JP2008522376A - リチウム・硫黄電池用電解質及びこれを使用するリチウム・硫黄電池 - Google Patents
リチウム・硫黄電池用電解質及びこれを使用するリチウム・硫黄電池 Download PDFInfo
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- JP2008522376A JP2008522376A JP2007543904A JP2007543904A JP2008522376A JP 2008522376 A JP2008522376 A JP 2008522376A JP 2007543904 A JP2007543904 A JP 2007543904A JP 2007543904 A JP2007543904 A JP 2007543904A JP 2008522376 A JP2008522376 A JP 2008522376A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 78
- 229910052744 lithium Inorganic materials 0.000 title claims description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 15
- 229910052717 sulfur Inorganic materials 0.000 title claims description 14
- 239000011593 sulfur Substances 0.000 title claims description 12
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 230000005496 eutectics Effects 0.000 claims abstract description 12
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 37
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 26
- 150000003457 sulfones Chemical class 0.000 claims description 21
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000001351 cycling effect Effects 0.000 claims description 3
- 239000011262 electrochemically active material Substances 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 238000009830 intercalation Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 claims description 2
- 125000005463 sulfonylimide group Chemical group 0.000 claims description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 claims 1
- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical compound [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 0.000 claims 1
- 239000011149 active material Substances 0.000 claims 1
- 239000000374 eutectic mixture Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 description 27
- 230000008018 melting Effects 0.000 description 21
- 238000002844 melting Methods 0.000 description 21
- 210000004027 cell Anatomy 0.000 description 17
- 239000011255 nonaqueous electrolyte Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical class CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 7
- 230000014233 sulfur utilization Effects 0.000 description 7
- QAPSIUMUNHNUPW-UHFFFAOYSA-N 1-methylsulfonylpropane Chemical compound CCCS(C)(=O)=O QAPSIUMUNHNUPW-UHFFFAOYSA-N 0.000 description 5
- 229910013684 LiClO 4 Inorganic materials 0.000 description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- WKFQMDFSDQFAIC-UHFFFAOYSA-N 2,4-dimethylthiolane 1,1-dioxide Chemical compound CC1CC(C)S(=O)(=O)C1 WKFQMDFSDQFAIC-UHFFFAOYSA-N 0.000 description 3
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- PVSJGAIWOIMZFG-UHFFFAOYSA-N 1-ethylsulfonylbutane Chemical compound CCCCS(=O)(=O)CC PVSJGAIWOIMZFG-UHFFFAOYSA-N 0.000 description 2
- JEXYCADTAFPULN-UHFFFAOYSA-N 1-propylsulfonylpropane Chemical class CCCS(=O)(=O)CCC JEXYCADTAFPULN-UHFFFAOYSA-N 0.000 description 2
- 229910003003 Li-S Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000004028 organic sulfates Chemical class 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- JQEOQFFGAGBEKI-UHFFFAOYSA-N 1-methylsulfonylpropane;thiolane 1,1-dioxide Chemical compound CCCS(C)(=O)=O.O=S1(=O)CCCC1 JQEOQFFGAGBEKI-UHFFFAOYSA-N 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 231100000817 safety factor Toxicity 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- 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
- 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
- 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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Description
組成物を、メチルプロピルスルホン(融点32.5℃)0.8mlとスルホラン(融点28.4℃)0.2mlから調製した。混合物の融点は+21℃であった。
組成物を、メチルプロピルスルホン(融点32.5℃)0.6mlとスルホラン(融点28.4℃)0.4mlから調製した。混合物の融点は+6℃であった。
組成物を、メチルプロピルスルホン(融点32.5℃)0.4mlとスルホラン(融点28.4℃)0.6mlから調製した。混合物の融点は−8.5℃であった。
組成物を、メチルプロピルスルホン(融点32.5℃)0.2mlとスルホラン(融点28.4℃)0.8mlから調製した。混合物の融点は+0.5℃であった。
金属リチウムホイル製負極と、Celgard(登録商標)セパレーターと、減極剤としての硫黄元素(70重量%)、炭素−導電性添加剤(Ketjenblack EC−600JD、10重量%)及び結合剤(分子量4000000のポリエチレンオキシド、20重量%)を含有する硫黄正極とを含んでなるリチウム・硫黄電池を製造した。正極の比エネルギーは、2mAh/cm2であることが測定された。組み立てられた電池に、スルホラン中のLiClO4の1M溶液の形態の電解質を充填した。電池は、25℃で、電流密度0.3mA/cm2でサイクルを行った。最初のサイクルでの放電容量は、1.45mAh/cm2であった。硫黄利用度は、72.5%であった。
リチウム・硫黄電池を実施例6に記載のようにして製造した。電池は、0℃で、電流密度0.3mA/cm2でサイクルを行った。最初のサイクルでの放電容量は、0.42mAh/cm2であった。硫黄利用度は、21%であった。
リチウム・硫黄電池を実施例6に記載のようにして製造した。電池は、−10℃で、電流密度0.3mA/cm2でサイクルを行った。最初のサイクルでの放電容量は、0.02mAh/cm2であった。硫黄利用度は、1%であった。
電解質として、代わりに、スルホラン(2M)及びエチルブチルスルホン(1M)の共融混合物中のLiClO4の1M溶液を使用したほかは実施例6に記載のようにしてリチウム・硫黄電池を製造した。電池は、25℃で、電流密度0.3mA/cm2でサイクルを行った。最初のサイクルでの放電容量は、1.53mAh/cm2であった。硫黄利用度は、76.5%であった。
電解質として、代わりに、スルホラン(2M)及びエチルブチルスルホン(1M)の共融混合物中のLiClO4の1M溶液を使用したほかは実施例6に記載のようにしてリチウム・硫黄電池を製造した。電池は、−10℃で、電流密度0.3mA/cm2を用いてサイクルを行った。最初のサイクルでの放電容量は、1.01mAh/cm2であった。硫黄利用度は、50.5%であった。
電解質として、代わりに、2,4−ジメチルスルホラン中のLiClO4の1M溶液を使用したほかは実施例6に記載のようにしてリチウム・硫黄電池を製造した。電池は、−10℃で、電流密度0.3mA/cm2でサイクルを行った。最初のサイクルでの放電容量は、0.13mAh/cm2であった。硫黄利用度は、6.5%であった。
Claims (16)
- 少なくとも2つの非プロトン性溶媒中の少なくとも1つの電解質塩の溶液を含み、溶液成分の濃度は、溶液がその共晶濃度にあるか又はその共晶濃度の高々±30%以内にあるように選択される、リチウム・硫黄電池用電解質。
- 前記溶液成分の濃度が、溶液がその共晶濃度の高々±20%以内にあるように選択される、請求項1に記載の電解質。
- 前記溶液成分の濃度が、溶液がその共晶濃度の高々±10%以内にあるように選択される、請求項1に記載の電解質。
- 前記非プロトン性溶媒が、テトラヒドロフラン、2−メチルテトラヒドロフラン、炭酸ジメチル、炭酸エチルメチル、炭酸ジエチル、炭酸メチルプロピル、プロピオン酸メチル、プロピオン酸エチル、酢酸メチル、酢酸エチル、酢酸プロピル、ジメトキシエタン、1,3−ジオキソラン、ジグライム(2−メトキシエチルエーテル)、テトラグライム、炭酸エチレン、炭酸プロピレン、γ−ブチロラクトン、及びスルホランを包含するスルホンを含む群から選択される、請求項1乃至3のいずれか1項に記載の電解質。
- 前記非プロトン性溶媒が、スルホランを包含するスルホンを含む群から選択される、請求項1乃至3のいずれか1項に記載の電解質。
- 前記スルホンが、分子量94から150までを有する、請求項4又は5に記載の電解質。
- 前記電解質塩は、六フルオロリン酸リチウム(LiPF6)、六フルオロヒ酸リチウム(LiAsF6)、過塩素酸リチウム(LiClO4)、リチウムスルホニルイミドトリフルオロメタン(LiN(CF3SO2)2)及びトリフルオロスルホン酸リチウム(CF3SO3Li)を含む群から選択される塩又は塩の混合物少なくとも1つである、請求項1乃至6のいずれか1項に記載の電解質。
- 前記少なくとも1つの電解質塩の濃度は、0.1Mから飽和濃度までである、請求項1乃至7のいずれか1項に記載の電解質。
- 負極表面上への固体電解質界面(SEI)相形成に寄与し、かつ負極のサイクリングを改良するための有機又は無機添加剤1つ以上を、添加剤として更に含む、請求項1乃至8のいずれか1項に記載の電解質。
- 前記添加剤は、S、Li2Sn、CO2、SO2、N2O、Cl2、Br、I及びアミンを含む群から選択される物質又は物質の混合物少なくとも1つである、請求項9に記載の電解質。
- 添加剤の量は、電解質の総質量の0.2%〜10%である、請求項9又は10に記載の電解質。
- リチウム含有材料を含む負極と、硫黄含有材料を含む正極と、請求項1乃至11のいずれか1項に記載の電解質とを含んでなる、リチウム・硫黄電池。
- 負極は、金属リチウム、リチウム含有合金、不活性硫黄と結合したリチウム、リチウムイオンを可逆的にインターカレートできる化合物(金属粉末、リチウム金属−炭素及びリチウム金属−グラファイト層間物質、並びにこれらの混合物を含むが、これらに限定はされない)及びリチウムイオンとの酸化還元プロセスを可逆的に遂行できる化合物を含むリストから選択される陰性の電気化学的活物質を含む、請求項12に記載の電池。
- 正極は、硫黄元素、Li2Sn化合物(n≧1)、有機硫黄化合物及び硫黄含有ポリマーを含むリストから選択される、硫黄をベースとする材料少なくとも1つを含む陽性の電気化学的活物質を含む、請求項12又は13に記載の電池。
- 実質的に前文に記載される、リチウム・硫黄電池用の電解質。
- 実質的に前文に記載される、リチウム・硫黄電池。
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US65743605P | 2005-03-02 | 2005-03-02 | |
US60/657,436 | 2005-03-02 | ||
GB0504290A GB2420907B (en) | 2004-12-02 | 2005-03-02 | Electrolyte for lithium-sulphur batteries and lithium-sulphur batteries using the same |
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JP2017511591A (ja) * | 2014-03-25 | 2017-04-20 | テンプル ユニヴァーシティ − オブ ザ コモンウェルス システム オブ ハイアー エデュケーション | 柔らかい固体結晶電解質組成物 |
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JPWO2019049826A1 (ja) * | 2017-09-07 | 2020-10-22 | 国立大学法人横浜国立大学 | リチウム硫黄電池 |
Also Published As
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US8679684B2 (en) | 2014-03-25 |
US20060121355A1 (en) | 2006-06-08 |
JP5466364B2 (ja) | 2014-04-09 |
JP2014017256A (ja) | 2014-01-30 |
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