CN115369444A - High-performance integrated oxygen evolution reaction electrode material, preparation method and application - Google Patents

High-performance integrated oxygen evolution reaction electrode material, preparation method and application Download PDF

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CN115369444A
CN115369444A CN202210932416.1A CN202210932416A CN115369444A CN 115369444 A CN115369444 A CN 115369444A CN 202210932416 A CN202210932416 A CN 202210932416A CN 115369444 A CN115369444 A CN 115369444A
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electrode material
oxygen evolution
evolution reaction
performance integrated
integrated oxygen
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徐丞桢
林超
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Shanghai Hannuo Jingneng Hydrogen Energy Development Co ltd
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Shanghai Hannuo Jingneng Hydrogen Energy Development Co ltd
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    • 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
    • C25B11/093—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 noble metal or noble metal oxide and at least one non-noble metal oxide
    • 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

Abstract

The invention provides a high-performance integrated oxygen evolution reaction electrode material, a preparation method and application thereof, and the method comprises the following steps: the in-situ growth of the amorphous manganese oxide is realized on the surface of the high-conductivity three-dimensional electrode material by adopting an electrochemical deposition technology; different manganese oxide crystal structures are realized through high-temperature calcination treatment; and by combining a cation exchange technology, modifying high-activity sites on the surface interfaces of different manganese oxide loaded three-dimensional electrode materials, and realizing the preparation of the high-performance acid oxygen evolution electrode. The manganese oxide obtained by the method has a crystal structure and is rich in MnO shared at the edge 6 The octahedral structural element is beneficial to maintaining the structural stability of the catalyst in an acid reaction system and improving the catalytic activity. The three-dimensional electrode material prepared by the method has higher acidic oxygen evolution reaction activity, and has the characteristics of convenient operation, strong controllability and repeatability and the like.

Description

High-performance integrated oxygen evolution reaction electrode material, preparation method and application
Technical Field
The invention relates to the technical field of nano materials and energy technology, in particular to a high-performance integrated oxygen evolution reaction electrode material, a preparation method and application.
Background
The technology for preparing high-purity hydrogen by electrolyzing water is one of the important fields of the development of new energy at present. Electrochemical energy storage and conversion technology represented by a Proton Exchange Membrane (PEM) water electrolysis hydrogen production technology can effectively overcome the defect of intermittent energy supply of renewable clean energy and has environmental-friendly characteristics, so that the electrochemical energy storage and conversion technology attracts global wide attention. However, the energy consumption for hydrogen production by water electrolysis, which is dominated by the catalytic performance of Oxygen Evolution Reaction (OER), is problematic, so that the technical economy of PEM hydrogen production by water electrolysis still cannot meet the large-scale marketization requirement. Despite significant advances in research relating to acidic oxygen evolution reaction catalysts suitable for PEM technology, major efforts have been directed to the development and design of powdered active materials. Therefore, the bonding force between the active material and the conductive current collector is subject to the mechanical properties of the adhesive. Maintaining the stability of the working electrode under external conditions such as binder aging caused by the oxidative reaction environment and mechanical scouring of the electrolyte remains a significant challenge. Moreover, the multi-interface system caused by the load type structure also reduces the conductivity of the electrode, improves the internal resistance of the system, and has limited active material load. The in-situ growth is carried out on the surface of the conductive substrate in a certain mode, and the integrated design of the conductive current collector and the catalytic material is realized by utilizing the action of chemical bonds or non-chemical bonds, so that the method becomes an ideal electrode preparation means. The in-situ compounding strategy can improve the effective loading capacity of the active material, and the close connection mode takes the electric contact between the active material and the current collector and the stability of the electrode structure into consideration.
Oxides of manganese are low cost, environmentally friendly and acid stable transition metal oxides based on MnO 6 Different bonding patterns of octahedral units, exhibiting abundant polymorphic structural features, e.g. MnO, mnO 2 ，Mn 2 O 3 ，Mn 3 O 4 And the like. The polymorphic structure of manganese is considered to be an ideal material with a wide range of electrochemical applications. MnO with large number of corner-sharing structures (corner-sharing) 2 Is the most widely studied basic OER catalytic material. However, leading edge studies have found that the relevant materials tend to change phase into edge-sharing (edge-sharing) octahedral structures at the interface after the OER reaction. Description of related findings: compared with the traditional MnO 2 Edge-shared polycrystalline manganese oxide (MnO, mn) with shorter Mn atomic distance and more connecting sites 2 O 3 Etc.) may be more advantageousAnd (3) carrying out OER reaction. However, the rich meta-stable character poses certain challenges for the controlled synthesis of manganese oxides of specific crystalline phase structure. Meanwhile, the acidic OER catalytic performance of a single manganese oxide is limited, the basic performance requirements of commercial application cannot be met, and the problem of further improving the intrinsic catalytic activity of the material is another challenge to be solved by relying on the atomic structure characteristics of the manganese oxide.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in view of the defects of the prior art, the invention provides a high-performance integrated oxygen evolution reaction electrode material, a preparation method and application thereof, so as to solve the problems of difficult integrated design, low catalytic performance and the like of the conventional electrode material. The ruthenium-loaded manganese oxide electrode material which grows in situ and is obtained by the preparation method can realize in-situ controllable synthesis of manganese oxide polycrystalline materials (MnO, mn) with rich edge sharing atomic structure characteristics on the surface of the conductive current collector 2 O 3 ，Mn 3 O 4 And the like) and by a cation exchange method, substituting the manganese oxide interface cations with high-activity noble metal elements (ruthenium, iridium and the like) to realize further jump of OER performance and greatly improve the intrinsic activity of active sites.
The technical scheme adopted for solving the technical problems is as follows: a preparation method of a high-performance integrated oxygen evolution reaction electrode material comprises the following steps:
s1: in a three-electrode system, a high-conductivity three-dimensional electrode material is placed in an acid electrolyte containing manganese ions, and an electrochemical deposition means is adopted to grow amorphous manganese oxide in situ on the surface of the electrode material;
s2: carrying out high-temperature calcination treatment on the electrode material with the amorphous manganese oxide on the surface obtained in the step S1 to controllably synthesize different manganese oxide crystal structures, wherein the manganese oxide comprises MnO and Mn 2 O 3 、 Mn 3 O 4 One or more of (a);
s3: and (3) modifying the surface interfaces of the different manganese oxide loaded three-dimensional electrode materials obtained in the step (S2) by combining a cation exchange means to obtain a high-performance acidic oxygen evolution electrode material, so that the preparation of the high-performance acidic oxygen evolution electrode is realized.
Preferably, the high-conductivity three-dimensional electrode material is one or more of carbon paper, carbon cloth, titanium felt and stainless steel.
Further, before the electrochemical deposition treatment in step S1, the substrate of the three-dimensional high-conductivity electrode material is treated with one or more of acetone, methanol, ethanol, deionized water, nitric acid, hydrochloric acid, and sulfuric acid. The treatment can firstly wash away impurities on the surface of the substrate, and then can effectively change the hydrophilic characteristic of the interface (the untreated substrate surface has the characteristic of local hydrophobicity), which is beneficial to improving the effective contact between the substrate and the electrolyte in the electrodeposition process.
Further, the acid electrolyte containing manganese ions in step S1 is 0.5M H 2 SO 4 0.2M manganese salt and 0.6M potassium salt, wherein M is mol/L.
Preferably, the manganese salt refers to one or more of manganese acetate, manganese sulfate, manganese nitrate, manganese chloride and manganese perchlorate.
Preferably, the potassium salt refers to one or more of potassium acetate, potassium sulfate, potassium nitrate, potassium chloride and potassium perchlorate.
Specifically, the electrochemical deposition means in step S1 is to perform in-situ electrochemical deposition under a constant current density of 30 to 10000S, wherein the constant current density is 0.1 to 10 mA cm -2 。
Further, the high-temperature calcination process in step S2 is performed under the protection of inert gases such as nitrogen or argon.
Furthermore, the high-temperature calcination temperature in the step S2 is 100-900 ℃, and the time is 1-3 hours. And maintaining a temperature all the time in the high-temperature calcination process, and carrying out constant-temperature heat treatment on the material, wherein the temperature does not change in the constant-temperature process.
Specifically, the cation exchange means in step S3 is to soak the three-dimensional electrode material loaded with manganese oxide in an aqueous solution containing ruthenium or iridium ions for 0.01 to 1 hour, and after the soaking is finished, the three-dimensional electrode material is washed with deionized water for multiple times, and then dried and baked.
The aqueous solution of ruthenium ions is prepared by adopting ruthenium salt, and the concentration of salt ions is 19 mol/L; the ruthenium salt is selected from one or more of ruthenium acetate, ruthenium nitrate and ruthenium chloride;
the iridium ion aqueous solution is prepared from iridium salt, and the salt ion concentration is 19 mol/L; the iridium salt is selected from one or more of iridium acetate, iridium nitrate or iridium chloride.
Further, the drying step is drying at 50-80 ℃ for 2-24h.
Furthermore, the roasting atmosphere is air, the temperature is 150-250 ℃, and the roasting time is 0.5-3h.
The preparation method comprises the following steps: the in-situ growth of the amorphous manganese oxide is realized on the surface of the high-conductivity three-dimensional electrode material by adopting an electrochemical deposition technology; different manganese oxide crystal structures (MnO and Mn) are realized through high-temperature calcination treatment 2 O 3 , Mn 3 O 4 ) Controllable synthesis of (2); and modifying high-activity sites (such as Ru) on the surface interfaces of different manganese oxide-loaded three-dimensional electrode materials by combining a cation exchange technology, so as to realize the preparation of the high-performance acidic oxygen evolution electrode. Manganese oxide crystal structure (MnO, mn) obtained by using the preparation method 2 O 3 , Mn 3 O 4 ) Enriched edge-shared MnO 6 The octahedral structural element is beneficial to maintaining the structural stability of the catalyst in an acid reaction system and improving the catalytic activity. The three-dimensional electrode material prepared by the method has higher acidic oxygen evolution reaction activity. The method is convenient to operate, has strong controllability and repeatability, and is an ideal technical means for preparing a new generation of acid oxygen evolution electrode material.
A high-performance integrated oxygen evolution reaction electrode material is obtained by adopting the preparation method.
Further, the electrode material includes noble metal element active sites with edge-shared MnO 6 Manganese oxide crystal structure of octahedral structure elements and a corrosion-resistant high-conductivity three-dimensional electrode material substrate.
The application of a high-performance integrated oxygen evolution reaction electrode material which is used as an anode material of an acidic aqueous solution electrolytic cell.
The beneficial effects of the invention are:
(1) The high-performance integrated oxygen evolution reaction electrode material realizes the integration of a manganese oxide polycrystalline structure and a conductive current collector, and effectively improves the electrical contact of an active material and the current collector and the stability of the electrode structure. And the manganese-based polycrystalline material rich in the edge sharing structure is controllably synthesized, and the in-situ interface in-situ substitution of the ruthenium component is realized through cation exchange, so that the catalytic performance of the oxygen evolution reaction of the active material is remarkably improved.
(2) The high-performance integrated oxygen evolution reaction electrode material is used as a high-performance acidic oxygen evolution reaction electrocatalytic material, can efficiently perform Oxygen Evolution Reaction (OER) in an acidic electrolyte environment, can be used as an anode material for water electrolysis hydrogen production, is used in a proton conducting polymer membrane electrolysis hydrogen production electrolytic cell, and solves the problems of easy falling off, poor structural stability and the like of the existing acidic oxygen evolution powder catalyst.
Drawings
The invention is further illustrated by the following figures and examples.
FIG. 1 is a schematic diagram of the atomic structures of manganese oxides in different crystal forms in the examples.
FIG. 2 shows XRD diffraction patterns of the in-situ grown electrode materials described in various embodiments.
Fig. 3 shows scanning electron microscopy test patterns of in situ grown manganese oxide samples of various examples.
FIG. 4 shows Ru-MnO/CC and Ru-Mn after ruthenium cation exchange 2 O 3 CC sample scanning electron microscopy test pattern.
Figure 5 shows the oxygen evolution catalytic performance of the integrated electrode material.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the processing equipment or devices not specifically mentioned in the following examples are conventional in the art; all pressure values and ranges refer to relative pressures.
Furthermore, it is to be understood that one or more method steps recited in the present disclosure are not exclusive of other method steps that may also be present before or after the recited combination of steps or that other method steps may also be inserted between the explicitly recited steps, unless otherwise indicated; it should also be understood that a combinational connection relationship between one or more devices/apparatuses mentioned in the present invention does not exclude that other devices/apparatuses may also be present before or after the combinational device/apparatus or that other devices/apparatuses may also be interposed between the two devices/apparatuses explicitly mentioned, unless otherwise stated. Moreover, unless otherwise indicated, the numbering of the method steps is only a convenient tool for identifying each method step, and is not intended to limit the order of the method steps or the scope of the invention, and changes or modifications in the relative relationship thereof may be regarded as the scope of the invention without substantial change in the technical content.
Example 1:
0.05 mol of sulfuric acid, 0.02 mol of manganese sulfate and 0.06 mol of potassium sulfate are fully dispersed and dissolved in 100 ml of deionized water to obtain a mixed solution. The mixed solution is taken as electrolyte, carbon cloth washed by ethanol is taken as a working electrode, carbon paper is taken as a counter electrode, and the concentration of the electrolyte is 10 mA cm -2 Under the condition of current density, after 180s of treatment, the working electrode is taken out, washed by deionized water and ethanol and dried for 2h under the condition of 70 ℃. Then in N 2 Roasting at 300 ℃ for 1h under the atmosphere condition to obtain MnO x /CC。
Mixing Mn with a solventO x the/CC sample is 19 mmol/l RuCl 3 Performing cation exchange reaction in the solution, taking out a sample after reacting for 1h, washing with a large amount of deionized water for multiple times, drying at 80 ℃ for 12h, roasting at 200 ℃ for 1h in air atmosphere, and naturally cooling to room temperature to obtain Ru-MnO x A/CC electrode sample.
Example 2:
0.05 mol of sulfuric acid, 0.02 mol of manganese nitrate and 0.06 mol of potassium nitrate were sufficiently dispersed and dissolved in 100 ml of deionized water to obtain a mixed solution. The mixed solution is taken as electrolyte, carbon cloth washed by ethanol is taken as a working electrode, carbon paper is taken as a counter electrode, and the concentration of the electrolyte is 11 mA cm -2 And (4) under the current density condition, after treating for 1800s, taking out the working electrode, washing with deionized water and ethanol, and drying at 70 ℃ for 2h. Then in N 2 Roasting for 1h at 450 ℃ under the atmosphere condition to obtain Mn 2 O 3 /CC。
Adding Mn 2 O 3 the/CC sample is 19 mmol/l RuCl 3 Carrying out cation exchange reaction in the solution, taking out a sample after reacting for 1h, washing with a large amount of deionized water for multiple times, drying at 80 ℃ for 12h, roasting at 200 ℃ for 1h in air atmosphere, and naturally cooling to room temperature to obtain Ru-Mn 2 O 3 the/CC electrode samples.
Example 3:
0.05 mol of sulfuric acid, 0.02 mol of manganese acetate and 0.06 mol of potassium acetate are fully dispersed and dissolved in 100 ml of deionized water to obtain a mixed solution. The mixed solution is taken as electrolyte, carbon cloth washed by ethanol is taken as a working electrode, carbon paper is taken as a counter electrode, and the concentration of the electrolyte is controlled at 0.2 mA cm -2 Under the condition of current density, after 9000s of treatment, the working electrode is taken out, washed by deionized water and ethanol and dried for 2 hours at the temperature of 70 ℃. Then in N 2 Roasting at 600 ℃ for 1h under the atmosphere condition to obtain MnO/CC.
MnO/CC sample was treated at 19 mmol/l RuCl 3 Performing cation exchange reaction in the solution, taking out the sample after reacting for 0.5h, washing with a large amount of deionized water for multiple times, drying at 80 ℃ for 12h, roasting at 200 ℃ in air atmosphere for 1h, and naturally cooling to room temperature to obtain Ru-MnO/CC electricityA polar sample.
Example 4:
0.05 mol of sulfuric acid, 0.02 mol of manganese sulfate and 0.06 mol of potassium sulfate are fully dispersed and dissolved in 100 ml of deionized water to obtain a mixed solution. The mixed solution is taken as electrolyte, carbon cloth washed by ethanol is taken as a working electrode, carbon paper is taken as a counter electrode, and the concentration of the electrolyte is 10 mA cm -2 Under the condition of current density, after 180s of treatment, the working electrode is taken out, washed by deionized water and ethanol and dried for 2h under the condition of 70 ℃. Then in N 2 Roasting at 750 deg.c for 1 hr in atmosphere to obtain MnO-Mn 3 O 4 /CC。
MnO-Mn 3 O 4 the/CC sample is 19 mmol/l RuCl 3 Performing cation exchange reaction in the solution, taking out a sample after reacting for 0.05h, washing with a large amount of deionized water for multiple times, drying at 80 ℃ for 12h, roasting at 200 ℃ in air atmosphere for 1h, and naturally cooling to room temperature to obtain Ru-MnO-Mn 3 O 4 the/CC electrode samples.
Example 5:
0.05 mol of sulfuric acid, 0.02 mol of manganese sulfate and 0.06 mol of potassium sulfate are fully dispersed and dissolved in 100 ml of deionized water to obtain a mixed solution. The mixed solution is taken as electrolyte, carbon cloth washed by ethanol is taken as a working electrode, carbon paper is taken as a counter electrode, and the concentration of the electrolyte is 10 mA cm -2 And (3) under the condition of current density, taking out the working electrode after 180s of treatment, washing the working electrode by using deionized water and ethanol, and drying the working electrode for 2h at the temperature of 70 ℃. Then in N 2 Roasting at 900 ℃ for 1h under the atmosphere condition to obtain Mn 3 O 4 /CC。
MnO to Mn 3 O 4 the/CC sample is 19 mmol/l RuCl 3 Performing cation exchange reaction in the solution, taking out a sample after reacting for 0.05h, washing with a large amount of deionized water for multiple times, drying at 80 ℃ for 12h, roasting at 200 ℃ in air atmosphere for 1h, and naturally cooling to room temperature to obtain Ru-MnO-Mn 3 O 4 the/CC electrode samples.
Example 6:
0.05 mol of sulfuric acid, 0.02 mol of manganese sulfate and 0.06 mol of potassium sulfate are fully dispersed and dissolved in 100 ml of deionized waterAnd adding water to obtain a mixed solution. The mixed solution is taken as electrolyte, carbon cloth washed by ethanol is taken as a working electrode, carbon paper is taken as a counter electrode, and the concentration of the electrolyte is 10 mA cm -2 And (3) under the condition of current density, taking out the working electrode after 180s of treatment, washing the working electrode by using deionized water and ethanol, and drying the working electrode for 2h at the temperature of 70 ℃. Then in N 2 And roasting at 600 ℃ for 1h under the atmosphere condition to obtain MnO/CC.
MnO-Mn 3 O 4 The concentration of the/CC sample is 19 mmol/l IrCl 3 And (2) carrying out cation exchange reaction in the solution, taking out a sample after reacting for 0.05h, washing the sample by using a large amount of deionized water for multiple times, drying the sample at 80 ℃ for 12h, roasting the dried sample at 200 ℃ for 1h in an air atmosphere, and naturally cooling the roasted sample to room temperature to obtain the Ir-MnO/CC electrode sample.
Description of the invention: the main differences in examples 1 to 6 are that the conditions of electrochemical deposition are different, the temperature of high-temperature calcination is different, the aqueous solution of ruthenium or iridium ions used for cation exchange is different, and different manganese oxide crystal structures are synthesized by controlling the conditions of electrochemical deposition and the temperature of high-temperature calcination.
Description of the test:
the in-situ grown electrode materials obtained in examples 1 to 5 were subjected to an X-ray test, and the test results are shown in FIG. 1. As can be seen from FIG. 1, this includes Mn 2 O 3 ，MnO, Mn 3 O 4 Manganese oxides of different crystalline phase structures are successfully combined with the conductive current collector. As can be seen from fig. 2, the manganese oxides of different phases have rich octahedral edge-sharing atomic structural features, which are beneficial to the improvement of catalytic performance of active components and the improvement of stability.
The in-situ grown electrode material samples obtained in examples 1-5 were subjected to scanning electron microscopy characterization tests and the results are shown in fig. 3. As can be seen from fig. 3, the manganese oxide catalytic material is uniformly distributed on the surface of the conductive current collector in examples 1 to 5, and the structural characteristics of the manganese oxide change with the change of the baking conditions, but the manganese oxide catalytic material is always in close contact with the current collector interface, which is beneficial to accelerating the charge transport rate and reducing the internal resistance of the system.
Ru-Mn obtained in examples 2 and 3 2 O 3 /CC and Ru-MnO/CC electrode samples, scanning electron microscopy characterization test, results are shown in FIG. 4. As can be seen from fig. 4, the microstructure of the electrode material after the cation exchange reaction treatment does not change significantly, and the active component is still in close contact with the current collector.
The integrated electrode materials obtained in examples 1 to 4, 6 were measured at 0.1M HClO 4 The catalytic activity of the oxygen evolution reaction in aqueous solution is shown in figure 5. As can be seen from FIG. 5, different integrated electrode materials all exhibited excellent OER catalytic performance of the acidic electrolyte system, where Ru-Mn 2 O 3 the/CC integrated electrode material shows the optimal OER catalytic performance at 10 mA cm -2 The overpotential under the current density condition is only 170 mV, which is superior to most of other reported acidic OER catalysts.
In conclusion, the high-performance integrated electrode material suitable for the acidic electrolyte system and the preparation method thereof provided by the invention can be used as an anode material of an electrolytic water hydrogen production electrolytic cell, the problems of low performance, poor structural stability and the like of the existing acidic electrolyte system oxygen evolution reaction catalyst are solved, and the prepared integrated electrode material shows excellent oxygen evolution reaction activity under the acidic system and is far superior to most of reported related catalysts. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
In light of the foregoing description of preferred embodiments in accordance with the invention, it is to be understood that numerous changes and modifications may be made by those skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.

Claims (16)

1. A preparation method of a high-performance integrated oxygen evolution reaction electrode material is characterized by comprising the following steps: the method comprises the following steps:
s1: in a three-electrode system, a high-conductivity three-dimensional electrode material is placed in an acid electrolyte containing manganese ions, and an electrochemical deposition means is adopted to grow amorphous manganese oxide on the surface of the electrode material in situ;
s2: carrying out high-temperature calcination treatment on the electrode material with the amorphous manganese oxide on the surface obtained in the step S1 to controllably synthesize different manganese oxide crystal structures, wherein the manganese oxide comprises MnO and Mn 2 O 3 、 Mn 3 O 4 One or more of;
s3: and (3) carrying out ruthenium site modification on the surface interfaces of the different manganese oxide loaded three-dimensional electrode materials obtained in the step (S2) by combining a cation exchange means to obtain the high-performance acidic oxygen evolution electrode material.
2. The method for preparing the high-performance integrated oxygen evolution reaction electrode material of claim 1, wherein: the high-conductivity three-dimensional electrode material is one or more of carbon paper, carbon cloth, titanium felt and stainless steel.
3. The method for preparing the high-performance integrated oxygen evolution reaction electrode material as claimed in claim 1, wherein: before the electrochemical deposition treatment in the step S1, the substrate of the three-dimensional high-conductivity electrode material is treated by using one or more of acetone, methanol, ethanol, deionized water, nitric acid, hydrochloric acid and sulfuric acid.
4. The method for preparing the high-performance integrated oxygen evolution reaction electrode material as claimed in claim 1, wherein: the acid electrolyte containing manganese ions in the step S1 contains 0.5M H 2 SO 4 0.2M manganese salt and 0.6M potassium salt.
5. The method for preparing the high-performance integrated oxygen evolution reaction electrode material as claimed in claim 4, wherein: the manganese salt is one or more of manganese acetate, manganese sulfate, manganese nitrate, manganese chloride and manganese perchlorate.
6. The method for preparing the high-performance integrated oxygen evolution reaction electrode material as claimed in claim 4, wherein: the potassium salt is one or more of potassium acetate, potassium sulfate, potassium nitrate, potassium chloride and potassium perchlorate.
7. The method for preparing the high-performance integrated oxygen evolution reaction electrode material of claim 1, wherein: the electrochemical deposition means in the step S1 is that the in-situ electrochemical deposition treatment is carried out under the condition of constant current density of 30-10000S, wherein the constant current density is 0.1-10 mA cm -2 。
8. The method for preparing the high-performance integrated oxygen evolution reaction electrode material as claimed in claim 1, wherein: and the high-temperature calcination process in the step S2 is carried out under the protection of inert gas.
9. The method for preparing the high-performance integrated oxygen evolution reaction electrode material as claimed in claim 1, wherein: the high-temperature calcination temperature in the step S2 is 100-900 ℃, and the time is 1-3 hours.
10. The method for preparing the high-performance integrated oxygen evolution reaction electrode material of claim 1, wherein: and the cation exchange means in the step S3 is to soak the three-dimensional electrode material loaded with the manganese oxide in aqueous solution containing ruthenium or iridium ions for 0.01-1 hour, and after the soaking is finished, the three-dimensional electrode material is washed with deionized water for multiple times, then dried and roasted.
11. The method for preparing the high-performance integrated oxygen evolution reaction electrode material according to claim 10, wherein: the aqueous solution of ruthenium ions is prepared by ruthenium salt, and the concentration of salt ions is 19 mol/L; the ruthenium salt is selected from one or more of ruthenium acetate, ruthenium nitrate and ruthenium chloride;
the iridium ion aqueous solution is prepared from iridium salt, and the salt ion concentration is 19 mol/L; the iridium salt is selected from one or more of iridium acetate, iridium nitrate or iridium chloride.
12. The method of claim 10 for preparing a high performance integrated oxygen evolution reaction electrode material, wherein: the drying step is drying at 50-80 ℃ for 2-24h.
13. The method of claim 10 for preparing a high performance integrated oxygen evolution reaction electrode material, wherein: the roasting atmosphere is air, the temperature is 150-250 ℃, and the roasting time is 0.5-3h.
14. A high-performance integrated oxygen evolution reaction electrode material is characterized in that: obtained by the preparation process according to any one of claims 1 to 13.
15. The high performance integrated oxygen evolution reaction electrode material according to claim 14, characterized in that: the electrode material includes noble metal element active sites with edge-shared MnO 6 Manganese oxide crystal structure of octahedral structural elements and a corrosion-resistant high-conductivity three-dimensional electrode material substrate.
16. The application of the high-performance integrated oxygen evolution reaction electrode material is characterized in that: the high-performance integrated oxygen evolution reaction electrode material is used as an anode material of an acidic aqueous solution electrolytic cell.
CN202210932416.1A 2022-08-04 2022-08-04 High-performance integrated oxygen evolution reaction electrode material, preparation method and application Pending CN115369444A (en)

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