CN117904659A - Electrolysis hydrogen production catalytic electrode based on electromagnetic composite field and preparation method and application thereof - Google Patents
Electrolysis hydrogen production catalytic electrode based on electromagnetic composite field and preparation method and application thereof Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 77
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 77
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 71
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000005868 electrolysis reaction Methods 0.000 title abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000007772 electrode material Substances 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims description 67
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 230000000694 effects Effects 0.000 claims description 43
- 239000000956 alloy Substances 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 29
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000005530 etching Methods 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
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- 229910052721 tungsten Inorganic materials 0.000 claims description 5
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- 238000005406 washing Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 238000004026 adhesive bonding Methods 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 238000005240 physical vapour deposition Methods 0.000 claims description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses an electrolytic hydrogen production catalytic electrode based on an electromagnetic composite field, a preparation method and application thereof, belonging to the field of new energy and hydrogen energy, wherein the designed catalytic electrode material has a large three-dimensional specific surface structure, high conductivity and high catalytic activity, and is suitable for a hydrogen production system driven by electromagnetic field, electric field drive and the like; the energy use efficiency in the electrolysis process can be effectively improved, the starting time of the electrolytic tank can be reduced, the running temperature of the electrolytic tank system can be reduced, and the service life of the electrolytic hydrogen production system can be prolonged; meanwhile, the hydrogen production amount per unit volume can be effectively increased, the low-temperature performance of the electrolytic tank is improved, the number and the scale of heat exchange equipment of the system can be effectively reduced, and the energy consumption is reduced, and the method belongs to the field of new energy and hydrogen energy.
Description
Technical Field
The invention belongs to the technical field of new energy and hydrogen energy, and particularly relates to an electrolytic hydrogen production catalytic electrode based on an electromagnetic composite field, and a preparation method and application thereof.
Background
Electrolytic hydrogen production is the most commonly used method for producing high-purity green hydrogen, and the most commonly used electrolytic system is an alkaline water hydrogen production or PEM electrolytic water electrolysis tank at present, and the core component is a catalytic electrode material. The traditional electrode materials are mainly nickel-based coating electrode materials (corresponding to an alkaline water hydrogen production electrolysis system) or noble metal-based membrane electrode materials (corresponding to a pure water hydrogen production electrolysis system), so that the electrode materials have good water decomposition effect; however, the current electrolysis system needs to raise the temperature of the electrolyte to 70-90 ℃ to maintain high electrode reaction activity and improve the productivity of hydrogen production unit volume; however, the high electrolyte temperature has a bad influence on the service life and comprehensive energy utilization efficiency of the whole electrolysis system, so that the realization and preparation of the electrode material for the low-temperature high-efficiency electrolysis of water become an important path for solving the situation.
Patent publication No. CN 115449846A, CN115341232A describes a method for improving hydrogen production efficiency by alkali lye water electrolysis by using a magnetic field, and the whole electrolysis is put into an electromagnetic field by adopting a design of adding a coil outside an electrolytic tank, and the method is characterized in that Lorentz force in a periodically changing direction can be generated on an electrode, so that bubbles generated by electrolysis on the electrode can horizontally shake, the bubbles are accelerated to fall off, the coverage rate of bubbles on the surface of the electrode is reduced, and the hydrogen production capacity is improved; CN114411163 a describes the influence of a magnetic field on the effect of electrolyzed water, which shows that certain activation of the magnetic field has certain promotion effect on electrolytic hydrogen production; according to the traditional action mode of the magnetic field, the invention creatively provides a synthesis and manufacturing method of the electrode material applied to the magnetic field, enhances the electrode reaction performance, reduces the temperature of an electrolytic cell reaction system on the basis of the magnetic field, simultaneously reduces the adhesion of precipitated bubbles to the electrode, reduces the resistance of an electrolytic cell, and reduces the energy consumption of an additional system required by maintaining the high temperature of electrolyte.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field.
In order to solve the technical problems, the invention provides the following technical scheme: the electrolytic hydrogen production catalytic electrode is obtained by loading a magnetocaloric high-activity alloy material on a nickel carrier;
Wherein the magnetocaloric high activity alloy material is a material satisfying the following conditions (i) to (iv);
(i) The atomic composition general formula of the material is shown as formula (I);
Formula (I): x b(FeaCo(20-a)Ni30)50Y(50-b);
(ii) The value of a in the formula (I) is 5-15, and the value of b is 5-30;
(iii) The X element is selected from one or more of Mo, V, W, cr, mn, cu, zn, pb, ta, and the Y element is selected from one or more of Sc, ti, zr, er, nb, sr, ce, pm, eu, yb, ba, nd;
(iv) X, Y the atomic number ratio satisfies the atomic total content ratio of formula (I), specifically, means that the sum of all the atomic subscripts in X b(FeaCo(20-a)Ni30)50Y(50-b) is 100, and the atomic number ratio satisfies the ratio requirement corresponding to the subscripts.
It is still another object of the present invention to provide a method for preparing an electrolytic hydrogen production catalytic electrode based on an electromagnetic composite field.
In order to solve the technical problems, the invention provides the following technical scheme: comprising the steps of (a) a step of,
Dissolving the soluble salt of the X element in water at 50-80 ℃ to obtain a solution I, wherein the total concentration of the X element is 0.5-1.5M/L;
Dissolving soluble salts of the Y element in water at 50-80 ℃ to obtain a solution II, wherein the total concentration of the Y element is 0.5-1.5M/L;
Fe. Dissolving soluble salts of Co and Ni in water at 50-80 ℃ to obtain a solution III, wherein the total concentration of Fe, co and Ni elements is 1.5-2.5M/L; ;
Sequentially adding the solution I, II into the solution III, heating and stirring, performing ultrasonic treatment on the obtained mixed solution for 1-2 h, standing and cooling to room temperature to obtain the mixed solution;
Adding alloy powder of nickel, aluminum, iron and cobalt into the mixed solution, firstly adding alkaline substances to adjust the pH value of the solution to 8-10, and then adding strong alkaline substances to adjust the pH value of the solution to 10-12 to obtain solution IV;
Placing the solution IV in a hydrothermal kettle for hydrothermal reaction, simultaneously applying a magnetic field for treatment, cooling the product to 0-15 ℃ in a cooling range of 20-50 ℃/min after the reaction is finished, performing precise filtration, washing, and drying at 15-50 ℃ for 12-24 hours to obtain the magnetic heating type high-activity alloy material powder;
And (3) carrying out electrochemical etching after the surface of the nickel carrier is cleaned, coating the powder material of the magnetocaloric high-activity alloy material on the surface of the carrier, and then placing the carrier in alkaline water for activation treatment to obtain the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field.
As a preferable scheme of the preparation method of the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field, the invention comprises the following steps: the total addition amount of the alloy powder of nickel, aluminum, iron and cobalt is 50-200 g/L compared with the solution IV, wherein the mass ratio of the nickel, the aluminum, the iron and the cobalt is 1:1:0.1:0.01, and the particle size is 10-200 mu m.
As a preferable scheme of the preparation method of the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field, the invention comprises the following steps: the alkaline substance comprises one or more of ammonia water/(NH 4)2CO3、(NH4)HCO3), and the alkaline substance comprises one or more of KOH and NaOH.
As a preferable scheme of the preparation method of the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field, the invention comprises the following steps: the reaction temperature of the hydrothermal reaction is 120-180 ℃ and the reaction time is 12-48 h.
As a preferable scheme of the preparation method of the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field, the invention comprises the following steps: the strength of the magnetic field applied at the same time of the hydrothermal reaction is 100-1000 GS.
As a preferable scheme of the preparation method of the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field, the invention comprises the following steps: the electrochemical etching conditions of the nickel support include,
The etching solution comprises the following components: ethylene glycol=1:1-5, 0.1-0.5 wt% of F-containing salt is added, and the F-containing salt comprises one of NaF and NH 4 F;
the etching current density is 100-500A/m 2, and the etching time is 5-60 min.
As a preferable scheme of the preparation method of the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field, the invention comprises the following steps: the coating mode of the powder material of the magnetocaloric high-activity alloy coated on the surface of the carrier comprises one of thermal spraying, laser meltallizing, chemical vapor deposition, physical vapor deposition, electrodeposition, phase inversion and conductive glue bonding.
As a preferable scheme of the preparation method of the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field, the invention comprises the following steps: the alkali water solution is placed in alkali water for activation treatment, wherein the alkali water solution comprises one or more of NaOH and KOH, the concentration is 3-6 mol/L, the treatment temperature is 50-80 ℃, and the treatment time is 1-5 min.
It is still another object of the present invention to provide an application of an electrolytic hydrogen production catalytic electrode based on an electromagnetic composite field.
In order to solve the technical problems, the invention provides the following technical scheme: comprising, using the electrolytic hydrogen production catalytic electrode as the catalytic electrode material of the alkaline water hydrogen production system as the catalytic electrode material to carry out electrolytic hydrogen production reaction, and applying a magnetic field in the reaction process;
Wherein, the temperature of the electrolyte in the alkaline water hydrogen production system is 30-90 ℃, the intensity of the externally applied magnetic field is 100 GS-2.0T, and the current frequency of the magnetic field is controlled to be 10-60 kHz.
The invention has the beneficial effects that:
(1) The electrolytic hydrogen production catalytic magneto-caloric electrode material prepared by the invention has a large three-dimensional specific surface structure, high conductivity and high catalytic activity, can improve hydrogen production capacity under the condition of an electric field and magnetic field composite field, effectively solves the electrode polarization problem caused by large mass transfer resistance in the traditional electrolytic hydrogen production process, can reduce electric energy consumption and mass transfer resistance, reduce the voltage in the reaction process, improve the reaction current density, and improve the performance and the electrolysis efficiency of a reactor, thereby reducing the reaction energy consumption.
(2) The magneto-thermal electrode material generates local heat on the surface of the catalyst under the electromagnetic action, so that the partial temperature of the surface reaction of the contact electrode is higher, the electrode electrolytic reaction is quicker, the low-temperature electrolytic system is formed without heating to the reaction temperature of 80-90 ℃ of the electrolyte of the traditional electrolytic tank, the degradation phenomenon of the electrolytic tank material and the system performance thereof caused by high temperature and the like is effectively reduced, and the service lives of the water electrolytic tank and a post-treatment system are greatly prolonged.
(3) The invention can control the temperature of the electrode reaction interface by controlling the component proportion of the material, the magnetic flux intensity and the frequency variation parameter, and simultaneously control the strengthening reaction rate and the bubble oscillation desorption effect, thereby having good operation controllability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being 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. Wherein:
FIG. 1 is an electron microscope image of a powder of a magnetocaloric high activity alloy material prepared in example 1 of the present invention.
FIG. 2 is a diagram of a catalytic electrode electron microscope prepared in example 1 of the present invention.
FIG. 3 is an electron microscope image of the powder of the magnetocaloric high activity alloy material prepared in example 2 of the present invention.
FIG. 4 is an electron microscope image of the powder of the magnetocaloric high activity alloy material prepared in example 3 of the present invention.
FIG. 5 is a schematic diagram of an apparatus for producing hydrogen by alkali electrolysis and catalysis in the invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The raw materials used in the invention are all commonly and commercially available in the field without special description.
Example 1
The embodiment provides a preparation method of an electrolytic hydrogen production catalytic electrode, which comprises the following steps:
1) Magnetically heated high-activity alloy material ingredients;
The chemical formula of the atomic composition of the designed material is X b(FeaCo(20-a)Ni30)50Y(50-b); wherein:
a＝5，b＝30；
X is: v, W, mn, atomic ratio is 1:1:1, a step of;
Y is: the atomic ratio of Ti, nb and Nd is 1:1:1, a step of;
2) Preparing a solution:
Fully dissolving the soluble salt of the X element in water at 65 ℃ to obtain a solution I, wherein the total concentration of the X element is 1.0M/L;
Fully dissolving soluble salt of the element Y in water at 65 ℃ to obtain solution II, wherein the total concentration of the element Y is 1.0M/L;
Fe. Fully dissolving soluble salts of Co and Ni in 65 ℃ water, wherein the total concentration of Fe, co and Ni elements is 2.0M/L, and obtaining solution III;
Sequentially adding the solution I, II into the solution III, heating and stirring at 60 ℃, performing ultrasonic treatment on the obtained solution for 1h, standing and cooling to room temperature after the treatment to obtain a mixed solution;
Adding 50g/L of alloy powder (the mass ratio of 1:1:0.1:0.01 and the particle size of 50 mu m) of nickel, aluminum, iron and cobalt into the mixed solution, firstly adding (NH 4)2CO3 for regulating the pH value of the solution to 8 and then adding NaOH for regulating the pH value to 12 to obtain a solution IV, and carrying out ultrasonic treatment and stirring when all materials are added;
3) Preparing powder:
Placing the solution IV in a hydrothermal kettle for hydrothermal reaction, wherein the reaction temperature is 150 ℃, and simultaneously, applying magnetic field treatment, wherein the magnetic field strength is 100GS, and the reaction time is 12 hours;
And cooling the product to 0 ℃ with the cooling amplitude of 30 ℃/min after the reaction is finished, performing precise filtration, performing ultrasonic washing on the product with deionized water for 5 times, and drying the product at 50 ℃ for 12 hours to obtain the magnetic heating type high-activity alloy material powder, wherein an electron microscope diagram of the magnetic heating type high-activity alloy material powder is shown in figure 1.
4) Load shaping and activation of the catalyst:
The method comprises the steps of carrying out electrochemical etching after cleaning the surface of a netlike carrier made of nickel alloy metal, wherein the etching solution comprises the following components in proportion: ethylene glycol=1:1, 0.1% wt F-containing salt (NaF) was added, current density 100A/m 2, time 30min;
Spraying the powder of the magnetocaloric high-activity alloy material obtained in the step 3) on the surface of a carrier by laser meltallizing, wherein the spraying amount is 200g/m 2;
the coated high-activity magnetic thermal material is placed in alkaline water for activation treatment, the alkaline water is NaOH, the concentration is 5.0mol/l, the temperature is 60 ℃ and the time is 2.0min, and the electrolytic hydrogen production catalytic electrode based on an electromagnetic composite field is obtained, and an electron microscopic diagram of the electrolytic hydrogen production catalytic electrode is shown in figure 2.
Example 2
The embodiment provides a preparation method of an electrolytic hydrogen production catalytic electrode, which comprises the following steps:
1) Magnetically heated high-activity alloy material ingredients;
The chemical formula of the atomic composition of the designed material is X b(FeaCo(20-a)Ni30)50Y(50-b); wherein:
a＝15，b＝20；
x is: mn, cu, pb, ta, ti, atomic ratio is 1:1:1:1:1, a step of;
Y is: nd, nb, sr, pm, atomic ratio is 1:1:1:1, a step of;
2) Preparing a solution:
fully dissolving the soluble salt of the X element in water at 80 ℃ to obtain a solution I, wherein the total concentration of the X element is 1.0M/L;
Fully dissolving soluble salt of the element Y in water at 80 ℃ to obtain solution II, wherein the total concentration of the element Y is 1.0M/L;
Fe. Fully dissolving soluble salts of Co and Ni in water at 80 ℃ to obtain solution III, wherein the total concentration of Fe, co and Ni elements is 2.0M/L;
Sequentially adding the solution I, II into the solution III, heating and stirring at 60 ℃, performing ultrasonic treatment on the obtained solution for 1h, standing and cooling to room temperature after the treatment to obtain a mixed solution;
Adding 100g/l of alloy powder (the mass ratio of 1:1:0.1:0.01 and the particle size of 100 mu m) of nickel, aluminum, iron and cobalt into the mixed solution, firstly adding (NH 4)2CO3 for regulating the pH value of the solution to 9 and then adding KOH for regulating the pH value to 12 to obtain a solution IV, and carrying out ultrasonic treatment and stirring when all materials are added;
3) Preparing powder:
placing the solution IV in a hydrothermal kettle for hydrothermal reaction, wherein the reaction temperature is 150 ℃, and simultaneously, applying magnetic field treatment, wherein the magnetic field strength is 500GS, and the reaction time is 24 hours;
And cooling the product to-10 ℃ in a cooling range of 30 ℃/min after the reaction is finished, performing precise filtration, performing ultrasonic washing on the product with deionized water for 3 times, and drying the product at 50 ℃ for 12 hours to obtain the magnetic heating type high-activity alloy material powder, wherein an electron microscope diagram of the magnetic heating type high-activity alloy material powder is shown in figure 3.
4) Load shaping and activation of the catalyst:
The method comprises the steps of carrying out electrochemical etching after cleaning the surface of a netlike carrier made of nickel alloy metal, wherein the etching solution comprises the following components in proportion: ethylene glycol=1:2, 0.3% wt F-containing salt (NaF) was added, current density 300A/m 2, time 20min;
Spraying the powder of the magnetocaloric high-activity alloy material obtained in the step 3) on the surface of a carrier by using a supersonic flame, wherein the spraying amount is 200g/m 2;
The coated high-activity magnetic heating material is placed in alkaline water for activation treatment, the alkaline water is NaOH with the concentration of 5.0mol/l and the temperature of 80 ℃ solution, and the time is 2.0min, so that the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field is obtained.
Example 3
The embodiment provides a preparation method of an electrolytic hydrogen production catalytic electrode, which comprises the following steps:
1) Magnetically heated high-activity alloy material ingredients;
The chemical formula of the atomic composition of the designed material is X b(FeaCo(20-a)Ni30)50Y(50-b); wherein:
a＝10，b＝15；
x is: mn, cu, pb, ta, ti, atomic ratio is 1:1:1:1:1, a step of;
Y is: nd, nb, sr, pm, atomic ratio is 1:1:1:1, a step of;
2) Preparing a solution:
fully dissolving the soluble salt of the X element in water at 80 ℃ to obtain a solution I, wherein the total concentration of the X element is 1.0M/L;
Fully dissolving soluble salt of the element Y in water at 80 ℃ to obtain solution II, wherein the total concentration of the element Y is 1.0M/L;
Fe. Fully dissolving soluble salts of Co and Ni in water at 80 ℃ to obtain solution III, wherein the total concentration of Fe, co and Ni elements is 2.0M/L;
Sequentially adding the solution I, II into the solution III, heating and stirring at 60 ℃, performing ultrasonic treatment on the obtained solution for 1h, standing and cooling to room temperature after the treatment to obtain a mixed solution;
Adding 100g/l of alloy powder (the mass ratio of 1:1:0.1:0.01 and the particle size of 100 mu m) of nickel, aluminum, iron and cobalt into the mixed solution, firstly adding ammonia water to adjust the pH value of the solution to 8, then adding KOH to adjust the pH value to 12, and obtaining solution IV, wherein ultrasonic and stirring are needed when all materials are added;
3) Preparing powder:
Placing the solution IV in a hydrothermal kettle for hydrothermal reaction, wherein the reaction temperature is 180 ℃, and simultaneously, applying magnetic field treatment, wherein the magnetic field strength is 1000GS, and the reaction time is 12 hours;
And cooling the product to-15 ℃ in a cooling range of 50 ℃/min after the reaction is finished, performing precise filtration, performing ultrasonic washing on the product with deionized water for 5 times, and drying the product at 50 ℃ for 12 hours to obtain the magnetic heating type high-activity alloy material powder, wherein an electron microscope diagram of the magnetic heating type high-activity alloy material powder is shown in figure 4.
4) Load shaping and activation of the catalyst:
The method comprises the steps of carrying out electrochemical etching after cleaning the surface of a netlike carrier made of nickel alloy metal, wherein the etching solution comprises the following components in proportion: ethylene glycol=1:5, 0.5% wt F-containing salt (NH 4 F) was added, current density 500A/m 2, time 30min;
Grinding the powder of the magnetocaloric high-activity alloy material obtained in the step 3) into nano powder with the particle size less than or equal to 50nm, further preparing particle deposition electrolyte (the salt solution of the electrolyte is the mixed solution of I, II and III of the non-alloy powder in the solution configuration in the embodiment 2), adding 50g/l of the nano high-activity alloy powder, fully stirring, and carrying out electrodeposition on the surface of the carrier material.
The loaded high-activity magnetic thermal material is placed in alkaline water for activation treatment, the alkaline water is NaOH with the concentration of 6.0mol/l and the temperature of 80 ℃ solution, and the time is 5.0min, so that the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field is obtained.
As can be seen from the powder electron microscope pictures prepared in step 3) of each of examples 1 to 3, the magnetocaloric electrode material prepared by the invention has a larger three-dimensional specific surface structure, and the structure can enable the catalytic material to have high catalytic activity and high conductivity.
Comparative example 1
The comparative example is different from example 1 in that the traditional nickel-aluminum alloy powder is directly adopted, the mass ratio of the nickel to the aluminum powder is 1:2, referring to step 4) of example 1, the nickel-aluminum alloy powder of the comparative example is used for replacing the powder of the magnetic heating type high activity alloy material, and the rest of the steps refer to example 1, so that the electrolytic hydrogen production catalytic electrode material of the comparative example is obtained.
Alkaline water tank electrolytic reaction test
Referring to fig. 5, the alkaline water tank electrolytic reaction device used in the invention is characterized in that 1 is an electrolytic tank H 2/O2 gas outlet, 2 is an electrolytic tank drain, 3 is an electrolytic tank binding post, 4 is an electrolytic tank magnetic field emission module shielding material, 5 is an electrolytic tank middle binding post, 6 is a magnetic field collecting and emitting device cavity structure, 7 is a magnetic field shielding material, 8 is a magnetic field emission block, 9 is an electrolyte inlet, 10 is an electrolytic tank O 2/H2 gas outlet, 11 is an electrolytic tank end pressing plate, 12 is a diaphragm material or a membrane electrode, and 13 is a catalytic electrode;
Test conditions:
the electrolyte is a 30wt% NaOH solution;
pressure of produced gas: 1.6MPa,10Nm 3/h alkali water tank device test, and the effective electrode area is 550mm;
When in electrolysis, the change range of the peripheral magnetic field intensity is 100GS-2.0T, the current frequency change range is 10-60 kHz, and the interface temperature of the electrode catalytic reaction is controlled by regulating and controlling the magnetic field intensity and the frequency change;
The percentage of influence of the fluctuation of the power supply (5%/min power change) on the hydrogen production is expressed as the influence of the power change 5%/min on the hydrogen production in the standard stage, and the calculation formula is as follows:
The yield influence (%) = |100% [ V H2 (first stage standard hydrogen yield) -V H2 (second stage standard hydrogen yield) ]|/V H2 (first stage standard hydrogen yield) |.A change rate of hydrogen production input power (5%/min) is measured at an initial current density of 3000A/m 2 and is based on the initial current density, and the change rate is measured according to the average yield influence change rate of 100% -120% -100% -80% -100% after 10 times of circulation.
The electrode materials prepared in examples 1 to 3 and comparative example 1 were subjected to an alkaline water bath electrolytic reaction test, and specific conditions and corresponding results are shown in table 1.
TABLE 1 results of testing different electrode materials under different electrolysis conditions
(Note:/means not tested)
As can be seen from table 1, the magnetic field applied in the electrolytic reaction process has a certain effect of reducing hydrogen production energy consumption, and under the same conditions of reaction temperature and the like, the effect of the high-efficiency magneto-thermal electrode catalytic material is far higher than that of the traditional electrode material, and the magneto-thermal high-efficiency electrolytic catalytic material has good adaptability to power fluctuation, can meet the power fluctuation condition under unstable energy sources such as photovoltaic, wind power and the like, has a good effect of reducing cell voltage under current density working conditions, and can fully save energy; the magnetic field strength and the frequency change can influence the hydrogen production, in a certain range, the higher the intensity and the frequency are, the higher the reaction interface temperature of the magneto-thermal electrode is, the higher the reaction rate is, the faster the bubble is desorbed, the higher the hydrogen production is, the energy-saving effect is obvious, and the electrolyte temperature of the traditional electrolytic tank at 90 ℃ is not needed.
Example 4
The present example was used to explore the effect of the material composition ratios on the performance of the prepared electrolytic hydrogen production catalytic electrode, and was different from example 1 in that only the material formulation of the design of step 1) was adjusted, specifically:
A: x 30(Fe5Co15Ni30)50Y20 material;
That is, the corresponding a=5, b=30 in the general formula (I);
x is selected from V, W, mn, and the atomic ratio is 2:1:1, a step of;
Y is selected from Ti, nb and Nd, and the atomic ratio is 2:1:1, a step of;
B: x 30(Fe5Co15Ni30)50Y20 material;
That is, the corresponding a=5, b=30 in the general formula (I);
x is selected from V, W, and the atomic ratio is 1:1, a step of;
Y is selected from Ti, nb and Nd, and the atomic ratio is 1:1, a step of;
c: x 15(Fe10Co(10)Ni30)50Y35 material;
That is, the corresponding a=10, b=15 in the general formula (I);
X is selected from V, W, mn, and the atomic ratio is 1:1:1, a step of;
y is selected from Ti, nb and Nd, and the atomic ratio is 1:1:1, a step of;
The rest steps are all referred to example 2, so as to obtain electrolytic hydrogen production catalytic electrodes of different magnetocaloric high-activity alloy materials, namely electrode A-4 and electrode B-4, and electrode C-4 is subjected to alkaline water tank electrolytic reaction test under the conditions that the temperature of electrolyte is 50 ℃, the magnetic field is assisted, the magnetic field strength is 1.0T, the current frequency is 25kHz, and the test result is compared with the electrode of example 1, as shown in Table 2.
Table 2 test results of electrode materials made of different magnetocaloric high activity alloy materials
In conclusion, the electrolytic hydrogen production catalytic magneto-caloric electrode material prepared by the invention has a large three-dimensional specific surface structure, high conductivity and high catalytic activity, can improve hydrogen production capacity under the condition of electric field and magnetic field composite field, effectively solves the electrode polarization problem caused by large mass transfer resistance in the traditional electrolytic hydrogen production process, can reduce electric energy consumption and mass transfer resistance, reduce the voltage in the reaction process, improve the reaction current density, and improve the performance and the electrolysis efficiency of the reactor, thereby reducing the reaction energy consumption.
The magneto-thermal electrode material generates local heat under the electromagnetic action, so that the temperature of the part which is in contact with the surface of the electrode is higher, the electrode electrolytic reaction is quicker, the heating to the reaction temperature of 80-90 ℃ of the electrolyte of the traditional electrolytic tank is not needed, a low-temperature electrolytic system is formed, the degradation phenomenon of the electrolytic tank material and the system performance thereof caused by high temperature and the like is effectively reduced, and the service life of the water electrolytic tank is greatly prolonged.
The invention can control the temperature of the electrode reaction interface by controlling the component proportion of the material, the magnetic flux intensity and the frequency variation parameter, and simultaneously control the reaction rate and the bubble desorption effect, thereby having good operation controllability.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (10)
1. An electrolytic hydrogen production catalytic electrode based on electromagnetic composite field is characterized in that: the electrolytic hydrogen production catalytic electrode is obtained by loading a magnetocaloric high-activity alloy material on a nickel carrier;
Wherein the magnetocaloric high activity alloy material is a material satisfying the following conditions (i) to (iv);
(i) The atomic composition general formula of the material is shown as formula (I);
Formula (I): x b(FeaCo(20-a)Ni30)50Y(50-b);
(ii) The value of a in the formula (I) is 5-15, and the value of b is 5-30;
(iii) The X element is selected from one or more of Mo, V, W, cr, mn, cu, zn, pb, ta, and the Y element is selected from one or more of Sc, ti, zr, er, nb, sr, ce, pm, eu, yb, ba, nd;
(iv) X, Y satisfy the atomic number ratio of formula (I).
2. The method for preparing the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field as claimed in claim 1, wherein the method comprises the following steps: comprising the steps of (a) a step of,
Dissolving the soluble salt of the X element in water at 50-80 ℃ to obtain a solution I, wherein the total concentration of the X element is 0.5-1.5M/L;
Dissolving soluble salts of the Y element in water at 50-80 ℃ to obtain a solution II, wherein the total concentration of the Y element is 0.5-1.5M/L;
Fe. Dissolving soluble salts of Co and Ni in water at 50-80 ℃ to obtain a solution III, wherein the total concentration of Fe, co and Ni elements is 1.5-2.5M/L; ;
Sequentially adding the solution I, II into the solution III, heating and stirring, performing ultrasonic treatment on the obtained mixed solution for 1-2 h, standing and cooling to room temperature to obtain the mixed solution;
Adding alloy powder of nickel, aluminum, iron and cobalt into the mixed solution, firstly adding alkaline substances to adjust the pH value of the solution to 8-10, and then adding strong alkaline substances to adjust the pH value of the solution to 10-12 to obtain solution IV;
Placing the solution IV in a hydrothermal kettle for hydrothermal reaction, simultaneously applying a magnetic field for treatment, cooling the product to 0-15 ℃ in a cooling range of 20-50 ℃/min after the reaction is finished, performing precise filtration, washing, and drying at 15-50 ℃ for 12-24 hours to obtain the magnetic heating type high-activity alloy material powder;
And (3) carrying out electrochemical etching after the surface of the nickel carrier is cleaned, coating the powder material of the magnetocaloric high-activity alloy material on the surface of the carrier, and then placing the carrier in alkaline water for activation treatment to obtain the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field.
3. The method for preparing the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field as claimed in claim 2, wherein the method comprises the following steps: the total addition amount of the alloy powder of nickel, aluminum, iron and cobalt is 50-200 g/L compared with the solution IV, wherein the mass ratio of the nickel, the aluminum, the iron and the cobalt is 1:1:0.1:0.01, and the particle size is 10-200 mu m.
4. The method for preparing the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field as claimed in claim 2, wherein the method comprises the following steps: the alkaline substance comprises one or more of ammonia water/(NH 4)2CO3、(NH4)HCO3), and the alkaline substance comprises one or more of KOH and NaOH.
5. The method for preparing the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field as claimed in claim 2, wherein the method comprises the following steps: the reaction temperature of the hydrothermal reaction is 120-180 ℃ and the reaction time is 12-48 h.
6. The method for preparing the catalytic electrode for electrolytic hydrogen production based on electromagnetic composite field as claimed in any one of claims 2 or 5, characterized by: the strength of the magnetic field applied at the same time of the hydrothermal reaction is 100-1000 GS.
7. The method for preparing the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field as claimed in claim 2, wherein the method comprises the following steps: the electrochemical etching conditions of the nickel support include,
The etching solution comprises the following components: ethylene glycol=1:1-5, 0.1-0.5 wt% of F-containing salt is added, and the F-containing salt comprises one of NaF and NH 4 F;
the etching current density is 100-500A/m 2, and the etching time is 5-60 min.
8. The method for preparing the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field as claimed in claim 2, wherein the method comprises the following steps: the coating mode of the powder material of the magnetocaloric high-activity alloy coated on the surface of the carrier comprises one of thermal spraying, laser meltallizing, chemical vapor deposition, physical vapor deposition, electrodeposition and conductive glue bonding.
9. The method for preparing the electrolytic hydrogen production catalytic electrode based on the electromagnetic composite field as claimed in claim 2, wherein the method comprises the following steps: the alkali water solution is placed in alkali water for activation treatment, wherein the alkali water solution comprises one or more of NaOH and KOH, the concentration is 3-6 mol/L, the treatment temperature is 50-80 ℃, and the treatment time is 1-5 min.
10. The use of an electromagnetic composite field based electrolytic hydrogen production catalytic electrode as claimed in claim 1, characterized in that: comprising, using the electrolytic hydrogen production catalytic electrode as the catalytic electrode material of the alkaline water hydrogen production system as the catalytic electrode material to carry out electrolytic hydrogen production reaction, and applying a magnetic field in the reaction process;
Wherein, the temperature of the electrolyte in the alkaline water hydrogen production system is 30-90 ℃, the intensity of the externally applied magnetic field is 100 GS-2.0T, and the current frequency is 10-60 kHz.
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