CN113249749B - Electrochemical hydrogen evolution electrode and preparation method thereof - Google Patents
Electrochemical hydrogen evolution electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an electrochemical hydrogen evolution electrode and a preparation method thereof, wherein a sol-gel method is adopted to prepare a fine-particle perovskite type hydrogen storage material, and the prepared perovskite type hydrogen storage material and a nickel-based alloy are co-deposited on the surface of a base material through composite electrodeposition to form a nickel-based alloy coating layer doped with the hydrogen storage alloy, so that the catalytic activity and the stability of the nickel-based hydrogen evolution electrode are improved. The electrochemical hydrogen evolution electrode is simple to prepare, has higher catalytic activity in acidic, neutral and alkaline aqueous solutions, high stability and stronger practicability, and can achieve the effects of saving electricity and gaining gain when being applied to the fields of water electrolysis, water photolysis and the like.
Description
Technical Field
The invention relates to an electrochemical hydrogen evolution electrode and a preparation method thereof.
Background
Currently, energy supply in China is increasingly tense, and tasks of improving energy utilization efficiency, saving energy and the like are very urgent. In addition to improving the utilization efficiency of energy, the task of finding energy sources for sustainable application to replace the traditional fossil fuel energy sources is urgent. The hydrogen is a well-known renewable clean energy source, has the advantages of high heat value, environmental friendliness and the like, and can reduce the dependence on the increasingly exhausted fossil energy. However, the excessive hydrogen production cost and energy consumption and the environmental pollution in the hydrogen production process become unfavorable factors for limiting the large-scale development of hydrogen energy. Therefore, the development of an economic, environment-friendly and simple-to-operate hydrogen production technology is a primary task in the field of hydrogen production.
The hydrogen production by electrolyzing water is a sustainable, high-safety, green and environment-friendly hydrogen production mode, and the purity of the produced hydrogen is very high. At present, the hydrogen production by electrolyzing water with alkaline solution is a mature hydrogen production method in industry, but the hydrogen production industry by alkaline electrolysis is influenced by the problems of energy consumption, high overpotential of a cathode, activity and durability of a catalyst and the like. Although the Pt-based electrode has higher catalytic activity and stability, the application of the Pt-based electrode in the field of hydrogen production is limited by the high cost and the resource scarcity of the Pt-based electrode. Ni-based alloys are known as non-noble metal materials with high catalytic activity, such as binary alloys Ni-Mo, ni-Co and the like, and ternary alloys Ni-Mo-Co, ni-Mo-Fe and the like are formed by introducing other elements into nickel to form alloys, and the adsorption/desorption capacity on adjacent Ni atoms is changed to promote the catalytic process of Ni. However, the Ni-based alloy has low oxidation resistance, the polarization is continuously increased in the hydrogen evolution process, and the Ni-based alloy is more easily oxidized and inactivated after power failure.
In the prior art, there are researchers who transform LaNi into LaNi 5 The base hydrogen storage alloy is used as an electrolytic water hydrogen evolution cathode; there are researchers using composite electrodeposition technologyMixing LaNi 5 The solid particles of the base hydrogen storage alloy are embedded into the Ni metal coating to form a composite coating, and the specific surface area and the catalytic activity of the hydrogen evolution electrode are improved by the composite electrodeposition method. However, due to LaNi 5 The hydrogen evolution electrode has poor stability due to the hydrogen embrittlement pulverization phenomenon caused by the continuous expansion and contraction of the volume of the hydrogen storage alloy in the process of continuously adsorbing/desorbing hydrogen by the hydrogen storage alloy.
Noble transition metals such as Ru and Ir and their oxides have excellent stability, but are expensive and scarce, and thus are difficult to be applied on a large scale. Some transition metal oxides also exhibit certain catalytic properties and higher durability, but the oxides exhibit certain hydrogen evolution inertness, increase the polarization of hydrogen evolution, and lead to increased energy consumption in the hydrogen evolution process, as compared to noble metal or nickel-based hydrogen evolution catalyst electrodes.
Disclosure of Invention
The invention aims to provide an electrochemical hydrogen evolution electrode and a preparation method thereof, which can improve the hydrogen evolution catalytic activity and stability of the electrochemical hydrogen evolution electrode.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of an electrochemical hydrogen evolution electrode comprises the following steps:
s1: preparing a hydrogen storage material by a sol-gel method;
dissolving lanthanum salt and at least one of ferric salt, chromium salt and manganese salt in deionized water, continuously stirring, adding at least one of citric acid, tartaric acid, nitrilotriacetic acid and tricarballylic acid, adjusting the pH value to 5-9 by using ammonia water or triethanolamine, continuously stirring, heating to 60-105 ℃, and continuously stirring until gel is generated; drying the gel in a drying oven at 60-150 ℃, transferring the gel into a muffle furnace, heating the gel to 300-900 ℃ at the heating rate of 0.1-25 ℃/min, preserving the temperature for 0.5-6h, cooling and crushing to obtain the hydrogen storage material;
s2: suspending the hydrogen storage material in an electroplating solution;
the electroplating solution comprises nickel salt and at least one of copper salt, tin salt, molybdenum salt and manganese salt;
s3: and co-depositing the hydrogen storage material and cations in the electroplating solution on the surface of a base material through composite electrodeposition to form a nickel-based alloy plating layer doped with the hydrogen storage material so as to obtain the hydrogen evolution electrode.
Preferably, in S1, stirring and heating to 65-95 ℃ is continued until the gel is formed.
More preferably, in S1, stirring and heating to 75-85 ℃ is continued until the gel is formed.
Preferably, the dried gel is transferred to the muffle furnace, heated to 350-850 ℃ at the heating rate of 1-15 ℃/min, and kept for 0.5-6h.
More preferably, the dried gel is transferred to the muffle furnace, heated to 400-850 ℃ at the heating rate of 2-8 ℃/min, and kept for 1-4h.
Still more preferably, the dried gel is transferred to the muffle furnace, heated to 660-810 ℃ at the heating rate of 3-6 ℃/min, and kept for 2-3h.
Preferably, the concentration of the nickel salt in the electroplating solution is 0.05-1mol/L.
More preferably, the concentration of the nickel salt in the plating solution is 0.15 to 0.5mol/L.
Preferably, the atomic proportion of nickel in the nickel-based alloy plating layer in the alloy is 40-98% by adjusting the concentration ratio of the other salt forming the nickel-based alloy plating layer to the nickel salt in the electroplating solution to adjust the atomic proportion of nickel in the nickel-based alloy plating layer.
More preferably, the nickel-based alloy plating has a nickel content of 64 to 90 atomic% in the alloy.
Still more preferably, the nickel-base alloy plating layer has a nickel content of 66-82% by atomic weight of the alloy.
Preferably, the hydrogen storage material is LaFeO 3 (lanthanum ferrite), laCrO 3 Lanthanum chromate, laMnO 3 (lanthanum manganate), laFe x Cr 1-x O 3 (lanthanum ferrochromate), laMn y Cr 1-y O 3 Lanthanum manganese chromate, laFe z Mn 1-z O 3 At least one of (lanthanum ferromanganese);
wherein: x is more than 0 and less than 1; y is more than 0 and less than 1; z is more than 0 and less than 1.
Preferably, in S1, the anions of the lanthanum salt, the iron salt, the chromium salt and the manganese salt are at least one of nitrate, nitrite, formate, acetate, propionate, benzoate, phenylacetate, lactate, amino acid, citrate and salicylate, respectively.
Preferably, in S2, the anion of the nickel salt, the copper salt, the tin salt, the molybdenum salt and the manganese salt is at least one of sulfate, methylsulfonate, fluorosulfonate, sulfamate, fluoromethylsulfonate, phenylsulfonate, chloride, chlorate, perchlorate, nitrate, nitrite, formate, acetate, propionate, benzoate, phenylacetate, lactate, amino acid radical, citrate and salicylate.
Preferably, in S2 or S3, an additive is added to the plating solution, the additive being at least one of boric acid, citric acid, lactic acid, formic acid, acetic acid, nitrilotriacetic acid, tartaric acid, tricarballylic acid, ammonia water, ethylenediamine, triethanolamine, urea, thiourea, semicarbazide, ammonium chloride, sodium chloride, lithium chloride, potassium chloride, and gelatin.
Preferably, in S2, the hydrogen storage material is added to the plating solution in an amount of 2 to 50g/L.
More preferably, the hydrogen storage material is added in an amount of 10 to 45g/L in the plating solution.
Still more preferably, the hydrogen storage material is added to the plating solution in an amount of 18 to 32g/L.
Preferably, in S3, the base material is stainless steel, titanium, nickel-copper alloy, nickel-molybdenum alloy, or copper.
Preferably, in S3, the hydrogen storage material is suspended in the constant temperature plating solution and continuously stirred, and the plating tank is formed by using the matrix material as a cathode at 1-200mA/cm 2 And carrying out electrodeposition for 1-60min under the electroplating current density, and drying to obtain the hydrogen evolution electrode.
More preferably, in5-100mA/cm 2 And electrodepositing for 1-60min under the electroplating current density.
Even more preferably, in the range of 10-60mA/cm 2 And electrodepositing for 1-60min under the electroplating current density.
More preferably, in S3, the constant temperature of the plating solution is 0 to 95 ℃.
Still more preferably, the constant temperature of the plating solution is 15 to 55 ℃.
Still more preferably, the constant temperature of the plating solution is 20 to 45 ℃.
More preferably, the stirring speed is 10 to 500r/min.
Even more preferably, the stirring speed is 100-400r/min.
Even more preferably, the stirring speed is 150-300r/min.
An electrochemical hydrogen evolution electrode is prepared by the preparation method.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the electrochemical hydrogen evolution electrode and the preparation method thereof have the following advantages:
1. the preparation method is simple and has lower cost than the noble metal electrode;
2. the prepared electrochemical hydrogen evolution electrode has smaller and more stable polarization than a nickel-based alloy electrode under the condition of controlling the same hydrogen evolution current;
3. in the hydrogen evolution process of the prepared electrochemical hydrogen evolution electrode, hydrogen storage material particles mixed in the nickel-based alloy can adsorb hydrogen atoms generated on the surfaces of the nickel-based alloy particles and store the hydrogen atoms in a solid phase of the hydrogen storage material particles, and the hydrogen storage material can also become a surface on which the hydrogen atoms are compounded into hydrogen and are evolved, so that the reduction process and the hydrogen atom compounding process of hydrogen ions are promoted;
4. when in use, the prepared electrochemical hydrogen evolution electrode has certain hydrogen atom storage capacity due to the hydrogen storage material, thereby providing partial reduction environment for the nickel-based alloy particles and preventing oxygen in the solution from poisoning the catalytic surface, thereby improving the application stability and the placement stability of the electrochemical hydrogen evolution electrode.
In summary, according to the electrochemical hydrogen evolution electrode and the preparation method thereof, the perovskite type hydrogen storage material with fine particles is prepared by adopting a sol-gel method, and the prepared perovskite type hydrogen storage material and the nickel-based alloy are co-deposited on the surface of the base material through composite electrodeposition to form the nickel-based alloy coating layer doped with the hydrogen storage alloy, so that the catalytic activity and the stability of the nickel-based hydrogen evolution electrode are improved. The electrochemical hydrogen evolution electrode is simple to prepare, has higher catalytic activity in acidic, neutral and alkaline aqueous solutions, high stability and stronger practicability, and can achieve the effects of saving electricity and gaining gain when being applied to the fields of water electrolysis, water photolysis and the like.
Drawings
FIG. 1 is a graph showing the results of particle distribution measurement of a sample of hydrogen storage material by a particle sizer in example 1;
FIG. 2 shows the composite electrodeposited Ni-Cu-LaFeO in example 1 3 A sectional SEM image of the electrochemical hydrogen evolution electrode;
fig. 3 is a discharge curve diagram obtained by testing the electrochemical hydrogen evolution electrode as a hydrogen evolution cathode (positive electrode) and the metal zinc sheet as a metal anode (negative electrode) under the set conditions by using a LAND charge and discharge instrument in example 1.
Detailed Description
The technical solution of the present invention is further explained below with reference to the specific embodiments and the accompanying drawings. However, the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other. Unless otherwise specified, the raw materials and reagents in the examples of the present invention were all purchased from commercial sources.
Example 1
The preparation method of the lanthanum ferrite hydrogen storage material comprises the following steps: weighing La (NO) 3 ) 3 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 Respectively dissolving 0.02mol of O in 40mL of deionized water, mixing and stirring uniformly after completely dissolving, and adding 0.06mol of citric acid into the mixtureAnd (3) mixing the solution, stirring the mixed solution uniformly, and adding a proper amount of ammonia water to adjust the pH to be neutral (pH = 7). The solution is treated by ultrasonic wave for 30min and then placed on a magnetic stirrer of a constant temperature water bath at 80 ℃ for continuous stirring at 200r/min until gel is generated. Drying the wet gel in a drying oven at 110 ℃, then putting the dried wet gel into a muffle furnace, heating the wet gel to 800 ℃ at the heating rate of 5 ℃/min, and keeping the temperature of the wet gel constant at 800 ℃ for 2 hours to finally obtain yellow LaFeO 3 A sample of the hydrogen storage material is subjected to ball milling for 5 hours, and then is dispersed in water, the particle distribution result of the sample is tested by a particle size analyzer, the particle distribution result is shown in figure 1, and the particles are concentrated to about 0.6 micron.
Composite electrodeposited Ni-Cu-LaFeO 3 The electroplating solution composition and the electrodeposition process method of the electrochemical hydrogen evolution electrode are as follows: the main salt is nickel salt, niSO 4 ·6H 2 O (0.5 mol/L); other salts for forming the nickel-base alloy coating are copper salts, cuSO 4 ·5H 2 O (0.05 mol/L); the additive is boric acid (H) 3 BO 3 30 g/L), citric acid (C) 6 H 5 Na 3 O 7 ·2H 2 O,70 g/L), sodium chloride (NaCl, 8 g/L); the hydrogen storage material is lanthanum ferrite (LaFeO) 3 15 g/L); current density 50mA/cm 2 The constant temperature of the electroplating solution is 20 ℃, the electro-deposition time is 10min, and the stirring speed of the solution is 200r/min. Before electrodeposition, the electrodeposition solution is treated by ultrasonic for 30min to ensure that LaFeO is obtained 3 The particles were uniformly dispersed and then subjected to continuous magnetic stirring for 24 h. Carrying out composite electrodeposition by adopting a two-electrode method; before electrodeposition, a working electrode of a finely ground constantan alloy (nickel-copper alloy) sheet is placed in acetone for ultrasonic treatment for 30min and is washed clean by deionized water for later use, a platinum sheet is adopted as a counter electrode, and the working electrode obtained after electrodeposition is Ni-Cu-LaFeO 3 A composite electrode wherein the nickel-based alloy coating has a nickel content of about 90 atomic percent in the alloy. Composite electrodeposited Ni-Cu-LaFeO 3 The SEM image of the section of the electrochemical hydrogen evolution electrode is shown in the attached figure 2, and the thickness of the plating layer is about 5 microns. The EDS analysis of the coating can show the definite distribution of lanthanum element, and the SEM analysis can also show LaFeO 3 Is relatively uniformly mixed among the nickel-copper alloy particles.
Composite electrodeposited Ni-Cu-LaFeO 3 Hydrogen evolution of electrochemical hydrogen evolution electrodesThe stability test method comprises the following steps: the metal hydrogen production battery is formed. Composite electrodeposition of Ni-Cu-LaFeO 3 The electrochemical hydrogen evolution electrode is a hydrogen evolution cathode (positive electrode); the metal zinc sheet is used as a metal anode (negative electrode), and the metal zinc sheet is a pure zinc foil sold in the market. 0.5mol/L H is selected as the acid electrolyte 2 SO 4 +0.5mol/L MnSO 4 An aqueous solution; the alkaline electrolyte is 6mol/L KOH aqueous solution; the neutral electrolyte adopts 0.5mol/L K 2 SO 4 An aqueous solution. Wherein the hydrogen evolution cathode is in an acidic electrolyte, and the acidic electrolyte is separated from a neutral electrolyte by an anion exchange membrane (Huamotech corporation); the metal anode is in an alkaline electrolyte, which is separated from the neutral electrolyte by a cation exchange membrane (Nafion 117, dupont). Testing with LAND charging and discharging instrument to set the discharging current density at 10mA/cm 2 The discharge curve of the discharge 1h is shown in figure 3. As can be seen from the attached figure 3, the discharge voltage of the metal zinc hydrogen battery provided by the invention can be maintained at about 1.05V (reduced by about 200mV compared with the theoretical value of 1.216V, mainly caused by various polarizations), the discharge voltage is basically not attenuated after 1h, and the stability of the metal zinc hydrogen battery is better than that of a commercially available Raney nickel hydrogen evolution electrode.
When the metal zinc hydrogen production battery discharges to produce hydrogen, anion sulfate ions enter neutral electrolyte from acid electrolyte through an anion exchange membrane, and cation potassium ions enter the neutral electrolyte from alkaline electrolyte through a cation exchange membrane, so that the electric quantity balance is achieved.
Example 2
The preparation method of the lanthanum manganate hydrogen storage material comprises the following steps: weighing La (NO) 3 ) 3 ·6H 2 O and manganese acetate (MnAc) 2 ) Respectively dissolving 0.02mol of the components in 40mL of deionized water, mixing and stirring the components uniformly after the components are completely dissolved, adding 0.06mol of citric acid into the mixed solution, stirring the mixed solution uniformly, adding a proper amount of triethanolamine and adjusting the pH value to 9. The solution is treated by ultrasonic wave for 30min and then placed on a magnetic stirrer of a constant temperature water bath at 60 ℃ for continuous stirring at 200r/min until gel is generated. Drying the wet gel in a drying oven at 150 ℃, putting the dried wet gel into a muffle furnace, heating the wet gel to 810 ℃ at the heating rate of 2 ℃/min, and keeping the temperature of the wet gel at 810 ℃ for 2 hours to finally obtain LaMnO 3 Sample of Hydrogen storage MaterialAnd (5) preparing the product. The sample was ball milled for 5 hours and dispersed in water and the particle size distribution was measured using a particle sizer with particles centered around 0.3 microns.
Composite electrodeposited Ni-Cu-LaMnO 3 The electroplating solution composition and the electrodeposition process method of the electrochemical hydrogen evolution electrode are as follows: the main salt is nickel salt, nickel methane sulfonate (0.5 mol/L); other salts for forming the nickel-based alloy plating layer are copper salt, copper methylsulfonate (0.25 mol/L); the additive is boric acid (H) 3 BO 3 10 g/L), citric acid (C) 6 H 5 Na 3 O 7 ·2H 2 O,50 g/L), gelatin (2 g/L); the hydrogen storage material is lanthanum manganate (LaMnO) 3 32 g/L); current density 10mA/cm 2 The constant temperature of the electroplating solution is 45 ℃, the electrodeposition time is 60min, and the stirring speed of the solution is 300r/min. Before electrodeposition, the electrodeposition solution is treated by ultrasonic for 30min to ensure that LaMnO is formed 3 The particles were uniformly dispersed and then subjected to continuous magnetic stirring for 24 h. Carrying out composite electrodeposition by adopting a two-electrode method; before electrodeposition, a finely ground Monel alloy (nickel-copper alloy) sheet working electrode is placed in acetone for ultrasonic treatment for 30min and is washed clean by deionized water for standby, a platinum sheet is adopted as a counter electrode, and the working electrode obtained after electrodeposition is Ni-Cu-LaMnO 3 A composite electrode wherein the nickel-based alloy coating has a nickel content of about 66 atomic percent in the alloy. Composite electrodeposition Ni-Cu-LaMnO 3 The electrochemical hydrogen evolution electrode transects the interface and is observed to have a coating thickness of about 10 microns. The EDS analysis of the coating can show clear lanthanum element distribution, and the SEM analysis can also show LaMnO 3 Is relatively uniformly mixed among the nickel-copper alloy particles.
Composite electrodeposited Ni-Cu-LaMnO 3 The hydrogen evolution stability test method of the electrochemical hydrogen evolution electrode comprises the following steps: the metal hydrogen production battery is formed. Composite electrodeposition of Ni-Cu-LaMnO 3 The electrochemical hydrogen evolution electrode is a hydrogen evolution cathode (positive electrode); the metal zinc sheet is used as a metal anode (negative electrode), and the metal zinc sheet is a commercially available pure zinc foil. 0.5mol/L H is selected as the acid electrolyte 2 SO 4 +0.5mol/L MnSO 4 An aqueous solution; the alkaline electrolyte is 6mol/L KOH aqueous solution; the neutral electrolyte adopts 0.5mol/L K 2 SO 4 An aqueous solution. Wherein the hydrogen evolution cathode is acidicIn the electrolyte, an acid electrolyte and a neutral electrolyte are separated by an anion exchange membrane (Huamotech company); the metal anode is in alkaline electrolyte, which is separated from the neutral electrolyte by a cation exchange membrane (Nafion 117 from dupont). Testing with LAND charging and discharging instrument to set the discharging current density at 10mA/cm 2 As can be seen from the fact that the discharge voltage of the metal zinc hydrogen battery provided by the invention can be maintained at about 1.0V (reduced by about 200mV compared with the theoretical value of 1.216V, mainly caused by various polarizations), the 1h discharge voltage basically has no attenuation, and the metal zinc hydrogen battery has better stability than a commercial Raney nickel hydrogen evolution electrode.
When the metal zinc hydrogen production battery discharges to produce hydrogen, anion sulfate ions enter neutral electrolyte from acid electrolyte through an anion exchange membrane, and cation potassium ions enter the neutral electrolyte from alkaline electrolyte through a cation exchange membrane, so that the electric quantity balance is achieved.
Example 3
The preparation method of the iron lanthanum chromate hydrogen storage material is as follows. Weighing La (NO) 3 ) 3 ·6H 2 O and [ Fe (NO) 3 ) 3 ·9H 2 O and Cr (NO) 3 ) 3 ·9H 2 O, fe/Cr are shown in Table 1]Respectively dissolving 0.02mol of the above components in 40mL of deionized water, mixing and stirring uniformly after the components are completely dissolved, adding 0.06mol of nitrilotriacetic acid into the mixed solution, stirring uniformly, adding a proper amount of triethanolamine, and adjusting the pH value to be neutral (pH = 7). The solution is treated by ultrasonic wave for 30min and then placed on a magnetic stirrer of a thermostatic water bath at 85 ℃ for continuous stirring at 200r/min until gel is generated. Drying the wet gel in a drying oven at 110 ℃, putting the dried wet gel into a muffle furnace (air atmosphere), heating the wet gel to 350 ℃ at the heating rate of 5 ℃/min, and keeping the temperature of the wet gel at 350 ℃ for 6 hours to finally obtain the LaFe x Cr 1-x O 3 The sample of the hydrogen storage material is ball-milled for 5 hours and then dispersed in water, and the particle distribution of the sample is tested by a particle size analyzer.
TABLE 1LaFe x Cr 1-x O 3 Preparation of hydrogen storage material and performance meter
| Expression LaFe x Cr 1-x O 3 | x | 1-x | Particle size (concentration)/nm |
| LaFe 0.88 Cr 0.12 O 3 | 0.88 | 0.12 | 330 |
| LaFe 0.78 Cr 0.22 O 3 | 0.78 | 0.22 | 311 |
| LaFe 0.75 Cr 0.25 O 3 | 0.75 | 0.25 | 298 |
| LaFe 0.42 Cr 0.58 O 3 | 0.42 | 0.58 | 265 |
| LaFe 0.12 Cr 0.88 O 3 | 0.12 | 0.88 | 218 |
Composite electro-deposition Ni-Cu-LaFe x Cr 1-x O 3 The electroplating solution composition and the electrodeposition process method of the electrochemical hydrogen evolution electrode are as follows: the main salt is nickel salt, niSO 4 ·6H 2 O (0.5 mol/L); other salts for forming the nickel-base alloy coating are copper salts, cuSO 4 ·5H 2 O (0.05 mol/L); the additive is boric acid (H) 3 BO 3 30 g/L), citric acid (C) 6 H 5 Na 3 O 7 ·2H 2 O,70 g/L), sodium chloride (NaCl, 8 g/L); the hydrogen storage material is lanthanum ferrochromate (LaFe) x Cr 1-x O 3 15 g/L); current density 20mA/cm 2 The constant temperature of the electroplating solution is 20 ℃, the electrodeposition time is 30min, and the stirring speed of the solution is 200r/min. Before electrodeposition, the electrodeposition solution is treated by ultrasonic for 30min to ensure that LaFeO is obtained 3 The particles were uniformly dispersed and then subjected to continuous magnetic stirring for 24 h. Carrying out composite electrodeposition by adopting a two-electrode method; before electrodeposition, a finely ground constantan alloy (nickel-copper alloy) sheet working electrode is placed in acetone for ultrasonic treatment for 30min, the working electrode is washed clean by deionized water for later use, a platinum sheet is adopted as a counter electrode, and the working electrode obtained after electrodeposition is Ni-Cu-LaFe x Cr 1-x O 3 A composite electrode wherein the nickel-base alloy coating has a nickel content of about 90 atomic percent in the alloy. Composite electro-deposition Ni-Cu-LaFe x Cr 1-x O 3 The thickness of the visible coating of the section of the electrochemical hydrogen evolution electrode is about 8 microns, and LaFe x Cr 1-x O 3 Is evenly included among the nickel-copper alloy particles.
Composite electro-deposition Ni-Cu-LaFe x Cr 1-x O 3 The hydrogen evolution stability test method of the electrochemical hydrogen evolution electrode comprises the following steps: composite electrodeposition of Ni-Cu-LaFe x Cr 1-x O 3 The electrochemical hydrogen evolution electrode is a hydrogen evolution cathode (anode), a metal zinc sheet is used as a metal anode (cathode, the metal zinc sheet is a commercially available pure zinc foil), and the electrolyte is selected from 0.5mol/L H 2 SO 4 +0.5mol/L MnSO 4 An aqueous solution; wherein is analyzedThe hydrogen cathode and the metal anode were co-immersed in the electrolyte at a distance of 5mm. Testing with LAND charging and discharging instrument to set the discharging current density at 10mA/cm 2 It can be seen that the discharge voltage of the metal zinc hydrogen battery provided by the invention can be maintained at about 0.54V (200 mV lower than the theoretical value of 0.762V, mainly caused by various polarizations), the 1h discharge voltage basically has no attenuation, and the stability of the metal zinc hydrogen battery is better than that of a commercial Raney nickel hydrogen evolution electrode.
Example 4
The preparation method of the manganese chromate hydrogen storage material is as follows. Weighing La (NO) 3 ) 3 ·6H 2 O and [ manganese acetate (MnAc) 2 ) And chromium acetate (CrAc) 3 ) Mn/Cr are shown in Table 2]Respectively dissolving 0.02mol of the components in 40mL of deionized water, mixing and stirring the components uniformly after the components are completely dissolved, adding 0.06mol of tricarballylic acid into the mixed solution, stirring the mixed solution uniformly, and then adding a proper amount of triethanolamine to adjust the pH value to 7. The solution is treated by ultrasonic wave for 30min and then placed on a magnetic stirrer of constant temperature water bath at 95 ℃ for 200r/min to continue stirring until gel is generated. Drying the wet gel in a drying oven at 150 ℃, putting the dried wet gel into a muffle furnace, heating the wet gel to 850 ℃ at the heating rate of 2 ℃/min, and keeping the temperature constant at 850 ℃ for 0.5h to finally obtain the LaMn x Cr 1-x O 3 A sample of hydrogen storage material. After ball milling for 5h, the sample was dispersed in water and the particle distribution was measured with a particle sizer.
TABLE 2LaMn x Cr 1-x O 3 Preparation of Hydrogen storage Material and Performance Table
| Represented by the formula LaMn x Cr 1-x O 3 | x | 1-x | Particle size (concentration)/nm |
| LaMn 0.92 Cr 0.08 O 3 | 0.92 | 0.08 | 315 |
| LaMn 0.82 Cr 0.18 O 3 | 0.82 | 0.18 | 285 |
| LaMn 0.75 Cr 0.25 O 3 | 0.75 | 0.25 | 274 |
| LaMn 0.38 Cr 0.62 O 3 | 0.38 | 0.62 | 195 |
| LaMn 0.16 Cr 0.84 O 3 | 0.16 | 0.84 | 146 |
Composite electrodeposition Ni-Cu-LaMn x Cr 1-x O 3 The electroplating solution composition and the electrodeposition process method of the electrochemical hydrogen evolution electrode are as follows: the main salt is nickel salt, nickel methane sulfonate (0.5 mol/L); other salts for forming the nickel-based alloy plating layer are copper salt, copper methylsulfonate (0.25 mol/L); the additive is boric acid (H) 3 BO 3 10 g/L), citric acid (C) 6 H 5 Na 3 O 7 ·2H 2 O,50 g/L), gelatin (2 g/L); the hydrogen storage material is manganese lanthanum chromate (LaMn) x Cr 1-x O 3 22 g/L); current density 10mA/cm 2 The constant temperature of the electroplating solution is 45 ℃, the electrodeposition time is 60min, and the stirring speed of the solution is 300r/min. Before electrodeposition, the electrodeposition solution is treated by ultrasonic for 30min to ensure that the LaMn is x Cr 1-x O 3 The particles were uniformly dispersed and then subjected to continuous magnetic stirring for 24 h. Carrying out composite electrodeposition by adopting a two-electrode method; before electrodeposition, a finely ground Monel alloy (nickel-copper alloy) sheet working electrode is placed in acetone for ultrasonic treatment for 30min, the working electrode is washed clean by deionized water for later use, a platinum sheet is adopted as a counter electrode, and the working electrode obtained after electrodeposition is Ni-Cu-LaMn x Cr 1-x O 3 A composite electrode wherein the nickel-based alloy coating has a nickel content of about 66 atomic percent in the alloy. Composite electrodeposition Ni-Cu-LaMn x Cr 1-x O 3 The electrochemical hydrogen evolution electrode was cross-sectioned and observed to have a coating thickness of about 10 microns. The EDS analysis of the coating can show the definite distribution of lanthanum element, and the SEM analysis can also show LaMn x Cr 1-x O 3 Is relatively uniformly mixed among the nickel-copper alloy particles.
Composite electrodeposition Ni-Cu-LaMn x Cr 1-x O 3 The hydrogen evolution stability test method of the electrochemical hydrogen evolution electrode comprises the following steps: the metal hydrogen production battery is formed. Composite electrodeposition of Ni-Cu-LaMn x Cr 1-x O 3 The electrochemical hydrogen evolution electrode is a hydrogen evolution cathode (positive electrode); the metal zinc sheet is used as a metal anode (the negative electrode, the metal zinc sheet is a pure zinc foil sold in the market). The electrolyte is 6mol/L KOH aqueous solution. Wherein the hydrogen-evolving cathode and the metal anode are both in an alkaline electrolyte and are spaced apart by 5mm. Testing with LAND charging/discharging instrument, and setting the discharge current density at 10mA/cm 2 It can be seen that the discharge voltage of the metal zinc hydrogen battery provided by the invention can be maintained at about 0.18V (reduced by about 200mV compared with the theoretical value of 0.366V, mainly caused by various polarizations), the discharge voltage is basically not attenuated after 1h, and the stability of the metal zinc hydrogen battery is better than that of a commercially available Raney nickel hydrogen evolution electrode.
Perovskite oxides are a class of ceramicsPorcelain oxide of the general formula ABO 3 (a = rare earth or alkaline earth metal cation, B = transition metal ion) due to calcium titanate (CaTiO) found in perovskite 3 ) The compound is named as a novel functional material, wherein the A site and the B site can be partially replaced by other metal ions with similar radiuses to keep the crystal structure of the compound basically unchanged, and the compound has a stable crystal structure, unique electromagnetic performance, high activities of oxidation reduction, hydrogenolysis, electrocatalysis and the like. Hydrogen evolution research aspects of perovskite oxides, e.g. Pr x (Ba 0.5 Sr 0.5 ) 1-x Co 0.8 Fe 0.2 O 3-δ (A＝Pr x (Ba 0.5 Sr 0.5 ) 1-x ，B＝Co 0.8 Fe 0.2 ) Perovskite oxides (see Adv. Mater.2016,28 (30): 6442), srCo 0.7 Fe 0.25 Mo 0.05 O 3-δ (A＝Sr，B＝Co 0.7 Fe 0.25 Mo 0.05 ) Perovskite type oxides (see literature Electrochimica Acta 2019, 312). The perovskite type hydrogen storage material prepared by the sol-gel method also belongs to the structure.
The above-mentioned embodiments are merely illustrative of the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered in the scope of the present invention.
Claims (10)
1. A preparation method of an electrochemical hydrogen evolution electrode is characterized by comprising the following steps: the method comprises the following steps:
s1: preparing a hydrogen storage material by a sol-gel method;
dissolving lanthanum salt and at least one of ferric salt, chromium salt and manganese salt in deionized water, continuously stirring and adding at least one of citric acid, tartaric acid, nitrilotriacetic acid and tricarballylic acid, adjusting the pH to 5-9 by using ammonia water or triethanolamine, and continuously stirring and heating to 60-105 ℃ until gel is generated; drying the gel at 60-150 ℃, heating to 300-900 ℃ at a heating rate of 0.1-25 ℃/min, preserving heat for 0.5-6h, cooling and crushing to obtain the hydrogen storage material;
s2: suspending the hydrogen storage material in an electroplating solution;
the electroplating solution comprises nickel salt and at least one of copper salt, tin salt, molybdenum salt and manganese salt;
s3: and co-depositing the hydrogen storage material and cations in the electroplating solution on the surface of a base material through composite electrodeposition to form a nickel-based alloy plating layer which is intercalated with the hydrogen storage material so as to obtain the hydrogen evolution electrode.
2. The method for preparing an electrochemical hydrogen evolution electrode according to claim 1, characterized in that: the hydrogen storage material is LaFeO 3 、LaCrO 3 、LaMnO 3 、LaFe x Cr 1-x O 3 、LaMn y Cr 1-y O 3 、LaFe z Mn 1-z O 3 One of (1);
wherein: x is more than 0 and less than 1; y is more than 0 and less than 1; z is more than 0 and less than 1.
3. The method for preparing an electrochemical hydrogen evolution electrode according to claim 1, characterized in that: in S1, the anions of the lanthanum salt, the iron salt, the chromium salt and the manganese salt are respectively at least one of nitrate radical, nitrite radical, formate radical, acetate radical, propionate radical, benzoate radical, phenylacetate radical, lactate radical, amino acid radical, citrate radical and salicylate radical.
4. The method for manufacturing an electrochemical hydrogen evolution electrode according to claim 1, characterized in that: in S2, the anions of the nickel salt, the copper salt, the tin salt, the molybdenum salt and the manganese salt are respectively at least one of sulfate radical, methylsulfonate radical, fluorosulfonate radical, sulfamate radical, fluoromethylsulfonate radical, phenylsulfonate radical, chloride radical, chlorate radical, perchlorate radical, nitrate radical, nitrite radical, formate radical, acetate radical, propionate radical, benzoate radical, phenylacetate radical, lactate radical, amino acid radical, citrate radical and salicylate radical.
5. The method for preparing an electrochemical hydrogen evolution electrode according to claim 1, characterized in that: and in S2 or S3, adding an additive into the electroplating solution, wherein the additive is at least one of boric acid, citric acid, lactic acid, formic acid, acetic acid, nitrilotriacetic acid, tartaric acid, tricarballylic acid, ammonia water, ethylenediamine, triethanolamine, urea, thiourea, semicarbazide, ammonium chloride, sodium chloride, lithium chloride, potassium chloride and gelatin.
6. The method for preparing an electrochemical hydrogen evolution electrode according to claim 1, characterized in that: in S2, the adding amount of the hydrogen storage material in the electroplating solution is 2-50g/L.
7. The method for manufacturing an electrochemical hydrogen evolution electrode according to claim 1, characterized in that: in S3, the base material is stainless steel, titanium, nickel-copper alloy, nickel-molybdenum alloy or copper.
8. The method for preparing an electrochemical hydrogen evolution electrode according to claim 1, characterized in that: in S3, the hydrogen storage material is suspended in the constant-temperature electroplating solution and continuously stirred, the base material is used as a cathode to form an electroplating bath, and the concentration of the hydrogen storage material is 1-200mA/cm 2 And carrying out electrodeposition for 1-60min under the electroplating current density, and drying to obtain the hydrogen evolution electrode.
9. The method for manufacturing an electrochemical hydrogen evolution electrode according to claim 8, characterized in that: in S3, the constant temperature of the electroplating solution is 0-45 ℃.
10. An electrochemical hydrogen evolution electrode produced by the production method according to any one of claims 1 to 9.
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