary battery.
- the term lithium secondary battery is used as a concept including a so-called lithium ion secondary battery.
- the lithium battery of the present invention comprises the nonaqueous electrolyte solution in which an electrolyte salt is dissolved in a positive electrode, a negative electrode, and a nonaqueous solvent.
- Components other than the non-aqueous electrolyte, such as a positive electrode and a negative electrode can be used without particular limitation.
- a composite metal oxide with lithium containing one or more selected from cobalt, manganese, and nickel is used as the positive electrode active material for a lithium secondary battery.
- lithium composite metal oxides include LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiCo 1-x Ni x O 2 (0.01 ⁇ x ⁇ 1), LiCo 1/3 Ni 1/3. Examples thereof include one or more selected from Mn 1/3 O 2 , LiNi 1/2 Mn 3/2 O 4 , LiCo 0.98 Mg 0.02 O 2, and the like. Further, LiCoO 2 and LiMn 2 O 4 , LiCoO 2 and LiNiO 2 , LiMn 2 O 4 and LiNiO 2 may be used in combination.
- a part of the lithium composite metal oxide may be substituted with another element.
- a part of cobalt, manganese, nickel is replaced with at least one element selected from Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, Cu, Bi, Mo, La, etc.
- a part of O may be substituted with S or F, or a compound containing these other elements may be coated.
- a lithium composite metal that can be used at a charging potential of the positive electrode in a fully charged state such as one or more selected from LiCoO 2 , LiMn 2 O 4 , and LiNiO 2 at 4.3 V or more on the basis of Li.
- An oxide is preferable, and LiCo 1-x M x O 2 (where M is at least one element selected from Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, Cu, 0 .001 ⁇ x ⁇ 0.05), LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 1/2 Mn 3/2 O 4 , Li 2 MnO 3 and LiMO 2 (M is Co, Ni More preferable are lithium composite metal oxides usable at 4.4 V or higher, such as one or more selected from solid solutions with transition metals such as Mn and Fe).
- the electrochemical characteristics in a wide temperature range are likely to be deteriorated due to a reaction with the electrolyte during charging, but in the lithium secondary battery according to the present invention, these A decrease in electrochemical characteristics can be suppressed.
- the resistance of the battery tends to increase with the elution of Mn ions from the positive electrode, so that the electrochemical characteristics in a wide temperature range tend to be lowered.
- Lithium secondary batteries are preferred because they can suppress a decrease in these electrochemical characteristics.
- lithium-containing olivine-type phosphate can also be used as the positive electrode active material.
- a lithium-containing olivine-type phosphate containing one or more selected from iron, cobalt, nickel, and manganese is preferable. Specific examples thereof include one or more selected from LiFePO 4 , LiCoPO 4 , LiNiPO 4 , LiMnPO 4 , and the like. Some of these lithium-containing olivine-type phosphates may be substituted with other elements, and some of iron, cobalt, nickel, and manganese are replaced with Co, Mn, Ni, Mg, Al, B, Ti, V, and Nb.
- Cu, Zn, Mo, Ca, Sr, W and Zr can be substituted with one or more elements selected from these, or can be coated with a compound or carbon material containing these other elements.
- LiFePO 4 or LiMnPO 4 is preferable.
- mold phosphate can also be mixed with the said positive electrode active material, for example, and can be used.
- the positive electrode for lithium primary battery CuO, Cu 2 O, Ag 2 O, Ag 2 CrO 4, CuS, CuSO 4, TiO 2, TiS 2, SiO 2, SnO, V 2 O 5, V 6 O 12 , VO x , Nb 2 O 5 , Bi 2 O 3 , Bi 2 Pb 2 O 5 , Sb 2 O 3 , CrO 3 , Cr 2 O 3 , MoO 3 , WO 3 , SeO 2 , MnO 2 , Mn 2 O 3 , Fe 2 O 3 , FeO, Fe 3 O 4 , Ni 2 O 3 , NiO, CoO 3 , CoO, and other oxides or chalcogen compounds of one or more metal elements, SO 2 , SOCl 2, etc.
- Examples thereof include a sulfur compound and fluorocarbon (fluorinated graphite) represented by the general formula (CF x ) n .
- fluorocarbon fluorinated graphite
- one or more selected from MnO 2 , V 2 O 5 and fluorinated graphite are preferable.
- the positive electrode conductive agent is not particularly limited as long as it is an electron conductive material that does not cause a chemical change.
- Examples thereof include graphite such as natural graphite (flaky graphite and the like) and artificial graphite, carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black and thermal black. Further, graphite and carbon black may be appropriately mixed and used.
- the addition amount of the conductive agent to the positive electrode mixture is preferably 1 to 10% by mass, and more preferably 2 to 5% by mass.
- the positive electrode is composed of a conductive agent such as acetylene black and carbon black, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), a copolymer of styrene and butadiene (SBR), acrylonitrile and butadiene.
- a conductive agent such as acetylene black and carbon black, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), a copolymer of styrene and butadiene (SBR), acrylonitrile and butadiene.
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- SBR styrene and butadiene
- SBR styrene and butadiene
- acrylonitrile and butadiene acrylonitrile and butadiene.
- binder such as copolymer (NBR), carb
- this positive electrode mixture was applied to a current collector aluminum foil, a stainless steel lath plate, etc., dried and pressure-molded, and then subjected to vacuum at a temperature of about 50 ° C. to 250 ° C. for about 2 hours. It can be manufactured by heat treatment.
- the density of the part except the collector of the positive electrode is usually at 1.5 g / cm 3 or more, for further increasing the capacity of the battery, is preferably 2 g / cm 3 or more, more preferably 3 g / cm 3 or more More preferably, it is 3.6 g / cm 3 or more.
- the upper limit is preferably 4 g / cm 3 or less.
- Examples of the negative electrode active material for a lithium secondary battery include lithium metal, lithium alloy, and a carbon material capable of occluding and releasing lithium (easily graphitized carbon and a (002) plane spacing of 0.37 nm or more).
- One or two or more selected from compounds are preferred.
- a highly crystalline carbon material such as artificial graphite and natural graphite
- the lattice spacing (002) of the lattice plane ( 002 ) is 0.00.
- a carbon material having a graphite type crystal structure of 340 nm (nanometer) or less, particularly 0.335 to 0.337 nm.
- a mechanical action such as compression force, friction force, shear force, etc.
- the density of the portion excluding the current collector of the negative electrode can be obtained from X-ray diffraction measurement of the negative electrode sheet when pressure-molded to a density of 1.5 g / cm 3 or more.
- the ratio I (110) / I (004) of the peak intensity I (110) of the (110) plane of the graphite crystal and the peak intensity I (004) of the (004) plane is 0.01 or more, the temperature becomes even wider.
- the highly crystalline carbon material is coated with a carbon material having lower crystallinity than the core material because electrochemical characteristics in a wide temperature range are further improved.
- the crystallinity of the carbon material of the coating can be confirmed by TEM.
- Examples of the metal compound capable of inserting and extracting lithium as the negative electrode active material include Si, Ge, Sn, Pb, P, Sb, Bi, Al, Ga, In, Ti, Mn, Fe, Co, Ni, and Cu. , Zn, Ag, Mg, Sr, Ba, and other compounds containing at least one metal element.
- These metal compounds may be used in any form such as a simple substance, an alloy, an oxide, a nitride, a sulfide, a boride, and an alloy with lithium, but any of a simple substance, an alloy, an oxide, and an alloy with lithium. Is preferable because the capacity can be increased.
- those containing at least one element selected from Si, Ge and Sn are preferable, and those containing at least one element selected from Si and Sn are particularly preferable because the capacity of the battery can be increased.
- the negative electrode is kneaded using the same conductive agent, binder, and high-boiling solvent as in the preparation of the positive electrode described above to form a negative electrode mixture, and then this negative electrode mixture is applied to the copper foil of the current collector. After being dried and pressure-molded, it can be produced by heat treatment under vacuum at a temperature of about 50 ° C. to 250 ° C. for about 2 hours.
- the density of the portion excluding the current collector of the negative electrode is usually 1.1 g / cm 3 or more, and is preferably 1.5 g / cm 3 or more, more preferably 1.7 g / cm 3 in order to further increase the battery capacity. 3 or more.
- the upper limit is preferably 2 g / cm 3 or less.
- examples of the negative electrode active material for a lithium primary battery include lithium metal and lithium alloy.
- the structure of the lithium battery is not particularly limited, and a coin-type battery, a cylindrical battery, a square battery, a laminated battery, or the like having a single-layer or multi-layer separator can be applied. Although it does not restrict
- the lithium secondary battery according to the present invention has excellent electrochemical characteristics in a wide temperature range even when the end-of-charge voltage is 4.2 V or more, particularly 4.3 V or more, and the characteristics are also good at 4.4 V or more. is there.
- the end-of-discharge voltage is usually 2.8 V or higher, and more preferably 2.5 V or higher, but the lithium secondary battery in the present invention can be 2.0 V or higher.
- the current value is not particularly limited, but is usually used in the range of 0.1 to 30C. Further, the lithium battery in the present invention can be charged and discharged at ⁇ 40 to 100 ° C., preferably ⁇ 10 to 80 ° C.
- a method of providing a safety valve on the battery lid or cutting a member such as a battery can or a gasket can be employed.
- the battery lid can be provided with a current interruption mechanism that senses the internal pressure of the battery and interrupts the current.
- Electrode double layer capacitor It is an electricity storage device that stores energy by using the electric double layer capacity at the interface between the electrolyte and the electrode.
- An example of the present invention is an electric double layer capacitor.
- the most typical electrode active material used for this electricity storage device is activated carbon. Double layer capacity increases roughly in proportion to surface area.
- Examples of the positive electrode include those using an electric double layer between an activated carbon electrode and an electrolytic solution, and those using a ⁇ -conjugated polymer electrode doping / dedoping reaction.
- the electrolyte contains at least a lithium salt such as LiPF 6 .
- Examples 1 to 23 and Comparative Examples 1 to 5 [Production of lithium ion secondary battery] 94% by mass of LiNi 1/3 Mn 1/3 Co 1/3 O 2 and 3% by mass of acetylene black (conductive agent) are mixed, and 3% by mass of polyvinylidene fluoride (binder) is previously added to 1-methyl-2-
- a positive electrode mixture paste was prepared by adding to and mixing with the solution dissolved in pyrrolidone. This positive electrode mixture paste was applied to one side of an aluminum foil (current collector), dried and pressurized, punched out to a predetermined size, and a positive electrode sheet was produced. The density of the portion excluding the current collector of the positive electrode was 3.6 g / cm 3 .
- the ratio of the peak intensity I (110) of the (110) plane of the graphite crystal to the peak intensity I (004) of the (004) plane [I (110) / I (004)] was 0.1.
- a positive electrode sheet, a microporous polyethylene film separator, and a negative electrode sheet were laminated in this order, and the compositions shown in Table 1 (the cyclic acid anhydrides of Examples 1 to 6, 10 to 23 were 3-allyldihydrofuran-2,5- Dione, the cyclic acid anhydride of Example 7 is 3- (3-methylallyl) dihydrofuran-2,5-dione, and the cyclic acid anhydride of Example 8 is 3- (2-methylallyl) dihydrofuran-2,5- A non-aqueous electrolyte of dione, 3- (2-propyn-1-yl) dihydrofuran-2,5-dione) as a cyclic acid anhydride of Example 9, was added to prepare a 2032 type coin battery.
- Example 24 and Comparative Example 6 In place of the negative electrode active material used in Example 1 and Comparative Example 1, a negative electrode sheet was prepared using silicon (single element) (negative electrode active material). 80% by mass of silicon (elemental) and 15% by mass of acetylene black (conductive agent) are mixed and added to a solution in which 5% by mass of polyvinylidene fluoride (binder) is previously dissolved in 1-methyl-2-pyrrolidone. And mixed to prepare a negative electrode mixture paste. Example 1 and Comparative Example 1 except that this negative electrode mixture paste was applied onto a copper foil (current collector), dried and pressurized, punched to a predetermined size, and a negative electrode sheet was produced. Similarly, a coin battery was prepared and battery evaluation was performed. The results are shown in Table 4.
- Example 25 and Comparative Example 7 In place of the positive electrode active material used in Example 1 and Comparative Example 1, a positive electrode sheet was prepared using lithium-containing olivine-type iron phosphate salt (LiFePO 4 ) (positive electrode active material) coated with amorphous carbon. did. 90% by mass of LiFePO 4 coated with amorphous carbon and 5% by mass of acetylene black (conductive agent) are mixed, and 5% by mass of polyvinylidene fluoride (binder) is dissolved in 1-methyl-2-pyrrolidone in advance. A positive electrode mixture paste was prepared by adding to and mixing with the previously prepared solution.
- LiFePO 4 lithium-containing olivine-type iron phosphate salt
- This positive electrode mixture paste was applied onto an aluminum foil (current collector), dried, pressurized and punched to a predetermined size to produce a positive electrode sheet, and the end-of-charge voltage during battery evaluation was 3.
- a coin battery was produced and evaluated in the same manner as in Example 1 and Comparative Example 1 except that the voltage was 6 V and the discharge end voltage was 2.0 V. The results are shown in Table 5.
- Example 3 (using a cyclic acid anhydride represented by the general formula (I)) and Comparative Example 2 (using a cyclic acid anhydride having a double bond inside the ring structure: maleic anhydride), Comparative Example 3 (Use of a cyclic acid anhydride having a double bond at the end of the ring structure and a side chain having 3 or more carbon atoms bonded to the end), Comparative Example 4 (the number of carbon atoms having a double bond at the end) Comparison of Comparative Example 5 (Use of a cyclic acid anhydride having a side chain of 3 or more carbon atoms having a double bond at a non-terminal position) and Comparative Example 5 It has been found that this effect is specific to the cyclic
- the effect of the present invention is that, in a non-aqueous electrolyte solution in which an electrolyte salt is dissolved in a non-aqueous solvent, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate are contained in the non-aqueous solvent.
- the non-aqueous electrolyte of the present invention has an effect of improving the discharge characteristics in a wide temperature range of the lithium primary battery.
- the nonaqueous electrolytic solution of the present invention is used, an electricity storage device having excellent electrochemical characteristics in a wide temperature range can be obtained.
- an electricity storage device capable of improving electrochemical characteristics in a wide temperature range. it can.
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Abstract
Description
特に地球温暖化防止のため、CO2排出量を削減することが急務となっており、リチウム二次電池やキャパシタ等の蓄電デバイスからなる蓄電装置を搭載した環境対応車の中でも、ハイブリッド電気自動車(HEV)、プラグインハイブリッド電気自動車(PHEV)、バッテリー電気自動車(BEV)の早期普及が求められている。自動車は移動距離が長いため、熱帯の非常に暑い地域から極寒の地域まで幅広い温度範囲の地域で使用される可能性がある。従って、特にこれらの車載用の蓄電デバイスは、高温から低温まで幅広い温度範囲で使用しても電気化学特性が劣化しないことが要求されている。
なお、本明細書において、リチウム二次電池という用語は、いわゆるリチウムイオン二次電池も含む概念として用いる。
また、負極としては、金属リチウム、リチウムを吸蔵及び放出可能な金属化合物(金属単体、酸化物、リチウムとの合金等)や炭素材料が知られており、特にリチウムを吸蔵及び放出することが可能なコークス、人造黒鉛、天然黒鉛等の炭素材料を用いたリチウム二次電池が広く実用化されている。
更に、リチウム金属やその合金、スズ又はケイ素等の金属単体や酸化物を負極材料として用いたリチウム二次電池は、初期の容量は高いもののサイクル中に微粉化が進むため、炭素材料の負極に比べて非水溶媒の還元分解が加速的に起こり、電池容量やサイクル特性のような電池性能が大きく低下することが知られている。また、これらの負極材料の微粉化が進んだり、非水溶媒の分解物が蓄積すると、負極へのリチウムの吸蔵及び放出がスムーズにできなくなり、広い温度範囲での電気化学特性が低下しやすくなる。
一方、正極として、例えばLiCoO2、LiMn2O4、LiNiO2、LiFePO4等を用いたリチウム二次電池は、非水電解液中の非水溶媒が充電状態で正極材料と非水電解液との界面において、局部的に一部酸化分解することにより発生した分解物やガスが電池の望ましい電気化学的反応を阻害するため、やはり広い温度範囲での電気化学特性の低下を生じることが分かっている。
特許文献1には、特定の不飽和環状酸無水物を添加した非水電解液が提案されており、サイクル特性を向上させることが開示されている。
特許文献2には、無水マレイン酸と1-ペンテンとを反応させて得られるカルボン酸無水有機化合物を含有する非水電解液が提案されており、保存特性に優れることが開示されている。
特許文献3には、無水マレイン酸とN-メチルスクシンイミドを混合して含有する非水電解液が提案されており、充電保存特性を向上させることが開示されている。
そこで、本発明者らは、上記課題を解決するために鋭意研究を重ね、非水溶媒中にエチレンカーボネート、プロピレンカーボネート、1,2-ブチレンカーボネート、2,3-ブチレンカーボネート、4-フルオロ-1,3-ジオキソラン-2-オン、トランス又はシス-4,5-ジフルオロ-1,3-ジオキソラン-2-オン、ビニレンカーボネート、ビニルエチレンカーボネート、及び4-エチニル-1,3-ジオキソラン-2-オンから選ばれる2種以上の環状カーボネートを含み、且つ、非水電解液中に二重結合又は三重結合を末端に有する炭素数3以上の側鎖が結合した特定の環状酸無水物を含有することで、広い温度範囲での電気化学特性、特にリチウム電池の電気化学特性を改善できることを見出し、本発明を完成した。
(1)非水溶媒に電解質塩が溶解されている非水電解液において、該非水溶媒がエチレンカーボネート、プロピレンカーボネート、1,2-ブチレンカーボネート、2,3-ブチレンカーボネート、4-フルオロ-1,3-ジオキソラン-2-オン、トランス又はシス-4,5-ジフルオロ-1,3-ジオキソラン-2-オン、ビニレンカーボネート、ビニルエチレンカーボネート、及び4-エチニル-1,3-ジオキソラン-2-オンから選ばれる2種以上の環状カーボネートを含み、更に非水電解液中に、下記一般式(I)で表される二重結合又は三重結合を末端に有する炭素数3以上の側鎖が結合した環状酸無水物を0.01~10質量%含有することを特徴とする非水電解液。
本発明の非水電解液は、非水溶媒に電解質塩が溶解されている非水電解液において、該非水溶媒中にエチレンカーボネート、プロピレンカーボネート、1,2-ブチレンカーボネート、2,3-ブチレンカーボネート、4-フルオロ-1,3-ジオキソラン-2-オン、トランス又はシス-4,5-ジフルオロ-1,3-ジオキソラン-2-オン、ビニレンカーボネート、ビニルエチレンカーボネート、及び4-エチニル-1,3-ジオキソラン-2-オンから選ばれる2種以上の環状カーボネートを含み、更に非水電解液中に前記一般式(I)で表される二重結合又は三重結合を末端に有する炭素数3以上の側鎖が結合した環状酸無水物(以下、単に「一般式(I)で表される環状酸無水物」ともいう)を0.01~10重量%含有することを特徴とする非水電解液である。
本発明の非水電解液が含有する前記一般式(I)で表される環状酸無水物は、初回充電時に負極上で還元分解し、緻密で耐熱性の高い被膜を形成することで高温保存後の容量低下を抑制する効果を得ることができる。しかしながら、前記一般式(I)で表される環状酸無水物由来の被膜は、側鎖の末端に二重結合又は三重結合を有するため、高抵抗となりやすく、高温保存後の低温特性が低下しやすいという課題があった。
ここで、エチレンカーボネート、プロピレンカーボネート、1,2-ブチレンカーボネート、2,3-ブチレンカーボネート、4-フルオロ-1,3-ジオキソラン-2-オン、トランス又はシス-4,5-ジフルオロ-1,3-ジオキソラン-2-オン、ビニレンカーボネート、ビニルエチレンカーボネート、及び4-エチニル-1,3-ジオキソラン-2-オンから選ばれる2種以上の環状カーボネートを前記一般式(I)で表される環状酸無水物と混合して使用すると、2種以上の異なる環状カーボネートの分解生成物と前記一般式(I)で表される環状酸無水物の分解生成物とが相俟って被膜成分として取り込まれることから、被膜が過度に緻密化することなく、低抵抗な被膜が形成される。そのため、高温保存後の低温特性が著しく向上する特異的な効果をもたらすと考えられる。
更に、上記の環状カーボネートの中でも、エチレンカーボネートの他に、エチレンカーボネートの4位にメチル基を有する環状カーボネート、即ちプロピレンカーボネート、炭素-炭素二重結合又は炭素-炭素三重結合を有する環状カーボネート、即ちビニレンカーボネート、ビニルエチレンカーボネート、及び4-エチニル-1,3-ジオキソラン-2-オンから選ばれる1種以上を含むと上記の効果がより一層高まることが判明した。
前記一般式(I)のR1及びR2は、より好ましくは水素原子、ハロゲン原子、又は炭素数1~6のアルキル基、更に好ましくは水素原子、フッ素原子、メチル基、又はエチル基、特に好ましくは水素原子、フッ素原子、又はメチル基である。
前記一般式(I)のR3は、より好ましくは末端に二重結合を有する直鎖又は分枝の炭素数2~3のアルケニル基、末端に三重結合を有する直鎖又は分枝の炭素数2~3のアルキニル基であり、更に好ましくはビニル基、イソプロペニル基、エチニル基、2-プロピン-1-イル基、又は3-ブチン-1-イル基であり、特に好ましくはビニル基、イソプロペニル基、又はエチニル基である。
本発明の非水電解液に使用される非水溶媒としては、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、1,2-ブチレンカーボネート、2,3-ブチレンカーボネート、4-フルオロ-1,3-ジオキソラン-2-オン(FEC)、トランス又はシス-4,5-ジフルオロ-1,3-ジオキソラン-2-オン(以下、両者を総称して「DFEC」という)、ビニレンカーボネート(VC)、ビニルエチレンカーボネート(VEC)、及び4-エチニル-1,3-ジオキソラン-2-オン(EEC)から選ばれる2種以上の環状カーボネートの他、その他の環状カーボネート、鎖状エステル、ラクトン、エーテル、アミド、スルホン等が挙げられる。
非水溶媒は、環状カーボネートのみ、又は環状カーボネートと鎖状エステルの両方が含まれることが好ましい。
なお、鎖状エステルなる用語は、鎖状カーボネート及び鎖状カルボン酸エステルを含む概念として用いる。
環状カーボネートとして、2種以上の環状カーボネートを含むと高温保存後の低温特性が向上するので好ましい。
特にエチレンカーボネートの他に、エチレンカーボネートの4位にメチル基を有する環状カーボネート、即ちプロピレンカーボネート(PC)、炭素-炭素二重結合又は炭素-炭素三重結合を有する環状カーボネート、即ちビニレンカーボネート(VC)、ビニルエチレンカーボネート(VEC)、及び4-エチニル-1,3-ジオキソラン-2-オン(EEC)から選ばれる1種以上を含むと、高温保存後の低温特性が一段と向上するので好ましい。より好ましくはPC、VCであり、PC及びVCを含むと高温保存後の低温特性が格段に向上するので好ましい。
炭素-炭素二重結合を有する環状カーボネート(即ちVC、VEC)の含有量は、非水溶媒の総体積に対して、好ましくは0.07体積%以上、より好ましくは0.2体積%以上、更に好ましくは0.7体積%以上であり、その上限が、好ましくは7体積%以下、より好ましくは4体積%以下、更に好ましくは2.5体積%以下であると、低温でのLiイオン透過性を損なうことなく一段と高温保存時の被膜の安定性を増すことができるので好ましい。
前記鎖状エステルの中でも、ジメチルカーボネート(DMC)、ジエチルカーボネート(DEC)、ジプロピルカーボネート、及びジブチルカーボネートから選ばれる1種又は2種以上の対称鎖状カーボネートが好ましく、ジエチルカーボネート(DEC)がより好ましい。
前記鎖状エステル中に、第3級カルボン酸エステルであるピバリン酸エステルが含有されていると、本願発明の二重結合又は三重結合を末端に有する炭素数3以上の側鎖が結合した環状酸無水物と相俟って負極上に被膜を形成する際に、被膜が過度に緻密化することなく、しかもリチウムイオン透過性を向上させるという予想し得ない効果が発揮され、広い温度範囲での電気化学特性を一段と向上させることができるので好ましく、特にピバリン酸メチルが含有されていることが好ましい。
鎖状エステル中にピバリン酸エステルが占める体積の割合は、5体積%以上が好ましく、15体積%以上がより好ましく、55体積%以上が更に好ましい。上限としては、100体積%以下が好ましく、95体積%以下がより好ましく、85体積%以下が更に好ましい。
上記の場合に一段と広い温度範囲での電気化学特性が向上するので好ましい。
その他の添加剤の具体例としては、リン酸トリメチル、リン酸トリブチル、及びリン酸トリオクチル、エチル 2-(ジエトキシホスホリル)アセテート、2-プロピニル 2-(ジエトキシホスホリル)アセテート、エチル 2-(ジエトキシホスホリル)-2-フルオロアセテート、2-(ジエトキシホスホリル)-2,2-ジフルオロアセテート等のリン酸エステル、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、オクタメチレンジイソシアネート等のイソシアネート、1,3-プロパンスルトン、1,3-ブタンスルトン、2,4-ブタンスルトン、1,4-ブタンスルトン、2,2-ジオキシド-1,2-オキサチオラン-4-イル アセテート、5,5-ジメチル-1,2-オキサチオラン-4-オン 2,2-ジオキシド等のスルトン、エチレンサルファイト、ヘキサヒドロベンゾ[1,3,2]ジオキサチオラン-2-オキシド(1,2-シクロヘキサンジオールサイクリックサルファイトともいう)、5-ビニル-ヘキサヒドロ1,3,2-ベンゾジオキサチオール-2-オキシド等の環状サルファイト、メタンスルホン酸2-プロピニル、ブタン-1,4-ジイル ジメタンスルホネート、ブチン-1,4-ジイル ジメタンスルホネート、ペンタン-1,5-ジイル ジメタンスルホネート、プロパン-1,2-ジイル ジメタンスルホネート、ブタン-2,3-ジイル ジメタンスルホネート、メチレンメタンジスルホネート、2-トリフルオロメチルフェニル メタンスルホネート、ペンタフルオロフェニル メタンスルホネート、メチレンメタンジスルホネート等のスルホン酸エステル、ジビニルスルホン、1,2-ビス(ビニルスルホニル)エタン、ビス(2-ビニルスルホニルエチル)エーテル等のビニルスルホン等から選ばれるS=O結合含有化合物、無水酢酸、無水プロピオン酸等の鎖状のカルボン酸無水物、無水コハク酸、無水マレイン酸、無水グルタル酸、無水イタコン酸等の前記一般式(I)で表される環状酸無水物以外の環状酸無水物、メトキシペンタフルオロシクロトリホスファゼン、エトキシペンタフルオロシクロトリホスファゼン、フェノキシペンタフルオロシクロトリホスファゼン、エトキシヘプタフルオロシクロテトラホスファゼン等の環状ホスファゼン化合物が好適に挙げられる。
上記の中でも、フッ素原子、tert-アルキル基、又はそれらの両方を有する芳香族化合物が含有されていると、前記一般式(I)で表される環状酸無水物と相俟って負極上に被膜を形成する際に、被膜が過度に緻密化することなく、しかもリチウムイオン透過性を向上させるという予想し得ない効果が発揮され、一段と広い温度範囲での電気化学特性が向上するので好ましい。
フッ素原子、tert-アルキル基、又はそれらの両方を有する芳香族化合物の含有量は、非水電解液中に0.1~15質量%が好ましい。この範囲では、被膜が厚くなり過ぎずに十分に形成され、広い温度範囲での電気化学特性の改善効果が高まる。該含有量は、非水電解液中に0.5質量%以上がより好ましく、1質量%以上が更に好ましく、その上限は、13質量%以下がより好ましい。
リン酸エステル化合物としては、エチル 2-(ジエトキシホスホリル)アセテート、2-プロピニル 2-(ジエトキシホスホリル)アセテート、エチル 2-(ジエトキシホスホリル)-2-フルオロアセテート、2-(ジエトキシホスホリル)-2,2-ジフルオロアセテートが好適に挙げられ、中でも、2-プロピニル 2-(ジエトキシホスホリル)アセテート、エチル 2-(ジエトキシホスホリル)-2-フルオロアセテート、2-(ジエトキシホスホリル)-2,2-ジフルオロアセテートが好ましい。
イソシアネートとしては、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、オクタメチレンジイソシアネー等のジイソシアネートが好適に挙げられ、中でも、ヘキサメチレンジイソシアネートが好ましい。
スルトン化合物としては、1,3-プロパンスルトン、2,4-ブタンスルトン、2,2-ジオキシド-1,2-オキサチオラン-4-イル アセテート、5,5-ジメチル-1,2-オキサチオラン-4-オン 2,2-ジオキシドが好適に挙げられ、中でも、1,3-プロパンスルトン、2,2-ジオキシド-1,2-オキサチオラン-4-イル アセテート、5,5-ジメチル-1,2-オキサチオラン-4-オン 2,2-ジオキシドが好ましい。
スルホン酸エステルとしては、メタンスルホン酸2-プロピニル、ブチン-1,4-ジイル ジメタンスルホネート、ペンタン-1,5-ジイル ジメタンスルホネート、ブタン-2,3-ジイル ジメタンスルホネート、メチレンメタンジスルホネート、ペンタフルオロフェニル メタンスルホネート、メチレンメタンジスルホネートが好適に挙げられ、中でも、メタンスルホン酸2-プロピニル、ブチン-1,4-ジイル ジメタンスルホネート、ペンタフルオロフェニル メタンスルホネートが好ましい。
ニトリルとしては、アセトニトリル、プロピオニトリル、スクシノニトリル、グルタロニトリル、アジポニトリル、ピメロニトリル等が挙げられるが、スクシノニトリル、グルタロニトリル、アジポニトリル、ピメロニトリル等のジニトリルが好ましく、スクシノニトリル、アジポニトリル、ピメロニトリルがより好ましく、アジポニトリル、ピメロニトリルが更に好ましい。
その他の添加剤の含有量は、広い温度範囲での電気化学特性向上の観点から、非水電解液中に0.05質量%以上が好ましく、0.2質量%以上がより好ましい。また、その上限は、8質量%以下が好ましく、5質量%以下がより好ましく、3質量%以下が特に好ましい。
本発明に使用される電解質塩としては、下記のリチウム塩、オニウム塩が好適に挙げられる。
リチウム塩としては、LiPF6、LiPO2F2、Li2PO3F、LiBF4、LiClO4、LiSO3F等の無機リチウム塩、LiN(SO2F)2、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiCF3SO3、LiC(SO2CF3)3、LiPF4(CF3)2、LiPF3(C2F5)3、LiPF3(CF3)3、LiPF3(iso-C3F7)3、LiPF5(iso-C3F7)等の鎖状のフッ化アルキル基を含有するリチウム塩や、(CF2)2(SO2)2NLi、(CF2)3(SO2)2NLi等の環状のフッ化アルキレン鎖を有するリチウム塩、ビス[オキサレート-O,O’]ホウ酸リチウムやジフルオロ[オキサレート-O,O’]ホウ酸リチウム、ジフルオロビス[オキサレート-O,O’]リン酸リチウム、及びテトラフルオロ[オキサレート-O,O’]リン酸リチウム等のオキサレート錯体をアニオンとするリチウム塩が好適に挙げられ、これらの1種又は2種以上を混合して使用することができる。
これらの中でも、LiPF6、LiPO2F2、Li2PO3F、LiBF4、LiSO3F、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiN(SO2F)2、ジフルオロビス[オキサレート-O,O’]リン酸リチウム、及びテトラフルオロ[オキサレート-O,O’]リン酸リチウムから選ばれる1種又は2種以上が好ましく、LiPF6、LiPO2F2、LiBF4、LiN(SO2CF3)2、LiN(SO2F)2、及びジフルオロビス[オキサレート-O,O’]リン酸リチウムから選ばれる1種又は2種以上が更に好ましい。
リチウム塩の濃度は、前記の非水溶媒に対して、通常0.3M以上が好ましく、0.7M以上がより好ましく、1.1M以上が更に好ましい。またその上限は、2.5M以下が好ましく、2.0M以下がより好ましく、1.6M以下が更に好ましい。
また、これらのリチウム塩の好適な組み合わせとしては、LiPF6を含み、更にLiPO2F2、LiBF4、LiN(SO2CF3)2、LiN(SO2F)2、及びジフルオロビス[オキサレート-O,O’]リン酸リチウムから選ばれる1種又は2種以上のリチウム塩が非水電解液中に含まれている場合が好ましい。
LiPF6以外のリチウム塩が非水溶媒中に占める割合は、0.001M以上であると、高温での電気化学特性の向上効果発揮されやすく、0.5M以下であると高温での電気化学特性の向上効果が低下する懸念が少ないので好ましい。より好ましくは0.01M以上、更に好ましくは0.03M以上、特に好ましくは0.04M以上である。その上限は、より好ましくは0.4M以下、更に好ましくは0.2M以下である。
また、オニウム塩としては、下記に示すオニウムカチオンとアニオンを組み合わせた各種塩が好適に挙げられる。
オニウムカチオンの具体例としては、テトラメチルアンモニウムカチオン、エチルトリメチルアンモニウムカチオン、ジエチルジメチルアンモニウムカチオン、トリエチルメチルアンモニウムカチオン、テトラエチルアンモニウムカチオン、N,N-ジメチルピロリジニウムカチオン、N-エチル-N-メチルピロリジニウムカチオン、N,N-ジエチルピロリジニウムカチオン、スピロ-(N,N')-ビピロリジニウムカチオン、N,N'-ジメチルイミダゾリニウムカチオン、N-エチル-N'-メチルイミダゾリニウムカチオン、N,N'-ジエチルイミダゾリニウムカチオン、N,N'-ジメチルイミダゾリウムカチオン、N-エチル-N'-メチルイミダゾリウムカチオン、N,N'-ジエチルイミダゾリウムカチオン等が好適に挙げられる。
アニオンの具体例としては、PF6アニオン、BF4アニオン、ClO4アニオン、AsF6アニオン、CF3SO3アニオン、N(CF3SO2)2アニオン、N(C2F5SO2)2アニオン等が好適に挙げられる。
これらの電解質塩は、1種単独で又は2種以上を組み合わせて使用することができる。
本発明の非水電解液は、例えば、前記の非水溶媒を混合し、これに前記の電解質塩を添加し、さらに得られた非水電解液に対して前記一般式(I)で表される環状酸無水物を添加することにより得ることができる。
この際、用いる非水溶媒及び非水電解液に加える化合物は、生産性を著しく低下させない範囲内で、予め精製して、不純物が極力少ないものを用いることが好ましい。
本発明のリチウム電池は、リチウム一次電池及びリチウム二次電池を総称する。また、本明細書において、リチウム二次電池という用語は、いわゆるリチウムイオン二次電池も含む概念として用いる。本発明のリチウム電池は、正極、負極及び非水溶媒に電解質塩が溶解されている前記非水電解液からなる。非水電解液以外の正極、負極等の構成部材は特に制限なく使用できる。
例えば、リチウム二次電池用正極活物質としては、コバルト、マンガン、及びニッケルから選ばれる1種又は2種以上を含有するリチウムとの複合金属酸化物が使用される。これらの正極活物質は、1種単独で又は2種以上を組み合わせて用いることができる。
このようなリチウム複合金属酸化物としては、例えば、LiCoO2、LiMn2O4、LiNiO2、LiCo1-xNixO2(0.01<x<1)、LiCo1/3Ni1/3Mn1/3O2、LiNi1/2Mn3/2O4、及びLiCo0.98Mg0.02O2等から選ばれる1種又は2種以上が挙げられる。また、LiCoO2とLiMn2O4、LiCoO2とLiNiO2、LiMn2O4とLiNiO2のように併用してもよい。
これらの中では、LiCoO2、LiMn2O4、LiNiO2から選ばれる1種又は2種以上のような満充電状態における正極の充電電位がLi基準で4.3V以上で使用可能なリチウム複合金属酸化物が好ましく、LiCo1-xMxO2(但し、MはSn、Mg、Fe、Ti、Al、Zr、Cr、V、Ga、Zn、Cuから選ばれる少なくとも1種類以上の元素、0.001≦x≦0.05)、LiCo1/3Ni1/3Mn1/3O2、LiNi1/2Mn3/2O4、Li2MnO3とLiMO2(Mは、Co、Ni、Mn、Fe等の遷移金属)との固溶体から選ばれる1種又は2種以上のような4.4V以上で使用可能なリチウム複合金属酸化物がより好ましい。高充電電圧で動作するリチウム複合金属酸化物を使用すると、充電時における電解液との反応により特に広い温度範囲での電気化学特性が低下しやすいが、本発明に係るリチウム二次電池ではこれらの電気化学特性の低下を抑制することができる。
特にMnを含む正極の場合に正極からのMnイオンの溶出に伴い電池の抵抗が増加しやすい傾向にあるため、広い温度範囲での電気化学特性が低下しやすい傾向にあるが、本発明に係るリチウム二次電池ではこれらの電気化学特性の低下を抑制することができるので好ましい。
これらのリチウム含有オリビン型リン酸塩の一部は他元素で置換してもよく、鉄、コバルト、ニッケル、マンガンの一部をCo、Mn、Ni、Mg、Al、B、Ti、V、Nb、Cu、Zn、Mo、Ca、Sr、W及びZr等から選ばれる1種以上の元素で置換したり、又はこれらの他元素を含有する化合物や炭素材料で被覆することもできる。これらの中では、LiFePO4又はLiMnPO4が好ましい。
また、リチウム含有オリビン型リン酸塩は、例えば前記の正極活物質と混合して用いることもできる。
正極の集電体を除く部分の密度は、通常は1.5g/cm3以上であり、電池の容量をさらに高めるため、好ましくは2g/cm3以上であり、より好ましくは3g/cm3以上であり、更に好ましくは3.6g/cm3以上である。なお、その上限としては、4g/cm3以下が好ましい。
これらの中では、リチウムイオンの吸蔵及び放出能力において、人造黒鉛や天然黒鉛等の高結晶性の炭素材料を使用することが更に好ましく、格子面(002)の面間隔(d002)が0.340nm(ナノメータ)以下、特に0.335~0.337nmである黒鉛型結晶構造を有する炭素材料を使用することが特に好ましい。
複数の扁平状の黒鉛質微粒子が互いに非平行に集合或いは結合した塊状構造を有する人造黒鉛粒子や、例えば鱗片状天然黒鉛粒子に圧縮力、摩擦力、剪断力等の機械的作用を繰り返し与え、球形化処理を施した黒鉛粒子を用いることにより、負極の集電体を除く部分の密度を1.5g/cm3以上の密度に加圧成形したときの負極シートのX線回折測定から得られる黒鉛結晶の(110)面のピーク強度I(110)と(004)面のピーク強度I(004)の比I(110)/I(004)が0.01以上となると一段と広い温度範囲での電気化学特性が向上するので好ましく、0.05以上となることがより好ましく、0.1以上となることが更に好ましい。また、過度に処理し過ぎて結晶性が低下し電池の放電容量が低下する場合があるので、その上限は0.5以下が好ましく、0.3以下がより好ましい。
また、高結晶性の炭素材料(コア材)はコア材よりも低結晶性の炭素材料によって被膜されていると、広い温度範囲での電気化学特性が一段と良好となるので好ましい。被覆の炭素材料の結晶性は、TEMにより確認することができる。
高結晶性の炭素材料を使用すると、充電時において非水電解液と反応し、界面抵抗の増加によって低温もしくは高温における電気化学特性を低下させる傾向があるが、本発明に係るリチウム二次電池では広い温度範囲での電気化学特性が良好となる。
負極の集電体を除く部分の密度は、通常は1.1g/cm3以上であり、電池の容量をさらに高めるため、好ましくは1.5g/cm3以上、より好ましくは1.7g/cm3以上である。なお、その上限としては、2g/cm3以下が好ましい。
電池用セパレータとしては、特に制限はされないが、ポリプロピレン、ポリエチレン等のポリオレフィンの単層又は積層の微多孔性フィルム、織布、不織布等を使用できる。
電解液と電極界面の電気二重層容量を利用してエネルギーを貯蔵する蓄電デバイスである。本発明の一例は、電気二重層キャパシタである。この蓄電デバイスに用いられる最も典型的な電極活物質は、活性炭である。二重層容量は概ね表面積に比例して増加する。
電極のドープ/脱ドープ反応を利用してエネルギーを貯蔵する蓄電デバイスである。この蓄電デバイスに用いられる電極活物質として、酸化ルテニウム、酸化イリジウム、酸化タングステン、酸化モリブデン、酸化銅等の金属酸化物や、ポリアセン、ポリチオフェン誘導体等のπ共役高分子が挙げられる。これらの電極活物質を用いたキャパシタは、電極のドープ/脱ドープ反応にともなうエネルギー貯蔵が可能である。
負極であるグラファイト等の炭素材料へのリチウムイオンのインターカレーションを利用してエネルギーを貯蔵する蓄電デバイスである。リチウムイオンキャパシタ(LIC)と呼ばれる。正極は、例えば活性炭電極と電解液との間の電気ニ重層を利用したものや、π共役高分子電極のドープ/脱ドープ反応を利用したもの等が挙げられる。電解液には少なくともLiPF6等のリチウム塩が含まれる。
〔リチウムイオン二次電池の作製〕
LiNi1/3Mn1/3Co1/3O2 94質量%、アセチレンブラック(導電剤)3質量%を混合し、予めポリフッ化ビニリデン(結着剤)3質量%を1-メチル-2-ピロリドンに溶解させておいた溶液に加えて混合し、正極合剤ペーストを調製した。この正極合剤ペーストをアルミニウム箔(集電体)上の片面に塗布し、乾燥、加圧処理して所定の大きさに打ち抜き、正極シートを作製した。正極の集電体を除く部分の密度は3.6g/cm3であった。
また、人造黒鉛(d002=0.335nm、負極活物質)95質量%を、予めポリフッ化ビニリデン(結着剤)5質量%を1-メチル-2-ピロリドンに溶解させておいた溶液に加えて混合し、負極合剤ペーストを調製した。この負極合剤ペーストを銅箔(集電体)上の片面に塗布し、乾燥、加圧処理して所定の大きさに打ち抜き負極シートを作製した。負極の集電体を除く部分の密度は1.5g/cm3であった。また、この電極シートを用いてX線回折測定した結果、黒鉛結晶の(110)面のピーク強度I(110)と(004)面のピーク強度I(004)の比〔I(110)/I(004)〕は0.1であった。
正極シート、微多孔性ポリエチレンフィルム製セパレータ、負極シートの順に積層し、表1に記載の組成(実施例1~6、10~23の環状酸無水物は3-アリルジヒドロフラン-2,5-ジオン、実施例7の環状酸無水物は3-(3-メチルアリル)ジヒドロフラン-2,5-ジオン、実施例8の環状酸無水物は3-(2-メチルアリル)ジヒドロフラン-2,5-ジオン、実施例9の環状酸無水物は3-(2-プロピン-1-イル)ジヒドロフラン-2,5-ジオン)の非水電解液を加えて、2032型コイン電池を作製した。
(i)初期の放電容量
上記の方法で作製したコイン電池を用いて、25℃の恒温槽中、1Cの定電流及び定電圧で、終止電圧4.3Vまで3時間充電し、0℃に恒温槽の温度を下げ、1Cの定電流下終止電圧2.75Vまで放電して、初期の0℃の放電容量を求めた。
(ii)高温充電保存試験
次に、このコイン電池を85℃の恒温槽中、1Cの定電流及び定電圧で終止電圧4.2Vまで3時間充電し、4.3Vに保持した状態で3日間保存を行った。その後、25℃の恒温槽に入れ、一旦1Cの定電流下終止電圧2.75Vまで放電した。
(iii)高温充電保存後の放電容量
更にその後、初期の放電容量の測定と同様にして、高温充電保存後(前記(ii)のとおり、満充電後、85℃で高温で保存した後)の0℃の放電容量を求めた。
(iv)高温充電保存後の低温特性
高温充電保存後の低温特性を下記の0℃放電容量の維持率より求めた。
高温充電保存後の0℃放電容量維持率(%)=(高温充電保存後の0℃の放電容量/初期の0℃の放電容量)×100
また、電池の作製条件及び電池特性を表1~表3に示す。
実施例1及び比較例1で用いた負極活物質に変えて、ケイ素(単体)(負極活物質)を用いて、負極シートを作製した。ケイ素(単体)80質量%、アセチレンブラック(導電剤)15質量%を混合し、予めポリフッ化ビニリデン(結着剤)5質量%を1-メチル-2-ピロリドンに溶解させておいた溶液に加えて混合し、負極合剤ペーストを調製した。
この負極合剤ペーストを銅箔(集電体)上に塗布し、乾燥、加圧処理して所定の大きさに打ち抜き、負極シートを作製したことの他は、実施例1及び比較例1と同様にコイン電池を作製し、電池評価を行った。結果を表4に示す。
実施例1及び比較例1で用いた正極活物質に変えて、非晶質炭素で被覆されたリチウム含有オリビン型リン酸鉄塩(LiFePO4)(正極活物質)を用いて、正極シートを作製した。非晶質炭素で被覆されたLiFePO4 90質量%、アセチレンブラック(導電剤)5質量%を混合し、予めポリフッ化ビニリデン(結着剤)5質量%を1-メチル-2-ピロリドンに溶解させておいた溶液に加えて混合し、正極合剤ペーストを調製した。
この正極合剤ペーストをアルミニウム箔(集電体)上に塗布し、乾燥、加圧処理して所定の大きさに打ち抜き、正極シートを作製したこと、電池評価の際の充電終止電圧を3.6V、放電終止電圧を2.0Vとしたことの他は、実施例1及び比較例1と同様にコイン電池を作製し、電池評価を行った。結果を表5に示す。
また、実施例3(一般式(I)で表される環状酸無水物使用)と比較例2(環構造の内部に二重結合を有する環状酸無水物:無水マレイン酸使用)、比較例3(環構造の内部に二重結合を有し、且つ二重を末端に有する炭素数3以上の側鎖が結合した環状酸無水物使用)、比較例4(二重結合を末端に有する炭素数2の側鎖が結合した環状酸無水物使用)、比較例5(末端でない位置に二重結合を有する炭素数3以上の側鎖が結合した環状酸無水物使用)の対比から本願発明の一般式(I)で表される環状酸無水物に特有の効果であることが判明した。
以上より、本発明の効果は、非水溶媒に電解質塩が溶解されている非水電解液において、非水溶媒中にエチレンカーボネート、プロピレンカーボネート、1,2-ブチレンカーボネート、2,3-ブチレンカーボネート、4-フルオロ-1,3-ジオキソラン-2-オン、トランス又はシス-4,5-ジフルオロ-1,3-ジオキソラン-2-オン、ビニレンカーボネート、ビニルエチレンカーボネート、及び4-エチニル-1,3-ジオキソラン-2-オンから選ばれる2種以上の環状カーボネートを含み、更に一般式(I)で表される環状酸無水物を0.001~10質量%含有させた場合に特有の効果であることが判明した。
また、実施例24と比較例6の対比、実施例25と比較例7の対比から、負極にケイ素(単体)Siを用いた場合や、正極にリチウム含有オリビン型リン酸鉄塩(LiFePO4)を用いた場合にも同様な効果がみられる。従って、本発明の効果は、特定の正極や負極に依存した効果でないことは明らかである。
Claims (12)
- 非水溶媒に電解質塩が溶解されている非水電解液において、該非水溶媒がエチレンカーボネート、プロピレンカーボネート、1,2-ブチレンカーボネート、2,3-ブチレンカーボネート、4-フルオロ-1,3-ジオキソラン-2-オン、トランス又はシス-4,5-ジフルオロ-1,3-ジオキソラン-2-オン、ビニレンカーボネート、ビニルエチレンカーボネート、及び4-エチニル-1,3-ジオキソラン-2-オンから選ばれる2種以上の環状カーボネートを含み、更に非水電解液中に、下記一般式(I)で表される二重結合又は三重結合を末端に有する炭素数3以上の側鎖が結合した環状酸無水物を0.01~10質量%含有することを特徴とする非水電解液。
- 一般式(I)で表される環状酸無水物が、3-アリルジヒドロフラン-2,5-ジオン、3-(3-メチルアリル)ジヒドロフラン-2,5-ジオン、3-(3,3-ジメチルアリル)ジヒドロフラン-2,5-ジオン、3-(2-メチルアリル)ジヒドロフラン-2,5-ジオン、3-(2,3-ジメチルアリル)ジヒドロフラン-2,5-ジオン、3-(2,3,3-トリメチルアリル)ジヒドロフラン-2,5-ジオン、3-(2-プロピン-1-イル)ジヒドロフラン-2,5-ジオン、3-(1-メチル-2-プロピン-1-イル)ジヒドロフラン-2,5-ジオン)、及び3-(1,2-ジメチル-2-プロピン-1-イル)ジヒドロフラン-2,5-ジオンから選ばれる1種又は2種以上である、請求項1に記載の非水電解液。
- 環状カーボネートが、エチレンカーボネートと、プロピレンカーボネート、ビニレンカーボネート及びビニルエチレンカーボネートから選ばれる1種以上である、請求項1又は2に記載の非水電解液。
- 非水溶媒が、更に鎖状エステルを含有する、請求項1~3のいずれかに記載の非水電解液。
- 鎖状エステルが、メチルエチルカーボネート、メチルプロピルカーボネート、メチルイソプロピルカーボネート、メチルブチルカーボネート、及びエチルプロピルカーボネートから選ばれる非対称鎖状カーボネート、ジメチルカーボネート、ジエチルカーボネート、ジプロピルカーボネート、及びジブチルカーボネートから選ばれる対称鎖状カーボネート、及び鎖状カルボン酸エステルから選ばれる1種又は2種以上である、請求項4に記載の非水電解液。
- 非水溶媒が、更にフッ素原子、tert-アルキル基、又はそれらの両方を有する芳香族化合物を含有する、請求項1~5のいずれかに記載の非水電解液。
- 非水溶媒が、更にニトリルを含有する、請求項1~6のいずれかに記載の非水電解液。
- 電解質塩が、LiPF6、LiPO2F2、Li2PO3F、LiBF4、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiN(SO2F)2、ジフルオロビス[オキサレート-O,O']リン酸リチウム、及びテトラフルオロ[オキサレート-O,O']リン酸リチウムから選ばれる1種又は2種以上を含む、請求項1~7のいずれかに記載の非水電解液。
- 電解質塩の濃度が、非水溶媒に対して、0.3~2.5Mである、請求項1~8のいずれかに記載の非水電解液。
- 正極、負極及び非水溶媒に電解質塩が溶解されている非水電解液を備えた蓄電デバイスであって、該非水電解液が請求項1~9に記載の非水電解液であることを特徴とする蓄電デバイス。
- 正極活物質が、コバルト、マンガン、及びニッケルから選ばれる1種以上を含有するリチウムとの複合金属酸化物、又は鉄、コバルト、ニッケル、及びマンガンから選ばれる1種又は2種以上を含有するリチウム含有オリビン型リン酸塩である、請求項10に記載の蓄電デバイス。
- 負極活物質が、リチウム金属、リチウム合金、リチウムを吸蔵及び放出することが可能な炭素材料、スズ、スズ化合物、ケイ素、ケイ素化合物、及びチタン酸リチウム化合物から選ばれる1種又は2種以上を含む、請求項10又は11に記載の蓄電デバイス。
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JP2015509271A (ja) * | 2012-12-24 | 2015-03-26 | エルジー・ケム・リミテッド | 非水性電解液及びこれを含むリチウム二次電池 |
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JP2015509271A (ja) * | 2012-12-24 | 2015-03-26 | エルジー・ケム・リミテッド | 非水性電解液及びこれを含むリチウム二次電池 |
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KR20160125978A (ko) * | 2014-02-25 | 2016-11-01 | 미쓰비시 가가꾸 가부시키가이샤 | 비수계 전해액 및 그것을 사용한 비수계 전해액 2 차 전지 |
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CN112735850A (zh) * | 2020-12-24 | 2021-04-30 | 清华大学深圳国际研究生院 | 一种可任意裁剪的柔性超级电容器及其制备方法 |
Also Published As
Publication number | Publication date |
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CN103891036A (zh) | 2014-06-25 |
JP6007915B2 (ja) | 2016-10-19 |
EP2770572A1 (en) | 2014-08-27 |
IN2014CN02844A (ja) | 2015-07-03 |
KR20140082978A (ko) | 2014-07-03 |
US9620816B2 (en) | 2017-04-11 |
CN103891036B (zh) | 2016-01-06 |
EP2770572B1 (en) | 2018-12-05 |
JPWO2013058235A1 (ja) | 2015-04-02 |
EP2770572A4 (en) | 2015-10-14 |
US20140234727A1 (en) | 2014-08-21 |
CA2851830A1 (en) | 2013-04-25 |
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