CN113046775A - Electrode based on dual effects of induction and sacrifice and preparation method thereof - Google Patents

Electrode based on dual effects of induction and sacrifice and preparation method thereof Download PDF

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CN113046775A
CN113046775A CN202110256143.9A CN202110256143A CN113046775A CN 113046775 A CN113046775 A CN 113046775A CN 202110256143 A CN202110256143 A CN 202110256143A CN 113046775 A CN113046775 A CN 113046775A
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nickel
iron
solution
mixed hydroxide
substrate
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CN113046775B (en
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周清稳
许程源
石菲扬
郭艳玲
潘忠芹
叶长青
姜启玉
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Shandong Aohydrogen Power Technology Co Ltd
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Nantong University
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    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/62—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract

The invention provides an electrode based on induction and sacrifice double effects and a preparation method thereof, wherein the preparation method comprises the following steps: s10, cleaning the surface of the metal ferronickel substrate; s20, performing induced corrosion treatment, namely soaking the cleaned metal nickel-iron substrate in a halogen salt solution at normal temperature and normal pressure for 1-36 h to perform induced corrosion treatment to obtain the metal nickel-iron substrate subjected to induced corrosion; s30 sacrificial activation treatment, namely soaking the metal nickel-iron substrate subjected to induced corrosion in a strong alkaline solution at normal temperature and normal pressure for 4-48 h to perform sacrificial activation treatment, and obtaining the electrode based on dual effects of induction and sacrificial treatment. Compared with the traditional electrode preparation method, the electrode based on the induction and sacrifice dual effects and the preparation method thereof have the advantages that the preparation conditions are mild and simple, the energy consumption and cost are greatly reduced, the electrode is suitable for industrial popularization and application, and meanwhile, the prepared nickel-iron mixed hydroxide contains cation defects, and compared with the traditional nickel-iron mixed hydroxide, the electrocatalytic oxygen evolution activity is higher.

Description

Electrode based on dual effects of induction and sacrifice and preparation method thereof
Technical Field
The invention relates to the technical field of electrolytic water oxygen evolution side electrode preparation, in particular to an electrode based on induction and sacrifice double effects and a preparation method thereof.
Background
The energy problem is one of the most important problems to be solved urgently by human beings in the future. With the rapid development of new energy industries, emerging energy systems such as long-endurance batteries, efficient solar energy conversion, green chemical production, hydrogen energy and the like are gradually applied to daily work and life. In different types of energy conversion processes, the electrode plays a crucial role, and determines the energy conversion efficiency, such as a battery, electrocatalysis, hydrogen production by water electrolysis, and the like.
The hydrogen energy is a green energy with great potential in the future, and the attention on the hydrogen energy is particularly obvious recently. The hydrogen production by alkaline electrolysis of water is one of important ways for obtaining hydrogen sources, and has the advantages of no pollution emission, high hydrogen production purity, simple process and the like compared with the hydrogen production by fossil energy. At present, the whole electrode for producing hydrogen by alkaline electrolysis of water still stays at the technological level for decades, for example, the oxygen evolution side electrode still adopts a pure nickel anode.
At present, the ferronickel mixed hydroxide-based electrode is a hot research point of an alkaline water electrolysis hydrogen production oxygen evolution side electrode. The traditional preparation methods mainly comprise a hydrothermal method and an electrodeposition method, and the methods need to provide certain extra energy artificially and have strict conditions. For example, hydrothermal processes require the use of high temperature, high temperature resistant, sealed hydrothermal kettles and provide sufficient thermal energy, and electrodeposition processes require the provision of sufficient electrical energy. Therefore, the method for preparing the ferronickel mixed hydroxide-based electrode under mild conditions is of great significance, and particularly, other forms of energy such as heat energy, electric energy and the like do not need to be provided artificially. On the other hand, defect engineering is an effective means to provide intrinsic catalytic performance of the catalyst. For example, cation defect engineering, anion defect engineering, and the like can unbalance the proportion of anions and cations in the catalyst, but show more excellent catalytic performance than the original catalyst.
Disclosure of Invention
In order to solve the problems, the invention provides an electrode based on induction and sacrifice double effects and a preparation method thereof, compared with the traditional electrode preparation method, the preparation conditions are mild and simple, the energy consumption and cost are greatly reduced, the method is suitable for industrial popularization and application, and meanwhile, the prepared nickel-iron mixed hydroxide contains cation defects, and compared with the traditional nickel-iron mixed hydroxide, the electrocatalytic oxygen evolution activity is higher.
In order to achieve the above purpose, the invention adopts a technical scheme that:
an electrode based on dual effects of induction and sacrifice comprises a metal ferronickel substrate and ferronickel mixed hydroxide containing cation defects arranged on the metal ferronickel substrate, wherein the cation defects of the ferronickel mixed hydroxide contain Ni2+Defect, Fe3+At least one of the defects.
The invention also provides an electrode preparation method based on induction and sacrifice double effects, which comprises the following steps: s10, cleaning the surface of the metal nickel-iron substrate to obtain a cleaned metal nickel-iron substrate; s20, performing induced corrosion treatment, namely soaking the cleaned metal nickel-iron substrate in a halogen salt solution at normal temperature and normal pressure for 1-36 h to perform induced corrosion treatment, forming a nickel-iron mixed hydroxide doped with specific induced cations on the surface of the metal nickel-iron substrate, and cleaning and drying to obtain the metal nickel-iron substrate subjected to induced corrosion; s30, performing sacrificial activation treatment, namely soaking the metal nickel-iron substrate subjected to induced corrosion in a strong alkaline solution at normal temperature and normal pressure for 4-48 h to perform sacrificial activation treatment, forming nickel-iron mixed hydroxide containing cation defects on the surface of the metal nickel-iron substrate, and cleaning and drying to obtain the electrode based on the dual effects of induction and sacrificial.
Further, the specific inducing cation is Al3+、Zn2+At least one of (1).
Further, the step S10 includes: s11, placing the metal nickel-iron substrate in an acetone solution for ultrasonic cleaning for 10-30 min, and then repeatedly cleaning with ethanol to remove a grease layer on the surface of the metal nickel-iron substrate; s12, placing the metal nickel-iron substrate with the surface grease layer removed in a hydrochloric acid solution with the concentration of 1-6 mol/L for 5-25 min by ultrasonic treatment, standing in the hydrochloric acid solution for 10-30 min, taking out, and repeatedly cleaning with distilled water to remove the oxide layer on the surface of the metal nickel-iron substrate; s13, drying the metal nickel-iron substrate with the oxide layer removed to obtain the cleaned metal nickel-iron substrate.
Further, the halogen salt solution is at least one of a potassium chloride solution, a magnesium chloride solution, a lithium chloride solution, a sodium fluoride solution, a potassium bromide solution or a sodium bromide solution.
Furthermore, the concentration of the halogen ions in the halogen salt solution is 0.1-10 mol/L, and the concentration of the specific induced cation is 0.001-0.5 mmol/L.
Further, the strong alkali solution is at least one of sodium hydroxide solution or potassium hydroxide solution, and OH in the strong alkali solution-The concentration is 3-12 mol/L.
Further, the specially induced cation doped nickel-iron mixed hydroxide is one of nickel-iron-aluminum ternary mixed hydroxide, nickel-iron-zinc ternary mixed hydroxide or nickel-iron-aluminum-zinc quaternary mixed hydroxide.
Further, in the nickel-iron-aluminum ternary mixed hydroxide, aluminum is doped in iron sites in the nickel-iron mixed hydroxide; in the nickel-iron-zinc ternary mixed hydroxide, zinc is doped in nickel sites in the nickel-iron mixed hydroxide; in the nickel-iron-aluminum-zinc quaternary mixed hydroxide, aluminum is doped at iron sites in the nickel-iron mixed hydroxide, and zinc is doped at nickel sites in the nickel-iron mixed hydroxide.
Further comprisesCation deficient nickel iron mixed hydroxide has a cation deficiency of Ni2+Defects or Fe3+At least one of the defects.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) according to the electrode based on the dual effects of induction and sacrifice and the preparation method thereof, through a normal-temperature and normal-pressure treatment process, the nickel-iron mixed hydroxide doped with specific induction cations is formed on the surface of the metal nickel-iron substrate on the premise of not requiring external energy input, then the doped specific induction cations are corroded through sacrifice activation treatment to obtain the nickel-iron mixed hydroxide containing cation defects, and the electrode based on the dual effects of induction and sacrifice is obtained.
(2) According to the electrode based on the induction and sacrifice dual effects and the preparation method thereof, the prepared nickel-iron mixed hydroxide contains cation defects, and compared with the traditional nickel-iron mixed hydroxide, the electrocatalytic oxygen evolution activity is higher.
Drawings
The technical solution and the advantages of the present invention will be apparent from the following detailed description of the embodiments of the present invention with reference to the accompanying drawings.
Fig. 1 is a flow chart of a method for preparing an electrode based on dual effects of induction and sacrifice according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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.
The embodiment provides an electrode based on dual effects of induction and sacrifice, which comprises a metal nickel-iron baseA base and a nickel-iron mixed hydroxide containing cationic defects disposed on the metallic nickel-iron substrate, the cationic defects of the nickel-iron mixed hydroxide comprising Ni2+Defect, Fe3+At least one of the defects.
The embodiment also provides an electrode preparation method based on dual effects of induction and sacrifice, as shown in fig. 1, including the following steps: s10, cleaning the surface of the metal nickel-iron substrate to obtain the cleaned metal nickel-iron substrate. S20, performing induced corrosion treatment, namely soaking the cleaned metal nickel-iron substrate in a halogen salt solution at normal temperature and normal pressure for 1-36 h to perform induced corrosion treatment, forming a nickel-iron mixed hydroxide doped with specific induced cations on the surface of the metal nickel-iron substrate, and cleaning and drying to obtain the metal nickel-iron substrate subjected to induced corrosion. S30, performing sacrificial activation treatment, namely soaking the metal nickel-iron substrate subjected to induced corrosion in a strong alkaline solution at normal temperature and normal pressure for 4-48 h to perform sacrificial activation treatment, forming nickel-iron mixed hydroxide containing cation defects on the surface of the metal nickel-iron substrate, and cleaning and drying to obtain the electrode based on the dual effects of induction and sacrificial.
The step S10 includes: s11, placing the metal nickel-iron substrate in an acetone solution for ultrasonic cleaning for 10-30 min, and then repeatedly cleaning with ethanol to remove the grease layer on the surface of the metal nickel-iron substrate. Preferably, the ultrasonic cleaning time is 10min, 15min, 20min, 25min or 30min, and the metal nickel iron substrate is preferably one of nickel iron alloy mesh, foamed nickel iron or nickel iron alloy sheet. S12, placing the metal nickel-iron substrate with the surface grease layer removed in a hydrochloric acid solution with the concentration of 1-6 mol/L for 5-25 min by ultrasonic treatment, standing in the hydrochloric acid solution for 10-30 min, taking out, and repeatedly cleaning with distilled water to remove the oxide layer on the surface of the metal nickel-iron substrate. Preferably, the concentration of the hydrochloric acid solution is 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L or 6mol/L, the ultrasonic time is preferably 5min, 10min, 15min, 20min or 25min, and the standing time is preferably 10min, 15min, 20min, 25min or 30 min. S13, drying the metal nickel-iron substrate with the oxide layer removed to obtain the cleaned metal nickel-iron substrate.
In the step S20, the soaking time is preferably 1h, 5h, 10h, 15h, 18h, 20h, 25hh. 30h, 35h or 36 h. The concentration of the halogen ion in the halogen salt solution is 0.1-10 mol/L, preferably 0.1mol/L, 1mol/L, 2.0mol/L, 3mol/L, 4.8mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10 mol/L. The halogen salt solution is at least one of potassium chloride solution, magnesium chloride solution, lithium chloride solution, sodium fluoride solution, potassium bromide solution or sodium bromide solution. The specific induced cation concentration is 0.001-0.5 mmol/L, preferably 0.001mmol/L, 0.005mmol/L, 0.01mmol/L, 0.05mmol/L, 0.1mmol/L, 0.2mmol/L, 0.3mmol/L, 0.4mmol/L or 0.5mmol/L, and the specific induced cation is Al3+、Zn2+At least one of (1).
In the step S30, the soaking time is preferably 4h, 12h, 24h, 36h or 48h, and the strong alkali solution is at least one of a sodium hydroxide solution or a potassium hydroxide solution. OH in strong alkaline solution-The concentration is 3-12 mol/L, preferably 3mol/L, 4.5mol/L, 6mol/L, 7.5mol/L, 9mol/L, 10.5mol/L or 12 mol/L. The nickel-iron mixed hydroxide doped with specific induced cations is one of nickel-iron-aluminum ternary mixed hydroxide, nickel-iron-zinc ternary mixed hydroxide or nickel-iron-aluminum-zinc quaternary mixed hydroxide. In the nickel-iron-aluminum ternary mixed hydroxide, aluminum is doped at iron sites in the nickel-iron mixed hydroxide; in the nickel-iron-zinc ternary mixed hydroxide, zinc is doped in nickel sites in the nickel-iron mixed hydroxide; in the nickel-iron-aluminum-zinc quaternary mixed hydroxide, aluminum is doped at iron sites in the nickel-iron mixed hydroxide, and zinc is doped at nickel sites in the nickel-iron mixed hydroxide. The cation defect of the nickel-iron mixed hydroxide containing cation defects is Ni2+Defects or Fe3+At least one of the defects. The cleaning in the step S20 and the step S30 is rinsed with distilled water.
Example 1
S11, placing the 40-mesh plain-woven metal nickel-iron alloy net in an acetone solution for ultrasonic cleaning for 20min, and repeatedly cleaning with ethanol to remove the grease layer on the surface of the metal nickel-iron alloy net. S12, placing the nickel-iron alloy net with the surface grease layer removed in a hydrochloric acid solution with the concentration of 4mol/L for ultrasonic treatment for 15min, standing in the hydrochloric acid solution for 20min, taking out, and repeatedly cleaning with distilled water to remove the oxide layer on the surface of the metal nickel-iron alloy net. S13, drying the metal nickel-iron alloy net with the oxide layer removed to obtain the cleaned metal nickel-iron alloy net.
S20, performing induced corrosion treatment, namely soaking the cleaned metal nickel-iron alloy net in a mixed solution of 0.45mol/L potassium fluoride, 4.55mol/L potassium bromide and 0.05mmol/L zinc sulfate at normal temperature and normal pressure for 18h to perform induced corrosion treatment, forming nickel-iron mixed hydroxide doped with specific induced cations on the surface of the metal nickel-iron alloy net, and cleaning and drying to obtain the metal nickel-iron alloy net subjected to induced corrosion.
S30 sacrificial activation treatment, namely, placing the metal nickel-iron alloy net subjected to induced corrosion in 6mol/L potassium hydroxide solution, soaking for 12h at normal temperature and normal pressure for sacrificial activation treatment, forming nickel-iron mixed hydroxide containing cation defects on the surface of the metal nickel-iron alloy net, and cleaning and drying to obtain the electrode based on the dual effects of induction and sacrificial.
Example 2
S11, placing the foam nickel iron in acetone solution for ultrasonic cleaning for 30min, and repeatedly cleaning with ethanol to remove the grease layer on the surface of the foam nickel iron. S12, placing the foam ferronickel with the surface grease layer removed in a hydrochloric acid solution with the concentration of 6mol/L for ultrasonic treatment for 5min, then standing in the hydrochloric acid solution for 30min, taking out, and repeatedly cleaning with distilled water to remove the oxide layer on the surface of the foam ferronickel. S13, drying the foam ferronickel with the oxide layer removed to obtain the cleaned foam ferronickel.
S20, performing induced corrosion treatment, namely soaking the cleaned foam nickel iron in a mixed solution of 0.25mol/L potassium chloride, 1.75mol/L lithium chloride and 0.2mmol/L aluminum nitrate for 1h at normal temperature and normal pressure to perform induced corrosion treatment, forming nickel iron mixed hydroxide doped with specific induced cations on the surface of the foam nickel iron, and cleaning and drying to obtain the foam nickel iron after induced corrosion.
S30 sacrificial activation treatment, namely, placing the foam ferronickel subjected to induced corrosion in 10.5mol/L potassium hydroxide solution, soaking for 4 hours at normal temperature and normal pressure for sacrificial activation treatment, forming ferronickel mixed hydroxide containing cation defects on the surface of the foam ferronickel, and cleaning and drying to obtain the electrode based on the dual effects of induction and sacrificial.
Example 3
S11, the nickel-iron alloy sheet is placed in acetone solution for ultrasonic cleaning for 10min, and then is repeatedly cleaned by ethanol to remove the grease layer on the surface of the nickel-iron alloy sheet. S12, placing the nickel-iron alloy net with the surface grease layer removed in a hydrochloric acid solution with the concentration of 1mol/L for ultrasonic treatment for 25min, standing in the hydrochloric acid solution for 10min, taking out, and repeatedly cleaning with distilled water to remove the oxide layer on the surface of the nickel-iron alloy sheet. S13, drying the nickel-iron alloy sheet with the oxide layer removed to obtain the cleaned nickel-iron alloy sheet.
S20, performing induced corrosion treatment, namely soaking the cleaned ferronickel alloy sheet in a mixed solution of 0.1mol/L sodium chloride, 0.0005mmol/L aluminum nitrate and 0.0005mmol/L zinc sulfate at normal temperature and normal pressure for 36h to perform induced corrosion treatment, forming a ferronickel mixed hydroxide doped with specific induced cations on the surface of the ferronickel alloy sheet, and cleaning and drying to obtain the ferronickel alloy sheet after induced corrosion.
S30 sacrificial activation treatment, namely, placing the nickel-iron alloy sheet after induced corrosion in 3mol/L potassium hydroxide solution, soaking for 48h at normal temperature and normal pressure for sacrificial activation treatment, forming nickel-iron mixed hydroxide containing cation defects on the surface of the nickel-iron alloy sheet, and cleaning and drying to obtain the electrode based on the dual effects of induction and sacrificial.
Example 4
S11, placing the foam nickel iron in acetone solution for ultrasonic cleaning for 25min, and repeatedly cleaning with ethanol to remove the grease layer on the surface of the foam nickel iron. S12, placing the nickel-iron alloy net with the surface grease layer removed in a hydrochloric acid solution with the concentration of 3mol/L for ultrasonic treatment for 10min, then standing in the hydrochloric acid solution for 25min, taking out, and repeatedly cleaning with distilled water to remove the oxide layer on the surface of the foamed nickel-iron. S13, drying the foam ferronickel with the oxide layer removed to obtain the cleaned foam ferronickel.
S20, performing induced corrosion treatment, namely soaking the cleaned foam nickel iron in a mixed solution of 10mol/L lithium chloride, 0.2mmol/L aluminum nitrate and 0.3mmol/L zinc sulfate for 25h at normal temperature and normal pressure to perform induced corrosion treatment, forming nickel iron mixed hydroxide doped with specific induced cations on the surface of the foam nickel iron, and cleaning and drying to obtain the foam nickel iron after induced corrosion.
S30 sacrificial activation treatment, namely, placing the foam ferronickel subjected to induced corrosion in a potassium hydroxide solution of 12mol/L, soaking for 36h at normal temperature and normal pressure for sacrificial activation treatment, forming ferronickel mixed hydroxide containing cation defects on the surface of the foam ferronickel, and cleaning and drying to obtain the electrode based on the dual effects of induction and sacrificial.
Comparative example 1
This comparative example directly adopts 40 mesh plain weave ferronickel net as the electrode:
placing the 40-mesh plain ferronickel alloy net in an acetone solution, ultrasonically cleaning for 20min, and repeatedly cleaning with ethanol to remove a grease layer on the surface of the ferronickel alloy net; s12, placing the nickel-iron alloy net with the surface grease layer removed in a hydrochloric acid solution with the concentration of 4mol/L for ultrasonic treatment for 15min, standing for 20min, repeatedly washing with distilled water, removing the metal surface oxide layer, and drying to obtain the clean nickel-iron alloy net.
Comparative example 2:
this comparative example directly uses foam ferronickel as the electrode:
placing the foamed nickel-iron in an acetone solution, ultrasonically cleaning for 30min, repeatedly cleaning with ethanol, and removing the surface grease layer of the foamed nickel-iron; s12, placing the foam ferronickel with the surface grease layer removed in a hydrochloric acid solution with the concentration of 6mol/L for ultrasonic treatment for 5min, standing for 30min, repeatedly washing with distilled water, removing the metal surface oxidation layer, and drying to obtain clean foam ferronickel.
Comparative example 3:
this comparative example directly uses foam ferronickel as the electrode:
placing the foamed nickel-iron in an acetone solution, ultrasonically cleaning for 10min, repeatedly cleaning with ethanol, and removing the surface grease layer of the foamed nickel-iron; s12, placing the foam ferronickel with the surface grease layer removed in a hydrochloric acid solution with the concentration of 1mol/L for ultrasonic treatment for 25min, standing for 10min, repeatedly washing with distilled water, removing the metal surface oxidation layer, and drying to obtain clean foam ferronickel.
Comparative example 4:
this comparative example adopts the foam ferronickel as metal ferronickel base, only adopts induced corrosion to handle preparation electrode:
s10, placing the foamed nickel iron in an acetone solution for ultrasonic cleaning for 25min, and repeatedly cleaning with ethanol to remove the surface grease layer of the foamed nickel iron; and (3) placing the foamed nickel iron with the surface grease layer removed in a hydrochloric acid solution with the concentration of 3mol/L for ultrasonic treatment for 10min, standing for 25min, repeatedly washing with distilled water, removing the metal surface oxidation layer, and drying to obtain the clean foamed nickel iron.
S20, soaking the clean foam nickel iron in a mixed solution containing 10mol/L lithium chloride, 0.2mmol/L aluminum nitrate and 0.3mmol/L zinc sulfate for 25 hours at room temperature; washing the soaked foam ferronickel with distilled water and drying to obtain the foam ferronickel after the induced corrosion treatment.
Analysis of electrode catalytic performance:
and respectively carrying out oxygen evolution electrocatalysis performance tests on the electrodes obtained in examples 1-4 and comparative examples 1-4 by adopting a linear voltammetry scanning test method. The test uses a three-electrode system, with the electrodes obtained in the various examples and comparative examples as working electrodes, mercury/mercury oxide as reference electrode, platinum mesh as auxiliary electrode, electrolyte solution of potassium hydroxide of 1mol/L mass, scanning rate of 5 mv per second, and scanning range of 0 v to 2 v. The oxygen evolution electrocatalysis performance was tested on an electrochemical workstation (CHI760E, shanghai chenhua instruments ltd) and the test results corresponded to table 1.
TABLE 1 overpotential of oxygen evolution reaction at certain current density for different test electrodes
Figure BDA0002967312150000081
According to the data in table 1, it can be seen that, when different metal nickel-iron substrates are adopted to prepare the electrodes of the related examples, the oxygen evolution reaction performance of the obtained electrodes of the examples is obviously improved compared with that of comparative examples based on original metal substrates, particularly, when the electrodes are prepared by adopting foamed nickel-iron, the overpotential of the electrodes under the current density of 10 milliamperes per square centimeter is only 1.493 volts, the overpotential of the electrodes is reduced by 0.414 volts compared with that of the electrodes prepared by only carrying out induced corrosion treatment, and the overpotential of the electrodes is reduced by 0.193 volts. Meanwhile, the overpotential of the electrode prepared by adopting the foam ferronickel is only improved by 3 millivolts after the continuous oxygen evolution reaction for 20 hours.
The above description is only an exemplary embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent structures or equivalent processes that are transformed by the content of the present specification and the attached drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (10)

1. An electrode based on dual effects of induction and sacrifice, which is characterized by comprising a metal ferronickel substrate and ferronickel mixed hydroxide containing cation defects, wherein the cation defects of the ferronickel mixed hydroxide comprise Ni, and the ferronickel mixed hydroxide is arranged on the metal ferronickel substrate2+Defect, Fe3+At least one of the defects.
2. A preparation method of an electrode based on dual effects of induction and sacrifice is characterized by comprising the following steps:
s10, cleaning the surface of the metal nickel-iron substrate to obtain a cleaned metal nickel-iron substrate;
s20, performing induced corrosion treatment, namely soaking the cleaned metal nickel-iron substrate in a halogen salt solution at normal temperature and normal pressure for 1-36 h to perform induced corrosion treatment, forming a nickel-iron mixed hydroxide doped with specific induced cations on the surface of the metal nickel-iron substrate, and cleaning and drying to obtain the metal nickel-iron substrate subjected to induced corrosion;
s30, performing sacrificial activation treatment, namely soaking the metal nickel-iron substrate subjected to induced corrosion in a strong alkaline solution at normal temperature and normal pressure for 4-48 h to perform sacrificial activation treatment, forming nickel-iron mixed hydroxide containing cation defects on the surface of the metal nickel-iron substrate, and cleaning and drying to obtain the electrode based on the dual effects of induction and sacrificial.
3. The method of claim 2, wherein the specific inducing cation is Al3+、Zn2+At least one of (1).
4. The method for preparing an electrode based on dual inducing and sacrificing effects according to claim 2, wherein said step S10 comprises:
s11, placing the metal nickel-iron substrate in an acetone solution for ultrasonic cleaning for 10-30 min, and then repeatedly cleaning with ethanol to remove a grease layer on the surface of the metal nickel-iron substrate;
s12, placing the metal nickel-iron substrate with the surface grease layer removed in a hydrochloric acid solution with the concentration of 1-6 mol/L for 5-25 min by ultrasonic treatment, standing in the hydrochloric acid solution for 10-30 min, taking out, and repeatedly cleaning with distilled water to remove the oxide layer on the surface of the metal nickel-iron substrate;
s13, drying the metal nickel-iron substrate with the oxide layer removed to obtain the cleaned metal nickel-iron substrate.
5. The method of claim 2, wherein the halide salt solution is at least one of potassium chloride solution, magnesium chloride solution, lithium chloride solution, sodium fluoride solution, potassium bromide solution, or sodium bromide solution.
6. The method of claim 2, wherein the halogen ion concentration in the halide solution is 0.1-10 mol/L, and the specific inducing cation concentration is 0.001-0.5 mmol/L.
7. The method of claim 2, wherein the alkali solution is at least one of sodium hydroxide solution or potassium hydroxide solution, and OH is contained in the alkali solution-The concentration is 3-12 mol/L.
8. The method of claim 2, wherein the specifically inducing cation doped mixed nickel-iron hydroxide is one of nickel-iron-aluminum ternary mixed hydroxide, nickel-iron-zinc ternary mixed hydroxide or nickel-iron-aluminum-zinc quaternary mixed hydroxide.
9. The method for preparing an electrode based on the dual effect of induction and sacrifice according to claim 8, characterized in that, in the nickel-iron-aluminum ternary mixed hydroxide, aluminum is doped in iron sites in the nickel-iron mixed hydroxide; in the nickel-iron-zinc ternary mixed hydroxide, zinc is doped in nickel sites in the nickel-iron mixed hydroxide; in the nickel-iron-aluminum-zinc quaternary mixed hydroxide, aluminum is doped at iron sites in the nickel-iron mixed hydroxide, and zinc is doped at nickel sites in the nickel-iron mixed hydroxide.
10. The method of claim 2, wherein the cation defect of the nickel-iron mixed hydroxide containing cation defect is at least one of Ni2+ defect or Fe3+ defect.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114134531A (en) * 2021-11-22 2022-03-04 清华大学 General method for preparing self-supporting layered metal hydroxide
CN114959791A (en) * 2022-06-15 2022-08-30 河北工业大学 Preparation method of Mg-doped NiFe-based (oxy) hydroxide and oxygen evolution electrocatalysis application thereof
CN114990607A (en) * 2022-06-20 2022-09-02 南通大学 Simple and efficient preparation method based on surface modification electrode

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114134531A (en) * 2021-11-22 2022-03-04 清华大学 General method for preparing self-supporting layered metal hydroxide
CN114959791A (en) * 2022-06-15 2022-08-30 河北工业大学 Preparation method of Mg-doped NiFe-based (oxy) hydroxide and oxygen evolution electrocatalysis application thereof
CN114990607A (en) * 2022-06-20 2022-09-02 南通大学 Simple and efficient preparation method based on surface modification electrode

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