CN111477462B - Preparation method of nickel-cobalt-manganese hydroxide nanoneedle/nitrogen-doped carbon/foamed nickel electrode material - Google Patents

Preparation method of nickel-cobalt-manganese hydroxide nanoneedle/nitrogen-doped carbon/foamed nickel electrode material Download PDF

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CN111477462B
CN111477462B CN202010156864.8A CN202010156864A CN111477462B CN 111477462 B CN111477462 B CN 111477462B CN 202010156864 A CN202010156864 A CN 202010156864A CN 111477462 B CN111477462 B CN 111477462B
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nickel
metal salt
cobalt
mixed solution
urea
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CN111477462A (en
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王连邦
占静
刘林辉
苏利伟
吴昊
林威
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Zhejiang University of Technology ZJUT
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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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • 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
    • H01G11/32—Carbon-based
    • 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

Abstract

A preparation method of a nickel-cobalt-manganese hydroxide nanoneedle/nitrogen-doped carbon/foamed nickel electrode material is implemented as follows: (1) cleaning and drying the foamed nickel substrate; (2) dissolving nickel metal salt, citric acid and urea in an alcohol solvent to obtain a mixed solution A; (3) placing the processed foamed nickel in the mixed solution A, heating the mixed solution A in the air to 40-80 ℃ for processing until crystals in the solution are completely separated out; (4) roasting the treated foamed nickel in argon; (5) dissolving nickel metal salt, cobalt metal salt, manganese metal salt and urea in deionized water to obtain a mixed solution B; (6) placing the obtained nickel foam into the mixed solution B for hydrothermal treatment; (7) and cooling, washing and drying to obtain the electrode material. The invention greatly improves the specific surface area of the foamed nickel, improves the loading capacity and ensures the appearance and the size of the active substance, thereby realizing high specific area capacity and cycling stability.

Description

Preparation method of nickel-cobalt-manganese hydroxide nanoneedle/nitrogen-doped carbon/foamed nickel electrode material
Technical Field
The invention relates to a preparation method of a nickel-cobalt-manganese hydroxide nanoneedle/nitrogen-doped carbon/foamed nickel electrode material.
Background
The super capacitor is a novel energy storage device, has the characteristics of large discharge power, light and quick use, no pollution to the environment, long cycle life, high stability, wide use temperature range, high safety performance and the like, and is increasingly valued by people. The electrode material has great influence on the performance development of the super capacitor and the appearance and the group of the super capacitorThe optimal regulation and control of the formation and the size are the main research directions of the current electrode materials. The area specific capacitance is an important evaluation parameter, and the morphology, size and loading of the active material directly influence the area specific capacitance. Under the same appearance and size, the higher the load capacity is, the higher the specific energy and the higher the cost performance are; the single load quantity is increased, and simultaneously, the change of the shape and the size of the material is often caused, so that the problems of material agglomeration, activity reduction, incapability of buffering of volume change, unstable structure and the like are caused. The active substance loading amount reported in the current research is mostly 0.5-5mg/cm2Meanwhile, the requirements of industrial production on high specific energy and low cost cannot be met. Therefore, by designing and optimizing the structures of the current collector and the active material, it is very important to ensure high area specific capacity and cycle stability while realizing high loading capacity.
The ternary nickel-cobalt-manganese hydroxide as the electrode material of the supercapacitor has the following advantages: (1) the conductivity is good; (2) the ternary metal has a plurality of reversible oxidation states and can play a role in synergy and complementation; (3) a faradaic pseudocapacitance much greater than that of carbon material can be provided. Thus arousing a wide interest in the people. Therefore, the present invention combines nickel-cobalt-manganese hydroxide with high specific surface area foamed nickel to prepare and study electrode materials with high loading capacity and exhibit high area specific capacitance specific capacity and excellent cycling performance.
Disclosure of Invention
The invention provides a preparation method of nickel-cobalt-manganese hydroxide nanoneedles/nitrogen-doped carbon/foamed nickel, which is simple, feasible and can be produced in large scale.
In order to achieve the purpose, the invention adopts the following technical scheme. The method comprises the following steps:
a preparation method of a nickel-cobalt-manganese hydroxide nanoneedle/nitrogen-doped carbon/foamed nickel electrode material is implemented according to the following steps:
(1) cleaning and drying the foamed nickel substrate;
(2) weighing nickel metal salt, citric acid and urea in a dissolved alcohol solvent, and uniformly stirring to completely dissolve the nickel metal salt, the citric acid and the urea to obtain a mixed solution A, wherein the nickel metal salt: citric acid: the mass ratio of urea is 1:2: 5-10; the concentration of the nickel metal salt is 30-50 mM;
(3) placing the foamed nickel treated in the step (1) into the mixed solution A in the step (2), and heating the mixed solution A in the air to 40-80 ℃ for treatment until crystals in the solution are completely separated out; wherein the volume dosage of the mixed solution A is 100-500mL/8cm in terms of the area of the nickel foam2；
(4) Roasting the foamed nickel treated in the step (3) in argon at 300-800 ℃;
(5) weighing nickel metal salt, cobalt metal salt, manganese metal salt and urea, dissolving the nickel metal salt, the cobalt metal salt, the manganese metal salt and the urea in deionized water, and uniformly stirring to completely dissolve the nickel metal salt, the cobalt metal salt and the manganese metal salt to obtain a mixed solution B, wherein the molar ratio of the nickel metal salt to the cobalt metal salt to the manganese metal salt is 1:1:1, the molar concentration of the nickel metal salt is 0.1-2 mmol/30mL, and the molar concentration of the urea is 0.5-5 mmol/30 mL;
(6) placing the foamed nickel obtained in the step (4) into the mixed solution B obtained in the step (5), and performing high-temperature treatment at 100-180 ℃;
(7) and (4) naturally cooling the foamed nickel subjected to the high-temperature treatment in the step (6) to room temperature, washing and then drying in vacuum to obtain the nickel-cobalt-manganese hydroxide nanoneedle/nitrogen-doped carbon/foamed nickel electrode material.
The core of the preparation method is that the carbon sheet with high specific surface area is loaded on the foamed nickel, so that the specific surface area of the foamed nickel is greatly increased, the loading of the active material with high active quality is realized, and finally, high specific area capacity and excellent cycle performance are achieved. Wherein the concentration of the metal salt in the hydrothermal solution is critical to the loading of the active material: too small concentration can result in lower loading capacity, and too large concentration can cause the nanoneedles to agglomerate seriously, resulting in the sharp reduction of specific area capacity and cycle performance.
Preferably, step (1) is carried out as follows: and ultrasonically cleaning the foamed nickel substrate by using acetone, 0.5-3M hydrochloric acid, deionized water and ethanol in sequence, wherein the cleaning time is 10-30 min each time, and the drying temperature is 35-80 ℃.
Preferably, in the step (2), the nickel metal salt is nickel acetate, nickel chloride or nickel nitrate, the concentration is 30-50 mM, and the alcohol solvent is ethanol, ethylene glycol or glycerol.
Preferably, the temperature rise rate of the roasting in the step (4) is 5-20 ℃/min, the roasting temperature is 300-800 ℃, and the roasting time is 2-10 h. Further preferably, the roasting is carried out step by step, firstly roasting at 350-400 ℃ for 2-3h, and then heating to 600-650 ℃ for 2-3 h.
Preferably, the nickel metal salt, the cobalt metal salt and the manganese metal salt in the step (5) are respectively nitrate, chloride or acetate, the molar concentration of the metal salt is 2mmol/30mL, and the molar concentration of the urea is 2.5mmol/30 mL.
Preferably, the heat treatment temperature in the step (6) is 100-180 ℃, and the treatment time is 6-8 h.
Preferably, the vacuum drying temperature in the step (7) is 40-90 ℃, and the drying time is 5-12 h.
Compared with the prior art, the invention has the following characteristics and advantages:
(1) the method realizes 23-40 mg-cm on the foamed nickel substrate for the first time-2In situ growth of ultra-high loading active species.
(2) In the known electrode material of foamed nickel loaded with metal oxide, hydroxide and sulfide, the hydroxide nanoneedles are uniformly distributed and have the largest loading amount.
(3) The controllable adjustment of the loading capacity of the nickel-cobalt-manganese hydroxide nanometer needle on the foamed nickel is realized.
(4) The preparation method has the advantages of wide raw material source, low cost, short preparation time, safe and reliable operation process, no hazardous chemicals, greenness, no pollution and suitability for large-scale production, and is a preparation process conforming to the principle of green chemistry.
(5) The nickel-cobalt-manganese hydroxide nanoneedle/nitrogen-doped carbon/foamed nickel electrode material prepared by the method has high specific area capacity and excellent cycle performance.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a foamed nickel substrate of example 1.
Figure 2 is an SEM image of nitrogen doped carbon/nickel foam produced in example 1.
Fig. 3 is an SEM image of the nickel cobalt manganese hydroxide/nitrogen doped carbon/nickel foam electrode prepared in example 1.
Fig. 4 is an X-ray diffraction (XRD) pattern of the nickel foam substrate and nickel cobalt manganese hydroxide/nitrogen-doped carbon/nickel foam electrode prepared in example 1.
Fig. 5 is a graph of Cyclic Voltammetry (CV) of the nickel cobalt manganese hydroxide/nitrogen doped carbon/nickel foam electrode prepared in example 1.
Fig. 6 is a graph of constant current charge and discharge (GCD) for the nickel cobalt manganese hydroxide/nitrogen doped carbon/nickel foam electrode prepared in example 1.
Figure 7 is a graph of the long cycle performance of nickel cobalt manganese hydroxide/nitrogen doped carbon/nickel foam prepared in example 1.
Fig. 8 is an SEM image of the nickel cobalt manganese hydroxide/nitrogen doped carbon/nickel foam electrode of example 2.
Figure 9 is a GCD diagram of a nickel cobalt manganese hydroxide/nitrogen doped carbon/nickel foam electrode prepared in example 2.
Fig. 10 is an SEM image of the nickel cobalt manganese hydroxide/nitrogen doped carbon/nickel foam electrode of example 2.
Figure 11 is a GCD diagram of a nickel cobalt manganese hydroxide/nitrogen doped carbon/nickel foam electrode prepared in example 3.
Fig. 12 is an SEM image of the nickel cobalt manganese hydroxide/nitrogen doped carbon/nickel foam electrode of example 2.
Figure 13 is a GCD diagram of a nickel cobalt manganese hydroxide/nitrogen doped carbon/nickel foam electrode prepared in example 4.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the accompanying drawings and embodiments, but is not limited thereto:
in the embodiment of the invention, CV and GCD tests of the nickel-cobalt-manganese hydroxide/nitrogen-doped carbon/foamed nickel composite electrode are completed in an electrochemical workstation, a three-electrode system is adopted, the electrolyte is 3M KOH solution, the reference electrode is a mercury/mercury oxide electrode, and the counter electrode is a platinum electrode.
Example 1:
(1) and (3) ultrasonically cleaning foamed nickel with the size of 2cm multiplied by 4cm for 10min by acetone, 3M HCl, deionized water and absolute ethyl alcohol respectively, and drying at 45 ℃.
(2) Weighing nickel acetate (with the concentration of 45mM), citric acid and urea, dissolving in 250ml of ethanol, and stirring to completely dissolve, wherein the mass ratio of the nickel acetate to the citric acid to the urea is 1:2: 5;
(3) placing the foamed nickel treated in the step (1) into 250mL of the mixed solution obtained in the step (2), and heating to 80 ℃ until crystals in the solution are completely separated out;
(4) and (4) roasting the foamed nickel treated in the step (3) in argon at 350 ℃ for 2h, and then roasting at 650 ℃ for 2h, wherein the heating rate is 5 ℃/min.
(5) Weighing 2mmol of nickel nitrate, 2mmol of cobalt nitrate, 2mmol of manganese nitrate and 2.5mmol of urea, dissolving in 30mL of deionized water, and stirring uniformly to completely dissolve;
(6) placing the foamed nickel obtained in the step (4) into 30mL of the mixed solution obtained in the step (5), and treating at 120 ℃ for 6 h;
(7) naturally cooling the foamed nickel treated at the high temperature in the step (6) to room temperature, washing, then drying in vacuum at 45 ℃ for 12h, and weighing before and after reaction to obtain a mass difference value (namely m)Electrode material of nickel cobalt manganese hydroxide/nitrogen-doped carbon/foamed nickel-mFoamed nickel) To obtain a supported amount of 23 mg. cm-2The nickel-cobalt-manganese hydroxide/nitrogen-doped carbon/nickel foam electrode material.
The electrode material of nickel cobalt manganese hydroxide/nitrogen doped carbon/nickel foam prepared in example 1 was based on nickel foam. The foam nickel firstly loads a large number of carbon sheets, and the specific surface area of the foam nickel is increased. FIG. 1 is an SEM image of foamed nickel, which can be seen to be in a sponge-like porous structure. FIG. 2 is an SEM image of the carbon plate loaded on the nickel foam, and it can be seen that a large amount of carbon plates are accumulated on the surface and in the pore structure of the nickel foam. FIG. 3 is an SEM photograph of the electrode material prepared in example 1, and it can be seen that Ni-Co-Mn-HNeedle-like structure of the oxide. Fig. 4 is an XRD pattern of the electrode material prepared in example 1, and a characteristic peak of manganese oxyhydroxide can be seen. The accompanying figures 5 and 6 are CV and GCD diagrams of the electrode material respectively, the diagram shows that the electrode material is reversible in the charging and discharging process, and the specific capacity of the discharging area reaches 19360mF cm-2The capacity retention after 10000 cycles was 98% (FIG. 7).
Example 2:
(1) and (3) ultrasonically cleaning foamed nickel with the size of 2cm multiplied by 4cm for 15min by acetone, 2M HCl, deionized water and absolute ethyl alcohol respectively, and drying at 60 ℃.
(2) Weighing nickel chloride (with the concentration of 30mM), citric acid and urea, dissolving in 100ml of ethylene glycol, and stirring to completely dissolve, wherein the mass ratio of nickel chloride to citric acid to urea is 1:2: 7;
(3) placing the foamed nickel treated in the step (1) in 100ml of the mixed solution obtained in the step (2) and heating to 60 ℃ until crystals in the solution are completely separated out;
(4) and (4) roasting the foamed nickel treated in the step (3) for 8 hours at 350 ℃ in argon, wherein the heating rate is 8 ℃/min.
(5) Weighing 1mmol of nickel chloride, 1mmol of cobalt chloride, 1mmol of manganese chloride and 1.5mmol of urea, dissolving in 30ml of deionized water, and stirring uniformly to completely dissolve;
(6) placing the foamed nickel obtained in the step (4) into 30ml of the mixed solution obtained in the step (5), and carrying out high-temperature treatment at 160 ℃ for 7 h;
(7) naturally cooling the foamed nickel treated at the high temperature in the step (6) to room temperature, washing, drying at the temperature of 60 ℃ for 8 hours in vacuum, and weighing before and after reaction to obtain a mass difference value, wherein the loading capacity is 11mg cm-2The nickel-cobalt-manganese hydroxide/nitrogen-doped carbon/nickel foam electrode material.
Fig. 8 is an SEM image of the electrode material prepared in example 2. FIG. 9 is a GCD diagram of the electrode material, which shows that the electrode material has good rate capability and a specific discharge area capacity of 12840mF cm-2。
Example 3:
(1) and (3) ultrasonically cleaning foamed nickel with the size of 2cm multiplied by 4cm with acetone, 1M HCl, deionized water and absolute ethyl alcohol respectively for 20min, and drying at 70 ℃.
(2) Weighing nickel nitrate (with the concentration of 40mM), citric acid and urea, dissolving in 200ml of glycerol, and stirring to completely dissolve, wherein the mass ratio of the nickel nitrate to the citric acid to the urea is 1:2: 10;
(3) putting 200ml of foamed nickel treated in the step (1) into the mixed solution in the step (2), and heating to 40 ℃ until crystals in the solution are completely separated out;
(4) and (4) roasting the foamed nickel treated in the step (3) for 2 hours at 650 ℃ in argon, wherein the heating rate is 20 ℃/min.
(5) Weighing 0.1mmol of nickel nitrate, 0.1mmol of cobalt nitrate, 0.1mmol of manganese nitrate and 0.5mmol of urea, dissolving in 30ml of deionized water, and stirring uniformly to completely dissolve;
(6) placing the foamed nickel obtained in the step (4) in 30ml of the mixed solution obtained in the step (5), and carrying out high-temperature treatment at 180 ℃ for 7.5 h;
(7) naturally cooling the foamed nickel treated at the high temperature in the step (6) to room temperature, washing, drying at the temperature of 80 ℃ for 7 hours in vacuum, and weighing before and after reaction to obtain a mass difference value to obtain the load of 5mg cm-2The nickel-cobalt-manganese hydroxide/nitrogen-doped carbon/nickel foam electrode material.
FIG. 10 is an SEM image of the electrode material prepared in example 3, FIG. 11 is a GCD image of the electrode material, and the graph shows that the electrode material has good rate capability and specific discharge area capacity of 7248mF cm-2。
Example 4:
(1) ultrasonically cleaning foamed nickel with the size of 2cm multiplied by 4cm with acetone, 0.5M HCl, deionized water and absolute ethyl alcohol respectively for 30min, and drying at 80 ℃.
(2) Weighing nickel nitrate (40mM), citric acid and urea, dissolving in 500ml ethanol, and stirring to completely dissolve, wherein the mass ratio of nickel nitrate to citric acid to urea is 1:2: 8;
(3) placing the foamed nickel treated in the step (1) in 500ml of the mixed solution obtained in the step (2), and heating to 80 ℃ until crystals in the solution are completely separated out;
(4) and (4) roasting the foamed nickel treated in the step (3) for 10 hours at 650 ℃ in argon, wherein the heating rate is 20 ℃/min.
(5) Weighing 2mmol of nickel acetate, cobalt acetate, manganese acetate and 5mmol of urea, dissolving in 30ml of deionized water, and stirring uniformly to completely dissolve;
(6) placing the foamed nickel obtained in the step (4) into 30ml of the mixed solution obtained in the step (5), and carrying out high-temperature treatment at 100 ℃ for 8 h;
(7) naturally cooling the foamed nickel treated at the high temperature in the step (6) to room temperature, washing, drying at the temperature of 60 ℃ for 12 hours in vacuum, and weighing before and after reaction to obtain a mass difference value to obtain the load of 40mg cm-2The nickel-cobalt-manganese hydroxide/nitrogen-doped carbon/nickel foam electrode material.
FIG. 12 is an SEM image of the electrode material prepared in example 3, from which it can be seen that the partial agglomeration of the nanoneedle is caused by the too high loading amount, and FIG. 13 is a GCD image of the electrode material, from which it is found that the rate capability of the electrode material is better, but the specific capacity of the discharge area is reduced to 3984mF cm-2。
The above-mentioned embodiments are only a part of the preferred embodiments of the present invention, not all embodiments, and are not intended to limit the scope of the present invention, and any modifications, substitutions, etc. made under the concept and principle of the present invention should be included in the scope of the present invention.

Claims (8)

1. A preparation method of a nickel-cobalt-manganese hydroxide nanoneedle/nitrogen-doped carbon/foamed nickel electrode material is implemented according to the following steps:
(1) cleaning and drying the foamed nickel substrate;
(2) weighing nickel metal salt, citric acid and urea in a dissolved alcohol solvent, and uniformly stirring to completely dissolve the nickel metal salt, the citric acid and the urea to obtain a mixed solution A, wherein the nickel metal salt: citric acid: the mass ratio of urea is 1:2: 5-10; the concentration of the nickel metal salt is 30-50 mM;
(3) placing the foamed nickel treated in the step (1) into the mixed solution A in the step (2), and heating the mixed solution A in the air to 40-80 ℃ for treatment until crystals in the solution are completely separated out; wherein the volume dosage of the mixed solution A is 100-500mL/8cm in terms of the area of the nickel foam2；
(4) Roasting the foamed nickel treated in the step (3) in argon at 300-800 ℃;
(5) weighing nickel metal salt, cobalt metal salt, manganese metal salt and urea, dissolving the nickel metal salt, the cobalt metal salt, the manganese metal salt and the urea in deionized water, and uniformly stirring to completely dissolve the nickel metal salt, the cobalt metal salt and the manganese metal salt to obtain a mixed solution B, wherein the molar ratio of the nickel metal salt to the cobalt metal salt to the manganese metal salt is 1:1:1, the molar concentration of the nickel metal salt is 0.1-2 mmol/30mL, and the molar mass of the urea is 0.5-5 mmol/30 mL;
(6) placing the foamed nickel obtained in the step (4) into the mixed solution B obtained in the step (5), and performing high-temperature treatment at 100-180 ℃;
(7) and (4) naturally cooling the foamed nickel subjected to the high-temperature treatment in the step (6) to room temperature, washing and then drying in vacuum to obtain the nickel-cobalt-manganese hydroxide nanoneedle/nitrogen-doped carbon/foamed nickel electrode material.
2. The method of claim 1, wherein: the nickel metal salt, the cobalt metal salt and the manganese metal salt in the step (5) are respectively nitrate, chloride or acetate, the molar concentrations of the nickel metal salt, the cobalt metal salt and the manganese metal salt are respectively 2mmol/30mL, and the molar concentration of the urea is 2.5mmol/30 mL.
3. The method of claim 1 or 2, wherein: in the step (2), the nickel metal salt is nickel acetate, nickel chloride or nickel nitrate, and the alcohol solvent is ethanol, ethylene glycol or glycerol.
4. The method of claim 1 or 2, wherein: in the step (4), the heating rate of the roasting is 5-20 ℃/min, the roasting temperature is 300-800 ℃, and the roasting time is 2-10 h.
5. The method of claim 4, wherein: the roasting in the step (4) is carried out step by step, firstly roasting for 2-3h at the temperature of 350-.
6. The method of claim 1 or 2, wherein: the heat treatment temperature in the step (6) is 100-180 ℃, and the treatment time is 6-8 h.
7. The method of claim 1 or 2, wherein: in the step (7), the vacuum drying temperature is 40-90 ℃, and the drying time is 5-12 h.
8. The method of claim 1 or 2, wherein: the step (1) is implemented as follows: and ultrasonically cleaning the foamed nickel substrate by using acetone, 0.5-3M hydrochloric acid, deionized water and ethanol in sequence, wherein the cleaning time is 10-30 min each time, and the drying temperature is 35-80 ℃.
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