CN116555812A - Hydrogen evolution electrode containing light rare earth and preparation method thereof - Google Patents
Hydrogen evolution electrode containing light rare earth and preparation method thereof Download PDFInfo
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- CN116555812A CN116555812A CN202310686506.1A CN202310686506A CN116555812A CN 116555812 A CN116555812 A CN 116555812A CN 202310686506 A CN202310686506 A CN 202310686506A CN 116555812 A CN116555812 A CN 116555812A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 51
- 239000001257 hydrogen Substances 0.000 title claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 26
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000009713 electroplating Methods 0.000 claims abstract description 55
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- 239000006260 foam Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- 238000007747 plating Methods 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 17
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 15
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 15
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 14
- 239000001393 triammonium citrate Substances 0.000 claims description 14
- 235000011046 triammonium citrate Nutrition 0.000 claims description 14
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910000765 intermetallic Inorganic materials 0.000 claims description 4
- 238000005457 optimization Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 33
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000004070 electrodeposition Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 239000011669 selenium Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 238000001075 voltammogram Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910018502 Ni—H Inorganic materials 0.000 description 1
- 229910001370 Se alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002815 nickel Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography 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
- C25B11/075—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
- C25B11/055—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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to the technical field of hydrogen production by water electrolysis, in particular to a hydrogen evolution electrode containing light rare earth and a preparation method thereof. The hydrogen evolution electrode containing light rare earth comprises a foam nickel substrate and a Ni-Se-La coating electroplated on the surface of the substrate, wherein the coating comprises the following components in percentage by atom: ni: 30-50%; se: 20-40%; la: 30-40%. The preparation method comprises the following steps: using the foam nickel with clean and dry surface as a working electrode, immersing the working electrode in electroplating solution at 15-3Electroplating at 0 deg.c for at least 10min, washing and drying to obtain the product with current density of 10-80 mA and pH value of 4-6. The electrode designed and prepared by the invention is tested in KOH solution with the temperature of 25 ℃ and the mol/L, and the obtained electrode is tested in 10mA cm ‑2 The overpotential at the current density of (c) can be reduced to 29mV.
Description
Technical Field
The invention relates to the technical field of hydrogen production by water electrolysis, in particular to a hydrogen evolution electrode containing light rare earth and a preparation method thereof.
Background
Increasingly, there is an increase inLong energy consumption and environmental pressures make technical development challenging. Hydrogen (H) 2 ) As potential clean energy source candidate energy source, the energy density is high (120-140 MJ.kg -1 ) The characteristics of high energy efficiency, no pollution and the like are paid attention to. In various hydrogen production methods, the electrochemical splitting water Hydrogen Evolution Reaction (HER) has the advantages of stable operation, clean production and high purity. Considering the improvement of renewable energy (such as hydrogen, wind energy and solar energy) efficiency and the high cost of noble metal catalysts, electrochemical water electrolysis HER is expected to become a mainstream hydrogen production method. Therefore, the non-noble metal-based electrocatalyst with high cost performance is developed, high HER performance is realized, and the method has important significance for water electrolysis.
Various non-noble metal electrocatalysts, such as nickel-based electrocatalysts, have good chemical stability and HER activity in alkaline media. The outer layer of the nickel atom is provided with unpaired 3d electrons, and Ni-H adsorption bonds are easily formed with 1s orbits of H atoms in hydrogen evolution reaction, so that the electrocatalytic performance of the alloy electrocatalyst is improved, but the electrocatalytic performance of pure nickel is limited, so that the electrocatalytic performance of the alloy electrocatalyst is improved by adopting an alloying thought. As in patent CN202210948444.2, an attempt was made to use Ni-Se-Co as a hydrogen evolution electrode, in which an electrodeposition process was used to prepare a product which was tested in a KOH solution at 25℃and 1mol/L, and the electrode was obtained at 10mA cm -2 The overpotential at current density is greater than 76mv; dy was also attempted to be introduced into Ni-Se in the early stage of the subject group, specifically, see "One-step galvanostatic electrodeposition of Ni-Se-Dy film on Ni foam for hydrogen evolution reaction in alkaline solution", in which the obtained product was obtained at 10 mA.cm -2 The overpotential at the current density is about 72mV. And meanwhile, searching and finding: the technology for preparing high-quality hydrogen evolution electrodes by using Ni-Se alloy as a matrix and introducing light rare earth through electrodeposition has been recently reported.
Disclosure of Invention
The invention is based on the prior art, especially on the basis of the earlier study of the subject group, and attempts are made for the first time to further reduce the hydrogen evolution potential of the product and ensure the stability of the product by utilizing light rare earth.
The hydrogen evolution electrode with lower overpotential and better stability is obtained after the optimization.
The invention relates to a hydrogen evolution electrode containing light rare earth, which comprises a foam nickel substrate and a Ni-Se-La coating electroplated on the surface of the substrate, wherein the coating comprises the following components in percentage by atom: ni: 30-50%; se: 20-40%; la: 30-40%. La in the present invention means La element.
The invention relates to a hydrogen evolution electrode containing light rare earth, which is electroplated on a Ni-Se-La coating on the surface of a substrate, wherein intermetallic compounds are in a hexagonal structure and form a micron-level structure in a form of embedding a sheet layer.
Preferably, the hydrogen evolution electrode containing light rare earth comprises the following components in atom percent: ni: 45-46%; se: 24-25%; la: 30-31%.
As a further preferred aspect, the present invention provides a hydrogen evolution electrode comprising a light rare earth, wherein the plating layer comprises the following components in atomic percent: ni:45.4 to 45.6 percent; se:24.1 to 24.2 percent; la:30.1 to 30.4 percent.
The invention relates to a preparation method of a hydrogen evolution electrode containing light rare earth, which comprises the following steps:
taking the foam nickel with clean and dry surface as a working electrode, immersing the working electrode into electroplating solution, electroplating at 15-30 ℃ for at least 10min, cleaning and drying to obtain a product after electroplating, controlling the current density to be 10-80 mA and the pH value of the electroplating solution to be 4-6 during electroplating, wherein the electroplating solution consists of the following components:
50-140 g/L of nickel sulfate, 1-10 g/L of selenium oxide, 25-35g/L of sodium chloride, 13-14g/L of boric acid, 13-13.5g/L of sulfosalicylic acid, 15-25g/L of tri-ammonium citrate and 1-5 g/L of lanthanum chloride.
Preferably, the electroplating solution consists of the following components:
130-140 g/L of nickel sulfate, 5-6 g/L of selenium oxide, 28-30g/L of sodium chloride, 13-14g/L of boric acid, 13-13.5g/L of sulfosalicylic acid, 18-22g/L of tri-ammonium citrate and 4-5 g/L of lanthanum chloride.
As a further preferred aspect, the plating solution is composed of the following components:
139-140 g/L of nickel sulfate, 5.8-6 g/L of selenium oxide, 29.5-30g/L of sodium chloride, 13.3-13.4g/L of boric acid, 13.3-13.4g/L of sulfosalicylic acid, 19.5-22g/L of tri-ammonium citrate and 4.9-5 g/L of lanthanum chloride.
In industrial application, the foam nickel with clean and dry surface can be obtained by washing with hydrochloric acid, washing with absolute ethyl alcohol or ultrasonic treatment and then drying.
Preferably, the temperature is controlled to 18 to 22 ℃ during plating.
Preferably, the current density is controlled to be 48-52 mA during electroplating.
Preferably, the control time for plating is 55 to 65 minutes.
In the electrodeposition process developed by the invention, the composition of the electroplating solution (comprising the concentration of each component) and the electroplating process parameters have very obvious influence on Se and La deposition.
As a further preferable scheme, the foam nickel with clean and dry surface is used as a working electrode, the working electrode is immersed into electroplating solution, electroplating is carried out for 60min at 20 ℃, after the electroplating is finished, the product is obtained by cleaning and drying, the electroplating control current density is 50mA, the pH value of the electroplating solution is 4-6, and the electroplating solution consists of the following components:
140g/L of nickel sulfate, 6g/L of selenium oxide, 30g/L of sodium chloride, 13.3-13.4g/L of boric acid, 13-13.5g/L of sulfosalicylic acid, 18-22g/L of tri-ammonium citrate and 4.9-5 g/L of lanthanum chloride.
The intermetallic compound formed by the invention is of a hexagonal structure and forms a micron-level structure in a form of embedding a sheet layer, which can enable a large amount of hydrogen to be dissolved in gaps of the hexagonal structure, thereby realizing a hydrogen storage function in the electrolysis process, and the absorbed hydrogen can generate discharge reaction at a cathode to prevent the electrode from being corroded by air oxidation, thereby protecting the electrocatalytic activity of the electrode and enhancing the stability of products.
The invention discovers that the light rare earth is easier to electrodeposit than the heavy rare earth. Even with low concentrations of plating solution, it can accomplish deposition quickly. Meanwhile, it was also found that: the introduction of light rare earth is beneficial to the rapid deposition of low concentration Se.
Advantages and positive effects of the invention
(1) The method is simple, can be carried out at lower temperature and lower current density, is easy to operate and execute, and reduces the cost of noble metals;
(2) The prepared Ni-Se-La composite electrode has lower hydrogen evolution overpotential, higher hydrogen evolution catalytic activity and good stability, and can be widely applied to the field of hydrogen production by alkaline water electrolysis.
(3) The Ni-Se-La composite electrode developed and prepared by the invention is tested in KOH solution with the temperature of 25 ℃ and the mol/L of KOH solution, and the obtained electrode is tested in the temperature of 10mA cm -2 The overpotential under the current density is 29-55 mV, and can reach 29mV after optimization.
Drawings
FIG. 1 is a linear voltammogram of the electrode obtained in example 1 and comparative series 1;
FIG. 2 is a surface topography of the Ni-Se-La electrode obtained in example 1;
FIG. 3 is an EDS spectrum of the Ni-Se-La electrode obtained in example 1;
FIG. 4 is an X-ray diffraction chart of the Ni-Se-La electrode obtained in example 1;
FIG. 5 is a distribution electrolytic diagram of the Ni-Se-La electrode obtained in example 1;
FIG. 6 is a long-term electrolysis chart of the Ni-Se-La electrode obtained in example 1;
FIG. 7 is a LSV curve of the Ni-Se-La electrode obtained in example 1 before and after 5000 cycles of cyclic voltammetry scanning.
FIG. 8 is an LSV diagram of the electrode obtained in examples 2 and 3.
It can be seen from FIG. 1 that the Ni-Se-La hydrogen evolution overpotential is superior to that of Ni-Se, ni-La, se-La electrodes.
It can be seen from fig. 2 that the electrode surface appeared as needle-like and sphere-like nanoparticles after doping with La.
It can be seen from fig. 3 that La, se are deposited on Ni after electrodeposition.
It can be seen from fig. 4 that after doping La, an amorphous structure appears on the electrode surface.
It can be seen from fig. 5 that analytical electrolysis is consistent with LSV.
It can be seen from fig. 6 that the long-term electrolysis is consistent with LSV.
From fig. 7, LSV curves before and after 5000 cycles of cyclic voltammetry scanning can be seen.
The hydrogen evolution potential distribution of the electrodes obtained in examples 2 and 3 can be seen from fig. 8.
Detailed Description
Example 1:
(1) Pretreatment of foam nickel substrates
The whole piece of nickel foam purchased was cut to a size of 1cm by 1 cm. The nickel foam was first rinsed three times with deionized water, then rinsed three times with absolute ethanol, and immersed in a beaker containing absolute ethanol for 6 minutes of ultrasound. After the ultrasonic treatment, the beaker is taken out to be washed three times by deionized water, washed three times by 1mol/L hydrochloric acid, and immersed into the beaker filled with 1mol/L hydrochloric acid for ultrasonic treatment for 6 minutes. After the ultrasonic treatment, the mixture was washed with deionized water again. And finally, pouring a certain amount of absolute ethyl alcohol to store for later use.
(2) Preparing electroplating solution and electrodeposited Ni-Se-La electrode
Adopting a three-electrode system to prepare the Ni-Se-La electrode by performing electrodeposition experiments on a CHI660E electrochemical workstation,
the reference electrode is a Saturated Calomel Electrode (SCE), the working electrode is the foam nickel NF (1 cm multiplied by 0.03 cm) processed in the step (1), and the counter electrode is a graphite plate (2 cm multiplied by 0.5 cm). Preparing electroplating liquid, which comprises the following components: 140g/L of nickel sulfate, 6g/L of selenium dioxide, 30g/L of sodium chloride, 13.33g/L of boric acid, 13.33g/L of sulfosalicylic acid, 20g/L of tri-ammonium citrate and 5g/L of lanthanum chloride. The electroplating time is 60min, the electroplating temperature is 20 ℃, the pH value of the solution is 4.5, and the current density is 50mA/cm 2 . And after the electroplating process is finished, the electroplating piece is cleaned by deionized water, then the electroplating piece is taken down and is placed on paper for air drying, and the next step of testing is performed.
The plating layer of the obtained electrode is calculated by atomic percent: ni:45.51%; se:24.19%; la:30.30%. (3) The Ni-Se-La electrode hydrogen evolution performance test and the structural characterization adopt a three-electrode system to test the Ni-Se-La electrode prepared by an electrodeposition experiment on a CHI660E electrochemical workstation, wherein a reference electrode is a Saturated Calomel Electrode (SCE), a working electrode is Ni-Se-La, and a counter electrode is a graphite plate. The hydrogen evolution performance of the Ni-Se-La electrode is tested under the condition that the water bath heating maintaining temperature is 25 ℃ by taking 1mol/L KOH solution as electrolyte, the linear voltammogram (LSV curve) of the electrode is shown in figure 1, the surface morphology is shown in figure 2, and the EDS energy spectrum is shown in figure 3.
As can be seen from FIG. 1, the resulting electrode was tested in a KOH solution at 25℃and 1mol/L, and the resulting electrode was tested at 10 mA.cm -2 The overpotential at the current density of (2) was 29mV.
At 10 mA.cm -2 The over-potential rise amplitude of the product is less than 2.3% after 5000 circles of circulation under the current density.
At 30 mA.cm -2 At a current density of 5000 cycles, the product overpotential rise amplitude is about 2.4%.
At 50 mA.cm -2 At a current density of 5000 cycles, the product overpotential rise amplitude is about 2.6%. This is a significant difference from the existing hydrogen evolution properties of electrodes.
Comparative example series 1
Ni-Se, ni-La, se-La electrodes were prepared under the same conditions as in example 1, and their linear voltammograms (LSV curves) were as shown in FIG. 1.
In the present invention, la was not contained in the plating solution used in the preparation of Ni-Se, the other was the same as in example 1, se was not contained in the plating solution used in the preparation of Ni-La, the other was the same as in example 1, and nickel sulfate was not contained in the plating solution used in the preparation of Se-La, the other was the same as in example 1.
Example 2:
(1) Pretreatment of foam nickel substrates
The whole piece of nickel foam purchased was cut to a size of 1cm by 1 cm. The nickel foam was first rinsed three times with deionized water, then rinsed three times with absolute ethanol, and immersed in a beaker containing absolute ethanol for 6 minutes of ultrasound. After the ultrasonic treatment, the beaker is taken out to be washed three times by deionized water, washed three times by 0.5mol/L hydrochloric acid, and immersed into the beaker filled with 0.5mol/L hydrochloric acid for ultrasonic treatment for 8 minutes. After the ultrasonic treatment, the mixture was washed with deionized water again. And finally, pouring a certain amount of absolute ethyl alcohol to store for later use.
(2) Preparing electroplating solution and electrodeposited Ni-Se-La electrode
An electrodeposition experiment is carried out on a CHI660E electrochemical workstation by adopting a three-electrode system to prepare a Ni-Se-La electrode, wherein a reference electrode is a Saturated Calomel Electrode (SCE), a working electrode is foam nickel NF (1 cm multiplied by 0.03 cm) processed in the step (1), and a counter electrode is a graphite plate (2 cm multiplied by 0.5 cm). Preparing electroplating liquid, which comprises the following components: 50g/L of nickel sulfate, 1g/L of selenium dioxide, 30g/L of sodium chloride, 13.33g/L of boric acid, 13.33g/L of sulfosalicylic acid, 20g/L of tri-ammonium citrate and 1g/L of lanthanum chloride. The plating time was 50 minutes, the plating temperature was 15℃and the current density was 10mA. And after the electroplating process is finished, the electroplating piece is cleaned by deionized water, then the electroplating piece is taken down and is placed on paper for air drying, and the next step of testing is performed.
The plating layer of the obtained electrode is calculated by atomic percent: ni:35.21%; se:32.15%; la:32.64%. (3) The Ni-Se-La electrode hydrogen evolution performance test and the structural characterization adopt a three-electrode system to test the Ni-Se-La electrode prepared by an electrodeposition experiment on a CHI660E electrochemical workstation, wherein a reference electrode is a Saturated Calomel Electrode (SCE), a working electrode is Ni-Se-La, and a counter electrode is a graphite plate. Taking 1mol/L KOH solution as electrolyte, testing the hydrogen evolution performance of the Ni-Se-La electrode under the condition that the water bath heating and the maintaining temperature are 25 ℃,
the resulting electrode was tested in a KOH solution at 25℃and 1mol/L, and the resulting electrode was tested at 10 mA.cm -2 The overpotential at the current density of (2) was 53mV.
At 10 mA.cm -2 The over-potential rise amplitude of the product is less than 2.3% after 5000 circles of circulation under the current density.
At 30 mA.cm -2 At a current density of 5000 cycles, the product overpotential rise amplitude is about 2.5%.
At 50 mA.cm -2 At a current density of 5000 cycles, the product overpotential rise amplitude is about 3.1%.
Example 3:
(1) Pretreatment of foam nickel substrates
The whole piece of nickel foam purchased was cut to a size of 1cm by 1 cm. The nickel foam was first rinsed three times with deionized water, then rinsed three times with absolute ethanol, and immersed in a beaker containing absolute ethanol for 10 minutes of ultrasound. After the completion of the ultrasonic treatment, the beaker was taken out to be washed three times with deionized water, washed three times with 2.5mol/L hydrochloric acid, and immersed in a beaker containing 205mol/L hydrochloric acid for ultrasonic treatment for 10 minutes. After the ultrasonic treatment, the mixture was washed with deionized water again. And finally, pouring a certain amount of absolute ethyl alcohol to store for later use.
(2) Preparing electroplating solution and electrodeposited Ni-Se-La electrode
An electrodeposition experiment is carried out on a CHI660E electrochemical workstation by adopting a three-electrode system to prepare a Ni-Se-La electrode, wherein a reference electrode is a Saturated Calomel Electrode (SCE), a working electrode is foam nickel NF (1 cm multiplied by 0.03 cm) processed in the step (1), and a counter electrode is a graphite plate (2 cm multiplied by 0.5 cm). Preparing electroplating liquid, which comprises the following components: 100g/L of nickel sulfate, 5g/L of selenium dioxide, 30g/L of sodium chloride, 13.33g/L of boric acid, 13.33g/L of sulfosalicylic acid, 20g/L of tri-ammonium citrate and 3g/L of lanthanum chloride. The plating time was 80min, the plating temperature was 30℃and the current density was 80mA. And after the electroplating process is finished, the electroplating piece is cleaned by deionized water, then the electroplating piece is taken down and is placed on paper for air drying, and the next step of testing is performed. The plating layer of the obtained electrode is calculated by atomic percent: ni:45.21%; se:21.12%; la:33.67%.
(3) Ni-Se-La electrode hydrogen evolution performance test and structural characterization
The Ni-Se-La electrode prepared by the electrodeposition experiment is tested on a CHI660E electrochemical workstation by adopting a three-electrode system, the reference electrode is a Saturated Calomel Electrode (SCE), the working electrode is Ni-Se-La, and the counter electrode is a graphite plate. And taking a 1mol/L KOH solution as an electrolyte, and testing the hydrogen evolution performance of the Ni-Se-La electrode under the condition that the water bath heating maintaining temperature is 25 ℃.
The resulting electrode was tested in a KOH solution at 25℃and 1mol/L, and the resulting electrode was tested at 10 mA.cm -2 The overpotential at the current density of (2) was 53mV.
At 10 mA.cm -2 The over-potential rise amplitude of the product is less than 2.2% after 5000 circles of circulation under the current density.
At 30 mA.cm -2 At a current density of 5000 cycles, the product overpotential rise amplitude is about 2.4%.
At 50 mA.cm -2 At a current density of 5000 cycles, the product overpotential rise amplitude is about 2.9%.
Example 4
Other conditions were identical to example 1 except that:
the electroplating solution comprises the following components: 140g/L of nickel sulfate, 5g/L of selenium oxide, 30g/L of sodium chloride, 13.33g/L of boric acid, 14g/L of sulfosalicylic acid, 20g/L of tri-ammonium citrate and 3g/L of lanthanum chloride. The plating time was 40min, the plating temperature was 30℃and the current density was 40mA. The plating layer of the obtained electrode is calculated by atomic percent: ni:42.1%; se:23.5%; la:34.4%.
The resulting electrode was tested in a KOH solution at 25℃and 1mol/L, and the resulting electrode was tested at 10 mA.cm -2 The overpotential at the current density of (2) was 56mV. Ni: 30-50%; se: 20-40%; la:30 to 40 percent
At 10 mA.cm -2 At a current density of 5000 cycles, the product overpotential rise amplitude is about 2.6%.
At 30 mA.cm -2 At 5000 cycles, the product overpotential rise amplitude was about 2.7%.
At 50 mA.cm -2 At a current density of 5000 cycles, the product overpotential rise amplitude is about 3.2%.
Comparative example 2
Other conditions were identical to example 1 except that: preparing electroplating liquid, which comprises the following components: 140g/L of nickel sulfate, 5g/L of selenium oxide, 3g/L of sodium chloride, 1.33g/L of boric acid, 1.33g/L of sulfosalicylic acid, 2g/L of tri-ammonium citrate and 3g/L of lanthanum chloride; the obtained product is tested in KOH solution with the temperature of 25 ℃ and the mol/L, and the obtained electrode is tested in 10mA cm -2 The overpotential at the current density of (2) was 63mV.
At 10 mA.cm -2 At a current density of 5000 cycles, the product overpotential rise amplitude is about 3.3%.
At 30 mA.cm -2 Is circulated for 5000 circles under the current density to produceThe magnitude of the overpotential rise was about 3.5%.
At 50 mA.cm -2 At a current density of 5000 cycles, the product overpotential rise amplitude is about 4.2%.
Comparative example 3
Other conditions were identical to example 1 except that: preparing electroplating liquid, which comprises the following components: 140g/L of nickel sulfate, 5g/L of selenium oxide, 3g/L of sodium chloride, 1.33g/L of boric acid, 1.33g/L of sulfosalicylic acid, 2g/L of tri-ammonium citrate and 3g/L of lanthanum chloride; the plating time was 40min, the plating temperature was 30℃and the current density was 40mA. The obtained product is tested in KOH solution with the temperature of 25 ℃ and the mol/L, and the obtained electrode is tested in 10mA cm -2 The overpotential at the current density of (2) was 68mV.
At 10 mA.cm -2 At a current density of 5000 cycles, the product overpotential rise amplitude is about 3.5%.
At 30 mA.cm -2 At a current density of 5000 cycles, the product overpotential rise amplitude is about 3.6%.
At 50 mA.cm -2 At a current density of 5000 cycles, the product overpotential rise amplitude is about 3.8%.
Comparative example 4
(1) Pretreatment of foam nickel substrates
The whole piece of nickel foam purchased was cut to a size of 1cm by 1 cm. The nickel foam was first rinsed three times with deionized water, then rinsed three times with absolute ethanol, and immersed in a beaker containing absolute ethanol for 6 minutes of ultrasound. After the ultrasonic treatment, the beaker is taken out to be washed three times by deionized water, washed three times by 2mol/L hydrochloric acid, and immersed into the beaker filled with 2mol/L hydrochloric acid for ultrasonic treatment for 10 minutes. After the ultrasonic treatment, the mixture was washed with deionized water again. And finally, pouring a certain amount of absolute ethyl alcohol to store for later use.
(2) Preparing electroplating solution and electrodeposited electrode
An electrodeposition experiment is carried out on a CHI660E electrochemical workstation by adopting a three-electrode system to prepare a Ni-Se-Gd electrode, wherein a reference electrode is a Saturated Calomel Electrode (SCE), a working electrode is foam nickel NF (1 cm multiplied by 0.03 cm) processed in the step (1), and a counter electrode is a graphite plate (2 cm multiplied by 0.5 cm). Preparing electroplating liquid, which comprises the following components: 160g/L of nickel sulfate, 1g/L of selenium oxide, 30g/L of sodium chloride, 13.33g/L of boric acid, 14g/L of sulfosalicylic acid, 20g/L of tri-ammonium citrate and 1g/L of gadolinium chloride. The plating time was 40min, the plating temperature was 20℃and the current density was 40mA. And after the electroplating process is finished, the electroplating piece is cleaned by deionized water, then the electroplating piece is taken down and is placed on paper for air drying, and the next step of testing is performed.
The plating layer of the obtained electrode is calculated by atomic percent; ni:93.5%; se:6.1%; gd:0.4%.
(3) Ni-Se-Gd electrode hydrogen evolution performance test and structural characterization
The Ni-Se-Gd electrode prepared by the electrodeposition experiment is tested on a CHI660E electrochemical workstation by adopting a three-electrode system, the reference electrode is a Saturated Calomel Electrode (SCE), the working electrode is Ni-Se-Gd, and the counter electrode is a graphite plate. Taking 1mol/L KOH solution as electrolyte, testing the hydrogen evolution performance of the Ni-Se-Gd electrode under the condition of water bath heating and maintaining the temperature to 25 ℃,
the obtained product was tested in a KOH solution of 1mol/L at 25℃and the electrode obtained was measured at 10mA cm -2 The overpotential at the current density of (2) was 71mV.
Claims (10)
1. A hydrogen evolution electrode containing light rare earth is characterized in that: the hydrogen evolution electrode containing light rare earth comprises a foam nickel substrate and a Ni-Se-La coating electroplated on the surface of the substrate, wherein the coating comprises the following components in percentage by atom: ni: 30-50%; se: 20-40%; la: 30-40%.
2. The light rare earth-containing hydrogen evolution electrode of claim 1, wherein: intermetallic compounds exist in the Ni-Se-La plating layer electroplated on the substrate surface, and the intermetallic compounds are hexagonal structures and form micron-scale structures in the form of lamellar inlay.
3. The preparation method of the hydrogen evolution electrode containing the light rare earth is characterized by comprising the following steps of:
taking the foam nickel with clean and dry surface as a working electrode, immersing the working electrode into electroplating solution, electroplating at 15-30 ℃ for at least 10min, cleaning and drying to obtain a product after electroplating, controlling the current density to be 10-80 mA and the pH value of the electroplating solution to be 4-6 during electroplating, wherein the electroplating solution consists of the following components:
50-140 g/L of nickel sulfate, 1-10 g/L of selenium oxide, 25-35g/L of sodium chloride, 13-14g/L of boric acid, 13-13.5g/L of sulfosalicylic acid, 15-25g/L of tri-ammonium citrate and 1-5 g/L of lanthanum chloride.
4. The method for preparing a hydrogen evolution electrode containing light rare earth according to claim 3, wherein: the electroplating solution consists of the following components:
130-140 g/L of nickel sulfate, 5-6 g/L of selenium oxide, 28-30g/L of sodium chloride, 13-14g/L of boric acid, 13-13.5g/L of sulfosalicylic acid, 18-22g/L of tri-ammonium citrate and 4-5 g/L of lanthanum chloride.
5. The method for preparing a hydrogen evolution electrode containing light rare earth according to claim 3, wherein: the foam nickel with clean and dry surface is obtained by washing with hydrochloric acid, washing with absolute ethyl alcohol or ultrasonic treatment and drying.
6. The method for preparing a hydrogen evolution electrode containing light rare earth according to claim 3, wherein: the control temperature of electroplating is 10-30 ℃.
7. The method for preparing a hydrogen evolution electrode containing light rare earth according to claim 3, wherein: the current density is controlled to be 48-52 mA during electroplating.
8. The method for preparing a hydrogen evolution electrode containing light rare earth according to claim 3, wherein: the control time of electroplating is 55-65 min.
9. The method for preparing a hydrogen evolution electrode containing light rare earth according to claim 3, wherein: immersing the working electrode into electroplating solution, electroplating for 60min at 20 ℃, cleaning and drying to obtain a product, wherein the electroplating solution comprises the following components:
140g/L of nickel sulfate, 6g/L of selenium oxide, 30g/L of sodium chloride, 13-14g/L of boric acid, 13-13.5g/L of sulfosalicylic acid, 18-22g/L of tri-ammonium citrate and 4.5-5 g/L of lanthanum chloride.
10. The method for preparing a hydrogen evolution electrode containing light rare earth according to claim 3, wherein: the resulting electrode was tested in a KOH solution at 25℃and 1mol/L, and the resulting electrode was tested at 10 mA.cm -2 The overpotential under the current density is 29-55 mV, and can reach 29mV after optimization.
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