JP5515307B2 - 薄膜固体リチウムイオン二次電池 - Google Patents
薄膜固体リチウムイオン二次電池 Download PDFInfo
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- JP5515307B2 JP5515307B2 JP2009022595A JP2009022595A JP5515307B2 JP 5515307 B2 JP5515307 B2 JP 5515307B2 JP 2009022595 A JP2009022595 A JP 2009022595A JP 2009022595 A JP2009022595 A JP 2009022595A JP 5515307 B2 JP5515307 B2 JP 5515307B2
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- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 60
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 60
- 239000007787 solid Substances 0.000 title claims description 56
- 239000010409 thin film Substances 0.000 title claims description 50
- 239000010408 film Substances 0.000 claims description 372
- 239000000758 substrate Substances 0.000 claims description 116
- 239000007784 solid electrolyte Substances 0.000 claims description 45
- 239000007774 positive electrode material Substances 0.000 claims description 39
- 239000007773 negative electrode material Substances 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- 239000004417 polycarbonate Substances 0.000 claims description 17
- 229920000515 polycarbonate Polymers 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 description 34
- 238000004544 sputter deposition Methods 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 24
- 239000010936 titanium Substances 0.000 description 24
- 230000001681 protective effect Effects 0.000 description 20
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 13
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000007599 discharging Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 230000007547 defect Effects 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000002950 deficient Effects 0.000 description 8
- 229910010272 inorganic material Inorganic materials 0.000 description 8
- 239000011147 inorganic material Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 239000011245 gel electrolyte Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- -1 LiMnCoO 4 Chemical class 0.000 description 4
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910012050 Li4SiO4-Li3PO4 Inorganic materials 0.000 description 2
- 229910012053 Li4SiO4-Li3VO4 Inorganic materials 0.000 description 2
- 229910012069 Li4SiO4—Li3PO4 Inorganic materials 0.000 description 2
- 229910012072 Li4SiO4—Li3VO4 Inorganic materials 0.000 description 2
- 229910013184 LiBO Inorganic materials 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005224 laser annealing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910021484 silicon-nickel alloy Inorganic materials 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
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910012305 LiPON Inorganic materials 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- VIEVWNYBKMKQIH-UHFFFAOYSA-N [Co]=O.[Mn].[Li] Chemical class [Co]=O.[Mn].[Li] VIEVWNYBKMKQIH-UHFFFAOYSA-N 0.000 description 1
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- CXRFFSKFQFGBOT-UHFFFAOYSA-N bis(selanylidene)niobium Chemical compound [Se]=[Nb]=[Se] CXRFFSKFQFGBOT-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- AIOWANYIHSOXQY-UHFFFAOYSA-N cobalt silicon Chemical compound [Si].[Co] AIOWANYIHSOXQY-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical class [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H01M10/0436—Small-sized flat cells or batteries for portable equipment
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
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- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
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- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
- H01M50/141—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against humidity
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/547—Terminals characterised by the disposition of the terminals on the cells
- H01M50/548—Terminals characterised by the disposition of the terminals on the cells on opposite sides of the cell
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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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- H01M50/562—Terminals characterised by the material
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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
- H01M50/50—Current conducting connections for cells or batteries
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- H01M50/564—Terminals characterised by their manufacturing process
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- H—ELECTRICITY
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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
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- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
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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
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Description
図1は、本発明の実施の形態(その1)における、固体リチウムイオン電池の概略構造を説明する図であり、図1(A)は平面図、図1(B)はX−X断面図、図1(C)はY−Y断面図である。
図2は、本発明の実施の形態(その2)における、固体リチウムイオン電池の概略構造を説明する図であり、図2(A)は平面図、図2(B)はX−X断面図である。
図3は、本発明の実施の形態における、固体リチウムイオン電池の製造工程の概略を説明する図である。
[実施例及び比較例における構成、並びに、これらにおける初期ショートの発生頻度]
図4は、本発明の実施例及び比較例における、固体リチウムイオン電池の各層の構成を説明する図であり、以下で説明する固体リチウムイオン電池の各層の材質及びその厚さを、(A)実施例、(B)比較例に関してそれぞれ示している。
図1に示す構成を有する固体リチウムイオン電池を作成した。量産性、コストを勘案して、基板10として厚さ1.1mmのポリカーボネート(PC)基板を用いた。この他にもガラス材、アクリル等からなる基板を使用することができ、導電性がなく表面の平滑性が作成する電池の膜厚に応じて十分平坦であればよい。基板10の上に全面に無機絶縁膜20としてSi3N4を厚さ200nmで成膜した。
ターゲット組成:Ti
スパッタリングガス:Ar70sccm、0.45Pa
スパッタリングパワー:1000W(DC)
(2)LiMn2O4膜の形成
スパッタリングガス:(Ar 80%+O2 20%混合ガス)20sccm、0.20Pa
スパッタリングパワー:300W(RF)
(3)Li3PO4Nx膜の形成
ターゲット組成:Li3PO4
スパッタリングガス:Ar 20sccm+N2 20sccm、0.26Pa
スパッタリングパワー:300W(RF)
(4)ITO膜の形成
ここでは、アネルバ社製C−3103を用い、ターゲットサイズはφ6インチである。スパッタリング条件を次に示す。
ターゲット組成:ITO(In2O3 90wt.%+SnO2 10wt.%)
スパッタリングガス:Ar 120sccm+(Ar 80%+O2 20%混合ガス)30sccm、0.10Pa
スパッタリングパワー:1000W(DC)
なお、スパッタリング時間に関しては、所望の膜厚が得られるよう調整した。
比較のために、無機絶縁膜20がない以外は全て実施例1と同一の構成を有する電池を同時スパッタリングにより10個作成した。電池の膜構成は、ポリカーボネート基板/Ti(100nm)/LiMn2O4(125nm)/Li3PO4Nx(145nm)/ITO(20nm)/Ti(200nm)/紫外線硬化樹脂(20μm)である(図4(B)を参照。)。この10個の全数について初期の導通状況を調べたところ、10個中、5個が初期のショートを起こしていた。
次に、無機絶縁膜としてSCZ(SiO2、Cr2O3、ZrO2の混合物である。)を50nm形成して実施例1と同様の電池を作成した。電池の膜構成は、ポリカーボネート基板/SCZ(50nm)/Ti(100nm)/LiMn2O4(125nm)/Li3PO4Nx(145nm)/ITO(20nm)/Ti(200nm)/紫外線硬化樹脂(20μm)である(図4(A)を参照。)。
ターゲットリング組成:SCZ(SiO2 35at.%+Cr2O3 30at.%+ZrO2 35at.%)
スパッタリングガス:Ar100sccm、0.13Pa
スパッタリングパワー:1000W(RF)
実施例1と同様にして、同一の試料50個を作成し、初期の導通状態を調べたところ不良であったのは3個であった(図5、図6を参照。)。また、充放電特性は実施例1とほぼ同等であり、無機絶縁膜を設けこの上に電池を搭載する構成は非常に有効である。
無機絶縁膜20として、Si3N4 を500nm形成して実施例1と同様の電池を作成した。電池の膜構成は、ポリカーボネート基板/Si3N4(500nm)/Ti(100nm)/LiMn2O4(125nm)/Li3PO4Nx(145nm)/ITO(20nm)/Ti(200nm)/紫外線硬化樹脂(20μm)である(図4(A)を参照。)。この構成の電池では、初期の充放電、繰返し充放電特性は問題なかった。
基板10としてポリカーボネート基板を用い、無機絶縁膜20としてSiO2、SCZを用いた場合には、無機絶縁膜20の膜厚が500nmを超えるとポリカーボネート基板を曲率半径30cm程度に曲げると、電池を構成する膜のクラックが観測された。
図6に示すように、電池の初期のショートの発生頻度は、無機絶縁膜20の膜厚の増加と共に低下する。電池の初期のショートによる不良率(発生頻度)を10%以下にするためには、無機絶縁膜20の膜厚が5nm以上、500nm以下とするのが好ましい。
40…正極活物質膜、50…固体電解質膜、60…負極活物質膜、
70…負極側集電体膜、80…全体保護膜
Claims (7)
- 有機樹脂から成る電気絶縁性基板と、前記電気絶縁性基板の面に形成された絶縁膜と、集電体膜と、活物質膜と、固体電解質膜とを含む薄膜固体リチウムイオン二次電池であって、
前記活物質膜、及び、前記固体電解質膜はアモルファス膜によって形成されており、
前記絶縁膜は、前記集電体膜、前記活物質膜、及び、前記固体電解質膜の前記電気絶縁性基板への正射影を含む領域に形成されていると共に、前記集電体膜は、前記絶縁膜の面に形成されており、
前記絶縁膜は、SiO 2 、Cr 2 O 3 、ZrO 2 の混合物から成る50nm以上200nm以下の厚さの膜によって構成されている、
薄膜固体リチウムイオン二次電池。 - 前記集電体膜は正極側集電体膜と負極側集電体膜を含み、
前記活物質膜は正極活物質膜と負極活物質膜を含み、
前記正極側集電体膜又は/及び前記負極側集電体膜は前記絶縁膜の面に形成されている、
請求項1に記載の薄膜固体リチウムイオン二次電池。 - 前記電気絶縁性基板は可撓性を有する、
請求項1に記載の薄膜固体リチウムイオン二次電池。 - 前記電気絶縁性基板はポリカーボネートから成る、
請求項3に記載の薄膜固体リチウムイオン二次電池。 - 前記正極活物質膜は、Mn、Co、Fe、P、Ni、Siの少なくとも1つ、及び、Liを含む酸化物から成る、
請求項2に記載の薄膜固体リチウムイオン二次電池。 - 前記負極活物質膜は、Sn、Si、Al、Ge、Sb、Ag、Ga、In、Fe、Co、Ni、Ti、Mn、Ca、Ba、La、Zr、Ce、Cu、Mg、Sr、Cr、Mo、Nb、V、Znの少なくとも1つを含む酸化物から成る、
請求項2に記載の薄膜固体リチウムイオン二次電池。 - 前記集電体膜は、Ti、Au、Pt、Cu、若しくは、これらの合金を含む金属材料から成る、
請求項1に記載の薄膜固体リチウムイオン二次電池。
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US13/146,594 US20110287296A1 (en) | 2009-02-03 | 2010-01-28 | Thin film solid state lithium ion secondary battery and method of manufacturing the same |
PCT/JP2010/051126 WO2010090124A1 (ja) | 2009-02-03 | 2010-01-28 | 薄膜固体リチウムイオン二次電池及びその製造方法 |
CN2010800057601A CN102301519A (zh) | 2009-02-03 | 2010-01-28 | 薄膜固态锂离子二次电池及其制造方法 |
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JP5821270B2 (ja) | 2011-05-16 | 2015-11-24 | ソニー株式会社 | 固体電解質電池および正極活物質 |
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