CN116356389A - Alloy coating preparation method, alloy coating, battery and battery assembly - Google Patents
Alloy coating preparation method, alloy coating, battery and battery assembly Download PDFInfo
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- CN116356389A CN116356389A CN202310637712.3A CN202310637712A CN116356389A CN 116356389 A CN116356389 A CN 116356389A CN 202310637712 A CN202310637712 A CN 202310637712A CN 116356389 A CN116356389 A CN 116356389A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 153
- 239000000956 alloy Substances 0.000 title claims abstract description 153
- 239000011248 coating agent Substances 0.000 title claims abstract description 88
- 238000000576 coating method Methods 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007762 w/o emulsion Substances 0.000 claims abstract description 85
- 238000004070 electrodeposition Methods 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 54
- 230000008569 process Effects 0.000 claims abstract description 43
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 18
- 150000002815 nickel Chemical class 0.000 claims abstract description 18
- 239000000872 buffer Substances 0.000 claims abstract description 17
- 150000001868 cobalt Chemical class 0.000 claims abstract description 11
- 150000001879 copper Chemical class 0.000 claims abstract description 11
- 238000007747 plating Methods 0.000 claims description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 239000003921 oil Substances 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 17
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001453 nickel ion Inorganic materials 0.000 claims description 13
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 11
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 10
- 230000000737 periodic effect Effects 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 4
- 229910000531 Co alloy Inorganic materials 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- FBELJLCOAHMRJK-UHFFFAOYSA-L disodium;2,2-bis(2-ethylhexyl)-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCC(CC)CC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CC(CC)CCCC FBELJLCOAHMRJK-UHFFFAOYSA-L 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 claims description 2
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 claims description 2
- 239000006172 buffering agent Substances 0.000 claims 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 23
- 239000002184 metal Substances 0.000 abstract description 21
- 150000002739 metals Chemical class 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 73
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 description 29
- 239000012071 phase Substances 0.000 description 28
- 239000010408 film Substances 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 230000010287 polarization Effects 0.000 description 10
- 239000012266 salt solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- 238000006479 redox reaction Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000000306 component Substances 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PHXQIAWFIIMOKG-UHFFFAOYSA-N NClO Chemical compound NClO PHXQIAWFIIMOKG-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 229910001325 element alloy Inorganic materials 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000009347 mechanical transmission Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/20—Electroplating using ultrasonics, vibrations
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to a preparation method of an alloy coating, a battery and a battery component. The preparation method of the alloy coating provided by the invention comprises the following steps: preparing a first solution comprising an organic solute, a cobalt salt, a nickel salt, and a copper salt; adding an emulsifying agent and a buffer into the first solution to obtain a second solution; adding a second solution into the oil phase to obtain a water-in-oil emulsion; performing electrodeposition treatment on the auxiliary electrode, the working electrode and the reference electrode in water-in-oil emulsion to form a target alloy coating on the working electrode; wherein, in the process of carrying out electrodeposition treatment on the auxiliary electrode, the working electrode and the reference electrode in the water-in-oil emulsion, ultrasonic irradiation treatment is carried out on the water-in-oil emulsion. The method provided by the invention ensures that three metals with larger electrode potential difference are co-deposited to form a uniform medium-entropy alloy coating with good mechanical property.
Description
Technical Field
The invention relates to the technical field of alloy coating preparation, in particular to a preparation method of an alloy coating, the alloy coating, a battery and a battery assembly.
Background
In the related art, the mid-entropy of the equal atomic ratio or the near-equal atomic ratio can be prepared by adopting an electrodeposition mode, but the mode can only prepare an alloy coating with small electrode potential difference, and meanwhile, the continuity of a metal coating with large electrode potential difference is difficult to ensure.
Disclosure of Invention
In view of the above, the present invention provides a method for producing an alloy plating layer, a battery and a battery assembly.
Specifically, the invention is realized by the following technical scheme:
according to a first aspect of the present invention, there is provided a method of producing an alloy plating layer, the method comprising: preparing a first solution comprising an organic solute, a cobalt salt, a nickel salt, and a copper salt; adding an emulsifying agent and a buffer into the first solution to obtain a second solution; adding a second solution into the oil phase to obtain a water-in-oil emulsion; performing electrodeposition treatment on the auxiliary electrode, the working electrode and the reference electrode in water-in-oil emulsion to form a target alloy coating on the working electrode; wherein, in the process of carrying out electrodeposition treatment on the auxiliary electrode, the working electrode and the reference electrode in the water-in-oil emulsion, ultrasonic irradiation treatment is carried out on the water-in-oil emulsion.
In the invention, in the process of carrying out electrodeposition treatment on an auxiliary electrode, a working electrode and a reference electrode in water-in-oil emulsion, carrying out ultrasonic irradiation treatment on the water-in-oil emulsion, adding a water phase for dissolving metal salt into an oil phase to form the water-in-oil emulsion, and limiting the diffusion of the water-in-oil emulsion and the concentration distribution of the water-in-oil emulsion so as to realize the redox reaction of ions; meanwhile, by applying potential through three-electrode deposition, the three metals with larger potential difference of the electrodes are jointly deposited to form a uniform medium-entropy alloy film with good mechanical properties, and the medium-entropy alloy film is applied to the field of multifunctional catalysts, so that nano-particle-level medium-entropy alloy is used as a multifunctional catalyst and simultaneously catalyzes substances with multiple reaction functions, and multiple steps of catalytic reactions of different types are completed in one reaction process, thereby improving the chemical reaction efficiency in a battery, realizing the continuous production of a film electrode, simplifying the production flow, improving the application degree of an entropy alloy coating in cobalt-nickel-copper to multiple application occasions, and improving the application range of the battery and a battery pack.
According to a second aspect of the present invention, an alloy plating layer is produced by the method for producing an alloy plating layer according to the first aspect.
The alloy coating according to the invention is produced by the method for producing an alloy coating according to the first aspect, and has all the technical advantages of the first aspect or any possible implementation of the first aspect, which are not described in detail here.
According to a third aspect of the present invention, a battery includes: a cathode; an anode; and an alloy coating as in the second aspect, the alloy coating being located between the cathode and the anode.
The battery comprises a cathode, an anode and an alloy coating in the second aspect, wherein the electrolytic solution at the cathode is subjected to reduction reaction, the electrolytic solution at the anode is subjected to oxidation reaction, the working distance between the cathode and the anode can be reasonably adjusted according to working requirements, so that enough installation space is reserved between the anode and the cathode for the entropy alloy coating in compact, continuous and uniform cobalt-nickel-copper in the electrodeposition process, and the alloy coating is arranged between the anode and the cathode, thereby having all the beneficial effects of any possible implementation mode of the second aspect and being not repeated herein.
In a fourth aspect of the present invention, a battery assembly includes: a housing; and a battery as in the third aspect, the battery being located within the housing.
The battery assembly of the present invention comprises a housing and a battery as in the third aspect, the housing being capable of providing an installation space for the battery and assisting in protecting the battery, the battery being located within the housing, thus having all the advantages of any possible implementation of the third aspect, which is not described in detail herein.
The technical scheme provided by the invention has at least the following beneficial effects: according to the invention, through ultrasonic irradiation treatment of the water-in-oil emulsion, a water phase for dissolving metal salt can be added into an oil phase to form the water-in-oil emulsion, and through limiting the diffusion of the water-in-oil emulsion and the concentration distribution of the water-in-oil emulsion, the redox reaction of ions is realized; meanwhile, by applying potential through three-electrode deposition, the three metals with larger potential difference of the electrodes are jointly deposited to form a uniform medium-entropy alloy film with good mechanical properties, and the medium-entropy alloy film is applied to the field of multifunctional catalysts, so that nano-particle-level medium-entropy alloy is used as a multifunctional catalyst and simultaneously catalyzes substances with multiple reaction functions, and multiple steps of catalytic reactions of different types are completed in one reaction process, thereby improving the chemical reaction efficiency in a battery, realizing the continuous production of a film electrode, simplifying the production flow, improving the application degree of an entropy alloy coating in cobalt-nickel-copper to multiple application occasions, and improving the application range of the battery and a battery pack.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the related art will be briefly described below, and it will be apparent to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a schematic flow chart of a method for preparing an alloy coating according to some embodiments of the present invention;
fig. 2 is a schematic structural view of a battery according to some embodiments of the present invention;
fig. 3 is a schematic structural view of a battery assembly according to some embodiments of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In a first aspect, the present invention provides a method for preparing an alloy plating layer, the method comprising:
s1, preparing a first solution containing organic solute, cobalt salt, nickel salt and copper salt;
by preparing the first solution, a metal salt solution for dissolving copper ions, nickel ions and cobalt ions can be obtained, so that the metal salt solution is added into an oil phase such as 1, 2-dichloroethane to form a water-in-oil emulsion, the preparation of an entropy alloy coating in cobalt-nickel-copper is facilitated, and the phenomenon that the oxidation-reduction potential difference of metals in the related art is large and a stable intermediate entropy alloy coating cannot be prepared through electrodeposition is avoided.
It is understood that the first solution comprising the organic solute, cobalt salt, nickel salt and copper salt is the aqueous phase for preparing the water-in-oil emulsion.
S2, adding an emulsifying agent and a buffer into the first solution to obtain a second solution;
and adding an emulsifier into the first solution to ensure the stable state of the water-in-oil emulsion formed by the oil phase and the water phase, thereby ensuring the stable performance of the subsequent electrodeposition.
The buffer is added into the first solution, so that the increase of the pH value in the electrodeposition process can be inhibited, and a stable acidic environment is ensured, thereby avoiding the precipitation of a large amount of hydroxides in the electrodeposition process, preventing the electrolysis from being carried out, and simultaneously ensuring that the alloy plating obtained by electrolysis has good mechanical properties.
It is understood that the second solution is a mixed solution of aqueous phase and emulsifier, buffer.
S3, adding a second solution into the oil phase to obtain water-in-oil emulsion;
the mixed solution of the water phase, the emulsifier and the buffer is added into the oil phase, and the water-in-oil emulsion is formed by stirring, so that the cobalt-nickel-copper alloy coating with larger component electrode potential difference can be prepared in a system with the water phase and the oil phase not separated by electrolysis of the water-in-oil emulsion, and the problem that the alloy coating with larger point position difference is difficult to prepare is solved.
S4, performing electrodeposition treatment on the auxiliary electrode, the working electrode and the reference electrode in water-in-oil emulsion to form a target alloy coating on the working electrode;
the auxiliary electrode, the working electrode and the reference electrode are subjected to electrodeposition treatment in water-in-oil emulsion, and a three-electrode system is used for electrodeposition, so that larger errors of electrode potential due to polarized current can be eliminated. In a system formed by three electrodes, a polarization loop is formed at one side of the working electrode and one side of the auxiliary electrode, and polarization current passes through the polarization loop, so that the reference electrode can be measured and controlled; and a measurement control loop is formed on one side of the working electrode and the reference electrode, so that the electric potential of the working electrode can be measured and controlled. The measurement control loop has no polarized current passing through, and the polarization state of the working electrode and the stability of the reference electrode are not affected, so that the potential of the working electrode can be measured and controlled simultaneously under the condition that the polarized current passes through the surface of the working electrode.
Wherein, in the process of carrying out electrodeposition treatment on the auxiliary electrode, the working electrode and the reference electrode in the water-in-oil emulsion, ultrasonic irradiation treatment is carried out on the water-in-oil emulsion.
In some embodiments, the ultrasonic irradiation treatment is a periodic ultrasonic irradiation treatment, wherein the periodic interval is 1 second to 5 seconds, for example, 2s, 3s, or 4s. In the present invention, the periodic ultrasonic irradiation treatment at regular intervals represents ultrasonic irradiation treatment at regular intervals, stopping at regular intervals, and ultrasonic irradiation treatment at regular intervals, for example, when the periodic interval is 1 second, ultrasonic irradiation treatment is performed for 1s, ultrasonic irradiation treatment is stopped for 1s, and ultrasonic irradiation treatment is performed for 1s.
The ultrasonic irradiation is periodically carried out on the water-in-oil emulsion, so that particles in the water-in-oil emulsion can be better dispersed, agglomeration among the particles is reduced, the particles are more uniform, the particles are promoted to be more uniformly embedded into the alloy coating, and the mass fraction of the particles in the alloy coating is improved. Meanwhile, compared with mechanical stirring, the ultrasonic wave can refine the crystal grains of the alloy coating, so that the surface of the alloy coating is smoother.
It can be understood that the ultrasonic irradiation is periodically performed on the water-in-oil emulsion, so that the nano particles can be uniformly dispersed on the working electrode, dislocation and sliding of crystal grains are hindered, and the refined crystal grains can enable the alloy coating to have higher hardness and better wear resistance, so that the plastic deformation resistance of the alloy coating is improved. Meanwhile, the ultrasonic wave irradiation can reduce the occurrence of the pitting phenomenon in the electrodeposition process, so that the corrosion resistance of the alloy plating layer is improved.
Further, in the electrodeposition process, periodic ultrasonic irradiation is used, so that the ion concentration distribution and mass transfer process can be changed, concentration polarization is reduced, ion activity and energy are enhanced, deformation of hydrated metal ions is promoted, the electrode reaction process is accelerated, electrochemical polarization is inhibited, primary hydrogen bubbles in an acid system do not have enough time to stay and grow on the surface of an electrode, the inclusion tendency of the hydrogen bubbles is reduced, cavitation in water-in-oil emulsion is enhanced, a microlayer on the surface of the electrode is promoted to generate plastic deformation, the surface dislocation density and nucleation center are increased, nucleation rate is improved, crystallization refinement is facilitated, and mechanical properties of a composite coating can be effectively improved by acoustic streaming, microjet, shock waves and the like, so that a compact and uniformly distributed cobalt-nickel-copper entropy alloy coating is obtained.
In some embodiments, the molar content of the nickel salt in the first solution is more than 2 times the molar content of the cobalt salt, based on the nickel element and the cobalt element. In some embodiments, the molar content of nickel salt in the first solution is more than 2 times the molar content of copper salt, calculated as nickel element and copper element. In the deposition solution, the charge transfer resistance of Ni electrodeposition is high. Thus, co and Cu electrodepositions are likely to reach diffusion limits, whereas Ni electrodepositions are not necessarily. In this case, double concentrations of Ni salts are required to obtain Co, cu, ni in nearly the same atomic proportions.
In some embodiments, the concentration of the organic solute in the first solution is from 0.05 moles per liter to 0.5 moles per liter, for example, 0.1 moles per liter, 0.15 moles per liter, 0.2 moles per liter, 0.3 moles per liter, or 0.4 moles per liter.
In some embodiments, the concentration of cobalt salt in the first solution is 5 to 15 millimoles per liter, for example 6 millimoles per liter, 7 millimoles per liter, 8 millimoles per liter, 9 millimoles per liter, 10 millimoles per liter, 11 millimoles per liter, 12 millimoles per liter, 13 millimoles per liter, or 14 millimoles per liter.
In some embodiments, the concentration of nickel salt in the first solution is from 10 millimoles per liter to 30 millimoles per liter, for example, 12 millimoles per liter, 14 millimoles per liter, 16 millimoles per liter, 18 millimoles per liter, 20 millimoles per liter, 22 millimoles per liter, 24 millimoles per liter, 26 millimoles per liter, or 28 millimoles per liter.
In some embodiments, the concentration of copper salt in the first solution is 5 millimoles per liter to 15 millimoles per liter, for example 6 millimoles per liter, 7 millimoles per liter, 8 millimoles per liter, 9 millimoles per liter, 10 millimoles per liter, 11 millimoles per liter, 12 millimoles per liter, 13 millimoles per liter, or 14 millimoles per liter.
In some embodiments, the organic solute is selected from one or more of tetrabutylammonium perchlorate, tetramethylammonium perchlorate, tetraethylammonium perchlorate, and tetrapropylammonium perchlorate.
In some embodiments, the cobalt salt is selected from one or more of cobalt chloride, cobalt nitrate, cobalt sulfate, and cobalt acetate.
In some embodiments, the nickel salt is selected from one or more of nickel chloride, nickel nitrate, nickel sulfate, and nickel acetate.
In some embodiments, the copper salt is selected from one or more of copper chloride, copper nitrate, copper sulfate, and copper acetate.
In some embodiments, the emulsifier is one or more of sodium dodecyl sulfate and sodium bis (2-ethylhexyl) sulfosuccinate. Sodium bis (2-ethylhexyl) sulfosuccinate having the formula C 20 H 37 Na 7 S。
In some embodiments, the buffer is boric acid. The boric acid can inhibit the increase of the pH value in the second solution, and particularly can control the pH value to be between 6.7 and 9.2, so that the smooth proceeding of the electrodeposition process is ensured.
In some embodiments, the oil phase is 1, 2-dichloroethane. The 1, 2-dichloroethane does not react with cobalt ions, nickel ions and copper ions, so that smooth progress of the electrodeposition process is ensured, and a certain amount of water exists in the 1, 2-dichloroethane oil phase in the electrolytic oxidation-reduction process, so that the 1, 2-dichloroethane and water can be reduced simultaneously, further smooth progress of the electrodeposition process in the water-in-oil emulsion is enhanced, and meanwhile, the 1, 2-dichloroethane is not decomposed, and further, a stable and uniform cobalt-nickel-copper entropy alloy coating is formed.
In some embodiments, the concentration of the emulsifier in the second solution is greater than the critical micelle constant of the emulsifier, e.g., at least 5 times, or at least 10 times, or at least 15 times its critical micelle constant. In some embodiments, the concentration of the emulsifier in the second solution is 50 to 150 millimoles per liter, for example 60 millimoles per liter, 70 millimoles per liter, 80 millimoles per liter, 90 millimoles per liter, 100 millimoles per liter, 110 millimoles per liter, 120 millimoles per liter, 130 millimoles per liter, or 140 millimoles per liter.
In the invention, the concentration of the emulsifier in the second solution is far higher than the critical constraint constant, so that the stability of the emulsion state of the water-in-oil emulsion can be ensured, and the subsequent electrodeposition in the water-in-oil emulsion is facilitated, and the stable cobalt-nickel-copper entropy alloy coating is obtained.
In some embodiments, the concentration of the buffer in the second solution is such that the pH of the second solution is between 6.7 and 9.2. In some embodiments, the concentration of buffer in the second solution is 300 millimoles per liter to 500 millimoles per liter, for example 320 millimoles per liter, 340 millimoles per liter, 360 millimoles per liter, 380 millimoles per liter, 400 millimoles per liter, 420 millimoles per liter, 440 millimoles per liter, 460 millimoles per liter, or 480 millimoles per liter.
According to the invention, the concentration of the buffer in the second solution can timely supplement hydrogen in the electrodeposition process, so that shortage of hydrogen ions is avoided, thereby inhibiting the increase of pH value in the electrodeposition process, avoiding the formation of hydroxide, ensuring the smooth progress of the electrodeposition process, and further obtaining a stable cobalt-nickel-copper entropy alloy coating.
In some embodiments, the volume ratio of oil phase to second solution is 1 (0.002-0.009), e.g., 1:0.003, 1:0.004, 1:0.005, 1:0.006, 1:0.007, or 1:0.008. In the application, the volume of the oil phase is larger than that of the second solution, so that the oil phase is larger than that of the water phase, and the water-in-oil emulsion with a stable emulsifying state is formed, so that the smooth proceeding of the electrodeposition process is ensured, and a stable and uniform cobalt-nickel-copper medium entropy alloy coating is formed.
In some embodiments, the pH of the water-in-oil emulsion is less than or equal to 1. In some embodiments, the pH of the water-in-oil emulsion is adjusted by an acidic solution, such as a hydrochloric acid solution. The acidic environment of the water-in-oil emulsion ensures that enough hydrogen ions are separated out in the oxidation-reduction reaction, thereby ensuring the smooth proceeding of the electrodeposition process.
The hydrochloric acid solution is easy to obtain and low in cost, can reduce that chloride ions of the hydrochloric acid solution can not react with other ions in the electrolyte solution, and the preset pH value is 1, so that enough hydrogen ions can participate in redox reaction, the acidic environment of the water-in-oil emulsion is ensured, and the smooth implementation of the electrodeposition process is ensured. The volume and the concentration of the dropwise added hydrochloric acid solution are not strictly limited, and the volume and the concentration can be flexibly adjusted under the condition of meeting actual requirements. It is understood that the specific concentration of the hydrochloric acid solution is not strictly limited in this application. The concentration of the hydrochloric acid solution can be reasonably set according to actual needs.
In some embodiments, in the process of adding an acid solution to adjust the pH of the water-in-oil emulsion, dynamic light scattering is used for measuring water drops in the water-in-oil emulsion, so that the sizes of cobalt, nickel and copper alloy particles can be detected in a visual way and used as a judging basis for the mixing effect of the water-in-oil emulsion, the uniformity and stability of the water-in-oil emulsion are ensured, and a compact and uniformly distributed cobalt-nickel copper entropy alloy coating is obtained through electrodeposition.
In some embodiments, the preparation method of the alloy plating layer provided by the invention comprises the following specific steps: preparing a first solution of tetrabutylammonium perchlorate, cobalt chloride hexahydrate, nickel chloride hexahydrate and copper chloride dihydrate; adding an emulsifying agent and a buffer into the first solution to obtain a second solution; adding a second solution into the oil phase to obtain a water-in-oil emulsion; performing electrodeposition treatment on the auxiliary electrode, the working electrode and the reference electrode in water-in-oil emulsion to form a target alloy coating on the working electrode; wherein, in the process of carrying out electrodeposition treatment on the auxiliary electrode, the working electrode and the reference electrode in the water-in-oil emulsion, periodically-spaced ultrasonic irradiation treatment is carried out on the water-in-oil emulsion.
In some embodiments, the reference electrode is a silver-silver chloride electrode; the auxiliary electrode is a platinum electrode. The silver-silver chloride electrode is easy to obtain and low in price, the preparation cost of the alloy plating layer can be reduced, and meanwhile, the electrode position of the working electrode can be accurately controlled, so that the electrochemical reaction process of the working electrode is tested in a loop of the reference electrode and the working electrode; the auxiliary electrode is a platinum electrode, is easy to obtain and low in price, can reduce the preparation cost of the alloy plating layer, and ensures the balance of electrochemical reaction in a loop formed by the working electrode and the auxiliary electrode.
Wherein a silver-silver chloride electrode was used as a reference electrode in 1 mole sodium chloride solution per liter.
In some embodiments, the auxiliary electrode, the working electrode, and the reference electrode are subjected to an electrodeposition treatment in a water-in-oil emulsion to form a target alloy coating on the working electrode, further comprising: and carrying out mechanical polishing treatment on the working electrode. And carrying out mechanical polishing treatment on the working electrode to obtain a flat working electrode, thereby ensuring that a uniform, compact and continuous cobalt-nickel-copper medium-entropy alloy coating is formed on the working electrode and ensuring the mechanical property of the alloy coating.
In some embodiments, the working electrode is one of a molybdenum electrode, a nickel electrode, a gold electrode, or a silicon electrode. The working electrode is one of a molybdenum electrode, a nickel electrode, a gold electrode or a silicon electrode, so that a medium entropy alloy coating which does not react with an electrolytic solution can be deposited on the working electrode, a uniform and continuous cobalt-nickel-copper medium entropy alloy coating is obtained, and metals with larger potential differences of the three electrodes are jointly deposited, so that continuous production of the film electrode is realized. It is understood that the material of the working electrode is not strictly limited, and the preparation material can be reasonably selected according to actual needs and cost requirements.
In some embodiments, the working electrode is a disk electrode; the diameter of the disk electrode is more than or equal to 5 mm and less than or equal to 20 mm. The working electrode is a disc electrode, and enough places can be provided for the deposition of cobalt-nickel-copper, so that a continuous medium-entropy alloy coating is formed, wherein the diameter of the disc electrode is more than or equal to 5 mm and less than or equal to 20 mm, the reasonable arrangement of the working electrode can be facilitated, a compact, continuous and uniform medium-entropy alloy coating of cobalt-nickel-copper is formed more conveniently, and the mechanical property of the alloy coating is ensured.
Illustratively, the disk electrode has a volume of 0.785 square centimeters when it has a diameter of 10 millimeters.
In some embodiments, the voltage of the electrodeposition process is greater than or equal to minus 1.6 volts and less than or equal to minus 1.4 volts. The voltage within this range can ensure that the water-in-oil emulsion is electrodeposited at a constant potential, and the oil phase is not decomposed while enhancing the progress of the redox reaction in the water-in-oil emulsion.
In some embodiments, the total concentration of cobalt ions, nickel ions, and copper ions in the water-in-oil emulsion is maintained at 0.2 millimoles per liter to 0.3 millimoles per liter, for example, 0.20 millimoles per liter, 0.22 millimoles per liter, 0.24 millimoles per liter, 0.26 millimoles per liter, 0.28 millimoles per liter, and 0.30 millimoles per liter, in the electrodeposition process. The total concentration of cobalt ions, nickel ions and copper ions in the aqueous solution is kept between 0.35 millimoles per liter and 0.45 millimoles per liter, for example between 0.35 millimoles per liter, 0.40 millimoles per liter and 0.45 millimoles per liter. Compared with electrodeposition in the related art, the apparent concentration is lower, so that the electrodeposition irradiated by ultrasonic can be smoothly carried out by adding the aqueous solution containing the metal salt to maintain the aqueous solution at a certain concentration, a compact, continuous and uniform cobalt-nickel-copper entropy alloy coating is obtained, and the mechanical property of the cobalt-nickel-copper entropy alloy coating is ensured.
In some embodiments, electrodepositing the auxiliary electrode, the working electrode, and the reference electrode in a water-in-oil emulsion to form a target alloy coating on the working electrode comprises:
applying a preset voltage to the water-in-oil emulsion;
the preset voltage is applied to the water-in-oil emulsion, so that the water-in-oil emulsion can be ensured to carry out electrodeposition under constant potential, and 1, 2-dichloroethane is not decomposed while the oxidation-reduction reaction in the water-in-oil emulsion is enhanced, thereby ensuring the smooth implementation of the electrodeposition process.
And adding a third volume of a fourth solution to the water-in-oil emulsion every second preset period to form a target alloy coating on the working electrode;
the transfer resistance of nickel ions in the electrodeposition process is higher, and the nickel ions are incompletely electrodeposited under the condition that the cobalt ions and the copper ions possibly reach the diffusion limit, so that a certain volume of nickel salt solution is increased, the nickel ions, the cobalt ions and the copper ions which are close to the same proportion can be obtained, and the entropy alloy plating layer in cobalt nickel copper with larger electrode potential distance is prepared.
It can be understood that the nickel salt solution can be a first solution prepared from tetrabutylammonium perchlorate, cobalt chloride hexahydrate, nickel chloride hexahydrate and copper chloride dihydrate, and the first solution is used as the nickel salt solution, so that the consistency of components can be ensured, impurities are prevented from entering, an additional treatment process is avoided, and the performance of an entropy alloy coating in the prepared cobalt nickel copper is ensured. Meanwhile, the apparent concentration of metal ions in the water-in-oil emulsion is 0.24 millimoles per liter, and compared with electrodeposition in the related art, the apparent concentration is lower, so that the addition of the aqueous solution containing metal salt can help smooth electrodeposition under ultrasonic irradiation to obtain a compact, continuous and uniform cobalt-nickel-copper entropy alloy coating, and the mechanical property of the cobalt-nickel-copper entropy alloy coating is ensured.
The preset voltage is applied to the water-in-oil emulsion, so that electrodeposition of the water-in-oil emulsion under constant potential can be ensured, 1, 2-dichloroethane is not decomposed while oxidation-reduction reaction in the water-in-oil emulsion is enhanced, and a fourth solution with a third volume is added to the water-in-oil emulsion every a second preset period so as to form a target alloy coating on a working electrode, nickel ions, cobalt ions and copper ions which are close to the same proportion can be obtained, and compactness, continuity, uniformity and mechanical property of the entropy alloy coating in cobalt-nickel-copper are ensured while the entropy alloy coating in cobalt-nickel-copper with larger electrode potential distance from each other is prepared.
In some embodiments, the preset voltage is greater than or equal to minus 1.6 volts and less than or equal to minus 1.4 volts. The preset voltage is set to be more than or equal to minus 1.6 volts and less than or equal to minus 1.4 volts, and reasonable voltage can be selected with the electrochemical measurement result, so that the water-in-oil emulsion is ensured to carry out electrodeposition under constant potential, and 1, 2-dichloroethane is not decomposed while the oxidation-reduction reaction in the water-in-oil emulsion is enhanced, and the smooth implementation of the electrodeposition process is ensured.
For example, the preset voltage may be set to minus 1.5 volts according to the electrochemical measurement result.
In some embodiments, the second preset period is 40 minutes. In some embodiments, the third volume is 10 microliters. In some embodiments, the fourth solution is a nickel salt solution or the first solution. 10 microliters of nickel salt solution or first solution is added into the water-in-oil emulsion every 40 minutes, so that the metal ions consumed in the redox process of the complementary electrodeposition can be ensured, the concentration of the metal ions is ensured to be kept constant, and the cobalt-nickel-copper entropy alloy coating with the thickness of 350 nanometers is obtained on the working electrode after three hours.
Referring to fig. 1, in some embodiments, the method for preparing the alloy plating layer specifically includes:
s102, preparing a first solution of tetrabutylammonium perchlorate, cobalt chloride hexahydrate, nickel chloride hexahydrate and copper chloride dihydrate;
the first solution of tetrabutylammonium perchlorate, cobalt chloride hexahydrate, nickel chloride hexahydrate and copper chloride dihydrate is prepared, and a metal salt solution for dissolving copper ions, nickel ions and cobalt ions can be obtained, so that the metal salt solution is added into an oil phase of 1, 2-dichloroethane in the subsequent process to form water-in-oil emulsion, the preparation of an entropy alloy coating in cobalt-nickel-copper is facilitated, the phenomenon that the oxidation-reduction potential difference of metal in the related art is large, and a stable intermediate entropy alloy coating cannot be prepared through electrodeposition is avoided.
S104, adding an emulsifying agent and a buffer into the first solution to obtain a second solution;
and adding an emulsifier into the first solution to ensure the stable state of the water-in-oil emulsion formed by the oil phase and the water phase, thereby ensuring the stable performance of the subsequent electrodeposition.
The buffer is added into the first solution, so that the increase of the pH value in the electrodeposition process can be inhibited, and a stable acidic environment is ensured, thereby avoiding the precipitation of a large amount of hydroxides in the electrodeposition process, preventing the electrolysis from being carried out, and simultaneously ensuring that the alloy plating obtained by electrolysis has good mechanical properties.
S106, adding the first solution with the second volume into the oil phase with the first volume to obtain a third solution;
the first volume of the oil phase is larger than the second volume of the first solution, the oil phase and the second solution are mixed by an ultrasonic processor at the output power of 130 watts, and the third solution is obtained under the action of the emulsifier of the first solution. The third solution may be understood as a non-acidified water-in-oil emulsion.
S108, dropwise adding an acid solution into the third solution to obtain water-in-oil emulsion with preset pH value;
and (3) dropwise adding an acid solution into the third solution to obtain water-in-oil emulsion with preset pH value, thereby ensuring the acidic environment of electrolysis and ensuring the smooth implementation of the electrodeposition process.
S110, mechanically polishing the working electrode;
and carrying out mechanical polishing treatment on the working electrode to obtain a flat working electrode, thereby ensuring that a uniform, compact and continuous cobalt-nickel-copper medium-entropy alloy coating is formed on the working electrode and ensuring the mechanical property of the alloy coating.
S112, performing electrodeposition treatment on the auxiliary electrode, the working electrode and the reference electrode in water-in-oil emulsion;
the auxiliary electrode, the working electrode and the reference electrode are subjected to electrodeposition treatment in water-in-oil emulsion, and a three-electrode system is used for electrodeposition, so that larger errors of electrode potential due to polarized current can be eliminated. In a three-electrode system, one side of a working electrode and one side of an auxiliary electrode are provided with polarization loops, and polarization currents pass through the polarization loops, so that the reference electrode can be measured and controlled; and a measurement control loop is formed on one side of the working electrode and the reference electrode, so that the electric potential of the working electrode can be measured and controlled. The measurement control loop has no polarized current passing through, and the polarization state of the working electrode and the stability of the reference electrode are not affected, so that the potential of the working electrode can be measured and controlled simultaneously under the condition that the polarized current passes through the surface of the working electrode.
S114, applying a preset voltage to the water-in-oil emulsion;
the preset voltage is applied to the water-in-oil emulsion, so that the water-in-oil emulsion can be ensured to carry out electrodeposition under constant potential, and 1, 2-dichloroethane is not decomposed while the oxidation-reduction reaction in the water-in-oil emulsion is enhanced, thereby ensuring the smooth implementation of the electrodeposition process.
S116, adding a third volume of a fourth solution into the water-in-oil emulsion every a second preset period;
the transfer resistance of nickel ions in the electrodeposition process is higher, and the nickel ions are incompletely electrodeposited under the condition that the cobalt ions and the copper ions possibly reach the diffusion limit, so that a certain volume of nickel salt solution is increased, the nickel ions, the cobalt ions and the copper ions which are close to the same proportion can be obtained, and the entropy alloy plating layer in cobalt nickel copper with larger electrode potential distance is prepared.
S118, carrying out ultrasonic irradiation treatment on the water-in-oil emulsion at a first preset period interval, and forming a target alloy coating on the working electrode.
Based on the same inventive concept, the alloy coating of the invention is prepared by the preparation method of the alloy coating in any possible implementation manner.
The alloy coating is prepared by the preparation method of the alloy coating in any one of the possible implementation manners, and has all the beneficial technical effects of the preparation method of the alloy coating in any one of the possible implementation manners, which are not repeated herein.
In some embodiments, the alloy plating is a copper, nickel, cobalt alloy plating. The alloy coating is a uniform and continuous medium-entropy alloy film formed by co-deposition of three metals with larger electrode potential difference, namely copper, nickel and cobalt, and particles in the medium-entropy alloy film are uniformly distributed and have refined grains. The refined grains can enable the alloy coating to have higher hardness and better wear resistance, thereby improving the plastic deformation resistance of the alloy coating. Meanwhile, the corrosion resistance of the alloy coating is improved, so that the mechanical properties of the composite coating can be effectively improved by acoustic streaming, microjet, shock waves and the like, and the compact and uniformly distributed cobalt-nickel-copper entropy alloy coating is obtained.
In some embodiments, the molar ratio of copper element, nickel element and cobalt element in the alloy coating is 1 (0.9-1.1): 0.9-1.1.
Medium and high entropy alloys differ in the types and amounts of principal elements. In general, a medium-entropy alloy contains three metal elements in equal atomic ratios, and a high-entropy alloy contains five or more metal elements in equal atomic ratios. The distribution of elements in the solid solution is four kinds of elements including completely disordered, partially polymerized, partially ordered and completely ordered. Different from the traditional alloy with chemical disorder, the probability that different or same atoms meet each other in the medium-high entropy alloy is very large, interaction can be generated, namely adjacent atoms are preferentially selected to avoid or gather to form structural characteristics of chemical short-range order, so that strain localization of the material is inhibited, the work hardening capacity of the material is improved, and better shaping is kept while the strength is improved.
Furthermore, the high-entropy alloy of the information multi-principal component material composed of a plurality of elements in equimolar ratio or near equimolar ratio can be prepared according to the process requirement. The high-entropy alloy comprises transition element high-entropy alloy, refractory high-entropy alloy, eutectic high-entropy alloy, high-entropy amorphous alloy, high-entropy high-temperature alloy, high-entropy ceramic, high-entropy intermetallic compound and the like. The high-entropy alloy is also called multi-principal element alloy, and has excellent comprehensive properties, such as ultrahigh strength, ultrahigh fracture toughness, high wear resistance and corrosion resistance, lower modulus, high-temperature hardness, no obvious ductile-brittle transition temperature and the like.
The high entropy alloy is an alloy formed from five or more equal or about equal amounts of metals. The major metal components in the prior alloy may be only one to two. For example, iron-based alloys are obtained by adding trace elements to improve their properties. In the conventional concept, the more the metal species added to the alloy, the embrittlement of the material is caused, but the high-entropy alloy is different from the conventional metal, and various metals are not catalyzed, so that the alloy is a new material. The mixed entropy of the high-entropy alloy is higher than that of a common alloy, and a high-entropy solid solution phase alloy is generally formed, wherein a solid solution phase region is often present in the middle position in a five-element alloy phase diagram, and the solid solution is a solid solution with stable mixed entropy.
Based on the same inventive concept, referring to fig. 2, the battery 200 of the present invention includes: a cathode 202; an anode 204; and the alloy plating layer 206 of any of the above embodiments, the alloy plating layer 206 being located between the cathode 202 and the anode 204.
The battery of the present invention includes a cathode 202, an anode 204, and an alloy coating 206 according to any of the foregoing embodiments, wherein the electrolytic solution at the cathode 202 undergoes a reduction reaction, and the electrolytic solution at the anode 204 undergoes an oxidation reaction, while the alloy coating 206 is disposed therebetween, so that the battery has all the advantages of the alloy coating 206 according to any of the foregoing possible embodiments, which are not described herein.
It can be appreciated that the working distance between the cathode 202 and the anode 204 is less than or equal to 1 cm, and the working distance between the cathode 202 and the anode 204 can be reasonably adjusted according to actual needs, so that enough installation space is reserved between the anode 204 and the cathode 202 for the compact, continuous and uniform cobalt-nickel-copper intermediate entropy alloy coating 206 in the electrodeposition process, the nano-particle-level intermediate entropy alloy is used as a multifunctional catalyst, and substances with multiple reaction functions are catalyzed at the same time, and multi-step different types of catalytic reactions are completed in one reaction process, so that the chemical reaction efficiency in the battery is improved.
The cell 200 of the present application may be, for example, a fuel cell, which is a chemical device that directly converts chemical energy possessed by fuel into electrical energy, also called an electrochemical generator. Fuel cells are the fourth power generation technology following hydroelectric power generation, thermal power generation, and nuclear power generation. The fuel cell converts the Gibbs free energy in the chemical energy of the fuel into electric energy through electrochemical reaction, and is not limited by the Carnot cycle effect, so the efficiency is higher, the fuel cell uses fuel and oxygen as raw materials, no mechanical transmission part exists, the discharged harmful gas is very little, and the service life is long. A membrane electrode of a fuel cell, i.e. a membrane electrode assembly, also known as a membrane electrode, is understood to be an electrode structurally equipped with a membrane assembly, which is a key core component for power generation of a fuel cell.
Based on the same inventive concept, referring to fig. 3, the battery assembly 300 of the present invention includes: a housing 302; and the battery 200 of any of the above embodiments, the battery 200 is located within the housing 302.
The battery assembly 300 of the present invention includes a housing 302 and the battery 200 of any of the foregoing embodiments, where the housing 302 can provide an installation space for the battery 200 and assist in protecting the battery, and the battery 200 is located in the housing 302, so that all the advantages of any of the foregoing possible implementations are not repeated herein.
It is to be understood that the present application is not limited to the particular shape of the housing 302, and the housing 302 may support the shape of a plate or tube as desired without departing from the inventive concepts.
While this specification contains many specific implementation details, these should not be construed as limitations on the scope of any invention or of what may be claimed, but rather as descriptions of features specific to particular implementations of particular inventions. Certain features that are described in this specification in the context of separate embodiments can also be implemented in combination in a single embodiment. On the other hand, the various features described in the individual embodiments may also be implemented separately in the various embodiments or in any suitable subcombination. Furthermore, although features may be acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a subcombination or variation of a subcombination.
Thus, particular embodiments of the subject matter have been described. Other embodiments are within the scope of the following claims. In some cases, the actions recited in the claims can be performed in a different order and still achieve desirable results. Furthermore, the processes depicted in the accompanying drawings are not necessarily required to be in the particular order shown, or sequential order, to achieve desirable results. In some implementations, multitasking and parallel processing may be advantageous.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises an element.
The present invention will be described in detail by way of embodiments.
Example 1
Step 1) preparing a mixed solution, wherein the components comprise: 0.1M (C 4 H 9 ) 4 NClO 4 、10mMCoCl 2 ·6H 2 O、20 mM NiCl 2 ·6H 2 O and 10 mM CuCl 2 ·2H 2 Aqueous solution of O. Then adding Sodium Dodecyl Sulfate (SDS) and H 3 BO 3 The concentrations were set to 100mM and 400mM, respectively. The concentration of SDS was chosen to be well above its critical micelle constant (8.5 mM). H 3 BO 3 As a buffer to inhibit an increase in pH during electrolysis, at a concentration similar to that of a conventional electrodeposition system.
Step 2) 10ml of the CE solution and 60. Mu.L of the aqueous solution in step 1) were mixed using a high intensity ultrasonic processor at an output of 130W. The aqueous solution was pH adjusted to 1 using hydrochloric acid. The size of the water droplets was measured using dynamic light scattering.
And 3) performing deposition by using a three-electrode system, wherein a mechanically polished molybdenum (Mo) sheet is used as a working electrode and horizontally placed at the bottom of the battery to facilitate the deposition of a medium entropy alloy film, a platinum rod is used as a counter electrode, and Ag|AgCl is used as a reference electrode in 1.0M NaCl. The emulsion had a volume of about 10mL and an area of the disk electrode of 0.785 cm 2 The diameter is 10 mm.
Step 4) potentiostatic electrodeposition was performed at-1.5V under periodic ultrasonic irradiation (once every 1. 1 s on/off) under which the emulsion remained in its emulsified state during electrodeposition.
Taking the throughput of 75 liters of solution as an example, the ultrasonic power is 60 watts.
Step 5) during electrodeposition under periodic ultrasonic irradiation, 10 μl of the aqueous solution of step (1) was added every 40 minutes to avoid consumption of metal ions and to ensure that the concentration of metal ions remained constant at 0.24 mmol/liter.
After electrodeposition for 3 hours, a continuous film was obtained on the working electrode, the film thickness being about 350nm.
Example 2
Step 1) to step 3): as in example 1.
Step 4) potentiostatic electrodeposition was performed under periodic ultrasonic irradiation (on/off every 5 s) at-1.5. 1.5V, under which the emulsion maintained its emulsified state during electrodeposition.
Step 5) during electrodeposition under ultrasonic irradiation, 10 μl of the aqueous solution of step (1) was added every 40 minutes to avoid consumption of metal ions and to ensure that the concentration of metal ions remained constant at 0.24 mmol/liter.
After electrodeposition for 3 hours, a suspension is formed or a small amount of nanoparticles are deposited on the surface of the working electrode, a thin film is not formed, or a discontinuous thin film is obtained.
Comparative example 1
Step 1) preparing a mixed solution, wherein the components comprise: 0.1M (C 4 H 9 ) 4 NClO 4 10mM CoCl 2 ·6H 2 NiCl of O, 20 mM 2 ·6H 2 CuCl of O and 10mM 2 ·2H 2 Aqueous solution of O. Then adding Sodium Dodecyl Sulfate (SDS) and H 3 BO 3 The concentrations were set to 100mM and 400mM, respectively. The concentration of SDS was chosen to be well above its critical micelle constant (8.5 mM). H 3 BO 3 As a buffer to inhibit an increase in pH during electrolysis, at a concentration similar to that of a conventional electrodeposition system.
Step 2) 10ml of the CE solution and 60. Mu.L of the aqueous solution in step 1) were mixed using a high intensity ultrasonic processor at an output of 130W. The aqueous solution was pH adjusted to 1 using hydrochloric acid. The size of the water droplets was measured using dynamic light scattering.
And 3) performing deposition by using a three-electrode system, wherein a mechanically polished molybdenum (Mo) sheet is used as a working electrode and horizontally placed at the bottom of the battery to facilitate the deposition of a medium entropy alloy film, a platinum rod is used as a counter electrode, and Ag|AgCl is used as a reference electrode in 1.0M NaCl. The emulsion had a volume of about 10mL and an area of the disk electrode of 0.785 cm 2 The diameter is 10 mm.
Step 4) potentiostatic electrodeposition was performed under-1.5. 1.5V without ultrasonic irradiation.
Step 5) during electrodeposition under periodic ultrasonic irradiation, 10 μl of the aqueous solution of step (1) was added every 40 minutes to avoid consumption of metal ions and to ensure that the concentration of metal ions remained constant at 0.24 mmol/liter.
Only a small amount of nanoparticles was deposited and no continuous film was obtained.
And (3) carrying out scanning projection electron microscope (Scanning Transmission Electron Microscopy, STEM) -energy spectrometer (Energy Dispersive Spectroscopy, EDS) ray analysis on the obtained continuous film, determining the atomic ratio of copper element, nickel element and cobalt element in the continuous film through the intensity and wavelength distribution of X-rays, ensuring the detection speed, reducing the damage to a sample and reducing the detection cost. The analysis proves that the atomic ratio of copper element, nickel element and cobalt element in the continuous film is close to 1:1:1. STEM-EDS ray analysis can detect relevant mechanical performance indexes such as compactness of the medium-entropy alloy film. Compared with the discontinuous films in comparative example 1 and example 2, the medium entropy alloy film is deposited uniformly, and has better mechanical performance indexes such as hardness, wear resistance, compactness and the like. The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (18)
1. The preparation method of the alloy coating is characterized by comprising the following steps of:
preparing a first solution comprising an organic solute, a cobalt salt, a nickel salt, and a copper salt;
adding an emulsifying agent and a buffer into the first solution to obtain a second solution;
adding the second solution into an oil phase to obtain a water-in-oil emulsion;
performing electrodeposition treatment on an auxiliary electrode, a working electrode and a reference electrode in the water-in-oil emulsion to form a target alloy coating on the working electrode;
and in the process of carrying out electrodeposition treatment on the auxiliary electrode, the working electrode and the reference electrode in the water-in-oil emulsion, carrying out ultrasonic irradiation treatment on the water-in-oil emulsion.
2. The method for producing an alloy plating layer according to claim 1, wherein,
the ultrasonic irradiation treatment is a periodic ultrasonic irradiation treatment in which the period interval is 1 second to 5 seconds.
3. The method according to claim 1, wherein the molar content of the nickel salt in the first solution is 2 times or more the molar content of the cobalt salt and 2 times or more the molar content of the copper salt as calculated from nickel element, cobalt element and copper element.
4. The method for producing an alloy plating layer according to claim 1, wherein,
the concentration of the organic solute in the first solution is from 0.05 moles per liter to 0.5 moles per liter;
the concentration of the cobalt salt in the first solution is from 5 millimoles per liter to 15 millimoles per liter;
the concentration of the nickel salt in the first solution is from 10 millimoles per liter to 30 millimoles per liter;
the concentration of the copper salt in the first solution is from 5 millimoles per liter to 15 millimoles per liter.
5. The method for producing an alloy plating layer according to claim 1, wherein,
the organic solute is one or more selected from tetrabutylammonium perchlorate, tetramethyl ammonium perchlorate, tetraethylammonium perchlorate and tetrapropyl ammonium perchlorate; and/or
The cobalt salt is selected from one or more of cobalt chloride, cobalt nitrate, cobalt sulfate and cobalt acetate; and/or
The nickel salt is selected from one or more of nickel chloride, nickel nitrate, nickel sulfate and nickel acetate; and/or
The copper salt is selected from one or more of copper chloride, copper nitrate, copper sulfate and copper acetate; and/or
The emulsifier is one or more of sodium dodecyl sulfate and sodium bis (2-ethylhexyl) sulfosuccinate; and/or
The buffering agent is boric acid; and/or
The oil phase is 1, 2-dichloroethane.
6. The method for producing an alloy plating layer according to claim 1, wherein,
the concentration of the emulsifier in the second solution is 50 millimoles per liter to 150 millimoles per liter;
the concentration of the buffer in the second solution is 300 millimoles per liter to 500 millimoles per liter.
7. The method for producing an alloy plating layer according to claim 1, wherein the volume ratio of the oil phase to the second solution is 1 (0.002-0.009); and/or
The pH value of the water-in-oil emulsion is less than or equal to 1.
8. The method for producing an alloy plating layer according to claim 1, wherein,
the reference electrode is a silver-silver chloride electrode;
the auxiliary electrode is a platinum electrode.
9. The method for producing an alloy plating layer according to claim 1, wherein before said subjecting the auxiliary electrode, the working electrode and the reference electrode to electrodeposition treatment in said water-in-oil emulsion to form a target alloy plating layer on said working electrode, further comprising:
and carrying out mechanical polishing treatment on the working electrode.
10. The method for producing an alloy plating layer according to claim 9, wherein,
The working electrode is one of a molybdenum electrode, a nickel electrode, a gold electrode or a silicon electrode.
11. The method for producing an alloy plating layer according to claim 10, wherein,
the working electrode is a disc electrode;
the diameter of the disc electrode is more than or equal to 5 mm and less than or equal to 20 mm.
12. The method for producing an alloy plating layer according to claim 1, wherein,
the voltage of the electrodeposition treatment is more than or equal to minus 1.6 volts and less than or equal to minus 1.4 volts.
13. The method for producing an alloy plating layer according to claim 1, wherein,
in the electrodeposition treatment, the total concentration of cobalt ions, nickel ions and copper ions in the water-in-oil emulsion is maintained at 0.2 millimoles per liter to 0.3 millimoles per liter.
14. An alloy coating is characterized in that,
the alloy plating layer is produced by the production method of an alloy plating layer according to any one of claims 1 to 13.
15. The alloy plating layer according to claim 14, wherein,
the alloy plating layer is copper, nickel and cobalt alloy plating layer.
16. The alloy coating according to claim 15, wherein the molar ratio of copper element, nickel element and cobalt element in the alloy coating is 1 (0.9-1.1): 0.9-1.1.
17. A battery, the battery comprising:
a cathode;
an anode;
and the alloy plating of any of claims 14-16, the alloy plating being located between the cathode and the anode.
18. A battery assembly, the battery assembly comprising:
a housing;
and the battery of claim 17, the battery being located within the housing.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU560010A1 (en) * | 1975-09-18 | 1977-05-30 | Ордена Трудового Красного Знамени Институт Сверхтвердых Материалов Ан Украинской Сср | Electrolyte for deposition of nickel-cobalt alloys |
| GB1583216A (en) * | 1976-10-04 | 1981-01-21 | M & T Chemicals Inc | Electrodeposition of nickel cobalt and alloys thereof |
| CN115702512A (en) * | 2020-04-17 | 2023-02-14 | 城市电力公司 | Performance improvement of zinc-manganese dioxide cells by interlayers |
-
2023
- 2023-06-01 CN CN202310637712.3A patent/CN116356389A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU560010A1 (en) * | 1975-09-18 | 1977-05-30 | Ордена Трудового Красного Знамени Институт Сверхтвердых Материалов Ан Украинской Сср | Electrolyte for deposition of nickel-cobalt alloys |
| GB1583216A (en) * | 1976-10-04 | 1981-01-21 | M & T Chemicals Inc | Electrodeposition of nickel cobalt and alloys thereof |
| CN115702512A (en) * | 2020-04-17 | 2023-02-14 | 城市电力公司 | Performance improvement of zinc-manganese dioxide cells by interlayers |
Non-Patent Citations (1)
| Title |
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| YUKI MURAKAMI等: ""Electrodeposition of a CoNiCu medium-entropy alloy in a water-in-oil emulsion"", ELECTROCHEMISTRY COMMUNICATIONS, vol. 128, pages 1 - 6 * |
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