WO2022138295A1 - 積層体、リチウムイオン二次電池用の負極集電体、及びリチウムイオン二次電池用の負極 - Google Patents
積層体、リチウムイオン二次電池用の負極集電体、及びリチウムイオン二次電池用の負極 Download PDFInfo
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- WO2022138295A1 WO2022138295A1 PCT/JP2021/045877 JP2021045877W WO2022138295A1 WO 2022138295 A1 WO2022138295 A1 WO 2022138295A1 JP 2021045877 W JP2021045877 W JP 2021045877W WO 2022138295 A1 WO2022138295 A1 WO 2022138295A1
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- WO
- WIPO (PCT)
- Prior art keywords
- metal layer
- negative electrode
- ray diffraction
- laminate
- ion secondary
- Prior art date
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 144
- 239000002184 metal Substances 0.000 claims abstract description 144
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 61
- 239000013078 crystal Substances 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000007773 negative electrode material Substances 0.000 claims description 33
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 238000007747 plating Methods 0.000 description 48
- 239000000243 solution Substances 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 30
- 238000009713 electroplating Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 15
- 238000007772 electroless plating Methods 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 7
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 7
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000001509 sodium citrate Substances 0.000 description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 6
- 229940038773 trisodium citrate Drugs 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229940085605 saccharin sodium Drugs 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229920003026 Acene Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910004706 CaSi2 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910019001 CoSi Inorganic materials 0.000 description 1
- 229910019974 CrSi Inorganic materials 0.000 description 1
- 229910005329 FeSi 2 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012573 LiSiO Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019018 Mg 2 Si Inorganic materials 0.000 description 1
- 229910017028 MnSi Inorganic materials 0.000 description 1
- 229910016006 MoSi Inorganic materials 0.000 description 1
- 229910005881 NiSi 2 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910008484 TiSi Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000011889 copper foil Substances 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
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 239000003960 organic solvent Substances 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
- 239000012466 permeate Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure relates to a laminate, a negative electrode current collector for a lithium ion secondary battery, and a negative electrode for a lithium ion secondary battery.
- the negative electrode current collector for a lithium ion secondary battery undergoes repeated loads (compressive stress and tensile stress) because the volume of the negative electrode active material layer laminated on the negative electrode current collector fluctuates with charge and discharge. receive. Deformation of the negative electrode current collector due to this load causes deformation of the battery body or short circuit between the electrodes. Therefore, the negative electrode current collector is required to have durability (high tensile strength) against a load (particularly tensile stress). (See Patent Document 1 below.)
- a metal layer such as a current collector receives tensile stress
- cracks are formed in the metal layer due to slippage of crystal grain boundaries in the metal layer, and the cracks expand. As a result, the metal layer breaks.
- the metal layer is made of an amorphous iron-based alloy having low crystallinity
- the metal layer tends to have high tensile resistance.
- the inventors have found that even if the metal layer is amorphous, high tensile strength cannot always be obtained, and high tensile strength can be obtained because the metal layer has a certain degree of crystallinity.
- An object of one aspect of the present invention is to provide a laminate having high tensile strength, a negative electrode current collector and a negative electrode for a lithium ion secondary battery containing the laminate.
- the laminate according to one aspect of the present invention includes a first metal layer containing copper and a second metal layer containing nickel and directly laminated on the first metal layer.
- the full width at half maximum of the X-ray diffraction peak having the highest intensity among at least one X-ray diffraction peak derived from the nickel-containing crystal in the second metal layer is 0.3 ° or more and 1.2 ° or less.
- the second metal layer may further contain at least one element selected from the group consisting of carbon, phosphorus and tungsten.
- the negative electrode current collector for a lithium ion secondary battery according to one aspect of the present invention includes the above-mentioned laminated body.
- the negative electrode for a lithium ion secondary battery includes the above-mentioned negative electrode current collector and a negative electrode active material layer containing a negative electrode active material, and the negative electrode active material layer is directly attached to the second metal layer. It is laminated.
- the negative electrode active material may contain silicon.
- a laminate having high tensile strength, a negative electrode current collector for a lithium ion secondary battery provided with the laminate, and a negative electrode are provided.
- FIG. 1 is a schematic perspective view of a laminate (negative electrode current collector) according to an embodiment of the present invention and a negative electrode including the laminate.
- FIG. 2 is an example of an X-ray diffraction pattern measured by incident X-rays on the surface of a second metal layer provided in a laminated body.
- FIG. 3 is an enlarged view of FIG. 2, and is an example of an X-ray diffraction peak (X-ray diffraction peak having the maximum intensity) derived from a nickel-containing crystal in the second metal layer.
- the laminate according to this embodiment is a negative electrode current collector for a lithium ion secondary battery.
- the laminate 10 according to the present embodiment has a first metal layer 1 and a second metal layer 2.
- the first metal layer 1 contains copper (Cu).
- the second metal layer 2 contains nickel (Ni).
- the second metal layer 2 is directly laminated on both surfaces of the first metal layer 1.
- the second metal layer 2 may be directly laminated on only one surface of the first metal layer 1.
- the negative electrode 20 for a lithium ion secondary battery according to the present embodiment has a laminated body 10 (negative electrode current collector) and a negative electrode active material layer 3.
- the negative electrode active material layer 3 contains a negative electrode active material.
- the negative electrode active material layer 3 is directly laminated on the surface of each second metal layer 2.
- the lithium ion secondary battery according to the present embodiment may include a negative electrode 20, a positive electrode, a separator and an electrolytic solution.
- the separator and the electrolytic solution are arranged between the negative electrode 20 and the positive electrode.
- the electrolyte permeates the separator.
- the positive electrode may include a positive electrode current collector and a positive electrode active material layer laminated on the positive electrode current collector.
- the positive electrode current collector may be an aluminum foil or a nickel foil.
- the positive electrode active material layer contains a positive electrode active material.
- the positive electrode active material layer may further contain a conductive auxiliary agent such as carbon or metal powder.
- the positive electrode active material layer may further contain a binder (adhesive or resin).
- the separator may be one or more films (films or laminates) made of a porous polymer having electrical insulation.
- the electrolytic solution contains a solvent and an electrolyte (lithium salt).
- the solvent may be water or an organic solvent.
- the electrolyte (lithium salt) is LiPF 6 , LiClO 4 , LiBF 4 , LiCF 3 SO 3 , LiCF 3 CF 2 SO 3 , LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiN ( One or more lithium compounds selected from the group consisting of CF 3 CF 2 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiN (CF 3 CF 2 CO) 2 and LiBOB. good.
- the full width at half maximum of the X-ray diffraction peak PMAX which has the highest intensity among at least one X-ray diffraction peak derived from the Ni-containing crystal in the second metal layer 2, is 0.3 ° or more and 1.2 ° or less. be.
- the laminated body 10 can have high tensile strength.
- the tensile strength means the durability of the laminated body 10 against the tensile stress in the direction parallel to the surface of the second metal layer 2.
- the mechanism by which the laminated body 10 has a high tensile strength when the full width at half maximum of the X-ray diffraction peak PMAX is 0.3 ° or more and 1.2 ° or less is as follows. However, the following mechanism is a hypothesis, and the technical scope of the present invention is not limited by the following mechanism.
- the laminated body 10 Since the laminated body 10 has not only the first metal layer 1 but also the second metal layer 2 laminated on the first metal layer 1, the laminated body 10 is a conventional current collector composed of only one metal layer containing Cu. It can have higher tensile strength than the body. However, the high tensile strength of the laminated body 10 is due not only to the laminated structure but also to the crystallinity of the second metal layer 2.
- the second metal layer 2 contains a large number of crystal grains containing Ni. As the full width at half maximum of the X-ray diffraction peak PMAX decreases, the particle size of each crystal grain in the second metal layer 2 increases, and the crystallinity of the second metal layer 2 increases.
- the entire laminate 10 can have high tensile strength.
- the full width at half maximum of the X-ray diffraction peak PMAX is 0.3 ° or more, the crystal grains are appropriately finely divided and the area of the grain boundaries is also moderately small, so that cracks along the grain boundaries are formed. Progress is suppressed.
- the full width at half maximum of the X-ray diffraction peak PMAX increases, the particle size of each crystal grain in the second metal layer 2 decreases, and the crystallinity of the second metal layer 2 decreases.
- the full width at half maximum of the X-ray diffraction peak PMAX increases, the second metal layer 2 gradually becomes amorphous.
- the tensile strength of the laminate 10 may be, for example, 800 MPa or more and 1300 MPa or less, 890 MPa or more and 1200 MPa or less, 897 MPa or more and 1200 MPa or less, 1000 MPa or more and 1200 MPa or less, or 1006 MPa or more and 1200 MPa or less.
- the full width at half maximum of the X-ray diffraction peak PMAX is 0.36 ° or more and 1.06 ° or less, 0.37 ° or more and 1.06 ° or less, or 0. It may be 39 ° or more and 1.06 ° or less.
- At least one X-ray diffraction peak derived from the Ni-containing crystal in the second metal layer 2 is included in the X-ray diffraction pattern measured by incident X-rays on the surface of the second metal layer 2.
- An example of an X-ray diffraction pattern is shown in FIG.
- FIG. 3 is an enlarged view of FIG. 2 and shows the maximum X-ray diffraction peak PMAX derived from a crystal containing Ni in the second metal layer 2.
- the horizontal axis of the X-ray diffraction pattern is the diffraction angle 2 ⁇ (unit: degrees) of the X-ray diffraction
- the vertical axis of the X-ray diffraction pattern is the intensity of the X-ray diffraction (unit: c thoroughlyunts).
- the X-ray diffraction pattern may include an X-ray diffraction peak derived from another crystal in addition to an X-ray diffraction peak derived from a crystal containing Ni. For example, as shown in FIGS.
- the X-ray diffraction pattern has at least one derived from the Cu-containing crystal in the first metal layer 1 in addition to the X-ray diffraction peak derived from the Ni-containing crystal. It may include an X-ray diffraction peak. Of the plurality of X-ray diffraction peaks included in the X-ray diffraction pattern, the number of X-ray diffraction peaks derived from the crystal containing Ni may be one or more. The X-ray diffraction peak derived from the crystal containing Ni may be distinguished from the X-ray diffraction peak derived from another crystal based on the diffraction angle 2 ⁇ .
- the Ni-containing crystals in the second metal layer 2 may have a face-centered cubic (fcc) structure.
- the X-ray diffraction peak PMAX having the highest intensity among at least one X-ray diffraction peak derived from the crystal containing Ni in the second metal layer 2 is the (111) plane of the crystal plane of the face-to-center cubic structure. It may be an X-ray diffraction peak derived from a kind of crystal plane selected from the group consisting of the (200) plane and the (220) plane.
- the crystal containing Ni in the second metal layer 2 may be a crystal composed of only Ni. As long as the face-centered cubic structure of the crystal containing Ni is maintained, the crystal containing Ni may further contain an element other than Ni.
- the diffraction angle 2 ⁇ of the X-ray diffraction peak PMAX may vary depending on the wavelength of the incident X-ray, the crystal composition, and the lattice constant, and is not particularly limited.
- Ni may be the main component of the second metal layer 2. That is, when the second metal layer 2 contains a plurality of kinds of elements, the Ni content (unit: mass%) may be the largest.
- the content of Ni in the second metal layer 2 may be, for example, 60% by mass or more and 100% by mass or less, 60% by mass or more and less than 100% by mass, or 60% by mass or more and 99.5% by mass or less.
- the content of Ni in the second metal layer 2 may be less than 50% by mass.
- At least a part or the whole of the second metal layer 2 may be a simple substance of Ni, an alloy containing Ni, or an intermetallic compound containing Ni.
- the second metal layer 2 may further contain at least one element selected from the group consisting of carbon (C), phosphorus (P) and tungsten (W).
- C carbon
- P phosphorus
- W tungsten
- the Ni-containing crystal in the second metal layer 2 may further contain at least one element selected from the group consisting of C, P and W.
- the crystal containing Ni in the second metal layer 2 may be a solid solution containing at least one element selected from the group consisting of C, P and W.
- the second metal layer 2 may be formed by an electrolytic plating method or an electroless plating method.
- the half-value full width of the X-ray diffraction peak PMAX can be controlled within the range of 0.3 ° or more and 1.2 ° or less. It is possible.
- the control factors for the half-value full width of the X-ray diffraction peak PMAX are the composition of the plating solution, the concentration of the raw material (compound containing Ni) in the plating solution, the temperature of the plating solution, the pH of the plating solution, and the first metal layer 1. It may be the current density, the plating implementation time, and the like.
- the half-value full width of the X-ray diffraction peak PMAX may be adjusted by the heat treatment of the second metal layer 2 formed by the electrolytic plating method or the electroless plating method.
- the Cu may be the main component of the first metal layer 1.
- the first metal layer 1 may be composed of only Cu.
- the first metal layer 1 may be made of an alloy containing Cu. Since the first metal layer 1 contains Cu, the laminated body 10 can have high conductivity required for a negative electrode current collector for a lithium ion secondary battery.
- the negative electrode active material contained in the negative electrode active material layer 3 may be any material that can occlude and release lithium ions, and is not particularly limited.
- the negative electrode active material contained in the negative electrode active material layer 3 may contain silicon (Si).
- the negative electrode active material containing silicon is more likely to expand and contract with the charging and discharging of the lithium ion secondary battery than other negative electrode active materials. Due to the fluctuation of the volume of the negative electrode active material layer 3 due to charging and discharging, the laminated body 10 (second metal layer 2) is repeatedly subjected to tensile stress. However, since the laminated body 10 according to the present embodiment has high tensile strength, breakage of the laminated body 10 due to the fluctuation of the volume of the negative electrode active material layer 3 is suppressed.
- the negative electrode active material containing silicon may be a simple substance of silicon, an alloy containing silicon, or a compound containing silicon (oxide, silicate, etc.).
- alloys containing silicon include tin (Sn), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), and silver ( It may contain at least one element selected from the group consisting of Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr).
- the silicon-containing compound may contain at least one element selected from the group consisting of boron (B), nitrogen (N), oxygen (O) and carbon (C).
- the negative electrode active materials containing silicon are SiB 4 , SiB 6 , Mg 2 Si, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , CaSi 2 , CrSi 2 , Cu 5 Si, FeSi 2 , MnSi. 2 , NbSi 2 , TaSi 2 , VSi 2 , WSi 2 , ZnSi 2 , SiC, Si 2 N 2 , Si 2 N 2 O, SiO X (0 ⁇ X ⁇ 2) and LiSiO at least one selected from the group. It may be a compound.
- the negative electrode active material may be a fiber containing silicon (nanowire or the like) or a particle containing silicon (nanoparticle or the like).
- the negative electrode active material layer 3 may further contain a binder. The binder binds the negative electrode active materials to each other, and binds the negative electrode active material layer 3 to the surface of the second metal layer 2.
- the thickness T1 of the first metal layer 1 may be, for example, 1 ⁇ m or more and 8 ⁇ m or less.
- the thickness T2 of one second metal layer 2 may be, for example, 0.3 ⁇ m or more and 4 ⁇ m or less, or 1.1 ⁇ m or more and 2.0 ⁇ m or less.
- the total thickness T2 of the second metal layer 2 may be expressed as T2 TOTAL , and T2 TOTAL / T1 may be 0.6 or more and 1.0 or less.
- T2 TOTAL is the sum of the thicknesses of the two second metal layers 2.
- T2 TOTAL / T1 is 0.6 or more, the laminated body 10 tends to have a sufficiently high tensile strength.
- T2 TOTAL / T1 When T2 TOTAL / T1 is 1.0 or less, the lithium ion secondary battery provided with the laminate 10 tends to have a sufficiently high energy density.
- the thickness T3 of one negative electrode active material layer 3 may be, for example, 10 ⁇ m or more and 300 ⁇ m or less.
- the thickness T1 of the first metal layer 1, the thickness T2 of the second metal layer 2, and the thickness T3 of the negative electrode active material layer 3 may be uniform.
- the dimensions of the first metal layer 1, the second metal layer 2, and the negative electrode active material layer 3 in the direction perpendicular to the stacking direction may be substantially the same as each other.
- the width of each of the first metal layer 1, the second metal layer 2, and the negative electrode active material layer 3 in the direction perpendicular to the stacking direction may be several tens of mm or more and several hundreds of mm or less.
- the lengths of the first metal layer 1, the second metal layer 2, and the negative electrode active material layer 3 in the direction perpendicular to the stacking direction may be several tens of mm or more and several thousand mm or less.
- the second metal layer may be formed by a vapor phase growth method such as sputtering, an organometallic chemical vapor deposition method (MOCVD), or an organometallic physical vapor deposition method (MOPVD).
- a vapor phase growth method such as sputtering, an organometallic chemical vapor deposition method (MOCVD), or an organometallic physical vapor deposition method (MOPVD).
- the laminate according to the present invention may be used as a heat radiating material or an electromagnetic wave shielding material. With the processing of the heat radiating material or the electromagnetic wave shielding material, tensile stress acts on the heat radiating material or the electromagnetic wave shielding material. Since the laminate according to the present invention has high tensile strength, it is possible to suppress damage to the heat radiating material or the electromagnetic wave shielding material due to processing.
- Pretreatment of the first metal layer A commercially available electrolytic copper foil was used as the first metal layer.
- the thickness of the first metal layer was 4.5 ⁇ m.
- the thickness of the first metal layer was uniform.
- organic substances adhering to the surface of the first metal layer were removed.
- As the degreasing liquid Sulcup MSC-3-A manufactured by C. Uyemura & Co., Ltd. was used. After degreasing, the first metal layer was washed by immersing the first metal layer in pure water for 1 minute.
- the natural oxide film existing on the surface of the first metal layer was removed by immersing the first metal layer in dilute sulfuric acid for 1 minute.
- the concentration of dilute sulfuric acid was 10% by mass.
- the first metal layer was washed by immersing the first metal layer in pure water for 1 minute.
- Laminates of Examples 1 to 10 and Comparative Examples 1 to 4 were produced by the following methods using the first metal layer that had undergone the above pretreatment.
- Example 1 The following electrolytic plating formed a second metal layer on both surfaces of the first metal layer. That is, by electrolytic plating, a laminate composed of a second metal layer laminated on the surfaces of both the first metal layer and the first metal layer was formed. In electrolytic plating, the second metal layer and other electrodes connected to the power supply were immersed in the plating solution, and a current was applied to the second metal layer and other electrodes.
- the plating solution contained nickel sulfate hexahydrate, sodium tungstate dihydrate, and trisodium citrate. The content of nickel sulfate hexahydrate in the plating solution was 60 g / L. The content of sodium tungstate dihydrate hydrate in the plating solution was 100 g / L.
- the content of trisodium citrate in the plating solution was 145 g / L.
- the pH of the plating solution was adjusted to 5.0.
- the temperature of the plating solution was adjusted to 50 ° C.
- the current density of the first metal layer during electroplating was adjusted to 5 A / dm 2 .
- the duration of electroplating was 1 minute.
- the laminate was washed by immersing the laminate in pure water for 1 minute. After cleaning the laminate, the water adhering to the laminate was removed. After removing the water, the laminate was heat-treated at 110 ° C. for 6 hours.
- Example 1 The laminate of Example 1 was produced by the above method.
- Example 2 The duration of the electrolytic plating of Example 2 was 1.5 minutes.
- the laminate of Example 2 was produced in the same manner as in Example 1 except for the duration of electrolytic plating.
- Example 3 In the case of Example 3, the second metal layer was formed on both surfaces of the first metal layer by the following electroless plating instead of electrolytic plating.
- the catalyst treatment of the first metal layer was carried out before electroless plating.
- the catalyst (palladium sulfate) was adhered to the surface of the first metal layer by immersing the first metal layer in the catalyst treatment liquid for 1 minute.
- the temperature of the catalytic treatment liquid was adjusted to 40 ° C.
- As the catalyst treatment liquid Axemalta MNK-4-M manufactured by C. Uyemura & Co., Ltd. was used.
- the catalyst-treated first metal layer was immersed in the electroless nickel plating solution for 1 minute.
- the electroless nickel plating solution contained sodium hypophosphite as a reducing agent.
- the temperature of the electroless nickel plating solution was adjusted to 90 ° C.
- the duration of electroless plating was 7 minutes.
- Nimden KLP manufactured by C. Uyemura & Co., Ltd. was used as the electroless nickel plating solution.
- the laminate of Example 3 was produced by the above method.
- Example 4 The duration of electroless plating in Example 4 was 10 minutes.
- the laminate of Example 4 was produced in the same manner as in Example 3 except for the duration of electroless plating.
- Example 5 Electrolytic plating of Example 5 was carried out using a plating solution having a composition different from that of the plating solution of Example 1.
- the plating solution of Example 5 contained nickel sulfate hexahydrate, nickel chloride hexahydrate, boric acid, and sodium saccharin.
- the content of nickel sulfate hexahydrate in the plating solution of Example 5 was 240 g / L.
- the content of nickel chloride hexahydrate in the plating solution of Example 5 was 45 g / L.
- the content of boric acid in the plating solution of Example 5 was 30 g / L.
- the content of saccharin sodium in the plating solution of Example 5 was 2 g / L.
- the pH of the plating solution of Example 5 was adjusted to 4.2.
- the temperature of the plating solution of Example 5 was adjusted to 40 ° C.
- the duration of the electrolytic plating of Example 5 was 1.5 minutes.
- Example 5 The laminate of Example 5 was produced by the same method as in Example 1 except for the above items.
- Example 6 The duration of the electrolytic plating of Example 6 was 2 minutes.
- the laminate of Example 6 was produced in the same manner as in Example 5 except for the duration of electrolytic plating.
- Example 7 The content of sodium tungstate dihydrate in the plating solution of Example 7 was 30 g / L. The content of trisodium citrate in the plating solution of Example 7 was 80 g / L. The pH of the plating solution of Example 7 was adjusted to 7.0. The duration of the electrolytic plating of Example 7 was 4 minutes. A laminate of Example 7 was produced in the same manner as in Example 1 except for the above items.
- Example 8 The content of nickel sulfate hexahydrate in the plating solution of Example 8 was 70 g / L. The content of sodium tungstate dihydrate in the plating solution of Example 8 was 15 g / L. The content of trisodium citrate in the plating solution of Example 8 was 80 g / L. The pH of the plating solution of Example 8 was adjusted to 7.0. The duration of the electrolytic plating of Example 8 was 3 minutes. A laminate of Example 8 was produced in the same manner as in Example 1 except for the above items.
- Example 9 The content of nickel sulfate hexahydrate in the plating solution of Example 9 was 75 g / L. The content of sodium tungstate dihydrate in the plating solution of Example 9 was 8 g / L. The content of trisodium citrate in the plating solution of Example 9 was 80 g / L. The pH of the plating solution of Example 9 was adjusted to 7.0. The duration of the electrolytic plating of Example 9 was 3 minutes. A laminate of Example 9 was produced in the same manner as in Example 1 except for the above items.
- Example 10 The content of nickel sulfate hexahydrate in the plating solution of Example 10 was 80 g / L.
- the content of sodium tungstate dihydrate in the plating solution of Example 10 was 4 g / L.
- the content of trisodium citrate in the plating solution of Example 10 was 80 g / L.
- the pH of the plating solution of Example 10 was adjusted to 7.0.
- the duration of electroplating in Example 10 was 3 minutes.
- a laminate of Example 10 was produced in the same manner as in Example 1 except for the above items.
- Comparative Example 1 The plating solution of Comparative Example 1 did not contain saccharin sodium.
- the laminate of Comparative Example 1 was produced in the same manner as in Example 5 except that the plating solution did not contain saccharin sodium.
- Comparative Example 2 The duration of the electrolytic plating of Comparative Example 2 was 2 minutes. A laminate of Comparative Example 2 was produced in the same manner as in Comparative Example 1 except for the duration of electrolytic plating.
- Comparative Example 3 The electroless plating of Comparative Example 3 was carried out using an electroless nickel plating solution having a composition different from that of the electroless nickel plating solution of Example 3.
- the content of sodium hypophosphite in the electroless nickel plating solution of Comparative Example 3 was larger than the content of sodium hypophosphite in the electroless nickel plating solution of Example 3.
- ICP Nicolon SOF manufactured by Okuno Pharmaceutical Industry Co., Ltd. was used as the electroless nickel plating solution of Comparative Example 3.
- the temperature of the electroless nickel plating solution of Comparative Example 3 was adjusted to 85 ° C.
- the laminate of Comparative Example 3 was produced by the same method as in Example 3 except for the above items.
- Comparative Example 4 The duration of electroless plating in Comparative Example 4 was 10 minutes.
- the laminate of Comparative Example 4 was produced in the same manner as in Comparative Example 3 except for the duration of electroless plating.
- the laminated body was cut in the laminating direction (direction perpendicular to the surface of the second metal layer).
- the cross section of the laminate was observed with a scanning electron microscope (SEM).
- the composition of the second metal layer exposed on the cross section of the laminate was analyzed by energy dispersive X-ray spectroscopy (EDS). It was confirmed that the second metal layers of Examples 1 to 10 and Comparative Examples 1 to 4 each contained the constituent elements shown in Table 1 below. The contents of Ni in the second metal layer of Examples 1 to 10 and Comparative Examples 1 to 4 are shown in Table 1 below.
- the thickness of each of the second metal layers laminated on both surfaces of the first metal layer was uniform.
- the thickness of the second metal layer was measured in the cross section of the laminate.
- the thickness T2 of the second metal layer is shown in Table 1 below.
- the total T2 TOTAL of the thickness T2 of the two second metal layers 2 is also shown in Table 1 below.
- the X-ray diffraction pattern was measured by injecting X-rays onto the surface of the second metal layer provided in the laminate. CuK ⁇ rays were used as the incident X-rays.
- the full width at half maximum of the X-ray diffraction peak PMAX having the highest intensity among at least one X-ray diffraction peak derived from the Ni crystal in the second metal layer is , Shown in Table 1 below.
- the X-ray diffraction peak PMAX having the maximum intensity is the X-ray diffraction derived from the (111) plane of the Ni crystal (face-centered cubic structure). It was a peak.
- Example 4 The X-ray diffraction pattern of Example 4 is shown in FIG.
- the X-ray diffraction peak PMAX of Example 4 is shown in FIG.
- a test piece was produced by punching the laminated body in the stacking direction.
- the shape of the test piece was dumbbell-shaped. Tension was applied to the test piece and the tension was gradually increased until the test piece broke.
- the value obtained by dividing the maximum tension (unit: N) immediately before the test piece breaks by the cross-sectional area (unit: m 2 ) of the test piece is the tensile strength (unit: MPa).
- the tensile strengths of Examples 1 to 10 and Comparative Examples 1 to 4 are shown in Table 1 below.
- the laminate according to one aspect of the present invention may be used as a negative electrode current collector of a lithium ion secondary battery.
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Abstract
Description
本実施形態に係るリチウムイオン二次電池は、負極20、正極、セパレータ及び電解液を含んでよい。セパレータ及び電解液は、負極20及び正極の間に配置される。電解液はセパレータを透過する。正極は、正極集電体と、正極集電体に積層された正極活物質層とを含んでよい。例えば、正極集電体は、アルミニウム箔又はニッケル箔であってよい。正極活物質層は、正極活物質を含む。例えば、正極活物質は、コバルト酸リチウム(LiCoO2)、ニッケル酸リチウム(LiNiO2)、マンガン酸リチウム(LiMnO2)、リチウムマンガンスピネル(LiMn2O4)、LiNixCoyMnzMaO2(x+y+z+a=1、0≦x<1、0≦y<1、0≦z<1、0≦a<1、MはAl、Mg、Nb、Ti、Cu、Zn及びCrからなる群より選ばれる一種類以上の元素である。)、リチウムバナジウム化合物(LiV2O5)、オリビン型LiMPO4(Mは、Co、Ni、Mn、Fe、Mg、Nb、Ti、Al及びZrより選ばれる一種類以上の元素、又はVOである。)、チタン酸リチウム(Li4Ti5O12)、LiNixCoyAlzO2(0.9<x+y+z<1.1)、ポリアセチレン、ポリアニリン、ポリピロール、ポリチオフェン及びポリアセンからなる群より選ばれる一種以上の化合物であってよい。正極活物質層は、炭素又は金属粉等の導電助剤を更に含んでよい。正極活物質層は、バインダー(接着剤又は樹脂)を更に含んでよい。セパレータは、電気的絶縁性を有する多孔質の高分子からなる一つ以上の膜(フィルム又は積層体)であってよい。電解液は、溶媒及び電解質(リチウム塩)を含む。溶媒は、水又は有機溶媒であってよい。例えば、電解質(リチウム塩)は、LiPF6、LiClO4、LiBF4、LiCF3SO3、LiCF3CF2SO3、LiC(CF3SO2)3、LiN(CF3SO2)2、LiN(CF3CF2SO2)2、LiN(CF3SO2)(C4F9SO2)、LiN(CF3CF2CO)2及びLiBOBからなる群より選ばれる一種以上のリチウム化合物であってよい。
第二金属層2は、Niを含む多数の結晶粒を含む。X線回折ピークPMAXの半値全幅の減少に伴って、第二金属層2中の各結晶粒の粒子径は増加し、第二金属層2の結晶性は高まる。X線回折ピークPMAXの半値全幅が小さ過ぎる場合、各結晶粒が大き過ぎて、隣り合う一対の結晶粒間の粒界の面積が広過ぎる。その結果、第二金属層2が受ける引張応力に因り、広い粒界に沿った大きい亀裂が一気に形成され易く、亀裂が第二金属層2内へ伝播(成長)し易く、第二金属層2及び積層体10全体が破断し易い。しかし、X線回折ピークPMAXの半値全幅が0.3°以上である場合、大き過ぎる結晶粒(高い結晶性)に起因する亀裂の伝播(成長)が抑制され、第二金属層2を含む積層体10全体が高い引張強度を有することができる。換言すれば、X線回折ピークPMAXの半値全幅が0.3°以上である場合、結晶粒が適度に微細化されており、粒界の面積も適度に小さいので、粒界に沿った亀裂の進展が抑制される。
X線回折ピークPMAXの半値全幅の増加に伴って、第二金属層2中の各結晶粒の粒子径は減少し、第二金属層2の結晶性は低下する。換言すれば、X線回折ピークPMAXの半値全幅の増加に伴って、第二金属層2は徐々に非晶質に似た状態になる。X線回折ピークPMAXの半値全幅が大き過ぎる場合、各結晶粒が微細過ぎるので、多数の微細な粒界が第二金属層2中に形成される。その結果、第二金属層2が受ける引張応力に因り、多数の微細な粒界から構成される経路に沿って亀裂が第二金属層2内で直線的に伝播(成長)し易く、第二金属層2及び積層体10全体が破断し易い。しかし、X線回折ピークPMAXの半値全幅が1.2°以下である場合、微細な結晶粒(低い結晶性)に起因する亀裂が抑制され、第二金属層2を含む積層体10全体が高い引張強度を有することができる。換言すれば、X線回折ピークPMAXの半値全幅が1.2°以下である場合、粒界に沿った亀裂の進展が、適度に大きい結晶粒によって中断され易く、亀裂が進展する方向が、適度に大きい結晶粒によって変更され易く、直線的な亀裂の進展が抑制される。
積層体10の引張強度は、例えば、800MPa以上1300MPa以下、890MPa以上1200MPa以下、897MPa以上1200MPa以下、1000MPa以上1200MPa以下、又は1006MPa以上1200MPa以下であってよい。
第一金属層として、市販の電解銅箔が用いられた。第一金属層の厚みは、4.5μmであった。第一金属層の厚みは均一であった。第一金属層を酸性の脱脂液中に1分間浸漬することにより、第一の金属層の表面に付着した有機物が除去された。脱脂液としては、上村工業株式会社製のスルカップMSC‐3‐Aが用いられた。脱脂後、第一金属層を純水に1分間浸漬することにより、第一金属層が洗浄された。
以下の電解めっきにより、第一金属層の両方の表面に第二金属層が形成された。つまり、電解めっきにより、第一金属層と第一金属層の両方の表面に積層された第二金属層から構成される積層体が形成された。
電解めっきでは、電源に接続された第二金属層及び他の電極がめっき液中に浸漬され、第二金属層及び他の電極に電流が印加された。めっき液は、硫酸ニッケル六水和物、タングステン酸ナトリウム二水和物、及びクエン酸三ナトリウムを含んでいた。めっき液中の硫酸ニッケル六水和物の含有量は、60g/Lであった。めっき液中のタングステン酸ナトリウム二水水和物の含有量は、100g/Lであった。めっき液中のクエン酸三ナトリウムの含有量は、145g/Lであった。めっき液のpHは、5.0に調整された。めっき液の温度は50℃に調整された。電解めっき中の第一金属層の電流密度は、5A/dm2に調整された。電解めっきの継続時間は1分であった。
実施例2の電解めっきの継続時間は1.5分であった。電解めっきの継続時間を除いて実施例1と同様の方法で、実施例2の積層体が作製された。
実施例3の場合、電解めっきではなく以下の無電解めっきにより、第一金属層の両方の表面に第二金属層が形成された。
実施例4の無電解めっきの継続時間は10分であった。無電解めっきの継続時間を除いて実施例3と同様の方法で、実施例4の積層体が作製された。
実施例1のめっき液とは組成が異なるめっき液を用いて、実施例5の電解めっきが実施された。実施例5のめっき液は、硫酸ニッケル六水和物、塩化ニッケル六水和物、ホウ酸、及びサッカリンナトリウムを含んでいた。実施例5のめっき液中の硫酸ニッケル六水和物の含有量は、240g/Lであった。実施例5のめっき液中の塩化ニッケル六水和物の含有量は、45g/Lであった。実施例5のめっき液中のホウ酸の含有量は、30g/Lであった。実施例5のめっき液中のサッカリンナトリウムの含有量は、2g/Lであった。実施例5のめっき液のpHは、4.2に調整された。実施例5のめっき液の温度は40℃に調整された。実施例5の電解めっきの継続時間は1.5分であった。
実施例6の電解めっきの継続時間は2分であった。電解めっきの継続時間を除いて実施例5と同様の方法で、実施例6の積層体が作製された。
実施例7のめっき液中のタングステン酸ナトリウム二水和物の含有量は、30g/Lであった。実施例7のめっき液中のクエン酸三ナトリウムの含有量は、80g/Lであった。実施例7のめっき液のpHは、7.0に調整された。実施例7の電解めっきの継続時間は4分であった。
上記事項を除いて実施例1と同様の方法で、実施例7の積層体が作製された。
実施例8のめっき液中の硫酸ニッケル六水和物の含有量は、70g/Lであった。実施例8のめっき液中のタングステン酸ナトリウム二水和物の含有量は、15g/Lであった。実施例8のめっき液中のクエン酸三ナトリウムの含有量は、80g/Lであった。実施例8のめっき液のpHは、7.0に調整された。実施例8の電解めっきの継続時間は3分であった。
上記事項を除いて実施例1と同様の方法で、実施例8の積層体が作製された。
実施例9のめっき液中の硫酸ニッケル六水和物の含有量は、75g/Lであった。実施例9のめっき液中のタングステン酸ナトリウム二水和物の含有量は、8g/Lであった。実施例9のめっき液中のクエン酸三ナトリウムの含有量は、80g/Lであった。実施例9のめっき液のpHは、7.0に調整された。実施例9の電解めっきの継続時間は3分であった。
上記事項を除いて実施例1と同様の方法で、実施例9の積層体が作製された。
実施例10のめっき液中の硫酸ニッケル六水和物の含有量は、80g/Lであった。実施例10のめっき液中のタングステン酸ナトリウム二水和物の含有量は、4g/Lであった。実施例10のめっき液中のクエン酸三ナトリウムの含有量は、80g/Lであった。実施例10のめっき液のpHは、7.0に調整された。実施例10の電解めっきの継続時間は3分であった。
上記事項を除いて実施例1と同様の方法で、実施例10の積層体が作製された。
比較例1のめっき液は、サッカリンナトリウムを含んでいなかった。めっき液がサッカリンナトリウムを含まないことを除いて実施例5と同様の方法で、比較例1の積層体が作製された。
比較例2の電解めっきの継続時間は2分であった。電解めっきの継続時間を除いて比較例1と同様の方法で、比較例2の積層体が作製された。
実施例3の無電解ニッケルめっき液とは組成が異なる無電解ニッケルめっき液を用いて、比較例3の無電解めっきが実施された。比較例3の無電解ニッケルめっき液中の次亜リン酸ナトリウムの含有量は、実施例3の無電解ニッケルめっき液中の次亜リン酸ナトリウムの含有量よりも大きかった。比較例3の無電解ニッケルめっき液としては、奥野製薬工業株式会社製のICPニコロンSOFが用いられた。比較例3の無電解ニッケルめっき液の温度は85℃に調整された。
比較例4の無電解めっきの継続時間は10分であった。無電解めっきの継続時間を除いて比較例3と同様の方法で、比較例4の積層体が作製された。
以下の方法により、実施例1~10及び比較例1~4其々の積層体が分析された。
荷重試験機に用いた以下の引張試験により、実施例1~10及び比較例1~4其々の積層体の引張強度が測定された。荷重試験機としては、アイコーエンジニアリング株式会社製のFTN1‐13Aが用いられた。
Claims (5)
- 銅を含む第一金属層と、
ニッケルを含み、前記第一金属層に直接積層された第二金属層と、
を備え、
前記第二金属層中のニッケルを含む結晶に由来する少なくとも一つのX線回折ピークのうち強度が最大であるX線回折ピークの半値全幅が、0.3°以上1.2°以下である、
積層体。 - 前記第二金属層が、炭素、リン及びタングステンからなる群より選ばれる少なくとも一種の元素を更に含む、
請求項1に記載の積層体。 - 請求項1又は2に記載の積層体を備える、
リチウムイオン二次電池用の負極集電体。 - 請求項3に記載の負極集電体と、
負極活物質を含む負極活物質層と、
を備え、
前記負極活物質層が前記第二金属層に直接積層されている、
リチウムイオン二次電池用の負極。 - 前記負極活物質がケイ素を含む、
請求項4に記載の負極。
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JP2019026941A (ja) * | 2015-09-28 | 2019-02-21 | 日本軽金属株式会社 | 導電部材及びその製造方法 |
JP2021038445A (ja) * | 2019-09-04 | 2021-03-11 | 公立大学法人兵庫県立大学 | 多層材及びその製造方法、多層材メッキ方法 |
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