CN114921704A - Cobalt-nickel-molybdenum-based composite material, preparation method thereof, hydrogen evolution electrode based on cobalt-nickel-molybdenum-based composite material and household appliance - Google Patents

Cobalt-nickel-molybdenum-based composite material, preparation method thereof, hydrogen evolution electrode based on cobalt-nickel-molybdenum-based composite material and household appliance Download PDF

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CN114921704A
CN114921704A CN202110138195.6A CN202110138195A CN114921704A CN 114921704 A CN114921704 A CN 114921704A CN 202110138195 A CN202110138195 A CN 202110138195A CN 114921704 A CN114921704 A CN 114921704A
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nickel
cobalt
molybdenum
composite material
based composite
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CN114921704B (en
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辛森森
王府
王明
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Midea Group Co Ltd
Wuhu Midea Kitchen and Bath Appliances Manufacturing Co Ltd
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Midea Group Co Ltd
Wuhu Midea Kitchen and Bath Appliances Manufacturing Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention discloses a cobalt-nickel-molybdenum-based composite material, a preparation method thereof, a hydrogen evolution electrode based on the cobalt-nickel-molybdenum-based composite material and household electrical appliances, wherein the cobalt-nickel-molybdenum-based composite material contains Co, Mo and Ni; wherein the mass percent of Co is 25% -35%; the mass percent of Ni is 40-50%; the mass percent of Mo is 15-35%. According to the electroplating process, citrate is added into the electrolyte, so that the deposition of molybdenum is facilitated. The hydrogen evolution electrode prepared by the composite material of the scheme of the invention has good catalytic hydrogen evolution performance, can replace expensive noble metal-based electrodes used in the field of catalytic hydrogen production, and in addition, the material can also be used as a corrosion-resistant coating and has good application prospect.

Description

Cobalt-nickel-molybdenum-based composite material, preparation method thereof, hydrogen evolution electrode based on cobalt-nickel-molybdenum-based composite material and household appliance
Technical Field
The invention belongs to the technical field of hydrogen evolution electrodes, and particularly relates to a cobalt-nickel-molybdenum-based composite material, a preparation method thereof, a hydrogen evolution electrode based on the cobalt-nickel-molybdenum-based composite material and household electrical appliances.
Background
With the increasing exhaustion of fossil fuels, various new energy sources are continuously developed and utilized. The hydrogen energy is used as a renewable secondary energy source, has wide source, high heat value, cleanness and good combustion stability, and is a new generation of energy carrier widely adopted after non-renewable energy sources such as fossil fuel and the like.
At present, the most important hydrogen production means is hydrogen production by alkaline electrolysis of water. However, the hydrogen production cost is too high to be effectively popularized due to the existence of hydrogen evolution and oxygen evolution overpotential in the electrolysis process, which causes large reaction energy consumption.
On the other hand, the selection of the high-activity hydrogen evolution electrocatalyst is also a big pain point of the current hydrogen production technology. Platinum (Pt) -containing noble metal catalysts are well-known hydrogen evolution electrocatalysts with high activity, but platinum is rarely stored in nature and is expensive, thereby limiting its large-scale use. In recent years, some non-noble metal sulfides (e.g., MoS) 2 、CoS 2 Etc.), phosphides (e.g. FeP, MoP, Co) 2 P, etc.), carbide (Mo) 2 C) And nitrides and the like and composite materials of the nitrides and the carrier materials (such as graphene, carbon nano tubes, foamed nickel and the like) for catalytic hydrogen production are widely researched and developed, but the preparation of the composite materials needs high temperature, the yield is low, the preparation process is too harsh, and the materials have the problems of poor composite property and the like.
Therefore, in order to reduce energy consumption, it is important to develop a hydrogen evolution material having high catalytic activity at low cost.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides a cobalt-nickel-molybdenum-based composite material which not only has a good catalytic hydrogen evolution effect, but also can effectively reduce the production cost.
The invention also provides a preparation method of the cobalt-nickel-molybdenum-based composite material.
The invention also provides the application of the cobalt-nickel-molybdenum-based composite material.
Specifically, according to a first aspect of the present invention, there is provided a cobalt-nickel-molybdenum-based composite material containing Co, Ni, and Mo; wherein the mass percent of Co is 25-35%; the mass percent of Ni is 40% -50%; the mass percent of Mo is 15% -35%.
The cobalt-nickel-molybdenum-based composite material has the beneficial effects that the cobalt element, the nickel element and the molybdenum element which are relatively low in price are selected as main raw materials in the scheme of the invention, precious metals platinum and ruthenium in the prior art are replaced, and the preparation cost and the use cost of the material are saved while the low overpotential is realized.
According to an embodiment of the present invention, the mass percentage of Co is 30% to 35%; the mass percent of Ni is 45-50%; the mass percent of Mo is 20-35%.
According to an embodiment of the present invention, the cobalt-nickel-molybdenum-based composite material further comprises other elements, wherein the other elements include one or more of Fe, Cu, Cr and W.
The cobalt-nickel-molybdenum-based composite material can be used in the field of catalytic hydrogen evolution and corrosion-resistant coatings, and can improve the hydrogen evolution performance by adding a small amount of Cu or Fe group elements and improve the corrosion resistance by adding Cr or W; in addition, the addition of Cu can also reduce the generation of surface cracks of the material and improve the stability of the material.
The second aspect of the present invention provides a method for preparing the cobalt-nickel-molybdenum-based composite material according to the first aspect of the present invention, comprising the steps of:
putting a base material into an electroplating solution, and forming a cobalt-nickel-molybdenum-based composite material on the surface of the base material in an electrodeposition mode to obtain the composite material;
wherein the deposition current density of the electrodeposition is 130mA/cm 2 ～150mA/cm 2 The deposition time is 20min to 30 min.
When the cobalt-nickel-molybdenum-based composite material in the scheme of the invention is prepared, as the electro-deposition current density is high and the deposition speed of the plating layer is high, the obtained cobalt-nickel-molybdenum-based composite material has small particle appearance and larger surface area, and can provide more active sites for the catalytic hydrogen evolution process, and the cobalt-nickel-molybdenum-based composite material also has certain corrosion resistance, so that the material has higher catalytic hydrogen evolution effect.
The deposition current density in the embodiment of the invention is 130mA/cm 2 ～150mA/cm 2 If the deposition current density is too high, the hydrogen evolution phenomenon on the surface of the material is obvious in the deposition process of the coating, which affects the deposition quality, and moreover, the excessive current density can cause the over-burning blackening phenomenon on the edge of the coating, which is not beneficial to the deposition. According to one embodiment of the present invention, the substrate has a size of 10mm × 10mm × 3mm (length × width × thickness).
The preparation method of the cobalt-nickel-molybdenum-based composite material according to the embodiment of the invention has at least the following beneficial effects that the size of the matrix used for preparing the cobalt-nickel-molybdenum-based composite material in the preparation method in the scheme of the invention is 10mm multiplied by 3mm (length multiplied by width multiplied by thickness), and the exposed area can be ensured to be 1cm of standard 2 The accuracy of the deposition process and the detection result is ensured.
According to one embodiment of the present invention, the pH of the plating solution is 8 to 9.
According to one embodiment of the present invention, the plating solution contains at least a soluble cobalt salt, a soluble molybdate salt, a soluble nickel salt and a citrate salt.
According to an embodiment of the present invention, the citrate is selected from sodium citrate or potassium citrate.
According to an embodiment of the present invention, the citrate is sodium citrate.
In the embodiment of the invention, the existence of the sodium citrate can generate an excitation effect on the induced codeposition process of the molybdenum, so that the molybdenum element is more convenient to deposit, and the performance of the coating can be influenced by replacing other ions.
According to an embodiment of the present invention, the mass ratio of the soluble cobalt salt, the soluble nickel salt, the soluble molybdate and the citrate is (5-8), (120-140), (3-5) and (20-35).
According to an embodiment of the present invention, the electroplating solution further comprises a brightener and a buffer.
According to one embodiment of the present invention, the brightener is selected from sodium dodecyl sulfate or 1, 4-butynediol.
According to an embodiment of the present invention, the brightener is sodium dodecyl sulfate.
The addition of the sodium dodecyl sulfate can improve the surface appearance of a plating layer of the prepared cobalt-nickel-molybdenum-based composite material, and the preparation of the cobalt-nickel-molybdenum-based composite material needs a nickel element, and the addition of the sodium dodecyl sulfate as a brightening agent is necessary, but other brightening agents such as 1, 4-butynediol can be used, but the 1, 4-butynediol is unstable and is easy to change in the electroplating process, so the sodium dodecyl sulfate is more preferable.
According to one embodiment of the invention, the above buffer is selected from boric acid.
According to an embodiment of the present invention, the soluble cobalt salt is selected from any one of cobalt sulfate, cobalt chloride, cobalt acetate, and cobalt nitrate, or a combination thereof.
According to an embodiment of the present invention, the soluble nickel salt is selected from any one of nickel sulfate, nickel chloride, nickel acetate, and nickel nitrate, or a combination thereof.
Of course, the soluble cobalt salts and the soluble nickel salts also include hydrated salts thereof.
According to an embodiment of the present invention, the soluble cobalt salt is cobalt sulfate hexahydrate; the soluble nickel salt is nickel sulfate hexahydrate.
According to one embodiment of the present invention, the base material is selected from copper, carbon steel, stainless steel, titanium, cobalt, nickel, or carbon.
According to an embodiment of the present invention, the base material is copper. According to one embodiment of the invention, the electrodeposition is carried out under stirring; the stirring speed is 380rpm to 420 rpm.
Because the temperature can influence the deposition effect by influencing the thermal motion state of ions in the plating solution in the deposition process, the invention replaces the influence of the temperature by magnetic stirring, and the temperature in the plating solution is kept between 26 ℃ and 27 ℃ under the condition that the stirring speed is 380rpm to 420 rpm.
According to an embodiment of the invention, the cobalt-nickel-molybdenum-based composite material prepared by the preparation method has a plating layer thickness of 15-30 μm on the surface of the base material, and the plating layer is directly deposited on the surface of the base material and cannot be removed.
In a third aspect, the invention provides a hydrogen evolution electrode, which comprises the cobalt-nickel-molybdenum-based composite material according to the first aspect of the invention or the cobalt-nickel-molybdenum-based composite material prepared by the preparation method according to the second aspect of the invention.
According to the hydrogen evolution electrode in the embodiment of the invention, at least the following beneficial effects are achieved: the hydrogen evolution electrode uses the cobalt-nickel-molybdenum-based composite material in the embodiment of the invention as the cathode, so that the preparation cost and the use cost of the hydrogen evolution electrode are saved while the low overpotential is realized. Moreover, the hydrogen evolution electrode has large cathode surface area, more hydrogen evolution active sites and corrosion resistance, so the hydrogen evolution electrode has higher catalytic hydrogen evolution effect and practical value.
In a fourth aspect, the present invention provides an electrolytic water device comprising the hydrogen evolution electrode according to the third aspect of the present invention.
According to an embodiment of the present invention, the cathode of the water electrolysis apparatus is the hydrogen evolution electrode, and the anode is a carbon-based material.
According to an embodiment of the present invention, the carbon-based material is graphite.
According to the water electrolysis device in the embodiment of the invention, at least the following beneficial effects are achieved: the water electrolysis device comprises the hydrogen evolution electrode in the embodiment of the invention, and the preparation cost and the use cost of the water electrolysis device are saved while the low overpotential is realized. Moreover, the cathode surface area of the contained hydrogen evolution electrode is large, the hydrogen evolution active sites are more, and the corrosion resistance is realized, so that the water electrolysis device has higher catalytic hydrogen evolution effect and practical value.
In a fifth aspect, the present invention provides a household electrical appliance comprising the cobalt-nickel-molybdenum-based composite material according to the first aspect of the present invention or the hydrogen evolution electrode according to the third aspect of the present invention.
According to the household appliance in the embodiment of the invention, at least the following beneficial effects are achieved: the household appliance contains the cobalt-nickel-molybdenum-based composite material or the hydrogen evolution electrode in the embodiment of the invention, so that the preparation cost of the electrolyzed water is saved while the low overpotential is realized. Moreover, the cathode surface area of the contained hydrogen evolution electrode is large, the hydrogen evolution active sites are more, and the cathode has corrosion resistance, so that the household appliance has higher catalytic hydrogen evolution effect and practical value.
A sixth aspect of the invention provides the use of a cobalt-nickel-molybdenum-based composite material according to the first aspect of the invention in the production of hydrogen by electrolysis of water.
According to the application of the cobalt-nickel-molybdenum-based composite material in the embodiment of the invention in water electrolysis hydrogen production, at least the following beneficial effects are achieved, the scheme of the invention selects the cobalt element, the nickel element and the molybdenum element with relatively low price as main raw materials to prepare the hydrogen evolution electrode of the cobalt-nickel-molybdenum-based composite material, the noble metal platinum and ruthenium electrode in the prior art is replaced, when the cobalt-nickel-molybdenum-based composite material is actually applied in water electrolysis hydrogen production, low overpotential can be realized, and the preparation cost and the use cost of the electrolytic material can be effectively saved.
A seventh aspect of the invention provides the use of a cobalt-nickel-molybdenum-based composite material according to the first aspect of the invention for the preparation of a corrosion resistant material.
The application of the cobalt-nickel-molybdenum-based composite material in the embodiment of the invention in hydrogen production by water electrolysis has at least the following beneficial effects:
according to the cobalt-nickel-molybdenum-based composite material provided by the scheme of the invention, the corrosion resistance can be improved by adding Cr or W, the generation of surface cracks of the material is reduced by adding Cu, and the stability of the material is improved, so that the corrosion-resistant material is prepared.
Drawings
FIG. 1 is a graph showing the polarization curves of cobalt-nickel-molybdenum-based composites as hydrogen evolution electrodes, obtained in examples 1 and 2 of the present invention;
fig. 2 is a Tafel (Tafel) plot of the cobalt-nickel-molybdenum-based composite materials prepared in examples 1 and 2 of the present invention as hydrogen evolution electrodes.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
The embodiment prepares a cobalt-nickel-molybdenum-based composite material, and the specific method comprises the following steps:
preparing an electrolyte: each liter of electroplating solution contains 5g of cobalt sulfate hexahydrate, 120g of nickel sulfate hexahydrate, 3g of sodium molybdate and 20g of sodium citrate, boric acid is added according to the concentration of final concentration of 30g/L, and sodium dodecyl sulfate is added according to the concentration of final concentration of 0.1 g/L. The pH of the bath was adjusted to 9 by sulfuric acid and sodium hydroxide.
Preparing a matrix: red copper (with the size of 10mm multiplied by 3mm) is used as a substrate of a deposition coating, after a lead is welded, an epoxy resin is used for sealing a sample, and after the sample is sealed, the deposition can be carried out after grinding, polishing, acid cleaning, oil removing and drying treatment. During the deposition process, the matrix is used as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electro-deposition: putting a base material serving as a cathode into electroplating liquid, forming a cobalt-nickel-molybdenum alloy catalytic coating on the surface of the base material by adopting a graphite rod as an anode in an electrodeposition mode, wherein the electrodeposition current density is 130mA/cm 2 The deposition time was 20 min. During the electrodeposition process, a magnetic stirrer is used for stirring (400rpm), and the temperature of the plating solution is maintained at the normal temperature of 26-27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is directly deposited on the surface of the base material and cannot be taken down. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for hydrogen production by electrolyzing water after being cleaned by pure water and dried.
Example 2
The embodiment prepares a cobalt-nickel-molybdenum-based composite material, and the specific method comprises the following steps:
preparing electrolyte: each liter of electroplating solution contains 8g of cobalt sulfate hexahydrate, 140g of nickel sulfate hexahydrate, 5g of sodium molybdate and 35g of sodium citrate, boric acid is added according to the concentration of 50g/L of final concentration, and sodium dodecyl sulfate is added according to the concentration of 0.4g/L of final concentration. The pH of the bath was adjusted to 9 by sulfuric acid and sodium hydroxide.
Preparing a matrix: red copper (with the size of 10mm multiplied by 3mm) is used as a substrate of a deposition coating, after a lead is welded, an epoxy resin is used for sealing a sample, and after the sample is sealed, the deposition can be carried out after grinding, polishing, acid cleaning, oil removing and drying treatment. During the deposition process, the matrix is used as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electro-deposition: putting a substrate material serving as a cathode in an electroplating solution, forming a cobalt-nickel-molybdenum alloy catalytic coating on the surface of the substrate material by adopting a graphite rod as an anode in an electrodeposition mode, wherein the electrodeposition current density is 150mA/cm 2 The deposition time was 30 min. During the electrodeposition process, a magnetic stirrer is used for stirring (400rpm), and the temperature of the plating solution is maintained at the normal temperature of 26-27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is directly deposited on the surface of the base material and cannot be taken down. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for hydrogen production by electrolyzing water after being cleaned by pure water and dried.
Component optimization testing and material property analysis
(1) Compositional optimization test
According to the method for preparing the cobalt-nickel-molybdenum-based composite material in example 1, the composition ratio was adjusted to verify the effect on the performance of the prepared cobalt-nickel-molybdenum-based composite material.
Comparative example 1
The embodiment prepares a cobalt-nickel-molybdenum-based composite material, and the specific method comprises the following steps:
preparing an electrolyte: each liter of electroplating solution contains 10g of cobalt sulfate hexahydrate, 120g of nickel sulfate hexahydrate, 3g of sodium molybdate and 20g of sodium citrate, boric acid is added according to the concentration of 30g/L, and sodium dodecyl sulfate is added according to the concentration of 0.1 g/L. The pH value of the plating solution is adjusted to 8-9 by sulfuric acid and sodium hydroxide.
Preparing a matrix: red copper (with the size of 10mm multiplied by 3mm) is used as a substrate of a deposition coating, after a lead is welded, an epoxy resin is used for sealing a sample, and after the sample is sealed, the deposition can be carried out after grinding, polishing, acid cleaning, oil removing and drying treatment. During the deposition process, the matrix is used as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electro-deposition: putting a base material as a cathode in electroplating solution, forming a cobalt-nickel-molybdenum alloy catalytic coating on the surface of the base material by adopting a graphite rod as an anode in an electrodeposition mode, wherein the electrodeposition current density is 130mA/cm 2 The deposition time was 20 min. During the electrodeposition process, a magnetic stirrer is used for stirring (400rpm), and the temperature of the plating solution is maintained at the normal temperature of 26-27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is directly deposited on the surface of the base material and cannot be taken down. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for hydrogen production by electrolyzing water after being cleaned by pure water and dried.
Comparative example 1 increased the amount of cobalt sulfate hexahydrate only as compared to example 1.
Comparative example 2
The embodiment prepares a cobalt-nickel-molybdenum-based composite material, and the specific method comprises the following steps:
preparing an electrolyte: each liter of electroplating solution contains 5g of cobalt sulfate hexahydrate, 150g of nickel sulfate hexahydrate, 3g of sodium molybdate and 20g of sodium citrate, boric acid is added according to the concentration of final concentration of 30g/L, and sodium dodecyl sulfate is added according to the concentration of final concentration of 0.1 g/L. The pH value of the plating solution is adjusted to 8-9 by sulfuric acid and sodium hydroxide.
Preparing a matrix: red copper (with the size of 10mm multiplied by 3mm) is used as a substrate for depositing a plating layer, after a lead is welded, an epoxy resin is used for sealing a sample, and after the sample is sealed, the red copper can be deposited after grinding, polishing, acid cleaning, oil removing and drying treatment. During the deposition process, the matrix is used as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electro-deposition: putting a base material as a cathode in electroplating solution, forming a cobalt-nickel-molybdenum alloy catalytic coating on the surface of the base material by adopting a graphite rod as an anode in an electrodeposition mode, wherein the electrodeposition current density is 130mA/cm 2 The deposition time was 20 min. During the electrodeposition process, a magnetic stirrer is used for stirring (400rpm), and the temperature of the plating solution is maintained at the normal temperature of 26-27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is directly deposited on the surface of the base material and cannot be taken down. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for hydrogen production by electrolyzing water after being cleaned by pure water and dried.
Comparative example 2 only increased the amount of nickel sulfate hexahydrate compared to example 1.
Comparative example 3
The embodiment prepares a cobalt-nickel-molybdenum-based composite material, and the specific method comprises the following steps:
preparing an electrolyte: each liter of electroplating solution contains 5g of cobalt sulfate hexahydrate, 120g of nickel sulfate hexahydrate, 10g of sodium molybdate and 20g of sodium citrate, boric acid is added according to the concentration of 30g/L, and sodium dodecyl sulfate is added according to the concentration of 0.1 g/L. The pH value of the plating solution is adjusted to 8-9 by sulfuric acid and sodium hydroxide.
Preparing a matrix: red copper (with the size of 10mm multiplied by 3mm) is used as a substrate of a deposition coating, after a lead is welded, an epoxy resin is used for sealing a sample, and after the sample is sealed, the deposition can be carried out after grinding, polishing, acid cleaning, oil removing and drying treatment. During the deposition process, the matrix is used as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electro-deposition: putting a base material serving as a cathode into electroplating liquid, forming a cobalt-nickel-molybdenum alloy catalytic coating on the surface of the base material by adopting a graphite rod as an anode in an electrodeposition mode, wherein the electrodeposition current density is 130mA/cm 2 The deposition time was 20 min. During the electrodeposition process, a magnetic stirrer is used for stirring (400rpm), and the temperature of the plating solution is maintained at the normal temperature of 26-27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is directly deposited on the surface of the base material and cannot be taken down. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for hydrogen production by electrolyzing water after being cleaned by pure water and dried.
Comparative example 3 only increased the amount of sodium molybdate compared to example 1.
Comparative example 4
The embodiment prepares a cobalt-nickel-molybdenum-based composite material, and the specific method comprises the following steps:
preparing electrolyte: each liter of electroplating solution contains 5g of cobalt sulfate hexahydrate, 120g of nickel sulfate hexahydrate and 3g of sodium molybdate, boric acid is added according to the concentration of 30g/L, and sodium dodecyl sulfate is added according to the concentration of 0.1 g/L. And regulating the pH value of the plating solution to 8-9 by using sulfuric acid and sodium hydroxide.
Preparing a matrix: red copper (with the size of 10mm multiplied by 3mm) is used as a substrate of a deposition coating, after a lead is welded, an epoxy resin is used for sealing a sample, and after the sample is sealed, the deposition can be carried out after grinding, polishing, acid cleaning, oil removing and drying treatment. During the deposition process, the matrix is used as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electro-deposition: putting a base material as a cathode in electroplating solution, forming a cobalt-nickel-molybdenum alloy catalytic coating on the surface of the base material by adopting a graphite rod as an anode in an electrodeposition mode, wherein the electrodeposition current density is 130mA/cm 2 The deposition time was 20 min. During the electrodeposition process, a magnetic stirrer is used for stirring (400rpm), and the temperature of the plating solution is maintained at the normal temperature of 26-27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is directly deposited on the surface of the base material and cannot be taken down. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for hydrogen production by electrolyzing water after being cleaned by pure water and dried.
In comparison with example 1, comparative example 4 has no sodium citrate added.
Detection of Hydrogen evolution Performance
The samples prepared in the above examples 1 and 2 were passed through Chenghua 660e electrochemical workstation and detected in 1mol/L KOH solution by using three electrodes, the counter electrode was a platinum electrode and the reference electrode was an HgO electrode. When detecting the hydrogen evolution performance, a scanning Linear Voltammetry (LSV) is used, and the current density is observed to be 10mA/cm 2 The corresponding voltage value in the state. Generally, the smaller the voltage value, the better the hydrogen evolution performance.
The test results of examples 1 and 2 are shown in fig. 1 and 2, wherein the potential interval is from the open circuit potential (VS HgO) of the plating layer to-0.3V (VS HgO), the scanning speed is 0.001V/s, and the Tafel curve is obtained by calculation and transformation according to the LSV test results. The smaller the slope of the Tafel curve, the better the plating performance.
As shown in fig. 1, the overpotential of the cobalt-nickel-molybdenum-based composite material prepared in example 1 was-0.076V with respect to the standard hydrogen electrode potential, and the overpotential of the cobalt-nickel-molybdenum-based composite material prepared in example 2 was-0.073V with respect to the standard hydrogen electrode potential.
While the slope of the fitted Tafel curve for the Tafel plot obtained after processing through LSV data is shown in FIG. 2. The smaller the slope of the Tafel curve is, the better the hydrogen evolution catalysis performance is represented, wherein, the slope of the Tafel curve of the hydrogen evolution electrode in example 1 is only 75.48mV/dec, and the slope of the Tafel curve of the hydrogen evolution electrode in example 2 is only 81.32mV/dec, which proves that the Tafel curve has excellent hydrogen evolution catalysis performance.
Comparative examples 1-4 were tested using the same test method. As a result, the hydrogen evolution activity of comparative examples 1-4 is lower than that of example 1, especially the cobalt-nickel-molybdenum-based composite material prepared according to the formula of comparative example 4, and the content of molybdenum element in the cobalt-nickel-molybdenum-based composite material is low under the condition of not adding sodium citrate, which indicates that the sodium citrate influences the deposition efficiency of the molybdenum element in the electrodeposition process. Furthermore, it can be illustrated by comparing example 1 with comparative examples 1 to 4 that the contents of the components of the cobalt-nickel-molybdenum-based composite material according to the embodiment of the present invention have a large influence on the properties of the prepared cobalt-nickel-molybdenum-based composite material. When the type or content range of the used components is different from that of the components used in the invention, the performance of the cobalt-nickel-molybdenum-based composite material prepared by the same preparation method is obviously lower than the use requirement of the cobalt-nickel-molybdenum-based composite material, and the expected hydrogen evolution effect cannot be achieved.
(2) Analysis of material Properties
Performing component detection on the cobalt-nickel-molybdenum-based composite material prepared in the example 1, repeating the component detection for 3 times, and determining that the mass percent of Co in the cobalt-nickel-molybdenum-based composite material prepared in the example 1 is 30-35%; the mass percent of Ni is 45-50%; the mass percent of Mo is 20-35%.
Comparative example 5
The embodiment prepares a cobalt-nickel-molybdenum-based composite material, and the specific method comprises the following steps:
preparing an electrolyte: each liter of electroplating solution contains 5g of cobalt sulfate hexahydrate, 120g of nickel sulfate hexahydrate, 3g of sodium molybdate and 20g of sodium citrate, boric acid is added according to the concentration of final concentration of 30g/L, and sodium dodecyl sulfate is added according to the concentration of final concentration of 0.1 g/L. The pH value of the plating solution is adjusted to 8-9 by sulfuric acid and sodium hydroxide.
Preparing a matrix: red copper (with the size of 10mm multiplied by 3mm) is used as a substrate of a deposition coating, after a lead is welded, an epoxy resin is used for sealing a sample, and after the sample is sealed, the deposition can be carried out after grinding, polishing, acid cleaning, oil removing and drying treatment. During the deposition process, the matrix is used as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electro-deposition: putting a base material as a cathode in electroplating solution, forming a cobalt-nickel-molybdenum alloy catalytic coating on the surface of the base material by adopting a graphite rod as an anode in an electrodeposition mode, wherein the electrodeposition current density is 160mA/cm 2 The deposition time was 20 min.During the electrodeposition process, a magnetic stirrer is used for stirring (400rpm), and the temperature of the plating solution is maintained at the normal temperature of 26-27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is directly deposited on the surface of the base material and cannot be taken down. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for hydrogen production by electrolyzing water after being cleaned by pure water and dried.
Comparative example 5 increased the deposition current density of electrodeposition compared to example 1.
When the cobalt-nickel-molybdenum-based composite material prepared in the comparative example 5 is observed by an electron microscope, the number of the small balls on the surface of the coating is less than that in the example 1, the main reason is that hydrogen evolution phenomenon is generated in the deposition process of the coating due to overlarge current density, so that the deposition of cobalt element, nickel element and molybdenum element is influenced, and the quality of the obtained cobalt-nickel-molybdenum-based composite material is poor. Moreover, the cobalt-nickel-molybdenum-based composite material prepared in comparative example 5 exhibited a significant phenomenon of scorching due to overheating at the edges of the plating layer, also due to an excessively high current density. When the current density is too low, the deposition time is too long, and the production efficiency is reduced. Thus, the deposition current density in embodiments of the present invention is based on the optimal range for the formulation of the ingredients in embodiments of the present invention.
Example 1 comparison of the cobalt-nickel-molybdenum-based composite prepared in example 1 with the prior art
Comparative example 6
Example 1, publication No. CN102127776A, is used as a comparative example, and the entirety of this example is incorporated by reference into this example, which specifically includes the following steps:
a copper sheet is taken and cut into a sample with the thickness of 15mm multiplied by 4mm, a copper conducting wire is welded on the sample, and the non-working surface is sealed by epoxy resin. Sequentially grinding a working surface by using No. 360-No. 1000 water sand paper, polishing by using a polishing machine, performing pretreatment processes such as alkali cleaning for removing oil, acetone for removing oil, hot water cleaning, strong etching, weak etching and the like, finally cleaning by using deionized water, and putting into a plating solution. The selected anode is a nickel plate, and the area ratio of the anode to the cathode is 1: 3. The process conditions for electrodeposition are as follows: plating solution pH is 8, temperature T is 25 deg.C, electrodeposition time T is 60min, and currentDensity Dk 10mA/cm 2 . The electroplating solution comprises the following components: NiSO 4 ·6H 2 O 40g/L、CoSO 4 ·7H 2 O 2g/L、Na 2 MoO 4 ·2H 2 O 15g/L、Na 3 C 6 H 5 O 7 ·2H 2 O10g/L and Na 2 CO 3 60 g/L. The resulting amorphous plating layer was tested to have Ni, Mo, and Co contents of 47.51%, 38.97%, and 13.52% by weight, respectively, and a thickness of 4 μm.
This comparative example 6 differs from example 1 in that:
compared with the embodiment 1, the size of the matrix of the comparative example 6 is increased, the content of cobalt element in each liter of electroplating solution is reduced, the content of nickel element is reduced, the content of molybdenum element is increased, and sodium carbonate is also added.
The anode of the electrode in comparative example 6 was a nickel plate, and example 1 was graphite.
The electrodeposition of comparative example 6 had a deposition current density of 10mA/cm 2 The deposition time was 60 min.
The electrodeposition of example 1 had a deposition current density of 130mA/cm 2 The deposition time was 20 min.
Comparative example 7
Example 2, publication No. CN102127776A, is used as a comparative example, and the entirety of this example is incorporated by reference into this example, which specifically includes the following steps:
a copper sheet is taken and cut into a sample of 15mm multiplied by 4mm, copper wires are welded on, and the non-working surface is sealed by epoxy resin. Sequentially grinding a working surface by using No. 360-No. 1000 water sand paper, polishing by using a polishing machine, performing pretreatment processes such as alkali cleaning for removing oil, acetone for removing oil, hot water cleaning, strong etching, weak etching and the like, finally cleaning by using deionized water, and putting into a plating solution. The selected anode is a nickel plate, and the area ratio of the anode to the cathode is 1: 3. The process conditions for electrodeposition are as follows: the pH value of the plating solution is 9, the temperature T is 30 ℃, the electrodeposition time T is 60min, and the current density Dk is 20mA/cm 2 . The electroplating solution comprises NiSO 4 ·6H 2 O 60g/L、CoSO 4 ·7H 2 O 5g/L、Na 2 MoO 4 ·2H 2 O 20g/L、Na 3 C 6 H 5 O 7 ·2H 2 O10g/L and Na 2 CO 3 80 g/L. The prepared amorphous plating layer was tested to have a thickness of 5 μm in which the weight percentages of Ni, Mo, and Co were 49.78%, 37.06%, and 13.16%, respectively.
This comparative example 7 differs from example 1 in that:
compared with example 1, the size of the matrix of comparative example 7 is increased, the content of nickel element in each liter of electroplating solution is reduced, the content of molybdenum element is increased, the content of sodium citrate is increased, and sodium carbonate is also added.
The anode of the electrode in comparative example 7 was a nickel plate, and example 1 was graphite.
The deposition current density of the electrodeposition of comparative example 7 was 20mA/cm 2 The deposition time was 60 min.
The electrodeposition of example 1 had a deposition current density of 130mA/cm 2 The deposition time was 20 min.
Comparative example 8
Example 3, publication No. CN102127776A, is used as a comparative example, and the entire content of this example is incorporated by reference into this example, which specifically includes the following steps:
a copper sheet is taken and cut into a sample with the thickness of 15mm multiplied by 4mm, a copper conducting wire is welded on the sample, and the non-working surface is sealed by epoxy resin. Sequentially grinding a working surface by using No. 360-No. 1000 water sand paper, polishing by using a polishing machine, performing pretreatment processes such as alkali cleaning for removing oil, acetone for removing oil, hot water cleaning, strong etching, weak etching and the like, finally cleaning by using deionized water, and putting into a plating solution. The selected anode is a nickel plate, and the area ratio of the anode to the cathode is 1: 3. The process conditions for electrodeposition are as follows: the pH value of the plating solution is 10, the temperature T is 35 ℃, the electrodeposition time T is 60min, and the current density Dk is 20mA/cm 2 . The electroplating solution comprises NiSO 4 ·6H 2 O 80g/L、CoSO 4 ·7H 2 O 8g/L、Na 2 MoO 4 ·2H 2 O 30g/L、Na 3 C 6 H 5 O 7 ·2H 2 O15 g/L and Na 2 CO 3 100 g/L. The obtained amorphous coating has been tested, and the weight of Ni, Mo and Co in the amorphous coatingThe amounts were 49.78%, 37.06% and 13.16%, respectively, and the thickness of the amorphous plating layer was 5 μm.
This comparative example 8 differs from example 1 in that:
compared with example 1, the matrix size of comparative example 8 is increased, the content of nickel element in each liter of electroplating solution is reduced, the content of molybdenum element is increased, the content of sodium citrate is increased, and sodium carbonate is also added.
The anode of the electrode in comparative example 8 was a nickel plate, and example 1 was graphite.
The deposition current density of the electrodeposition of comparative example 8 was 20mA/cm 2 The deposition time was 60 min.
The deposition current density of the electrodeposition of example 1 was 130mA/cm 2 The deposition time was 20 min.
The results of comparative examples 6 to 8 are directly derived from CN102127776A (the test method is the same as in the example), and comparative example 8 has the best hydrogen evolution catalytic activity and hydrogen evolution overpotential eta 100 ＝112mV。
Compared with the comparative example 8, the overpotentials of the cobalt-nickel-molybdenum-based composite materials prepared in the examples 1 and 2 are obviously lower (the overpotential of the cobalt-nickel-molybdenum-based composite materials prepared in the example 1 is-76 mV relative to the potential of a standard hydrogen electrode, and the overpotential of the cobalt-nickel-molybdenum-based composite materials prepared in the example 2 is-73 mV relative to the potential of the standard hydrogen electrode), namely, the cobalt-nickel-molybdenum-based composite materials prepared in the examples 1 and 2 have stronger hydrogen evolution activity.
The examples, the comparative examples and the detection results show that when the cobalt-nickel-molybdenum-based composite material is prepared, the deposition process can be promoted by adopting an electrodeposition deposition mode and adjusting parameters such as deposition current density and component ratio, and the like, so that the improvement of the performance of a plating layer is facilitated. The preparation method disclosed by the invention is used for preparing the hydrogen evolution electrode, and the prepared hydrogen evolution electrode has good catalytic hydrogen evolution performance and corrosion resistance, can replace expensive noble metal-based electrodes used in the field of catalysis, and has a good application prospect.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.

Claims (18)

1. The cobalt-nickel-molybdenum-based composite material is characterized in that the cobalt-nickel-molybdenum-based composite material contains Co, Ni and Mo; wherein the mass percent of Co is 25-35%; the mass percent of Ni is 40% -50%; the mass percent of Mo is 15-35%.
2. The cobalt-nickel-molybdenum-based composite material according to claim 1, wherein the mass percentage of Co is 30% to 35%; the mass percent of Ni is 45-50%; the mass percent of Mo is 20-35%.
3. The cobalt-nickel-molybdenum-based composite material according to claim 1, wherein the cobalt-nickel-molybdenum-based composite material further comprises other elements, the other elements comprising one or more of Fe, Cu, Cr and W.
4. A method for preparing a cobalt-nickel-molybdenum-based composite material as claimed in any one of claims 1 to 3, comprising the steps of:
putting a base material into an electroplating solution, and forming a cobalt-nickel-molybdenum-based composite material on the surface of the base material in an electrodeposition mode to obtain the composite material;
wherein the deposition current density of the electrodeposition is 130mA/cm 2 ～150mA/cm 2 The deposition time is 20min to 30 min.
5. The method for preparing the cobalt-nickel-molybdenum-based composite material as claimed in claim 4, wherein the thickness of the cobalt-nickel-molybdenum-based composite material prepared by the preparation method is 15 to 30 μm.
6. The method for producing a cobalt-nickel-molybdenum-based composite material according to claim 4, wherein the pH of the plating solution is 8 to 9.
7. The method as set forth in claim 4, wherein the plating solution contains at least a soluble cobalt salt, a soluble nickel salt, a soluble molybdate salt and a citrate salt.
8. The method for preparing a cobalt-nickel-molybdenum-based composite material according to claim 7, wherein the mass ratio of the soluble cobalt salt, the soluble nickel salt, the soluble molybdate and the citrate is (5-8): (120-140): (3-5): (20-35).
9. The method of claim 7, wherein the plating solution further comprises a brightener and a buffer.
10. The method for preparing a cobalt-nickel-molybdenum-based composite material according to claim 7, wherein the soluble cobalt salt is selected from any one of cobalt sulfate, cobalt chloride, cobalt acetate, and cobalt nitrate, or a combination thereof.
11. The method for preparing a cobalt-nickel-molybdenum-based composite material according to claim 7, wherein the soluble nickel salt is selected from any one of nickel sulfate, nickel chloride, nickel acetate, nickel nitrate, or a combination thereof.
12. The method of preparing a cobalt-nickel-molybdenum-based composite material according to claim 4, wherein the matrix material is selected from copper, carbon steel, stainless steel, titanium, cobalt, nickel or carbon.
13. The method for preparing a cobalt-nickel-molybdenum-based composite material according to claim 4, wherein the electrodeposition is carried out under stirring; the stirring speed is 380 rpm-420 rpm.
14. Hydrogen-evolving electrode comprising a cobalt-nickel-molybdenum-based composite material according to any one of claims 1 to 3.
15. An electrolytic water device characterized by comprising the hydrogen evolution electrode according to claim 14.
16. Electrical household appliance comprising a cobalt-nickel-molybdenum-based composite material according to any one of claims 1 to 3 or a hydrogen-evolving electrode according to claim 14.
17. Use of a cobalt-nickel-molybdenum-based composite material according to any one of claims 1 to 3 for the production of hydrogen by electrolysis of water.
18. Use of the cobalt-nickel-molybdenum-based composite material according to any one of claims 1 to 3 for the preparation of a corrosion resistant material.
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