JP5515308B2 - 薄膜固体リチウムイオン二次電池及びその製造方法 - Google Patents
薄膜固体リチウムイオン二次電池及びその製造方法 Download PDFInfo
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- JP5515308B2 JP5515308B2 JP2009022597A JP2009022597A JP5515308B2 JP 5515308 B2 JP5515308 B2 JP 5515308B2 JP 2009022597 A JP2009022597 A JP 2009022597A JP 2009022597 A JP2009022597 A JP 2009022597A JP 5515308 B2 JP5515308 B2 JP 5515308B2
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- 229910001416 lithium ion Inorganic materials 0.000 title claims description 95
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 91
- 239000007787 solid Substances 0.000 title claims description 84
- 239000010409 thin film Substances 0.000 title claims description 72
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- 239000000758 substrate Substances 0.000 claims description 139
- 239000007774 positive electrode material Substances 0.000 claims description 82
- 239000007784 solid electrolyte Substances 0.000 claims description 78
- 239000007773 negative electrode material Substances 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 39
- 238000007599 discharging Methods 0.000 claims description 37
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- 230000006870 function Effects 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 238000009792 diffusion process Methods 0.000 claims description 7
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- 239000011147 inorganic material Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
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- 239000010936 titanium Substances 0.000 description 32
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- 230000000052 comparative effect Effects 0.000 description 21
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- 238000010586 diagram Methods 0.000 description 17
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- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
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- 229910052804 chromium Inorganic materials 0.000 description 3
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- 238000002425 crystallisation Methods 0.000 description 3
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- 239000011777 magnesium Substances 0.000 description 3
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- 229910052718 tin Inorganic materials 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 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
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- 239000004696 Poly ether ether ketone Substances 0.000 description 2
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- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 229910052802 copper Inorganic materials 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
- 230000002950 deficient Effects 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
- 229910052732 germanium Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052737 gold Inorganic materials 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
- 239000007788 liquid Substances 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
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- 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
- 229910052715 tantalum 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
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-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
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- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008033 biological extinction 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
- 229910052791 calcium 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
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- 239000013078 crystal Substances 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
- 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
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- 239000011737 fluorine Substances 0.000 description 1
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- 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
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
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- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 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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- 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
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- 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
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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
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- 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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- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/552—Terminals characterised by their shape
- H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
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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
- H01M4/1397—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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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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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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
できる。
図1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概略構造を説明する図であり、図3(A)は平面図、図3(B)はX−X断面図、図3(c)はY−Y断面図である。
図4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概略構造を説明する図であり、図4(A)は平面図、図4(B)はX−X断面図である。
図5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。図5(A)は図1に示す固体リチウムイオン電池の製造工程、図5(B)は図3に示す固体リチウムイオン電池の製造工程をそれぞれ示す。
[実施例及び比較例における構成]
図6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。
なお、TEMによる観察では微結晶化している可能性も見出された。
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)
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。
ターゲット組成:ZnO
スパッタリングガス:Ar 150sccm、0.10Pa
スパッタリングパワー:1500W(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。
負極集電体側保護膜68を用いないで、実施例1と同様の成膜方法により作成した比較例1を示す。比較例1における電池の膜構成は、負極側集電体保護膜68が成膜されていない他は実施例1と全く同一である。比較例1における電池の膜構成は、ポリカーボネート基板/Si3N4(200nm)/Ti(100nm)/LiMn2O4(125nm)/Li3PO4Nx(145nm)/Ti(200nm)/紫外線硬化樹脂(20μm)である(図6(B)を参照。)。
負極側集電体保護膜68の膜厚が厚い場合、つまり、負極側集電体保護膜68を負極活物質として機能させる場合を、実施例1Aとして示す。実施例1Aでは、実施例1と同様に、負極側集電体保護膜68としてZnOを用い、その膜厚を50nmとした以外は全て実施例1と同様とした。
負極側集電体保護膜68としてSnO2を用い、膜厚は3nmとした例を示す。
ターゲット組成:SnO2
スパッタリングガス:Ar 50sccm+(Ar 80%+O2 20%混合ガス)20sccm、0.10Pa
スパッタリングパワー:1000W(DC)
電池を構成するその他の膜は、実施例1と同様にして形成し、電池特性の測定条件は実施例1と同様とした。実施例2の電池の膜構成は、ポリカーボネート基板/Si3N4(200nm)/Ti(100nm)/LiMn2O4(125nm)/Li3PO4Nx(145nm)/SnO2(3nm)/Ti(200nm)/紫外線硬化樹脂(20μm)である(図6(A)を参照。)。
実施例2において、負極側集電体保護膜68、SnO2の膜厚を35nmとした実施例2Aを示す。電池の膜構成は、ポリカーボネート基板/Si3N4(200nm)/Ti(100nm)/LiMn2O4(125nm)/Li3PO4Nx(145nm)/SnO2(35nm)/Ti(200nm)/紫外線硬化樹脂(20μm)である(図6(B)を参照。)。
負極側集電体保護膜68としてITO(ITOはIn2O3にSnO2を添加したもので、特に導電性が高い透明導電体膜として広く知られている。)を用いた例を示す。ITOの膜厚は2nmである。
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)
電池を構成するその他の膜は、実施例1と同様にして形成し、電池特性の測定条件は実施例1と同様とした。実施例3の電池の膜構成は、ポリカーボネート基板/Si3N4(200nm)/Ti(100nm)/LiMn2O4(125nm)/Li3PO4Nx(145nm)/ITO(2nm)/Ti(200nm)/紫外線硬化樹脂(20μm)である(図6(A)を参照。)。
実施例3において、負極側集電体保護膜68であるITOの膜厚を22nmとした実施例3Aを示す。ここでは、LiMn2O4の膜厚を180nmとした。電池の膜構成は、ポリカーボネート基板/Si3N4(200nm)/Ti(100nm)/LiMn2O4(180nm)/Li3PO4Nx(145nm)/ITO(22nm)/Ti(200nm)/紫外線硬化樹脂(20μm)である(図6(B)を参照。)。
図17は、本発明の実施例において、固体リチウムイオン電池おける利用効率と負極側集電体保護膜の膜厚の関係を説明するする図であり、横軸は負極側集電体保護膜の膜厚を示し、縦軸は電池おける利用効率を示す。
40…正極活物質膜、50…固体電解質膜、68…負極側集電体保護膜、
70…負極側集電体膜、80…全体保護膜
Claims (13)
- 電気絶縁性基板と、前記電気絶縁性基板に形成された、正極側集電体膜、正極活物質膜、固体電解質膜、負極側集電体保護膜、及び、負極側集電体膜とを含む薄膜固体リチウムイオン二次電池であって、
前記正極活物質膜、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、
前記負極側集電体保護膜は、前記固体電解質膜と前記負極側集電体膜の間に配置された、導電性酸化物から成る層であり、
前記負極側集電体保護膜の膜厚は、前記負極側集電体保護膜を負極活物質と見做したときのリチウム含有の理論容量が前記正極活物質膜のリチウム含有理論容量の半分以下となり且つ2nm以上である条件を満たすように設定されており、
前記負極側集電体保護膜が満充電となった状態で前記固体電解質膜の界面に生ずるリチウム過剰層が負極活物質として機能すると共に、満充電となった前記負極側集電体保護膜がリチウムの前記負極側集電体膜への拡散を防ぐように機能する、
薄膜固体リチウムイオン二次電池。 - 前記負極側集電体保護膜によって、充放電に伴うリチウムの総量が略一定に保持される、
請求項1に記載の薄膜固体リチウムイオン二次電池。 - 前記負極側集電体保護膜の膜厚が2nm以上、22nm以下である、
請求項1に記載の薄膜固体リチウムイオン二次電池。 - 前記負極側集電体保護膜の膜厚が3nm以上、15nm以下である、
請求項1に記載の薄膜固体リチウムイオン二次電池。 - 前記負極側集電体保護膜は、Snの酸化物、Inの酸化物、Znの酸化物の何れかを少なくとも1つ含む、
請求項1に記載の薄膜固体リチウムイオン二次電池。 - 前記負極側集電体保護膜は、導電性を高めるための元素が添加された酸化物である、
請求項5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有機樹脂によって形成された基板でありこの基板の面に無機材料によって形成された絶縁膜を有し、
前記絶縁膜は、前記正極側集電体膜、前記正極活物質膜、前記固体電解質膜、前記負極側集電体保護膜、及び、前記負極側集電体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、
請求項1から請求項6のいずれか1項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Liを含有する材料から成る、
請求項1に記載の薄膜固体リチウムイオン二次電池。 - 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1に記載の薄膜固体リチウムイオン二次電池。 - 前記正極側集電体膜、前記正極活物質膜、前記固体電解質膜、前記負極側集電体保護膜、及び、前記負極側集電体膜を覆い、紫外線硬化樹脂によって形成された保護膜を有する、
請求項1に記載の薄膜固体リチウムイオン二次電池。 - 前記負極側集電体膜は、Ti、又は、Tiを主成分とする合金から成る、
請求項1に記載の薄膜固体リチウムイオン二次電池。 - 電気絶縁性基板と、前記電気絶縁性基板に形成された、正極側集電体膜、正極活物質膜、固体電解質膜、負極側集電体保護膜、及び、負極側集電体膜とを含む薄膜固体リチウムイオン二次電池の製造方法であって、
前記正極活物質膜、及び、前記固体電解質膜をアモルファス膜によって形成すると共に、
前記固体電解質膜と前記負極側集電体膜の間に配置される前記負極側集電体保護膜を導電性酸化物によって形成し、
前記負極側集電体保護膜の膜厚を、前記負極側集電体保護膜を負極活物質と見做したときのリチウム含有の理論容量が前記正極活物質膜のリチウム含有理論容量の半分以下となり且つ2nm以上である条件を満たすように設定する、
薄膜固体リチウムイオン二次電池の製造方法。 - 前記電気絶縁性基板は有機樹脂によって形成された基板であり、
前記正極側集電体膜、前記正極活物質膜、前記固体電解質膜、前記負極側集電体保護膜、及び、前記負極側集電体膜が形成される領域の正射影を含む前記電気絶縁性基板の面に、無機材料によって絶縁膜を形成する工程を有する、
請求項12に記載の薄膜固体リチウムイオン二次電池の製造方法。
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KR20110126599A (ko) | 2011-11-23 |
CN102301520A (zh) | 2011-12-28 |
EP2395591A1 (en) | 2011-12-14 |
US20110281167A1 (en) | 2011-11-17 |
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