CN110820035B - Cobalt hydroxide/foamed nickel composite electrode prepared based on multi-potential cyclic step method and method - Google Patents

Cobalt hydroxide/foamed nickel composite electrode prepared based on multi-potential cyclic step method and method Download PDF

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CN110820035B
CN110820035B CN201911097581.4A CN201911097581A CN110820035B CN 110820035 B CN110820035 B CN 110820035B CN 201911097581 A CN201911097581 A CN 201911097581A CN 110820035 B CN110820035 B CN 110820035B
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electrode
cobalt hydroxide
foamed nickel
potential
deposition
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CN110820035A (en
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徐加应
陈松
仓辉
陈建军
薛海燕
韩鑫
赵晶
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Jiangsu Rongsheng Electronic Co ltd
Yancheng Institute of Technology
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Jiangsu Rongsheng Electronic Co ltd
Yancheng Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials

Abstract

A cobalt hydroxide/foamed nickel composite electrode prepared based on a multi-potential cyclic step method and a method belong to the field of metal electrochemical deposition. The method comprises the following steps: firstly, ultrasonically cleaning foamed nickel by acetone, deionized water, 1mol/L dilute hydrochloric acid and deionized water in sequence, and then drying; the method comprises the steps of taking dried foamed nickel as a working electrode, taking a saturated calomel electrode as a reference electrode, placing the working electrode, the reference electrode and a counter electrode in a cobalt nitrate solution, then respectively connecting the working electrode, the counter electrode and the reference electrode into an electrochemical workstation, then electrodepositing a cobalt hydroxide layered structure which is vertically arranged in an oriented mode by adopting a multi-potential cyclic step method, taking out after deposition is finished, and drying. The preparation method has the advantages that the preparation method is simple, the structure and the appearance of the prepared cobalt hydroxide/foamed nickel composite electrode are easy to control, and the prepared cobalt hydroxide/foamed nickel composite electrode has a layered structure which is vertically arranged.

Description

Cobalt hydroxide/foamed nickel composite electrode prepared based on multi-potential cyclic step method and method
Technical Field
The invention belongs to the technical field of metal electrochemical deposition, and particularly relates to a cobalt hydroxide/foamed nickel composite electrode prepared based on a multi-potential cyclic step method and a method.
Background
The foamed Nickel (NF) based layered hydroxide is widely applied to the field of electrochemical energy storage and catalytic materials by virtue of the advantages of high conductivity, high specific surface area, high active sites of two-dimensional materials and the like, wherein electrochemical deposition is a simple, convenient and effective method for preparing the composite material. However, the problems of micropore defects or crack defects and the like of the deposited layer can be caused by concentration polarization, cathodic hydrogen evolution and the like in the electrochemical deposition process. At present, the traditional constant potential deposition method, the constant current deposition method and the like are difficult to effectively control the side reactions, and the microstructure of the deposit is difficult to effectively regulate and control, and no reference is provided for performance design.
In recent years, studies have shown that hydroxides, due to their layered structure, play an important role in the fields of electrochemical catalysis and the like, in particular in OER reactions. At present, the reported high-activity hydroxide catalysts adopt nickel foam, graphene, carbon nanotubes and the like as substrate materials, and methods such as hydrothermal synthesis methods and electrochemical deposition are often adopted.
In the past, the electrochemical deposition mostly adopts a constant current, constant potential or cyclic voltammetry technology, the traditional cobalt hydroxide electrochemical preparation technology is a constant potential or constant current technology, a potential-time curve (figure 2 a) of the constant current technology and a current-time curve (figure 2 b) of the constant potential technology are shown in figure 2, the deposition process is continuous no matter the constant current deposition or the constant potential deposition, the growth of the crystal has a great relationship with the mass transfer process of the solution, and the concentration polarization of the solution cannot be eliminated in the continuous deposition process, which is not favorable for the directional growth of the crystal.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the technical problems, the invention provides the cobalt hydroxide/foamed nickel composite electrode prepared based on the multi-potential cyclic step method and the preparation method thereof, and the cobalt hydroxide/foamed nickel composite electrode prepared by the method has the advantages of simple preparation method, easily controllable structure and appearance and the like.
The technical scheme is as follows: a method for preparing a cobalt hydroxide/foamed nickel composite electrode based on a multi-potential cyclic step method comprises the following steps: s1: firstly, ultrasonically cleaning foamed nickel by acetone, deionized water, 1mol/L dilute hydrochloric acid and deionized water in sequence, and then drying; s2: and (4) taking the foamed nickel dried in the step (S1) as a working electrode and the saturated calomel electrode as a reference electrode, placing the working electrode, the reference electrode and the counter electrode in a cobalt nitrate solution, then respectively connecting the working electrode, the counter electrode and the reference electrode into an electrochemical workstation, then electrodepositing a cobalt hydroxide layer-shaped structure vertically arranged in an oriented manner by adopting a multi-potential cyclic step method, and taking out and drying after deposition is finished.
Preferably, the concentration of the cobalt nitrate solution is 0.02-0.1 mol/L, and the solvent is water.
Preferably, the foamed nickel is a rectangular foamed nickel sheet.
Preferably, the specific process of electrodepositing the vertically-oriented cobalt hydroxide layered structure by the multi-potential cyclic step method is as follows: at the deposition potential E1 for a time t1, stepped to the deposition potential E2 for a time t2, which is one cycle; the deposition potential then transitions again to E1 for a time t1 to begin a new cycle for a total number of cycles N.
Preferably, the deposition potential E1Is-1.2 to-1V, and has a duration t15 to 10 s, E20-0.3V, duration t2The total number of cycles N is 10-40 s and 100-360.
Preferably, the counter electrode in S2 is a platinum sheet counter electrode.
The cobalt hydroxide/foamed nickel composite electrode prepared by the method.
Has the advantages that: 1. compared with constant current and constant potential, the potential-time curve (figure 2 a) of the constant current technology and the current-time curve (figure 2 b) of the constant potential technology are shown in figure 2, the deposition process is continuous no matter constant current deposition or constant potential deposition, the growth of the crystal has a great relationship with the mass transfer process of the solution, and the concentration polarization of the solution cannot be eliminated in the continuous deposition process, so that the directional growth of the crystal is not facilitated. The SEM characteristic diagrams of the cobalt hydroxide/foamed nickel composite electrode prepared by the constant current and constant potential deposition technology are respectively shown in fig. 3 and fig. 4, while the SEM characteristic diagram of the cobalt hydroxide/foamed nickel composite structure prepared by the invention is shown in fig. 5, and as can be seen from the diagrams, the cobalt hydroxide/foamed nickel composite structure prepared and grown by the method disclosed by the invention has a clear and vertically-arranged layered structure, and the method disclosed by the invention is obviously superior to the prior art.
2. The preparation process parameters of the method are easy to control and strong in adjustability. Compared with the traditional constant current and constant potential deposition technology, the method realizes the control of the morphology, the arrangement orientation and the like of the cobalt hydroxide by periodically regulating and controlling the applied step potential, the duration, the periodicity and the combination thereof, and can ensure that the prepared cobalt hydroxide/foamed nickel composite electrode has a vertically-oriented layered structure.
3. The cobalt hydroxide/foamed nickel composite structure prepared by the invention greatly inhibits the peeling of the cobalt hydroxide coating, remarkably improves the combination degree of the cobalt hydroxide and the foamed nickel, and improves the stability of the composite electrode in the electrochemical catalysis process.
Drawings
FIG. 1 is an i-t curve of the deposition of cobalt hydroxide by multi-level step pulse as described in example 1;
FIG. 2 is a CP curve and i-t plot of the prior art for electrochemically deposited cobalt hydroxide at different current densities and potentials, wherein a is the CP curve for electrochemically deposited cobalt hydroxide at different current densities; b is an i-t curve for electrochemical deposition of cobalt hydroxide under different potentials;
FIG. 3 is an SEM image of a cobalt hydroxide/nickel foam composite electrode prepared by a constant current deposition technique in the prior art, wherein a is an SEM image with a scale length of 50 μm, b is an SEM image with a scale length of 1 μm, and c is an SEM image with a scale length of 500 nm.
FIG. 4 is an SEM image of a cobalt hydroxide/nickel foam composite electrode prepared by a potentiostatic deposition technique in the prior art, wherein a is an SEM image with a scale length of 50 μm, b is an SEM image with a scale length of 2 μm, and c is an SEM image with a scale length of 500 nm.
FIG. 5 is an SEM photograph of a cobalt hydroxide/nickel foam composite electrode prepared by the multi-potential cyclic step process in example 1, in which a is an SEM photograph with a scale length of 20 μm, b is an SEM photograph with a scale length of 10 μm, and c is an SEM photograph with a scale length of 2 μm.
Fig. 6 is an XRD pattern of the cobalt hydroxide/nickel foam composite electrode prepared by the multi-potential cyclic step process of example 1.
Detailed Description
The invention is further described below with reference to the accompanying drawings and specific embodiments.
Example 1
A method for preparing a cobalt hydroxide/foamed nickel composite electrode based on a multi-potential cyclic step method comprises the following steps: s1: firstly, ultrasonically cleaning foamed nickel by acetone, deionized water, 1mol/L dilute hydrochloric acid and deionized water in sequence, and then drying; s2: and (4) taking the foamed nickel dried in the step (S1) as a working electrode and a saturated calomel electrode as a reference electrode, placing the working electrode, the reference electrode and a counter electrode in 20 mL of 0.1 mol/L cobalt nitrate solution, respectively connecting the working electrode, the counter electrode and the reference electrode into an electrochemical workstation, electrodepositing a cobalt hydroxide layered structure vertically arranged in an oriented manner by adopting a multi-potential cyclic step method, taking out the layered structure after deposition is finished, and drying the layered structure. The electrochemical workstation is an electrochemical workstation manufactured by Shanghai Chenghua instruments Inc. and having model number CHI 660D.
The specific process of electrodepositing the vertically-oriented cobalt hydroxide layered structure by the multi-potential cyclic step method comprises the following steps: at the deposition potential E1 for a time t1, stepped to the deposition potential E2 for a time t 2; the deposition potential then transitions again to E1 for a time t1 to begin a new cycle for a total number of cycles, N.
In the electrochemical deposition process of cobalt hydroxide, the cathode electrodeposition method selected by the application has the following reaction process:
NO3 − + 7 H2O + 8 e−→ NH4 + + 10 OH− (1)
Co2+ + 2 OH− → Co(OH)2 (2)
the deposition process mainly comprises the following steps: (1) formation of hydroxide ions, NO in cobalt nitrate solution3 −Generated by reduction reaction of electrons obtained at the cathodeOH−A large amount of OH is formed on the surface of the electrode−(2) these OH groups−By electrostatic attraction with Co in the electrolyte2+Combined to form Co (OH)2As shown in formula (I).
Example E1is-1.1V, t1Is 10 s, E2Is 0V, t2It is 40 s, and N is 300. The i-t curve of cobalt hydroxide deposition by multi-potential cyclic step pulse method is shown in FIG. 1, and two sets of potential and time are set, one set is E1 V，t1 s; another set of potentials is E2 V，t2 s, the total time of deposition can be adjusted by the number of cycles. As can be seen in the figure, at E1The current density is maintained at-5 mA cm under the deposition potential of V-2At this potential, t is held1s, then the potential is E2 V, the current density at this time was 0 mA cm-2Hold t2 And s, repeating the steps. The purpose of setting two groups of electric potentials is to give the time of ion mass transfer, thereby realizing the regulation and control of the structure and the growth direction of the deposition product.
Fig. 5 is a scanning electron microscope SEM characterization diagram of cobalt hydroxide generated by deposition on a nickel foam substrate by a multi-potential cyclic transition method in this example, and fig. 6 is an XRD diagram of the cobalt hydroxide/nickel foam composite electrode prepared by the multi-potential cyclic step method in this example. As can be seen from FIGS. 5 and 6, the cobalt hydroxide sheets prepared by the method of the present invention have a morphology that is vertically aligned, unlike the constant current method and the constant potential method.
Example 2
Cutting 99.9 wt.% pure nickel foam into 1 x 2 cm pieces2Then, the rectangular foam nickel sheet is subjected to ultrasonic cleaning for 15 min by sequentially passing through acetone, deionized water, 1mol/L diluted hydrochloric acid and deionized water to remove organic matters and oxides on the surface of the foam nickel, and then drying treatment is carried out; the dried foam nickel sheet was used as a working electrode (the area immersed in the deposition solution was 1 x 1 cm)2) The counter electrode adopts a platinum sheet counter electrode and a saturated calomel electrode as reference electrodes, and the working electrode, the reference electrode and the counter electrode are placed in 20 mL with a certain concentration of 0.1 molCo of/L (NO)3)2In solution; then respectively connecting the working electrode, the reference electrode and the counter electrode into an electrochemical workstation (the electrochemical workstation is an electrochemical workstation with the model number of CHI660D produced by Shanghai Chenghua instruments Co., Ltd.), and electrodepositing a cobalt hydroxide layered structure which is vertically arranged by adopting a multi-potential cyclic step method, wherein the specific process comprises the following steps: electrodeposition is first carried out at a deposition potential E1Duration t at (-1.2V) potential1(10 s) and then stepped to the deposition potential E2(0V) duration t2(40 s), which is one cycle; subsequent potential step to E1Duration t1And starting a new period, wherein the total period number is the cycle number and is represented by N, and N is 100. And taking out the substrate after the deposition is finished and drying the substrate.
Example 3
The difference from example 2 is that the deposition solution Co (NO)3)2The solution concentration is 0.02 mol/L, the electrodeposition is carried out first at a deposition potential E1Duration t at (-1V) potential1(5 s) and then stepped to deposition potential E2(0.3V) duration t2(10 s), which is one cycle; subsequent potential step to E1Duration t1And starting a new period, wherein the total period number is the cycle number and is represented by N, and N is 360.

Claims (5)

1. A method for preparing a cobalt hydroxide/foamed nickel composite electrode based on a multi-potential cyclic step method is characterized by comprising the following steps: s1: firstly, ultrasonically cleaning foamed nickel by acetone, deionized water, 1mol/L dilute hydrochloric acid and deionized water in sequence, and then drying; s2: taking the foamed nickel dried in the step S1 as a working electrode, taking a saturated calomel electrode as a reference electrode, placing the working electrode, the reference electrode and a counter electrode in a cobalt nitrate solution, respectively connecting the working electrode, the counter electrode and the reference electrode into an electrochemical workstation, electrodepositing a cobalt hydroxide layer-shaped structure vertically arranged in an oriented manner by adopting a multi-potential cyclic step method, taking out the cobalt hydroxide layer-shaped structure after deposition is finished, and drying the cobalt hydroxide layer-shaped structureThe method comprises the following specific steps of treating the cobalt hydroxide layer structure in the vertical directional arrangement through electrodeposition by a multi-potential cyclic step method: at the deposition potential E1 for a time t1, stepped to the deposition potential E2 for a time t2, which is one cycle; then the deposition potential is transited to E1 again for a time t1, a new period is started, and the total period number is N; the deposition potential E1Is-1.2 to-1V, and has a duration t15 to 10 s, E20-0.3V, duration t2The total number of cycles N is 10-40 s and 100-360.
2. The method for preparing the cobalt hydroxide/foamed nickel composite electrode based on the multi-potential cyclic step method according to claim 1, wherein the concentration of the cobalt nitrate solution is 0.02-0.1 mol/L, and the solvent is water.
3. The method for preparing the cobalt hydroxide/foamed nickel composite electrode based on the multi-potential cyclic step method according to claim 1, wherein the foamed nickel is a rectangular foamed nickel sheet.
4. The method for preparing the cobalt hydroxide/foamed nickel composite electrode based on the multi-potential cyclic step method according to claim 1, wherein the counter electrode in S2 is a platinum sheet counter electrode.
5. A cobalt hydroxide/nickel foam composite electrode made by the method of any one of claims 1-4.
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