JP2022104957A - リチウム金属アノードのための、カルコゲナイドを用いたエクスシトゥ固体電解質界面修飾 - Google Patents
リチウム金属アノードのための、カルコゲナイドを用いたエクスシトゥ固体電解質界面修飾 Download PDFInfo
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- JP2022104957A JP2022104957A JP2022055933A JP2022055933A JP2022104957A JP 2022104957 A JP2022104957 A JP 2022104957A JP 2022055933 A JP2022055933 A JP 2022055933A JP 2022055933 A JP2022055933 A JP 2022055933A JP 2022104957 A JP2022104957 A JP 2022104957A
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- Prior art keywords
- film
- lithium
- sei
- chalcogenide
- lithium metal
- Prior art date
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- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 224
- 150000004770 chalcogenides Chemical class 0.000 title claims abstract description 94
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 28
- 238000012986 modification Methods 0.000 title description 5
- 230000004048 modification Effects 0.000 title description 5
- 238000011066 ex-situ storage Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 121
- 239000010949 copper Substances 0.000 claims abstract description 86
- 229910052802 copper Inorganic materials 0.000 claims abstract description 67
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 49
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 33
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 33
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 23
- 239000012528 membrane Substances 0.000 claims description 159
- 230000008569 process Effects 0.000 claims description 89
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- -1 copper chalcogenides Chemical class 0.000 claims description 28
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 claims description 25
- 239000003792 electrolyte Substances 0.000 claims description 22
- 229910002531 CuTe Inorganic materials 0.000 claims description 14
- 239000011651 chromium Substances 0.000 claims description 14
- 229910052711 selenium Inorganic materials 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229920000307 polymer substrate Polymers 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 238000009832 plasma treatment Methods 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 239000011368 organic material Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 3
- 238000001947 vapour-phase growth Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 74
- 229910052751 metal Inorganic materials 0.000 abstract description 21
- 239000002184 metal Substances 0.000 abstract description 21
- 239000010408 film Substances 0.000 description 301
- 239000000758 substrate Substances 0.000 description 82
- 238000000151 deposition Methods 0.000 description 66
- 210000004027 cell Anatomy 0.000 description 51
- 239000000463 material Substances 0.000 description 47
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- 238000012545 processing Methods 0.000 description 41
- 239000010409 thin film Substances 0.000 description 35
- 238000005240 physical vapour deposition Methods 0.000 description 33
- 238000012546 transfer Methods 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 26
- 238000000576 coating method Methods 0.000 description 26
- 238000004544 sputter deposition Methods 0.000 description 25
- 238000007740 vapor deposition Methods 0.000 description 25
- 238000004146 energy storage Methods 0.000 description 22
- 239000010410 layer Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000005137 deposition process Methods 0.000 description 14
- 238000007639 printing Methods 0.000 description 14
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 13
- 239000002131 composite material Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
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- 238000010894 electron beam technology Methods 0.000 description 6
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
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- 239000010935 stainless steel Substances 0.000 description 6
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- 229910012851 LiCoO 2 Inorganic materials 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- 229910017052 cobalt Inorganic materials 0.000 description 5
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
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- 239000002904 solvent Substances 0.000 description 5
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 5
- 229910018068 Li 2 O Inorganic materials 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 238000000313 electron-beam-induced deposition Methods 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 238000001453 impedance spectrum Methods 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- 229910001152 Bi alloy Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000013068 control sample Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
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- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
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- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910004424 Li(Ni0.8Co0.15Al0.05)O2 Inorganic materials 0.000 description 1
- 229910010678 Li5Cr(PO4)2F2 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
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- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
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- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
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- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
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- VWYHCWVXCWCOPV-UHFFFAOYSA-L dilithium trifluoromethanesulfonate Chemical compound [Li+].[Li+].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F VWYHCWVXCWCOPV-UHFFFAOYSA-L 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
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- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
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- 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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
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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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
Description
Claims (15)
- 銅膜を含む集電体上にリチウム金属膜を形成することと、
前記リチウム金属膜上に形成されたカルコゲナイド膜であって、ビスマスカルコゲナイド、銅カルコゲナイド、およびそれらの組み合わせの群から選択されるカルコゲナイド膜を形成することを含む、前記リチウム金属膜上にSEI膜スタックを形成することと、
を含む方法。 - 前記SEI膜スタックが、フッ化リチウム(LiF)膜、炭酸リチウム(Li2CO3)膜、酸化リチウム膜、窒化リチウム(Li3N)膜、およびそれらの組み合わせのうちの少なくとも1つを、さらに含む、請求項1に記載の方法。
- 前記リチウム金属膜が、約1マイクロメートルと約20マイクロメートルとの間の厚さを有する、請求項2に記載の方法。
- 前記集電体が、約2マイクロメートルと約8マイクロメートルとの間の厚さを有する、請求項3に記載の方法。
- 前記集電体が、
第1のニッケルまたはクロム含有膜、
前記第1のニッケルまたはクロム含有膜上に形成され、約50ナノメートルと約500ナノメートルとの間の厚さを有する前記銅膜、および
前記銅膜上に形成され、約20ナノメートルと約50ナノメートルとの間の厚さを有する第2のニッケルまたはクロム含有膜、
を含む、請求項1に記載の方法。 - 前記集電体が、
ポリエチレンテレフタレート(PET)ポリマー基材、および
前記PETポリマー基材上に形成された前記銅膜であって、物理的気相堆積プロセスによって堆積された前記銅膜、
を含む、請求項1に記載の方法。 - 前記銅膜を含む前記集電体が、プラズマ処理またはコロナ放電プロセスに曝されて、前記集電体の曝された表面から有機材料を除去する、請求項1に記載の方法。
- 銅膜を含む集電体、
前記集電体上に形成されたリチウム金属膜、および
前記リチウム金属膜上に形成された固体電解質界面(SEI)膜スタックであって、前記リチウム金属膜上に形成されたカルコゲナイド膜を含む、固体電解質界面(SEI)膜スタック、
を含むアノード電極構造体。 - 前記SEI膜スタックが、前記カルコゲナイド膜上に形成されたフッ化リチウムを、さらに含む、請求項8に記載のアノード電極構造体。
- 前記カルコゲナイド膜が、ビスマスカルコゲナイド、銅カルコゲナイド、およびそれらの組み合わせの群から選択される、請求項8に記載のアノード電極構造体。
- 前記カルコゲナイド膜が、CuS、Cu2Se、Cu2S、Cu2Te、CuTe、Bi2Te3、Bi2Se3、およびそれらの組み合わせの群から選択される、請求項10に記載のアノード電極構造体。
- 前記SEI膜スタックが、前記カルコゲナイド膜上に形成された酸化リチウム膜を、さらに含む、請求項8に記載のアノード電極構造体。
- 前記SEI膜スタックが、前記酸化リチウム膜上に形成された炭酸リチウム膜を、さらに含む、請求項12に記載のアノード電極構造体。
- 銅膜を含む集電体、
前記集電体上に形成されたリチウム金属膜、ならびに
前記リチウム金属膜上に形成された固体電解質界面(SEI)膜スタックであって、
酸化リチウム膜、
前記酸化リチウム膜上に形成された炭酸リチウム膜、および
前記炭酸リチウム膜上に形成されたカルコゲナイド膜、
を含む固体電解質界面(SEI)膜スタック、
を含むアノード電極構造体。 - 前記SEI膜スタックが、前記リチウム金属膜と前記酸化リチウム膜との間に形成された窒化リチウム膜を、さらに含む、請求項14に記載のアノード電極構造体。
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JP2017182905A (ja) * | 2016-03-28 | 2017-10-05 | 古河電気工業株式会社 | タブリード付き負極集電銅箔およびこのタブリード付き負極集電銅箔を有する電池 |
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KR102643656B1 (ko) | 2024-03-05 |
WO2019094121A1 (en) | 2019-05-16 |
EP3707767B1 (en) | 2024-07-10 |
KR20230041092A (ko) | 2023-03-23 |
CN111316478A (zh) | 2020-06-19 |
KR20200068752A (ko) | 2020-06-15 |
EP3707767A4 (en) | 2021-08-18 |
EP3707767A1 (en) | 2020-09-16 |
JP2024023248A (ja) | 2024-02-21 |
JP7383749B2 (ja) | 2023-11-20 |
KR102512001B1 (ko) | 2023-03-21 |
KR20230148279A (ko) | 2023-10-24 |
JP7052035B2 (ja) | 2022-04-11 |
US20190140267A1 (en) | 2019-05-09 |
US10944103B2 (en) | 2021-03-09 |
US11462733B2 (en) | 2022-10-04 |
KR102591474B1 (ko) | 2023-10-20 |
JP2021502671A (ja) | 2021-01-28 |
US11735723B2 (en) | 2023-08-22 |
US20230006197A1 (en) | 2023-01-05 |
US20210210752A1 (en) | 2021-07-08 |
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