JP2014523083A - リチウム/硫黄蓄電池 - Google Patents
リチウム/硫黄蓄電池 Download PDFInfo
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- JP2014523083A JP2014523083A JP2014517885A JP2014517885A JP2014523083A JP 2014523083 A JP2014523083 A JP 2014523083A JP 2014517885 A JP2014517885 A JP 2014517885A JP 2014517885 A JP2014517885 A JP 2014517885A JP 2014523083 A JP2014523083 A JP 2014523083A
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- lithium
- electrolyte
- sulfur
- separator
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 41
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 35
- 239000011593 sulfur Substances 0.000 title claims abstract description 35
- 239000003792 electrolyte Substances 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 238000009736 wetting Methods 0.000 claims abstract description 5
- 229920000098 polyolefin Polymers 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 10
- -1 polyethylene terephthalate Polymers 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 9
- 229910018091 Li 2 S Inorganic materials 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 229920001021 polysulfide Polymers 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 229910013553 LiNO Inorganic materials 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-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
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000003780 insertion Methods 0.000 claims description 2
- 230000037431 insertion Effects 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000008116 organic polysulfides Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 150000002898 organic sulfur compounds Chemical class 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 208000028659 discharge Diseases 0.000 description 13
- 239000011888 foil Substances 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 7
- 238000002161 passivation Methods 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000005486 organic electrolyte Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 125000006091 1,3-dioxolane group Chemical group 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000698776 Duma Species 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
− 陰極
− 少なくとも1つの不織布を含み、且つ、50〜96%の範囲内の空隙率と、50〜200マイクロメーターの範囲内の厚さとを有する、電解質で含浸させた材料を含む電極セパレータ
− 陽極
を含む少なくとも1つの単位電池を含み、
前記電解質は過剰量で導入され、少なくとも1つのリチウム塩を含み、前記電解質の過剰量が、電極及びセパレータの湿潤を確保する電解質の量の20〜200%の量である、リチウム/硫黄蓄電池に関する。
Description
16Li+S8 → 8Li2S
− 陰極
− 少なくとも1つの不織布と、50〜96%の範囲内の空隙率と、50〜200マイクロメーターの範囲内、より有利には50〜100マイクロメーターの間の厚さとを有する、電解質で含浸させた材料を含む電極セパレータ
− 陽極
を含む少なくとも1つの単位電池を含むリチウム/硫黄蓄電池(Li/S)に関する。
− ポリオレフィン/PVAナノ繊維の不織布の二重層
− ポリオレフン/PVAナノ繊維/ポリオレフィン不織布の不織布の三重層、
− PVAナノ繊維
を含む群から選択される、少なくとも1つの不織布を含んでもよい。
− LiN(CF3SO2)2(リチウムビス[(トリフルオロメチル)スルホニル]イミド又はLiTFSI)、
− LiCF3SO3(リチウムトリフルオロメタンスルホネート又はLiTf又はLi−トリフラート)、
− LiClO4、
− LiAsF6、
− LiPF6、
− LiBF4、
− LiI、
− LiB(C2O4)2(リチウムビス(オキサラト)ボレート又はLiBOB)、
− LiN(CF3CF2SO2)2(リチウムビス(パーフルオロエチルスルホニル)イミド又はLiBETI)、
− LiNO3、
− LiOH(水酸化リチウム)、
を含む群から選択され得る少なくとも1つのリチウム塩をさらに含む。
− PC(プロピレンカーボネート)、DMC(ジメチルカーボネート)、EC(エチレンカーボネート)、及びDEC(ジエチルカーボネート)等のカーボネート類;
− DIOX(1,3−ジオキソラン)、THF(テトラヒドロフラン)、DME(1,2−ジメトキシエタン)、又はより一般的には、ポリエチレングリコールジメチルエーテル等の、式CH3O−(CH2CH2O)n−CH3(n=1〜10)のグリム類の群等のエーテル類、
を含む群から選択され得る。
− 金属リチウム;
− LiAl等の金属リチウム合金;
− グラファイト等のリチウム挿入化合物
を含む群から選択される少なくとも1つの活性電極材料から調製され得る。
− 銅箔の上に設けられた金属リチウム陰極;
− 50〜96%の範囲内の空隙率を有し、30〜100%の間の過剰量の電界質で浸漬された不織布の電極セパレータ;
− アルミニウム箔状に設けられた、硫黄元素から調製された陽極;
− PFGDME/DIOXの50/50混合物中に溶解されたLiTFSIを含む電解質
を含む、少なくとも1つの単位電池を含み得る。
− 電極;
− リチウム塩を含む電解質で浸漬された電極セパレータ;
− 陽極
を含む単位電池を積層することによる、「積層」タイプのLi/S蓄電池の形成に関する。
これらの単位電池の陰極は、リチウム製であり、140マイクロメーターの厚さを有し、4.15cm×4.15cmの寸法の正方形の形状を有する。電流を集めるのに使用される10マイクロメーターの厚さを有する銅製のタブが、さらに陰極に接続される。
これらの単位電池の両面型の陽極は、N−メチルピロリドン(NMP)中に溶解した、
− 75質量%の活性材料としての硫黄(Refined(登録商標)、Aldrich社から市販されている硫黄元素)
− 10質量%のカーボンブラック(Timcal社から市販されているSuper P(登録商標))
− 5質量%のカーボンファイバー(Showa Denko社から市販されているVGCF(登録商標))
− 10質量%の結合剤(Solvay社から市販されているポリビニリデンジフルオリドPVdF)
から調製されるインクから形成される。
以下で説明する実施例1、2、及び比較例のTi/S蓄電池は、電極セパレータの特徴によって互いに区別することができる。
− 55%の空隙率を有するVILEDON(登録商標)タイプFS 2206−14(Freudenbergから市販されている);
− Celgard(登録商標)2325(Celgard社により市販されている):140マイクロメーターの厚さと39%の空隙率を有する、ポリプロピレン又はPPタイプの、ポリオレフィン不織布;
− BERNARD DUMAS(登録商標)、タイプ1C1755(Bernard Dumas社より市販されている):非常に高い空隙率をもたらしつつ、膜の良好な機械的挙動を付与するポリ(エチレンテレフタレート)(PET)ファイバーにより補強されている、ガラス繊維不織布。このタイプのセパレータの厚さは一般的に、90%の空隙率において80マイクロメーターである。
セパレータは、PEGDME/DIOX(過剰量:30%)の、容積で50/50の混合物中に溶解されたLiTFSI塩(1mol/L)を含む液状電解質で浸漬された、ポリオレフィン不織布であるViledon(登録商標)(140μmの厚さを有するPP)と一体となったCelgard(登録商標)2325不織布(PP/PE/PP)である。
− PP = ポリプロピレン
− PE = ポリエチレン
− PEGDME = ポリエチレングリコールジメチルエーテル
− DIOX = 1,3−ジオキソラン
− LiTFSI = LiN(CF3SO2)2 (リチウムビス[(トリフルオロメチル)スルホニル]イミド)
セパレータは、PEGDME/DIOX(過剰量:30%)の、容積で50/50の混合物の溶液中に溶解されたLiTFSI塩(1mol/L)を含む液状電解質で浸漬された、ガラス繊維不織布(Bernard Dumas(登録商標)、タイプ1C1755)である。
セパレータは、PEGDME/DIOX(過剰量:30%)の、容積で50/50の混合物の溶液中に溶解されたLiTFSI塩(1mol/L)を含む液状電解質で浸漬された、Celgard(登録商標)2325不織布である。
実施例1及び2のそれぞれの蓄電池は、39%の空隙率を有するポリオレフィン不織布(図4)で形成された電極セパレータを有する従来技術の蓄電池(比較例)よりも、大きな質量貯蔵容量(電解質中に含まれる硫黄の量により表わされる、硫黄1グラムあたりのmAh)を有する。
Claims (9)
- − 陰極
− 少なくとも1つの不織布を含み、且つ、50〜96%の範囲内の空隙率と、50〜200マイクロメーターの範囲内の厚さとを有する、電解質で含浸させた材料を含む電極セパレータ
− 陽極
を含む少なくとも1つの単位電池を含み、
前記電解質は過剰量で導入され、少なくとも1つのリチウム塩を含み、前記電解質の過剰量が、電極及びセパレータの湿潤を確保する電解質の量の20〜200%の量である、リチウム/硫黄蓄電池。 - 前記陽極が、硫黄元素;硫化リチウム(Li2S);一般式Li2Sn(nは2〜8の範囲内である)の多硫化リチウム;一般式R2S(Rは2〜10の炭素原子を含むことができる直鎖状のアルキル基であり、nは2〜50の範囲内である)の有機多硫化物;ポリカーボンジスルフィドタイプの有機硫黄化合物;及び、Li/S蓄電池の放電サイクルの間に破断され、充電サイクルの間に元どおりに形成されるS−S結合を有するあらゆるジスルフィドポリマーを含む群から選択される、少なくとも1つの硫黄材料から調製されることを特徴とする、請求項1に記載のリチウム/硫黄蓄電池。
- 前記陰極が、金属リチウム、金属リチウム合金、及びリチウム挿入化合物を含む群から選択される少なくとも1つの活性材料を含むことを特徴とする、請求項1又は2に記載のリチウム/硫黄蓄電池。
- 前記電解質のリチウム塩が、LiN(CF3SO2)2;LiCF3SO3;LiClO4;LiAsF6;LiPF6;LiBF4; LiI;LiB(C2O4)2;LiN(CF3CF2SO2)2;LiNO3;及びLiOHを含む群から選択されることを特徴とする、請求項1〜3のいずれか一項に記載のリチウム/硫黄蓄電池。
- 前記電解質の過剰量が、電極及びセパレータの湿潤を確保する電解質量の50〜100%の間の量であることを特徴とする、請求項1〜4のいずれか一項に記載のリチウム/硫黄蓄電池。
- 前記電解質が、
− プロピレンカーボネート、ジメチルカーボネート、エチレンカーボネート、及びジエチルカーボネート等のカーボネート類;
− 1,3−ジオキソラン、テトラヒドロフラン、及び1,2−ジメトキシエタン、又はより一般的には、ポリエチレングリコールジメチルエーテル等の、式CH3O−(CH2CH2O)n−CH3(n=1〜10)のグリム類の群等のエーテル類、
− 水
を含む群から選択される少なくとも1つの溶媒を含むことを特徴とする、請求項1に記載のリチウム/硫黄蓄電池。 - 前記材料が、50〜90%の範囲内の空隙率を有することを特徴とする、請求項1〜6のいずれか一項に記載のリチウム/硫黄蓄電池。
- 前記材料が、50〜100マイクロメーターの範囲内の厚さを有する、請求項1〜7のいずれか一項に記載のリチウム/硫黄蓄電池。
- 前記不織布が、ガラス、ポリエチレンテレフタレート、ポリプロピレン及びポリエチレン等のポリオレフィン類、ポリ(ビニルアルコール)、ポリアミド、ポリ(テトラフルオロエチレン)、ポリ塩化ビニル、及びポリフッ化ビニリデン、並びにそれらの混合物の繊維を含む群から選択される繊維を含むことを特徴とする、請求項1〜8のいずれか一項に記載のリチウム/硫黄蓄電池。
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JP2018530132A (ja) * | 2016-04-22 | 2018-10-11 | エルジー・ケム・リミテッド | リチウム−硫黄電池用電解液及びこれを含むリチウム−硫黄電池 |
JP2019506725A (ja) * | 2016-06-28 | 2019-03-07 | エルジー・ケム・リミテッド | リチウム−硫黄電池用電解液及びこれを含むリチウム−硫黄電池 |
JP2019507482A (ja) * | 2016-06-28 | 2019-03-14 | エルジー・ケム・リミテッド | リチウム−硫黄電池用電解液及びこれを含むリチウム−硫黄電池 |
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JPWO2015092959A1 (ja) * | 2013-12-18 | 2017-03-16 | 株式会社アルバック | リチウム硫黄二次電池 |
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JP2015210848A (ja) * | 2014-04-23 | 2015-11-24 | オートモーティブエナジーサプライ株式会社 | 非水電解質二次電池 |
FR3023982B1 (fr) * | 2014-07-17 | 2016-08-12 | Blue Solutions | Batterie lithium soufre |
US10090554B2 (en) * | 2014-12-18 | 2018-10-02 | Ricoh Company, Ltd. | Non-aqueous electrolyte storage element |
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FR3071362B1 (fr) * | 2017-09-15 | 2019-09-13 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Procede de fabrication d'une electrode pour accumulateur lithium-soufre a surface active importante |
CN111370631A (zh) * | 2020-03-17 | 2020-07-03 | 绍兴望竹新能源科技有限公司 | 一种锂电池的电池隔膜 |
CN112125283A (zh) * | 2020-08-03 | 2020-12-25 | 浙江工业大学 | 一种利用固液混合加热制备硫化锂的方法 |
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WO2013004945A1 (fr) | 2013-01-10 |
US20140106239A1 (en) | 2014-04-17 |
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EP2729978A1 (fr) | 2014-05-14 |
US9391310B2 (en) | 2016-07-12 |
FR2977722B1 (fr) | 2014-03-14 |
KR20140048153A (ko) | 2014-04-23 |
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