CN114622238B - Preparation and application of transition metal-based hydrogen and oxygen evolution dual-functional electrode - Google Patents
Preparation and application of transition metal-based hydrogen and oxygen evolution dual-functional electrode Download PDFInfo
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- CN114622238B CN114622238B CN202011368191.9A CN202011368191A CN114622238B CN 114622238 B CN114622238 B CN 114622238B CN 202011368191 A CN202011368191 A CN 202011368191A CN 114622238 B CN114622238 B CN 114622238B
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 105
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 103
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000001257 hydrogen Substances 0.000 title claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 44
- 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 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 30
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 49
- 239000000956 alloy Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000000151 deposition Methods 0.000 claims abstract description 26
- 238000004070 electrodeposition Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000003486 chemical etching Methods 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 238000005530 etching Methods 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000001588 bifunctional effect Effects 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003115 supporting electrolyte Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 230000009977 dual effect Effects 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- -1 transition metal salt Chemical class 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 7
- 239000002659 electrodeposit Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 230000002195 synergetic effect Effects 0.000 abstract description 10
- 229910002545 FeCoNi Inorganic materials 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 229910002555 FeNi Inorganic materials 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 241000219053 Rumex Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
-
- 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
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention provides a transition metal-based hydrogen evolution/oxygen evolution dual-functional electrode and a preparation method thereof, wherein a mixed phase of transition metal alloy and transition metal phosphide is deposited on a conductive substrate by adopting an electrochemical deposition method, a corresponding transition metal hydroxide sheet layer is generated on the surface of the electrode by adopting a chemical etching oxidation deposition method, the electrode has excellent hydrogen evolution and oxygen evolution activity by means of the synergistic effect among the transition metal alloy, phosphide and hydroxide, and the electrode is applied to an alkaline electrolytic water tank. Meanwhile, the hydrogen evolution/oxygen evolution dual-function electrode provided by the invention can reduce the preparation cost of the electrolytic water electrode by reducing the electrode preparation process and the equipment quantity.
Description
Technical Field
The invention belongs to the field of hydrogen production by water electrolysis, and particularly relates to preparation of a transition metal-based hydrogen evolution/oxygen evolution dual-function electrode and application of the electrode in an electrolytic water tank. The method adopts an electrochemical deposition method to deposit a mixed phase of transition metal alloy and transition metal phosphide on a conductive substrate, and then generates a corresponding transition metal hydroxide sheet layer on the surface of an electrode by a chemical etching oxidation deposition method, so that the electrode has excellent hydrogen evolution and oxygen evolution activity by means of the synergistic effect among the transition metal alloy, the phosphide and the hydroxide.
Background
In order to reduce the cost of hydrogen production by water electrolysis, a non-noble metal catalyst is necessary. However, the activation of the non-noble metal material is relatively low, for example, although the transition metal-based material is widely used in the alkaline water electrolysis industry, the hydrogen evolution activity is not high enough, so that the water electrolysis efficiency is low; the transition metal-based material exhibits very high hydrogen evolution properties under alkaline conditions, but still has a lower activity than its properties under acidic conditions. In addition, the electrode with the dual functions of hydrogen evolution and oxygen evolution can effectively reduce the preparation process cost of the electrode, but the dual-function electrode with high hydrogen evolution and oxygen evolution activity is difficult to prepare.
To increase the activity of transition metals and transition metal phosphides, the use of multicomponent transition metal composition regulation is a common effective strategy, where Fe, co, ni are some common elements. The intrinsic activity of the material can be improved by adjusting the electronic structure of the material, the specific surface area of the material can be optimized to change the hydrogen evolution active area or site of the material, the polarization of the electrode is reduced to improve the performance, the structure and the morphology of the material are changed, the mass transfer of the material is optimized, the polarization of the mass transfer is reduced, and the performance of the electrode is improved.
However, the above-mentioned electrolytic water electrode still has a problem that the activity is not sufficiently high. The performance of the electrode can be further improved by adopting the combination of the hydroxide of the transition metal, the transition metal/alloy and the transition metal phosphide. However, a method for jointly improving the hydrogen evolution and oxygen evolution activities of the electrode through the synergistic effect among the transition metal alloy, phosphide and hydroxide is not reported. In particular to a double-function electrode for hydrogen evolution/oxygen evolution of transition metals or alloys such as Fe, co, ni and the like which are uniformly distributed by adopting a simple process, and has quite wide application prospect.
Disclosure of Invention
Aiming at the lower hydrogen evolution/oxygen evolution activity of the transition metal alloy and the transition metal phosphide in alkaline electrolyzed water, the transition metal-based electrode rich in interfaces of the transition metal alloy, the phosphide and the hydroxide is prepared by adopting electrochemical deposition and chemical etching oxidation deposition methods, and the electrode has excellent hydrogen evolution/oxygen evolution dual-function activity.
The invention comprises the following technical scheme:
in one aspect, the invention provides a transition metal-based hydrogen evolution/oxygen evolution dual-function electrode comprising a conductive substrate, wherein a mixed phase of a transition metal alloy and a transition metal phosphide is deposited on the surface of the conductive substrate, and a hydroxide layer of the transition metal is deposited on the surface of the mixed phase.
Preferably, the mixed phase of the transition metal alloy and the transition metal phosphide is a granular coating, the diameter of the granules is 300-800nm, and the thickness of the coating is 1-20 mu m; the hydroxide layer is a sheet layer or a porous layer stacked by sheets, and the thickness of the hydroxide layer is 50-300nm.
Preferably, the conductive substrate is a sheet, mesh or foam of copper, nickel, stainless steel, titanium.
Preferably, the transition metal is two or three of Fe, co and Ni; in the same bifunctional electrode, the types of transition metals used in the transition metal alloy, the transition metal phosphide, and the transition metal hydroxide are the same.
In another aspect, the present invention provides a method for preparing the above-mentioned bifunctional electrode, where the method is: and depositing a mixed phase of transition metal alloy and transition metal phosphide on the surface of the conductive substrate by adopting an electrochemical deposition method, and generating a corresponding transition metal hydroxide layer on the surface of the mixed phase by adopting a chemical etching oxidation deposition method.
Preferably, the electrochemical deposition method comprises the steps of:
(1) Cleaning pretreatment is carried out on the conductive substrate;
(2) Placing the pretreated conductive substrate in an electrodeposition solution, and performing constant current deposition under the stirring condition to obtain a mixed phase electrode of transition metal alloy and transition metal phosphide after the deposition is finished;
the electrodeposition liquid is a mixed liquid of transition metal salt solution, sodium hypophosphite and supporting electrolyte.
Preferably, in the step (1), the pretreatment method is as follows: respectively ultrasonically cleaning the conductive substrate in acetone, sulfuric acid with the mass fraction of 20% and deionized water for 5-10min, and blowing and drying the conductive substrate with air for later use; in the step (2), the transition metal salt is Fe 2+ 、Co 2+ And Ni 2+ Corresponding chlorides, sulfates or nitrates of two or three of the above; the total concentration of the transition metal salt solution is 10mM-1M; the concentration of the sodium hypophosphite is 10mM-1M, and the concentration of the supporting electrolyte is 0.2-3M NH 4 Cl; the pH value of the electrodeposition liquid is regulated to 2-3 by adopting HCl;
the counter electrode of the electro-deposition is a graphite plate, and the current density is 0.1-3A cm -2 Deposition time is 10-600s, electrodeposition liquidThe temperature is controlled at 20-80 ℃, and the stirring speed is controlled at 60-1600rpm; and (3) washing the electrodeposited electrode by adopting clear water, and drying the electrode for 4-8 hours at 60 ℃ by air to obtain the mixed phase electrode of the transition metal alloy and the transition metal phosphide.
Preferably, the chemical etching oxidation deposition method comprises the following steps: the mixed phase electrode is arranged in the H-containing state + And Cl - Etching and oxidizing in the etching liquid to form a hydroxide sheet layer on the surface of the electrode mixed phase.
Preferably, in the etching solution, H + Provided by HCl, with a concentration of 0.02-0.2mM, cl - Provided by HCl together with a salt containing chloride ions, cl - The total concentration is 0.5-5mM, and the chloride ion-containing salt is NaCl, KCl, mgCl 2 And CaCl 2 One or two or more of them; the temperature of the etching liquid is 40-80 ℃ and the etching time is 0.5-4h.
Specifically, the preparation method of the invention comprises the following steps:
the core methods of the preparation of the dual-function electrode are an electrochemical deposition method and a chemical etching oxidation deposition method. And preparing an electrode of a mixed phase of the transition metal alloy and the transition metal phosphide by an electrochemical deposition method, and forming a hydroxide sheet layer on the surface of the electrode by a chemical etching oxidation deposition method to obtain the transition metal-based electrode.
The electrochemical deposition method comprises the steps of forming a substrate containing Fe 2+ 、Co 2+ And Ni 2+ Two or three of (a) and sodium hypophosphite (NaH) 2 PO 2 ) And a step of preparing a mixed phase electrode of the transition metal alloy and the transition metal phosphide by constant current deposition for a certain time under the stirring condition in the supporting electrolyte.
The electrode substrate is a sheet, net or foam material of alkali corrosion resistant copper, nickel, stainless steel, titanium. Prior to electrochemical deposition, the substrate is cut to a specified size, such as, but not limited to, 2cm x 3cm. And then the substrate material is pretreated, wherein the pretreatment method is to ultrasonically clean the substrate in acetone, sulfuric acid with the mass percent of 20% and deionized water for 5-10min respectively, and then air-blowing and drying are carried out for later use. Fe (Fe) 2+ 、Co 2+ And Ni 2+ The salt solutions of two or three of the above are corresponding chloridizationThe total concentration of the metal salt solution is 10mM-1M. Sodium hypophosphite with a concentration of 10mM-1M and a supporting electrolyte with a concentration of 0.2-3M NH 4 Cl. The pH of the solution was adjusted to 2-3 using 1M HCl. The electrodeposited counter electrode is graphite plate with current density of 0.1-3A cm -2 The deposition time is 10-600s, the temperature of the electrolyte is controlled at 20-80 ℃, and the stirring speed is controlled at 60-1600rpm. And (3) washing the electrodeposited electrode with a large amount of clear water, and then drying the electrode in air at 60 ℃ for 4-8 hours to obtain the mixed phase electrode of the transition metal alloy and the transition metal phosphide. Wherein the mixed phase of the transition metal alloy and the transition metal phosphide is a granular coating, the particle diameter is 300-800nm, and the thickness of the coating is 1-20 mu m.
The chemical etching oxidation method comprises mixing phase electrodes with H + And Cl - And (3) etching and oxidizing in the solution to form a hydroxide sheet layer on the surface of the electrode. H + Provided by HCl, with a concentration of 0.02-0.2mM, cl - Provided by HCl together with a salt containing chloride ions, cl - The concentration is 0.5-5mM, and the chloride ion-containing salt is NaCl, KCl, mgCl 2 And CaCl 2 One or two or more of them. The temperature of the etching liquid is 40-80 ℃ and the etching time is 0.5-4h. After etching, the hydroxide layer on the surface of the electrode is a sheet layer or a porous layer stacked by sheets, and the thickness of the layer is 50-300nm. During etching, the surface of the etching liquid contacts with air, the etching container is opened, and oxygen in the air is dissolved into the etching liquid and H in the etching liquid during etching + And (3) oxidizing the alloy and phosphide in the electrode together to generate corresponding metal ions, and depositing the metal ions on the surface of the electrode in a hydroxide form along with the increase of the pH value of etching solution to form a lamellar structure so as to obtain the transition metal-based electrode containing rich transition metal alloy, phosphide and hydroxide interfaces.
The electrode provided by the invention can be applied to the field of hydrogen production by water electrolysis.
The invention has the following advantages:
according to the invention, the transition metal alloy and the transition metal phosphide form a mixed phase on the surface of the conductive substrate, and then the hydroxide layer of the transition metal is deposited on the surface of the mixed phase, so that the three layers of the transition metal alloy, the transition metal phosphide and the hydroxide layer of the transition metal can play a synergistic effect, and the synergistic effect between the hydroxide and the corresponding phosphide and alloy can be utilized to promote water cracking in hydrogen evolution reaction, reduce hydrogen evolution activation energy, accelerate hydrogen evolution reaction rate and improve electrode performance.
In the bifunctional electrode with the specific structure, the transition metal hydroxide not only can form a synergistic hydrogen evolution effect with the corresponding alloy and phosphide, but also has excellent electrocatalytic oxygen evolution activity, and also has a synergistic oxygen evolution effect with the transition metal alloy and the transition metal phosphide, so that the oxygen evolution performance of the electrode is improved.
The invention utilizes the interaction among transition metal alloy, phosphide and hydroxide to promote the hydrogen evolution and oxygen evolution activities of the electrode under alkaline conditions, so that the assembled alkaline electrolytic water tank has high electrolytic efficiency of 200mA cm in 1M KOH -2 The electrolysis efficiency at the time exceeds 75%.
The hydrogen evolution/oxygen evolution dual-function electrode provided by the invention can reduce the preparation cost of the electrolytic water electrode by reducing the electrode preparation process and the equipment quantity, has a simple preparation process and uniformly distributed components, and has a quite wide application prospect.
Drawings
FIG. 1 is a schematic diagram of a transition metal-based electrode preparation flow chart and electrode plating and etched oxide layer structures.
Fig. 2 SEM image of the mixed phase electrode obtained in example 2.
FIG. 3 is an SEM image of a transition metal-based electrode obtained in example 4.
FIG. 4 shows a comparison of hydrogen evolution properties of the electrodes obtained in examples 1 to 9.
FIG. 5 shows a comparison of oxygen evolution properties of the electrodes obtained in examples 1 to 9.
FIG. 6 is a graph showing the electrolytic water properties of the electrode obtained in example 4.
In fig. 1, 1 is an electrode substrate, 2 is mixed phase particles of a transition metal alloy and phosphide obtained by electrochemical deposition, and 3 is a hydroxide layer on the surface of the mixed phase particles.
Detailed Description
Example 1
The electrode takes a copper sheet as a substrate, firstly the copper sheet is cut into 2cm multiplied by 4cm, and the working size is 2cm multiplied by 3cm. And then pretreating the copper sheet, wherein the pretreatment method is to ultrasonically clean the substrate in acetone, sulfuric acid with the mass percent of 20% and deionized water for 10min respectively, and then air-blowing and drying the substrate for later use. Fe. The Co and Ni source is Fe 2+ 、Co 2+ And Ni 2+ The concentrations of the chlorides were 0.04, 0.04 and 0.02M, respectively. The supporting electrolyte is 1M NH without sodium hypophosphite 4 Cl. The solution was adjusted to pH 2.5 with 1M HCl. The electrodeposited counter electrode is a graphite plate, and the current density is 1A cm -2 The deposition time was 60s, the electrolyte temperature was controlled at 45℃and the stirring speed was controlled at 1000rpm. And (3) washing the electrodeposited electrode with a large amount of clear water, and then drying the electrode for 4 hours at 60 ℃ to obtain the FeCoNi alloy electrode. The diameter of the alloy particles is 160nm, and the thickness of the coating is about 7 mu m.
Example 2
The preparation conditions were substantially the same as in example 1 except that the electrodeposition bath contained a 0.25M sodium hypophosphite solution, and the electrode obtained was a mixed phase electrode of FeCoNi alloy and FeCoNi phosphide. The diameter of the mixed phase particles is 700nm, and the thickness of the coating is about 8 mu m.
Example 3
On the basis of example 1, the obtained FeCoNi alloy electrode was subjected to a chemical etching oxidation deposition reaction. The conditions were as follows: h + At a concentration of 0.1mM, cl - Provided by HCl and NaCl, cl - The concentration was 1mM. The etching liquid temperature is 60 ℃ and the etching time is 2h. After etching, the hydroxide layer on the electrode surface is a porous layer with a thickness of about 50nm. The electrode obtained is FeCoNi alloy modified FeCoNi hydroxide electrode.
Example 4
On the basis of example 2, a chemical etching oxidation deposition reaction was performed under the same etching conditions as in example 3. The obtained electrode is a transition metal-based electrode with FeCoNi hydroxide modified on the surface of a mixed phase of FeCoNi alloy and FeCoNi phosphide, and the hydroxide layer on the surface of the electrode is of a lamellar structure and has a thickness of about 300nm.
Example 5
The reaction conditions were substantially the same as in example 4, except that the concentrations of Fe, co and Ni in the electrode were adjusted to FeCl 2 0.04M，NiCl 2 0.06M. The obtained electrode is a transition metal base electrode of FeNi hydroxide modified on the surface of a mixed phase of FeNi alloy and FeNi phosphide.
Example 6
The reaction conditions were substantially the same as in example 4, except that the concentrations of Fe, co and Ni in the electrode were adjusted to NiCl 2 0.1M. The obtained electrode is a transition metal base electrode of nickel hydroxide modified on the surface of a mixed phase of Ni metal and Ni phosphide.
Example 7
The reaction conditions were substantially the same as in example 4 except that the electrode substrate was replaced with nickel foam.
Example 8
The reaction conditions were substantially the same as in example 4 except that the electrodeposition current was adjusted to 0.1A and the electrodeposition time was adjusted to 600s.
Example 9
The reaction conditions were substantially the same as in example 4, except that the temperature of the chemical etching oxidative deposition was adjusted to 40℃and the etching time was adjusted to 4 hours.
The electrodes prepared in examples 1-9 above were subjected to performance testing.
FIG. 4 is a comparison of hydrogen evolution properties of the electrodes obtained in examples 1-9. In the figures, 1-9 correspond to the electrode properties of examples 1-9, respectively.
Test conditions: the three-electrode system is adopted for testing, the working electrodes are the electrodes in the examples 1-9 respectively, the counter electrode is foam nickel, the reference electrode is a saturated glycerol common electrode of a double-salt bridge system, the reference electrode is connected with the working electrode through a Rumex capillary, and the working electrode chamber is separated from the counter electrode chamber by a sand core. The electrolyte was a 1M KOH aqueous solution at a temperature of 20℃at room temperature. Electrode performance was corrected for 95% iR. The scanning speed of the linear scanning is 2mV/s, and the scanning is performed from low potential to high potential.
Description of the properties: the hydrogen evolution performance of the electrode of the example 2 is obviously better than that of the electrode of the example 1, which shows that the electrode performance of the mixed phase of FeCoNi alloy and phosphide is obviously better than that of the electrode of the FeCoNi alloy; the hydrogen evolution performance of example 3 is significantly better than that of example 1, indicating that there is significant synergy between the FeCoNi alloy and the corresponding FeCoNi hydroxide to promote the hydrogen evolution reaction; the hydrogen evolution performance of example 4 is superior to that of examples 1-3, indicating that there is a synergistic effect between the FeCoNi alloy, phosphide and hydroxide to further enhance the electrode performance. The hydrogen evolution performance of example 6 is lower than examples 4 and 5, indicating that the performance of the single metal transition metal based electrode is lower than the performance of the multi-metal transition metal based electrode. The hydrogen evolution performance of example 7 is superior to that of example 4, indicating that the electrode performance can be further improved after the electrode is replaced with a three-dimensional porous structure material. Examples 8 and 9 perform better than or near example 4, demonstrating that the different electrochemical deposition and chemical etching oxidation deposition conditions within the scope of the present invention can produce high hydrogen evolution performance electrodes.
The oxygen evolution performance of the electrode obtained in the example of fig. 5 is compared. In the figures, 1-9 correspond to the electrode properties of examples 1-9, respectively.
Test conditions: the test conditions are substantially the same as those in fig. 4, except that the scanning potential interval is different, and the scanning direction scans from high potential to low potential.
Description of the properties: the oxygen evolution performance of the electrode of the example 2 is obviously better than that of the electrode of the example 1, which shows that the electrode performance of the mixed phase of FeCoNi alloy and phosphide is obviously better than that of the electrode of the FeCoNi alloy; the oxygen evolution performance of example 3 is slightly better than that of example 1, which shows that the FeCoNi alloy and the corresponding FeCoNi hydroxide have certain synergistic effect to promote the oxygen evolution reaction; the oxygen evolution performance of example 4 is superior to that of examples 1-3, demonstrating that there is a synergistic effect between FeCoNi alloy, phosphide and hydroxide to further enhance electrode performance. Example 6 has lower performance than examples 4 and 5, indicating that the single metal transition metal based electrode has lower oxygen evolution performance than the multi-metal transition metal based electrode. The oxygen evolution performance of example 7 is superior to that of example 4, indicating that the electrode performance can be further improved after the electrode is replaced with a three-dimensional porous structure material. Examples 8 and 9 perform better than or near example 4, demonstrating that the different electrochemical deposition and chemical etch oxide deposition conditions within the described range of the present invention can produce high oxygen evolution performance electrodes.
FIG. 6 is a graph showing the electrolytic water properties of the electrode obtained in example 4.
Test conditions: both the hydrogen evolution and oxygen evolution electrodes of the electrolytic cell were prepared from example 4. The working area of the electrode is 1cm 2 The distance is 1cm, the electrolyte is 1M KOH aqueous solution, and the temperature is controlled at 60 ℃. The electrolytic water performance was subjected to iR correction of 95%. And (3) electrode constant current testing, namely lifting electrode current every 10min, and recording the change of the voltage of the electrolyzed water along with the current and time.
Description of the properties: the electrolytic water tank assembled by the electrodes has excellent performance, and can be used for treating the electrolytic water tank with the thickness of 200mA cm -2 When the water electrolysis efficiency exceeds 75%.
Claims (7)
1. The preparation method of the transition metal-based hydrogen evolution/oxygen evolution dual-function electrode is characterized by comprising the following steps of: depositing a mixed phase of transition metal alloy and transition metal phosphide on the surface of a conductive substrate by adopting an electrochemical deposition method, and generating a corresponding transition metal hydroxide layer on the surface of the mixed phase by adopting a chemical etching oxidation deposition method;
the electrochemical deposition method comprises the following steps:
(1) Cleaning pretreatment is carried out on the conductive substrate;
(2) Placing the pretreated conductive substrate in an electrodeposition solution, and performing constant current deposition under the stirring condition to obtain a mixed phase electrode of transition metal alloy and transition metal phosphide after the deposition is finished;
the electrodeposition liquid is a mixed liquid of transition metal salt solution, sodium hypophosphite and supporting electrolyte;
the chemical etching oxidation deposition method comprises the following steps: the mixed phase electrode is arranged in a phase-locked state and contains H + And Cl - Etching and oxidizing in the etching liquid to form a hydroxide sheet layer on the surface of the electrode mixed phase.
2. The method for preparing the transition metal-based hydrogen evolution/oxygen evolution dual-function electrode according to claim 1, wherein,
in the step (1), the pretreatment method comprises the following steps: respectively ultrasonically cleaning the conductive substrate in acetone, sulfuric acid with the mass fraction of 20% and deionized water for 5-10min, and blowing and drying the conductive substrate with air for later use;
in the step (2), the transition metal salt is Fe 2+ 、Co 2+ And Ni 2+ Corresponding chlorides, sulfates or nitrates of two or three of the above; the total concentration of the transition metal salt solution is 10mM-1M; the concentration of the sodium hypophosphite is 10mM-1M, and the concentration of the supporting electrolyte is 0.2-3M NH 4 Cl; the pH value of the electrodeposition liquid is regulated to 2-3 by adopting HCl;
the counter electrode of the electro-deposition is a graphite plate, and the current density is 0.1-3A cm -2 The deposition time is 10-600s, the temperature of the electrodeposit liquid is controlled at 20-80 ℃, and the stirring speed is controlled at 60-1600rpm; and (3) washing the electrodeposited electrode by adopting clear water, and drying the electrode for 4-8 hours at 60 ℃ by air to obtain the mixed phase electrode of the transition metal alloy and the transition metal phosphide.
3. The method for preparing a transition metal-based hydrogen evolution/oxygen evolution dual-function electrode according to claim 1, wherein H in the etching solution + Provided by HCl, with a concentration of 0.02-0.2mM, cl - Provided by HCl together with a salt containing chloride ions, cl - The total concentration is 0.5-5mM, and the chloride ion-containing salt is NaCl, KCl, mgCl 2 And CaCl 2 One or two or more of them; the temperature of the etching liquid is 40-80 ℃ and the etching time is 0.5-4h.
4. A transition metal-based hydrogen evolution/oxygen evolution bifunctional electrode obtained by the method of any one of claims 1 to 3, characterized in that the bifunctional electrode comprises a conductive substrate, a mixed phase of a transition metal alloy and a transition metal phosphide is deposited on the surface of the conductive substrate, and a hydroxide layer of the transition metal is deposited on the surface of the mixed phase;
the mixed phase of the transition metal alloy and the transition metal phosphide is a granular coating, the diameter of the granules is 300-800nm, and the thickness of the coating is 1-20 mu m; the hydroxide layer is a sheet layer or a porous layer stacked by sheets, and the thickness of the hydroxide layer is 50-300nm.
5. The transition metal based hydrogen evolution/oxygen evolution dual function electrode according to claim 4, wherein the conductive substrate is a sheet, mesh or foam of copper, nickel, stainless steel, titanium.
6. The transition metal-based hydrogen/oxygen evolution bifunctional electrode of claim 4, wherein the transition metal is two or three of Fe, co, ni; in the same bifunctional electrode, the transition metal alloy, the transition metal phosphide and the transition metal hydroxide are the same in the kind of the corresponding transition metal.
7. Use of a transition metal-based hydrogen/oxygen evolution bifunctional electrode according to any one of claims 4-6 in the field of hydrogen production by electrolysis of water.
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| CN108172850A (en) * | 2016-12-07 | 2018-06-15 | 中国科学院大连化学物理研究所 | A kind of hydrogen-precipitating electrode and its preparation and application |
| CN110344078A (en) * | 2019-07-03 | 2019-10-18 | 湖北大学 | A kind of nickel foam@cobalt molybdenum phosphide/ferronickel double-hydroxide electrode and the preparation method and application thereof |
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| CN108172850A (en) * | 2016-12-07 | 2018-06-15 | 中国科学院大连化学物理研究所 | A kind of hydrogen-precipitating electrode and its preparation and application |
| CN110344078A (en) * | 2019-07-03 | 2019-10-18 | 湖北大学 | A kind of nickel foam@cobalt molybdenum phosphide/ferronickel double-hydroxide electrode and the preparation method and application thereof |
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