CN117488357B - Oxygen evolution electrode material and preparation method and application thereof - Google Patents
Oxygen evolution electrode material and preparation method and application thereof Download PDFInfo
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- CN117488357B CN117488357B CN202311852455.1A CN202311852455A CN117488357B CN 117488357 B CN117488357 B CN 117488357B CN 202311852455 A CN202311852455 A CN 202311852455A CN 117488357 B CN117488357 B CN 117488357B
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 85
- 239000001301 oxygen Substances 0.000 title claims abstract description 85
- 239000007772 electrode material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000006260 foam Substances 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 37
- 238000004070 electrodeposition Methods 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 150000002815 nickel Chemical class 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 25
- 238000000151 deposition Methods 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052753 mercury Inorganic materials 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 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 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- -1 ammonium salt compound Chemical class 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 6
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 235000019270 ammonium chloride 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
- 229940075397 calomel Drugs 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 6
- 239000010452 phosphate Substances 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
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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
- C25B11/091—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- 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
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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
- C25B11/02—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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- 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
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
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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
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- General Physics & Mathematics (AREA)
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Abstract
The invention provides an oxygen evolution electrode material, a preparation method and application thereof, wherein the preparation method comprises the following steps: step S1, taking foam nickel for pretreatment to obtain pretreated foam nickel; s2, taking a reference electrode, a counter electrode and pretreated foam nickel as a working electrode, and performing constant current electrodeposition in electrolyte containing nickel salt and ferric salt under constant current to obtain an oxygen evolution electrode material precursor; and S3, taking a reference electrode, a counter electrode and an oxygen evolution electrode material precursor as working electrodes, and performing constant voltage electrodeposition in electrolyte containing phosphate and sulfate under constant voltage to obtain the oxygen evolution electrode material. The oxygen evolution electrode material obtained by the preparation method has higher catalytic active sites and shows better structural stability and catalytic performance.
Description
Technical Field
The application relates to the technical field of hydrogen production by water electrolysis, in particular to an oxygen evolution electrode material and a preparation method and application thereof.
Background
The hydrogen production technology by electrolysis of water is used as an environment-friendly hydrogen preparation mode, wherein doping of hetero atoms N, P, S and the like is one of the most promising methods for improving the activity and stability of the transition metal catalyst of the electrolysis of water, and can effectively adjust the electronic structure, improve the electronic conductivity and enhance the chemical stability and corrosion resistance of the catalyst. However, doping P, S and the like often requires high temperature heat treatment, which is often cumbersome and time consuming and can result in PH, for example 3 And toxic gases are not beneficial to large-scale industrial preparation.
Therefore, in order to solve the problems of complicated preparation steps or poor catalytic performance of the oxygen evolution electrode materials in the prior art, it is highly desirable to provide an oxygen evolution electrode material and a preparation method thereof, so as to improve the problems.
Disclosure of Invention
The invention mainly aims to provide an oxygen evolution electrode material, and a preparation method and application thereof, so as to solve the technical problems of complicated preparation steps or poor catalytic performance of the oxygen evolution electrode material in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for producing an oxygen evolution electrode material, comprising the steps of: step S1, taking foam nickel for pretreatment to obtain pretreated foam nickel; s2, taking a reference electrode, a counter electrode and pretreated foam nickel as a working electrode, and performing constant current electrodeposition in electrolyte containing nickel salt and ferric salt under constant current to obtain an oxygen evolution electrode material precursor; and S3, taking a reference electrode, a counter electrode and an oxygen evolution electrode material precursor as working electrodes, and performing constant voltage electrodeposition in electrolyte containing phosphate and sulfate under constant voltage to obtain the oxygen evolution electrode material.
Further, the phosphate is selected from one or more of sodium phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate or sodium hydrogen phosphate.
Further, the sulfate is selected from one or more of sodium thiosulfate, thioacetamide or thiourea.
Further, the current density of the constant current electrodeposition treatment is-50 to-500 mA/cm 2 The deposition time is 60-1800 s.
Further, the working voltage of the constant voltage electrodeposition treatment is 400-1000V, and the deposition time is 300-1800 s.
Further, the nickel salt is selected from one or more of nickel nitrate, nickel chloride or nickel sulfate.
Further, the iron salt is selected from one or more of ferric nitrate, ferric chloride or ferric sulfate.
Further, the counter electrodes in step S1, step S2 are each independently selected from stainless steel mesh as the counter electrode.
Further, in step S2, the electrolyte solution containing the nickel salt and the iron salt further includes an ammonium salt compound; preferably the ammonium salt compound is selected from one or more of ammonium nitrate, ammonium chloride or ammonium sulphate.
Further, in step S3, the concentration of the electrolyte is 0.01 to 1.0mol/L.
Further, the reference electrodes in step S2 and step S3 are respectively and independently selected from one of mercury/oxidized mercury electrode, silver/silver chloride electrode or calomel electrode as the reference electrode.
Further, the sulfate is sodium thiosulfate.
Further, in step S1, the pretreatment of the nickel foam includes: and (3) taking foam nickel, and sequentially carrying out ultrasonic washing in acetone, ethanol and ultrapure water for 20 minutes to obtain the pretreated foam nickel.
Further, the working voltage of the constant voltage electrodeposition treatment is 500-800V, and the deposition time is 500-1200 s.
Further, in the step S1, the current density of the constant current electrodeposition treatment is-50 to-250 mA/cm 2 The deposition time is 300-900 s.
In order to achieve the above object, according to one aspect of the present invention, there is provided an oxygen evolution electrode material, which is obtained by the above-described method for producing an oxygen evolution electrode material.
Furthermore, the oxygen evolution electrode material takes foam nickel as a carrier, is internally doped with P element and S element, and has the structural formula of P/S-NiFe-LDH/NF.
Further, the oxygen evolution electrode material is in a nano lamellar structure, the lamellar structure is 30-80 nm in thickness and 1-5 mu m in size.
Further, the morphology of the oxygen evolution electrode material is petal-shaped morphology, and the size is 2-5 mu m.
According to another aspect of the invention, there is provided the use of an oxygen evolution electrode material in the field of hydrogen production by electrolysis of water.
By applying the technical scheme of the invention, the liquid cathode plasma electrolytic method is adopted for electrodeposition treatment, so that different elements can be rapidly driven into the surface crystal lattice of the sample, the surface roughness is increased, and the catalytic performance and the electrochemical performance of the material are further improved, so that the comprehensive performance of the material is better.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application. In the drawings:
FIG. 1 shows an SEM image (magnification of 5000 times) of an oxygen evolution electrode material prepared in example 1 of the present invention;
FIG. 2 shows an SEM image (magnification 20000) of an oxygen evolution electrode material produced in example 1 of the present invention; and
Fig. 3 shows linear sweep voltammograms of oxygen evolution electrode materials prepared in example 1, comparative example 1 and comparative example 2 in the present invention.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
According to the technical problems of complicated preparation steps or poor catalytic performance of the oxygen evolution electrode material in the prior art described in the background art part of the invention, the invention provides a preparation method of the oxygen evolution electrode material, which comprises the following steps: step S1, taking foam nickel for pretreatment to obtain pretreated foam nickel; s2, taking a reference electrode, a counter electrode and pretreated foam nickel as a working electrode, and performing constant current electrodeposition in electrolyte containing nickel salt and ferric salt under constant current to obtain an oxygen evolution electrode material precursor; and S3, taking a reference electrode, a counter electrode and an oxygen evolution electrode material precursor as working electrodes, and performing constant voltage electrodeposition in electrolyte containing phosphate and sulfate under constant voltage to obtain the oxygen evolution electrode material.
The invention provides an oxygen evolution electrode material prepared by a liquid cathode plasma electrolytic method, which is characterized in that firstly, foam nickel is pretreated to obtain treated foam nickel, a reference electrode, a counter electrode and the pretreated foam nickel are used as working electrodes in electrolyte containing nickel salt and ferric salt, and constant current electrodeposition is carried out under constant current to obtain an oxygen evolution electrode material precursor; the precursor of the oxygen evolution electrode material is used as a working electrode, a reference electrode and a counter electrode, and constant voltage electrodeposition is carried out in electrolyte containing phosphate and sulfate under constant voltage to obtain the oxygen evolution electrode material. By adopting the electrodeposition method, different elements (such as P, S and other hetero atoms) can be driven into the surface lattice of the sample in a short time, and the surface roughness can be increased, so that the catalytic performance and the electrochemical performance of the material are improved.
The electrodeposition method adopted by the invention is a liquid cathode plasma electrolysis method, and the principle is as follows: in an extremely high voltage environment, when the electrode is surrounded by a continuous plasma gas envelope, electrical breakdown of this vapor envelope can be achieved and a plasma discharge is carried out in the region of the photocathode, the plasma bubbles formed of which have extremely high temperatures, can be cooled by the surrounding electrolyte and implode in the vicinity of the cathode surface, and the driving and accelerating elements are incorporated/deposited. Meanwhile, the formed plasma bubbles have high local temperature and can melt the surface of the electrode, so that the bubbles can be quenched by adjacent electrolyte after being broken, and the surface morphology of the electrode is rough. Therefore, different elements can be driven into the surface lattice of the sample, and meanwhile, the surface roughness is increased, so that the catalytic activity area is increased, the catalytic active sites are increased, and the catalytic performance of the material is improved.
In a preferred embodiment, the phosphate is selected from one or more of sodium phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate or sodium hydrogen phosphate; the sulfate is selected from one or more of sodium thiosulfate, thioacetamide or thiourea, and more preferably sodium thiosulfate, so as to further improve the ion transmission speed of the electrolyte in the electroelectrolyte and improve the catalytic activity and stability of the oxygen evolution electrode material.
In a preferred embodiment, the constant current electrodeposition process has a current density of-50 to-500 mA/cm 2 The deposition time is 60-1800 s; further preferably, the constant current electrodeposition treatment has a current density of-50 to-250 mA/cm 2 The deposition time is 300-900 s; preferably, the working voltage of constant voltage electrodeposition treatment is 400-1000V, and the deposition time is 300-1800 s; further preferably, the working voltage of the constant voltage electrodeposition treatment is 500-800V, and the deposition time is 300-900 s; so as to further promote the smooth progress of the electrodeposition process, ensure that the deposition layer is more uniform and stable, and improve the structural stability and electrochemical performance of the product.
To further facilitate the smooth progress of the electrodeposition process, it is preferable to achieve a larger area, more uniform, lower energy consumption deposition of the coating, preferably the nickel salt is selected from one or more of nickel nitrate, nickel chloride or nickel sulfate, and the iron salt is selected from one or more of iron nitrate, iron chloride or iron sulfate.
In a preferred embodiment, the counter electrodes in the step S2 and the step S3 respectively and independently adopt stainless steel mesh as the counter electrode, and the reference electrode is selected from one of mercury/mercury oxide electrode, silver/silver chloride electrode or calomel electrode as the reference electrode, so as to further promote the full process of electrodeposition, improve the ionic conductivity, promote the smooth progress of reaction and improve the electrochemical stability of the oxygen evolution electrode material.
In a preferred embodiment, in step S2, the electrolyte containing the nickel salt and the iron salt further comprises an ammonium salt compound, and the further ammonium salt compound is one or more selected from ammonium nitrate, ammonium chloride or ammonium sulfate, so as to further modify the electrolyte, and further preferably, in step S3, the concentration of the electrolyte is 0.01-1.0 mol/L, so as to better achieve coating deposition with larger area, more uniformity and lower energy consumption.
In order to further remove the oil impurities remaining on the surface of the nickel foam, it is preferable that the pretreatment of the nickel foam in step S1 includes: and sequentially performing ultrasonic washing on the foam nickel in acetone, ethanol and ultrapure water for 20 minutes to obtain the pretreated foam nickel, so as to further avoid the influence of impurities on the performance of the foam nickel, improve the purity of the oxygen evolution electrode and ensure that the catalytic performance and the stability of the oxygen evolution electrode are better.
The invention also provides an oxygen evolution electrode material, which is prepared by the preparation method of the oxygen evolution electrode material. As previously described, the oxygen evolution electrode material exhibits good catalytic performance and stability.
In order to further improve the chemical stability and the structural stability of the oxygen evolution electrode material and improve the comprehensive performance of the oxygen evolution electrode material, preferably, the oxygen evolution electrode material takes foam nickel as a carrier, is internally doped with P element and S element, and has the structural formula of P/S-NiFe-LDH/NF.
In a preferred embodiment, the oxygen evolution electrode material is in a nano lamellar structure, the thickness of the lamellar structure is 30-80 nm, and the size of the lamellar structure is 1-5 mu m, so that the oxygen evolution electrode has higher surface roughness, more preferably, the oxygen evolution electrode material is in a petal-shaped morphology, and the size of the oxygen evolution electrode material is 2-5 mu m, so that the electronic structure can be effectively regulated, the electronic conductivity can be improved, and the chemical stability and the corrosion resistance of the catalyst can be enhanced.
The invention also provides an application of the oxygen evolution electrode material in the field of hydrogen production by water electrolysis.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
And washing the foam nickel with acetone, ethanol and ultrapure water for 20 minutes in sequence to obtain the treated foam nickel. Then, a mixed solution of 0.1M nickel nitrate, 0.1M ferric nitrate and 0.2M ammonium nitrate is prepared, stainless steel is used as a counter electrode, the cleaned foam nickel is used as a working electrode, mercury/mercury oxide is used as a reference electrode, and the temperature is-100 mA/cm 2 And (3) electrodepositing at the current density for 600s to obtain the NiFe-LDH/NF precursor. Finally, 0.01M NaH is taken 2 PO 2 With 0.01M Na 2 S 2 O 3 And (3) taking stainless steel as a counter electrode, niFe-LDH/NF as a working electrode and mercury/mercury oxide as a reference electrode as electrolyte, and performing electrodeposition under the condition of 600V working voltage for 15min to obtain an oxygen evolution electrode material P/S-NiFe-LDH/NF, wherein an SEM image (magnification 5000 times) of the oxygen evolution electrode material is shown in figure 1, and an SEM image (magnification 20000 times) of the oxygen evolution electrode material is shown in figure 2. It can be seen that the oxygen evolution electrode materialThe form of the nano lamellar structure is 30-80 nm in thickness and 1-5 mu m in size. The shape of the oxygen evolution electrode material is petal-shaped, and the size is 2-5 mu m.
Comparative example 1
And washing the foam nickel with acetone, ethanol and ultrapure water for 20 minutes in sequence to obtain the treated foam nickel. Then, a mixed solution of 0.1M nickel nitrate, 0.1M ferric nitrate and 0.2M ammonium nitrate is prepared, stainless steel is used as a counter electrode, the cleaned foam nickel is used as a working electrode, mercury/mercury oxide is used as a reference electrode, and the temperature is-100 mA/cm 2 And (3) electrodepositing at the current density for 600s to obtain the NiFe-LDH/NF precursor. Finally, naH is taken 2 PO 2 And placing sulfur powder in a porcelain boat, and heating to 500 ℃ at a speed of 5 ℃/min at the upstream of a tube furnace sample, and keeping the temperature for 2 hours to obtain the oxygen evolution electrode material.
Comparative example 2
The foam nickel is washed by acetone, ethanol and ultrapure water for 20 minutes. Preparation of NiFe-LDH/NF precursor: preparing a mixed solution of 0.1M nickel nitrate, ferric nitrate and 0.2M ammonium nitrate, taking stainless steel as a counter electrode, taking cleaned foam nickel as a working electrode, taking mercury/mercury oxide as a reference electrode, and performing treatment on the mixture at-100 mA/cm 2 Electrodeposition was performed at a current density for 600s.
Performance test:
the oxygen evolution electrode materials prepared in the above examples and comparative examples were placed in a 1M KOH solution to test their oxygen evolution overpotential, and the results are shown in Table 1.
TABLE 1
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
from the test results of the above example 1 and the comparative examples 1 and 2, it can be found that when the technical scheme of the present invention is adopted, particularly after the electrode material precursor is prepared, the oxygen evolution electrode material obtained by further performing electrodeposition by a liquid cathode plasma electrolysis method has a lower oxygen evolution overpotential compared with the electrode material obtained by the conventional tube furnace heating method in the comparative example 1; and compared with the oxygen evolution electrode material obtained by performing constant current electrodeposition only once in comparative example 2, the oxygen evolution electrode material has lower oxygen evolution overpotential and better catalytic performance. In particular, the linear sweep voltammograms of the oxygen evolution electrode materials prepared in example 1, comparative example 1 and comparative example 2 in fig. 3 show that the oxygen evolution electrode materials prepared by the present invention have higher activity and better performance.
In summary, by adopting the technical scheme of the invention, the liquid cathode plasma electrolytic method is adopted for the electrodeposition treatment, so that different elements can be driven into the surface crystal lattice of the sample in a short time, the surface roughness can be increased, and the catalytic performance and the electrochemical performance of the material are further improved, so that the comprehensive performance of the material is better.
While this specification contains many specific implementation details, these should not be construed as limitations on the scope of any invention or of what may be claimed, but rather as descriptions of features of specific embodiments of particular inventions. Certain features that are described in this specification in the context of separate embodiments can also be implemented in combination in a single embodiment. On the other hand, the various features described in the individual embodiments may also be implemented separately in the various embodiments or in any suitable subcombination. Furthermore, although features may be acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a subcombination or variation of a subcombination.
Similarly, although operations are depicted in the drawings in a particular order, this should not be understood as requiring that such operations be performed in the particular order shown or in sequential order, or that all illustrated operations be performed, to achieve desirable results. In some cases, multitasking and parallel processing may be advantageous. Moreover, the separation of various system modules and components in the embodiments described above should not be understood as requiring such separation in all embodiments, and it should be understood that the described program components and systems can generally be integrated together in a single software product or packaged into multiple software products.
Thus, particular embodiments of the subject matter have been described. Other embodiments are within the scope of the following claims. In some cases, the actions recited in the claims can be performed in a different order and still achieve desirable results. Furthermore, the processes depicted in the accompanying drawings are not necessarily required to be in the particular order shown, or sequential order, to achieve desirable results. In some implementations, multitasking and parallel processing may be advantageous.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (16)
1. A method for preparing an oxygen evolution electrode material, which is characterized by comprising the following steps:
step S1, taking foam nickel for pretreatment to obtain pretreated foam nickel;
s2, taking a reference electrode, a counter electrode and the pretreated foam nickel as a working electrode, and performing constant current electrodeposition in electrolyte containing nickel salt and ferric salt under constant current to obtain an oxygen evolution electrode material precursor, wherein the precursor is NiFe-LDH/NF;
step S3, taking a reference electrode, a counter electrode and a precursor of the oxygen evolution electrode material as working electrodes, and adding NaH 2 PO 2 With Na and Na 2 S 2 O 3 In the electrolyte of (2), adopting a liquid cathode plasma electrolytic method under constant voltage to obtain the oxygen evolution electrode material; wherein the working voltage of the constant voltage treatment is 400-1000V, and the deposition time is 300-1800 s.
2. The method for preparing oxygen evolution electrode material according to claim 1, wherein the constant current electrodeposition treatment has a current density of-50 to-500 mA/cm 2 The deposition time is 60-1800 s.
3. The method for producing an oxygen evolution electrode material according to claim 1, wherein the nickel salt is selected from one or more of nickel nitrate, nickel chloride or nickel sulfate.
4. The method for producing an oxygen evolution electrode material according to claim 1, wherein the iron salt is one or more selected from the group consisting of ferric nitrate, ferric chloride and ferric sulfate.
5. The method according to claim 1, wherein the counter electrodes in step S2 and step S3 are each independently made of stainless steel mesh.
6. The method for producing an oxygen evolution electrode material according to claim 1, wherein in the step S2, the electrolyte containing the nickel salt and the iron salt further comprises an ammonium salt compound; and/or
The ammonium salt compound is selected from one or more of ammonium nitrate, ammonium chloride or ammonium sulfate.
7. The method for producing an oxygen evolution electrode material according to claim 1, wherein in the step S3, the concentration of the electrolyte is 0.01 to 1.0mol/L.
8. The method according to claim 1, wherein the reference electrode in step S2 and step S3 is independently selected from one of a mercury/mercury oxide electrode, a silver/silver chloride electrode and a calomel electrode.
9. The method for preparing an oxygen evolution electrode material according to claim 1, wherein the pre-treating of the foam nickel in the step S1 comprises: and sequentially performing ultrasonic washing on the foam nickel in acetone, ethanol and ultrapure water for 20min to obtain the pretreated foam nickel.
10. The method for preparing an oxygen evolution electrode material according to claim 1, wherein the constant voltage treatment has a working voltage of 500-800 v and a deposition time of 500-1200 s.
11. The method for producing oxygen evolution electrode material according to claim 1, wherein in the step S1, the constant current electrodeposition treatment has a current density of-50 to-250 mA/cm 2 The deposition time is 300-900 s.
12. Oxygen evolution electrode material, characterized in that it is obtained from the method of manufacturing an oxygen evolution electrode material according to any one of claims 1 to 11.
13. The oxygen evolution electrode material according to claim 12, wherein the oxygen evolution electrode material takes foam nickel as a carrier, is internally doped with P element and S element, and has a structural formula of P/S-NiFe-LDH/NF.
14. The oxygen evolution electrode material according to claim 12, wherein the oxygen evolution electrode material has a nano lamellar structure, the lamellar structure has a thickness of 30-80 nm and a size of 1-5 μm.
15. The oxygen evolution electrode material according to claim 12, wherein the oxygen evolution electrode material has a petal-shaped morphology and a size of 2-5 μm.
16. Use of an oxygen evolution electrode material according to any one of claims 12 to 15 in the field of hydrogen production by electrolysis of water.
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| CN113699548A (en) * | 2021-08-25 | 2021-11-26 | 北京化工大学 | Oxygen evolution catalytic electrode protected by weak acid salt layer, preparation and application thereof, and method for improving stability of oxygen evolution reaction of oxygen evolution catalytic electrode |
| CN114959768A (en) * | 2022-07-19 | 2022-08-30 | 清华大学 | Nickel-based oxygen evolution electrode, and preparation method and application thereof |
| CN115976567A (en) * | 2022-12-29 | 2023-04-18 | 陕西科技大学 | Chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst, and preparation method and application thereof |
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| CN113699548A (en) * | 2021-08-25 | 2021-11-26 | 北京化工大学 | Oxygen evolution catalytic electrode protected by weak acid salt layer, preparation and application thereof, and method for improving stability of oxygen evolution reaction of oxygen evolution catalytic electrode |
| CN114959768A (en) * | 2022-07-19 | 2022-08-30 | 清华大学 | Nickel-based oxygen evolution electrode, and preparation method and application thereof |
| CN115976567A (en) * | 2022-12-29 | 2023-04-18 | 陕西科技大学 | Chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst, and preparation method and application thereof |
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