CN117364138A - Self-supporting Ni-Fe alloy high-efficiency oxygen evolution electrode and preparation method thereof - Google Patents
Self-supporting Ni-Fe alloy high-efficiency oxygen evolution electrode and preparation method thereof Download PDFInfo
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- 229910003271 Ni-Fe Inorganic materials 0.000 title claims abstract description 53
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 53
- 239000000956 alloy Substances 0.000 title claims abstract description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000001301 oxygen Substances 0.000 title claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 59
- 150000003839 salts Chemical class 0.000 claims abstract description 56
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 44
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- DMTIXTXDJGWVCO-UHFFFAOYSA-N iron(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Fe++].[Ni++] DMTIXTXDJGWVCO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011241 protective layer Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 229910000990 Ni alloy Inorganic materials 0.000 description 6
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 description 6
- 239000003115 supporting electrolyte Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-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
- 241000080590 Niso Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005303 weighing 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
- C25B11/04—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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- 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)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention belongs to the technical field of hydrogen production by water electrolysis, and particularly relates to a self-supporting Ni-Fe alloy high-efficiency oxygen evolution electrode and a preparation method thereof, wherein the invention uses anhydrous FeCl 2 Or FeCl 3 And (3) carrying out electrolysis in a chloride molten salt system to enable iron generated by reduction to be alloyed into Ni-Fe alloy on a nickel matrix in situ, thus obtaining the self-supporting Ni-Fe alloy electrode. When the electrode is used as an electrode for an alkaline system electrolysis water oxygen evolution reaction, a nickel-iron oxide protective layer is formed on the surface, so that the electrode is protected, and the nickel-iron oxide has strong catalytic oxygen evolution activity, thereby being beneficial to improving the activity and stability of the electrode catalytic oxygen evolution reaction. The self-supporting Ni-Fe alloy electrode prepared by adopting the molten salt electrolysis method has the advantages of simple preparation process, low cost, easy industrialization and self-supporting catalysis electricityThe size of the electrode is adjustable, and the electrode has excellent electrocatalytic oxygen evolution performance.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by water electrolysis, and particularly relates to a self-supporting Ni-Fe alloy efficient oxygen evolution electrode and a preparation method thereof.
Background
Hydrogen energy has the characteristics of high energy density and zero carbon dioxide emission, and is considered to be the most ideal energy carrier for replacing fossil fuel. The electrolytic water hydrogen production is one of the hydrogen production technologies with the prospect due to high product purity and environmental friendliness. The electrolytic water reaction comprises two half reactions, namely a cathodic hydrogen evolution reaction and an anodic oxygen evolution reaction. The anodic oxygen evolution reaction is a four-electron process, has the defect of slow kinetic rate compared with a two-electron process of hydrogen evolution reaction, generally shows larger overpotential, and increases the energy consumption of hydrogen production by water electrolysis. The traditional oxygen evolution catalyst is mainly noble metal oxides of iridium and ruthenium, but is expensive, so that the large-scale industrial application of the catalyst is severely limited. Therefore, the development of the low-cost and high-efficiency oxygen evolution reaction electrocatalyst is a key point for realizing the industrial application of the water electrolysis hydrogen production technology and is also an important precondition for realizing the industrial application of hydrogen energy.
Among the non-noble metal catalysts that have been reported, the oxide AB having a spinel structure 2 O 4 (a= Ni, cu, zn, co, sr, la, etc., b=fe, A1, cr, mn, co, etc.) is considered as one of the most promising alkaline electrolyzed water anode materials. However, the uniformity of the industrially produced spinel oxide product is difficult to control, and the adhesion properties to the substrate are also to be improved. The Ni-Fe bi-component metal material has low price, and the oxygen evolution catalytic activity is higher than that of a single Ni material due to the synergistic effect of Fe, so that the Ni-Fe bi-component metal material has attracted wide attention as an oxygen evolution reaction catalyst.
Self-supporting electrodes prepared by in-situ growth of Ni-Fe alloy catalysts on substrates with high conductivity exhibit moreAdvantages are: firstly, the in-situ growth mode of the catalyst on the substrate avoids a coating process, simplifies an electrode preparation process and greatly reduces the cost; second, the catalytic material and substrate are tightly bonded and do not require the use of a polymeric binder, ensuring rapid charge transfer, exposing more catalytic sites and preventing catalyst shedding during long-term cycling. For example, chinese patent publication No. CN115074770A discloses a nickel screen as matrix, which contains NiSO 4 And FeSO 4 Method for preparing nickel-iron alloy high-efficiency oxygen evolution electrode by electrodeposition in solution of nickel-iron alloy 10mA/cm 2 The overpotential at current density was 250mV. The preparation process of the method is simple, but the deposited nickel-iron alloy in the low-temperature water solution and the matrix nickel screen are not in metallurgical bonding, and the stability of the electrode in long-time electrolysis under high current density still needs to be improved.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a self-supporting Ni-Fe alloy high-efficiency oxygen evolution electrode and a preparation method thereof. When the electrode is used as an alkaline electrolysis water oxygen evolution electrode, a nickel-iron oxide protective layer can be formed on the surface, so that the electrode has excellent electrocatalytic oxygen evolution activity and stability.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
the invention provides a preparation method of a self-supporting Ni-Fe alloy efficient oxygen evolution electrode, which comprises the following steps:
1) Pretreatment of a nickel matrix;
2) Preparing and purifying molten salt;
3) And preparing the self-supporting Ni-Fe alloy electrode by molten salt electrolysis.
Further, in step 1), the pretreatment of the nickel substrate is specifically performed as: firstly, soaking a nickel matrix in acetone for a period of time by ultrasonic waves, and removing grease on the surface of the nickel matrix; then ultrasonic cleaning is carried out on hydrochloric acid solution for a period of time, and an oxide film on the surface of the hydrochloric acid solution is removed; and finally, repeatedly washing with deionized water to remove residual acid, and naturally air-drying.
Further, the nickel matrix is nickel wire, nickel sheet, nickel net, nickel fiber felt or foam nickel, and the purity of the nickel matrix is above 99.9%.
Further, in the step 2), the specific operation of preparing and purifying the molten salt is as follows: the anhydrous chloride is weighed and placed in a corundum crucible, and is heated in a high-temperature furnace to be melted to obtain supported electrolyte molten salt; then removing trace impurity metal ions in the molten salt by a pre-electrolysis method. The above process is carried out in a protective atmosphere of high purity argon.
Further, the anhydrous chloride is any two of analytically pure lithium chloride, sodium chloride, potassium chloride, calcium chloride and barium chloride, and is dried in vacuum for more than 48 hours at 300 ℃ before use.
Further, in the step 3), the specific operation of preparing the self-supporting Ni-Fe alloy electrode by molten salt electrolysis is as follows: adding anhydrous FeCl into the molten salt system obtained in the step 2) 2 Or FeCl 3 Performing constant potential electrolysis by taking the metallic nickel obtained in the step 1) as a working electrode, high-purity graphite as a counter electrode and Ag/AgCl as a reference electrode; the electrolysis process is carried out in a protective atmosphere of high-purity argon; and after the electrolysis is finished, taking out the working electrode, and washing away residual molten salt on the surface by using deionized water to obtain the self-supporting Ni-Fe alloy electrode.
Further, anhydrous FeCl 2 Or FeCl 3 The purity of the molten salt is more than 99.9 percent, and the anhydrous FeCl in the adopted molten salt system 2 Or FeCl 3 The mass dispersion of (2) to (10).
Further, in step 3), the reaction is carried out with anhydrous FeCl 2 Or FeCl 3 Adding anhydrous NiCl together 2 Anhydrous NiCl 2 The purity is more than 99.9 percent; anhydrous NiCl added to molten salt system 2 The mass fraction of (2) is 0-5%.
Further, the temperature of the constant potential electrolysis process is 500-800 ℃, the potential is minus 0.8-minus 1.8V, the electrolysis time is 2-10 h,
the invention also provides a self-supporting Ni-Fe alloy high-efficiency oxygen evolution electrode which is prepared by the preparation method.
The beneficial effects of the invention are as follows:
1. according to the invention, by utilizing the characteristic of fast diffusion mass transfer in a high-temperature molten salt system, the self-supporting Ni-Fe alloy catalytic electrode with strong binding force with the substrate is grown in situ on the nickel substrate, and the excellent electrocatalytic oxygen evolution activity and stability of the electrode are ensured.
2. The self-supporting Ni-Fe alloy oxygen evolution electrode with uniform and stable structure and composition is prepared by optimizing the composition of a molten salt system, the molten salt electrolysis temperature, the potential and the time parameters, so that the prepared electrode is compared with commercial IrO 2 -RuO 2 Noble metal oxide catalysts have stronger electrocatalytic properties.
3. The preparation method of the magnesium-nickel alloy electrode is simple, low in cost and beneficial to industrial large-scale application.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction pattern of the surface of the self-supporting Ni-Fe alloy electrode prepared in example 1;
FIG. 2 is a self-supporting Ni-Fe alloy electrode and commercial IrO prepared in example 1 2 -RuO 2 Linear sweep voltammogram of the electrode;
FIG. 3 is a self-supporting Ni-Fe alloy electrode and commercial IrO prepared in example 2 2 -RuO 2 Linear sweep voltammogram of the electrode.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a self-supporting Ni-Fe alloy high-efficiency oxygen evolution electrode, which has the main advantages that a Ni-Fe alloy coating obtained by adopting a fused salt electrolysis method has uniform chemical composition, and the alloy coating is tightly combined with a nickel matrix due to the characteristic of high mass transfer rate in high-temperature fused salt, so that the electrode is not easy to fall off in the use process, thereby improving the stability of the electrode in the use process.
For a better understanding of the present invention, its objects, technical aspects and advantages, the present invention will be further described with reference to the following examples
Specific embodiments of the invention are as follows:
example 1
The self-supporting Ni-Fe alloy high-efficiency oxygen evolution electrode is prepared by a fused salt electrolysis method according to the following steps:
1) Activation of nickel matrix
Firstly, taking a nickel sheet with the thickness of 0.5mm, and carrying out ultrasonic soaking in acetone for 30min to remove grease on the surface of the nickel sheet; then ultrasonically cleaning the surface of the substrate for 30min in a hydrochloric acid solution with the concentration of 1mol/L, and removing an oxide film on the surface of the substrate; and finally, repeatedly washing with deionized water to remove residual acid, naturally air-drying, and storing in a glove box for later use.
2) Preparation and purification of molten salts
Weighing dried sodium chloride and potassium chloride according to a molar ratio of 1:1, uniformly mixing, placing into a corundum crucible, and heating to 700 ℃ in a high-temperature furnace to melt to obtain supported electrolyte molten salt; then pre-electrolyzing for 60min at-2.0V (relative to Ag/AgCl) to remove trace impurity metal ions in the molten salt. The above process is carried out in a protective atmosphere of high purity argon.
3) Preparation of self-supporting Ni-Fe alloy electrode by fused salt electrolysis
Adding 5% of anhydrous F into the molten salt system obtained in the step 2)eCl 3 And (3) taking the nickel sheet obtained in the step (1) as a working electrode, high-purity graphite as a counter electrode and Ag/AgCl as a reference electrode, and carrying out constant potential electrolysis for 5h at-0.8V. The electrolysis process is carried out in a protective atmosphere of high purity argon. And after the electrolysis is finished, taking out the working electrode, and washing away residual molten salt on the surface by using deionized water to obtain the self-supporting Ni-Fe alloy electrode.
4) Phase composition analysis of Ni-Fe alloy electrode
The phase composition of the prepared Ni-Fe alloy electrode was analyzed by an X-ray diffractometer, and the diffraction pattern (XRD) obtained was as shown in FIG. 1, and it can be seen that: the phase composition of the Ni-Fe alloy electrode prepared in example 1 was mainly Ni 3 And Fe phase.
5) Electrocatalytic oxygen evolution activity test of Ni-Fe alloy electrode
Commercial IrO by linear sweep voltammetry using electrochemical workstation 2 -RuO 2 The electrode and the Ni-Fe alloy electrode obtained in step 3) were tested for electrocatalytic properties. The testing process adopts a three-electrode system: the two electrodes are working electrodes, pt is a counter electrode, hg/HgO is a reference electrode, the electrolyte adopts KOH solution with the mass concentration of substances of 1mol/L, the catalytic hydrogen evolution performance of the electrolyte is tested on an electrochemical workstation, and the scanning rate is 5mV/s. The test results are shown in FIG. 2 (the test method is a linear potential scanning method, the test conditions are that the two electrodes are working electrodes, pt is a counter electrode and Hg/HgO is a reference electrode, the electrolyte adopts KOH solution with the mass concentration of 1mol/L, and the scanning rate is 5 mV/s), and can be seen: the prepared Ni-Fe alloy electrode is at 10mA/cm 2 And 100mA/cm 2 Oxygen evolution overpotential at current density versus commercial IrO 2 -RuO 2 The electrode is respectively lower than 102mV and 332mV, and the prepared self-supporting Ni-Fe alloy electrode has excellent electrocatalytic oxygen evolution activity.
6) Electrocatalytic stability test of Ni-Fe alloy electrode
And (5) testing the stability of the Ni-Fe alloy electrode by using an electrochemical workstation through a constant current method, wherein a testing system is the same as the step (5). At 100mA/cm 2 After continuous electrolysis for 50h under current density, the catalytic oxygen evolution overpotential of the prepared electrode only rises by 10mV, which indicates thatThe prepared self-supporting Ni-Fe alloy electrode has good stability under high current density.
Example 2
The preparation method of the self-supporting Ni-Fe alloy high-efficiency oxygen evolution electrode by the molten salt electrolysis method is basically the same as that of the embodiment 1, and the main difference is that: the nickel matrix in the embodiment is nickel wire with the diameter of 2 mm; when the magnesium-nickel alloy electrode is prepared by taking nickel wires as matrix through molten salt electrolysis, lithium chloride and potassium chloride with the molar ratio of 1:1 are adopted as supporting electrolyte molten salt, and anhydrous FeCl is adopted in the molten salt 3 The content of (2) is 5%, the electrolysis temperature is 500 ℃, the electrolysis potential is-1.0V, and the electrolysis time is 8h.
The method for testing the electrocatalytic performance of the Ni-Fe alloy electrode prepared above was the same as in example 1. The linear sweep voltammetry of the electrode in 1mol/L KOH solution is shown in figure 3 (the test method is a linear potential sweep method, the test condition is that the two electrodes are working electrodes, pt is counter electrodes and Hg/HgO is reference electrode, the electrolyte adopts KOH solution with the mass concentration of 1mol/L, the sweep rate is 5 mV/s), the alloy electrode prepared in the embodiment can be seen to be in a range of 10mA/cm 2 And 100mA/cm 2 Oxygen evolution overpotential at current density versus commercial IrO 2 -RuO 2 The electrode is respectively lower than 91mV and 337mV, and the prepared self-supporting Ni-Fe alloy electrode has excellent electrocatalytic oxygen evolution activity. In addition, the electrode was at 100mA/cm 2 Continuous electrolysis for 48 hours under high current density also shows good catalytic stability.
Example 3
The preparation method of the self-supporting Ni-Fe alloy high-efficiency oxygen evolution electrode by the molten salt electrolysis method is basically the same as that of the embodiment 1, and the main difference is that: the nickel matrix in the embodiment is a metal nickel screen; when the nickel screen is used as a matrix molten salt for preparing the magnesium-nickel alloy electrode by electrolysis, sodium chloride and barium chloride with the molar ratio of 3:2 are adopted as supporting electrolyte molten salt, and anhydrous FeCl is adopted in the molten salt 3 10% by weight of NiCl, 5% by weight of anhydrous NiCl was added 2 The electrolysis temperature is 800 ℃, the electrolysis potential is-1.2V, and the electrolysis time is 2h.
The characterization of the phase composition and the electrocatalytic performance of the Ni-Fe alloy electrodes prepared above were carried out in the same manner as in example 1, and the results were substantially the same as in example 1.
Example 4
The preparation method of the self-supporting Ni-Fe alloy high-efficiency oxygen evolution electrode by the molten salt electrolysis method is basically the same as that of the embodiment 1, and the main difference is that: the nickel matrix in the embodiment is a metal nickel fiber felt; when the magnesium-nickel alloy electrode is prepared by taking a nickel fiber felt as a matrix through molten salt electrolysis, lithium chloride and calcium chloride with a molar ratio of 3:2 are adopted as supporting electrolyte molten salt, and anhydrous FeCl is contained in the molten salt 2 2% and 1% of anhydrous NiCl was added 2 The electrolysis temperature is 650 ℃, the electrolysis potential is-1.8V, and the electrolysis time is 4 hours.
The characterization of the phase composition and the electrocatalytic performance of the Ni-Fe alloy electrodes prepared above were carried out in the same manner as in example 1, and the results were substantially the same as in example 1.
Example 5
The preparation method of the self-supporting Ni-Fe alloy high-efficiency oxygen evolution electrode by the molten salt electrolysis method is basically the same as that of the embodiment 1, and the main difference is that: the nickel matrix in the embodiment is foam nickel; when the magnesium-nickel alloy electrode is prepared by taking foam nickel as a matrix through molten salt electrolysis, sodium chloride and potassium chloride with the molar ratio of 1:1 are adopted as supporting electrolyte molten salt, and anhydrous FeCl is adopted in the molten salt 2 The content of (2) is 8%, the electrolysis temperature is 800 ℃, the electrolysis potential is-1.5V, and the electrolysis time is 10h.
The characterization of the phase composition and the electrocatalytic performance of the Ni-Fe alloy electrodes prepared above were carried out in the same manner as in example 1, and the results were substantially the same as in example 1.
Example 6
The preparation method of the self-supporting Ni-Fe alloy high-efficiency oxygen evolution electrode by the molten salt electrolysis method is basically the same as that of the embodiment 1, and the main difference is that: the nickel matrix in the embodiment is a metal nickel sheet; when the magnesium-nickel alloy electrode is prepared by using nickel sheets as matrix through molten salt electrolysis, potassium chloride and calcium chloride with the molar ratio of 3:1 are adopted as supporting electrolyte molten salt, and anhydrous FeCl is contained in the molten salt 2 6% and 2% of anhydrous NiCl was added 2 The electrolysis temperature is 720 ℃, the electrolysis potential is-1.2V, and the electrolysis time is 6h.
The characterization of the phase composition and the electrocatalytic performance of the Ni-Fe alloy electrodes prepared above were carried out in the same manner as in example 1, and the results were substantially the same as in example 1.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. The preparation method of the self-supporting Ni-Fe alloy high-efficiency oxygen evolution electrode is characterized by comprising the following steps of:
1) Pretreatment of a nickel matrix;
2) Preparing and purifying molten salt;
3) And preparing the self-supporting Ni-Fe alloy electrode by molten salt electrolysis.
2. The method of claim 1, wherein in step 1), the pretreatment of the nickel substrate is specifically performed as follows: firstly, soaking a nickel matrix in acetone for a period of time by ultrasonic waves, and removing grease on the surface of the nickel matrix; then ultrasonic cleaning is carried out on hydrochloric acid solution for a period of time, and an oxide film on the surface of the hydrochloric acid solution is removed; and finally, repeatedly washing with deionized water to remove residual acid, and naturally air-drying.
3. The preparation method according to claim 2, wherein the nickel matrix is nickel wire, nickel sheet, nickel net, nickel fiber felt or foam nickel, and the purity of the nickel matrix is above 99.9%.
4. The preparation method according to claim 2, wherein in step 2), the specific operations of preparing and purifying the molten salt are as follows: the anhydrous chloride is weighed and placed in a corundum crucible, and is heated in a high-temperature furnace to be melted to obtain supported electrolyte molten salt; then removing trace impurity metal ions in the molten salt by a pre-electrolysis method. The above process is carried out in a protective atmosphere of high purity argon.
5. The method according to claim 4, wherein the anhydrous chloride is any two of analytically pure lithium chloride, sodium chloride, potassium chloride, calcium chloride, and barium chloride, and is vacuum-dried at 300 ℃ for 48 hours or more before use.
6. The method of preparing a self-supporting Ni-Fe alloy electrode according to claim 4, wherein in the step 3), the specific operation of preparing the self-supporting Ni-Fe alloy electrode by molten salt electrolysis is as follows: adding anhydrous FeCl into the molten salt system obtained in the step 2) 2 Or FeCl 3 Performing constant potential electrolysis by taking the metallic nickel obtained in the step 1) as a working electrode, high-purity graphite as a counter electrode and Ag/AgCl as a reference electrode; the electrolysis process is carried out in a protective atmosphere of high-purity argon; and after the electrolysis is finished, taking out the working electrode, and washing away residual molten salt on the surface by using deionized water to obtain the self-supporting Ni-Fe alloy electrode.
7. The process according to claim 6, wherein the anhydrous FeCl is 2 Or FeCl 3 The purity of the molten salt is more than 99.9 percent, and the anhydrous FeCl in the adopted molten salt system 2 Or FeCl 3 The mass dispersion of (2) to (10).
8. The process according to claim 6, wherein in step 3), the reaction is carried out with anhydrous FeCl 2 Or FeCl 3 Adding anhydrous NiCl together 2 Anhydrous NiCl 2 The purity is more than 99.9 percent; anhydrous NiCl added to molten salt system 2 The mass fraction of (2) is 0-5%.
9. The method according to claim 6, wherein the temperature of the potentiostatic electrolysis process is 500 to 800 ℃, the potential is-0.8 to-1.8V, and the electrolysis time is 2 to 10 hours.
10. A self-supporting Ni-Fe alloy high efficiency oxygen evolution electrode, characterized in that it is prepared by the preparation method of any one of claims 1-9.
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