CN113930782A - Preparation method and application of self-supporting electrode - Google Patents
Preparation method and application of self-supporting electrode Download PDFInfo
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- CN113930782A CN113930782A CN202111120407.4A CN202111120407A CN113930782A CN 113930782 A CN113930782 A CN 113930782A CN 202111120407 A CN202111120407 A CN 202111120407A CN 113930782 A CN113930782 A CN 113930782A
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- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
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Abstract
The application discloses a preparation method and application of a self-supporting electrode, wherein a rodlike transition metal basic carbonate M (OH) grows on the surface of a support material, namely SM in situ2CO3/SM, ligand organic small molecules that reuse conductive metal organic framework MOFs, including but not limited to HHTP, HOB, HAB vs. Supported M (OH)2CO3Self-supporting electrode H-M (OH) with modified rod-shaped material surface2CO3Method for preparing/SM by in-situ modification of transition metal hydroxycarbonate with conductive MOF ligands to increase its charge transport capability, improving M (OH)2CO3The conductivity and the catalytic activity in the electrocatalysis process improve the comprehensive performance of the corresponding new energy device.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a preparation method and application of a self-supporting electrode.
Background
The development of high performance self-supporting electrodes is critical to promote the performance of energy storage and conversion devices. Hydrogen energy is characterized by environmental friendliness and high energy density and is recognized as an ideal substitute for fossil fuels. The water electrolysis is a green and efficient hydrogen production mode, and a good platform is provided for utilizing intermittent renewable energy sources (such as wind energy and solar energy). In an actual water electrolysis process, in order to improve water splitting efficiency, noble metals Pt-based and Ir/Ru-based electrocatalysts are generally used to lower the activation energy of two core half reactions related to water splitting, i.e., Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER). The large-scale use of these noble metal-based catalysts is severely hampered by their limited abundance and high cost. Therefore, in the past few decades, the development of materials to replace noble metal-based catalysts for the electrolysis of water has attracted extensive attention and has been developing.
Conventional powdered catalyst materials such as MOFs and MOFs-derived catalysts typically involve the use of polymers such as Nafion as a binder to bind the active material to the electrode. However, the adhesive not only easily blocks active sites, but also increases interfacial resistance and residence volume, reducing the utilization rate and mass transfer capability of the active sites. The fabrication of self-supporting electrodes using in situ growth methods to grow active species directly on the surface of a support is an effective strategy to address these problems.
In recent years, the active sites of the transition metal basic carbonate are abundant and easy to graft and grow on a carrier, so that the self-supporting electrode is widely concerned in designing and researching the self-supporting electrode. However, the pure transition metal alkali carbonate has poor conductivity, large internal resistance, large electrocatalytic overpotential and low water electrolysis efficiency. Therefore, it is imperative to design non-noble metal based self-supporting electrode materials with high conductivity and more active sites to electrolyze water.
The invention aims to develop a novel transition metal basic carbonate self-supporting electrode modified by organic small molecules based on conductive MOF ligands, which is applied to new energy devices, including but not limited to energy storage batteries, fuel cells, electrolyzed water and the like. The following is an example of the use of the heterostructure self-supporting electrode in electrolysis of water.
The invention content is as follows:
the technical problem to be solved is as follows: the application mainly provides a preparation method and application of a transition metal basic carbonate self-supporting electrode modified by organic small molecules based on a conductive MOF ligand, which are used for completely replacing a noble metal catalyst, greatly improving the catalytic activity stability of a non-noble metal nano catalyst, improving the comprehensive performance of a new energy device, solving the problems of low activity, poor stability, high cost and the like of catalyst components in the new energy device, and greatly promoting the large-scale application of the non-noble metal nano catalyst in the field of new energy.
The purpose of the invention is as follows:
the invention provides a preparation method of a self-supporting electrode, which uses organic small molecule conductive MOF ligand modified M (OH)2CO3The internal resistance of the catalyst is reduced, and the catalytic activity is improved. The process involved is first the in situ growth of transition metal hydroxycarbonates on a substrate using a hydrothermal process, followed by the use of a pair of conducting MOF ligands M (OH)2CO3The modified electrode can be applied to different types of new energy devices, including but not limited to energy storage batteries, fuel cells, water electrolysis and the like. The method provides a new idea and a new method for the design and the practical application of the high-efficiency self-supporting electrode, and simultaneously provides a reliable theoretical basis for the application of the material in the field of new energy.
The technical scheme is as follows:
a method for preparing self-supporting electrode on support material carrier (support mat)In situ growth of rod-like transition metal basic carbonates M (OH) on material, SM2CO3/SM, further use of conductive MOF ligand organic small molecule pairs M (OH)2CO3Self-supporting electrode H-M (OH) with modified rod-shaped material surface2CO3(ii)/SM; the conductive MOF ligand organic small molecule comprises but is not limited to 2,3,6,7,10, 11-hexahydroxytriphenylHHTP (2,3,6,7,10, 11-hexahydroxytriphenylene), hexahydroxybenzene HOB (1,2,3,4,5, 6-Benzenehexol), and hexaamino benzene HAB (1,2,3,4,5, 6-Benzenehexamine).
As a preferred technical scheme of the invention: the preparation method of the self-supporting electrode specifically comprises the following steps:
the first step is as follows: adding 0.1-5000 cm of the mixture into a reaction kettle2The carrier material is immersed in the metal precursor solution, the reaction kettle is sealed, the hydrothermal reaction is carried out for 8-24 hours at the temperature of 60-160 ℃, the material is taken out after the temperature is naturally reduced to room temperature, the deionized water is used for washing, and the vacuum drying is carried out for 6-12 hours at the temperature of 40-60 ℃, so as to obtain the basic carbonate matrix electrode material;
the second step is that: adding 0.1-5000 ml of deionized water and a conductive MOF ligand into a reaction kettle, wherein the mass of the conductive MOF ligand is 0.01-1000 mg, adding 0.1-50 ml of NMP, carrying out ultrasonic treatment until the mixture is uniform to obtain a ligand liquid, immersing an electrode obtained in the first step of reaction into the ligand liquid, sealing the reaction kettle at 60-160 ℃, reacting for 12-36 hours, naturally cooling to room temperature, washing with deionized water, drying at 40-60 ℃ in vacuum for 6-12 hours, and drying to obtain the self-supporting electrode material.
As a preferred technical scheme of the invention: the carrier material in the first step is carbon cloth, carbon fiber paper, foam copper or foam nickel.
As a preferred technical scheme of the invention: in the first step, the metal precursor solution is a mixed solution of metal salt and urea, the molar ratio of the urea to metal ions is 2: 1-20: 1, and the concentration of the metal salt is 0.01-2 mol/L.
As a preferred technical scheme of the invention: the metal salt in the precursor metal solution is nitrate, sulfate, hydrochloride or acetate of soluble metal, and the metal is one or more of cobalt, iron, nickel and copper.
As a preferred technical scheme of the invention: and in the second step, adding one or more of 2,3,6,7,10, 11-hexahydroxytriphenyl HHTP (2,3,6,7,10, 11-hexahydroxytriphenylene), hexahydroxybenzene HOB (1,2,3,4,5, 6-Benzenehexol) and HAB (1,2,3,4,5, 6-Benzenehexamine) as conductive MOF ligand organic micromolecules.
As a preferred technical scheme of the invention: in the second step, the ultrasonic frequency is 10-1000 Hz, and the ultrasonic time is 5-60 min.
The application also discloses application of the self-supporting electrode prepared by the preparation method as an electrode in an energy storage battery and a fuel battery.
As a preferred technical scheme of the invention: the self-supporting electrode is used as an active material in an energy storage battery.
As a preferred technical scheme of the invention: the self-supporting electrode is applied to the hydrogen evolution electrode and the oxygen evolution electrode of the electrolyzed water in the electrolyzed water.
Has the advantages that: compared with the prior art, the preparation method and the application of the self-supporting electrode adopt the technical scheme, and have the following technical effects:
1. after the organic micromolecules are modified, the internal resistance of the transition metal basic carbonate is reduced, the catalytic active sites are activated, and the electrocatalytic performance is improved. Basic cobalt carbonate was grown in situ on copper foam and HHTP modified at 10mA/cm2The hydrogen evolution overpotential under the current density is reduced from 265mV to 65mV, and the method has expansibility and potential application prospect.
2. The type and size of the self-supporting carrier can be flexibly selected and designed.
3. Can select various metal combinations to grow in situ and flexibly regulate and control the performance of the material.
4. The carbonization process is not used, so that the energy is saved, and the reduction of the reaction activity caused by the structural collapse and the metal aggregation in the carbonization process is avoided.
5. The invention provides a new method and a new way for improving the performance of the transition metal basic carbonate, and simultaneously provides reliable technical support for the application of the non-noble metal-based self-supporting electrode in the field of new energy.
Drawings
FIG. 1 shows HHTP-Co (OH) of the present application2CO3Scanning electron micrograph of/CF.
FIG. 2 shows HHTP-Co (OH) of the present application2CO3Transmission electron micrograph of/CF.
FIG. 3 shows example 1 of the present application, Co (OH)2CO3/CF，HHTP-Co(OH)2CO3HER performance test graphs for/CF, Pt-C/CF and copper foam substrates.
FIG. 4 shows example 2 of the present application, Co (OH)2CO3/CF，HHTP-Co(OH)2CO3HER performance test graphs for/CF, Pt-C/CF and copper foam substrates.
FIG. 5 shows the results of example 1 of the present application, Co (OH)2CO3/CF，HOB-Co(OH)2CO3OER performance test graphs of/CF, Pt-C/CF and copper foam substrates.
FIG. 6 is a schematic view of the electrode material of the present application applied to electrolyzed water.
Detailed Description
The present invention is further described with reference to specific examples to enable those skilled in the art to better understand the present invention and to practice the same, but the examples are not intended to limit the present invention.
Example 1:
HHTP-modified basic cobalt carbonate-loaded foamy copper self-supporting electrode (HHTP-Co (OH)2CO3The preparation method of/CF) comprises the following steps:
first step, Co (OH)2CO3The synthesis method of/CF comprises the following steps: adding 1cm multiplied by 2cm of foamy copper and 4mL of solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction for 12 hours at 95 ℃, taking out a carrier material after the temperature naturally drops to room temperature, washing the carrier material by deionized water, and carrying out reaction at 50 ℃ for 12 hoursAnd drying for 8-16 h.
Second, HHTP-Co (OH)2CO3The synthesis method of/CF comprises the following steps: adding 3-5 ml of deionized water and 7mg of HHTP into a reaction kettle, adding 0.18ml of NMP, carrying out ultrasonic treatment for 20-30 min under the condition of 100Hz until the mixture is uniformly mixed to form a dark color solution, immersing the carrier obtained after the first-step reaction into the dark color solution, carrying out reaction at 85 ℃ in the reaction kettle for 24 hours, naturally cooling to room temperature, washing with deionized water, and drying at 50 ℃ in vacuum for 8 hours.
Electron microscopy using electron microscopy on HHTP-Co (OH)2CO3the/CF, characterization results are shown in FIG. 1. The electron microscope image shows that the material is a rod-shaped structure of about 40 nanometers.
Transmission Electron microscopy using a Transmission Electron microscope pair HHTP-Co (OH)2CO3the/CF is characterized, the characterization result is shown in figure 2, and the transmission electron microscope image shows the rod-shaped structure of the material.
Example 2
HOB modified basic cobalt carbonate loaded foam copper self-supporting electrode (HOB-Co (OH)2CO3The preparation method of/CF) comprises the following steps:
first step, Co (OH)2CO3The synthesis method of/CF comprises the following steps: adding 2cm multiplied by 2cm of foamy copper and 4mL of solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction for 6 hours at 120 ℃, taking out the carrier material after the temperature naturally drops to room temperature, washing the carrier material by using deionized water, and drying the carrier material for 8 hours at 50 ℃ in vacuum.
Second, HOB-Co (OH)2CO3The synthesis method of/CF comprises the following steps: adding 5mg HOB, 4mL deionized water and 0.165mL NMP into the reaction kettle, dissolving by ultrasonic for 10min, adding a piece of Co (OH) with the size of 1cm multiplied by 2cm2CO3and/CF, sealing the reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 12 hours, naturally cooling to room temperature, taking out the carrier, washing with deionized water, and drying at 50 ℃ in vacuum for 8 hours.
Example 3
HHTP modified basic nickel cobalt carbonate supported carbon cloth self-supporting electrode (HHTP-NiCo (OH))2CO3The preparation method of/CC) comprises the following steps:
first, NiCo (OH)2CO3The synthesis method of/CC comprises the following steps: adding 0.5cm multiplied by 0.5cm hydrophilic carbon cloth and 1mL of solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction for 12 hours at 95 ℃, taking out the carrier material after the temperature is naturally reduced to room temperature, washing the carrier material by using deionized water, and drying the carrier material for 8 hours at 50 ℃ in vacuum.
Second, HHTP-NiCo (OH)2CO3The synthesis method of/CC comprises the following steps: the reaction vessel was charged with 1mg of HHTP, 4mL of deionized water and 0.165mL of NMP, sonicated for 30min to dissolve, and a 0.5cm by 0.5cm size piece of NiCo (OH) was added2CO3and/CC, sealing the reaction kettle, carrying out hydrothermal reaction at 85 ℃ for 24 hours, naturally cooling to room temperature, taking out the carrier, washing with deionized water, and drying at 50 ℃ for 8 hours in vacuum.
Example 4
HHTP modified basic nickel carbonate supported foamy copper self-supporting electrode (HHTP-Ni (OH))2CO3The preparation method of/CF) comprises the following steps:
first, Ni (OH)2CO3The synthesis method of/CF comprises the following steps: adding 4cm multiplied by 4cm of foamy copper and 20 mL of solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction at 95 ℃ for 12 hours, wherein the solution is a mixed solution of 1.2M of urea and 0.6M of nickel nitrate, taking out the carrier material after the temperature naturally drops to room temperature, washing the carrier material with deionized water, and drying the carrier material at 50 ℃ in vacuum for 12 hours.
Second, HHTP-Ni (OH)2CO3The synthesis method of/CF comprises the following steps: the reaction kettle is added with 20mg HHTP, 4mL deionized water and 1mL NMP, dissolved by ultrasonic for 30min, and added with a piece of Ni (OH) with the size of 4cm multiplied by 4cm2CO3and/CF, sealing the reaction kettle, carrying out hydrothermal reaction at 85 ℃ for 24 hours, naturally cooling to room temperature, taking out the carrier, washing with deionized water, and drying at 50 ℃ for 8 hours in vacuum.
Example 5
HHTP modified basic cobalt carbonate supported foam nickel self-supporting electrode (HHTP-Co (OH)2CO3The preparation method of/NF) comprises the following steps:
first step, Co (OH)2CO3The synthesis method of/NF comprises the following steps: adding foamed nickel with the size of 0.2cm multiplied by 0.5cm and 0.1mL of solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction for 12 hours at 95 ℃, taking out the carrier material after the temperature is naturally reduced to room temperature, washing the carrier material by using deionized water, and drying the carrier material at 50 ℃ in vacuum for 8 hours.
Second, HHTP-Co (OH)2CO3The synthesis method of/NF comprises the following steps: adding HHTP 0.1mg, deionized water 1mL and NMP 0.0165mL into the reaction kettle, dissolving with ultrasound for 30min, adding a piece of Co (OH) with size of 0.2cm × 0.5cm2CO3and/NF, sealing the reaction kettle, carrying out hydrothermal reaction at 85 ℃ for 24 hours, naturally cooling to room temperature, taking out the carrier, washing with deionized water, and drying at 50 ℃ in vacuum for 8 hours.
Example 6
HHTP modified basic cobalt carbonate supported foam nickel self-supporting electrode (HHTP-Co (OH)2CO3The preparation method of/NF) comprises the following steps:
first step, Co (OH)2CO3The synthesis method of/NF comprises the following steps: adding 4cm multiplied by 10cm of foamed nickel and 50mL of solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction for 12 hours at 160 ℃, taking out the carrier material after the temperature is naturally reduced to room temperature, washing the carrier material by using deionized water, and drying the carrier material at 50 ℃ in vacuum for 8 hours.
Second, HHTP-Co (OH)2CO3The synthesis method of/NF comprises the following steps: the reaction kettle was charged with 1000mg HHTP, 200mL deionized water and 8.9 mL NMP, sonicated for 60min to dissolve, and a 4cm by 10cm piece of Co (OH) was added2CO3and/NF, sealing the reaction kettle, carrying out hydrothermal reaction at 85 ℃ for 24 hours, naturally cooling to room temperature, taking out the carrier, washing with deionized water, and drying at 50 ℃ in vacuum for 8 hours.
Example 7
HHTP modified basic cobalt carbonate supported foam nickel self-supporting electrode (HHTP-Co (OH)2CO3The preparation method of/NF) comprises the following steps:
first step, Co (OH)2CO3The synthesis method of/NF comprises the following steps: adding 1cm multiplied by 2cm of foamed nickel and 4mL of solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction at 95 ℃ for 12 hours, wherein the solution is a mixed solution of 1.2M urea and 0.3M cobalt sulfate, taking out the carrier material after the temperature naturally drops to room temperature, washing the carrier material with deionized water, and drying the carrier material at 50 ℃ in vacuum for 8 hours.
Second, HHTP-Co (OH)2CO3The synthesis method of/NF comprises the following steps: the reaction vessel was charged with 7mg of HHTP, 4mL of deionized water and 0.165mL of NMP, sonicated for 30min to dissolve, and a 1cm by 2cm piece of Co (OH) was added2CO3and/NF, sealing the reaction kettle, carrying out hydrothermal reaction at 85 ℃ for 24 hours, naturally cooling to room temperature, taking out the carrier, washing with deionized water, and drying at 50 ℃ in vacuum for 8 hours.
Example 8
A standard Pt-C control sample was prepared by trimming copper foam to a size of 0.5cm by 2cm, and adding a mixture of 50. mu.L ethanol, 0.25 mg of 20% Pt-C and 1.25. mu.L of nafion (a binder) dropwise to a 0.5cm by 0.5cm area of one end of the copper foam. And drying at 50 ℃ for 6 h.
Example 9
RuO2A standard control sample was prepared by trimming unmodified copper foam to 0.5cm by 2cm, and adding a mixture of 50. mu.L ethanol, 0.25 mg 20% ruthenium dioxide, and 1.25. mu.L of nafion (a binder) dropwise to a 0.5cm by 0.5cm area of the end of the copper foam. Drying at 50 ℃ for 6 h.
Example 10
A Hydrogen Evolution (HER) catalytic performance test is carried out by using a three-electrode system and an electrochemical workstation to unmodified foamed copper, trimming the electrode in the first step in example 1 and the electrode in the second step in example 1 into 0.5cm multiplied by 2cm, connecting the electrode in the first step in example 1, the electrode in the second step in example 1 and a standard sample test electrode in example 5 to the electrochemical workstation by using a platinum sheet electrode clamp, using 0.1M KOH solution as electrolyte, introducing 30min of nitrogen into the electrolyte before the test to remove oxygen in the electrolyte, scanning 20 circles of CV curve in the range of 0.8-0V to remove surface impurities of the electrode material, scanning the LSV curve of the material to test HER performance, and testing the effective area of the testIs 0.5cm × 0.5 cm. Test results the results of the HER test at 10mA/cm for the second step electrode of example 1# 1 in FIG. 3 are shown in FIG. 32The potential of the electrode under the current density condition is 65mV, and the HER catalytic performance of the electrode is superior to the performance of the first step electrode (3#), the first step electrode (2#) and the unmodified foam copper (4#) in the example 1.
Example 11
A Hydrogen Evolution (HER) catalytic performance test is carried out by using a three-electrode system and an electrochemical workstation to unmodified foamed copper, trimming an electrode in the first step in example 2 and an electrode in the second step in example 2 into 0.5cm multiplied by 2cm, connecting the electrode in the first step in example 2, the electrode in the second step in example 2 and a standard sample test electrode in example 5 to the electrochemical workstation by using a platinum sheet electrode clamp, using 0.1M KOH solution as electrolyte, introducing nitrogen for 30min to remove oxygen in the electrolyte before the test, scanning a CV curve for 20 circles within the range of 0.8-0 to remove surface impurities of an electrode material, and scanning an LSV curve of the material to test HER performance, wherein the effective area of the test is 0.5cm multiplied by 0.5 cm. Test results the results of the HER test at 10mA/cm for the second step electrode of example 2# 1 in FIG. 3 are shown in FIG. 42The potential of the electrode under the current density condition is 65mV, and the HER catalytic performance of the electrode is superior to the performance of the first step electrode (3#), the first step electrode (2#) and the unmodified foam copper (4#) in the example 1.
Example 12
Oxygen Evolution (OER) catalytic performance test, an electrochemical test was performed on unmodified copper foam using a three-electrode system and an electrochemical workstation, the self-supporting electrode obtained in the first step of example 1, the second step of example 1, was trimmed to 0.5cm x 2cm, the electrode obtained in the first step of example 1, the second step of example 1, and the electrode of example 6 were attached to the electrochemical workstation using a platinum sheet electrode holder, the electrolyte was KOH at 0.1M, and the electrolyte was saturated with oxygen for 30min before the test. Scanning a CV curve of 20 circles within the range of 0.8-0 to remove surface impurities of the electrode material, and testing the OER performance of the material, wherein the effective area is 0.5cm multiplied by 0.5 cm. The test results are shown in FIG. 5, and # 1 in FIG. 5 is the OER test result of the second-step electrode of example 1 at 10mA/cm2Current density condition ofThe lower potential is 1575mV, and the OER catalytic performance is better than that of the electrode (3#), the unmodified foam copper (4#) and the electrode (2#) in the first step of the example 1.
Example 13
FIG. 6 is a schematic view showing the application of the self-supporting electrode of the present invention to electrolyzed water, which can be directly applied to electrolyzed water as a hydrogen evolution electrode and an oxygen evolution electrode.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a self-supporting electrode is characterized by comprising the following steps: in-situ growth of transition metal basic carbonates M (OH) in rod form on support material Supports (SM)2CO3/SM, further use of conductive MOF ligand organic small molecule pairs M (OH)2CO3Self-supporting electrode H-M (OH) with modified rod-shaped material surface2CO3(ii)/SM; the conductive MOF ligand organic small molecule comprises but is not limited to 2,3,6,7,10, 11-hexahydroxytriphenylHHTP (2,3,6,7,10, 11-hexahydroxytriphenylene), hexahydroxybenzene HOB (1,2,3,4,5, 6-Benzenehexol), and hexaamino benzene HAB (1,2,3,4,5, 6-Benzenehexamine).
2. The method for preparing a self-supporting electrode according to claim 1, comprising the following steps:
the first step is as follows: adding 0.1-5000 cm of the mixture into a reaction kettle2The carrier material is immersed in the metal precursor solution, the reaction kettle is sealed, the hydrothermal reaction is carried out for 8-24 hours at the temperature of 60-160 ℃, the material is taken out after the temperature is naturally reduced to room temperature, the deionized water is used for washing, and the vacuum drying is carried out for 6-12 hours at the temperature of 40-60 ℃, so as to obtain the basic carbonate matrix electrode material;
the second step is that: adding 0.1-5000 ml of deionized water and a conductive MOF ligand into a reaction kettle, wherein the mass of the conductive MOF ligand is 0.01-1000 mg, adding 0.1-50 ml of NMP, carrying out ultrasonic treatment until the mixture is uniform to obtain a ligand liquid, immersing an electrode obtained in the first step of reaction into the ligand liquid, sealing the reaction kettle at 60-160 ℃, reacting for 12-36 hours, naturally cooling to room temperature, washing with deionized water, drying at 40-60 ℃ in vacuum for 6-12 hours, and drying to obtain the self-supporting electrode material.
3. The method of preparing a self-supporting electrode according to claim 2, wherein: the carrier material in the first step is carbon cloth, carbon fiber paper, foam copper or foam nickel.
4. The method of preparing a self-supporting electrode according to claim 2, wherein: in the first step, the metal precursor solution is a mixed solution of metal salt and urea, the molar ratio of the urea to metal ions is 2: 1-20: 1, and the concentration of the metal salt is 0.01-2 mol/L.
5. The method of preparing a self-supporting electrode according to claim 2, wherein: the metal salt in the precursor metal solution is nitrate, sulfate, hydrochloride or acetate of soluble metal, and the metal is one or more of cobalt, iron, nickel and copper.
6. The method of preparing a self-supporting electrode according to claim 2, wherein: and in the second step, adding one or more of 2,3,6,7,10, 11-hexahydroxytriphenyl HHTP (2,3,6,7,10, 11-hexahydroxytriphenylene), hexahydroxybenzene HOB (1,2,3,4,5, 6-Benzenehexol) and HAB (1,2,3,4,5, 6-Benzenehexamine) as conductive MOF ligand organic micromolecules.
7. The method of preparing a self-supporting electrode according to claim 2, wherein: in the second step, the ultrasonic frequency is 10-1000 Hz, and the ultrasonic time is 5-60 min.
8. The self-supporting electrode prepared by the preparation method according to any one of claims 1 to 7 is applied to energy storage batteries and fuel cells as an electrode.
9. Use of a self-supporting electrode according to claim 8, wherein: the self-supporting electrode is used as an active material in an energy storage battery.
10. The self-supporting electrode prepared by the preparation method according to any one of claims 1 to 7 is applied to electrolytic water as a hydrogen evolution electrode and an oxygen evolution electrode of the electrolytic water.
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