CN114808021B - Preparation method of porous foam water electrolysis hydrogen production electrode - Google Patents
Preparation method of porous foam water electrolysis hydrogen production electrode Download PDFInfo
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- CN114808021B CN114808021B CN202210598381.2A CN202210598381A CN114808021B CN 114808021 B CN114808021 B CN 114808021B CN 202210598381 A CN202210598381 A CN 202210598381A CN 114808021 B CN114808021 B CN 114808021B
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- 239000006260 foam Substances 0.000 title claims abstract description 33
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000001257 hydrogen Substances 0.000 title claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000000151 deposition Methods 0.000 claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000004070 electrodeposition Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- 229910000640 Fe alloy Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 230000008021 deposition Effects 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 239000004619 high density foam Substances 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 229910052692 Dysprosium Inorganic materials 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 5
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 229910003266 NiCo Inorganic materials 0.000 description 13
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
-
- 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
- C25B11/053—Electrodes comprising one or more electrocatalytic coatings on a substrate characterised by multilayer electrocatalytic coatings
-
- 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
- C25D3/20—Electroplating: Baths therefor from solutions of iron
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- 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
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a porous foam water electrolysis hydrogen production electrode. The method comprises the steps of using foam as a template, and preparing conductive foam by simply soaking conductive ink; firstly, taking metal salt as a precursor, and depositing iron or iron alloy on the surface of foam in a quick electrolysis mode and an electrodeposition mode to provide support and strength requirements; then depositing a nickel-iron, cobalt-nickel, iron-cobalt-nickel and other catalytic layers; then depositing trace amounts of mono-, di-and multi-element compounds of ruthenium, iridium, rare earth to catalytically promote mono-atomic, cluster and nanoparticle sites; and finally, processing at different temperatures to realize stabilization. The preparation method solves the problems of low activity and poor stability faced by the alkaline water electrolysis electrode, has short process flow and simple method, and can realize batch continuous production.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a preparation method of a porous foam water electrolysis hydrogen production electrode.
Background
Currently, the use of fossil energy in large quantities poses a great hazard to the environment. In order to reduce the emission of carbon dioxide and achieve the goals of peak carbon number 2030 and carbon neutralization number 2060, the development of hydrogen energy is a vital link. In the current hydrogen production technology (methane reforming hydrogen production, coal hydrogen production, water electrolysis hydrogen production and the like), the water electrolysis hydrogen production is the most green hydrogen production mode, and has zero carbon emission, and the prepared hydrogen has high purity, so that the development energy of the water electrolysis hydrogen production can assist in accelerating decarburization process and energy structure transformation.
The electrolyzed water is mainly divided into two half reactions, hydrogen is separated out at the cathode, and oxygen is separated out at the anode. Because of the complex reaction process involving four electrons at the anode, the anode reaction requires a higher overpotential than the cathode reaction at the same current density, which is a rate control step of the electrolytic water reaction, making the development of anode catalysts more interesting to researchers. At present, commercial catalysts are all noble metal-based catalysts, such as ruthenium, iridium and the like, and although the performance of the catalysts is good, the reserves in the earth are very limited, the price is high, the stability is poor, and the original performance is difficult to maintain under high current density, so that the development of cheap and efficient catalytic materials is very important.
The research shows that the non-noble metal nickel, cobalt and iron-based catalyst has good OER performance in alkaline environment, and the foam material has good conductivity, is easy for electron transmission, has rich pores and is beneficial to gas discharge. Although many electrolytic water oxygen evolution catalysts with excellent performance are developed at present, some of them have complicated preparation methods, long time, high temperature treatment and continuous batch preparation.
Disclosure of Invention
The invention mainly aims to provide a preparation method of the porous foam water electrolysis hydrogen production electrode, which is simple in preparation method, short in preparation time, capable of continuously preparing in batches, and capable of simultaneously adding trace noble metals and rare earth elements, so that good OER catalytic performance and stability can be achieved.
In order to achieve the above purpose, the preparation method of the porous foam water electrolysis hydrogen production electrode provided by the invention comprises the following steps:
(1) Taking a high-density foam sheet material as a substrate, and soaking the substrate through conductive ink to obtain a high-conductivity foam substrate;
(2) Preparing an iron-based mixed solution as electrolyte, passing the high-conductivity foam substrate through an electrolytic tank in a roller mode, and carrying out electrolytic deposition for 5-200 seconds to enable iron or iron alloy to be deposited on the surface of the high-conductivity foam substrate, so as to obtain an iron-based foam skeleton;
(3) Electrodepositing the iron-based foam skeleton for 1-200 seconds through electrolyte containing at least one of Co, mn and Fe and Ni to prepare a water electrolysis catalytic layer;
(4) Depositing an Ir-rare earth catalytic layer or a Ru-rare earth catalytic layer on the water electrolysis catalytic layer by means of impregnation or electrodeposition;
(5) And calcining the substrate with the Ir-rare earth catalytic layer or Ru-rare earth catalytic layer prepared by the dipping method.
Preferably, the high-density foam sheet material in the step (1) comprises one or more of porous polyurethane, melamine sponge and polyester sponge, and the conductive ink is graphite or graphene.
Preferably, the iron-based foam skeleton in the step (2) has an iron content of more than 80%, the auxiliary metal comprises one or more of Cr, ni and Co, and the supporting layer formed by iron or an iron alloy has a thickness of 500 nm to 1000 μm.
Preferably, in the water electrolysis catalysis layer of the step (3), the content of Ni is more than 50%.
Preferably, the concentration of the total amount of metal in the electrolyte of step (3) is 0.1M/L.
Preferably, the deposition potential interval of the electrodeposition in the step (4) is-0.5V to-2.5V, and the deposition time is less than 30min.
Preferably, the concentration of the solution used for the impregnation in the step (4) is less than or equal to 0.01mol/L, and the time is 0.5-3h.
Preferably, the Ir-rare earth catalytic layer or Ru-rare earth catalytic layer in the step (4) has a Ir and Ru loading of less than 0.2mg cm -2 。
Preferably, the calcination temperature in the step (5) is 300-700 ℃ and the time is 1-4h.
According to the invention, a high-density foam sheet material is used as a substrate, graphite and graphene ink are soaked to prepare a high-conductivity foam substrate, a multi-stage continuous roll-to-roll electrolysis device is used for continuously depositing a multi-layer foam iron-based supporting layer, metal oxides such as cobalt, nickel, iron and manganese, a metal catalytic layer, ruthenium, iridium, rare earth single atoms, clusters and nanoparticle cocatalysts, and then oxygen and hydrogen are used for calcining to improve the stability and activity of the catalytic layer, so that a multi-layer foam electrode with an inner layer of iron and a surface layer of nickel-iron, cobalt-nickel, iron-cobalt-nickel and noble metals of ruthenium, iridium and rare earth cocatalytic layers is prepared. Wherein, the foam iron-based supporting layer is mainly cheaper iron-based single metal or bimetallic alloy, the iron content is more than 80%, the auxiliary metal can be Cr, ni, co and the like, and the thickness of the supporting layer is 500 nanometers to 1000 micrometers, so that the foam iron-based supporting layer has stronger mechanical strength. The noble metal loading in ruthenium, iridium, rare earth monoatoms, clusters and nanoparticle promoters is small.
Drawings
FIG. 1 is a comparison of the performance of the NiCo/NF catalyst prepared in example 1 by depositing Ni and Co in 0.1M KOH at different deposition potentials.
FIG. 2 is a comparison of the performance of the NiCo/NF catalyst produced in example 1 by depositing Ni and Co in 0.1M KOH at different deposition times.
FIG. 3 is a comparison of the performance of the NiCo/NF catalyst produced in example 1 by depositing Ni and Co at different nickel-cobalt concentration ratios in 0.1M KOH.
FIG. 4 is a comparison of the oxygen evolution performance of NF, niCo/NF, niCo-RuCe-air/NF in 1M KOH in example 1.
FIG. 5 is a graph comparing Tafel slopes of NiCo/NF and NiCo-RuCe-air/NF in example 1.
FIG. 6 is a NiCo-RuCe-air/NF at 50mA cm in example 1 -2 A chronograph potential at current density.
FIG. 7 is a schematic diagram of a three-stage electrolysis apparatus used in example 2;
FIG. 8 is a comparison of the performance of the NiFe/NF catalyst produced in example 2 by depositing Ni and Fe at different deposition potentials in 0.1M KOH.
FIG. 9 is a comparison of the performance of the NiFe/NF catalyst produced in example 2 with Ni and Fe deposited in 0.1M KOH at various deposition times.
FIG. 10 is a comparison of the performance of the NiFe/NF catalyst produced in example 2 with Ni and Fe deposited at different nickel-iron concentration ratios in 0.1M KOH.
FIG. 11 is a graph comparing the OER activities of NF, niFe/NF, and NiFe-RuDy/NF in example 2.
FIG. 12 is a graph comparing OER performance of NF, niCo/NF, and NiCo-IrCe-air/NF in example 3.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting thereof.
Example 1: preparation of NiCo-RuCe-air/NF and OER performance thereof
(1) The porous polyurethane sponge is used as a substrate, and the surface of the porous polyurethane sponge is uniformly coated with conductive graphite by soaking in graphite slurry.
(2) Preparing ferric salt solution, adding an electrolysis auxiliary reagent, and enabling the porous polyurethane conductive sponge to pass through an electrolytic tank in a roller mode, and carrying out electrolytic deposition for 120 seconds to realize iron deposition, wherein the thickness is 5-10 microns, so as to construct the porous iron-based alloy electrode skeleton.
(3) Nitrates of metallic nickel and cobalt were prepared and mixed uniformly as an electrodeposition solution, and the total metal concentration of the resulting solution was 0.1M/L.
(4) Soaking the porous iron-based alloy electrode skeleton in the deposition solution for about 1min to enable the electrode to be fully contacted with the deposition solution, and selecting the optimal deposition conditions by changing different deposition potentials, deposition time and nickel-cobalt concentration ratio, wherein the deposited NiCo/NF is dried for standby, referring to fig. 1-3.
(5) Preparing RuCe solution with concentration of 0.01M/L by using ruthenium chloride and cerium nitrate, immersing NiCo/NF obtained in the step (4) into the RuCe solution for 2 hours, then washing with pure water, and drying. Wherein the Ru loading is 0.087mg cm -2 。
(6) Calcining the electrode material impregnated with RuCe in a muffle furnace at 400 ℃ for 1h, wherein the heating rate is 5 ℃/min.
(7) The three-electrode system is adopted, mercury/oxidized mercury is used as a reference electrode, a graphite rod is used as a counter electrode, and the prepared material is used as a working electrode to test in 0.1M KOH and 1M KOH. The material was analyzed for overpotential with an LSV plot, where the sweep rate was 10mV/s, with no iR compensation.
FIGS. 1-3 are graphs showing that the performance of the catalyst under different deposition conditions in 0.1M KOH can be compared to obtain the optimal deposition condition, and the deposited NiCo/NF has the optimal performance at a deposition potential of-0.9V for a deposition time of 200s and a nickel-cobalt ratio of 1:1.
As can be seen from FIG. 4, the performance of NiCo/NF after being immersed in RuCe and calcined in air was improved, and it was found that NiCo-RuCe-air/NF was tested in 1M KOH at a current density of 50mA/cm 2 And 100mA/cm 2 The overpotential was 316mV and 364mV, respectively, which were higher than 378mV and 430mV of NiCo/NF. LSV plots were plotted at a scan rate of 1mV/s and test results plotted as overpotential versus logic to give a Tafil curve, as in FIG. 5, where the data were all manually IR 100% compensated. As can be seen from FIG. 3, the Tafil slope of NiCo-RuCe-air/NF was 57.82mV/dec, which is superior to that of NiCo/NF (59.09 mV/dec). FIG. 6 is a stability test of NiCo-RuCe-air/NF at 50mA/cm 2 Can be maintained for 38 hours under the current density, which shows that the catalyst has good OER catalytic activity and stability.
Example 2: preparation of NiFe-RuDy/NF and its OER Performance, the equipment used in the preparation method of this example is three-stage electrolysis equipment, please refer to FIG. 7.
(1) Melamine sponge is used as a substrate, and the surface of the substrate is uniformly coated with conductive graphene by soaking in graphene slurry.
(2) Preparing a mixed solution of ferric salt and nickel salt, adding an electrolysis auxiliary reagent, and carrying out electrolytic deposition on the melamine conductive sponge in a roller mode for 120 seconds through an electrolytic tank to realize iron-nickel alloy codeposition, wherein the thickness is 5-10 micrometers, so as to construct the porous iron-based alloy electrode framework.
(3) The nitrate of metallic nickel and iron is prepared and mixed uniformly, and the obtained solution is used as electrodeposition liquid, and the total metal concentration of the obtained solution is 0.1M/L.
(4) The porous iron-based alloy electrode skeleton is soaked in the deposition solution for about 1min, so that the electrode is fully contacted with the deposition solution, and the optimal deposition conditions are selected by changing different deposition potentials, deposition time and nickel-iron concentration ratio, specifically referring to fig. 8-10, and the deposited NiFe/NF is dried for standby.
(5) Preparing 0.01M/L RuDy solution by using ruthenium chloride and dysprosium nitrate, soaking the NiFe/NF obtained in the step (4) in the RuDy solution for about 1min, and filling the NiFe/NF with the deposition solutionAnd (3) carrying out CV (constant velocity) cyclic scanning deposition at-0.5V to-2.5V vs Hg/HgO, wherein the number of turns is 4, the scanning speed is 10mV/s, removing the deposition liquid on the surface by using pure water after deposition, and drying and testing. Wherein the Ru loading is 0.144mg cm -2 。
(6) The three-electrode system is adopted, mercury/oxidized mercury is used as a reference electrode, a graphite rod is used as a counter electrode, and the prepared material is used as a working electrode to test in 0.1M KOH and 1M KOH. The material was analyzed for overpotential with an LSV plot, where the sweep rate was 10mV/s, with no iR compensation.
FIGS. 8-10 are graphs showing that the performance of NiFe/NF catalysts at different deposition conditions in 0.1M KOH gave the optimum deposition conditions for NiFe/NF performance at a deposition potential of-1.1V for a deposition time of 400s and a nickel-iron ratio of 6:1.
FIG. 11 is a LSV plot of NiFe-RuDy/NF versus NiFe/NF, as can be seen at a current density of 10mA/cm 2 、100mA/cm 2 、200mA/cm 2 At current, the overpotential of NiFe-RuDy/NF is 126mV, 220mV and 353mV respectively, and compared with 137mV, 240mV and 370mV of NiFe/NF, the overpotential is reduced, and the over-potential is extremely excellent in OER activity and better than most of the OER catalysts reported at present.
Example 3: preparation of NiCo-IrCe-air/NF and OER performance thereof
(1) The porous polyurethane sponge is used as a substrate, and the surface of the porous polyurethane sponge is uniformly coated with conductive graphite by soaking in graphite slurry.
(2) Preparing ferric salt solution, adding an electrolysis auxiliary reagent, and enabling the porous polyurethane conductive sponge to pass through an electrolytic tank in a roller mode, and carrying out electrolytic deposition for 120 seconds to realize iron deposition, wherein the thickness is 5-10 microns, so as to construct the porous iron-based alloy electrode skeleton.
(3) Nitrates of metallic nickel and cobalt were prepared and mixed uniformly as an electrodeposition solution, and the total metal concentration of the resulting solution was 0.1M/L.
(4) The porous iron-based alloy electrode skeleton is soaked in the deposition solution for about 1min, so that the electrode is fully contacted with the deposition solution, and the optimal deposition conditions are selected by changing different deposition potentials, deposition time and nickel-cobalt concentration ratio, and the deposited NiCo/NF is dried for standby by referring to figures 1-3.
(5) IrCe solution with the concentration of 0.005M/L is prepared by using iridium chloride and cerium nitrate, and NiCo/NF obtained in the step (4) is immersed into the IrCe solution for 2 hours, and then is washed clean by pure water and dried. Wherein the Ir loading is 0.168mg cm -2 。
(6) Calcining the electrode material impregnated with IrCe in a muffle furnace at 400 ℃ for 1h, wherein the heating rate is 5 ℃/min.
(7) The three-electrode system is adopted, mercury/oxidized mercury is used as a reference electrode, a graphite rod is used as a counter electrode, and the prepared material is used as a working electrode to test in 0.1M KOH and 1M KOH. The material was analyzed for overpotential with an LSV plot, where the sweep rate was 10mV/s, with no iR compensation.
FIG. 12 is a LSV plot of NF, niCo/NF and NiCo-IrCe-air/NF, as can be seen at a current density of 50mA/cm 2 、100mA/cm 2 Under current, the overpotential of NiCo-IrCe-air/NF is 331mV and 378mV respectively, and compared with the overpotential of NiCo/NF which is 378mV and 430mV, the overpotential is reduced, and the OER activity is better.
Claims (7)
1. The preparation method of the porous foam water electrolysis hydrogen production electrode is characterized by comprising the following steps of:
(1) Taking a high-density foam sheet material as a substrate, and soaking the substrate through conductive ink to obtain a high-conductivity foam substrate;
(2) Preparing an iron-based mixed solution as electrolyte, passing the high-conductivity foam substrate through an electrolytic tank in a roller mode, and carrying out electrolytic deposition for 5-200 seconds to enable iron or iron alloy to be deposited on the surface of the high-conductivity foam substrate, so as to obtain an iron-based foam skeleton, wherein the iron-based foam skeleton in the step (2) contains more than 80% of iron, and auxiliary metals comprise one or more of Cr, ni and Co;
(3) Electrodepositing the iron-based foam skeleton for 1-200 seconds through electrolyte containing Ni and at least one of Co, mn and Fe to prepare a water electrolysis catalytic layer, wherein the content of Ni in the water electrolysis catalytic layer in the step (3) is more than 50%;
(4) Depositing an Ir-rare earth catalytic layer or a Ru-rare earth catalytic layer on the water electrolysis catalytic layer by dipping or electrodeposition, wherein the Ir-rare earth catalytic layer or the Ru-rare earth catalytic layer in the step (4) has the Ir and Ru loading less than 0.2mg cm -2 Rare earth elements are selected from Dy or Ce;
(5) And calcining the substrate with the Ir-rare earth catalytic layer or Ru-rare earth catalytic layer prepared by the dipping method.
2. The method for preparing a hydrogen-producing electrode by hydrolyzing porous foam water as claimed in claim 1, wherein the high-density foam sheet material in the step (1) comprises one or more of porous polyurethane, melamine sponge and polyester sponge, and the conductive ink is graphite or graphene.
3. The method for producing a hydrogen-producing electrode by the electrolysis of water with a porous foam according to claim 1, wherein the supporting layer formed of iron or an iron alloy has a thickness of 500 nm to 1000 μm.
4. The method for producing a hydrogen-producing electrode by electrolysis of water with a porous foam according to claim 1, wherein the concentration of the total amount of metal in the electrolyte of step (3) is 0.1M/L.
5. The method for producing a hydrogen-producing electrode by electrolysis of porous foam water as claimed in claim 1, wherein the deposition potential interval of electrodeposition in the step (4) is-0.5V to-2.5V, and the deposition time is less than 30min.
6. The method for producing a hydrogen-producing electrode by electrolysis of a porous foam water as claimed in claim 1, wherein the concentration of the solution used for the impregnation in the step (4) is 0.01mol/L or less for 0.5 to 3 hours.
7. The method for producing a hydrogen-producing electrode by electrolysis of a porous foam water as claimed in claim 1, wherein the calcination temperature in the step (5) is 300 to 700 ℃ for 1 to 4 hours.
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| US5084144A (en) * | 1990-07-31 | 1992-01-28 | Physical Sciences Inc. | High utilization supported catalytic metal-containing gas-diffusion electrode, process for making it, and cells utilizing it |
| CN109234755A (en) * | 2018-10-30 | 2019-01-18 | 江苏大学 | A kind of layered double hydroxide composite construction elctro-catalyst and preparation method |
| CN110106517A (en) * | 2019-04-22 | 2019-08-09 | 江苏大学 | Cobalt sulfide/layered double hydroxide composite electrocatalyst and preparation method thereof |
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| US5084144A (en) * | 1990-07-31 | 1992-01-28 | Physical Sciences Inc. | High utilization supported catalytic metal-containing gas-diffusion electrode, process for making it, and cells utilizing it |
| CN109234755A (en) * | 2018-10-30 | 2019-01-18 | 江苏大学 | A kind of layered double hydroxide composite construction elctro-catalyst and preparation method |
| CN110106517A (en) * | 2019-04-22 | 2019-08-09 | 江苏大学 | Cobalt sulfide/layered double hydroxide composite electrocatalyst and preparation method thereof |
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| "An outstanding NiFe/NF oxygen evolution reaction boosted by the hydroxyl oxides";Chen, Yuehui等;《ELECTROCHIMICA ACTA》;第442卷;文献号 141862 * |
| "High-performance Oxygen Evolution Catalyst Enabled by Interfacial Effect between CeO2 and FeNi Metal-organic Framework";Dai Mimi等;《ACTA CHIMICA SINICA》;第78卷(第4期);第355-362页 * |
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