CN114921704B - 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 PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
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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 percentage of Co is 25% -35%; the mass percentage of Ni is 40% -50%; the mass percentage of Mo is 15-35%. According to the electroplating process, citrate is added into the electrolyte, so that the deposition of molybdenum element is facilitated. The hydrogen evolution electrode prepared by the composite material has good catalytic hydrogen evolution performance, can replace expensive noble metal base electrodes used in the field of catalytic hydrogen production, can be used as a corrosion-resistant coating, and has good application prospect.
Description
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 appliances.
Background
As fossil fuels are increasingly exhausted, various new energy sources are increasingly 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 an energy carrier widely adopted in the next generation after non-renewable energy sources such as fossil fuel and the like.
Currently, the most dominant hydrogen production means is alkaline water electrolysis for hydrogen production. However, the existence of hydrogen evolution and oxygen evolution overpotential in the electrolysis process causes larger reaction energy consumption and too high hydrogen production cost to be effectively popularized.
On the other hand, the selection of the high-activity hydrogen evolution electrocatalyst is also a great pain point in the current hydrogen production technology. Platinum (Pt) -containing noble metal catalysts are well-known high-activity hydrogen evolution electrocatalysts, but platinum has a small reserves in nature and is expensive, thus 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) The preparation of the composite materials is required to be high temperature, the yield is low, the preparation process is too harsh, and the material has the problems of poor composivity and the like.
Therefore, in order to reduce the energy consumption, it is of great importance to develop hydrogen evolution materials which are low in cost and have high catalytic activity.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the cobalt-nickel-molybdenum-based composite material provided by the invention 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 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, which contains Co, ni and Mo; wherein the mass percentage of Co is 25% -35%; the mass percentage of Ni is 40-50%; the mass percentage of Mo is 15-35%.
The cobalt-nickel-molybdenum based composite material has the advantages that the cobalt element, the nickel element and the molybdenum element which are relatively low in price are selected as main raw materials, noble metals such as 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 one embodiment of the present invention, the cobalt-nickel-molybdenum-based composite material further contains other elements including one or more of Fe, cu, cr, and W.
The cobalt-nickel-molybdenum based composite material of the scheme of the invention not only can be used in the field of catalytic hydrogen evolution, but also can be used in the field of corrosion-resistant plating, and can improve the hydrogen evolution performance by adding a small amount of Cu or Fe group elements, and can also improve the corrosion resistance by adding Cr or W; in addition, the addition of Cu element can reduce the generation of cracks on the surface of the material and improve the stability of the material.
The second aspect of the invention provides a method for preparing the cobalt-nickel-molybdenum-based composite material according to the first aspect of the invention, which comprises the following steps:
placing a matrix material into electroplating solution, and forming a cobalt-nickel-molybdenum-based composite material on the surface of the matrix 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 20 min-30 min.
When the cobalt-nickel-molybdenum based composite material in the scheme of the invention is prepared, the electrodeposited current density is high, the plating layer deposition speed is high, the obtained cobalt-nickel-molybdenum based composite material has small particle morphology and larger surface area, more active sites can be provided 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 In the range of (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, the deposition quality is affected, and the excessive current density can cause the edge of the coatingThe edge is blackened due to over-burning, which is unfavorable for deposition. According to one embodiment of the present invention, the dimensions of the substrate are 10mm×10mm×3mm (length×width×thickness).
The preparation method of the cobalt-nickel-molybdenum-based composite material has at least the following beneficial effects that the size of the matrix used for preparation in the preparation method in the scheme of the invention is 10mm multiplied by 3mm (length multiplied by width multiplied by thickness), and the exposure area can be ensured to be 1cm with the 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, a soluble nickel salt, and a citrate.
According to one embodiment of the invention, the citrate is selected from sodium citrate or potassium citrate.
According to one embodiment of the present invention, the citrate is sodium citrate.
The existence of sodium citrate in the embodiment of the invention can excite the induced co-deposition process of molybdenum, is more convenient for the deposition of molybdenum element, and can influence the performance of the plating layer when other ions are replaced.
According to one embodiment of the 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): (20-35).
According to one embodiment of the present invention, the plating solution further contains a brightening agent and a buffer.
According to one embodiment of the invention, the brightening agent is selected from sodium dodecyl sulphate or 1, 4-butynediol.
According to one embodiment of the present invention, the brightening agent is sodium dodecyl sulfonate.
The addition of sodium dodecyl sulfate can improve the surface appearance of the coating of the prepared cobalt-nickel-molybdenum-based composite material, and because nickel element is needed for preparing the cobalt-nickel-molybdenum-based composite material, the addition of sodium dodecyl sulfate as a brightening agent is necessary, and of course, other brightening agents such as 1, 4-butynediol can be used, but because the 1, 4-butynediol is unstable, the plating process is easy to change, so the sodium dodecyl sulfate is a better choice.
According to one embodiment of the invention, the 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, 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, nickel nitrate, or a combination thereof.
Of course, the above soluble cobalt salts and soluble nickel salts also include hydrated salts thereof.
According to one embodiment of the present invention, the soluble cobalt salt is cobalt sulfate hexahydrate; the soluble nickel salt is nickel sulfate hexahydrate.
According to an embodiment of the present invention, the base material is selected from copper, carbon steel, stainless steel, titanium, cobalt, nickel or carbon.
According to one embodiment of the present invention, the base material is red copper. According to one embodiment of the invention, the above electrodeposition is carried out under stirring; the stirring speed is 380 rpm-420 rpm.
The temperature also affects the deposition effect by affecting the thermal motion state of ions in the plating solution during the deposition process, so the invention replaces the temperature effect by magnetic stirring, and the temperature in the plating solution is kept at 26-27 ℃ under the condition that the stirring speed is 380-420 rpm.
According to one embodiment of the invention, the thickness of the coating layer of the cobalt-nickel-molybdenum-based composite material prepared by the preparation method on the surface of the substrate is 15-30 mu m, and the coating layer is not removable when being directly deposited on the surface of the substrate.
The third aspect of the invention provides a hydrogen evolution electrode comprising 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.
The hydrogen evolution electrode in the embodiment of the invention has at least the following beneficial effects: the hydrogen evolution electrode uses the cobalt-nickel-molybdenum based composite material in the embodiment of the invention as a cathode, so that the preparation cost and the use cost of the hydrogen evolution electrode are saved while the low overpotential is realized. In addition, the hydrogen evolution electrode has high catalytic hydrogen evolution effect and practical value due to the large cathode surface area, more hydrogen evolution active sites and corrosion resistance.
A fourth aspect of the present invention provides an electrolytic water device comprising a hydrogen evolving electrode according to the third aspect of the present invention.
According to one embodiment of the present invention, the cathode of the water electrolysis device 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.
The water electrolysis device in the embodiment of the invention has at least the following beneficial effects: the water electrolysis device comprises the hydrogen evolution electrode in the embodiment of the invention, so that the preparation cost and the use cost of the water electrolysis device are saved while the low overpotential is realized. In addition, the cathode surface area in 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 an electric home appliance, which contains the cobalt-nickel-molybdenum-based composite material according to the first aspect or the hydrogen evolution electrode according to the third aspect of the present invention.
The household electrical appliance provided by the embodiment of the invention has at least the following beneficial effects: 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. In addition, the cathode surface area in the hydrogen evolution electrode is large, the hydrogen evolution active sites are more, and the household appliance 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 water electrolysis hydrogen production, the method has the advantages that the cobalt element, the nickel element and the molybdenum element which are relatively low in price are selected as main raw materials to prepare the hydrogen evolution electrode of the cobalt-nickel-molybdenum based composite material, noble metal platinum and ruthenium electrodes in the prior art are replaced, and when the method is practically applied to the 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 the hydrogen production by water electrolysis has at least the following beneficial effects:
according to the cobalt-nickel-molybdenum based composite material, the corrosion resistance can be improved by adding Cr or W, the generation of cracks on the surface of the material is reduced by adding Cu element, 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 of cobalt-nickel-molybdenum based composite materials as hydrogen evolution electrodes prepared in examples 1 and 2 of the present invention;
FIG. 2 is a Tafel plot of cobalt-nickel-molybdenum based composites prepared in examples 1 and 2 of the present invention as hydrogen evolution electrodes.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
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 the plating solution contained 5g of cobalt sulfate hexahydrate, 120g of nickel sulfate hexahydrate, 3g of sodium molybdate and 20g of sodium citrate, and boric acid was added at a final concentration of 30g/L, and sodium dodecyl sulfate was added at a final concentration of 0.1 g/L. The pH of the plating solution was adjusted to 9 by sulfuric acid and sodium hydroxide.
Preparation of a matrix: red copper (with the size of 10mm multiplied by 3 mm) is used as a matrix for depositing a coating, the lead is welded and then subjected to sample sealing by epoxy resin, and after sample sealing, the lead can be deposited after grinding, polishing, acid washing, degreasing and drying. During the deposition process, the substrate serves as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electrodeposition: placing a substrate as a cathode in electroplating solution, wherein a graphite rod is adopted as an anode, and a cobalt-nickel-molybdenum alloy catalytic coating is formed on the surface of the substrate in an electrodeposition manner, wherein the electrodeposition current density of electrodeposition is 130mA/cm 2 The deposition time was 20min. During electrodeposition, stirring (400 rpm) was performed with a magnetic stirrer, and the plating solution temperature was maintained at a normal temperature of 26 to 27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is not removed when being directly deposited on the surface of the substrate. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for producing hydrogen by water electrolysis after pure water cleaning and drying treatment.
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 the plating solution contained 8g of cobalt sulfate hexahydrate, 140g of nickel sulfate hexahydrate, 5g of sodium molybdate and 35g of sodium citrate, and boric acid was added at a final concentration of 50g/L, and sodium dodecyl sulfate was added at a final concentration of 0.4 g/L. The pH of the plating solution was adjusted to 9 by sulfuric acid and sodium hydroxide.
Preparation of a matrix: red copper (with the size of 10mm multiplied by 3 mm) is used as a matrix for depositing a coating, the lead is welded and then subjected to sample sealing by epoxy resin, and after sample sealing, the lead can be deposited after grinding, polishing, acid washing, degreasing and drying. During the deposition process, the substrate serves as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electrodeposition: placing a substrate as a cathode in electroplating solution, wherein a graphite rod is adopted as an anode, a cobalt-nickel-molybdenum alloy catalytic coating is formed on the surface of the substrate in an electrodeposition manner, and the electrodeposition current density of electrodeposition is 150mA/cm 2 The deposition time was 30min. During electrodeposition, stirring (400 rpm) was performed with a magnetic stirrer, and the plating solution temperature was maintained at a normal temperature of 26 to 27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is not removed when being directly deposited on the surface of the substrate. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for producing hydrogen by water electrolysis after pure water cleaning and drying treatment.
Component optimization testing and material property analysis
(1) Component optimization test
According to the preparation method of the cobalt-nickel-molybdenum-based composite material in example 1, the component proportion is adjusted, and the influence of the component proportion on the performance of the prepared cobalt-nickel-molybdenum-based composite material is verified.
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 the plating solution contained 10g of cobalt sulfate hexahydrate, 120g of nickel sulfate hexahydrate, 3g of sodium molybdate and 20g of sodium citrate, and boric acid was added at a final concentration of 30g/L, and sodium dodecyl sulfate was added at a final concentration of 0.1 g/L. The pH value of the plating solution is regulated to 8-9 by sulfuric acid and sodium hydroxide.
Preparation of a matrix: red copper (with the size of 10mm multiplied by 3 mm) is used as a matrix for depositing a coating, the lead is welded and then subjected to sample sealing by epoxy resin, and after sample sealing, the lead can be deposited after grinding, polishing, acid washing, degreasing and drying. During the deposition process, the substrate serves as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electrodeposition: placing a substrate as a cathode in an electroplating solution, wherein the anode adopts a graphite rod, and the substrate is formed by electrodepositionForming a cobalt-nickel-molybdenum alloy catalytic coating on the surface, wherein the deposition current density of electrodeposition is 130mA/cm 2 The deposition time was 20min. During electrodeposition, stirring (400 rpm) was performed with a magnetic stirrer, and the plating solution temperature was maintained at a normal temperature of 26 to 27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is not removed when being directly deposited on the surface of the substrate. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for producing hydrogen by water electrolysis after pure water cleaning and drying treatment.
Comparative example 1 only increased the amount of cobalt sulfate hexahydrate 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 the plating solution contained 5g of cobalt sulfate hexahydrate, 150g of nickel sulfate hexahydrate, 3g of sodium molybdate and 20g of sodium citrate, and boric acid was added at a final concentration of 30g/L, and sodium dodecyl sulfate was added at a final concentration of 0.1 g/L. The pH value of the plating solution is regulated to 8-9 by sulfuric acid and sodium hydroxide.
Preparation of a matrix: red copper (with the size of 10mm multiplied by 3 mm) is used as a matrix for depositing a coating, the lead is welded and then subjected to sample sealing by epoxy resin, and after sample sealing, the lead can be deposited after grinding, polishing, acid washing, degreasing and drying. During the deposition process, the substrate serves as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electrodeposition: placing a substrate as a cathode in electroplating solution, wherein a graphite rod is adopted as an anode, and a cobalt-nickel-molybdenum alloy catalytic coating is formed on the surface of the substrate in an electrodeposition manner, wherein the electrodeposition current density of electrodeposition is 130mA/cm 2 The deposition time was 20min. During electrodeposition, stirring (400 rpm) was performed with a magnetic stirrer, and the plating solution temperature was maintained at a normal temperature of 26 to 27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is not removed when being directly deposited on the surface of the substrate. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for producing hydrogen by water electrolysis after pure water cleaning and drying treatment.
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 the plating solution contained 5g of cobalt sulfate hexahydrate, 120g of nickel sulfate hexahydrate, 10g of sodium molybdate and 20g of sodium citrate, and boric acid was added at a final concentration of 30g/L, and sodium dodecyl sulfate was added at a final concentration of 0.1 g/L. The pH value of the plating solution is regulated to 8-9 by sulfuric acid and sodium hydroxide.
Preparation of a matrix: red copper (with the size of 10mm multiplied by 3 mm) is used as a matrix for depositing a coating, the lead is welded and then subjected to sample sealing by epoxy resin, and after sample sealing, the lead can be deposited after grinding, polishing, acid washing, degreasing and drying. During the deposition process, the substrate serves as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electrodeposition: placing a substrate as a cathode in electroplating solution, wherein a graphite rod is adopted as an anode, and a cobalt-nickel-molybdenum alloy catalytic coating is formed on the surface of the substrate in an electrodeposition manner, wherein the electrodeposition current density of electrodeposition is 130mA/cm 2 The deposition time was 20min. During electrodeposition, stirring (400 rpm) was performed with a magnetic stirrer, and the plating solution temperature was maintained at a normal temperature of 26 to 27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is not removed when being directly deposited on the surface of the substrate. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for producing hydrogen by water electrolysis after pure water cleaning and drying treatment.
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 an electrolyte: each liter of the plating solution contained 5g of cobalt sulfate hexahydrate, 120g of nickel sulfate hexahydrate and 3g of sodium molybdate, and boric acid was added at a final concentration of 30g/L, and sodium dodecyl sulfate was added at a final concentration of 0.1 g/L. The pH value of the plating solution is regulated to 8-9 by sulfuric acid and sodium hydroxide.
Preparation of a matrix: red copper (with the size of 10mm multiplied by 3 mm) is used as a matrix for depositing a coating, the lead is welded and then subjected to sample sealing by epoxy resin, and after sample sealing, the lead can be deposited after grinding, polishing, acid washing, degreasing and drying. During the deposition process, the substrate serves as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electrodeposition: placing a substrate as a cathode in electroplating solution, wherein a graphite rod is adopted as an anode, and a cobalt-nickel-molybdenum alloy catalytic coating is formed on the surface of the substrate in an electrodeposition manner, wherein the electrodeposition current density of electrodeposition is 130mA/cm 2 The deposition time was 20min. During electrodeposition, stirring (400 rpm) was performed with a magnetic stirrer, and the plating solution temperature was maintained at a normal temperature of 26 to 27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is not removed when being directly deposited on the surface of the substrate. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for producing hydrogen by water electrolysis after pure water cleaning and drying treatment.
In contrast to example 1, comparative example 4 was free of added sodium citrate.
Detection of Hydrogen evolution Performance
The samples prepared in the above examples 1 and 2 were detected in 1mol/L KOH solution by using a Chenhua 660e electrochemical workstation, wherein the detection was performed using a three-electrode method, the counter electrode was a platinum electrode, and the reference electrode was an HgO electrode. When detecting hydrogen evolution performance, a scanning linear voltammetry (Linear Sweep Voltammetry, abbreviated as LSV) was used by observing a current density of 10mA/cm 2 Corresponding voltage value in state. In general, the smaller the voltage value, the better the hydrogen evolution performance.
The detection 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) 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 result. The smaller the gradient of the Tafel curve, the better the coating performance.
As shown in FIG. 1, the overpotential of the cobalt-nickel-molybdenum-based composite material prepared in example 1 is-0.076V relative to the standard hydrogen electrode potential, and the overpotential of the cobalt-nickel-molybdenum-based composite material prepared in example 2 is-0.073V relative to the standard hydrogen electrode potential.
The slope of the fitted Tafel curve is shown in FIG. 2 by the Tafel plot obtained after LSV data processing. The smaller the Tafel curve slope, the better the hydrogen evolution catalytic performance, wherein the Tafel curve slope of the hydrogen evolution electrode of the embodiment 1 is only 75.48mV/dec, and the Tafel curve slope of the hydrogen evolution electrode of the embodiment 2 is only 81.32mV/dec, which proves that the hydrogen evolution electrode has excellent hydrogen evolution catalytic performance.
Comparative examples 1 to 4 were examined by the same examination method. As a result, the hydrogen evolution activities of comparative examples 1 to 4 were lower than those of example 1, and particularly, the cobalt-nickel-molybdenum based composite material prepared according to the formulation of comparative example 4 was found to have a low content of molybdenum element in the cobalt-nickel-molybdenum based composite material when sodium citrate was not added, indicating that sodium citrate affects the deposition efficiency of molybdenum element during electrodeposition. Also, it can be demonstrated by comparative example 1 and comparative examples 1 to 4 that the component content of the cobalt-nickel-molybdenum-based composite material in the embodiment of the present invention has a large influence on the properties of the prepared cobalt-nickel-molybdenum-based composite material. When the types or content ranges of the components are different from those of the components used in the invention, the performance of the cobalt-nickel-molybdenum-based composite material prepared by adopting 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
The cobalt-nickel-molybdenum-based composite material prepared in the above example 1 is taken for component detection, and is repeated for 3 times, and the mass percentage of Co in the cobalt-nickel-molybdenum-based composite material prepared in the above example 1 is measured to be 30% -35%; the mass percentage of Ni is 45% -50%; the mass percentage 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 the plating solution contained 5g of cobalt sulfate hexahydrate, 120g of nickel sulfate hexahydrate, 3g of sodium molybdate and 20g of sodium citrate, and boric acid was added at a final concentration of 30g/L, and sodium dodecyl sulfate was added at a final concentration of 0.1 g/L. The pH value of the plating solution is regulated to 8-9 by sulfuric acid and sodium hydroxide.
Preparation of a matrix: red copper (with the size of 10mm multiplied by 3 mm) is used as a matrix for depositing a coating, the lead is welded and then subjected to sample sealing by epoxy resin, and after sample sealing, the lead can be deposited after grinding, polishing, acid washing, degreasing and drying. During the deposition process, the substrate serves as a cathode for the deposition of cobalt ions, molybdenum ions and nickel ions.
Electrodeposition: placing a substrate as a cathode in electroplating solution, wherein a graphite rod is adopted as an anode, a cobalt-nickel-molybdenum alloy catalytic coating is formed on the surface of the substrate in an electrodeposition manner, and the electrodeposition current density of electrodeposition is 160mA/cm 2 The deposition time was 20min. During electrodeposition, stirring (400 rpm) was performed with a magnetic stirrer, and the plating solution temperature was maintained at a normal temperature of 26 to 27 ℃.
The thickness of the finally prepared cobalt-nickel-molybdenum alloy catalytic coating is 20 mu m, and the coating is not removed when being directly deposited on the surface of the substrate. The prepared cobalt-nickel-molybdenum-based composite material can be directly used for producing hydrogen by water electrolysis after pure water cleaning and drying treatment.
Comparative example 5 increased the deposition current density of the electrodeposition compared to example 1.
Electron microscopy observation is carried out on the cobalt-nickel-molybdenum based composite material prepared in the comparative example 5, and the number of the pellets on the surface of the plating layer is smaller than that of the example 1, mainly because the excessive current density causes hydrogen evolution phenomenon in the deposition process of the plating layer, thereby influencing the deposition of cobalt element, nickel element and molybdenum element, and resulting in poor quality of the obtained cobalt-nickel-molybdenum based composite material. Furthermore, the coating edge of the cobalt-nickel-molybdenum based composite material prepared in comparative example 5 has a significant blackening phenomenon due to excessive burning, and the reason is also that the current density is too high. However, too small a current density may make deposition time longer and reduce the preparation efficiency. Thus, the deposition current density in the embodiment of the present invention is based on the optimal range under the component formulation in the embodiment of the present invention.
Comparison of the cobalt-Nickel-molybdenum based composite Material prepared in example 1 with the prior art
Comparative example 6
Example 1 in publication number CN102127776a, which is incorporated by reference in its entirety into this example, is taken as a comparative example, and specifically includes the following steps:
the red copper sheet is cut into 15mm multiplied by 4mm samples, copper wires are welded, and the non-working surface is sealed by epoxy resin. The working surface is sequentially polished by 360-1000 # water sand paper, then polished by a polishing machine, and then pretreated by alkali cleaning and degreasing, acetone degreasing, hot water cleaning, strong etching, weak etching and the like, and finally cleaned by deionized water and placed into plating solution. The anode is 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=8, temperature t=25 ℃, electrodeposition time t=60 min, current density dk=10 mA/cm 2 . The composition of the electroplating solution is as follows: 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 60g/L. The amorphous plating layers were tested, in which the weight percentages of Ni, mo, co were 47.51%, 38.97% and 13.52%, respectively, and the thickness of the amorphous plating layers was 4. Mu.m.
This comparative example 6 differs from example 1 in that:
compared with example 1, the matrix of comparative example 6 was increased in size, the cobalt content per liter of plating solution was decreased, the nickel content was decreased, the molybdenum content was increased, and sodium carbonate was also added.
The electrode anode 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 60min.
The electrodeposition of example 1 had a deposition current density of 130mA/cm 2 The deposition time was 20min.
Comparative example 7
Example 2 in publication number CN102127776a, which is incorporated by reference in its entirety into this example, is taken as a comparative example, and specifically includes the following steps:
the red copper sheet is cut into 15mm multiplied by 4mm samples, copper wires are welded, and the non-working surface is sealed by epoxy resin. The working surface is sequentially polished by 360-1000 # water sand paper, then polished by a polishing machine, and then pretreated by alkali cleaning and degreasing, acetone degreasing, hot water cleaning, strong etching, weak etching and the like, and finally cleaned by deionized water and placed into plating solution. The anode is 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=9, temperature t=30 ℃, electrodeposition time t=60 min, current density dk=20 mA/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 80g/L. The amorphous plating layers were tested, wherein the weight percentages of Ni, mo and Co in the amorphous plating layers are 49.78%, 37.06% and 13.16%, respectively, and the thickness of the amorphous plating layers is 5 μm.
This comparative example 7 differs from example 1 in that:
compared with example 1, the matrix of comparative example 7 was increased in size, the nickel element content per liter of plating solution was decreased, the molybdenum element content was increased, the sodium citrate content was increased, and sodium carbonate was also added.
The electrode anode in comparative example 7 was a nickel plate, and example 1 was graphite.
The electrodeposition of comparative example 7 had a deposition current density of 20mA/cm 2 The deposition time was 60min.
The electrodeposition of example 1 had a deposition current density of 130mA/cm 2 The deposition time was 20min.
Comparative example 8
Example 3 in publication number CN102127776a, which is incorporated by reference in its entirety into this example, is taken as a comparative example, and specifically includes the following steps:
the red copper sheet is cut into 15mm multiplied by 4mm samples, copper wires are welded, and the non-working surface is sealed by epoxy resin. The working surface is sequentially polished by 360-1000 # water sand paper, then polished by a polishing machine, and then pretreated by alkali cleaning and degreasing, acetone degreasing, hot water cleaning, strong etching, weak etching and the like, and finally cleaned by deionized water and placed into plating solution. The anode is 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=10, temperature t=35 ℃, electrodeposition time t=60 min, current density dk=20 mA/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 O15g/L and Na 2 CO 3 100g/L. The amorphous plating layers were tested, wherein the weight percentages of Ni, mo and Co in the amorphous plating layers are 49.78%, 37.06% and 13.16%, respectively, and the thickness of the amorphous plating layers is 5 μm.
This comparative example 8 differs from example 1 in that:
compared with example 1, the matrix of comparative example 8 has increased size, reduced nickel content per liter of plating solution, increased molybdenum content, increased sodium citrate content, and sodium carbonate added.
The electrode anode in comparative example 8 was a nickel plate, and example 1 was graphite.
The electrodeposition of comparative example 8 had a deposition current density of 20mA/cm 2 The deposition time was 60min.
The electrodeposition of example 1 had a deposition current density of 130mA/cm 2 The deposition time was 20min.
The results of comparative examples 6 to 8 were directly derived from CN102127776A (the detection method is the same as in this example), and comparative example 8 has the best hydrogen evolution catalytic activity and its hydrogen evolution overpotential η 100 ＝112mV。
The overpotential of examples 1 and 2 was significantly lower than that of comparative example 8 (the overpotential of the cobalt-nickel-molybdenum-based composite material prepared in example 1 was-76 mV with respect to the standard hydrogen electrode potential, and the overpotential of the cobalt-nickel-molybdenum-based composite material prepared in example 2 was-73 mV with respect to the standard hydrogen electrode potential), i.e., the cobalt-nickel-molybdenum-based composite materials prepared in examples 1 and 2 had stronger hydrogen evolution activity.
The embodiment, the comparative example and the detection result show that when the cobalt-nickel-molybdenum based composite material is prepared, the deposition mode of electrodeposition is adopted, and the deposition process can be promoted by adjusting the deposition current density, the component proportion and other parameters, so that the improvement of the coating performance is facilitated. The preparation method 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 base electrodes used in the catalytic field, and has 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, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (14)
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 percentage of Co is 25% -35%; the mass percentage of Ni is 40-50%; the mass percentage of Mo is 15-35%, and the thickness of the cobalt-nickel-molybdenum based composite material is 15-30 mu m.
2. The cobalt-nickel-molybdenum based composite material according to claim 1, further comprising other elements, wherein the other elements are one or more of Fe, cu, cr, and W.
3. A method for preparing a cobalt-nickel-molybdenum based composite material according to any one of claims 1 to 2, comprising the steps of:
placing a matrix material into electroplating solution, and forming a cobalt-nickel-molybdenum-based composite material on the surface of the matrix material in an electrodeposition mode to obtain the composite material;
wherein the electrodeposition current density of the electrodeposition is 130mA/cm 2 ~150 mA/cm 2 The deposition time is 20 min-30 min;
the plating solution at least contains soluble cobalt salt, soluble nickel salt, soluble molybdate and citrate;
the mass ratio of the soluble cobalt salt to the soluble nickel salt to the soluble molybdate to the citrate is (5-8)/(120-140)/(3-5)/(20-35).
4. The method for preparing a cobalt-nickel-molybdenum-based composite material according to claim 3, wherein the pH of the plating solution is 8-9.
5. A method of preparing a cobalt-nickel-molybdenum based composite material according to claim 3, wherein the electroplating bath further comprises a brightening agent and a buffer.
6. The method for preparing a cobalt-nickel-molybdenum-based composite material according to claim 3, wherein the soluble cobalt salt is selected from any one of cobalt sulfate, cobalt chloride, cobalt acetate, cobalt nitrate or a combination thereof.
7. A method of preparing a cobalt-nickel-molybdenum based composite material according to claim 3, wherein the soluble nickel salt is selected from any one of nickel sulfate, nickel chloride, nickel acetate, nickel nitrate, or a combination thereof.
8. A method of preparing a cobalt-nickel-molybdenum based composite material according to claim 3, wherein the matrix material is selected from copper, carbon steel, stainless steel, titanium, cobalt, nickel or carbon.
9. A method of preparing a cobalt-nickel-molybdenum based composite material according to claim 3, wherein the electrodeposition is performed under agitation; the stirring speed is 380 rpm-420 rpm.
10. Hydrogen evolution electrode, characterized in that it comprises a cobalt-nickel-molybdenum based composite material according to any one of claims 1 to 2.
11. An electrolytic water device comprising the hydrogen evolution electrode according to claim 10.
12. An electrical home appliance, wherein the electrical home appliance comprises the cobalt-nickel-molybdenum-based composite material according to any one of claims 1 to 2 or the hydrogen evolution electrode according to claim 10.
13. Use of a cobalt-nickel-molybdenum based composite material according to any of claims 1 to 2 for the production of hydrogen by electrolysis of water.
14. Use of a cobalt-nickel-molybdenum based composite material according to any one of claims 1 to 2 for the preparation of a corrosion resistant material.
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