CN115216799A - Nickel-based alloy composite electrode with gradient component structure and preparation method and application thereof - Google Patents
Nickel-based alloy composite electrode with gradient component structure and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 52
- 239000000956 alloy Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000007864 aqueous solution Substances 0.000 claims abstract description 44
- 238000005530 etching Methods 0.000 claims abstract description 28
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 230000001276 controlling effect Effects 0.000 claims abstract description 3
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 238000004070 electrodeposition Methods 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 229910021645 metal ion Inorganic materials 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 150000004696 coordination complex Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 150000003868 ammonium compounds Chemical class 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 7
- 239000007788 liquid Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000000306 component Substances 0.000 description 22
- 238000005868 electrolysis reaction Methods 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 9
- 238000011068 loading method Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- -1 ammonium ions Chemical class 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910002058 ternary alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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- 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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
- C25D5/40—Nickel; Chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
Abstract
The invention relates to a nickel-based alloy composite electrode with a gradient component structure and a preparation method and application thereof, wherein a nickel-based body is placed in a weak acid solution for pretreatment to remove surface impurities; placing a nickel base body in a nickel base alloy catalyst precursor aqueous solution, depositing a nickel base alloy catalyst under an electrochemical condition, and continuously regulating and controlling the component concentration of a catalyst precursor to form a nickel base alloy catalyst layer with a gradient component structure; then, placing the composite electrode loaded with the catalyst in ammonium solution for selective electrochemical etching; and then, calcining to finally prepare the nickel-based alloy composite electrode with the gradient component structure. Compared with the prior art, the method realizes the in-situ growth of the catalyst on the surface of the substrate, enhances the binding force between the catalyst layer and the substrate, improves the stability of the electrode, further effectively increases the specific surface area of the catalyst layer by an ammonium liquid selective electrochemical etching method, and improves the catalytic activity of the composite electrode.
Description
Technical Field
The invention relates to the technical field of electrolytic hydrogen production, in particular to a nickel-based alloy composite electrode with a gradient component structure and a preparation method and application thereof.
Background
The hydrogen energy has the characteristics of high energy density and zero carbon emission, and is considered as ideal high-efficiency green secondary energy. The technology of hydrogen production by coupling renewable energy sources with electrolysis water can realize the large-scale preparation of green hydrogen and the decarburization of the hydrogen energy source in the whole industrial chain, is considered as an important means for realizing the double-carbon strategic target in China, meets the national major strategic demand, and has important significance for the sustainable development of the human society.
The water electrolysis hydrogen production technology can be divided into alkali water electrolysis hydrogen production, proton exchange membrane water electrolysis hydrogen production, anion exchange membrane water electrolysis hydrogen production, solid oxide water electrolysis hydrogen production and the like according to the electrolyte type. Among them, the alkaline water electrolysis hydrogen production technology is the most mature and has been commercially applied. The renewable energy has the characteristic of fluctuation, which puts higher requirements on the performance of the alkaline water electrolysis hydrogen production device. The nickel-based electrode is a core component of the alkaline water electrolytic cell, determines hydrogen evolution/oxygen evolution reaction kinetics in the water electrolysis process, further determines the energy efficiency and power fluctuation adaptability of the electrolytic cell, and has important influence on the improvement of the performance of the electrolytic cell. The improvement of the electrode performance can be realized by a method for loading a high-performance catalyst (namely preparing a composite electrode). The loading method of the catalyst influences the microstructure of the catalyst layer and the electrochemical active area of the composite electrode. The chinese invention patent CN113265675a discloses a method for spraying high-entropy alloy powder on the surface of an electrode substrate by using a spraying process. The Chinese invention patent CN113862727A discloses a method for loading a NiFe or NiCo alloy catalyst by electrochemical deposition by placing a nickel substrate in a catalyst precursor water solvent. The Chinese invention patent CN114318398A discloses a method for loading NiCoP alloy catalyst on the surface of a nickel-based body through electrochemical deposition. Chinese patent No. CN111663152a discloses a method of soaking a nickel substrate in a catalyst precursor aqueous solution with a certain concentration, and loading a catalyst through spontaneous redox reaction. The invention Chinese patent CN114293215A discloses a method for loading a catalyst by combining hydrothermal reaction with high-temperature treatment, wherein a nickel substrate is placed in a catalyst precursor aqueous solution for hydrothermal reaction, and then a reaction product is placed in a reducing atmosphere tube furnace for high-temperature reduction treatment to obtain a catalyst loading electrode.
In summary, according to the method disclosed in the above patent, the microstructure of the composite electrode after the catalyst is loaded is not controllable, and an amorphous pore channel microstructure is formed and closed pores may be formed during the process of forming a catalyst layer with a certain thickness, which reduces the release kinetic rate of bubbles generated during the hydrogen/oxygen evolution process, thereby restricting the performance of the electrode.
Disclosure of Invention
The invention aims to provide a nickel-based alloy composite electrode with a gradient component structure and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme: a preparation method of a nickel-based alloy composite electrode with a gradient component structure comprises the following steps of firstly, placing a nickel-based body in a weak acid solution for ultrasonic pretreatment to remove surface impurities; then, placing the nickel base body in a nickel base alloy catalyst precursor aqueous solution, depositing a nickel base alloy catalyst under an electrochemical condition, and continuously regulating and controlling the component concentration of the catalyst precursor to form a nickel base alloy catalyst layer with a gradient component structure; and then, placing the catalyst-loaded composite electrode in ammonium liquid (ammonium ion aqueous solution) for selective electrochemical etching, dissolving part of nickel in the ammonium liquid by utilizing the coordination and complexation reaction of the nickel and the ammonium ions and combining an electrochemical environment so as to increase the specific surface area of the catalyst layer and form a large number of open pore channel structures, and finally preparing the nickel-based alloy composite electrode with the gradient component structure.
The invention provides a novel nickel-based alloy composite electrode with a gradient component structure and a preparation method thereof, aiming at the problem that the microstructure of a composite electrode loaded by a catalyst is difficult to regulate, the microstructure of the composite electrode loaded by the catalyst can be effectively regulated, and the metal nickel in a catalyst layer is selectively etched under an electrochemical condition by utilizing the coordination and complexation reaction of the metal nickel and ammonium ions, so that the specific surface area of the catalyst layer is increased, a large number of open pore channel structures are formed, the removal kinetic rate of bubbles generated in the hydrogen/oxygen evolution process is increased, and the performance of the electrode is improved.
Preferably, the weak acid solution includes, but is not limited to, one or more of citric acid, oxalic acid, dilute hydrochloric acid, and dilute sulfuric acid, and has a pH of 1-4.
Preferably, the catalyst precursor aqueous solution contains Ni 2+ And M metal ions, M being a metal element which does not undergo a coordination complex reaction with the ammonium ion, the M metal ions including but not limited to Fe 2+ 、Mn 2+ One or more of them.
Further preferably, ni in the catalyst precursor aqueous solution 2+ Initial concentration of 0.2-1mol/L, initial concentration of M metal ion of 0.02-0.5mol/L, ni in initial electrodeposition solution 2+ The concentration is greater than the concentration of M metal ions.
Still more preferably, the metal ions with M and not Ni are continuously added during the electrochemical deposition process 2+ The concentration of M metal ions in the aqueous solution of the catalyst precursor of (1) is 0.02 to 0.5mol/L, so that Ni is present in the whole electrodeposition process 2+ The relative concentration and the relative concentration of M metal ions present continuous gradient change, ni 2+ The relative concentration is gradually reduced, the relative concentration of M metal ions is gradually increased, and finally the nickel-based alloy catalyst layer with continuously changed components is formed.
Preferably, the current density used in the electrochemical deposition process is 1-500mA/cm 2 The time is 1-60min.
Preferably, the concentration of the ammonium solution is 0.1-2mol/L, and the ammonium compound used for preparing the ammonium solution includes, but is not limited to, one or more of ammonium chloride, ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium carbonate, ammonium acetate and ammonium oxalate.
Preferably, the current density used for the electrochemical etching is 5-100mA/cm 2 The time is 5-60min.
Preferably, the preparation method of the nickel-based alloy composite electrode with the gradient component structure comprises the following steps:
(1) Surface impurity removal treatment of a nickel matrix: putting the nickel substrate into a weak acid solution for ultrasonic treatment for 15-60min to remove surface impurities, and then washing the nickel substrate with deionized water until the pH value is 7-8;
(2) Electrochemical deposition preparation of the nickel-based alloy catalyst: adopting a two-electrode system, placing the treated nickel substrate serving as a cathode in a catalyst precursor aqueous solution with a certain concentration for electrochemical deposition;
(3) Selective etching of the composite electrode: placing a composite electrode loaded with a nickel-based alloy catalyst layer with a gradient component structure in ammonium solution with certain concentration for selective electrochemical etching, and adopting a two-electrode system with the composite electrode as an anode;
(4) Calcining the composite electrode: and cleaning the composite electrode subjected to the treatment by using deionized water, drying, and then calcining in a protective atmosphere at the temperature of 200-600 ℃ for 0.5-4h to finally obtain the nickel-based alloy composite electrode with the gradient structure.
Preferably, the nickel matrix is nickel mesh or foam nickel.
A nickel-based alloy composite electrode with a gradient component structure is prepared by the preparation method.
The application of the nickel-based alloy composite electrode with the gradient component structure is to use the composite electrode for alkaline electrolysis hydrogen production.
According to the composite electrode prepared by the invention, the surface of the nickel-based alloy catalyst layer with continuously changed components is uniformly covered, from one side close to the matrix to one side of the electrode surface, the content of nickel in the components of the catalyst layer is gradually reduced, the content of other alloy components is gradually increased, the catalyst layer has a high specific surface area and a large number of open pore structures, and the prepared composite electrode shows excellent catalytic activity and stability.
Compared with the prior art, the invention has the following advantages:
1. the composite electrode has high catalytic activity and good stability, realizes the in-situ growth of the catalyst on the surface of the substrate by an electrochemical deposition method, enhances the binding force between the catalyst layer and the substrate, effectively prevents the problem that the catalyst layer falls off in the long-time operation process of the composite electrode, improves the stability of the electrode, further effectively increases the specific surface area of the catalyst layer by an ammonium liquid selective electrochemical etching method, and improves the catalytic activity of the composite electrode;
2. the composite electrode catalyst layer has large specific surface area, the etching method is mild and effective, the method can realize effective regulation and control of the composite electrode microstructure after catalyst loading, and metal nickel in the catalyst layer is selectively etched under electrochemical conditions by utilizing the coordination complex reaction of metal nickel and ammonium ions, so that the specific surface area of the catalyst layer is increased, a large number of open pore channel structures are formed, the removal kinetic rate of bubbles generated in the hydrogen evolution/oxygen evolution process is increased, and the electrode performance is improved;
3. compared with the existing acid etching method, the ammonium liquid electrochemical etching method is mild and effective, no dangerous products such as hydrogen are generated, and selective etching for nickel components can be realized;
4. the method is simple and easy to implement, safe to operate and easy to industrialize, and the nickel-based alloy composite electrode prepared by the method has excellent hydrogen evolution/oxygen evolution catalytic activity and stability in alkaline electrolytic hydrogen production.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a profile view of a nickel substrate;
FIG. 3 is a surface topography of a composite electrode made in example 1;
fig. 4 is a linear scanning graph of the oxygen evolution reaction of the composite electrode and nickel mesh prepared in example 1, and the test conditions are as follows: in the two-electrode system, a composite electrode or a nickel net is used as a working electrode, a platinum sheet is used as a counter electrode, a 30wt% KOH aqueous solution is used as an electrolyte solution, and the scanning speed is 5mV/s;
fig. 5 is a linear scanning graph of hydrogen evolution reaction of the composite electrode and nickel mesh prepared in example 1, and the test conditions are as follows: in the two-electrode system, a composite electrode or a nickel net is used as a working electrode, a platinum sheet is used as a counter electrode, a 30wt% KOH aqueous solution is used as an electrolyte solution, and the scanning speed is 5mV/s;
FIG. 6 shows the anode of the composite electrode and nickel mesh prepared in example 1 at 500mA/cm 2 A comparison graph of the oxygen evolution reaction timing potential curve under the current density, wherein the electrolysis time is 200 hours;
FIG. 7 shows the composite electrode and nickel mesh prepared separately in examples 1-5 at 500mA/cm 2 Hydrogen evolution and oxygen evolution potential contrast diagram under current density, test conditions: in the two-electrode system, a composite electrode or a nickel screen is used as a working electrode, a platinum sheet is used as a counter electrode, KOH aqueous solution with the concentration of 30wt% is used as electrolyte solution, and the scanning speed is 5mV/s.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples.
A nickel-based alloy composite electrode with a gradient component structure for an alkaline electrolytic cell and a preparation method thereof are disclosed, and the specific method comprises the following steps:
(1) Surface impurity removal treatment of nickel matrix
Putting the nickel substrate into a weak acid solution for ultrasonic treatment for 15-60min to remove surface impurities, wherein the weak acid solution comprises one or more of citric acid, oxalic acid, dilute hydrochloric acid and dilute sulfuric acid, and the pH value is 1-4; then the nickel substrate is washed clean by deionized water, and the pH value is 7-8. The nickel substrate is a nickel net or foam nickel.
(2) Electrochemical deposition preparation of nickel-based alloy catalyst
And placing the treated nickel substrate serving as a cathode in a catalyst precursor aqueous solution with a certain concentration for electrochemical deposition. A two-electrode system is adopted, and the treated nickel matrix is used as a cathode. The initial aqueous catalyst precursor solution contains Ni 2+ And M metal ions, M being a metal element which does not undergo a coordination complex reaction with the ammonium ion, the M metal ions including but not limited to Fe 2+ 、Mn 2+ One or more of them, wherein Ni 2+ Initial concentration of 0.2-1mol/L, initial concentration of M metal ion of 0.02-0.5mol/L, ni in initial electrodeposition solution 2+ The concentration is greater than the concentration of M metal ions. The current density for electrochemical deposition is 1-500mA/cm 2 The time is 1-60min. In the electrochemical deposition process, M metal ions without Ni are continuously added 2+ The concentration of M metal ions in the aqueous solution of the catalyst precursor of (1) is 0.02 to 0.5mol/L, so that Ni is present in the whole electrodeposition process 2+ The concentration and the concentration of M metal ions present continuous gradient change, ni 2+ The relative concentration is gradually reduced, the relative concentration of M metal ions is gradually increased, and finally the nickel-based alloy catalyst layer with continuously changed components is formed.
(3) Selective etching of composite electrodes
And (3) placing the composite electrode loaded with the nickel-based alloy catalyst layer with the gradient component structure in ammonium solution (ammonium ion aqueous solution) with certain concentration for selective electrochemical etching. A two-electrode system is adopted, and a composite electrode is used as an anode. The concentration of the ammonium liquid is 0.1-2mol/L, and the ammonium compound used for preparing the ammonium liquid comprises one or more of ammonium chloride, ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium carbonate, ammonium acetate and ammonium oxalate. The current density for electrochemical etching is 5-100mA/cm 2 The time is 5-60min.
(4) Calcination treatment of composite electrode
And cleaning the treated composite electrode by using deionized water, drying, and calcining in a protective atmosphere. The calcining temperature is 200-600 ℃, the calcining time is 0.5-4h, and the nickel-based alloy composite electrode with the gradient structure is finally obtained.
The following are specific examples:
example 1
Placing the nickel screen in oxalic acid solution with the pH value of 2 for ultrasonic treatment for 30min to remove surface impurities; placing the treated nickel net serving as a cathode in a catalyst precursor aqueous solution with a certain concentration for electrochemical deposition, wherein a two-electrode system is adopted, the nickel net serves as the cathode, the initial catalyst precursor aqueous solution is 0.5mol/L nickel chloride and 0.3mol/L ferrous chloride aqueous solution, and the current density for electrochemical deposition is 300mA/cm 2 Continuously adding 0.3mol/L ferrous chloride aqueous solution in the electrochemical deposition process for 30min to ensure that the relative content of nickel in the formed nickel-iron catalyst layer is gradually reduced and the relative content of iron is gradually increased, and finally forming the nickel-iron catalyst layer with continuously changed components; then placing the composite electrode loaded with the nickel-iron catalyst layer in 1mol/L ammonium chloride aqueous solution for selective electrochemical etching to dissolve out part of nickel component in the catalyst layer, wherein the current density for the electrochemical etching is 50mA/cm 2 The time is 30min; and (3) cleaning the treated composite electrode with deionized water, drying, and then calcining in a nitrogen atmosphere at 400 ℃ for 2h to finally obtain the nickel-iron alloy composite electrode with the gradient structure.
Fig. 2 shows a morphology of the nickel mesh substrate, and fig. 3 shows a morphology of the nickel-iron alloy composite electrode prepared in example 1, and it can be seen that the nickel mesh substrate is uniformly covered with the nickel-iron alloy catalyst, the catalytic layer is rough in surface and has a large number of open pores. In terms of performance, as shown in FIG. 4, the nickel-iron alloy composite electrode prepared in example 1 was used at 500mA/cm 2 The oxygen evolution overpotential under the current density is lower than that of the traditional nickel net; as shown in FIG. 5, the nickel-iron alloy composite electrode prepared in example 1 was used at 500mA/cm 2 The hydrogen evolution overpotential under the current density is lower than that of the traditional nickel net; as shown in FIG. 6, the nickel-iron alloy composite electrode prepared in example 1 was used as an anode at 500mA/cm 2 The performance stability under current density is obviously superior to that of the traditional nickel screen.
FIG. 7 shows the 500mA/cm Ni mesh for the Ni-based alloy composite electrodes and Ni nets prepared in examples 1-5, respectively 2 Comparison graph of hydrogen evolution and oxygen evolution potentials at current densityIt can be seen that the performance of the prepared nickel-based alloy composite electrode is superior to that of a nickel net.
Example 2
In this example, the initial catalyst precursor aqueous solution was 1mol/L nickel sulfate and 0.5mol/L ferrous sulfate aqueous solution, and the current density used for electrochemical deposition was 1mA/cm 2 Continuously adding 0.5mol/L ferrous sulfate aqueous solution in the electrochemical deposition process for 60min; then placing the composite electrode loaded with the nickel-iron catalyst layer in 2mol/L ammonium nitrate aqueous solution for selective electrochemical etching, wherein the current density used for the electrochemical etching is 5mA/cm 2 The time is 60min; and then, calcining the nickel-iron alloy composite electrode in a nitrogen atmosphere at the calcining temperature of 200 ℃ for 4 hours to finally obtain the nickel-iron alloy composite electrode with the gradient structure, wherein the rest is the same as that in the embodiment 1.
Example 3
In this example, the initial catalyst precursor aqueous solution was 0.2mol/L nickel nitrate and 0.02mol/L manganese nitrate aqueous solution, and the current density used for electrochemical deposition was 500mA/cm 2 Continuously adding 0.02mol/L manganese nitrate aqueous solution in the electrochemical deposition process for 1 min; then placing the composite electrode loaded with the nickel-manganese catalyst layer in 0.1mol/L ammonium nitrate aqueous solution for selective electrochemical etching, wherein the current density used for the electrochemical etching is 100mA/cm 2 The time is 5min; and then calcining under the argon atmosphere at the calcining temperature of 600 ℃ for 0.5h to finally obtain the nickel-manganese alloy composite electrode with the gradient structure, wherein the rest is the same as that of the embodiment 1.
Example 4
In this example, the initial catalyst precursor aqueous solution was 0.8mol/L nickel nitrate, 0.3mol/L ferrous nitrate aqueous solution, and 0.2mol/L manganese nitrate aqueous solution, and the current density used for electrochemical deposition was 200mA/cm 2 Continuously adding 0.3mol/L ferrous nitrate aqueous solution and 0.2mol/L manganese nitrate aqueous solution in the electrochemical deposition process for 60min; then the composite electrode loaded with the nickel-iron-manganese catalyst layer is placed in 1.5mol/L ammonium oxalate aqueous solution for selective electrochemical etching, and the current density used for the electrochemical etching is 80mA/cm 2 The time is 40min; and then calcining under the argon atmosphere at the calcining temperature of 500 ℃ for 4h to finally obtain the nickel-iron-manganese ternary alloy composite electrode with the gradient structure, wherein the rest is the same as that in the embodiment 1.
Example 5
In this example, the initial catalyst precursor aqueous solution was 0.5mol/L nickel chloride, 0.3mol/L manganese chloride aqueous solution, and 0.1mol/L ferrous chloride aqueous solution, and the current density used for electrochemical deposition was 100mA/cm 2 Continuously adding 0.3mol/L manganese chloride aqueous solution and 0.1mol/L ferrous chloride aqueous solution in the electrochemical deposition process for 30min; then placing the composite electrode loaded with the nickel-manganese-iron catalyst layer in 1mol/L ammonium chloride aqueous solution for selective electrochemical etching, wherein the current density used for the electrochemical etching is 60mA/cm 2 The time is 50min; and then calcining under the atmosphere of helium at the temperature of 600 ℃ for 4h to finally obtain the nickel-manganese-iron ternary alloy composite electrode with the gradient structure, wherein the rest is the same as that in the embodiment 1.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a nickel-based alloy composite electrode with a gradient component structure is characterized by comprising the following steps of firstly, placing a nickel-based body in a weak acid solution for pretreatment, and removing surface impurities; then, placing a nickel base body in a nickel base alloy catalyst precursor water solution, depositing a nickel base alloy catalyst under an electrochemical condition, and forming a nickel base alloy catalyst layer with a gradient component structure by continuously regulating and controlling the component concentration of the catalyst precursor; then, placing the composite electrode loaded with the catalyst in ammonium solution for selective electrochemical etching; and then, calcining to finally prepare the nickel-based alloy composite electrode with the gradient component structure.
2. The method for preparing a nickel-based alloy composite electrode with a gradient composition structure as claimed in claim 1, wherein the weak acid solution includes one or more of citric acid, oxalic acid, diluted hydrochloric acid, and diluted sulfuric acid, and has a pH of 1-4.
3. The method of claim 1, wherein the catalyst precursor aqueous solution contains Ni 2+ And M metal ions, M being a metal element which does not undergo a coordination complex reaction with the ammonium ion, the M metal ions including but not limited to Fe 2+ 、Mn 2+ One or more of them.
4. The method for preparing a nickel-based alloy composite electrode having a gradient composition structure as claimed in claim 3, wherein Ni is contained in the catalyst precursor aqueous solution 2+ Initial concentration of 0.2-1mol/L, initial concentration of M metal ion of 0.02-0.5mol/L, ni in initial electrodeposition solution 2+ The concentration is greater than the concentration of M metal ions.
5. The method for preparing a nickel-based alloy composite electrode having a gradient composition structure as claimed in claim 4, wherein the metal ions having M but not Ni are continuously added during the electrochemical deposition process 2+ The concentration of M metal ions in the aqueous solution of the catalyst precursor of (1) is 0.02 to 0.5mol/L, so that Ni is present in the whole electrodeposition process 2+ The relative concentration and the relative concentration of M metal ions present continuous gradient change, ni 2+ The relative concentration is gradually reduced, the relative concentration of M metal ions is gradually increased, and finally the nickel-based alloy catalyst layer with continuously changed components is formed.
6. The junction of claim 1 having a gradient compositionThe preparation method of the structured nickel-based alloy composite electrode is characterized in that the current density used in the electrochemical deposition process is 1-500mA/cm 2 The time is 1-60min; the current density used for the electrochemical etching is 5-100mA/cm 2 The time is 5-60min.
7. The method for preparing the nickel-based alloy composite electrode with the gradient composition structure according to claim 1, wherein the concentration of the ammonium solution is 0.1-2mol/L, and the ammonium compound used for preparing the ammonium solution includes one or more of ammonium chloride, ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium carbonate, ammonium acetate and ammonium oxalate.
8. The method for preparing a nickel-based alloy composite electrode having a gradient composition structure according to claim 1, comprising the steps of:
(1) Surface impurity removal treatment of a nickel matrix: putting the nickel substrate into a weak acid solution for ultrasonic treatment for 15-60min to remove surface impurities, and then washing the nickel substrate with deionized water until the pH value is 7-8;
(2) Electrochemical deposition preparation of the nickel-based alloy catalyst: adopting a two-electrode system, placing the treated nickel substrate serving as a cathode in a catalyst precursor aqueous solution with a certain concentration for electrochemical deposition;
(3) Selective etching of the composite electrode: placing a composite electrode loaded with a nickel-based alloy catalyst layer with a gradient component structure in ammonium solution with certain concentration for selective electrochemical etching, and adopting a two-electrode system with the composite electrode as an anode;
(4) Calcining the composite electrode: and cleaning the composite electrode subjected to the treatment by using deionized water, drying, and then calcining in a protective atmosphere at the temperature of 200-600 ℃ for 0.5-4h to finally obtain the nickel-based alloy composite electrode with the gradient structure.
9. A nickel-based alloy composite electrode having a gradient composition structure, which is manufactured by the manufacturing method according to any one of claims 1 to 8.
10. Use of a nickel base alloy composite electrode with a gradient composition structure according to claim 9, characterized in that the composite electrode is used for alkaline electrolytic hydrogen production.
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| PCT/CN2022/134839 WO2024021403A1 (en) | 2022-07-28 | 2022-11-29 | Nickel-based alloy composite electrode having gradient component structure, and preparation method therefor and use thereof |
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