CN113174607B - Electrochemical preparation method of porous Ni-Co/graphene electrode - Google Patents
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Abstract
The invention provides an electrochemical preparation method of a porous Ni-Co/graphene electrode, which comprises the following steps: removing oil from the foamed nickel in an ultrasonic cleaner by using alkaline degreasing fluid; heating the plating solution to 50 ℃, and adjusting the pH value of the plating solution to 2-2.5 by using a dilute sulfuric acid solution; vertically placing a nickel block and foamed nickel into an electrolytic bath, placing the electrolytic bath on a magnetic stirrer, connecting the nickel block serving as an anode and the foamed nickel serving as a cathode with the anode and the cathode of a pulse power supply respectively, pouring a plating solution into the electrolytic bath, and starting the magnetic stirrer; turning on a pulse power switch, setting electroplating parameters, connecting a load, and electroplating for 20-30 min; and after the electroplating is finished, washing the foamed nickel plated sheet for a plurality of times by using deionized water, and drying to obtain the porous Ni-Co/graphene electrode. Compared with the material prepared by a direct current method, the prepared porous Ni-Co/graphene composite material has a more compact surface and good electrocatalytic hydrogen evolution activity.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to an electrochemical preparation method of a porous Ni-Co/graphene electrode.
Background
Hydrogen is an ideal clean new energy source. The hydrogen production by water electrolysis is an important means for industrially preparing hydrogen at low cost, and the resources for hydrogen production by water electrolysis are very rich. Reduction of overpotential of hydrogen evolution reaction is the main approach to reduce energy consumption in the electrolytic hydrogen production industry. However, most electrode materials have high hydrogen evolution overpotentials and large power consumption. Therefore, the important problem of hydrogen preparation by water electrolysis is to develop a cathode material with low cost, high catalytic hydrogen evolution activity and low hydrogen evolution overpotential.
At present, the problems of over-high cell voltage, over-high energy consumption, over-high hydrogen evolution overpotential, high cost and the like generally exist in the industrial production of hydrogen production and chlor-alkali by electrolyzing water. The overpotential of the anode is greatly reduced by using a Dimensionally Stable Anode (DSA), and the selection of materials for the cathode, the design of the structure and the optimization of the preparation process are always the key of hydrogen production by electrolyzing water, which plays an important role in reducing the cost of the electrode, improving the catalytic utilization rate and reducing the energy consumption of electrolysis.
The electrocatalytic hydrogen evolution reaction is an effective way for converting electric energy into chemical energy, and two important factors influencing the electrocatalytic hydrogen evolution activity of the electrode are the specific surface area and the hydrogen evolution overpotential of the electrode respectively. The method for improving the electrocatalytic hydrogen evolution activity of the electrode material mainly comprises the following steps: the method has the advantages of increasing the porosity or surface roughness of a cathode electrode material, improving the real surface area of an electrode, reducing the real current density of the electrode surface in the electrolytic process and achieving the purpose of reducing the hydrogen evolution overpotential. A common method is to alloy Ni with easily dissolvable metals (such as Zn, Sn, etc.) to form a precursor alloy, and then dissolve alloy components by a chemical or electrochemical method to form a Raney Ni or porous nickel alloy electrode having a porous structure. Compared with a smooth Ni-based electrode, the porous electrode has larger specific surface area and higher catalytic activity, but the porous electrodes such as Raney Ni have poorer mechanical strength and current oxidation resistance, and catalytic components in the electrode can be oxidized and dissolved under the condition of long-time power failure, so the practicability is not strong. The electrochemical activity of the electrode is improved, and a novel hydrogen evolution cathode material with high catalytic activity is adopted.
The ideal electrocatalytic hydrogen evolution material not only has excellent hydrogen evolution catalytic activity, but also has the performances of excellent conductivity, high specific surface area, proper porosity, stronger bonding strength, proper catalyst crystal face structure and the like, and has low preparation cost. According to the Engel Brewer valence bond theory, the transition metal has unpaired d electrons and unfilled d orbitals, has a very obvious electrocatalytic synergistic effect on hydrogen evolution reaction, and is beneficial to the hydrogen evolution reaction.
The electrolytic water in industry usually adopts Ni-based electrode material, the energy consumption of electrolysis is mostly related to hydrogen evolution overpotential, however, the application of the electrode material is seriously inhibited by the excessively high hydrogen evolution overpotential. Therefore, to realize large-scale industrial hydrogen production, the most effective method is to reduce the overpotential of the cathodic hydrogen evolution reaction.
The main method for reducing the overpotential of hydrogen evolution is to increase the porosity or surface roughness of the electrode and improve the specific surface area; or a novel hydrogen evolution material with high catalytic activity is used to improve the electrochemical activity of the electrode. Pt, Pd, and the like have low hydrogen evolution overpotential and high electrocatalytic activity, but are expensive and not suitable for large-scale use in industrial production. The non-noble metal Ni and the Ni-based electrode show higher electrocatalytic hydrogen evolution activity, and the Ni has wide sources and low price and is favored by researchers. Therefore, many studies have been reported on nickel-based alloy hydrogen evolution electrodes, such as Ni-S, Ni-Mo, Ni-Co, Co-Ni-Fe-C, Ni-Co-Y, Ni-Co-Sn, Ni-W, Co-Ni-graphite, Ni-Co-Mo, etc., which are generally prepared on a bulk substrate.
Considering that the specific surface of the bulk matrix is small and the specific surface of the porous matrix is large, a three-dimensional porous sponge Ni mesh is used as the electrodeposition matrix. There are few reports on the electrocatalytic Hydrogen Evolution (HER) performance of porous Co-Ni-graphene composite electrodes. According to the preparation method, the nano graphene sheet is added into the Ni-Co alloy plating solution, and the porous Co-Ni-graphene composite electrode with a large specific surface and good electro-catalytic hydrogen evolution activity is prepared on a Ni net framework by a composite electro-deposition method. Ni and Co belong to the same group VIII elements and have the same electron shell structure, and the Ni-Co alloy not only has better electrocatalytic hydrogen evolution activity than single metals of Ni and Co, but also has lower hydrogen evolution overpotential than even a smooth Pt electrode. The Ni-Co/graphene composite material is a hydrogen evolution electrode material with good application prospect, and the graphene insoluble solid particles are doped into the Ni-Co alloy material through composite electrodeposition, so that the Ni-Co/graphene composite hydrogen evolution material with large specific surface area and high electrocatalytic hydrogen evolution activity can be formed. The real surface area of the electrode surface can be greatly improved, and the real current density of the electrode surface in the electrolytic process is reduced, so that the overpotential is reduced. Few research reports on electrocatalytic hydrogen evolution of the Ni-Co/graphene porous composite electrode at home and abroad are reported.
It is estimated that the value of the electric energy saved every year by the domestic equipment for producing hydrogen by electrolyzing water exceeds billion yuan if the cell voltage is reduced by 250 mV. Therefore, it is necessary to develop a new cathode material with high catalytic activity, low cost and effective reduction of hydrogen evolution overpotential, which is an important issue in the electrochemical industry, and has important practical significance and application value not only for hydrogen production by water electrolysis, but also for utilization of chlor-alkali industry, chemical power supply, fuel cell and solar energy.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the defects in the prior art, the invention provides an electrochemical preparation method of a porous Ni-Co/graphene electrode, which is a pulse electrodeposition method, compared with a material prepared by a direct current method, the surface of the prepared porous Ni-Co/graphene composite material is more compact, and a cathode prepared from the material has higher hydrogen evolution exchange current density, lower hydrogen evolution overpotential and good electrocatalytic hydrogen evolution activity when water is electrolyzed.
The technical scheme is as follows: an electrochemical preparation method of a porous Ni-Co/graphene electrode comprises the following steps:
(1) pretreatment of the base material: cutting the foamed nickel into required size, ultrasonically removing oil by using alkaline degreasing fluid in an ultrasonic cleaner, and ultrasonically cleaning for 3 times by using deionized water for 5min each time for later use;
(2) pretreatment of plating solution: adding the plating solution into a beaker, heating to 50 ℃, and adjusting the pH value of the plating solution to 2-2.5 by using a dilute sulfuric acid solution for later use, wherein the plating solution is prepared from deionized water and NiCl 2 ·6H 2 O、NiSO 4 ·7H 2 O、CoSO 4 ·7H 2 O, boric acid, saccharin, sodium dodecyl sulfate,Preparing nano graphene sheets;
(3) electroplating preparation: vertically placing a nickel block and the pretreated foamed nickel into an electrolytic bath and fixing the nickel block and the pretreated foamed nickel, wherein the distance between the nickel block and the pretreated foamed nickel is 6cm, placing the electrolytic bath on a magnetic stirrer, taking the nickel block as an anode and the foamed nickel as a cathode, respectively connecting the nickel block and the foamed nickel with a positive electrode and a negative electrode of a pulse power supply, pouring the pretreated plating solution into the electrolytic bath, starting the magnetic stirrer and regulating the rotating speed of the magnetic stirrer to be 350-one 450 r/min;
(4) electroplating: the apparent current density is 12.5A/dm 2 Turning on pulse power switch, setting waveform as pulse, working state as constant current and running period as circulation, and setting T 1 The positive pulse number is 1, the positive duty ratio is 50%, T 1 The negative pulse number is 0, the negative duty ratio is 0%, the frequency is 1200Hz, T 1 Time 30 seconds, current 0.5A, T 2 、T 3 The time is 0, then the load is connected, and the electroplating is started, wherein the electroplating time is 20-30 min;
(5) and (3) post-treatment of the foamed nickel plated sheet: and after the electroplating is finished, washing the foam nickel plated sheet for a plurality of times by using deionized water, and drying to obtain the porous Ni-Co/graphene electrode.
The aperture of the nickel foam in the step (1) is 200-300 μm, the porosity is 98%, and the thickness is 1 mm.
The alkaline degreasing fluid in the step (1) is prepared by adding 10-20 g of Na into each L of water 2 CO 3 、10～30gNa 2 SiO 3 、10～20g Na 3 PO 3 And 1-3 g of washing powder, wherein the temperature of the alkaline degreasing fluid is 70-80 ℃.
In the step (2), the nano graphene sheet has a thickness of 6-8nm and a width of 5 μm.
The preparation steps of the plating solution in the step (2) are as follows:
1) adding 500mL of deionized water into a 1000mL beaker, placing the beaker on an electronic universal furnace, heating the beaker until water boils, adding 30g of boric acid, stirring the mixture by using a glass rod until the boric acid is completely dissolved, and sequentially adding 2.0g of saccharin and 45-50g of NiCl 2 ·6H 2 O、100-120g NiSO 4 ·7H 2 O、20-30g CoSO 4 ·7H 2 O, stirring by a glass rod until the materials are completely dissolved;
2) adding 10mL of deionized water into another 20mL beaker, boiling, adding 0.1g of sodium dodecyl sulfate, stirring to dissolve, pouring the mixture into the 1000mL beaker in the step 1), and stirring and mixing uniformly;
3) adding 2.0g of nano graphene into the 1000mL beaker in the step 2), putting the beaker into an ultrasonic wave clearer, and vibrating for 20min by using ultrasonic waves;
4) and when the temperature of the solution in the beaker is cooled to room temperature, pouring the solution into a 1000mL measuring cylinder, adding deionized water into the measuring cylinder to ensure that the volume is 1000mL, then pouring the liquid in the measuring cylinder into a reagent bottle, and standing for 2 days to obtain the plating solution.
Has the advantages that: the electrochemical preparation method of the porous Ni-Co/graphene electrode provided by the invention has the following beneficial effects:
1. the Ni-Co/graphene electrode prepared by the preparation method is electrolyzed by 0.5mol/L H 2 SO 4 When the solution is used, the hydrogen evolution exchange current density is 8.30 multiplied by 10 within the range of 0.1-0.3V of overpotential -3 A/cm 2 ；
2. The material is used as a hydrogen evolution electrode material, so that the exchange current density of hydrogen evolution can be improved, the hydrogen evolution overpotential can be reduced, and the electric energy can be saved.
3. Compared with the material prepared by a direct current method, the surface of the prepared porous Ni-Co/graphene composite material is more compact, and a cathode prepared from the material has higher hydrogen evolution exchange current density, lower hydrogen evolution overpotential and good electrocatalytic hydrogen evolution activity when water is electrolyzed.
Drawings
FIG. 1 shows H at 0.5mol/L for Ni-Co/graphene electrode 2 SO 4 Cathodic polarization profile in solution.
FIG. 2 shows the Ni-Co/graphene electrode of FIG. 1 at 0.5M H 2 SO 4 Tafel profile in solution.
FIG. 3 shows H at 0.5mol/L for Ni-Co/graphene electrode 2 SO 4 Spectrum of ac impedance in solution.
Fig. 4 is a Scanning Electron Microscope (SEM) image at 1000 × magnification of the electrode surface measured by model HITACHI TM 3030.
Detailed Description
To further clarify the objects, summary and advantages of the present invention, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. It is to be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalents thereof which may be modified by one skilled in the art after reading this disclosure.
The following examples used instruments: BSA series electronic balance (Victoria instruments, Inc.), KQ-50B ultrasonic cleaner (Kunshan ultrasonic instruments, Inc.), smoothing/double pulse adjustable power supply (Shenzhen Chengxi electronic technology, Inc.), constant temperature and timing magnetic stirrer (Jinnan instruments, Inc., Jintan), HH-1 digital display constant temperature water bath (Shanghai Ke Sheng instruments, Inc.), pH meter (Hangzhou Aurlong instruments, Inc.), electronic universal furnace (Tianjin Fisher instruments, Inc.), thermometer, measuring cylinder, beaker, etc.
The reagent comprises the following components: anhydrous sodium carbonate, sodium silicate, sodium phosphate, washing powder and NiSO 4 ·7H 2 O、NiCl 2 ·6H 2 O、CoSO 4 ·7H 2 O, boric acid, saccharin, sodium dodecyl sulfate and sulfuric acid.
The materials are as follows: foam nickel with the pore diameter of 200-300 mu m, the porosity of 98% and the thickness of 1mm, wherein the size of the foam nickel is 10 mm-20 mm-1 mm; a nano graphene sheet having a thickness of 6-8nm and a width of 5 μm; and (4) electrolyzing the nickel block.
Example 1
The preparation steps of the plating solution are as follows:
1) adding 500mL of deionized water into a 1000mL beaker, placing the beaker on an electronic universal furnace, heating the beaker until water boils, adding 30g of boric acid, stirring the mixture by using a glass rod until the boric acid is completely dissolved, and sequentially adding 2.0g of saccharin and 45g of NiCl 2 ·6H 2 O、100g NiSO 4 ·7H 2 O、20g CoSO 4 ·7H 2 O，Stirring with a glass rod until the solution is completely dissolved;
2) adding 10mL of deionized water into another 20mL beaker, boiling, adding 0.1g of sodium dodecyl sulfate, stirring to dissolve, pouring the mixture into the 1000mL beaker in the step 1), and stirring and mixing uniformly;
3) adding 2.0g of nano graphene into the 1000mL beaker in the step 2), putting the beaker into an ultrasonic wave clearer, and vibrating for 20min by using ultrasonic waves;
4) and when the temperature of the solution in the beaker is cooled to room temperature, pouring the solution into a 1000mL measuring cylinder, adding deionized water into the measuring cylinder to ensure that the volume is 1000mL, then pouring the liquid in the measuring cylinder into a reagent bottle, and standing for 2 days to obtain the plating solution.
The preparation method of the alkaline degreasing fluid comprises the following steps: 20g of Na was added to 1L of water 2 CO 3 、15g Na 2 SiO 3 、20g Na 3 PO 3 And 2g of washing powder, and preheating to 80 ℃ for later use.
An electrochemical preparation method of a porous Ni-Co/graphene electrode comprises the following steps:
(1) pretreatment of the base material: ultrasonically degreasing foamed nickel in an ultrasonic cleaner by using alkaline degreasing liquid, and ultrasonically cleaning for 3 times by using deionized water for 5min each time for later use;
(2) pretreatment of plating solution: adding the plating solution into a beaker, heating to 50 ℃, and adjusting the pH value of the plating solution to 2 by using a dilute sulfuric acid solution for later use;
(3) electroplating preparation: vertically placing a nickel block and the pretreated foamed nickel into an electrolytic bath for fixation, wherein the distance between the nickel block and the pretreated foamed nickel is 6cm, placing the electrolytic bath on a magnetic stirrer, taking the nickel block as an anode and the foamed nickel as a cathode, respectively connecting a positive electrode and a negative electrode of a pulse power supply, pouring the pretreated plating solution into the electrolytic bath, starting the magnetic stirrer and adjusting the rotating speed of the magnetic stirrer to 350-;
(4) electroplating: the apparent current density is 12.5A/dm 2 Turning on pulse power switch, setting waveform as pulse, working state as constant current and running period as circulation, and setting T 1 The positive pulse number is 1, the positive duty ratio is 50%, T 1 The negative pulse number is 0, the negative duty ratio is 0%, the frequency is 1200Hz, T 1 Time 30 seconds, current 0.5A, T 2 、T 3 The time is 0, then the load is connected, and the electroplating is started, wherein the electroplating time is 20-30 min;
(5) and (3) post-treatment of the foamed nickel plated sheet: and after the electroplating is finished, washing the foamed nickel plated sheet with deionized water for a plurality of times, and drying to obtain the porous Ni-Co/graphene electrode.
The following experiment was performed using the Ni — Co/graphene electrode prepared in example 1.
At room temperature, the Ni-Co/graphene electrode is at 0.5mol/L of H 2 SO 4 The cathodic polarization curve, Tafel curve and AC impedance spectrum in the solution are shown in FIGS. 1, 2 and 3, respectively, using the measuring instrument electrochemical workstation CHI 660E.
During measurement, Ni-Co-graphene is used as a working electrode, a large-area platinum sheet is used as an auxiliary electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode. When measuring a cathode polarization curve, the linear scanning speed is 0.001V/s; when measuring AC impedance, the amplitude is 0.005V, the frequency is 100000 Hz-0.01 Hz, and the initial potential is-0.372V.
The tafel curve of fig. 2 is obtained on the basis of fig. 1, and the slope and intercept are obtained by linear fitting the tafel curve of fig. 2, and the exchange current density i obtained by calculation is obtained 0 Is 8.30 multiplied by 10 -3 A/cm 2 。
As can be seen from fig. 3, the hydrogen evolution ac impedance spectrum is two semi-circles with different sizes, which indicates that the surface state of the Ni-Co-graphene electrode has an influence on the hydrogen evolution reaction rate. From the size of the semicircular diameter of the ac impedance diagram, it is known that the hydrogen evolution resistance is small.
The Ni — Co/graphene electrode was subjected to measurement of the electrode surface using a Scanning Electron Microscope (SEM) model HITACHI TM3030, and an SEM image of the electrode surface at 1000 × magnification was obtained, as shown in fig. 4. Therefore, the electrode has the advantages that the surface of the electrode is densely covered with the flaky objects, the roughness is high, and the specific surface area of the electrode is greatly increased.
The embodiments of the present invention have been described in detail with reference to the above examples, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. The above description is only for the purpose of illustrating preferred embodiments of the present invention and is not intended to limit the scope of the present invention, which is defined by the appended claims.
Claims (3)
1. An electrochemical preparation method of a porous Ni-Co/graphene electrode is characterized by comprising the following steps:
(1) pretreatment of the base material: cutting the foamed nickel into required size, ultrasonically removing oil by using alkaline degreasing fluid in an ultrasonic cleaner, and ultrasonically cleaning for 3 times by using deionized water for 5min each time for later use;
(2) pretreatment of plating solution: adding the plating solution into a beaker, heating to 50 ℃, and adjusting the pH value of the plating solution to 2-2.5 by using a dilute sulfuric acid solution for later use, wherein the plating solution is prepared from deionized water and NiCl 2 ·6H 2 O、NiSO 4 ·7H 2 O、CoSO 4 ·7H 2 The preparation method comprises the following steps of:
1) adding 500mL of deionized water into a 1000mL beaker, placing the beaker on an electronic universal furnace, heating the beaker until water boils, adding 30g of boric acid, stirring the mixture by using a glass rod until the boric acid is completely dissolved, and sequentially adding 2.0g of saccharin and 45-50g of NiCl 2 ·6H 2 O、100-120g NiSO 4 ·7H 2 O、20-30g CoSO 4 ·7H 2 O, stirring by a glass rod until the materials are completely dissolved;
2) adding 10mL of deionized water into another 20mL beaker, boiling, adding 0.1g of sodium dodecyl sulfate, stirring to dissolve, pouring into the 1000mL beaker in the step 1), and stirring and mixing uniformly;
3) adding 2.0g of nano graphene into the 1000mL beaker in the step 2), putting the beaker into an ultrasonic cleaner, and vibrating for 20min by using ultrasonic waves;
4) when the temperature of the solution in the beaker is cooled to room temperature, pouring the solution into a 1000mL measuring cylinder, adding deionized water into the measuring cylinder to ensure that the volume is 1000mL, then pouring the liquid in the measuring cylinder into a reagent bottle, and standing for 2 days to obtain a plating solution;
(3) electroplating preparation: vertically placing a nickel block and the pretreated foamed nickel into an electrolytic bath and fixing the nickel block and the pretreated foamed nickel, wherein the distance between the nickel block and the pretreated foamed nickel is 6cm, placing the electrolytic bath on a magnetic stirrer, taking the nickel block as an anode and the foamed nickel as a cathode, respectively connecting a positive electrode and a negative electrode of a pulse power supply, pouring the pretreated plating solution into the electrolytic bath, starting the magnetic stirrer and adjusting the rotating speed of the magnetic stirrer to 350-450 r/min;
(4) electroplating: the apparent current density is 12.5A/dm 2 Turning on pulse power switch, setting waveform as pulse, working state as constant current and running period as circulation, and setting T 1 The positive pulse number is 1, the positive duty ratio is 50%, T 1 The negative pulse number is 0, the negative duty ratio is 0%, the frequency is 1200Hz, T 1 Time 30 seconds, current 0.5A, T 2 、T 3 The time is 0, then the load is connected, and the electroplating is started, wherein the electroplating time is 20-30 min;
(5) and (3) post-treatment of the foamed nickel plated sheet: after the electroplating is finished, washing the foam nickel plated sheet for a plurality of times by using deionized water, and drying to obtain a porous Ni-Co/graphene electrode;
the thickness of the nano graphene sheet in the step (2) is 6-8nm, and the width of the nano graphene sheet is 5 microns.
2. The electrochemical preparation method of the porous Ni-Co/graphene electrode according to claim 1, wherein: the aperture of the nickel foam in the step (1) is 200-300 mu m, the porosity is 98 percent, and the thickness is 1 mm.
3. The electrochemical preparation method of the porous Ni-Co/graphene electrode according to claim 1, wherein: the alkaline degreasing fluid in the step (1) comprises the following components of adding 10-20 g of Na into each L of water 2 CO 3 、10～30g Na 2 SiO 3 、10～20g Na 3 PO 3 And 1-3 g of washing powder, wherein the temperature of the alkaline degreasing fluid is 70-80 ℃.
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