CN112017872A - Preparation method and application of two-dimensional nickel hydroxide nanosheet electrode - Google Patents
Preparation method and application of two-dimensional nickel hydroxide nanosheet electrode Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a preparation method and application of a two-dimensional nickel hydroxide nanosheet electrode, which comprises the following steps: na (Na)4Ni3P4O15Synthesizing powder, preparing electrochemical slurry, preparing an electrode, and treating the electrode with an alkaline solution. The electrode prepared by the invention treats the current collector by alkaline solution to enable Na4Ni3P4O15And (4) converting to form a two-dimensional nickel hydroxide nanosheet layer, namely a novel electrochemical active material Ni-LH (Ni layered hydroxide). The nickel hydroxide prepared by in-situ synthesis is a distorted two-dimensional nanosheet layer, has a large surface area and can form good contact with a conductive material, so that the nickel hydroxide can be applied to the manufacturing field of electrocatalysis and energy storage equipment, and compared with the existing nickel hydroxide and ruthenium dioxide, the nickel hydroxide prepared by in-situ synthesis is a distorted two-dimensional nanosheet layerThe prepared electrode has lower overvoltage in the water electrolysis process of oxygen evolution reaction in a high-alkaline medium.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis materials, and particularly relates to a preparation method and application of a two-dimensional nickel hydroxide nanosheet electrode.
Background
The activity of Oxygen Evolution Reactions (OERs) in the electrolysis of water over iridium and ruthenium oxide based catalysts is one of the most active reactions known to date. The intrinsic activity and mass activity of the various forms of iridium oxide and ruthenium oxide when electrolyzed in alkaline solutions depends on their content and active surface area. The initial electrolysis voltage of these catalysts is only 1.3V (theoretical value 1.23V), but the overvoltage of Oxygen Evolution Reaction (OER) increases rapidly as the activity of these catalysts decreases during use. In addition, ruthenium oxide has also been proposed as a material for the cathode of a supercapacitor. However, the high cost and low natural distribution of iridium and ruthenium severely hamper the widespread use of these oxides and metals in industrial electrolysis of water or energy storage devices.
Transition metal oxides and hydroxides, particularly nickel hydroxide, are well known as lower cost cathode materials for OER electrocatalysts and supercapacitors. Nickel hydroxide is one of the most promising modern materials in electrochemical applications, and its performance depends on the method by which it is made into an electrode.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method and application of a two-dimensional nickel hydroxide nanosheet electrode.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a two-dimensional nickel hydroxide nanosheet electrode comprises the following steps:
(1)Na4Ni3P4O15synthesis of powder: dissolving nickel nitrate, ammonium dihydrogen phosphate and sodium phosphate in deionized water to form a mixed solution, and adding concentrated ammonia water while stirring to adjust the pH value of the solution6.8 to 7.2, evaporating the solution to dryness, heating the obtained powder to 550-650 ℃, calcining for 1.5 to 2.5 hours, and cooling to obtain light yellow Na4Ni3P4O15Powder;
(2) preparing electrochemical slurry: mixing the Na4Ni3P4O15Mixing the powder, the carbon conductive powder and the adhesive, adding a proper amount of N-methyl pyrrolidone, and stirring until uniform paste is formed to obtain the electrochemical slurry;
(3) preparing an electrode: uniformly coating the electrochemical slurry on the surface of a current collector, and drying in vacuum;
(4) treating the electrode with an alkali solution: and soaking the working part of the dried electrode in an alkaline solution, cleaning the working part of the electrode with deionized water, and drying the electrode in vacuum to obtain the two-dimensional nickel hydroxide nanosheet electrode.
Furthermore, in the step (1), the mass ratio of the elements in the mixed solution is Na: Ni: P ═ 4:3: 4.
Further, Na described in the step (1)4Ni3P4O15The diameter of the powder is 0.3-0.7 mm.
Na produced by the invention4Ni3P4O15The powder was all pale yellow round pellet.
The chemical equation generated during calcination in step (1) is as follows:
Na4P2O7+3Ni(NO3)2+2NH4H2PO4+2.5O2→Na4Ni3P4O15+8NO2+6H2O
further, in the step (2), 50-85% of Na is added according to the mass percentage4Ni3P4O15Powder, 10-40% of carbon conductive powder and 5-10% of adhesive.
Further, the carbon conductive powder is acetylene black, graphite or high-conductivity carbon, and the adhesive is an inert polymer. ,
further, the binder is polyvinylidene fluoride.
Further, the current collector in the step (3) is a grid or foam of dense metal, metal or alloy or a carbon material.
Further, the current collector in the step (3) is a titanium mesh, a nickel mesh, a stainless steel mesh or a foamed nickel mesh.
Further, the temperature of vacuum drying in the step (3) is 90-110 ℃, and the drying time is 22-26 h.
Further, the thickness of the electrochemical slurry coating in the step (3) is 0.1-3 mm.
Further, in the step (4), the alkaline solution accounts for 5-35% by mass, and is soaked for 1-3 hours, the temperature of the alkaline solution is 18-25 ℃, and the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution.
Further, washing for 12-18min for 2-4 times.
Further, the temperature of vacuum drying in the step (4) is 90-110 ℃, and the drying time is 22-26 h.
The reaction equation of the gold medal of the electrode in the alkaline solution in the step (4) is as follows:
Na4Ni3P4O15+8NaOH→3Ni(OH)2↓+4Na3PO4+H2O；
Na4Ni3P4O15+8KOH→3Ni(OH)2↓+4NaK2PO4+H2O。
the electrochemical capacity of the electrode prepared by the invention is reversible and the electrochemical transformation has probability
The transition occurs in a voltage window of 0 to 0.6V relative to Hg/HgO, in particular as a charge
And discharge of
With further increase in voltage in the aqueous medium, electricityThe polarization begins and oxygen evolution reaction occurs, and the two-dimensional nickel hydroxide nanosheet begins to exhibit the function of the OER electrocatalyst. The high efficiencies of the electrodes described in the present invention are attributable to the high surface area, high porosity and high conductivity of the two-dimensional nanoplates of the active material.
The electrode prepared by the method is applied to an oxygen evolution electrode or a cathode of an asymmetric super capacitor in the process of water electrolysis.
Compared with the prior art, the invention has the beneficial effects that:
(1) the electrode prepared by the invention treats the current collector by alkaline solution to enable Na4Ni3P4O15And (4) converting to form a two-dimensional nickel hydroxide nanosheet layer, namely a novel electrochemical active material Ni-LH (Ni layered hydroxide). The nickel hydroxide prepared by in-situ synthesis is a twisted two-dimensional nanosheet layer, has a large surface area and can form good contact with a conductive material (acetylene black and the like), so that the nickel hydroxide can be applied to the field of manufacturing of electrocatalysis and energy storage equipment, and compared with the existing nickel hydroxide and ruthenium dioxide, the electrode prepared by the method has lower overvoltage in the process of water electrolysis in an oxygen evolution reaction in a high-alkaline medium and has the overvoltage of 200 mA-cm & lt/100- & gt--2The overvoltage range is 290 mV and 330 mV. The electrode has high specific capacity in the voltage range of 0-0.6V and current density of 0.5-5 A.g-1Specific heat capacity within the range of 550-350 F.g-1；
(2) The nickel hydroxide on the electrode prepared by the method is converted in situ, is in a two-dimensional nanosheet form with high surface area, ensures the advantages of high surface area and high efficiency, can perform OER reaction for a long time, can be used for manufacturing a cathode material of a super capacitor and is IrO (iridium oxide) which is a commonly used raw material in industry2And RuO2Compared with the prior art, the brand-new electrode production method has outstanding advantages in terms of economy and sustainable development.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1a is an SEM image of an electrode prepared in example 1 of the present invention before soaking in KOH solution, when the electrode is used as a cathode of a capacitor;
FIG. 1b is an SEM image of an electrode prepared in example 1 of the present invention after soaking in KOH solution, when the electrode is used as a cathode of a capacitor;
FIG. 2a is a TEM image before KOH solution immersion when the electrode prepared in example 1 of the present invention is used as the cathode of a capacitor;
FIG. 2b is a TEM image of the electrode prepared in example 1 of the present invention after soaking in KOH solution, when it is used as the cathode of a capacitor;
FIG. 3a is an XRD pattern before immersion in KOH solution when the electrode prepared in example 1 of the present invention is used as a cathode of a capacitor;
FIG. 3b is an XRD pattern after immersion in KOH solution when the electrode prepared in example 1 of the present invention is used as a cathode of a capacitor;
FIG. 4a is an XPS plot of an electrode prepared in example 1 of the present invention before soaking in KOH solution when used as the cathode of a capacitor;
FIG. 4b is an XPS plot of an electrode prepared according to example 1 of the present invention after immersion in KOH solution, as the cathode of a capacitor;
FIG. 5 shows an electrode prepared according to example 1 of the invention and an industrial prototype electrode RuO2The polarization curve of (a);
FIG. 6 shows the current density of 10mA/cm of the electrode prepared in example 1 of the present invention-2An oxygen evolution overvoltage change diagram of the prepared electrode under the environment lasting for 20 hours;
FIG. 7 is a CV curve of an electrode prepared in example 4 of the present invention as a cathode of a supercapacitor;
FIG. 8 is a GCD curve of an electrode prepared according to example 4 of the present invention as the cathode of a supercapacitor;
FIG. 9 is a graph of specific capacitance versus current density for electrodes prepared in example 4 of the present invention as the cathode of a supercapacitor;
FIG. 10 is a graph of the electrode stability performance of the electrode prepared in example 4 of the present invention as the cathode of a supercapacitor after a charge-discharge cycle at a current density of 1A/g.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The embodiment of the invention provides a preparation method of a two-dimensional nickel hydroxide nanosheet electrode, which comprises the following steps:
(1)Na4Ni3P4O15synthesis of powder: 130.82g of nickel nitrate hexahydrate, 34.52g of ammonium dihydrogen phosphate and 66.92g of sodium diphosphate decahydrate are dissolved in deionized water to form a mixed solution, concentrated ammonia water is added while stirring to obtain a clear solution with the pH value of 7, the solution is evaporated and dried, the temperature is gradually increased to 180 ℃, the obtained powder is heated to 600 ℃ and calcined for 2 hours, and cooling is carried out to obtain light yellow round particle groups Na4Ni3P4O15Powder of Na4Ni3P4O15The diameter of the powder is 0.3-0.7 mm;
(2) preparing electrochemical slurry: according to the mass percent, the 85 percent of Na4Ni3P4O15Mixing the powder, 10% of acetylene black and 5% of polyvinylidene fluoride, adding a proper amount of N-methyl pyrrolidone, and stirring until a uniform paste is formed to obtain the electrochemical slurry;
(3) preparing an electrode: uniformly coating the electrochemical slurry on the surface of a current collector, wherein the current collector is carbon fiber and brand HCP331N, and drying in vacuum at 100 ℃ for 24 hours;
(4) treating the electrode with an alkali solution: and soaking the dried working part of the electrode in 30% KOH solution for 1h at the solution temperature of 18-25 ℃, cleaning the working part of the electrode with deionized water for 3 times, and drying the electrode in vacuum at the drying temperature of 100 ℃ for 24h to obtain the two-dimensional nickel hydroxide nanosheet electrode, wherein the cleaning is carried out for 15min each time.
Example 2
The embodiment of the invention provides a preparation method of a two-dimensional nickel hydroxide nanosheet electrode, which comprises the following steps:
(1)Na4Ni3P4O15synthesis of powder: 130.82g of nickel nitrate hexahydrate, 34.52g of ammonium dihydrogen phosphate and 66.92g of sodium diphosphate decahydrate are dissolved in deionized water to form a mixed solution, concentrated ammonia water is added while stirring to obtain a clear solution with the pH value of 6.8, the solution is evaporated and dried, the temperature is gradually increased to 180 ℃, the obtained powder is heated to 550 ℃ and calcined for 2.5 hours, and cooling is carried out to obtain light yellow round particle Na4Ni3P4O15Powder of Na4Ni3P4O15The diameter of the powder is 0.3-0.7 mm;
(2) preparing electrochemical slurry: according to the mass percent, mixing the 50 percent of Na4Ni3P4O15Mixing the powder, 40% of acetylene black and 10% of polyvinylidene fluoride, adding a proper amount of N-methyl pyrrolidone, and stirring until a uniform paste is formed to obtain the electrochemical slurry;
(3) preparing an electrode: uniformly coating the electrochemical slurry on the surface of a current collector, wherein the current collector is a foamed nickel net, and drying in vacuum at the temperature of 90 ℃ for 26 hours;
(4) treating the electrode with an alkali solution: and soaking the dried working part of the electrode in a NaOH solution with the mass fraction of 5% for 3h, wherein the solution temperature is 18-25 ℃, cleaning the working part of the electrode with deionized water for 2 times, each time for 18min, drying the electrode in vacuum, wherein the drying temperature is 90 ℃, and drying for 26h to obtain the two-dimensional nickel hydroxide nanosheet electrode.
Example 3
The embodiment of the invention provides a preparation method of a two-dimensional nickel hydroxide nanosheet electrode, which comprises the following steps:
(1)Na4Ni3P4O15synthesis of powder: 130.82g of nickel nitrate hexahydrate, 34.52g of ammonium dihydrogen phosphate and 66.92g of sodium diphosphate decahydrate are dissolved in deionized water to form a mixed solution, concentrated ammonia water is added while stirring to obtain a clear solution with the pH value of 7.2, the solution is evaporated and dried, the temperature is gradually increased to 180 ℃, the obtained powder is heated to 650 ℃ and calcined for 1.5h, and cooling is carried out to obtain light yellow round particle Na4Ni3P4O15Powder of Na4Ni3P4O15The diameter of the powder is 0.3-0.7 mm;
(2) preparing electrochemical slurry: according to the mass percent, 67.5 percent of Na is added4Ni3P4O15Mixing the powder, 25% of acetylene black and 7.5% of polyvinylidene fluoride, adding a proper amount of N-methyl pyrrolidone, and stirring until a uniform paste is formed to obtain the electrochemical slurry;
(3) preparing an electrode: uniformly coating the electrochemical slurry on the surface of a current collector, wherein the current collector is a titanium mesh, and drying in vacuum at the temperature of 110 ℃ for 22 h;
(4) treating the electrode with an alkali solution: and soaking the dried working part of the electrode in a NaOH solution with the mass fraction of 25% for 2h, wherein the solution temperature is 18-25 ℃, cleaning the working part of the electrode with deionized water for 4 times, each time for 12min, drying the electrode in vacuum, wherein the drying temperature is 110 ℃, and drying for 22h to obtain the two-dimensional nickel hydroxide nanosheet electrode.
Example 4
The preparation method of the two-dimensional nickel hydroxide nanosheet electrode in this embodiment is the same as that in embodiment 1, except that the current collector is a foamed nickel mesh.
Test example 1
When the electrode prepared in example 1 is used as a cathode of a capacitor, the SEM image before soaking in KOH solution is shown in FIG. 1a, and the SEM image after soaking is shown in FIG. 1 b;
when the electrode prepared in example 1 is used as the cathode of a capacitor, the TEM image before KOH solution soaking is shown in FIG. 2a, and the TEM image after soaking is shown in FIG. 2 b;
when the electrode prepared in example 1 is used as a cathode of a capacitor, the XRD pattern before soaking in KOH solution is shown in figure 3a, and the XRD pattern after soaking is shown in figure 3 b;
when the electrode prepared in example 1 was used as a cathode of a capacitor, the XPS pattern before KOH solution soaking was shown in fig. 4a, and the XPD pattern after soaking was shown in fig. 4 b.
The electrode prepared in example 1 was tested as an electrocatalyst for the evolution of oxygen during the water electrode process, using a three-electrode system, the electrode prepared in example 1 as anode, a platinum sheet as cathode and a Hg/HgO electrode as reference electrode, using an electrochemical workstation of model CHI760E (china). The polarization curves are shown in FIG. 5 (curve 1), and it can be seen from curve 1 in FIG. 5 that the resulting electrodes have oxygen evolution overvoltage of 355, 404 and 435mV at current densities of 100, 200 and 300mA/cm2, respectively. For comparison, a comparative electrode was made, which was an industrial prototype electrode made of IrO2 (Shanghai Aladdin reagent, China), "Super P" and PVDF based on HCP331N current collector, the polarization curve of which is shown in FIG. 5, Curve 2, and it can be seen from the data that the oxygen production threshold of the electrode made in accordance with the present invention was 17-20% lower than that of the industrial prototype.
The stability test of the electrode prepared in example 1 is shown in FIG. 6, and the calculation shows that the current density is 10mA/cm2The oxygen evolution overvoltage increased by only 0.2% when the electrolysis was continued for 20 hours under the conditions of (1). This indicates a high stability of the electrode.
The inventors also conducted the above experiments on electrodes prepared in other examples, and the results were substantially consistent and, due to the limited space, are not listed.
Test example 2
Example 4 electrode prepared as cathode for asymmetric supercapacitor
The test was carried out in a three-electrode system using a carbon electrode as anode and a Hg/HgO electrode as reference electrode, using an electrochemical workstation of model CHI760E (china).
The CV curve of the electrode prepared in example 4 as the cathode of the supercapacitor is shown in FIG. 7. from FIG. 7, it can be seen that two reversible peaks appear in the potential window of 0-0.6V at different scanning speeds, corresponding to the two reversible peaks
Is performed by electrochemical transformation.
The GCD curve of the electrode prepared in example 4 as the cathode of the supercapacitor is shown in FIG. 8, and the reversible charge-discharge curve has interval curves at different current densities, which shows that
Stability of the transition.
The specific capacitance versus current density of the electrode prepared in example 4 as the cathode of a supercapacitor is plotted in fig. 9, which data demonstrates the feasibility of the electrode as an asymmetric supercapacitor cathode, and fig. 9 shows the dependence of the specific capacitance of the electrode on the current density, which indicates the competitiveness of the electrode relative to the prototype. The electrode stability after a charge-discharge cycle at a current density of 1A/g is shown in FIG. 10, where the specific capacity is reduced by only 15% at a current density of 1A/g. This indicates that the prepared electrode is competitive with the industrial prototype.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A preparation method of a two-dimensional nickel hydroxide nanosheet electrode is characterized by comprising the following steps:
(1)Na4Ni3P4O15synthesis of powder: dissolving nickel nitrate, ammonium dihydrogen phosphate and sodium phosphate in deionized waterForming a mixed solution in water, adding concentrated ammonia water while stirring until the pH value of the solution is 6.8-7.2, evaporating the solution to dryness, heating the obtained powder to 550-650 ℃, calcining for 1.5-2.5h, and cooling to obtain light yellow Na4Ni3P4O15Powder;
(2) preparing electrochemical slurry: mixing the Na4Ni3P4O15Mixing the powder, the carbon conductive powder and the adhesive, adding a proper amount of N-methyl pyrrolidone, and stirring until uniform paste is formed to obtain the electrochemical slurry;
(3) preparing an electrode: uniformly coating the electrochemical slurry on the surface of a current collector, and drying in vacuum;
(4) treating the electrode with an alkali solution: and soaking the working part of the dried electrode in an alkaline solution, cleaning the working part of the electrode with deionized water, and drying the electrode in vacuum to obtain the two-dimensional nickel hydroxide nanosheet electrode.
2. The method for preparing a two-dimensional nickel hydroxide nanosheet electrode according to claim 1, wherein the mixed solution in step (1) contains the elements in a mass ratio of Na to Ni to P of 4 to 3 to 4.
3. The method for preparing two-dimensional nickel hydroxide nanosheet electrode according to claim 1, wherein the Na in step (1) is4Ni3P4O15The diameter of the powder is 0.3-0.7 mm.
4. The preparation method of a two-dimensional nickel hydroxide nanosheet electrode according to claim 1, wherein in step (2), 50-85% of Na is present in an amount of, by mass percent4Ni3P4O15Powder, 10-40% of carbon conductive powder and 5-10% of adhesive.
5. The method for preparing a two-dimensional nickel hydroxide nanosheet electrode of claim 1 or 4, wherein the carbon conductive powder is acetylene black, graphite or highly conductive carbon, and the binder is an inert polymer, preferably polyvinylidene fluoride.
6. A method for preparing a two-dimensional nickel hydroxide nanosheet electrode according to claim 1, wherein the current collector in step (3) is a grid of dense metal, metal or alloy or a foam or carbon material, preferably, the current collector is a titanium mesh, a nickel mesh, a stainless steel mesh or a foamed nickel mesh.
7. The preparation method of a two-dimensional nickel hydroxide nanosheet electrode according to claim 1, wherein the vacuum drying in step (3) is carried out at a temperature of 90-110 ℃ for a time of 22-26 h.
8. A method for preparing a two-dimensional nickel hydroxide nanosheet electrode as defined in claim 1, wherein the electrochemical slurry coating in step (3) is 0.1-3mm thick.
9. The preparation method of a two-dimensional nickel hydroxide nanosheet electrode according to claim 1, wherein in the step (4), the alkaline solution is 5-35% by mass, the soaking is carried out for 1-3h, the temperature of the alkaline solution is 18-25 ℃, the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution, preferably, the cleaning is carried out for 2-4 times, each time for 12-18min, preferably, the vacuum drying temperature is 90-110 ℃, and the drying is carried out for 22-26 h.
10. Use of an electrode prepared by the method of any one of claims 1 to 9 in the evolution of oxygen electrode or cathode of an asymmetric supercapacitor during electrolysis of water.
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| CN114334483A (en) * | 2021-12-31 | 2022-04-12 | 陕西师范大学 | Manganese-based mixed phosphate @ trimanganese tetroxide composite material with hierarchical structure for super capacitor |
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