CN112853392A - Alkaline electrolyzed water anode and preparation method thereof - Google Patents
Alkaline electrolyzed water anode and preparation method thereof Download PDFInfo
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- CN112853392A CN112853392A CN202110031426.3A CN202110031426A CN112853392A CN 112853392 A CN112853392 A CN 112853392A CN 202110031426 A CN202110031426 A CN 202110031426A CN 112853392 A CN112853392 A CN 112853392A
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- alloy
- nickel
- anode
- electrolyzed water
- cobalt
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 73
- 239000000956 alloy Substances 0.000 claims abstract description 73
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 39
- 239000001301 oxygen Substances 0.000 claims abstract description 39
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 22
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 20
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 20
- 239000002052 molecular layer Substances 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 238000004070 electrodeposition Methods 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 72
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 36
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 claims description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- IQYVXTLKMOTJKI-UHFFFAOYSA-L cobalt(ii) chlorate Chemical compound [Co+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O IQYVXTLKMOTJKI-UHFFFAOYSA-L 0.000 claims description 3
- HCFPRFJJTHMING-UHFFFAOYSA-N ethane-1,2-diamine;hydron;chloride Chemical compound [Cl-].NCC[NH3+] HCFPRFJJTHMING-UHFFFAOYSA-N 0.000 claims description 3
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- JRSGPUNYCADJCW-UHFFFAOYSA-K iron(3+);trichlorate Chemical compound [Fe+3].[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O JRSGPUNYCADJCW-UHFFFAOYSA-K 0.000 claims description 3
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- RZLUIDROFNIMHF-UHFFFAOYSA-L nickel(2+);dichlorate Chemical compound [Ni+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O RZLUIDROFNIMHF-UHFFFAOYSA-L 0.000 claims description 3
- ZLQBNKOPBDZKDP-UHFFFAOYSA-L nickel(2+);diperchlorate Chemical compound [Ni+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZLQBNKOPBDZKDP-UHFFFAOYSA-L 0.000 claims description 3
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 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 3
- NSRBDSZKIKAZHT-UHFFFAOYSA-N tellurium zinc Chemical compound [Zn].[Te] NSRBDSZKIKAZHT-UHFFFAOYSA-N 0.000 claims description 3
- 239000010413 mother solution Substances 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 6
- 238000001994 activation Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910003271 Ni-Fe Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- -1 hydroxyl ions Chemical class 0.000 description 2
- QJSRJXPVIMXHBW-UHFFFAOYSA-J iron(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Ni+2] QJSRJXPVIMXHBW-UHFFFAOYSA-J 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012048 reactive intermediate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- UEVWQBCYZNGCAI-UHFFFAOYSA-N O(O)O.[Fe].[Ni] Chemical compound O(O)O.[Fe].[Ni] UEVWQBCYZNGCAI-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- DMTIXTXDJGWVCO-UHFFFAOYSA-N iron(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Fe++].[Ni++] DMTIXTXDJGWVCO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses an alkaline electrolyzed water anode and a preparation method thereof, wherein a pretreated conductive matrix grows an alloy pointed cone array on the surface of the conductive matrix by cathode electrochemical deposition to obtain the alkaline electrolyzed water anode, which comprises the conductive matrix and the alloy pointed cone array loaded on the surface of the conductive matrix; when the anode of the alkaline electrolytic water is applied to the electrolytic water in the alkaline electrolyte, oxygen evolution reaction occurs, the part of the surface of each alloy pointed cone, which is contacted with the alkaline electrolyte, is firstly oxidized to form metal oxide and/or metal hydroxide and/or LDH, and then metal oxyhydroxide is generated and is stabilized in the state to be used as an active center of the oxygen evolution reaction; the metal oxyhydroxide becomes a metal oxide and/or a metal hydroxide and/or LDH upon stopping the operation and is stabilized in this state in the form of a nanolayer. The invention has ultrahigh oxygen evolution activity and can stably work for a long time under heavy current.
Description
Technical Field
The invention belongs to an electrode material technology and an electrochemical technology, and particularly relates to an alkaline electrolyzed water anode and a preparation method thereof.
Background
The alkaline water electrolysis technology is the most mature technology for producing hydrogen by electrolyzing water at present, and occupies the main market share of hydrogen production by electrolyzing water because the alkaline water electrolysis technology works in an alkaline environment and does not need to use noble metal as an electrode material, but the efficiency of electrolyzing water is lower (about 70 percent), and needs to be further improved to reduce the cost. Of the two half reactions of the electrolysis of water, the oxygen evolution reaction occurring at the anode requires higher energy to overcome the kinetic barrier and is the bottleneck of the electrolysis of water. Therefore, it is required to further improve the oxygen evolution electrocatalytic performance of the anode material and to reduce the overpotential of the oxygen evolution reaction to improve the efficiency of water electrolysis.
The typical route for electrocatalytic reactions mainly comprises three steps: charge transfer and surface conversion (e.g., chemisorption of reactants and desorption of products from the electrode surface), charge conduction, and mass transfer processes. Much research has been devoted to the charge transfer and surface conversion steps to achieve highly active electrolytic water anode materials by increasing the density of oxygen evolution reactive sites and optimizing the binding energy of the catalyst to the reactive intermediates, one possible way to optimize the binding energy of the catalyst to the reactive intermediates is to manipulate the composition of the catalyst, such as alloying and doping atoms of different valence states, and another way to introduce defects, such as oxygen vacancies, atomic distortion, phase boundaries, strain, twins, grain boundaries and stacking fault defects, etc. In terms of charge conduction, a binderless catalyst, a metal (alloy) core catalyst, and a highly conductive support can be used to reduce the electrical resistance. Improving the mass transfer process can generally accelerate bubble dissipation by increasing the surface wettability of the catalyst to assist the adsorption of polar reactants on the interface, or by surface roughening and functionalization to form a gas-phobic surface. However, most of the current researches on the alkaline water electrolysis anode optimize one step or two steps, and the three steps are rarely optimized simultaneously. And in the mass transfer step, the current alkaline electricityThe design of the water splitting anode does not consider the influence of the transmission process of reactants from the solution body to the surface of the electrode on the reaction activity. It is well known that mass transfer is often a bottleneck in the overall electrochemical reaction kinetics, particularly at high current densities (200-2). Therefore, the design and preparation of the alkaline electrolyzed water anode which is optimized in the processes are very important for improving the efficiency of electrolyzed water.
Disclosure of Invention
In order to make up the defects of the prior art, the invention provides an alkaline electrolyzed water anode and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
growing an alloy pointed cone array on the surface of the conductive aggregate by a cathode electrochemical deposition method on the pretreated conductive matrix to obtain the alkaline electrolyzed water anode, wherein the alkaline electrolyzed water anode comprises the conductive matrix and the alloy pointed cone array loaded on the surface of the conductive matrix; wherein, the alloy in the alloy pointed cone array is two or three of three metals of nickel, cobalt and iron; when the alkaline electrolyzed water anode is applied to electrolyzed water in alkaline electrolyte, oxygen evolution reaction is carried out, the part of the surface of each alloy pointed cone in the alloy pointed cone array, which is contacted with the alkaline electrolyte, is firstly oxidized to form metal oxide and/or metal hydroxide and/or layered double metal hydroxide (LDH), then metal oxyhydroxide is generated and is stabilized in a metal oxyhydroxide state, and the metal oxyhydroxide is an active center of the oxygen evolution reaction; the metal oxyhydroxide becomes the metal oxide and/or the metal hydroxide and/or the LDH upon stopping the operation and is stabilized in this state in the form of a nanolayer.
Further, the step includes the sub-steps of: s1, fully mixing and ultrasonically treating a mixed solution of two or three of nickel salt, cobalt salt and iron salt and an auxiliary agent to obtain a mixture mother liquor, wherein the concentration of all metal salts in the mixed solution is 0.6-1.2 mol/L; wherein the auxiliary agent is H3BO3Solution and NH4Cl solution, all metal salts, H in the mixed solution3BO3And NH4The mol ratio of Cl is 1:0.2-1.2: 0.5-5.0; or the auxiliary agent is H3BO3Solution and ethylenediamine hydrochloride solution, all metal salts and H in the mixed solution3BO3The molar ratio of the hydrochloric acid to the ethylenediamine is 1:0.2-1.2: 0.5-5.0; s2, taking an inert conductor as a first working anode, taking the conductive substrate as a first working cathode, inserting the conductive substrate into the mixture mother liquor with preset temperature and pH value, wherein the distance between the first working anode and the first working cathode is 0.1-20cm, and the current density between the first working anode and the first working cathode is 0.1-20A/dm2Performing electrochemical deposition; preferably, the predetermined temperature is 40-80 ℃, and the pH value is 3-5; preferably, the inert conductor is a platinum sheet; and S3, taking out the conductive substrate deposited in the step S2, washing with deionized water, and drying to obtain the alkaline electrolyzed water anode.
Further, the alloy in the alloy pointed cone array has a composition of one of the following: nixCo100-xX is between 65 and 95; nixFe100-xX is between 65 and 95; coxFe100-xX is between 65 and 95; ni100-x-yCoxFeyX is between 5 and 25 and y is between 5 and 25.
Further, the composition of the alloy is Ni83Fe17、Ni82Fe18、Ni88Co12、Co80Fe20Or Ni80Co10Fe10。
Further, in the step S1, the nickel salt is at least one of nickel chloride, nickel nitrate, nickel sulfate, nickel oxalate, nickel chlorate, nickel perchlorate and nickel acetate; the ferric salt is at least one of ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, ferric oxalate, ferrous oxalate, ferric acetate, ferric chlorate, ferric perchlorate and ferrous acetate; the cobalt salt is at least one of cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt oxalate, cobalt chlorate, cobalt perchlorate and cobalt acetate.
Further, the pretreatment is chemical mechanical polishing for 2 to 60 minutes.
Further, the conductive substrate is one of a copper sheet, a titanium sheet, a stainless steel sheet, a nickel sheet, a cobalt sheet, an iron sheet, a graphite sheet, carbon nanotube paper, graphene paper, an ITO film, copper foam, nickel foam, titanium foam, a copper mesh, a stainless steel mesh, a titanium mesh and a nickel mesh.
The alkaline electrolyzed water anode prepared by the method comprises a conductive substrate and an alloy pointed cone array loaded on the surface of the conductive substrate, wherein the alloy pointed cones in the alloy pointed cone array are consistent in orientation, and the height-to-width ratio of the pointed cones is 2-8: 1.
Further, the surface of each alloy sharp cone of the alloy array is further coated with a nano layer, and the nano layer is the metal oxide and/or the metal hydroxide and/or the LDH.
Further, the thickness of the conductive substrate is 1-3000 μm.
Further, the thickness of the nano layer is 1-50 nm; preferably 2-5 nm.
The beneficial effects of the invention include: the invention prepares an alloy pointed cone array with specific composition on a conductive substrate by a cathodic electrochemical deposition method, the alloy pointed end has a high curvature structure, when the alloy pointed cone array is applied to water electrolysis in alkaline electrolyte, the part of the surface of each alloy pointed cone in the alloy pointed cone array, which is contacted with the alkaline electrolyte, is finally oxidized to form a metal oxyhydroxide layer, the densely arranged nano pointed cone array provides rich active sites for oxygen evolution reaction, the nickel, iron and cobalt alloy has better adsorption energy of oxygen evolution reaction intermediates, the alloy grown in situ on the conductive substrate has good conductivity, the hydrophilic and gas-phobic shapes of the pointed cone array are favorable for bubble release, and the electric field concentration effect of the pointed structure accelerates the aggregation of hydroxyl ions (reactants of the oxygen evolution reaction) from a solution body to the surface of an electrode, thereby improving the reaction rate, and the metal oxyhydroxide layer not only has ultrahigh electrocatalytic activity under small current, has excellent electrocatalytic activity under high current density. And because the alloy sharp cone components are uniformly distributed, even if metal ions are lost, the alloy sharp cone components can be timely supplementedAnd the pointed cone structure has good mechanical stability, thereby having chemical stability and mechanical stability at the same time, and being capable of working at a large current (200-2) The next long-term operation. Therefore, the pointed cone array of the alkaline electrolyzed water anode not only has ultrahigh oxygen evolution electrocatalytic activity, but also can stably work for a long time under large current, effectively improves the efficiency of electrolyzed water reaction, and can be applied to the field of oxygen evolution of industrial electrolyzed water.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of an alkaline electrolyzed water anode prepared in example 1 of the present invention.
Fig. 2 is a partially enlarged view of fig. 1.
FIG. 3 is a Cyclic Voltammetry (CV) curve of an alkaline electrolyzed water anode prepared in example 1 of the present invention.
Fig. 4a and 4b are a Transmission Electron Microscopy (TEM) topographic map and an X-ray energy spectrum analysis (EDS) map of the alkaline electrolyzed water anode prepared in example 1 of the present invention, respectively.
FIG. 5 is a graph showing the Linear Sweep Voltammetry (LSV) curves of the alkaline electrolyzed water anode prepared in example 1 of the present invention and a control sample.
FIG. 6 is a graph of stability test current versus time for alkaline electrolyzed water anodes prepared in accordance with example 1 of the present invention.
FIG. 7 is a Scanning Electron Microscope (SEM) image of an alkaline electrolyzed water anode prepared in example 1 of the present invention after 120 hours of operation.
FIG. 8 is a comparison of the X-ray diffraction (XRD) patterns of the alkaline electrolyzed water anode of the present invention prepared in example 2 and a comparative example, in which: curve a is the XRD pattern of the pure nickel sharp cone of the comparative example, and curve b is the XRD pattern of the alkaline electrolyzed water anode prepared in example 2.
FIG. 9 is a Scanning Electron Microscope (SEM) image of an alkaline electrolyzed water anode prepared in example 3 of the present invention.
FIG. 10 is a Scanning Electron Microscope (SEM) image of an alkaline electrolyzed water anode prepared in example 5 of the present invention.
Detailed Description
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
In one embodiment, a method of making an alkaline electrolyzed water anode comprises the steps of: growing an alloy pointed cone array on the surface of the conductive aggregate by a cathode electrochemical deposition method on the pretreated conductive matrix to obtain the alkaline electrolyzed water anode, wherein the alkaline electrolyzed water anode comprises the conductive matrix and the alloy pointed cone array loaded on the surface of the conductive matrix; wherein, the alloy in the alloy pointed cone array is two or three of three metals of nickel, cobalt and iron; when the alkaline electrolyzed water anode is applied to electrolyzed water in alkaline electrolyte, oxygen evolution reaction is carried out, the part of the surface of each alloy pointed cone in the alloy pointed cone array, which is contacted with the alkaline electrolyte, is firstly oxidized to form metal oxide and/or metal hydroxide and/or layered double metal hydroxide (LDH), then metal oxyhydroxide is generated and is stabilized in a metal oxyhydroxide state, and the metal oxyhydroxide is an active center of the oxygen evolution reaction; the metal oxyhydroxide becomes the metal oxide and/or the metal hydroxide and/or the LDH upon stopping the operation and is stabilized in this state in the form of a nanolayer.
In a further preferred embodiment, said step comprises the sub-steps of: s1, fully mixing and ultrasonically treating a mixed solution of two or three of nickel salt, cobalt salt and iron salt and an auxiliary agent to obtain a mixture mother liquor, wherein the concentration of all metal salts in the mixed solution is 0.6-1.2 mol/L; wherein the auxiliary agent is H3BO3Solution and NH4Cl solution, all metal salts, H in the mixed solution3BO3And NH4The mol ratio of Cl is 1:0.2-1.2: 0.5-5.0; or the auxiliary agent is H3BO3Solution and ethylenediamine hydrochloride solution, all metal salts and H in the mixed solution3BO3The molar ratio of the hydrochloric acid to the ethylenediamine is 1:0.2-1.2: 0.5-5.0; s2, inserting inert conductor (preferably platinum sheet) as first working anode and conductive matrix as first working cathode into the mixture mother liquor with preset temperature and pH valueThe distance between a working anode and a first working cathode is 0.1-20cm, and the current density between the first working anode and the first working cathode is 0.1-20A/dm2Performing electrochemical deposition; preferably, the predetermined temperature is 40-80 ℃, and the pH value is 3-5; and S3, taking out the conductive substrate deposited in the step S2, washing with deionized water, and drying to obtain the alkaline electrolyzed water anode.
In a further preferred embodiment, the alloy in the alloy tip cone array has a composition that is one of: nixCo100-xX is between 65 and 95; nixFe100-xX is between 65 and 95; coxFe100-xX is between 65 and 95; ni100-x- yCoxFeyX is between 5 and 25 and y is between 5 and 25.
Further, the composition of the alloy is Ni83Fe17、Ni82Fe12、Ni80Co20、Co80Fe20Or Ni80Co10Fe10。
In a further preferred embodiment, in the step S1, the nickel salt is at least one of nickel chloride, nickel nitrate, nickel sulfate, nickel oxalate, nickel chlorate, nickel perchlorate and nickel acetate; the ferric salt is at least one of ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, ferric oxalate, ferrous oxalate, ferric acetate, ferric chlorate, ferric perchlorate and ferrous acetate; the cobalt salt is at least one of cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt oxalate, cobalt chlorate, cobalt perchlorate and cobalt acetate.
In a further preferred embodiment, the pretreatment is chemical mechanical polishing for a period of 2 to 60 minutes.
In a further preferred embodiment, the conductive substrate is one of a copper sheet, a titanium sheet, a stainless steel sheet, a nickel sheet, a cobalt sheet, an iron sheet, a graphite sheet, a carbon nanotube paper, a graphene paper, an ITO film, a copper foam, a nickel foam, a titanium foam, a copper mesh, a stainless steel mesh, a titanium mesh, and a nickel mesh.
In another embodiment, the alkaline electrolyzed water anode prepared by the method comprises a conductive substrate and an alloy pointed cone array loaded on the surface of the conductive substrate, wherein the alloy pointed cones in the alloy pointed cone array are uniformly oriented, and the height-to-width ratio of the pointed cones is 2-8:1 (wherein, the width refers to the widest part of the pointed cones, namely the combination part of the pointed cones and the conductive substrate).
In a further preferred embodiment, the surface of each alloy pointed cone of the alloy array is further coated with a nano-layer, and the nano-layer is the metal oxide and/or the metal hydroxide and/or the LDH.
In a further preferred embodiment, the thickness of the conductive matrix is 1 to 3000 μm.
In a further preferred embodiment, the thickness of the nanolayer is from 1 to 50nm, preferably from 2 to 5 nm.
At this thickness, it is ensured that not only enough active species participate in the reaction, but also the charge can be smoothly and rapidly conducted to the active sites.
The alkaline electrolyzed water anode prepared in the embodiment of the invention can be directly applied to electrolyzed water in alkaline electrolyte under the condition that the alloy pointed cones are alloy, in the working process, the parts of the surfaces of the alloy pointed cones in the alloy pointed cone array, which are contacted with the alkaline electrolyte, are firstly oxidized to form metal oxides and/or metal hydroxides and/or Layered Double Hydroxides (LDH), then metal oxyhydroxides are continuously generated and are stabilized in the state of the metal oxyhydroxides, the metal oxyhydroxide layer (the thickness of the metal oxyhydroxide layer is preferably 1-50nm, more preferably 2-5nm) coats the internal alloy, and the metal oxyhydroxides are the active centers of oxygen evolution reaction; when the operation is stopped, the metal oxyhydroxide becomes a metal oxide and/or a metal hydroxide and/or LDH and is stabilized in this state in the form of a nano-layer.
In other deformation modes, after the alloy pointed cone array is grown and loaded on the surface of the conductive substrate, firstly, the alloy sharp cones are subjected to anodic potential oxidation, the surfaces of the alloy sharp cones are oxidized into metal oxides and/or metal hydroxides and/or LDH nano layers, forming a pointed cone array which takes the alloy as a core and the outer surface of which is coated with the nano layer on the surface of the conductive matrix, applying the pointed cone array to the electrolytic water in alkaline electrolyte, and in the working process, the metal hydroxide and/or the LDH nano-layer on the surface of each alloy pointed cone generates metal oxyhydroxide, and is stabilized in the state of metal oxyhydroxide, the metal oxyhydroxide layer (the thickness of the metal oxyhydroxide layer is preferably 1-50nm, more preferably 2-5nm) covers the internal alloy, and the metal oxyhydroxide is the active center of oxygen evolution reaction; when the operation is stopped, the metal oxyhydroxide becomes a metal oxide and/or a metal hydroxide and/or LDH and is stabilized in this state in the form of a nano-layer. Wherein, the anodic potential oxidation can be specifically as follows: the conductive matrix loaded with the alloy pointed cone array is used as a working anode, and is inserted into oxygen-containing alkaline electrolyte with a working cathode to apply an anode potential for in-situ oxidation, wherein the anode potential is a potential above the standard hydrogen electrode potential by 0V, and the method for applying the anode potential comprises a cyclic voltammetry method, a constant current method, a constant potential method and the like, and aims to oxidize the surface of each alloy pointed cone of the alloy pointed cone array to form a nano layer of metal oxide and/or metal hydroxide and/or LDH wrapping the alloy pointed cone.
The present invention will be described in detail with reference to specific examples.
Example 1
(1) Selecting foamed nickel with the thickness of about 1500 mu m, cutting the foamed nickel into a rectangle with the thickness of 2cm multiplied by 3cm, carrying out chemical mechanical polishing treatment under the action of polishing solution, carrying out polishing for 5 minutes at room temperature, taking out, washing with deionized water for 2-3 times, and drying to obtain the conductive matrix.
(2) Using NiCl2·6H2O solution (NiCl)2·6H2O concentration of 0.84mol/L) and FeCl2Solution (FeCl)2Respectively, the concentration of (b) is 0.24mol/L) and H3BO3Solution and NH4Cl solution, preparing [ NiCl2·6H2O+FeCl2]、H3BO3And NH4Carrying out ultrasonic treatment on the mixed solution with the Cl molar ratio of 1:0.45:3.5 for 20-40 minutes, placing the mixed solution in a water bath kettle at the temperature of 40-80 ℃, and simultaneously adjusting the pH value to 3-5 to obtain the final productTo a mixture mother liquor.
(3) Inserting a platinum sheet serving as a first working anode and the conductive matrix serving as the first working cathode in the step (1) into the mixture mother liquor in the step (2), wherein the distance between the first working anode and the first working cathode is 0.5cm, and the current density is 0.3A/dm2The electrochemical deposition is carried out for 20 min.
(4) After the deposition is finished, the conductive matrix is taken out, washed by deionized water for 3 times and then dried in an oven at 50 ℃ for 1 hour to obtain a nickel-iron pointed cone array (Ni) with highly regular surface83Fe17) I.e. an alkaline electrolyzed water anode.
The shape of the nickel-iron pointed cone array is shown in fig. 1 and fig. 2, and it can be seen from the figure that the material has a pointed cone array structure, which is favorable for electron transfer of oxygen evolution reaction and removal of product oxygen, and the tip has an electric field concentration effect, which is favorable for accumulation of oxygen evolution reactant (i.e. hydroxyl ions).
The resulting alkaline electrolyzed water anode was subjected to the following electrochemical tests:
the electrochemical performance of the electrodes was tested at room temperature using the CHI 660E electrochemical workstation, the electrolytic cell was a standard three-electrode system, the alkaline electrolyzed water anode obtained in this example was clamped with a platinum electrode clamp as the working electrode, a graphite rod as the counter electrode, Hg/HgO as the reference electrode, and 1mol/L KOH as the electrolyte. For electrochemical characterization, the surface of the alloy tip cone is oxidized into a nano-layer before activation, and then the activation process is carried out, wherein the activation process is a cyclic voltammetry test at 50mV/s in a potential interval of 1.121-1.821V relative to the potential of a reversible hydrogen electrode (vs. RHE), and as shown in FIG. 3, the current density is mA 528/cm at a potential of 1.821V before activation (1 st cycle) without resistance compensation2After activation (20 th cycle) the current density was 553mA/cm2And the catalytic performance is improved after activation. FIGS. 4a and 4b are respectively a Transmission Electron Microscope (TEM) and an X-ray energy spectrum analysis (EDS) of the activated Ni-Fe tip cone array, which shows that the Ni-Fe tip cone is Ni-Fe alloy, and the surface of the Ni-Fe tip cone is irradiated after activationAnd (4) generating oxidation. The scanning rate of a Linear Scanning Voltammogram (LSV) was 5mV/s, the voltage was compensated by 93% iR, and the potential was scanned over a range of 1.121-1.821V, according to the formula: the overpotential was calculated to be the actual measured potential +0.059 × pH +0.095V-1.23V, and the alkaline electrolyzed water anode of this example was operated at 10mA/cm2The oxygen evolution overpotential at the current density of (a) is 190mV at 500mA/cm2The oxygen evolution overpotential at the current density of (1) is 255mV, as shown in FIG. 5. While a pure nickel tip cone was grown as a control on a foamed nickel substrate using the same method at 10mA/cm2And 500mA/cm2The oxygen evolution overpotential at the current density of (a) is 230 and 317mV, respectively; foamed nickel substrate as another control at 10mA/cm2The oxygen evolution overpotential at current density of 310mV, both controls performed far less than the nickel iron awl, as shown in fig. 5. As shown in FIG. 6, the alkaline electrolyzed water anode of the present example was operated continuously for 120 hours (including 200-500 mA/cm)2High current density) is almost kept unchanged, and the activity is proved to be almost not attenuated, so that the electrochemical stability is good. As shown in fig. 7, the alkaline electrolyzed water anode of the present embodiment can maintain a perfect sharp cone shape after 120 hours of operation, which proves its good mechanical stability.
The conductive matrix with the nickel-iron pointed cone array on the surface can be directly used as an alkaline electrolytic water anode to work, the metallic nickel-iron alloy on the surface can be oxidized under the oxygen evolution reaction potential, and nickel-iron oxide (NiO, FeOOH) and/or nickel-iron hydroxide (NiFe (OH) are generated in situ2]And/or layered nickel iron hydroxide (NiFe LDH) and then regenerated into nickel iron oxyhydroxide (nifeoh), and as the working time increases, more nifeoh is generated and the activity increases (as shown in fig. 3). After stopping working, NiFeOOH on the surface can be changed into ferronickel oxide and/or NiFe (OH)2And/or NiFe LDH, which is also responsible for the higher oxygen content in fig. 4 b.
Example 2
The difference from example 1 is that: replacing the foamed nickel with the thickness of about 1500 mu m in the step (1) with a titanium sheet with the thickness of about 10 mu m, and adopting NiCl in the step (2)2·6H2O solution (NiC)l2·6H2O concentration of 0.84mol/L) and FeCl2Solution (FeCl)2Respectively, the concentration of (b) is 0.39mol/L) and H3BO3Solution and NH4Cl solution, preparing [ NiCl2·6H2O+FeCl2]、H3BO3And NH4A mixed solution of Cl with a molar ratio of 1:0.4:3, and a current density of 0.2A/dm in the step (3)2The deposition time was 10 min.
The alkaline electrolyzed water anode prepared by the embodiment comprises a titanium sheet and nickel iron (Ni) loaded on the surface of the titanium sheet82Fe18) An array of pointed cones. In the same way, pure nickel pointed cone structure is grown on the surface of the titanium sheet, as a comparative example, the X-ray diffraction pattern of the alkaline electrolyzed water anode of the present embodiment is shown as the b curve in fig. 8, the peak position is shifted to the left relative to the peak position of the pure nickel pointed cone (e.g., the a curve in fig. 8), and the lattice distance is increased, which indicates that the nickel-iron alloy is a substituted nickel-based solid solution alloy containing iron.
The alkaline electrolyzed water anode obtained in the embodiment is tested at 10mA/cm2The oxygen evolution overpotential at the current density of (a) is 220mV at 500mA/cm2The oxygen evolution overpotential at the current density of (2) is 285mV, and the catalyst has excellent catalytic activity.
Example 3
The difference from example 1 is that: NiCl is adopted in the step (2)2·6H2O solution (NiCl)2·6H2O concentration of 0.84mol/L) and CoCl2·6H2O solution (CoCl)2·6H2O concentration of 0.1mol/L) and H3BO3Solution and NH4Cl solution, preparing [ NiCl2·6H2O+CoCl2·6H2O]、H3BO3And NH4A mixed solution of Cl in a molar ratio of 1:0.52: 4.
The alkaline electrolyzed water anode prepared in this example includes nickel foam and nickel cobalt (Ni) supported on the surface of the nickel foam88Co12) The appearance of the pointed cone array is shown in FIG. 9.
The alkaline electrolyzed water anode obtained in the embodiment is tested at 10mA/cm2The oxygen evolution overpotential at the current density of (1) is 202mV at 500mA/cm2Has an oxygen evolution overpotential of 268mV at a current density of 268mV, and has excellent catalytic activity.
Example 4
The difference from example 1 is that: CoCl is adopted in the step (2)2·6H2O solution (CoCl)2·6H2O concentration of 0.84mol/L) and FeCl2Solution (FeCl)2Respectively, the concentration of (b) is 0.24mol/L) and H3BO3Solution and NH4Cl solution, preparation of [ FeCl2+CoCl2·6H2O]、H3BO3And NH4A mixed solution of Cl in a molar ratio of 1:0.45: 3.5.
The alkaline electrolyzed water anode prepared in the embodiment comprises foamed nickel and cobalt iron (Co) loaded on the surface of the foamed nickel80Fe20) An array of alloy pyramids.
The electrode obtained in this example was tested at 10mA/cm2The oxygen evolution overpotential at the current density of (a) is 195mV at 500mA/cm2The overpotential for oxygen evolution at the current density of (2) is 265mV, and the catalyst has excellent catalytic activity.
Example 5
The difference from example 1 is that: using NiCl2·6H2O solution (NiCl)2·6H2Concentration of O0.84 mol/L), CoCl2·6H2O solution (CoCl)2·6H2O concentration of 0.12mol/L) and FeCl2Solution (FeCl)2Respectively in a concentration of 0.12mol/L) and H3BO3Solution and NH4Cl solution, preparation of [ FeCl2+CoCl2·6H2O+NiCl2·6H2O]、H3BO3And NH4A mixed solution of Cl in a molar ratio of 1:0.45: 3.5.
The alkaline electrolyzed water anode prepared in the embodiment comprises foamed nickel and nickel-cobalt-iron (Ni-Co-Fe) loaded on the surface of the foamed nickel80Co10Fe10) The scanning electron microscope image of the pointed cone array is shown in figure 10.
The electrode obtained in this example was tested at 10mA/cm2The oxygen evolution overpotential at the current density of (a) is 200mV at 500mA/cm2The oxygen evolution overpotential at the current density of (a) is 270 mV.
The present invention has been described in detail with reference to the specific embodiments, and the specific description should not be construed as limiting the invention to only the embodiments. Any modifications and equivalents of the invention in light of the above teachings and in light of the common general knowledge in the art are intended to be included within the scope of the appended claims.
Claims (10)
1. The preparation method of the alkaline electrolyzed water anode is characterized by comprising the following steps:
growing an alloy pointed cone array on the surface of the conductive aggregate by a cathode electrochemical deposition method on the pretreated conductive matrix to obtain the alkaline electrolyzed water anode, wherein the alkaline electrolyzed water anode comprises the conductive matrix and the alloy pointed cone array loaded on the surface of the conductive matrix; wherein, the alloy in the alloy pointed cone array is two or three of three metals of nickel, cobalt and iron; when the alkaline electrolyzed water anode is applied to electrolyzed water in alkaline electrolyte, oxygen evolution reaction is carried out, the part of the surface of each alloy pointed cone in the alloy pointed cone array, which is contacted with the alkaline electrolyte, is firstly oxidized to form metal oxide and/or metal hydroxide and/or layered double metal hydroxide (LDH), then metal oxyhydroxide is generated and is stabilized in a metal oxyhydroxide state, and the metal oxyhydroxide is an active center of the oxygen evolution reaction; the metal oxyhydroxide becomes the metal oxide and/or the metal hydroxide and/or the LDH upon stopping the operation and is stabilized in this state in the form of a nanolayer.
2. The method for preparing according to claim 1, wherein the step comprises the substeps of:
s1, fully mixing and ultrasonically treating a mixed solution of two or three of nickel salt, cobalt salt and iron salt and an auxiliary agent to obtain a mixture mother solution, wherein in the mixed solution, all metal salts areThe concentration is 0.6-1.2 mol/L; wherein the auxiliary agent is H3BO3Solution and NH4Cl solution, all metal salts, H in the mixed solution3BO3And NH4The mol ratio of Cl is 1:0.2-1.2: 0.5-5.0; or the auxiliary agent is H3BO3Solution and ethylenediamine hydrochloride solution, all metal salts and H in the mixed solution3BO3The molar ratio of the hydrochloric acid to the ethylenediamine is 1:0.2-1.2: 0.5-5.0;
s2, taking an inert conductor as a first working anode, taking the conductive substrate as a first working cathode, inserting the conductive substrate into the mixture mother liquor with preset temperature and pH value, wherein the distance between the first working anode and the first working cathode is 0.1-20cm, and the current density between the first working anode and the first working cathode is 0.1-20A/dm2Performing electrochemical deposition; preferably, the predetermined temperature is 40-80 ℃, and the pH value is 3-5; preferably, the inert conductor is a platinum sheet;
and S3, taking out the conductive substrate deposited in the step S2, washing with deionized water, and drying to obtain the alkaline electrolyzed water anode.
3. The method of claim 1 or 2, wherein the alloy in the alloy tip cone array has a composition that is one of: nixCo100-xX is between 65 and 95; nixFe100-xX is between 65 and 95; coxFe100-xX is between 65 and 95; ni100-x-yCoxFeyX is between 5 and 25 and y is between 5 and 25; preferably, the alloy has a composition of Ni83Fe17、Ni82Fe18、Ni88Co12、Co80Fe20Or Ni80Co10Fe10。
4. The method according to claim 2, wherein in step S1, the nickel salt is at least one of nickel chloride, nickel nitrate, nickel sulfate, nickel oxalate, nickel chlorate, nickel perchlorate, and nickel acetate; the ferric salt is at least one of ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, ferric oxalate, ferrous oxalate, ferric acetate, ferric chlorate, ferric perchlorate and ferrous acetate; the cobalt salt is at least one of cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt oxalate, cobalt chlorate, cobalt perchlorate and cobalt acetate.
5. The method of claim 1, wherein the pre-treatment is chemical mechanical polishing for a period of 2 to 60 minutes.
6. The method according to claim 1, wherein the conductive substrate is one of a copper sheet, a titanium sheet, a stainless steel sheet, a nickel sheet, a cobalt sheet, an iron sheet, a graphite sheet, carbon nanotube paper, graphene paper, an ITO film, copper foam, nickel foam, titanium foam, a copper mesh, a stainless steel mesh, a titanium mesh, and a nickel mesh.
7. An alkaline electrolyzed water anode prepared by the method of any one of claims 1-6, comprising a conductive substrate and an alloy pointed cone array loaded on the surface of the conductive substrate, wherein the alloy pointed cones in the alloy pointed cone array are consistent in orientation, and the height-to-width ratio of the pointed cones is 2-8: 1.
8. An alkaline electrolyzed water anode as claimed in claim 7 wherein the surface of each alloy pointed cone of the alloy array is further coated with a nanolayer of said metal oxide and/or said metal hydroxide and/or said LDH.
9. An alkaline electrolytic water anode according to claim 7 or 8, characterized in that the thickness of the conductive matrix is 1-3000 μm.
10. Alkaline aqueous electrolytic water anode according to claim 9, characterized in that the thickness of the nanolayer is 1-50nm, preferably 2-5 nm.
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