CN117660984A - Alkaline water electrolysis cell electrode and preparation method and application thereof - Google Patents
Alkaline water electrolysis cell electrode and preparation method and application thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 230000005291 magnetic effect Effects 0.000 claims abstract description 22
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 21
- 238000004070 electrodeposition Methods 0.000 claims abstract description 15
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 238000003475 lamination Methods 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 9
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 7
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 7
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 5
- 230000007547 defect Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910000531 Co alloy Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 2
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000009832 plasma treatment Methods 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000005611 electricity Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- -1 hydroxide anions Chemical class 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention relates to an alkaline water electrolysis cell electrode, a preparation method and application thereof, wherein the electrode comprises a nickel substrate and a hydroxyl oxide catalyst covered on the surface of the nickel substrate, and the hydroxyl oxide catalyst is NiFe with microcosmic lamination morphology x Co y (OH) z In situ preparation of NiFe by magnetic field assisted one-step electrodeposition x Co y (OH) z The coating is obtained on the surface of a nickel substrate and is used for water and electricity to analyze oxygen electrodes, especially in an alkali liquor electrolysis tank device with high current density. Compared with the prior art, the invention utilizes the spin pinning effect to reconstructThe electrode interface improves the charge transfer dynamics, improves the oxygen evolution dynamic activity and rate of the electrode, regulates and controls the microscopic morphology of the electrode catalytic material, increases the electrochemical activity area of the electrode surface, reduces the bubble separation resistance, and realizes the high-activity alkaline water electrolysis cell electrode under the condition of high current density.
Description
Technical Field
The invention relates to the technical field of hydrogen production by water electrolysis, in particular to an alkaline water electrolysis cell electrode and a preparation method and application thereof.
Background
The development of green hydrogen energy is critical to human sustainable development due to excessive consumption of fossil fuels leading to significant pollutant emissions and energy crisis. Electrocatalytic water splitting to produce hydrogen represents a clean and sustainable technique for converting renewable energy into green chemical fuels. Alkaline cells are a more mature, commercially widespread technology in which the cathode and anode electrodes immersed in an alkaline solution are separated by a membrane. At the cathode, water is split to form hydrogen and release hydroxide anions, which pass through the membrane and recombine at the anode to form oxygen.
In the electrochemical reaction process, the electrode needs to overcome the energy required by the activation barrier of the electrochemical reaction occurring at the electrode-electrolyte interface, bubble nucleation is formed at the active site of the electrode surface, and the bubbles can be separated from the electrode after the size of the bubbles grows to the critical size, so that the electrochemical hydrogen evolution or oxygen evolution reaction occurs and is kept. In fact, in the current alkaline water electrolysis technology, the kinetics of the nickel-based electrocatalyst used are slow, and in particular the complex four electron transfer process at the anode side generates a large overpotential, leading to increased production costs and reduced hydrogen production efficiency. In addition, a large number of documents indicate that the generated bubbles can cover the electrode surface due to the adhesion between the electrode and the bubbles, resulting in a reduction in the electrochemically active area, limiting the current density rise, causing voltage loss, generating unnecessary heat and causing uneven current distribution. The electrocatalytic property is related to the property of the material, so that in order to meet the requirements of industry on efficient hydrogen production, people are constantly striving to improve the oxygen evolution activity of the nickel electrocatalyst, improve bubble desorption to reduce electrode mass transmission, and realize a high-efficiency alkaline water electrolysis device.
In view of the above problems, recent researches have been made to achieve a great progress by adjusting and controlling the nickel electrode structure, microstructure, crystal structure, electrode composition and the like to enhance electrochemical activity and accelerate bubble elimination. As alkaline cells move toward higher operating current densities, nickel electrodes have also presented challenges in maintaining both efficient oxygen evolution kinetics and rapid bubble removal capabilities.
Disclosure of Invention
The invention aims to provide an alkaline water electrolysis cell electrode, a preparation method and application thereof, and the electrode activity of an alkaline water electrolysis cell under high current density is improved.
The aim of the invention can be achieved by the following technical scheme: an alkaline water electrolysis cell electrode comprises a nickel substrate and a hydroxyl oxide catalyst covered on the surface of the nickel substrate, wherein the hydroxyl oxide catalyst is NiFe with a microcosmic lamination shape x Co y (OH) z 。
Preferably, the value range of x is 0.5-0.8, the value range of y is 0.2-0.1, and the value range of z is 0.3-0.1.
The oxyhydroxide catalyst can generate spin pinning effect after magnetization or under the action of an external magnetic field.
Preferably, the nickel substrate is one of foam nickel, three-dimensional nickel-iron alloy, nickel-cobalt alloy and nickel-iron-cobalt alloy.
In-situ preparation of NiFe by magnetic field assisted one-step electrodeposition x Co y (OH) z Covering the surface of the nickel substrate.
Preferably, the preparation method of the alkaline water electrolysis cell electrode specifically comprises the following steps:
(1) Placing a nickel substrate in hydrochloric acid solution for ultrasonic cleaning, sequentially cleaning with ethanol and aqueous solution, fully drying, and treating with oxygen plasma to remove impurities on the surface of the nickel substrate and introduce surface defects;
(2) Dissolving a certain amount of nickel chloride hexahydrate, ferric chloride tetrahydrate, cobalt chloride hexahydrate and potassium sodium tartrate into deionized water to form electrolyte, and carrying out electrochemical deposition under a certain voltage by adopting a three-electrode system under the action of an externally applied magnetic field, wherein the treated nickel substrate is a working electrode, a platinum mesh is a counter electrode, ag/AgCl is a reference electrode, and washing with deionized water after the deposition is finished to obtain an alkali liquor electrode with a spin pinning effect.
Further preferably, the concentration of the hydrochloric acid solution in the step (1) is 0.5-2 mol/L, the ultrasonic duration is 5-20 min, and the plasma treatment is 6-12 min.
Further preferably, in the electrolyte described in step (2), nickel: iron: cobalt atomic ratio is (0.5-0.8): (0.2-0.1): (0.3 to 0.1), the content of transition metal in the electrolyte is 0.1 to 0.2mol/L, and the content of potassium sodium tartrate is 0.4 to 0.8mol/L.
Further preferably, the direction of the externally applied magnetic field in the step (2) is 45 degrees with the plane of the nickel substrate, and the magnetic field strength is 20-60 mT.
Further preferably, the electrochemical deposition voltage in the step (2) is 0.8-1.2V (vs. Ag/AgCl), and the deposition time is 10-40 min.
It is further preferred that step (2) is followed by a 2-3 rinse with deionized water after electrochemical deposition.
The electrode is used for water and electricity analysis of oxygen.
It is further preferred that the electrode is used in a high current density lye cell arrangement.
The invention prepares the NiFe with the lamination morphology of the spin pinning effect in situ by one-step electrodeposition assisted by a magnetic field x Co y (OH) z Covering the surface of the nickel substrate. The electrode interface is reconstructed by utilizing the spin pinning effect, so that the charge transfer dynamics is improved, the oxygen evolution dynamic activity and rate of the electrode are improved, the microcosmic appearance of the electrode catalytic material is regulated and controlled, the electrochemical activity area of the electrode surface is increased, the bubble separation resistance is reduced, and the high-activity alkaline water electrolysis cell electrode under the condition of high current density is realized.
Compared with the prior art, the invention has the following advantages:
1. the alkaline water electrolysis cell electrode provided by the invention utilizes magnetic field assisted one-step electrodeposition to prepare NiFe in situ x Co y (OH) z The hydroxyl oxide layer reconstructs an electrode interface by utilizing a spin pinning effect generated by paramagnetic hydroxyl oxide atom magnetic moment exchange action, optimizes an interface electronic structure and improves oxygen evolutionSpin polarization is performed in the process, so that the generation rate of oxygen molecules is improved, and the intrinsic oxygen evolution activity of the electrode catalytic material is realized;
2. the invention regulates and controls NiFe x Co y (OH) z The nano micro-morphology structure of the alkaline solution electrolyzer not only can increase the electrochemical active area, but also is beneficial to reducing the size of bubbles so as to promote the rapid transmission and release of the bubbles, thereby improving the electrode activity of the alkaline solution electrolyzer under high current density;
3. the alkaline water electrolysis cell electrode provided by the invention is characterized in that a layer of NiFe with a microcosmic lamination shape and a spin pinning effect is covered on a three-dimensional nickel substrate x Co y (OH) z The electrode interface structure is optimized, the charge transfer dynamics is improved, the oxygen evolution dynamic activity and rate of the electrode are improved, the microcosmic appearance of the electrode catalytic material is regulated and controlled, the electrochemical active area of the electrode surface is increased, the bubble separation resistance is reduced, and the high-activity alkaline water electrolysis cell electrode under the condition of high current density is realized.
Drawings
FIG. 1 is an X-ray diffraction spectrum of the electrode of example 3;
FIG. 2 is an X-ray photoelectron spectrum of the electrode of example 3;
FIG. 3 is a 5000 Ximage of the electrode of example 3 by a scanning electron microscope;
FIG. 4 is a 10000 Ximage of the electrode of example 3 by a scanning electron microscope;
FIG. 5 is a polarization curve of the electrodes of examples 1-3;
FIG. 6 shows electrodes of examples 1-3 at 0.1A cm -2 And 0.8A cm -2 The corresponding cell voltage;
FIG. 7 is a graph of impedance versus time for the electrodes of examples 1-3.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The following examples are given by way of illustration of detailed embodiments and specific procedures based on the technical scheme of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
(1) Cutting foam nickel into pieces of 3×3cm 2 Placing the cut nickel substrate in 30ml hydrochloric acid solution (1M) for ultrasonic cleaning for 10min, sequentially cleaning with ethanol and aqueous solution for 2 times, placing in a 60-DEG oven for full drying, and treating with oxygen plasma for 10min to remove impurities on the surface of the nickel substrate and introduce surface defects;
(2) 1.68g of nickel chloride hexahydrate, 0.36g of ferric chloride tetrahydrate, 0.26g of cobalt chloride hexahydrate and 0.88g of potassium sodium tartrate are dissolved in 100ml of deionized water to form electrolyte, a three-electrode system is adopted to carry out electrochemical deposition under the condition of 1.0V (vs. Ag/AgCl), wherein a treated nickel substrate is a working electrode, a platinum net is used as a counter electrode, ag/AgCl is used as a reference electrode, the deposition time period is 30min, and deionized water is used for washing 3 times after the deposition is finished to obtain an alkali liquor electrode.
Example 2
(1) Cutting foam nickel into pieces of 3×3cm 2 Placing the cut nickel substrate in 30ml hydrochloric acid solution (1M) for ultrasonic cleaning for 10min, sequentially cleaning with ethanol and aqueous solution for 2 times, placing in a 60-DEG oven for full drying, and treating with oxygen plasma for 10min to remove impurities on the surface of the nickel substrate and introduce surface defects;
(2) 1.68g of nickel chloride hexahydrate, 0.36g of ferric chloride tetrahydrate, 0.26g of cobalt chloride hexahydrate and 0.88g of potassium sodium tartrate are dissolved in 100ml of deionized water to form electrolyte, a three-electrode system is adopted to carry out electrochemical deposition under the action of an external magnetic field of 30mT under the condition of 1.0V (vs. Ag/AgCl), wherein the treated nickel substrate is a working electrode, a platinum net is a counter electrode, ag/AgCl is a reference electrode, the external magnetic field direction forms 45 degrees with the plane of the nickel substrate, the deposition time period is 30min, and deionized water is used for washing 3 times after the deposition is finished to obtain an alkali liquor electrode.
Example 3
(1) Cutting foam nickel into pieces of 3×3cm 2 Placing the cut nickel substrate in 30ml hydrochloric acid solution (1M) for ultrasonic cleaning for 10min, sequentially cleaning with ethanol and aqueous solution for 2 times, placing in a 60-DEG oven for full drying, and treating with oxygen plasma for 10min to remove impurities on the surface of the nickel substrate and introduce surface defects;
(2) 1.68g of nickel chloride hexahydrate, 0.36g of ferric chloride tetrahydrate, 0.26g of cobalt chloride hexahydrate and 0.88g of potassium sodium tartrate are dissolved in 100ml of deionized water to form electrolyte, a three-electrode system is adopted to carry out electrochemical deposition under the action of an external magnetic field of 60mT under the condition of 1.0V (vs. Ag/AgCl), wherein the treated nickel substrate is a working electrode, a platinum net is a counter electrode, ag/AgCl is a reference electrode, the external magnetic field direction forms 45 degrees with the plane of the nickel substrate, the deposition time period is 30min, and deionized water is used for washing 3 times after the deposition is finished to obtain an alkali liquor electrode.
FIG. 1 is an X-ray diffraction spectrum of the electrode prepared in example 3, diffraction angles of 11.1, 22.4, 34.2, 60.7 and 71.2 correspond to NiFe, respectively x Co y (OH) z The (003), (006), (012), (113) and (119) planes; FIG. 2 is an X-ray photoelectron spectrum of the electrode prepared in example 3, and it can be observed that NiFe was prepared x Co y (OH) z The electrode mainly comprises Ni, fe, co, O and other elements, wherein C is probably caused by pollutants. FIGS. 3-4 are scanning electron microscope images of example 3 electrodes at (a) 5000X and (b) 10000X, showing electrodeposited NiFe x Co y (OH) z The appearance of a laminated structure is shown, the microstructure can effectively improve the contact area with electrolyte, increase the electrochemical active area and simultaneously can promote the effective detachment of bubbles generated on the surface of the electrode.
The prepared electrode is used as an oxygen evolution electrode to be placed in a single electrolytic cell clamp of an alkaline water electrolysis cell for testing. FIGS. 5 to 6 show the polarization curves (a) and (b) at 0.1A cm for the electrodes of examples 1 to 3 at a reaction temperature of 60 ℃ -2 And 0.8A cm -2 Corresponding cell voltage. Example 1 electrochemical deposition of NiFe x Co y (OH) z No external magnetic field is applied in the process, and the current density is 0.1A cm -2 And 0.8A cm -2 The corresponding cell voltages are 1.631V and 2.137V respectively; example 2 NiFe was deposited electrochemically x Co y (OH) z In the process, an external magnetic field of 30mT is added, and the current density is 0.1A cm -2 And 0.8A cm -2 The corresponding voltages of the electrolytic cells are 1.609V and 1.975V respectively; example 3 electrochemical deposition of NiFe x Co y (OH) z In the process, an external magnetic field of 60mT is added, and the current density is 0.1A cm -2 And 0.8A cm -2 The corresponding cell voltages were 1.583V and 1.906V, respectively, indicating that NiFe was prepared under 60mT applied magnetic field x Co y (OH) z NiFe prepared by using external magnetic field and having optimal electrochemical oxygen evolution performance x Co y (OH) z The self-rotation pinning effect is achieved, the regulation and control of the electron spin state in the oxygen evolution reaction process is achieved, and the intrinsic activity of the electrode material is optimized.
FIG. 7 shows the impedance versus time for the electrodes prepared in examples 1-3 tested in an alkaline water electrolysis cell single cell fixture, with the impedance curves for examples 1 and 2 being serrated, and the impedance curve for example 3 being relatively very smooth. The increase in impedance is caused by the oxygen bubbles covering the electrode surface, which interrupts the supply of lye to the electrode and drops rapidly as the large bubbles detach from the surface. The obtained results indicate that the prepared NiFe x Co y (OH) z The laminated structure of the electrodes can promote the growth and separation of bubbles more quickly.
According to the invention, through optimizing the spintronic structure of the electrode catalytic material, the bonding energy of an oxygen intermediate is reduced, the charge transfer dynamics is improved, the oxygen evolution dynamic activity of the electrode is improved, the microcosmic appearance of the electrode catalytic material is regulated and controlled, the electrochemical activity area of the electrode surface is increased, the bubble separation resistance is reduced, and the high-activity alkaline water electrolysis cell electrode under the condition of high current density is realized.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. An alkaline water electrolysis cell electrode is characterized by comprising a nickel substrate and a hydroxyl oxide catalyst covered on the surface of the nickel substrate, wherein the hydroxyl oxide catalyst is NiFe with a microcosmic lamination shape x Co y (OH) z 。
2. The alkaline water electrolysis cell electrode of claim 1, wherein the nickel substrate is one of nickel foam, three-dimensional nickel-iron alloy, nickel-cobalt alloy, nickel-iron-cobalt alloy.
3. A method of preparing an alkaline water electrolysis cell electrode according to claim 1 or 2, wherein NiFe is prepared in situ by magnetic field assisted one-step electrodeposition x Co y (OH) z Covering the surface of the nickel substrate.
4. A method for preparing an alkaline water electrolysis cell electrode according to claim 3, comprising the specific steps of:
(1) Placing a nickel substrate in hydrochloric acid solution for ultrasonic cleaning, sequentially cleaning with ethanol and aqueous solution, fully drying, and treating with oxygen plasma to remove impurities on the surface of the nickel substrate and introduce surface defects;
(2) Dissolving a certain amount of nickel chloride hexahydrate, ferric chloride tetrahydrate, cobalt chloride hexahydrate and potassium sodium tartrate into deionized water to form electrolyte, and carrying out electrochemical deposition under a certain voltage by adopting a three-electrode system under the action of an externally applied magnetic field, wherein the treated nickel substrate is a working electrode, a platinum mesh is used as a counter electrode, ag/AgCl is used as a reference electrode, and washing with deionized water after the deposition is finished to obtain the alkaline water electrolytic tank electrode.
5. The method for preparing an alkaline water electrolysis cell electrode according to claim 4, wherein the concentration of the hydrochloric acid solution in the step (1) is 0.5-2 mol/L, the ultrasonic duration is 5-20 min, and the plasma treatment is 6-12 min.
6. The method for producing an alkaline water electrolysis cell electrode according to claim 4, wherein in the electrolyte of step (2), nickel: iron: cobalt atomic ratio is (0.5-0.8): (0.2-0.1): (0.3 to 0.1), the content of transition metal in the electrolyte is 0.1 to 0.2mol/L, and the content of potassium sodium tartrate is 0.4 to 0.8mol/L.
7. The method for preparing an alkaline water electrolysis cell electrode according to claim 4, wherein the direction of the externally applied magnetic field in the step (2) is 45 degrees with the plane of the nickel substrate, and the magnetic field strength is 20-60 mT.
8. The method for preparing an alkaline water electrolysis cell electrode according to claim 4, wherein the electrochemical deposition voltage in the step (2) is 0.8-1.2V, and the deposition time is 10-40 min.
9. Use of an alkaline water electrolysis cell electrode according to claim 1 or 2, wherein said electrode is used as a water electrolysis oxygen electrode.
10. Use of an alkaline water electrolysis cell electrode according to claim 9, wherein the electrode is used in a high current density lye electrolysis cell arrangement.
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| CN202211039646.1A CN117660984A (en) | 2022-08-29 | 2022-08-29 | Alkaline water electrolysis cell electrode and preparation method and application thereof |
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