CN113930782B - Preparation method and application of self-supporting electrode - Google Patents
Preparation method and application of self-supporting electrode Download PDFInfo
- Publication number
- CN113930782B CN113930782B CN202111120407.4A CN202111120407A CN113930782B CN 113930782 B CN113930782 B CN 113930782B CN 202111120407 A CN202111120407 A CN 202111120407A CN 113930782 B CN113930782 B CN 113930782B
- Authority
- CN
- China
- Prior art keywords
- self
- electrode
- supporting electrode
- preparation
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Inert Electrodes (AREA)
Abstract
The application discloses a preparation method and application of a self-supporting electrode, which is characterized in that a rod-shaped transition metal basic carbonate M (OH) grows on the surface of a supporting material SM in situ 2 CO 3 SM, ligand small organic molecules reusing conductive metal organic frameworks MOFs, including but not limited to HHTP, HOB, HAB pair loaded M (OH) 2 CO 3 Self-supporting electrode H-M (OH) for modifying surface of rod-shaped material 2 CO 3 Preparation method of/SM, in-situ modification of transition metal basic carbonate by conductive MOF ligand to improve charge transmission capacity and M (OH) 2 CO 3 The conductivity and the catalytic activity in the electrocatalytic process improve the comprehensiveness of corresponding new energy devicesCan be used.
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 facilitate the performance of energy storage and conversion devices. Hydrogen energy has the characteristics of being environmentally friendly and high energy density, and is recognized as an ideal substitute for fossil fuels. The electrolyzed water is a green and efficient hydrogen production mode, and provides a good platform for utilizing intermittent renewable energy sources (such as wind energy and solar energy). In practical electrolysis of water, noble metal Pt-based and Ir/Ru-based electrocatalysts are typically used to reduce the activation energy of the two core half reactions associated with water splitting, namely Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER), in order to increase the water splitting efficiency. But 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, development of materials for electrolysis of water instead of noble metal-based catalysts has attracted extensive attention and has been developed to some extent.
Conventional powdered catalyst materials such as MOFs and MOFs-derived catalysts typically involve the use of Nafion or like polymers as binders to bind the active material to the electrode. However, the binder not only tends to clog the active sites, but also increases interfacial resistance and residence volume, reducing active site utilization and mass transfer capacity. The use of in situ growth methods to grow active species directly onto the surface of a support to create a self-supporting electrode is an effective strategy to address these problems.
In recent years, since the active sites of the basic carbonate of the transition metal are abundant and are easy to graft and grow on a carrier, the basic carbonate of the transition metal is widely paid attention to the design and research of self-supporting electrodes. However, simple transition metal basic carbonate has poor conductivity, large internal resistance, large electrocatalytic overpotential and low water electrolysis efficiency. Therefore, it is urgent to design a non-noble metal-based self-supporting electrode material having high conductivity and more active sites to electrolyze water.
The invention aims to develop a novel transition metal basic carbonate self-supporting electrode based on conductive MOF ligand organic small molecule modification, which is applied to new energy devices including but not limited to energy storage batteries, fuel cells, electrolyzed water and the like. The application of the heterostructure self-supporting electrode in the electrolysis of water will be described below as an example.
The invention comprises the following steps:
the technical problems to be solved are as follows: the application mainly provides a preparation method and application of a transition metal basic carbonate self-supporting electrode based on conductive MOF ligand organic micromolecule modification, which are used for completely replacing a noble metal catalyst, greatly improving the stability of catalytic activity 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 new energy field.
The invention aims to:
the invention provides a preparation method of a self-supporting electrode, which uses organic micromolecule conductive MOF ligand to modify M (OH) 2 CO 3 Reduce internal resistance of catalyst and raise catalytic activity. The process involved is to first grow in situ transition metal hydroxycarbonates on a substrate using hydrothermal methods, followed by the use of a conductive MOF ligand pair M (OH) 2 CO 3 The electrode can be applied to different types of new energy devices by modification, including but not limited to energy storage batteries, fuel cells, electrolyzed water and the like. The method provides a new thought and a new method for the design and 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 comprises in-situ growing rod-shaped transition metal basic carbonate M (OH) on support material carrier (SM) 2 CO 3 SM, reuse of conductive MOF ligand organic small molecule pair M (OH) 2 CO 3 Self-supporting electrode H-M (OH) for modifying surface of rod-shaped material 2 CO 3 SM; the conductive MOF ligand organic small molecules include, but are not limited to, 2,3,6,7,10, 11-hexahydroxytriphenylHHTP (2, 3,6,7,10, 11-hexahydroxytriphenylene), hexahydroxyphenylHOB (1, 2,3,4,5, 6-Benzenehexol), and hexaaminobenzene HAB (1, 2,3,4,5, 6-Benzenehexmine).
As a preferred technical scheme of the invention: the preparation method of the self-supporting electrode specifically comprises the following steps:
the first step: 0.1-5000 cm is added into a reaction kettle 2 Immersing the carrier material in 0.1-5000 ml of metal precursor solution, sealing the reaction kettle, carrying out hydrothermal reaction at 60-160 ℃ for 8-24 hours, naturally cooling to room temperature, taking out the material, flushing with deionized water, and carrying out vacuum drying at 40-60 ℃ for 6-12 hours to obtain the basic carbonate matrix electrode material;
and a second step of: adding 0.1-5000 ml of deionized water and conductive MOF ligand with the mass of 0.01-1000 mg into a reaction kettle, adding 0.1-50 ml of NMP, carrying out ultrasonic treatment until the mixture is uniform to obtain ligand liquid, immersing an electrode obtained in the first step of reaction into the ligand liquid, sealing the reaction kettle, reacting for 12-36 hours at 60-160 ℃, naturally cooling to room temperature, washing with deionized water, drying at 40-60 ℃ in vacuum for 6-12 hours, and obtaining the self-supporting electrode material after drying.
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: the metal precursor solution in the first step is a mixed solution of metal salt and urea, the molar ratio of the urea to the 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 monobasic or polybasic mixture of cobalt, iron, nickel and copper.
As a preferred technical scheme of the invention: and in the second step, one or more of 2,3,6,7,10, 11-hexahydroxytriphenylHHTP (2, 3,6,7,10, 11-hexahydroxytriphenylene), hexahydroxyphenylHOB (1, 2,3,4,5, 6-Benzenehexol) and HAB (1, 2,3,4,5, 6-Benzenehexmine) are added.
As a preferred technical scheme of the invention: the frequency of the ultrasonic waves in the second step 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 in energy storage batteries and fuel cells as an electrode.
As a preferred technical scheme of the invention: the self-supporting electrode is used as an active material in an energy storage cell.
The application also discloses the application of the self-supporting electrode prepared by the preparation method in the electrolytic water as a hydrogen evolution electrode and an oxygen evolution electrode of the electrolytic water.
The beneficial effects are that: compared with the prior art, the preparation method and application of the self-supporting electrode have the following technical effects:
1. the internal resistance of the transition metal basic carbonate is reduced after the modification of the organic micromolecules, the catalytic active site is activated, and the electrocatalytic performance is improved. In situ growth of basic cobalt carbonate on copper foam and use of HHTP modified basic cobalt carbonate at 10mA/cm 2 The 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 a plurality of 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 energy is saved, structural collapse and metal aggregation in the carbonization process are avoided, and the reactivity is reduced.
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 application 2 CO 3 Scanning Electron Microscope (SEM) of/CF.
FIG. 2 shows HHTP-Co (OH) of the present application 2 CO 3 Transmission electron microscopy of/CF.
FIG. 3 is a graph of Co (OH) of example 1 of the present application 2 CO 3 /CF，HHTP-Co(OH) 2 CO 3 Graph of HER performance test of/CF, pt-C/CF versus copper foam substrate.
FIG. 4 is a graph of example 2Co (OH) of the present application 2 CO 3 /CF，HHTP-Co(OH) 2 CO 3 Graph of HER performance test of/CF, pt-C/CF versus copper foam substrate.
FIG. 5 is a graph of Co (OH) of example 1 of the present application 2 CO 3 /CF，HOB-Co(OH) 2 CO 3 OER performance test graph of/CF, pt-C/CF versus foam copper substrate.
Fig. 6 is a schematic view of the application of the electrode material of the present application to electrolyzed water.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
Example 1:
HHTP modified basic cobalt carbonate supported foam copper self-supporting electrode (HHTP-Co (OH) 2 CO 3 The preparation method of the (CF) comprises the following steps:
first step, co (OH) 2 CO 3 The synthesis method of/CF: adding 1cm multiplied by 2 cm-sized foamy copper and 4mL solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction for 12 hours at 95 ℃ with 0.6M mixed solution of urea and 0.3M cobalt nitrate, and standingNaturally cooling to room temperature, taking out the carrier material, washing with deionized water, and drying at 50 ℃ in vacuum for 8-16 hours.
Second step, HHTP-Co (OH) 2 CO 3 The synthesis method of/CF: 3-5 ml of deionized water and 7mg of HHTP are added into a reaction kettle, 0.18ml of NMP is added, ultrasound is carried out for 20-30 min under the condition of 100Hz until the mixture is uniformly mixed to form a dark solution, the carrier after the first step of reaction is immersed into the dark solution, the reaction kettle is sealed for 24 hours at 85 ℃, the temperature is naturally reduced to the room temperature, the reaction kettle is washed clean by the deionized water, and the reaction kettle is dried under the vacuum condition at 50 ℃ for 8 hours.
Electron microscopy test on HHTP-Co (OH) using electron microscopy 2 CO 3 The characterization result of the CF is shown in FIG. 1. The electron microscope image shows that the material is in a rod-shaped structure of about 40 nanometers.
Transmission electron microscopy test using transmission electron microscopy on HHTP-Co (OH) 2 CO 3 And the characterization is carried out by the/CF, the characterization result is shown in figure 2, and the transmission electron microscope image shows that the material has a rod-shaped structure.
Example 2
HOB modified basic cobalt carbonate supported copper foam self-supporting electrode (HOB-Co (OH) 2 CO 3 The preparation method of the (CF) comprises the following steps:
first step, co (OH) 2 CO 3 The synthesis method of/CF: adding 2cm multiplied by 2 cm-sized foam copper and 4mL solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 6 hours, taking out a carrier material after the temperature naturally drops to room temperature, washing with deionized water, and drying at 50 ℃ in vacuum for 8 hours.
Second step, HOB-Co (OH) 2 CO 3 The synthesis method of/CF: adding HOB 5mg, deionized water 4mL and NMP 0.165mL into a reaction kettle, dissolving by ultrasonic for 10min, and adding Co (OH) 1cm×2cm in size 2 CO 3 And (2) carrying out hydrothermal reaction for 12 hours at 120 ℃ in a sealed reaction kettle, naturally cooling to room temperature, taking out the carrier, washing with deionized water, and drying in vacuum for 8 hours at 50 ℃.
Example 3
HHTP modified basic nickel cobalt carbonate loaded carbon cloth self-supporting electricityPole (HHTP-NiCo (OH) 2 CO 3 The preparation method of the (CC) comprises the following steps:
first step, niCo (OH) 2 CO 3 The synthesis method of/CC: adding 0.5cm multiplied by 0.5cm hydrophilic carbon cloth and 1mL 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 0.6M urea, 0.1M cobalt nitrate and 0.1M nickel nitrate, taking out a carrier material after the temperature naturally drops to room temperature, washing the carrier material with deionized water, and drying the carrier material in vacuum at 50 ℃ for 8 hours.
Second step, HHTP-NiCo (OH) 2 CO 3 The synthesis method of/CC: 1mg of HHTP,4mL of deionized water and 0.165mL of NMP are added into a reaction kettle, dissolved by ultrasonic waves for 30min, and a piece of NiCo (OH) with the size of 0.5cm multiplied by 0.5cm is added 2 CO 3 And (C) carrying out hydrothermal reaction for 24 hours at 85 ℃ in a sealed reaction kettle, naturally cooling to room temperature, taking out the carrier, washing the carrier cleanly by using deionized water, and drying the carrier in vacuum for 8 hours at 50 ℃.
Example 4
HHTP modified basic nickel carbonate supported foam copper self-supporting electrode (HHTP-Ni (OH) 2 CO 3 The preparation method of the (CF) comprises the following steps:
first step, ni (OH) 2 CO 3 The synthesis method of/CF: adding foam copper with the size of 4cm multiplied by 4cm and 20 mL solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction for 12 hours at the temperature of 95 ℃, taking out a carrier material after the temperature naturally drops to room temperature, washing with deionized water, and drying in vacuum for 12 hours at the temperature of 50 ℃.
Second step, HHTP-Ni (OH) 2 CO 3 The synthesis method of/CF: 20mg of HHTP,4mL of deionized water and 1mL of NMP are added into a reaction kettle, dissolved by ultrasonic treatment for 30min, and a piece of Ni (OH) with the size of 4cm multiplied by 4cm is added 2 CO 3 And (2) carrying out hydrothermal reaction for 24 hours at 85 ℃ in a sealed reaction kettle, naturally cooling to room temperature, taking out the carrier, washing the carrier cleanly by using deionized water, and drying the carrier in vacuum for 8 hours at 50 ℃.
Example 5
HHTP modified basic cobalt carbonate supported foam nickel self-supporting electrode (HHT)P-Co(OH) 2 CO 3 /NF), comprising the following steps:
first step, co (OH) 2 CO 3 The synthesis method of/NF comprises the following steps: adding foam nickel with the size of 0.2cm multiplied by 0.5cm and 0.1mL 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 with deionized water, and drying at 50 ℃ in vacuum for 8 hours.
Second step, HHTP-Co (OH) 2 CO 3 The synthesis method of/NF comprises the following steps: 0.1mg of HHTP,1mL of deionized water and 0.0165mL of NMP are added into a reaction kettle, dissolved by ultrasonic treatment for 30min, and a piece of Co (OH) with the size of 0.2cm multiplied by 0.5cm is added 2 CO 3 and/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 in vacuum at 50 ℃ for 8 hours.
Example 6
HHTP modified basic cobalt carbonate supported foam nickel self-supporting electrode (HHTP-Co (OH) 2 CO 3 /NF), comprising the following steps:
first step, co (OH) 2 CO 3 The synthesis method of/NF comprises the following steps: adding foamed nickel with the size of 4cm multiplied by 10cm and 50mL of solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, taking out a carrier material after the temperature naturally drops to room temperature, washing with deionized water, and drying at 50 ℃ in vacuum for 8 hours.
Second step, HHTP-Co (OH) 2 CO 3 The synthesis method of/NF comprises the following steps: 1000mg of HHTP,200ml of deionized water and 8.9 of NMP of mL are added into a reaction kettle, dissolved by ultrasonic treatment for 60min, and a piece of Co (OH) with the size of 4cm multiplied by 10cm is added 2 CO 3 and/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 in vacuum at 50 ℃ for 8 hours.
Example 7
HHTP modified basic cobalt carbonate supported foam nickel self-supporting electrode (HHTP-Co (OH) 2 CO 3 /NF), comprising the following steps:
first step, co (OH) 2 CO 3 The synthesis method of/NF comprises the following steps: adding foam nickel with the size of 1cm multiplied by 2cm and 4mL solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction at 95 ℃ for 12 hours, taking out a carrier material after the temperature naturally drops to room temperature, washing with deionized water, and drying at 50 ℃ in vacuum for 8 hours.
Second step, HHTP-Co (OH) 2 CO 3 The synthesis method of/NF comprises the following steps: 7mg of HHTP,4mL of deionized water and 0.165mL of NMP are added into a reaction kettle, dissolved by ultrasonic waves for 30min, and a piece of Co (OH) with the size of 1cm multiplied by 2cm is added 2 CO 3 and/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 in vacuum at 50 ℃ for 8 hours.
Example 8
Preparation of Pt-C standard control, trimming the copper foam to 0.5cm×2cm, and dripping 50 microliter ethanol, 0.25 mg of 20% Pt-C and 1.25 microliter binder nafion into a position 0.5cm×0.5cm from one end of the copper foam. And (5) drying at 50 ℃ for 6 hours.
Example 9
RuO 2 Preparation of a Standard control, unmodified copper foam was trimmed to 0.5cm by 2cm, and a mixture of 50. Mu.l of ethanol, 0.25 mg of 20% ruthenium dioxide and 1.25. Mu.l of binder nafion was added dropwise to a 0.5cm portion at one end of the copper foam. And (5) drying at 50 ℃ for 6 hours.
Example 10
Hydrogen Evolution (HER) catalytic performance test, using a three electrode system and electrochemical workstation for unmodified copper foam metal, trimming the electrode of the first step in example 1, the electrode of the second step in example 1 to 0.5cm x 2cm, using a platinum sheet electrode clamp to connect the electrode of the first step in example 1, the electrode of the second step in example 1 and the standard sample test electrode in example 8 to the electrochemical workstation, using 0.1M KOH solution for the electrolyte, venting nitrogen for 30min to remove oxygen in the electrolyte before testing, and then, adding a catalyst to the electrolyteThe CV curve of 20 turns was scanned in the range of 0V to remove surface impurities of the electrode material, and the LSV curve of the scanned material was tested for HER performance with an effective area of 0.5cm x 0.5cm. Test results see FIG. 3, HER test results for the second step electrode of example 1, 1 in FIG. 3, at 10mA/cm 2 The HER catalytic performance of the current density condition of (C) is better than that of the first electrode (3#) in the example 1, the example 8 (2#) and the unmodified foam copper (4#).
Example 11
Hydrogen Evolution (HER) catalytic performance test, using a three electrode system and electrochemical workstation for unmodified copper foam metal, trimming the first step electrode in example 2, the second step electrode in example 2 to 0.5cm x 2cm, using a platinum sheet electrode clamp to connect the first step electrode in example 2, the second step electrode in example 2 and the standard sample test electrode in example 8 to the electrochemical workstation, using 0.1M KOH solution for the electrolyte, introducing nitrogen for 30min to remove oxygen in the electrolyte before testing, scanning 20 turns of CV curve in the range of 0.8-0 to remove surface impurities of the electrode material, and scanning the LSV curve of the material to test HER performance, wherein the effective area of the test is 0.5cm x 0.5cm. The test results are shown in FIG. 4, HER test results for the second step electrode of example 2, 1# in FIG. 4, at 10mA/cm 2 The HER catalytic performance of the current density condition of (C) is better than that of the first electrode (3#) in the example 2, the example 8 (2#) and the unmodified foam copper (4#).
Example 12
Oxygen Evolution (OER) catalytic performance test the unmodified copper foam metal was electrochemically tested using a three electrode system and electrochemical workstation, the self-supporting electrode obtained in the second step of example 1 was trimmed to 0.5cm x 2cm in the first step of example 1, the electrode obtained in the second step of example 1 and the electrode of example 9 were connected to the electrochemical workstation using a platinum sheet electrode clamp, the electrolyte was 0.1M KOH, and the electrolyte was saturated with oxygen for 30min before testing. Scanning 20 circles of CV curves within the range of 0.8-0 to remove surface impurities of the electrode material, testing the OER performance of the material, and testing the effective area0.5cm by 0.5cm. Test results are shown in FIG. 5, where # 1 in FIG. 5 is the OER test result for the second step electrode of example 1 at 10mA/cm 2 The OER catalytic performance of the electrode (3#) of example 1, the unmodified copper foam (4#) and the performance (2#) of example 9 were better than those of the electrode (3#) of example 1 under the current density condition of the potential of 1575 mV.
Example 13
Fig. 6 is a schematic view of the self-supporting electrode applied to electrolyzed water according to the present invention, which can be used as a hydrogen evolution electrode and an oxygen evolution electrode directly applied to electrolyzed water.
The foregoing is merely an embodiment of the present application, and is not intended to limit the present application, but the present application is disclosed in the preferred embodiment, however, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications using the disclosed technical content and equivalents to the equivalent embodiments without departing from the scope of the technical solution of the present application.
Claims (8)
1. A preparation method of a self-supporting electrode is characterized by comprising the following steps: in situ growth of a rod-like transition metal basic carbonate M (OH) on a support material support, SM for short 2 CO 3 SM, reuse of conductive MOF ligand organic small molecule pair M (OH) 2 CO 3 The surface of the rod-shaped material is modified to obtain a self-supporting electrode H-M (OH) 2 CO 3 SM; the conductive MOF ligand organic small molecule is selected from 2,3,6,7,10, 11-hexahydroxytriphenylHHTP 2,3,6,7,10, 11-hexahydroxytriphenylene, hexahydroxyphenylHOB 1,2,3,4,5, 6-Benzenehexol, hexaaminobenzene HAB 1,2,3,4,5, 6-Benzenehexamine;
the preparation method of the self-supporting electrode specifically comprises the following steps:
the first step: 0.1-5000 cm is added into a reaction kettle 2 The preparation method comprises the steps of immersing a carrier material and 0.1-5000 ml of a metal precursor solution in the carrier material, sealing a reaction kettle, carrying out hydrothermal reaction at 60-160 ℃ for 8-24 hours, naturally cooling to room temperature, taking out the material, flushing with deionized water, and carrying out vacuum drying at 40-60 ℃ for 6-12 hours to obtain alkaliCarbonate matrix electrode material;
and a second step of: adding 0.1-5000 ml of deionized water and conductive MOF ligand with the mass of 0.01-1000 mg into a reaction kettle, adding 0.1-50 ml of NMP, carrying out ultrasonic treatment until the mixture is uniform to obtain ligand liquid, immersing an electrode obtained in the first step of reaction into the ligand liquid, sealing the reaction kettle, reacting for 12-36 hours at 60-160 ℃, naturally cooling to room temperature, washing with deionized water, drying at 40-60 ℃ in vacuum for 6-12 hours, and obtaining the self-supporting electrode material after drying.
2. The method of preparing a self-supporting electrode according to claim 1, wherein: the carrier material in the first step is carbon cloth, carbon fiber paper, foam copper or foam nickel.
3. The method of preparing a self-supporting electrode according to claim 1, wherein: the metal precursor solution in the first step is a mixed solution of metal salt and urea, the molar ratio of the urea to the metal ions is 2:1-20:1, and the concentration of the metal salt is 0.01-2 mol/L.
4. The method of preparing a self-supporting electrode according to claim 1, wherein: the metal salt in the metal precursor solution is nitrate, sulfate, hydrochloride or acetate of soluble metal, and the metal is monobasic or polybasic mixture of cobalt, iron, nickel and copper.
5. The method of preparing a self-supporting electrode according to claim 1, wherein: the frequency of the ultrasonic waves in the second step is 10-1000 Hz, and the ultrasonic time is 5-60 min.
6. The self-supporting electrode prepared by the preparation method according to any one of claims 1-5 is used as an electrode in an energy storage battery and a fuel cell.
7. Use of a self-supporting electrode according to claim 6, characterized in that: the self-supporting electrode is used as an active material in an energy storage cell.
8. The self-supporting electrode prepared by the preparation method according to any one of claims 1-5 is used as a hydrogen evolution electrode and an oxygen evolution electrode of electrolytic water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111120407.4A CN113930782B (en) | 2021-09-24 | 2021-09-24 | Preparation method and application of self-supporting electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111120407.4A CN113930782B (en) | 2021-09-24 | 2021-09-24 | Preparation method and application of self-supporting electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113930782A CN113930782A (en) | 2022-01-14 |
| CN113930782B true CN113930782B (en) | 2023-06-20 |
Family
ID=79276605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111120407.4A Active CN113930782B (en) | 2021-09-24 | 2021-09-24 | Preparation method and application of self-supporting electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113930782B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116496495B (en) * | 2022-01-18 | 2024-05-28 | 闽都创新实验室 | Crown ether group covalent organic polymer and light-assisted lithium battery cell device thereof |
| CN115207278B (en) * | 2022-09-13 | 2022-12-20 | 深圳海润新能源科技有限公司 | Negative pole piece, preparation method thereof, battery and electric equipment |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104810160A (en) * | 2015-03-30 | 2015-07-29 | 安徽师范大学 | Alkali carbonate nickel copper nanowires array and preparation method and use thereof |
| CN106178982A (en) * | 2016-07-21 | 2016-12-07 | 北京工业大学 | A kind of preparation method of the metal organic framework film inverting based on subcarbonate |
| CN107488864A (en) * | 2017-07-26 | 2017-12-19 | 苏州大学 | The preparation method of the optoelectronic pole of zinc supported nickel cobalt subcarbonate |
| CN108439549A (en) * | 2018-04-03 | 2018-08-24 | 北京工业大学 | A kind of preparation of array structure transition metal selenides electrode and its application in electrolysis water |
| CN109208030A (en) * | 2018-11-16 | 2019-01-15 | 北京师范大学 | A kind of Metal Hydroxide-Metal organic frame composite material and preparation method |
| CN109321933A (en) * | 2018-08-30 | 2019-02-12 | 济南大学 | A kind of preparation method and application of MOF/ carbon dots nanocomposite catalyst |
| CN109518220A (en) * | 2018-12-29 | 2019-03-26 | 江苏大学 | Two-dimensional metallic organic frame nanometer, which is constructed, as substrate using foam copper hydrolyzes the preparation method and applications of elctro-catalyst in electrolysis water liberation of hydrogen |
| CN110465312A (en) * | 2019-05-30 | 2019-11-19 | 华南理工大学 | A kind of self-supporting carbon cloth load cobaltous selenide nickel nanowire preparation method and application |
| CN110683588A (en) * | 2019-09-06 | 2020-01-14 | 中南大学 | Self-supporting CoMoS4Super capacitor electrode material, preparation method and application |
| CN110787806A (en) * | 2019-08-28 | 2020-02-14 | 浙江工业大学 | Preparation method of full-hydrolysis catalyst with heterojunction structure |
| CN111440328A (en) * | 2020-04-30 | 2020-07-24 | 山东交通学院 | Boric acid modified metal oxide nano array-MOF composite material, and preparation method and application thereof |
| CN112058309A (en) * | 2020-08-14 | 2020-12-11 | 华南理工大学 | Fusiform MnFeNi-MOF-74 material growing in situ on foamed nickel and preparation method and application thereof |
| CN112553654A (en) * | 2020-12-03 | 2021-03-26 | 华中科技大学 | Preparation method and application of transition metal-based metal-organic framework composite material |
-
2021
- 2021-09-24 CN CN202111120407.4A patent/CN113930782B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104810160A (en) * | 2015-03-30 | 2015-07-29 | 安徽师范大学 | Alkali carbonate nickel copper nanowires array and preparation method and use thereof |
| CN106178982A (en) * | 2016-07-21 | 2016-12-07 | 北京工业大学 | A kind of preparation method of the metal organic framework film inverting based on subcarbonate |
| CN107488864A (en) * | 2017-07-26 | 2017-12-19 | 苏州大学 | The preparation method of the optoelectronic pole of zinc supported nickel cobalt subcarbonate |
| CN108439549A (en) * | 2018-04-03 | 2018-08-24 | 北京工业大学 | A kind of preparation of array structure transition metal selenides electrode and its application in electrolysis water |
| CN109321933A (en) * | 2018-08-30 | 2019-02-12 | 济南大学 | A kind of preparation method and application of MOF/ carbon dots nanocomposite catalyst |
| CN109208030A (en) * | 2018-11-16 | 2019-01-15 | 北京师范大学 | A kind of Metal Hydroxide-Metal organic frame composite material and preparation method |
| CN109518220A (en) * | 2018-12-29 | 2019-03-26 | 江苏大学 | Two-dimensional metallic organic frame nanometer, which is constructed, as substrate using foam copper hydrolyzes the preparation method and applications of elctro-catalyst in electrolysis water liberation of hydrogen |
| CN110465312A (en) * | 2019-05-30 | 2019-11-19 | 华南理工大学 | A kind of self-supporting carbon cloth load cobaltous selenide nickel nanowire preparation method and application |
| CN110787806A (en) * | 2019-08-28 | 2020-02-14 | 浙江工业大学 | Preparation method of full-hydrolysis catalyst with heterojunction structure |
| CN110683588A (en) * | 2019-09-06 | 2020-01-14 | 中南大学 | Self-supporting CoMoS4Super capacitor electrode material, preparation method and application |
| CN111440328A (en) * | 2020-04-30 | 2020-07-24 | 山东交通学院 | Boric acid modified metal oxide nano array-MOF composite material, and preparation method and application thereof |
| CN112058309A (en) * | 2020-08-14 | 2020-12-11 | 华南理工大学 | Fusiform MnFeNi-MOF-74 material growing in situ on foamed nickel and preparation method and application thereof |
| CN112553654A (en) * | 2020-12-03 | 2021-03-26 | 华中科技大学 | Preparation method and application of transition metal-based metal-organic framework composite material |
Non-Patent Citations (4)
| Title |
|---|
| Building CoP/Co-MOF heterostructure in 2D nanosheets for improving electrocatalytic hydrogen evolution over a wide pH range;Qiling Li等;Journal of Electroanalytical Chemistry;第895卷;1-10 * |
| Metal-organic frameworks (MOFs) and their composites as electrodes for lithium battery applications: Novel means for alternative energy storage;Vishal Shrivastav等;Coordination Chemistry Reviews;第393卷;48-78 * |
| Synergistic engineering of morphology and electronic structure in constructing metal-organic framework-derived Ru doped cobalt-nickel oxide heterostructure towards efficient alkaline hydrogen evolution reaction;Haotian Zhang等;Chemical Engineering Journal;第426卷;1-10 * |
| 导电金属有机骨架材料在超级电容器中的应用;李泽晖等;无 机 材 料 学 报;第35卷(第7期);669-780 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113930782A (en) | 2022-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109019602B (en) | Molybdenum carbide material, molybdenum carbide @ molybdenum sulfide composite material, and preparation method and application thereof | |
| CN111342066B (en) | Preparation method of transition metal-nitrogen-carbon nanotube co-doped active carbon oxygen reduction catalyst | |
| CN109852994B (en) | Co9S8Preparation method of nitrogen-doped carbon composite array electrode | |
| CN109174157B (en) | Preparation method of cobalt-nitrogen co-doped biomass carbon oxidation reduction catalyst | |
| CN113828300B (en) | Preparation method of metal doped bismuth layered oxide and electrocatalytic reduction of CO 2 Application in (a) | |
| CN111001428B (en) | Metal-free carbon-based electrocatalyst, preparation method and application | |
| CN113930782B (en) | Preparation method and application of self-supporting electrode | |
| CN109694071B (en) | Method for preparing nitrogen-doped porous carbon material by taking coconut shell as raw material and application | |
| CN112820886B (en) | Three-dimensional hierarchical porous nonmetal carbon-based material, and preparation method and application thereof | |
| CN108579718B (en) | Preparation method and application of indium-doped nano porous carbon material | |
| CN113512738B (en) | Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof | |
| CN111495394A (en) | Carbon cloth loaded CoS2/MoS2Heterojunction composite material and preparation method and application thereof | |
| CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| CN111686743A (en) | La/NF hydrogen evolution material and preparation method and application thereof | |
| CN112522726A (en) | Preparation method and application of nitrogen-doped porous carbon/molybdenum disulfide composite material derived from natural agar | |
| CN113270597A (en) | C3N4Coated carbon nano tube loaded NiFe dual-functional oxygen electrocatalyst and preparation method thereof | |
| CN114976063A (en) | Nitrogen-doped biomass carbon-based bifunctional catalyst and preparation method and application thereof | |
| CN114583191A (en) | Method for preparing anode catalyst of direct methanol fuel cell by electrodeposition | |
| CN114457365B (en) | Pt-Ni composite material, preparation method thereof and application of Pt-Ni composite material as catalyst for hydrogen production by water electrolysis | |
| CN112680745B (en) | Tungsten nitride nano porous film integrated electrode with ruthenium nanocluster loaded in limited domain and preparation method and application thereof | |
| CN114497583B (en) | Preparation method of PtRu/CN catalyst for fuel cell | |
| CN103120960A (en) | Pt-Nafion/C catalyst and preparation method and application for same | |
| CN113584513A (en) | Method for preparing RuNC-T composite nano material and application thereof | |
| CN115747874B (en) | Preparation method and application of rare earth element doped 2D RE@Fe-MOF efficient integrated membrane electrode | |
| CN113793942B (en) | Preparation method and application of nitrogen-doped porous carbon material based on medium-rank coal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |