JP2010225525A - ナトリウムイオン電池 - Google Patents
ナトリウムイオン電池 Download PDFInfo
- Publication number
- JP2010225525A JP2010225525A JP2009073714A JP2009073714A JP2010225525A JP 2010225525 A JP2010225525 A JP 2010225525A JP 2009073714 A JP2009073714 A JP 2009073714A JP 2009073714 A JP2009073714 A JP 2009073714A JP 2010225525 A JP2010225525 A JP 2010225525A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- active material
- battery
- electrode active
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 68
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000007773 negative electrode material Substances 0.000 claims abstract description 40
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 15
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 12
- -1 sodium inorganic compound Chemical class 0.000 claims description 34
- 239000007774 positive electrode material Substances 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 23
- 229910010272 inorganic material Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 230000006866 deterioration Effects 0.000 abstract 1
- 230000000452 restraining effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 63
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 37
- 239000010410 layer Substances 0.000 description 31
- 239000000843 powder Substances 0.000 description 26
- 239000011230 binding agent Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 18
- 239000002245 particle Substances 0.000 description 17
- 239000000945 filler Substances 0.000 description 16
- 229920003235 aromatic polyamide Polymers 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 14
- 229920006015 heat resistant resin Polymers 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000006258 conductive agent Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 229920001721 polyimide Polymers 0.000 description 10
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- 239000004642 Polyimide Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000005484 gravity Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000004962 Polyamide-imide Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229920002312 polyamide-imide Polymers 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 229910000528 Na alloy Inorganic materials 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000004760 aramid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000012643 polycondensation polymerization Methods 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003779 heat-resistant material Substances 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- 229910020808 NaBF Inorganic materials 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
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- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
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- 239000012300 argon atmosphere Substances 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
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- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
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- 238000003825 pressing Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical class FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- ZYAMKYAPIQPWQR-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-3-methoxypropane Chemical compound COCC(F)(F)C(F)(F)F ZYAMKYAPIQPWQR-UHFFFAOYSA-N 0.000 description 1
- JCSRVIQQOQNBKC-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-3-(2,2,3,3-tetrafluoropropoxy)propane Chemical class FC(F)C(F)(F)COCC(F)(F)C(F)F JCSRVIQQOQNBKC-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical class FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical class FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- UUAMLBIYJDPGFU-UHFFFAOYSA-N 1,3-dimethoxypropane Chemical compound COCCCOC UUAMLBIYJDPGFU-UHFFFAOYSA-N 0.000 description 1
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- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
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- POIUXCGIAGOITD-UHFFFAOYSA-N 2-[4-[2-[4-(2-hydroxyethyl)phenyl]propan-2-yl]phenyl]ethanol Chemical compound C=1C=C(CCO)C=CC=1C(C)(C)C1=CC=C(CCO)C=C1 POIUXCGIAGOITD-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- DOMLQXFMDFZAAL-UHFFFAOYSA-N 2-methoxycarbonyloxyethyl methyl carbonate Chemical compound COC(=O)OCCOC(=O)OC DOMLQXFMDFZAAL-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FYQFWFHDPNXORA-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C FYQFWFHDPNXORA-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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Abstract
【解決手段】正極、負極およびナトリウムイオン非水電解質を備え、該負極が、負極活物質と、アルミニウムまたはアルミニウム合金からなる負極集電体とを有することを特徴とするナトリウムイオン電池。アルミニウムまたはアルミニウム合金からなることを特徴とするナトリウムイオン二次電池用負極集電体。
【選択図】なし
Description
<1>正極、負極およびナトリウムイオン非水電解質を備え、該負極が、負極活物質と、アルミニウムまたはアルミニウム合金からなる負極集電体とを有することを特徴とするナトリウムイオン電池。
<2>負極活物質が、ナトリウムイオンをドープかつ脱ドープすることのできる負極活物質である前記<1>記載の電池。
<3>負極活物質が、ナトリウムイオンをドープかつ脱ドープすることのできる炭素材料である前記<2>記載の電池。
<4>正極が、ナトリウムイオンをドープかつ脱ドープすることのできる正極活物質を有する前記<1>記載の電池。
<5>正極活物質が、ナトリウムイオンをドープかつ脱ドープすることのできるナトリウム無機化合物である前記<4>記載の電池。
<6>ナトリウムイオン非水電解質が、液体状である前記<1>記載の電池。
<7>セパレータを備える前記<6>記載の電池。
<8>セパレータが、耐熱多孔層と多孔質フィルムとが積層されてなる積層フィルムを有するセパレータである前記<7>記載の電池。
<9>アルミニウムまたはアルミニウム合金からなることを特徴とするナトリウムイオン二次電池用負極集電体。
また、付加重合体として、例えば、エチレン・酢酸ビニル共重合体、スチレン・ブタジエン共重合体又はエチレン・プロピレン共重合体などの共重合体でもよい。また、カルボン酸ビニルエステル重合体は、ポリビニルアルコールなどのように、部分的又は完全にケン化されていてもよい。結合剤はフッ素化合物とフッ素原子を含まないエチレン性二重結合を含む単量体との共重合体であってもよい。
(1)正極活物質の合成
炭酸ナトリウム(Na2CO3:和光純薬工業株式会社製:純度99.8%)と酸化マンガン(IV)(MnO2:株式会社高純度化学研究所製:純度99.9%)を、Na:Mnのモル比が0.7:1.0となるように秤量し、乾式ボールミルで4時間にわたって混合して金属含有化合物の混合物を得た。得られた金属含有化合物の混合物を、アルミナボートに充填し、電気炉を用いて空気雰囲気において加熱して800℃で2時間にわたって保持することによって、正極活物質1を得た。
(2)正極の製造
正極活物質1、導電材としてのアセチレンブラック(電気化学工業株式会社製)、および結合剤としてのPVdF(株式会社クレハ製、PolyVinylideneDiFluoride)を、正極活物質1:導電材:結合剤=85:10:5(重量比)の組成となるようにそれぞれ秤量した。その後、まず正極活物質1とアセチレンブラックをメノウ乳鉢で十分に混合し、この混合物に、N−メチル−2−ピロリドン(NMP:東京化成工業株式会社製)を適量加え、さらにPVdFを加えて引き続き均一になるように分散混練し、正極合剤のペーストを得た。該ペーストを、正極集電体である厚さ40μmのアルミニウム箔上に、アプリケータを用いて100μmの厚さで塗布し、乾燥、ロールプレスし、正極シート1を得た。この正極シート1を電極打ち抜き機で直径1.5cmに打ち抜いて正極1を得た。
ナトリウムイオン非水電解液における有機溶媒として、プロピレンカーボネート(以下、PCということもある。C4H6O3:キシダ化学株式会社製:純度99.5%)を用い、PC1リットルに対してナトリウムイオン電解質としての過塩素酸ナトリウム(NaClO4:和光純薬工業株式会社製)を1モル(122g)となるように秤量して加え、室温で6時間撹拌することにより、ナトリウムイオン非水電解液1を得た。この調製はアルゴン雰囲気のグローブボックス中で行った。
(1)負極の製造
負極活物質として、非晶質炭素材料である市販の炭素材料(ICB0510、日本カーボン社製)を用いて、負極活物質と結合剤としてのポリフッ化ビニリデン(PVdF)とを、負極活物質:結合剤=95:5(重量比)の組成となるように秤量し、結合剤をNMPに溶解した後、これに負極活物質を加えて均一になるように分散混錬し、負極合剤のペーストを得た。該ペーストを、負極集電体である厚さ40μmのアルミニウム箔上に、アプリケータを用いて100μmの厚さで塗布し、乾燥、ロールプレスを行って負極シート1を得た。この負極シート1を電極打ち抜き機で直径1.5cmに打ち抜いて負極1を得た。
(2)ナトリウムイオン電池の製造
セパレータとしてのポリプロピレン多孔質フィルム(厚み20μm)と、製造例1における正極1と、製造例2におけるナトリウムイオン非水電解液1と、上記における負極1と、コインセル(宝泉株式会社製)を用いて、ナトリウムイオン電池1を製造した。すなわち、コインセル(宝泉株式会社製)の下側パーツの窪みに、製造例1における正極1をアルミニウム箔が下側に向くように(正極活物質が上側を向くように)置き、その上にセパレータを置き、ナトリウムイオン非水電解液1をピペットで0.5ミリリットル注入した。さらに、負極1を用いて、中蓋とを組み合わせて、これらをセパレータの上側に、アルミニウム箔が上側を向くように(負極活物質が下側を向くように)置き、ガスケットを介して上側パーツで蓋をし、かしめ機でかしめてナトリウムイオン電池1を作製した。なお、試験電池の組み立てはアルゴン雰囲気のグローブボックス内で行った。
上記のようにして得られたナトリウムイオン電池1を用いて、以下の充放電条件で定電流充放電試験を実施し、10サイクルの充放電を確認することができ、二次電池として、充分に使用可能であることがわかった。
充放電条件:充電は、4.0Vまで0.1Cレート(10時間で完全充電する速度)でCC(コンスタントカレント:定電流)充電を行った。放電は、該充電速度と同じ速度で、CC放電を行い、電圧1.5Vでカットオフした。次サイクル以降の充電、放電は、該充電速度と同じ速度で行い、1サイクル目と同様に、充電電圧4.0V、放電電圧1.5Vでカットオフした。
(1)電解質
リチウムイオン電解質としてLiPF6を用い、この電解質を、エチレンカーボネート(EC)とジメチルカーボネート(DMC)とエチルメチルカーボネート(EMC)とが体積比15:10:75(=EC:DMC:EMC)で混合されてなる有機溶媒に、LiPF6が1モル/リットルとなるように溶解させて、リチウムイオン非水電解液1を製造した。
正極活物質として、LiCoO2(セルシードC−10N(日本化学工業株式会社製)、BET比表面積0.2m2/g)を用いて、製造例1と同様にして正極2を製造した。正極1の代わりに正極2を用い、ナトリウムイオン非水電解液1の代わりに上記リチウムイオン非水電解液1を用いたこと以外は、実施例1と同様にして、リチウムイオン電池を組み立てて、実施例1と同様の充放電条件にて、定電流充放電試験を実施したが、充放電することができず、二次電池としては使用できないことがわかった。
(1)耐熱多孔層用塗工液の製造
NMP4200gに塩化カルシウム272.7gを溶解した後、パラフェニレンジアミン132.9gを添加して完全に溶解させた。得られた溶液に、テレフタル酸ジクロライド243.3gを徐々に添加して重合し、パラアラミドを得て、さらにNMPで希釈して、濃度2.0重量%のパラアラミド溶液(A)を得た。得られたパラアラミド溶液100gに、アルミナ粉末(a)2g(日本アエロジル社製、アルミナC、平均粒子径0.02μm)とアルミナ粉末(b)2g(住友化学株式会社製スミコランダム、AA03、平均粒子径0.3μm)とをフィラーとして計4g添加して混合し、ナノマイザーで3回処理し、さらに1000メッシュの金網で濾過、減圧下で脱泡して、スラリー状塗工液(B)を製造した。パラアラミドおよびアルミナ粉末の合計重量に対するアルミナ粉末(フィラー)の重量は、67重量%となる。
多孔質フィルムとしては、ポリエチレン製多孔質フィルム(膜厚12μm、透気度140秒/100cc、平均孔径0.1μm、空孔率50%)を用いた。厚み100μmのPETフィルムの上に上記ポリエチレン製多孔質フィルムを固定し、テスター産業株式会社製バーコーターにより、該多孔質フィルムの上に耐熱多孔層用スラリー状塗工液を塗工した。PETフィルム上の塗工された該多孔質フィルムを一体にしたまま、貧溶媒である水中に浸漬させ、パラアラミド多孔質膜(耐熱多孔層)を析出させた後、溶媒を乾燥させて、PETフィルムをはがして、耐熱多孔層と多孔質フィルムとが積層された積層フィルムを得た。積層フィルムの厚みは16μmであり、パラアラミド多孔質膜(耐熱多孔層)の厚みは4μmであった。積層フィルムの透気度は180秒/100cc、空孔率は50%であった。積層フィルムにおける耐熱多孔層の断面を走査型電子顕微鏡(SEM)により観察をしたところ、0.03μm〜0.06μm程度の比較的小さな微細孔と0.1μm〜1μm程度の比較的大きな微細孔とを有することがわかった。なお、積層フィルムの評価は、以下の(A)〜(C)のようにして行った。
積層フィルムの厚み、多孔質フィルムの厚みは、JIS規格(K7130−1992)に従い、測定した。また、耐熱多孔層の厚みとしては、積層フィルムの厚みから多孔質フィルムの厚みを差し引いた値を用いた。
(B)ガーレー法による透気度の測定
積層フィルムの透気度は、JIS P8117に基づいて、株式会社安田精機製作所製のデジタルタイマー式ガーレー式デンソメータで測定した。
(C)空孔率
得られた積層フィルムのサンプルを一辺の長さ10cmの正方形に切り取り、重量W(g)と厚みD(cm)を測定した。サンプル中のそれぞれの層の重量(Wi(g))を求め、Wiとそれぞれの層の材質の真比重(真比重i(g/cm3))とから、それぞれの層の体積を求めて、次式より空孔率(体積%)を求めた。
空孔率(体積%)=100×{1−(W1/真比重1+W2/真比重2+・・+Wn/真比重n)/(10×10×D)}
Claims (9)
- 正極、負極およびナトリウムイオン非水電解質を備え、該負極が、負極活物質と、アルミニウムまたはアルミニウム合金からなる負極集電体とを有することを特徴とするナトリウムイオン電池。
- 負極活物質が、ナトリウムイオンをドープかつ脱ドープすることのできる負極活物質である請求項1記載の電池。
- 負極活物質が、ナトリウムイオンをドープかつ脱ドープすることのできる炭素材料である請求項2記載の電池。
- 正極が、ナトリウムイオンをドープかつ脱ドープすることのできる正極活物質を有する請求項1記載の電池。
- 正極活物質が、ナトリウムイオンをドープかつ脱ドープすることのできるナトリウム無機化合物である請求項4記載の電池。
- ナトリウムイオン非水電解質が、液体状である請求項1記載の電池。
- セパレータを備える請求項6記載の電池。
- セパレータが、耐熱多孔層と多孔質フィルムとが積層されてなる積層フィルムを有するセパレータである請求項7記載の電池。
- アルミニウムまたはアルミニウム合金からなることを特徴とするナトリウムイオン二次電池用負極集電体。
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JP2009073714A JP5359442B2 (ja) | 2009-03-25 | 2009-03-25 | ナトリウムイオン電池 |
EP10756260A EP2413416A4 (en) | 2009-03-25 | 2010-03-23 | SODIUM ION BATTERY |
KR1020117021627A KR20110139224A (ko) | 2009-03-25 | 2010-03-23 | 나트륨 이온 전지 |
CN2010800130128A CN102362385A (zh) | 2009-03-25 | 2010-03-23 | 钠离子电池 |
PCT/JP2010/055486 WO2010110465A1 (ja) | 2009-03-25 | 2010-03-23 | ナトリウムイオン電池 |
US13/259,775 US20120021273A1 (en) | 2009-03-25 | 2010-03-23 | Sodium ion battery |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013015321A1 (ja) * | 2011-07-26 | 2013-01-31 | 公立大学法人大阪府立大学 | 全固体二次電池 |
JP2013168241A (ja) * | 2012-02-14 | 2013-08-29 | Sumitomo Chemical Co Ltd | ナトリウム二次電池用負極材、ナトリウム二次電池用電極及びナトリウム二次電池 |
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Also Published As
Publication number | Publication date |
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JP5359442B2 (ja) | 2013-12-04 |
WO2010110465A1 (ja) | 2010-09-30 |
EP2413416A1 (en) | 2012-02-01 |
EP2413416A4 (en) | 2012-07-11 |
CN102362385A (zh) | 2012-02-22 |
US20120021273A1 (en) | 2012-01-26 |
KR20110139224A (ko) | 2011-12-28 |
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