CN116288512A - Anode for alkaline water electrolysis hydrogen production and preparation method and application thereof - Google Patents
Anode for alkaline water electrolysis hydrogen production and preparation method and application thereof Download PDFInfo
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- CN116288512A CN116288512A CN202310204878.6A CN202310204878A CN116288512A CN 116288512 A CN116288512 A CN 116288512A CN 202310204878 A CN202310204878 A CN 202310204878A CN 116288512 A CN116288512 A CN 116288512A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000001257 hydrogen Substances 0.000 title claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 156
- 239000011248 coating agent Substances 0.000 claims abstract description 132
- 238000000576 coating method Methods 0.000 claims abstract description 132
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 230000003647 oxidation Effects 0.000 claims abstract description 55
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 55
- 239000000243 solution Substances 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000012266 salt solution Substances 0.000 claims abstract description 22
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- 150000001868 cobalt Chemical class 0.000 claims abstract description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 4
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 85
- 229910052759 nickel Inorganic materials 0.000 claims description 43
- 238000011068 loading method Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 13
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 12
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 11
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 11
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 7
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 abstract description 24
- 239000001301 oxygen Substances 0.000 abstract description 24
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 43
- 229910018068 Li 2 O Inorganic materials 0.000 description 43
- 238000005488 sandblasting Methods 0.000 description 38
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 239000002243 precursor Substances 0.000 description 22
- 238000005507 spraying Methods 0.000 description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 15
- 239000010941 cobalt Substances 0.000 description 15
- 229910052744 lithium Inorganic materials 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 229910017052 cobalt Inorganic materials 0.000 description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 11
- 239000010431 corundum Substances 0.000 description 11
- XATZQMXOIQGKKV-UHFFFAOYSA-N nickel;hydrochloride Chemical compound Cl.[Ni] XATZQMXOIQGKKV-UHFFFAOYSA-N 0.000 description 11
- 239000004576 sand Substances 0.000 description 11
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 nickel carboxylate Chemical class 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- XNZJTLSFOOXUAS-UHFFFAOYSA-N cobalt hydrochloride Chemical compound Cl.[Co] XNZJTLSFOOXUAS-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- 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
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- 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
Abstract
The invention relates to the technical field of preparation of electrolytic water anodes, in particular to an anode for hydrogen production by alkaline water electrolysis and a preparation method and application thereof. The preparation method of the anode comprises the following steps: 1) Mixing a nickel salt solution, a lithium salt solution, a cobalt salt solution and a noble metal salt solution to obtain a mixed coating solution; 2) And (3) carrying out first high-temperature thermal oxidation treatment on the metal electrode substrate at 300-500 ℃, then coating the mixed coating liquid on the surface of the metal electrode substrate, and carrying out second thermal oxidation after coating, so as to form a metal oxide catalyst coating on the surface of the electrode substrate, thereby obtaining the anode for hydrogen production by alkaline water electrolysis. The anode prepared by the preparation method has the advantages of greatly improving the binding force between the catalyst coating and the electrode substrate, along with effectively reducing the oxygen evolution potential, along with long service life of the electrode, high stability and the like.
Description
Technical Field
The invention relates to the technical field of preparation of electrolytic water anodes, in particular to an anode for hydrogen production by alkaline water electrolysis and a preparation method and application thereof.
Background
The water electrolysis process is easy to form industrialization due to high efficiency, is the most promising hydrogen production method, and has the characteristics of simple operation, high product purity, no pollution, economic raw material sources and the like. The electrolytic water is produced by decomposing water with a direct current through an acidic or alkaline aqueous solution, and precipitating hydrogen gas at the cathode, also called a hydrogen evolution electrode, and precipitating oxygen gas at the anode, also called an oxygen evolution electrode. The theoretical voltage required for water electrolysis is 1.23V, which is temperature dependent, but in practical applications the voltage required to decompose water is higher than this theoretical value, and the additional voltage required is overpotential. The alkaline water electrolysis hydrogen production technology is mature and has relatively low cost, so the alkaline water electrolysis hydrogen production technology is widely adopted at present.
In the alkaline water electrolysis hydrogen production technology, most of anodes do not adopt a catalytic layer, and nickel or nickel alloy base materials are directly used, so that the following problems exist: (1) The pure nickel or nickel alloy base material has high oxygen evolution potential and high energy consumption; (2) The binding force between the catalytic layer and the electrode substrate is not ideal, the catalytic material is easy to fall off at the initial stage of the electrolysis process or under high current density, the membrane is blocked, the current efficiency is reduced, and the service life of the electrode is limited.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of high oxygen evolution potential and poor binding force between the catalytic layer and the electrode substrate of the existing anode for producing hydrogen by electrolysis of water, so as to provide the anode for producing hydrogen by electrolysis of alkaline water, and the preparation method and application thereof.
The technical scheme of the invention is as follows:
the preparation method of the anode for producing hydrogen by alkaline water electrolysis comprises the following steps:
1) Mixing a nickel salt solution, a lithium salt solution, a cobalt salt solution and a noble metal salt solution to obtain a mixed coating solution;
2) And (3) carrying out first high-temperature thermal oxidation treatment on the metal electrode substrate at 300-500 ℃, then coating the mixed coating liquid on the surface of the metal electrode substrate, and carrying out second thermal oxidation treatment after coating so as to form a metal oxide catalyst coating on the surface of the metal electrode substrate, thereby obtaining the anode for hydrogen production by alkaline water electrolysis.
The temperature of the first high-temperature thermal oxidation treatment in the step 2) is 350-450 ℃; preferably, the temperature of the high-temperature thermal oxidation treatment is 400 ℃.
The time of the first high-temperature thermal oxidation treatment in the step 2) is 3-20min.
The noble metal in the noble metal salt solution is selected from any one or a combination of a plurality of Pt, ru, ir, pd, rh; preferably, the noble metal in the noble metal salt solution comprises any one or a combination of a plurality of Ru, pd and Rh.
The metal oxides in the metal oxide catalyst coating include nickel oxides, lithium oxides, cobalt oxides, and noble metal oxides.
The oxide of nickel is NiO 2 The oxide of lithium is Li 2 O, the oxide of cobalt is Co 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The noble metal oxide is IrO 2 、PtO 2 、RuO 2 、PdO 2 And RhO 2 Any one or more of the following.
The total loading of the nickel oxide, the lithium oxide and the cobalt oxide on the surface of the metal electrode substrate is 30-50g/m 2 The weight ratio of the nickel oxide to the lithium oxide to the cobalt oxide is (3-5): 4-6): 1-2; the loading capacity of the noble metal oxide on the surface of the metal electrode substrate is 1-3g/m 2 。
The thickness of the catalyst coating is 5-30 μm, depending on the coating loading.
The metal electrode substrate is made of nickel or nickel alloy; preferably, the metal electrode substrate is a woven or expanded mesh of nickel or nickel alloy.
The nickel salt solution is any one of nickel nitrate solution, nickel carboxylate solution and nickel hydrochloride solution; the lithium salt solution is any one of a nitrate solution of lithium, a carboxylate solution of lithium and a hydrochloride solution of lithium; the cobalt salt solution is any one of a cobalt nitrate solution, a cobalt carboxylate solution and a cobalt hydrochloride solution; the noble metal salt solution is a hydrochloride solution of noble metal. And adjusting the concentration of the salt solution in the mixed coating liquid and the spraying amount of the mixed coating liquid according to the loading amount of the metal oxide. When the content of nickel element in the mixed coating liquid is 80-125g/L, the content of lithium element is 75-110g/L, and the content of cobalt element30-55g/L, total content of noble metal element of 7-25g/L, total spraying amount of mixed coating liquid on the surface of metal electrode substrate of 70-155ml/m 2 When the total loading of the nickel oxide, the lithium oxide and the cobalt oxide in the formed metal oxide catalyst coating on the surface of the metal electrode substrate is 30-50g/m 2 The weight ratio of the nickel oxide to the lithium oxide to the cobalt oxide is (3-5): 4-6): 1-2; the loading capacity of the noble metal oxide on the surface of the metal electrode substrate is 1-3g/m 2 。
The temperature of the second thermal oxidation treatment in the step 2) is 400-600 ℃, and the heat preservation time is 100-2000 min.
The coating times in the step 2) are 10-40, the second thermal oxidation treatment is carried out after each coating, the temperature of the second thermal oxidation treatment is 400-600 ℃, and the heat preservation time of each time is 10-50min.
The first high temperature thermal oxidation process in step 2) is performed under an air atmosphere.
The second thermal oxidation treatment process in step 2) is performed under an air atmosphere.
The first high-temperature thermal oxidation treatment is preceded by a step of surface roughening the electrode substrate. Preferably, the step of roughening the electrode substrate comprises: sequentially carrying out sand blasting treatment and washing treatment on the electrode base material to obtain the electrode base material with rough surface; preferably, the sand blasting treatment is to perform sand blasting treatment on the surface of the electrode substrate by adopting a sand blasting medium, wherein the sand blasting medium is 100-mesh or 200-mesh corundum sand, the sand blasting times are 1-3 times, and the sand blasting surface comprises the front surface or the front surface and the back surface of the electrode substrate; the washing treatment is that acid washing treatment is carried out on the electrode base material after sand blasting by adopting acid solution or water washing treatment is carried out by adopting water, and the acid solution is any one or a mixture of a plurality of oxalic acid, sulfuric acid and hydrochloric acid; preferably, the acid solution is 2.0wt% to 4.0wt% sulfuric acid.
The method also comprises the step of alkali treatment of the metal oxide catalyst coating on the surface of the metal electrode substrate by alkali liquor.
The alkali liquor is an aqueous solution of sodium hydroxide, the concentration of the aqueous solution of sodium hydroxide is 20-30wt%, the treatment temperature is 20-40 ℃, and the treatment time is 10-20h.
The anode for alkaline water electrolysis hydrogen production is prepared by adopting the preparation method of the anode for alkaline water electrolysis hydrogen production.
The anode comprises a metal electrode substrate and a metal oxide catalyst coating layer positioned on the surface of the metal electrode substrate, wherein the metal oxide catalyst coating layer comprises nickel oxide, lithium oxide, cobalt oxide and noble metal oxide.
The anode for producing hydrogen by alkaline water electrolysis is applied to producing hydrogen by alkaline water electrolysis.
The technical scheme of the invention has the following advantages:
1. according to the preparation method of the anode for the alkaline water electrolysis hydrogen production, provided by the invention, on one hand, the metal electrode substrate is subjected to high-temperature thermal oxidation treatment at 300-500 ℃ before the catalyst coating is manufactured, so that the metal oxide is formed on the surface layer of the substrate, the base metal is prevented from being separated out from the coating and accelerating the falling of the coating caused by corrosion of the acidic coating liquid on the substrate, and the bonding stability of the catalyst coating and the electrode substrate is improved; on the other hand, a small amount of noble metal salt solution is doped in the salt solution of nickel, cobalt and lithium in the coating solution, so that the doping of noble metal oxide can not only reduce the oxygen evolution potential, but also improve the binding force of the catalyst coating and the electrode substrate and prolong the service life of the electrode. Therefore, the anode for alkaline water electrolysis hydrogen production, which is obtained by the method, can effectively reduce the oxygen evolution potential, simultaneously give consideration to better binding force between the coating and the electrode substrate, prolong the service life of the anode and improve the stability.
2. The method provided by the invention further optimizes the temperature and time of the first high-temperature thermal oxidation treatment, is beneficial to further improving the binding force of the coating and the electrode substrate and has lower oxygen evolution potential.
3. The method provided by the invention further optimizes any one or a combination of a plurality of noble metal types selected from Pt, ru, ir, pd, rh; preferably, the noble metal comprises any one or a combination of a plurality of Ru, pd and Rh, which is beneficial to further improving the binding force of the coating and the electrode substrate and further reducing the oxygen evolution potential.
4. The nickel oxide in the coating plays a role of a transition layer, the cobalt and lithium oxide plays a role of reducing oxygen evolution potential, and the noble metal oxide not only can reduce the oxygen evolution potential, but also can improve the binding force between the coating and an electrode substrate and prolong the service life of the electrode.
5. The method of the invention further optimizes the load capacity and proportion of each metal oxide, is favorable for further improving the bonding force of the coating and the electrode substrate and further reducing the oxygen evolution potential, so as to ensure that the bonding force of the coating and the substrate is more stable, the catalytic performance is better, and the electrode has better electrical performance.
6. According to the method provided by the invention, the metal electrode substrate is made of nickel or nickel alloy, and nickel oxide is formed during the first high-temperature thermal oxidation, so that the stability of the electrode substrate is improved, and the combination stability of the catalyst coating and the nickel electrode substrate is improved.
7. The method provided by the invention further comprises the step of carrying out alkali treatment on the metal oxide catalyst coating on the surface of the metal electrode substrate by adopting alkali liquor so as to form a nickel hydroxide protective layer on the surface of the catalyst coating; preferably, by treating the electrode with an alkaline solution having a concentration comparable to that of the electrolyte in an environment of 20-40 ℃, a uniform nickel hydroxide is formed so that the electrode no longer reacts with water vapor in the air, thereby protecting the electrode from corrosion.
Detailed Description
Example 1
The preparation method of the anode for producing hydrogen by alkaline water electrolysis comprises the following steps:
s1, uniformly mixing nickel hydrochloride, lithium acetate and cobalt nitrate to obtain a precursor solution, and uniformly mixing ruthenium trichloride with the precursor solution to obtain a mixed coating solution; the content of nickel in the mixed coating liquid is 85g/L, the content of lithium is 90g/L, the content of cobalt is 40g/L, and the content of ruthenium is 18g/L;
s2, performing 3 times of sand blasting treatment on the front and back surfaces of the nickel screen electrode substrate by taking 100-mesh white corundum sand as a sand blasting medium, and performing acid washing treatment on the electrode substrate subjected to sand blasting by using 2.5wt% sulfuric acid for 1h to form a roughened electrode substrate;
s3, performing first high-temperature thermal oxidation treatment on the roughened electrode substrate in an air atmosphere at 400 ℃, and preserving heat for 10 minutes;
s4, spraying the mixed coating liquid obtained in the step S1 onto the front and back surfaces of the electrode substrate subjected to the first high-temperature thermal oxidation treatment for 30 times, carrying out the second thermal oxidation treatment at 450 ℃ in an air atmosphere after each time of coating, and keeping the temperature for 30 minutes, wherein the total spraying amount of the mixed coating liquid on the surface of the electrode substrate is 105ml/m 2 Forming a metal oxide catalyst coating with the thickness of 30 mu m on the surface of an electrode substrate to obtain an anode for hydrogen production by alkaline water electrolysis;
the anode comprises a nickel screen electrode substrate and a catalyst coating positioned on the surface of the electrode substrate, wherein the catalyst coating comprises NiO 2 、Li 2 O、Co 3 O 4 And RuO (Ruo) 2 ，NiO 2 、Li 2 O and Co 3 O 4 The total loading on the electrode substrate surface was 40g/m 2 ，NiO 2 、Li 2 O、Co 3 O 4 Is NiO in mass ratio of 2 ：Li 2 O：Co 3 O 4 ＝2.4:3.6:1，RuO 2 The loading on the surface of the electrode substrate was 2.5g/m 2 。
Example 2
The present example provides a method for producing an anode for hydrogen production by alkaline water electrolysis, which is different from example 1 in that the temperature of the first high-temperature thermal oxidation treatment in step S3 is 450 ℃.
Example 3
The present example provides a method for producing an anode for hydrogen production by alkaline water electrolysis, which is different from example 1 in that the temperature of the first high-temperature thermal oxidation treatment in step S3 is 500 ℃.
Example 4
The present example provides a method for producing an anode for hydrogen production by alkaline water electrolysis, which is different from example 1 in that the temperature of the first high-temperature thermal oxidation treatment in step S3 is 300 ℃.
Example 5
The preparation method of the anode for hydrogen production by alkaline water electrolysis provided by the embodiment comprises the following steps:
s1, uniformly mixing nickel hydrochloride, lithium acetate and cobalt nitrate to obtain a precursor solution, and uniformly mixing palladium chloride with the precursor solution to obtain a mixed coating solution; the content of nickel in the mixed coating liquid is 85g/L, the content of lithium is 90g/L, the content of cobalt is 40g/L, and the content of palladium is 18.3g/L;
s2, performing 3 times of sand blasting treatment on the front and back surfaces of the nickel screen electrode substrate by taking 100-mesh white corundum sand as a sand blasting medium, and performing acid washing treatment on the electrode substrate subjected to sand blasting by using 2.5wt% sulfuric acid for 1h to form a roughened electrode substrate;
s3, performing first high-temperature thermal oxidation treatment on the roughened electrode substrate in an air atmosphere at 400 ℃, and preserving heat for 10 minutes;
s4, spraying the mixed coating liquid obtained in the step S1 to the front and back surfaces of the electrode substrate subjected to the first high-temperature thermal oxidation treatment for 30 times, carrying out the second thermal oxidation treatment at 450 ℃ in an air atmosphere after each time of coating, and keeping the temperature for 30 minutes, wherein the total spraying amount of the coating liquid on the surface of the electrode substrate is 105ml/m 2 Forming a metal oxide catalyst coating with the thickness of 30 mu m on the surface of an electrode substrate to obtain an anode for hydrogen production by alkaline water electrolysis;
the anode comprises a nickel screen electrode substrate and a catalyst coating positioned on the surface of the electrode substrate, wherein the catalyst coating comprises NiO 2 、Li 2 O、Co 3 O 4 And PdO 2 ，NiO 2 、Li 2 O and Co 3 O 4 The total loading on the electrode substrate surface was 40g/m 2 ，NiO 2 、Li 2 O、Co 3 O 4 Is NiO in mass ratio of 2 ：Li 2 O：Co 3 O 4 ＝2.4:3.6:1，PdO 2 The loading on the surface of the electrode substrate was 2.5g/m 2 。
Example 6
The preparation method of the anode for hydrogen production by alkaline water electrolysis provided by the embodiment comprises the following steps:
s1, uniformly mixing nickel hydrochloride, lithium acetate and cobalt nitrate to obtain a precursor solution, and uniformly mixing iridium chloride with the precursor solution to obtain a mixed coating solution; the content of nickel in the mixed coating liquid is 85g/L, the content of lithium is 90g/L, the content of cobalt is 40g/L, and the content of iridium is 20.4g/L;
s2, performing 3 times of sand blasting treatment on the front and back surfaces of the nickel screen electrode substrate by taking 100-mesh white corundum sand as a sand blasting medium, and performing acid washing treatment on the electrode substrate subjected to sand blasting by using 2.5wt% sulfuric acid for 1h to form a roughened electrode substrate;
s3, carrying out first high-temperature thermal oxidation treatment on the roughened electrode substrate in an air atmosphere at 400 ℃, and preserving heat for 10 minutes;
s4, spraying the mixed coating liquid obtained in the step S1 to the front and back surfaces of the electrode substrate subjected to the first high-temperature thermal oxidation treatment for 30 times, carrying out the second thermal oxidation treatment at 450 ℃ in an air atmosphere after each time of coating, and keeping the temperature for 30 minutes, wherein the total spraying amount of the coating liquid on the surface of the electrode substrate is 105ml/m 2 Forming a metal oxide catalyst coating with the thickness of 30 mu m on the surface of an electrode substrate to obtain an anode for hydrogen production by alkaline water electrolysis;
the anode comprises a nickel screen electrode substrate and a catalyst coating positioned on the surface of the electrode substrate, wherein the catalyst coating comprises NiO 2 、Li 2 O、Co 3 O 4 And IrO 2 ，NiO 2 、Li 2 O and Co 3 O 4 The total loading on the electrode substrate surface was 40g/m 2 ，NiO 2 、Li 2 O、Co 3 O 4 Is NiO in mass ratio of 2 ：Li 2 O：Co 3 O 4 ＝2.4:3.6:1，IrO 2 The loading on the surface of the electrode substrate was 2.5g/m 2 。
Example 7
The preparation method of the anode for hydrogen production by alkaline water electrolysis provided by the embodiment comprises the following steps:
s1, uniformly mixing nickel hydrochloride, lithium acetate and cobalt nitrate to obtain a precursor solution, and uniformly mixing rhodium chloride with the precursor solution to obtain a mixed coating solution; the content of nickel in the mixed coating liquid is 85g/L, the content of lithium is 90g/L, the content of cobalt is 40g/L, and the content of rhodium is 18.2g/L;
s2, performing 3 times of sand blasting treatment on the front and back surfaces of the nickel screen electrode substrate by taking 100-mesh white corundum sand as a sand blasting medium, and performing acid washing treatment on the electrode substrate subjected to sand blasting by using 2.5wt% sulfuric acid for 1h to form a roughened electrode substrate;
s3, performing first high-temperature thermal oxidation treatment on the roughened electrode substrate in an air atmosphere at 400 ℃, and preserving heat for 10 minutes;
s4, spraying the mixed coating liquid obtained in the step S1 onto the front and back surfaces of the electrode substrate subjected to the first high-temperature thermal oxidation treatment for 30 times, carrying out the second thermal oxidation treatment at 450 ℃ in an air atmosphere after each time of coating, and keeping the temperature for 30 minutes, wherein the total spraying amount of the mixed coating liquid on the surface of the electrode substrate is 105ml/m 2 Forming a metal oxide catalyst coating with the thickness of 30 mu m on the surface of an electrode substrate to obtain an anode for hydrogen production by alkaline water electrolysis;
the anode comprises a nickel screen electrode substrate and a catalyst coating positioned on the surface of the electrode substrate, wherein the catalyst coating comprises NiO 2 、Li 2 O、Co 3 O 4 And RhO 2 ，NiO 2 、Li 2 O and Co 3 O 4 The total loading on the electrode substrate surface was 40g/m 2 ，NiO 2 、Li 2 O、Co 3 O 4 Is NiO in mass ratio of 2 ：Li 2 O：Co 3 O 4 ＝2.4:3.6:1，RhO 2 The loading on the surface of the electrode substrate was 2.5g/m 2 。
Example 8
The preparation method of the anode for hydrogen production by alkaline water electrolysis provided by the embodiment comprises the following steps:
s1, uniformly mixing nickel hydrochloride, lithium acetate and cobalt nitrate to obtain a precursor solution, and uniformly mixing chloroplatinic acid, iridium chloride and the precursor solution to obtain a mixed coating solution; the content of nickel in the mixed coating liquid is 85g/L, the content of lithium is 90g/L, the content of cobalt is 40g/L, the content of platinum is 8.2g/L, and the content of iridium is 12g/L;
s2, performing 3 times of sand blasting treatment on the front and back surfaces of the nickel screen electrode substrate by taking 100-mesh white corundum sand as a sand blasting medium, and performing acid washing treatment on the electrode substrate subjected to sand blasting by using 2.5wt% sulfuric acid for 1h to form a roughened electrode substrate;
s3, performing first high-temperature thermal oxidation treatment on the roughened electrode substrate in an air atmosphere at 400 ℃, and preserving heat for 10 minutes;
s4, spraying the mixed coating liquid obtained in the step S1 to the front and back surfaces of the electrode substrate subjected to the first high-temperature thermal oxidation treatment for 30 times, carrying out the second thermal oxidation treatment at 450 ℃ in an air atmosphere after each time of coating, and keeping the temperature for 30 minutes, wherein the total spraying amount of the coating liquid on the surface of the electrode substrate is 105ml/m 2 Forming a catalyst coating with the thickness of 30 mu m on the surface of the electrode substrate to obtain an anode for hydrogen production by alkaline water electrolysis;
the anode comprises a nickel screen electrode substrate and a catalyst coating positioned on the surface of the electrode substrate, wherein the catalyst coating comprises NiO 2 、Li 2 O、Co 3 O 4 、IrO 2 And PtO 2 ，NiO 2 、Li 2 O and Co 3 O 4 The total loading on the electrode substrate surface was 40g/m 2 ，NiO 2 、Li 2 O、Co 3 O 4 Is NiO in mass ratio of 2 ：Li 2 O：Co 3 O 4 ＝2.4:3.6:1，IrO 2 The loading on the surface of the electrode substrate was 1.5g/m 2 ，PtO 2 Is 1g/m 2 。
Example 9
The preparation method of the anode for hydrogen production by alkaline water electrolysis in the embodiment comprises the following steps:
s1, uniformly mixing nickel hydrochloride, lithium acetate and cobalt nitrate to obtain a precursor solution, and uniformly mixing ruthenium trichloride with the precursor solution to obtain a mixed coating solution; the content of nickel in the mixed coating liquid is 85g/L, the content of lithium is 90g/L, the content of cobalt is 40g/L, and the content of Ru is 18g/L;
s2, performing 3 times of sand blasting treatment on the front and back surfaces of the nickel screen electrode substrate by taking 100-mesh white corundum sand as a sand blasting medium, and performing acid washing treatment on the electrode substrate subjected to sand blasting by using 2.5wt% sulfuric acid for 1h to form a roughened electrode substrate;
s3, performing first high-temperature thermal oxidation treatment on the roughened electrode substrate in an air atmosphere at 400 ℃, and preserving heat for 10 minutes;
s4, spraying the mixed coating liquid obtained in the step S1 to the front and back surfaces of the electrode substrate subjected to the first high-temperature thermal oxidation treatment for 30 times, carrying out the second thermal oxidation treatment at 450 ℃ in an air atmosphere after each time of coating, and keeping the temperature for 30 minutes, wherein the total spraying amount of the coating liquid on the surface of the electrode substrate is 105ml/m 2 Forming a catalyst coating with the thickness of 30 mu m on the surface of the electrode substrate to obtain an anode for hydrogen production by alkaline water electrolysis;
the anode comprises a nickel screen electrode substrate and a catalyst coating positioned on the surface of the electrode substrate, wherein the catalyst coating comprises NiO 2 、Li 2 O、Co 3 O 4 And RuO (Ruo) 2 ，NiO 2 、Li 2 O and Co 3 O 4 The total loading on the electrode substrate surface was 40g/m 2 ，NiO 2 、Li 2 O、Co 3 O 4 Is NiO in mass ratio of 2 ：Li 2 O：Co 3 O 4 ＝2.4:3.6:1，RuO 2 The loading on the surface of the electrode substrate was 2.5g/m 2 ；
S5, soaking the electrode substrate with the catalyst coating on the surface obtained in the step S4 for 10 hours by using 30 ℃ and 30wt% NaOH solution, washing with water and drying to obtain the anode after alkali treatment.
Example 10
The preparation method of the anode for hydrogen production by alkaline water electrolysis in the embodiment comprises the following steps:
s1, uniformly mixing nickel hydrochloride, lithium acetate and cobalt nitrate to obtain a precursor solution, and uniformly mixing ruthenium trichloride with the precursor solution to obtain a mixed coating solution; the content of nickel in the mixed coating liquid is 85g/L, the content of lithium is 90g/L, the content of cobalt is 40g/L, and the content of Ru is 7.2g/L;
s2, performing 3 times of sand blasting treatment on the front and back surfaces of the nickel screen electrode substrate by taking 100-mesh white corundum sand as a sand blasting medium, and performing acid washing treatment on the electrode substrate subjected to sand blasting by using 2.5wt% sulfuric acid for 1h to form a roughened electrode substrate;
s3, performing first high-temperature thermal oxidation treatment on the roughened electrode substrate in an air atmosphere at 400 ℃, and preserving heat for 10 minutes;
s4, spraying the mixed coating liquid obtained in the step S1 to the front and back surfaces of the electrode substrate subjected to the first high-temperature thermal oxidation treatment for 30 times, carrying out the second high-temperature thermal oxidation treatment at 450 ℃ in an air atmosphere after each time of coating, and keeping the temperature for 30 minutes, wherein the total spraying amount of the mixed coating liquid is 105ml/m 2 Forming a catalyst coating with the thickness of 30 mu m on the surface of the electrode substrate to obtain an anode for hydrogen production by alkaline water electrolysis;
the anode comprises a nickel screen electrode substrate and a catalyst coating positioned on the surface of the electrode substrate, wherein the catalyst coating comprises NiO 2 、Li 2 O、Co 3 O 4 And RuO (Ruo) 2 ，NiO 2 、Li 2 O and Co 3 O 4 The total loading on the electrode substrate surface was 40g/m 2 ，NiO 2 、Li 2 O、Co 3 O 4 Is NiO in mass ratio of 2 ：Li 2 O：Co 3 O 4 ＝2.4:3.6:1，RuO 2 The loading on the surface of the electrode substrate was 1.0g/m 2 。
Comparative example 1
The comparative example provides an anode for hydrogen production by alkaline water electrolysis, wherein the anode is made of nickel screen.
Comparative example 2
The preparation method of the anode for producing hydrogen by alkaline water electrolysis of the comparative example comprises the following steps:
s1, uniformly mixing nickel hydrochloride, lithium acetate and cobalt nitrate to obtain a precursor solution, wherein the content of nickel in the precursor solution is 85g/L, the content of lithium is 90g/L, and the content of cobalt is 40g/L;
s2, performing 3 times of sand blasting treatment on the front and back surfaces of the nickel screen electrode substrate by taking 100-mesh white corundum sand as a sand blasting medium, and performing acid washing treatment on the electrode substrate subjected to sand blasting by using 2.5wt% sulfuric acid for 1h to form a roughened electrode substrate;
s3, performing first high-temperature thermal oxidation treatment on the roughened electrode substrate in an air atmosphere at 400 ℃, and preserving heat for 10 minutes;
s4, spraying the precursor solution obtained in the step S1 onto the front and back surfaces of the electrode substrate subjected to the first high-temperature thermal oxidation treatment for 30 times, carrying out the second thermal oxidation treatment at 450 ℃ in an air atmosphere after each time of coating, and keeping the temperature for 30 minutes, wherein the total spraying amount of the precursor solution is 105ml/m 2 Forming a catalyst coating with the thickness of 30 mu m on the surface of the electrode substrate to obtain an anode for hydrogen production by alkaline water electrolysis;
the anode comprises a nickel screen electrode substrate and a catalyst coating positioned on the surface of the electrode substrate, wherein the catalyst coating comprises NiO 2 、Li 2 O and Co 3 O 4 ，NiO 2 、Li 2 O and Co 3 O 4 The total loading on the electrode substrate surface was 40g/m 2 ，NiO 2 、Li 2 O、Co 3 O 4 Is NiO in mass ratio of 2 ：Li 2 O：Co 3 O 4 ＝2.4:3.6:1。
Comparative example 3
The preparation method of the anode for producing hydrogen by alkaline water electrolysis of the comparative example comprises the following steps:
s1, uniformly mixing nickel hydrochloride, lithium acetate and cobalt nitrate to obtain a precursor solution, and uniformly mixing ruthenium trichloride with the precursor solution to obtain a mixed coating solution; the content of nickel in the mixed coating liquid is 85g/L, the content of lithium is 90g/L, the content of cobalt is 40g/L, and the content of Ru is 18g/L;
s2, performing 3 times of sand blasting treatment on the front and back surfaces of the nickel screen electrode substrate by taking 100-mesh white corundum sand as a sand blasting medium, and performing acid washing treatment on the electrode substrate subjected to sand blasting by using 2.5wt% sulfuric acid for 1h to form a roughened electrode substrate;
s3, spraying the mixed coating liquid obtained in the step S1 on the front and back surfaces of the roughened electrode substrate for 30 times, carrying out thermal oxidation treatment at 450 ℃ in an air atmosphere after each coating, and preserving the heat for 30 minutes, wherein the total spraying amount of the mixed coating liquid is 105ml/m 2 Forming a catalyst coating with the thickness of 30 mu m on the surface of the electrode substrate to obtain an anode for hydrogen production by alkaline water electrolysis;
the anode comprises a nickel screen electrode substrate and a catalyst coating positioned on the surface of the electrode substrate, wherein the catalyst coating comprises NiO 2 、Li 2 O、Co 3 O 4 And RuO (Ruo) 2 ，NiO 2 、Li 2 O and Co 3 O 4 The total loading on the electrode substrate surface was 40g/m 2 ，NiO 2 、Li 2 O、Co 3 O 4 Is NiO in mass ratio of 2 ：Li 2 O：Co 3 O 4 ＝2.4:3.6:1，RuO 2 The loading on the surface of the electrode substrate was 2.5g/m 2 。
Comparative example 4
The preparation method of the anode for producing hydrogen by alkaline water electrolysis of the comparative example comprises the following steps:
s1, uniformly mixing nickel hydrochloride, lithium acetate and cobalt nitrate to obtain a precursor solution, and uniformly mixing ruthenium trichloride with the precursor solution to obtain a mixed coating solution; the content of nickel in the mixed coating liquid is 85g/L, the content of lithium is 90g/L, the content of cobalt is 40g/L, and the content of Ru is 18g/L;
s2, performing 3 times of sand blasting treatment on the front and back surfaces of the nickel screen electrode substrate by taking 100-mesh white corundum sand as a sand blasting medium, and performing acid washing treatment on the electrode substrate subjected to sand blasting by using 2.5wt% sulfuric acid for 1h to form a roughened electrode substrate;
s3, performing first high-temperature thermal oxidation treatment on the roughened electrode substrate in an air atmosphere at 600 ℃, and preserving heat for 10 minutes;
s4, spraying the mixed coating liquid obtained in the step S1 to the front and back surfaces of the electrode substrate subjected to the first high-temperature thermal oxidation treatment for 30 times, and carrying out second high-temperature thermal oxidation at 450 ℃ in an air atmosphere after each time of coatingTreating, keeping the temperature for 30 minutes, wherein the total spraying amount of the mixed coating liquid on the surface of the electrode substrate is 105ml/m 2 Forming a metal oxide catalyst coating with the thickness of 30 mu m on the surface of an electrode substrate to obtain an anode for hydrogen production by alkaline water electrolysis;
the anode comprises a nickel screen electrode substrate and a catalyst coating positioned on the surface of the electrode substrate, wherein the catalyst coating comprises NiO 2 、Li 2 O、Co 3 O 4 And RuO (Ruo) 2 ，NiO 2 、Li 2 O and Co 3 O 4 The total loading on the electrode substrate surface was 40g/m 2 ，NiO 2 、Li 2 O、Co 3 O 4 Is NiO in mass ratio of 2 ：Li 2 O：Co 3 O 4 ＝2.4:3.6:1，RuO 2 The loading on the surface of the electrode substrate was 2.5g/m 2 。
Test case
The anodes for alkaline water electrolysis hydrogen production obtained in examples 1 to 10 and comparative examples 1 to 4 were subjected to electrochemical performance test using an electrochemical workstation.
The test system was a conventional three-electrode system, the anode in the above examples and comparative examples was used as a working electrode, the nickel screen was used as a counter electrode, the saturated calomel electrode was used as a reference electrode, the electrolyte was 30wt% potassium hydroxide, the temperature was 85℃and the oxygen evolution electrode was tested at 3kA/m 2 After the oxygen evolution potential was lowered, the current was adjusted to 10kA/m 2 The electrolysis was continued for 10 hours, the mass of the oxygen evolution electrode before and after the electrolysis was recorded, the weight loss value of the oxygen evolution electrode was calculated (the electrode "weight loss" before and after the electrolysis was small, which indicates that the electrode "life" was longer and the performance was more stable), and the results are shown in table 1.
TABLE 1 Performance test results
As can be seen from Table 1, the unmodified nickel mesh of comparative example 1 has a high oxygen evolution potential. Comparative example 2 catalyst coating contains only NiO 2 、Li 2 O and Co 3 O 4 Due to no oxidation of noble metalsThe binding force of the catalyst coating is poor and is 10kA/m 2 The anode loss is large under the high current density reinforcement, and the oxygen evolution potential is high. Comparative example 3 catalyst coating adhesion was poor at 10kA/m due to the first high temperature thermal oxidation treatment not performed before coating 2 The anode weight loss is larger and the oxygen evolution potential is higher under the high current density reinforcement.
NiO in the catalyst coating of examples 1-4, 10 2 、Li 2 O and Co 3 O 4 Moderate doping of small amounts of RuO 2 And meanwhile, the electrode substrate is subjected to first high-temperature thermal oxidation treatment before coating, so that the oxygen evolution potential is effectively reduced, the binding force between the catalyst coating and the electrode substrate is greatly improved, the reinforced weightlessness is low, and the service life of the anode is prolonged.
Comparative example 4 the first high-temperature thermal oxidation treatment performed before coating had too high a temperature, resulting in formation of cracks on the substrate surface, deterioration of life, and high oxygen evolution potential.
Examples 1 and 5 to 8 show that the noble metal oxide species slightly differ in the degree of improvement in the electrode life and in the degree of reduction in the oxygen evolution potential, ruO of example 1 2 PdO of example 5 2 RhO of example 7 2 IrO in example 8 2 And PtO 2 The anode has smaller weight loss under high current density and lower oxygen evolution potential; wherein RhO is doped 2 The strengthening weightlessness is the lowest, the electrode life is longer, more stable and the oxygen evolution potential is the lowest.
Example 9 the catalyst coating was further subjected to an alkali treatment on the basis of example 1, the oxygen evolution potential and the service life in electrolysis were substantially unchanged, but the catalyst coating could be prevented from falling off due to oxidation corrosion of the anode in air in the non-use state.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The preparation method of the anode for producing hydrogen by alkaline water electrolysis is characterized by comprising the following steps:
1) Mixing a nickel salt solution, a lithium salt solution, a cobalt salt solution and a noble metal salt solution to obtain a mixed coating solution;
2) And (3) carrying out first high-temperature thermal oxidation treatment on the metal electrode substrate at 300-500 ℃, then coating the mixed coating liquid on the surface of the metal electrode substrate, and carrying out second thermal oxidation treatment after coating so as to form a metal oxide catalyst coating on the surface of the metal electrode substrate, thereby obtaining the anode for hydrogen production by alkaline water electrolysis.
2. The method according to claim 1, wherein the temperature of the first high-temperature thermal oxidation treatment in step 2) is 350 to 450 ℃.
3. The method according to claim 1, wherein the noble metal in the noble metal salt solution is selected from one or a combination of several of Pt, ru, ir, pd, rh.
4. A method of preparing according to any one of claims 1 to 3, wherein the metal oxide in the metal oxide catalyst coating comprises nickel oxide, lithium oxide, cobalt oxide and noble metal oxide.
5. The method according to claim 4, wherein the total loading of the nickel oxide, the lithium oxide and the cobalt oxide on the surface of the metal electrode substrate is 30 to 50g/m 2 The weight ratio of the nickel oxide to the lithium oxide to the cobalt oxide is (3-5): 4-6): 1-2; the loading capacity of the noble metal oxide on the surface of the metal electrode substrate is 1-3g/m 2 。
6. A method according to any one of claims 1 to 3, wherein the metal electrode substrate is nickel or a nickel alloy.
7. A method according to any one of claims 1 to 3, further comprising the step of alkali treating the metal oxide catalyst coating on the surface of the metal electrode substrate with an alkali solution.
8. An anode for alkaline water electrolysis hydrogen production, characterized in that the anode is prepared by the preparation method of the anode for alkaline water electrolysis hydrogen production according to any one of claims 1 to 7.
9. The anode for hydrogen production by alkaline water electrolysis according to claim 8, comprising a metal electrode substrate and a metal oxide catalyst coating layer on the surface of the metal electrode substrate, wherein the metal oxide catalyst coating layer comprises nickel oxide, lithium oxide, cobalt oxide and noble metal oxide.
10. Use of an anode for alkaline water electrolysis hydrogen production according to claim 8 or 9 for alkaline water electrolysis hydrogen production.
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