CN112331491A - Preparation method of boron-doped nickel oxide/nickel hydroxide electrode material - Google Patents

Preparation method of boron-doped nickel oxide/nickel hydroxide electrode material Download PDF

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CN112331491A
CN112331491A CN202011171818.1A CN202011171818A CN112331491A CN 112331491 A CN112331491 A CN 112331491A CN 202011171818 A CN202011171818 A CN 202011171818A CN 112331491 A CN112331491 A CN 112331491A
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electrode material
copper sheet
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boron
doped
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张轲
周岩
曹中秋
王艳
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Shenyang Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides

Abstract

The invention discloses a preparation method of a boron-doped nickel oxide/nickel hydroxide electrode material, which comprises the following steps: 1) pretreating the surface of the copper sheet; 2) chemically plating a NiB film on the surface of the copper sheet; 3) the copper sheet after being coated is treated by adopting an in-situ electrochemical anodic oxidation method to obtain B-doped NiO/Ni (OH)2(B) An electrode material. The invention aims at the existing NiO/Ni (OH)2The defects of the preparation route of the electrode material are that the surface of a 0.1mm copper sheet flexible material is firstly chemically treatedThe NiB plating and electrochemical anode oxidation preparation process route obtains NiO/Ni (OH) which is simple and easy to operate, large in B doping amount and good in controllability2(B) The preparation process of the electrode material improves the prepared NiO/Ni (OH)2The capacitance performance and the electrochemical stability of the electrode material are improved, and the process method is beneficial to NiO/Ni (OH)2Commercial application and industrial production of electrode materials.

Description

Preparation method of boron-doped nickel oxide/nickel hydroxide electrode material
Technical Field
The invention belongs to the technical field of material synthesis, and relates to a preparation method of a boron-doped nickel oxide/nickel hydroxide electrode material.
Background
The greenhouse effect and environmental pollution caused by fossil fuels become more serious, and clean energy is forced to become a research hotspot for worldwide development and utilization, wherein the research hotspot has representative renewable energy sources such as wind energy, tidal energy, solar energy, geothermal energy and the like. However, due to the intermittent operation and often in remote areas, the integration of these renewable energy power generation systems into the transmission and power supply grid is technically difficult and cost-prohibitive, and therefore clean, safe, efficient and convenient energy storage technology becomes the key to the utilization of these clean energy sources. The super capacitor is used as an energy storage device between a physical capacitor and a chemical power supply, and is a novel energy storage device with partial characteristics of a battery and a capacitor. Compared with the traditional capacitor and a chemical battery, the super capacitor has the advantages of wide temperature application range, environmental protection and low price, higher power density and energy density and longer cycle life, and has important application value in the fields of clean energy power generation and storage, smart power grids, new energy automobiles and the like based on the characteristics.
The super capacitor is used as an energy storage device, all the components of the super capacitor can influence the electrochemical performance of the super capacitor, research shows that the performance of an electrode material plays a decisive role in the electrochemical performance of the super capacitor, the electrode materials commonly used at present mainly comprise carbon materials, transition metal oxides, conducting polymers and composite material electrodes, and the transition metal oxide electrode material has the characteristics of low price, high specific capacitance and excellent electrochemical charge and discharge performance and is widely researched in recent years. As the metal oxide electrode material, MnO is typically used2And RuO2Electrode material with low specific capacitance (usually less than 600F/g) and theoretical specific capacitance up to 2000F/g, but its priceExpensive and toxic, limiting their commercial development, and nickel oxide/hydroxide (labeled as NiO/Ni (OH))2) The NiO/Ni (OH) is an electrode material with high research and application values due to low price, high efficiency, environmental friendliness, large abundance in the crust, clear redox mechanism among variable valence metal ions and very high theoretical specific capacitance (the theoretical specific capacitance is 2584F/g), but NiO/Ni (OH)2Poor conductivity of electrode materials and insufficient electrochemical cycling stability are the main problems which need to be solved urgently in practical application.
To further improve NiO/Ni (OH)2The practical specific capacitance and electrochemical stability of the electrode material, researchers have used precipitation transformation, sol-gel, magnetron sputtering, electrochemical cathode/anode deposition, hydrothermal methods, etc. to prepare many NiO/Ni (OH) doped and undoped with other elements2An electrode material. Studies have shown that these NiO/Ni (OH)2The performance of the electrode material is closely related to the specific surface area and the surface structure of the electrode material, and the electrode material with higher specific surface area and a nano-porous network structure can show excellent capacitance characteristic and higher electrochemical stability; doping other elements such as N, Ag, Ce, La, B and the like also improves NiO/Ni (OH) to different degrees2The capacitance characteristics and electrochemical stability of the electrode material. It is worth noting that the valence electron of boron (B) is less than the valence orbital number, which belongs to the electron-deficient situation, so boron and its compound usually have the characteristics of high conductivity, high melting point, high hardness and high stability, and the doping of B is beneficial to simultaneously improve NiO/Ni (OH)2Conductivity, specific capacitance and electrochemical stability of the electrode material, B-doped NiO/Ni (OH)2Electrode material (labeled NiO/Ni (OH)2(B) Has great research and application value. But in NiO/Ni (OH)2In the preparation methods of the electrode material and the doping process, the magnetron sputtering technology needs vacuum conditions and the utilization rate of the metal target material is low; the hydrothermal method, the precipitation conversion method, the sol-gel method and other methods have the defects of complex process parameters, less doping amount of B, less oxide content on the surface of the prepared electrode material and the like, and are difficult to realize industrialization.
Disclosure of Invention
Aiming at the existing problems, the invention provides a preparation method of a boron-doped nickel oxide/nickel hydroxide electrode material, which is used for solving the technical problems in the background technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a boron-doped nickel oxide/nickel hydroxide electrode material comprises the following steps:
1) pretreating the surface of the copper sheet;
2) chemically plating a NiB film on the surface of the copper sheet;
3) the copper sheet after being coated is treated by adopting an in-situ electrochemical anodic oxidation method to obtain B-doped NiO/Ni (OH)2(B) An electrode material.
Preferably, the copper sheet is a 0.1mm thick copper sheet.
Preferably, the method for pretreating the surface of the copper sheet comprises the following steps: the following treatments were used in sequence: polishing a copper sheet by using 1000# waterproof abrasive paper, derusting the copper sheet by using a 10 wt% hydrochloric acid solution, removing oil from the copper sheet by using absolute ethyl alcohol ultrasound, and finally drying the copper sheet for later use.
Preferably, the NiB film is 3 microns thick.
Preferably, the plating solution used in the electroless plating consists of: 30g/L of nickel chloride, 0.8g/L of sodium borohydride, 15g/L of ethylenediamine and 40g/L of potassium sodium tartrate, and adjusting the pH value of the plating solution to 13 by adopting a 5 wt% NaOH solution; the temperature of the plating solution is 55 ℃ during chemical plating, and the chemical plating time is 60 min.
Preferably, the electrochemical anodic oxidation process comprises: constant-voltage anodic oxidation is carried out by adopting a two-electrode system, a stainless steel or platinum inert electrode is taken as a cathode, a chemically-plated NiB copper sheet is taken as an anode, the distance between the cathode and the anode is 1-2cm, the electrolyte comprises 1mol/L of potassium hydroxide and 1g/L of pro-oxidant aqueous solution, the reaction temperature is 30 ℃, the anodic oxidation tank pressure is 1.0-1.5V, and the reaction time is 60 min.
Preferably, the pro-oxidant adopts NaNO2An aqueous solution.
The invention has the beneficial effects that:
the invention aims at the existing NiO/Ni (OH)2Disadvantages of the preparation route of the electrode materialsA preparation process route of firstly chemically plating NiB on the surface of a 0.1mm copper sheet flexible material and then electrochemically anodizing is provided, and NiO/Ni (OH) which is simple and easy to implement, has large B doping amount and good controllability is obtained2(B) The preparation process of the electrode material improves the prepared NiO/Ni (OH)2The capacitance performance and the electrochemical stability of the electrode material are improved, and the process method is beneficial to NiO/Ni (OH)2Commercial application and industrial production of electrode materials.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
FIG. 1 shows NiO/Ni (OH) prepared by the preparation method of the invention2(B) Scanning electron microscope SEM photograph of (1);
FIG. 2 shows NiO/Ni (OH) prepared by the method of the present invention2(B) Cyclic voltammetry curves in 1mol/L NaOH solution at different sweep rates;
FIG. 3 shows NiO/Ni (OH) prepared by the method of the present invention2(B) Charge and discharge curves at different current densities;
FIG. 4 shows NiO/Ni (OH) as two electrode materials of the present invention2And NiO/Ni (OH)2(B) The cyclic charge and discharge performance when the charge and discharge current density is 1A/g in 1mol/L NaOH solution;
FIG. 5 shows NiO/Ni (OH) as two electrode materials of the present invention2And NiO/Ni (OH)2(B) Nyquist plot in 1mol/L NaOH solution;
FIG. 6 shows NiO/Ni (OH) as two electrode materials of the present invention2And NiO/Ni (OH)2(B) The relationship between the energy density and the power density of (a) is called a Ragon graph.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the prior art, for NiO/Ni (OH)2The preparation routes of the electrode material and doping are divided into a direct method and an indirect method: the direct method mainly represents that a hydrothermal method, sol-gel method, magnetron sputtering method and other methods are directly adopted to prepare nickel oxide or nickel hydroxide on the surface of a substrate material; the indirect method is to prepare nickel oxide and hydroxide on the surface of a substrate material by preparing a metal film by magnetron sputtering, electroplating and other methods and then oxidizing. The hydrothermal method and the sol-gel method in the direct method can prepare the nickel oxide/nickel hydroxide electrode material with the nano-porous surface appearance and excellent charge and discharge performance, but have the defects of complex process parameters, incapability of flexibly doping other elements or compounds, difficult industrialization and the like, and the magnetron sputtering requires vacuum and has the defects of complex process parameters, small doping amount and the like.
Comparative example 1:
the layered, porous and hollow nano NiO ball prepared by a template-free hydrothermal method has a high specific capacitance value (734F/g) and good circulation stability; in order to increase NiO/Ni (OH)2The specific capacitance performance of the electrode material is that the specific capacitance of the porous Ni/Co hydroxide nano composite material prepared by adopting a microwave-assisted hydrothermal method is about 1560F/g when the charge-discharge current density is 4A/g, and the specific capacitance is still about 1250F/g after 5000 cycles;
comparative example 2:
successfully synthesizes NiO/Fe doped with boron by adopting a one-step hydrothermal method3O4The nanometer structure is doped with boron, so that the band gap width can be reduced to improve the nanometer NiO/Fe3O4The conductivity of the composite electrode material, and the specific capacitance of the electrode material is up to 1467F/g by reducing the activation energy of the electrode material and shortening the ion diffusion path through synergistic effect.
Although the direct method has been advanced to some extent, it is comparable to NiO/Ni (OH)2For the theoretical specific capacitance of the electrode material to be 2584F/g, the actual specific capacitance of the electrode material still needs to be improved.
The magnetron sputtering in the indirect method also has the defects, and the method of electroplating and reoxidation has the defects of poor uniformity of a plating layer, poor controllability of surface nano-morphology and the like;
comparative example 3:
the CuNi alloy is firstly plated on the surface of a base material by adopting an electroplating method, in order to obtain a surface porous nano structure, Cu needs to be dissolved electrochemically and then reoxidized by adopting a cyclic voltammetry method, the requirement on a power supply of the oxidation process is high, the capacity retention rate is reduced to 94% after 1000 cycles, the stability is not good, and the initial capacity utilization rate of an electrode material is not high.
The invention provides the following technical scheme:
a layer of NiB film with the thickness of 3 microns is chemically plated on the surface of a copper sheet flexible material with the thickness of 0.1mm, and then an in-situ electrochemical anodic oxidation is carried out to prepare a large amount of B-doped NiO/Ni (OH) with the morphology of microspheres with uniform surface2(B) Electrode material, NiO/Ni (OH) prepared by adopting the preparation route2(B) The electrode material B has large doping amount, a large number of micron microsphere structures are arranged on the surface of the electrode material, so that the electrode material has a large specific surface area, the content of surface oxides (active substances of the pseudo-capacitance electrode material) is obviously improved, the contact with electrolyte in an electrochemical performance test is sufficient, the wetting action is enhanced, and NiO/Ni (OH) is enabled2(B) The surface ion diffusion path of the electrode material is shortened in the charging and discharging process, the surface energy band width of the electrode material is reduced by doping B, the electrochemical reaction resistance is reduced, and the electrode material has excellent specific capacitance characteristics and electrochemical stability. And the electrochemical NiB and the electrochemical anodic oxidation are common technologies in the industry, the process conditions are simple and easy to implement, and the controllability is good, so that the research and practical value potential of the route of the method is huge.
According to the above technical solution, the present invention provides the following embodiments:
a preparation method of a boron-doped nickel oxide/nickel hydroxide electrode material comprises the following steps:
surface pretreatment of a copper sheet with the thickness of 0.1 mm: the method comprises the steps of polishing with No. 1000 waterproof abrasive paper, derusting with 10 wt% hydrochloric acid solution, ultrasonic degreasing with absolute ethyl alcohol, and carrying out chemical NiB plating after blow-drying;
the chemical NiB plating process comprises the following steps: the plating solution is composed of nickel chloride (NiCl)2 6H2O)30g/L of boron hydrideSodium chloride (NaBH)4)0.8g/L of ethylenediamine (C)2H8N2)15g/L of potassium sodium tartrate (C)4H4KNaO6)40g/L, and adjusting the pH value of the plating solution to 13 by using a 5 wt% NaOH solution, wherein the temperature is 55 ℃ and the time is 60 min. Washing the surface for 2-3 times by deionized water, and then carrying out electrochemical anodic oxidation;
the electrochemical anodic oxidation process comprises the following steps: constant voltage anodic oxidation is carried out by adopting a two-electrode system, a stainless steel or platinum inert electrode is taken as a cathode, chemical plating NiB is taken as an anode, the distance between the cathode and the anode is 1-2cm, and the electrolyte comprises 1mol/L of potassium hydroxide and 1g/L of pro-oxidant (NaNO)2) Preparing NiO/Ni (OH) from aqueous solution at 30 deg.C and anode oxidation tank pressure of 1.0-1.5V for 60min2(B) An electrode material;
NiO/Ni (OH) is taken out after the anodic oxidation is finished2(B) And (5) washing the electrode material with deionized water for 2-3 times.
NiO/Ni (OH) prepared by adopting three-electrode system research2(B) The capacitance performance and electrochemical stability of the electrode material are shown as NiO/Ni (OH)2(B) The electrode material is a research electrode, the Pt electrode is a counter electrode, the Saturated Calomel Electrode (SCE) is a reference electrode, the capacitance performance and the electrochemical stability of the electrode material are evaluated by testing Cyclic Voltammetry (CV), constant current charge and discharge (GCD) and electrochemical impedance technology (EIS) in 1M NaOH aqueous solution, and the reference sample is NiO/Ni (OH) not doped with B2An electrode material.
As a result, it was found that NiO/Ni (OH) prepared by using a novel process line2(B) The electrode material is composed of Ni, NiO and Ni (OH)2The doping amount of B can reach 14.6 wt%; cyclic voltammetry measurement and constant current charge and discharge tests show that the two electrode materials have high electrochemical activity and reversibility; NiO/Ni (OH) at a charge-discharge current density of 1A/g2(B) The specific capacitance of the electrode material after 10000 charge-discharge cycles is still as high as 1930F/g, compared with that of undoped BNiO/Ni (OH)2The specific capacitance is 1380F/g, which is improved by about 40 percent and shows higher specific capacitance characteristic and good electrochemical stability; electrochemical impedance spectroscopy shows NiO/Ni (OH)2(B) Electrode material is NiO/Ni (OH)2Resistance drop of electrochemical reactionAbout 2 orders of magnitude lower; the energy density versus power density curve (Ragon curve) reveals the NiO/Ni (OH) produced2(B) The electrode material has a higher power density and a lower energy density. The experiment is repeated for more than 3 times, the data reproducibility is good, the process is simple and easy to implement, the controllability is good, the adopted technologies are mature processes, and industrialization and commercialization are easy to realize.
In this example, a thin copper sheet with a thickness of 0.1mm was used as a substrate, NiB plating layers with a thickness of 3 μm were deposited on the surface of the substrate by electroless plating, and then NiO/Ni (OH) doped with B was prepared by electrochemical anodization2Supercapacitor electrode material (NiO/Ni (OH)2(B) ). Scanning electron microscopy and energy spectroscopy (SEM/EDX), x-ray diffractometer and x-ray photoelectron spectroscopy showed that NiO/Ni (OH) was prepared using a novel process route2(B) The doping amount of the electrode material B can reach 14.6 wt%, the surface appearance is uniform, and a large number of micron microsphere structures exist (see figure 1), which shows that the electrode material has a large specific surface area, and the doping of the electrode material B is beneficial to the contact effect and the wetting effect of the surface of the electrode material on the electrolyte of the super capacitor, so that the specific capacitance and the electrochemical stability of the electrode material are improved;
as shown in FIGS. 2 and 3, the results of cyclic voltammetry and galvanostatic charge-discharge tests support this conclusion, the electrode material NiO/Ni (OH)2(B) Has high electrochemical activity and reversibility; NiO/Ni (OH) with undoped B2Compared with the electrode material, NiO/Ni (OH) under the charge-discharge current density of 1A/g2(B) The specific capacitance of the electrode material after 10000 charge-discharge cycles is still 1930F/g, which is higher than that of NiO/Ni (OH) without doping B2(1380F/g) as shown in FIG. 4, showing higher specific capacitance characteristics and good electrochemical stability;
electrochemical impedance spectroscopy shows NiO/Ni (OH)2(B) Electrode material is NiO/Ni (OH)2The electrochemical reaction resistance decreased by about 2 orders of magnitude as shown in figure 5; the energy density versus power density curve (Ragon curve see FIG. 6) reveals the NiO/Ni (OH) produced2(B) The electrode material has higher power density and lower energy densityAnd (4) degree. These test results show that NiO/Ni (OH) prepared by the novel technical route of the invention2(B) The sample has excellent specific capacitance and good electrochemical stability. The experiment is repeated for more than 3 times, the data reproducibility is good, and the method is simple and easy to implement, the adopted technology with good controllability is a mature technology, and industrialization and commercialization are easy to realize.
The preparation method of the boron-doped nickel oxide/nickel hydroxide electrode material provided by the embodiment is simple and easy to implement and has good controllability; the industrialization and the commercialization are easy to realize; realizing B on NiO/Ni (OH) by chemical plating2The doping amount of the electrode material is wide and controllable. And the chemical plating can realize flexible doping of other elements and compounds, and the doping amount is large, controllable and easy to implement. Prepared NiO/Ni (OH)2(B) The surface of the electrode material is uniform and presents a large number of micron microspheres, so that the specific surface area of the electrode material is increased, the contact effect and the wetting effect of the surface of the electrode material and electrolyte are improved, and the electrochemical reaction resistance of the surface of the electrode is reduced, so that the electrode material has higher capacitance performance and electrochemical stability.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are only preferred examples of the present invention and are not intended to limit the present invention, but rather that various changes and modifications may be made without departing from the spirit of the invention, which is intended to be covered by the claims and their full scope and equivalents.

Claims (7)

1. A preparation method of a boron-doped nickel oxide/nickel hydroxide electrode material is characterized by sequentially comprising the following steps:
1) pretreating the surface of the copper sheet;
2) chemically plating a NiB film on the surface of the copper sheet;
3) after the coating is treated by adopting an in-situ electrochemical anodic oxidation methodTo obtain B-doped NiO/Ni (OH)2(B) An electrode material.
2. The method for preparing the boron-doped nickel oxide/nickel hydroxide electrode material according to claim 1, wherein the copper sheet is a 0.1mm thick copper sheet.
3. The preparation method of the boron-doped nickel oxide/nickel hydroxide electrode material according to claim 1, wherein the surface pretreatment method of the copper sheet comprises the following steps: the following treatments were used in sequence: polishing a copper sheet by using 1000# waterproof abrasive paper, derusting the copper sheet by using a 10 wt% hydrochloric acid solution, removing oil from the copper sheet by using absolute ethyl alcohol ultrasound, and finally drying the copper sheet for later use.
4. The method of claim 1, wherein the NiB film is 3 μm thick.
5. The method for preparing a boron-doped nickel oxide/nickel hydroxide electrode material according to claim 1, wherein the electroless plating solution comprises the following components: 30g/L of nickel chloride, 0.8g/L of sodium borohydride, 15g/L of ethylenediamine and 40g/L of potassium sodium tartrate, and adjusting the pH value of the plating solution to 13 by adopting a 5 wt% NaOH solution; the temperature of the plating solution is 55 ℃ during chemical plating, and the chemical plating time is 60 min.
6. The method for preparing the boron-doped nickel oxide/nickel hydroxide electrode material according to claim 1, wherein the electrochemical anodic oxidation process comprises the following steps: constant-voltage anodic oxidation is carried out by adopting a two-electrode system, a stainless steel or platinum inert electrode is taken as a cathode, a chemically-plated NiB copper sheet is taken as an anode, the distance between the cathode and the anode is 1-2cm, the electrolyte comprises 1mol/L of potassium hydroxide and 1g/L of pro-oxidant aqueous solution, the reaction temperature is 30 ℃, the anodic oxidation tank pressure is 1.0-1.5V, and the reaction time is 60 min.
7. The boron-doped nickel oxide/hydroxide according to claim 1The preparation method of the nickel electrode material is characterized in that the pro-oxidant adopts NaNO2An aqueous solution.
CN202011171818.1A 2020-10-28 2020-10-28 Preparation method of boron-doped nickel oxide/nickel hydroxide electrode material Withdrawn CN112331491A (en)

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张轲，高晨，周岩，曹中秋: "电化学氧化工艺对NiO/Ni(OH)2电极材料电容性能的影响", 《沈阳师范大学学报（自然科学版）》 *

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Application publication date: 20210205