CN110813321A - Preparation method and application of Ag-supported MnS embedded flexible electrode material - Google Patents

Preparation method and application of Ag-supported MnS embedded flexible electrode material Download PDF

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CN110813321A
CN110813321A CN201911073376.4A CN201911073376A CN110813321A CN 110813321 A CN110813321 A CN 110813321A CN 201911073376 A CN201911073376 A CN 201911073376A CN 110813321 A CN110813321 A CN 110813321A
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尤俊华
王璐
赵耀
鲍婉婷
孟庆宇
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Shenyang University of Technology
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Abstract

The invention belongs to the field of energy materials, and particularly relates to a preparation method of an Ag-supported MnS embedded flexible electrode material. The preparation process is simple, the prepared material has porous pore canals, the specific surface area is large, the appearance is novel, the catalytic materials with different nano-scales and appearances and different catalytic performances can be prepared by adjusting positive and negative voltages, and the electrode can be popularized as a flexible wearable electrode material by selecting carbon cloth which can be folded for many times, and can be widely applied to the fields of energy conversion and storage, hydrogen production by full hydrolysis, oxygen production and the like.

Description

Preparation method and application of Ag-supported MnS embedded flexible electrode material
Technical Field
The invention belongs to the field of energy materials, and particularly relates to an Ag-supported MnS embedded flexible electrode material which not only can meet the application of a capacitive energy storage material, but also has a potential application space in the aspects of full hydrolysis hydrogen production and oxygen production.
Background
As energy consumption and environmental problems are increased due to the use of a large amount of fossil fuels, it is urgent to find some effective methods for utilizing and converting clean energy such as solar energy and electric power. Among them, the decomposition of water into hydrogen and oxygen by electricity is one of the most important methods to solve the future shortage of chemical fuels and to reduce environmental pollution associated with fossil fuel consumption. Water splitting consists of two half-reactions, namely the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER).
Transition metals have been extensively studied to date due to their abundance and low cost. Transition metal compounds such as bare metals, oxides, double hydroxides and sulfides have proven to be alternatives to OER catalysts. Furthermore, self-growth of materials on highly conductive substrates (such as Mn foams and carbon cloths) has proven to be an effective means of increasing OER activity. The laminated flexible multilayer structure is constructed, so that the overpotential generated by the interface resistance can be effectively eliminated.
CN109321959A discloses an electrochemical preparation method of nano Ag embedded electrode material, Co is prepared3O4By means of heating stripsTherefore, the Ag nano-rods can agglomerate at high temperature, and finally the conductivity of the nano-wires is reduced.
CN107275577A discloses a flexible electrode material, a preparation method and an application thereof, the flexible electrode is prepared by an electrostatic spinning method, the electrostatic spinning needs to be greatly influenced by the outside, the yield is low, no conductive supporting material is arranged in the flexible material, and the unit area single-loading capacity is small.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of an Ag-supported MnS embedded flexible electrode material, which forms a single-layer or multi-layer Ag/MnS structure by controlling the electrodeposition time and times so as to generate the required electrocatalysis effect.
The technical scheme of the invention is as follows:
a preparation method of an Ag-supported MnS embedded flexible electrode material comprises the following steps:
(1) dissolving silver nitrate in deionized water, wherein the using amount of the deionized water is 5-10 times of the molar weight of the silver nitrate, and uniformly mixing to obtain a solution A;
(2) dissolving ammonia water in deionized water, wherein the using amount of the deionized water is 10-20 times of the molar weight of the ammonia water, and uniformly stirring to obtain a solution B;
(3) dissolving sodium dodecyl sulfate in an alcohol solution, wherein the molar weight of the alcohol solution is 10-20 times of that of dodecylamine, and preparing a solution C; uniformly stirring the solution A and the solution B, slowly pouring the solution C, and performing ultrasonic treatment for 30-60 min; standing to obtain a solution D;
(4) mixing MnCl2·4H2Dissolving O in deionized water, wherein the dosage of the deionized water is MnCl2·4H2Adding 1.2 times of MnCl into the mixture 20-30 times of the molar weight of O2·4H2Thiourea with the molar weight of O is evenly stirred to obtain a solution E;
(5) preparing an original Ag support material in a D solution by an electrodeposition method by taking carbon cloth as a working electrode, a Pt electrode as a counter electrode and a saturated calomel electrode as a reference electrode, wherein the voltage of a positive direct current electric field and a negative direct current electric field is-10V to +10V, and the reaction time is 30s-90 s; rinsing and vacuum drying to obtain a product F;
(6) putting the product F into the solution E, taking the Pt electrode as a counter electrode, carrying out electrodeposition for 30-90 s, rinsing, and blow-drying to form an Ag/MnS electrode embedded with silver;
(7) and (5) repeating the steps (5) and (6) for 1-3 times to obtain the Ag-supported MnS embedded flexible electrode material.
And (3) magnetically stirring in the steps (1), (2) and (4), wherein the stirring speed is 500r/min-800 r/min.
In the step (2), the concentration of the ammonia water is 25%, and the ratio of the silver nitrate to the ammonia water is 1:1-1: 3.
The molar weight of the sodium dodecyl sulfate in the step (3) is 0.5-1 time of that of the silver nitrate;
the alcohol solution in the step (3) can be alcohol with small molecular weight such as methanol, ethanol, propanol, butanol and the like.
MnCl in the step (4)2·4H2The molar weight of O is 2 to 5 times of the molar weight of silver nitrate.
In the step (5), the carbon cloth is 1cm multiplied by 1 cm.
The carbon cloth electrode was carefully rinsed 3-5 times with deionized water and ethanol in steps (5) and (6).
The Ag-supported MnS embedded flexible electrode material can be applied to hydrogen production catalysts and capacitor materials by full decomposition.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the Ag-supported MnS embedded flexible electrode material, the shape and the structure of a nano material precipitated by a chemical reaction can be effectively controlled through controlling the electrodeposition time and controlling the magnitude and the direction (positive and negative voltages) of direct current voltage, so that the controllable preparation of different shapes of Ag/MnS embedding is realized; the electrodeposition time is short, so that the precipitated silver can present different nanometer appearances and scales, and the nanometer structure materials with different requirements can be obtained; the microstructure of the prepared material can be adjusted by controlling the electro-deposition of different times, and single-layer and multi-layer Ag/MnS structures can be formed to generate the required catalytic effect and capacitance; the preparation process is simple, the prepared material has porous pore channels, the specific surface area is large, the appearance is novel, the catalytic materials with different nano-scales and appearances and different catalytic performances can be prepared by adjusting positive and negative voltages, and the electrode can be popularized as a flexible wearable electrode material by selecting carbon cloth which can be folded for many times, and can be widely applied to the fields of energy conversion and storage, catalysis and the like.
Drawings
FIG. 1 is a scanning electron micrograph of the material prepared in example 1.
FIG. 2 is a scanning electron micrograph of the material prepared in example 2.
FIG. 3 is a scanning electron micrograph of the material prepared in example 3.
Figure 4 is a graph of HER activity for the different examples tested.
FIG. 5 is a graph of OER activity for various examples.
FIG. 6 is a graph of CV curves of planar capacitors prepared in different examples.
Detailed Description
To date, many methods have been used to prepare composites, such as the patent of Guo Rui et al, Qinhuang island, northeast university, an electrochemical preparation method of nano-Ag embedded electrode materials (application No. 201811236257.1). The carbon cloth adopted by the invention as the electrolyte carrier has wider applicability, and is embodied in flexible materials, larger specific surface area and stronger single-loading capacity. Different from the patents, the preparation method is completely prepared at normal temperature and normal pressure in the preparation process, and does not adopt any heating condition. In the electrochemical preparation method of nano Ag embedded electrode material, applied in Guo Rui et al, Co is prepared3O4By adopting a heating condition, the Ag nano-rod can agglomerate at a high temperature, and finally the conductivity of the nano-wire is reduced. Furthermore, the sulfides employed in the present invention have better activity than the oxides due to low coordination at the edges of the particles. The S atom is more active, which makes Ag/Co3O4The ORE over-potential of the prepared sample is 366mV, while the ORE over-potential of the nano Ag/MnS flexible electrode material prepared by the carbon cloth applied by the invention is 185 mV.
In addition, the patent of Gaoyu, et al, of Jilin university essentially differs from the method of preparing a flexible electrode by an electrostatic spinning method, which requires a large external influence on electrostatic spinning, and has low yield, no conductive support material inside the flexible material, and small unit area and single loading. The invention introduces the nano Ag as the inter-particle conductive material, so as to improve the inter-particle conductivity, inhibit the particle growth and enable the material particles to be nano. The Ag rods are used as conductive materials among particles, so that the unit area single-loading capacity is more, the preparation method is more suitable for preparing large-current devices, and samples prepared by the electro-deposition method are short in period, strong in adhesive force and better in cycle stability.
The Ag-supported MnS embedded flexible electrode material is prepared by adopting different external voltage electrodeposition methods and is used for HER and OER electrocatalysis. The material is deposited on the flexible material carbon cloth, and the result shows that MnS grown on the carbon cloth and the Ag layer has completely different appearances. When Ag/MnS is electrodeposited for 2 times alternately, a sheet-rod interweaving structure is presented, Ag presents a nanowire structure, and MnS presents a sheet layer. Due to this unique 3D layering and the large number of active sites on the outermost layer, the prepared flexible material shows very high catalytic activity towards HER and OER reactions.
The present invention will be described in detail with reference to the following embodiments and drawings, but the scope of the present invention is not limited by the embodiments and drawings.
Example 1
(1) Dissolving 1mmol of silver nitrate in 10mmol of deionized water, magnetically stirring for 30min at the stirring speed of 700r/min, and mixing uniformly to obtain solution A.
(2) Dissolving 1mmol of ammonia water in 20mmol of deionized water, magnetically stirring for 30min at the stirring speed of 700r/min, and mixing uniformly to obtain solution B.
(3) 0.5mmol of sodium dodecyl sulfate is dissolved in 5mmol of ethanol solution, and solution C is prepared after the sodium dodecyl sulfate is completely dissolved. Mixing A and B, slowly pouring the solution C, and performing ultrasonic treatment for 30 min; standing to obtain a solution D.
(4) 2mmol of MnCl2·4H2O was dissolved in 40mmol of deionized water, and 1.2 times M was addednCl2·4H2And (3) thiourea with the molar weight of O is magnetically stirred and uniformly mixed to prepare a solution E.
(5) And (2) preparing an original Ag support material in the solution D by using carbon cloth (1cm multiplied by 1cm) as a working electrode, a Pt electrode as a counter electrode and a saturated calomel electrode as a reference electrode through an electrodeposition method, adding a voltage of a direct current electric field +5V, reacting for 30s, and carefully rinsing the carbon cloth electrode for 3 times by using deionized water and ethanol to obtain a product F.
(6) And putting the product F into the solution E, using a Pt electrode as a counter electrode, and after electrodeposition for 30s, carefully rinsing with deionized water and ethanol for several times to form the Ag-supported MnS embedded flexible electrode material.
FIG. 1 is a scanning electron micrograph of the material prepared in example 1, FIG. 4 is a graph of HER activity measured in various examples, and FIG. 5 is a graph of OER activity measured in various examples.
As shown in FIG. 1, the prepared Ag/MnS electrode material embedded with silver is of a sheet-rod structure, the thickness of the sheet layer is 200 nanometers, the length of the rod is 50nm, the dispersion is uniform, and the boundary is unclear;
the electro-catalysis hydrogen evolution and oxygen evolution performance of the Ag/MnS embedded flexible electrode material is tested by adopting a three-electrode system, a Pt sheet is taken as a counter electrode, a Saturated Calomel Electrode (SCE) is taken as a reference electrode, and a working electrode is an ITO electrode of which the surface is dropwise coated with the Ag/MnS embedded flexible electrode material; the testing instrument is a PARSTAT 2273 electrochemical workstation; the test solution was 1mol/L KOH.
Fig. 4 is a HER curve, the starting point of the curve curving downward representing the starting potential for hydrogen production by reduction, the smaller the better. The slope of the bend represents the reduction rate versus overpotential, with larger being better.
Fig. 5 is an OER curve, and the starting point of the curve curving upward represents the starting potential for hydrogen production by oxidation, the smaller the better. The slope of the bend represents the reduction rate versus overpotential, with larger being better.
Example 2
(1) Dissolving 1mmol of silver nitrate in 10mmol of deionized water, magnetically stirring for 60min at the stirring speed of 800r/min, and uniformly mixing to obtain a solution A.
(2) Dissolving 3mmol of ammonia water in 30mmol of deionized water, magnetically stirring for 60min at the stirring speed of 800r/min, and mixing uniformly to obtain solution B.
(3) Dissolving 1mmol of sodium dodecyl sulfate in 15mmol of methanol solution, and obtaining solution C after the sodium dodecyl sulfate is completely dissolved. Mixing A and B, slowly pouring the solution C, carrying out ultrasonic treatment for 30min, and standing to obtain a solution D.
(4) Adding 5mmol of MnCl2·4H2O is dissolved in 100mmol of deionized water, 1.2 times of MnCl is added2·4H2And (3) thiourea with the molar weight of O is magnetically stirred and uniformly mixed to prepare a solution E.
(5) And (2) preparing an original Ag support material in the solution D by using carbon cloth (1cm multiplied by 1cm) as a working electrode, a Pt electrode as a counter electrode and a saturated calomel electrode as a reference electrode through an electrodeposition method, adding a voltage of a direct current electric field +10V, reacting for 30s, and carefully rinsing the carbon cloth electrode for 3 times by using deionized water and ethanol to obtain a product F.
(6) And putting the product F into the solution E, taking the Pt electrode as a counter electrode, carrying out electrodeposition for 30s, carefully rinsing for several times by using deionized water and ethanol, and drying by blowing to form the Ag/MnS electrode embedded with silver.
(7) And (5) repeating the steps (5) and (6) for 2 times, so that the Ag-supported MnS embedded flexible electrode material can be formed.
FIG. 2 is a scanning electron microscope image of the material prepared in example 2, and it can be seen from FIG. 2 that the prepared Ag/MnS electrode material has a sheet-rod structure, uniform pore size, 100 nm sheet thickness, 50nm rod length, uniform dispersion and clear boundary; figure 4 is a HER curve from which HER performance was best seen with 2 repeated depositions. FIG. 5 is an OER curve from which the best OER performance is seen with 2 repeated depositions. The catalyst prepared by the embodiment has the advantages of fast surface transmission, minimum charge transfer resistance and key role of the catalytic activity charge transfer speed in the catalytic process.
Example 3
(1) Dissolving 1mmol of silver nitrate in 10mmol of deionized water, magnetically stirring for 30min at the stirring speed of 800r/min, and mixing uniformly to obtain solution A.
(2) Dissolving 2mmol of ammonia water in 20mmol of deionized water, magnetically stirring for 30min at the stirring speed of 800r/min, and mixing uniformly to obtain solution B.
(3) 0.8mmol of sodium dodecyl sulfate is dissolved in 15mmol of butanol solution, and solution C is prepared after the sodium dodecyl sulfate is completely dissolved. Mixing A and B, slowly pouring the solution C, and performing ultrasonic treatment for 30 min; standing to obtain a solution D.
(4) 3mmol of MnCl2·4H2O is dissolved in 60mmol of deionized water, and 1.2 times of MnCl is added2·4H2And (3) thiourea with the molar weight of O is magnetically stirred and uniformly mixed to prepare a solution E.
(5) And (2) preparing an original Ag support material in the solution D by using carbon cloth (1cm multiplied by 1cm) as a working electrode, a Pt electrode as a counter electrode and a saturated calomel electrode as a reference electrode through an electrodeposition method, adding a voltage of a direct current electric field +8V, reacting for 30s, and carefully rinsing the carbon cloth electrode for 3 times by using deionized water and ethanol to obtain a product F.
(6) And putting the product F into the solution E, taking a Pt electrode as a counter electrode, carrying out electrodeposition for 30s, carefully rinsing for several times by using deionized water and ethanol, and blow-drying to form the Ag-supported MnS embedded flexible electrode material.
(7) And (5) repeating the steps (5) and (6) for 3 times, and forming the Ag-supported MnS embedded flexible electrode material.
FIG. 3 is a scanning electron micrograph of the material prepared in example 3, FIG. 4 is a HER curve, and FIG. 5 is an OER curve.
As can be seen from FIG. 3, the Ag-supported MnS embedded flexible electrode material structure nanosheets prepared by repeating the electrodeposition for 3 times are relatively compact and have relatively large blocks. The charge transfer resistance of this embodiment is large, and the diffusion behavior of the electrochemically active species on the surface is difficult.
Example 4
(1) Dissolving 1mmol of silver nitrate in 10mmol of deionized water, magnetically stirring for 30min at the stirring speed of 700r/min, and mixing uniformly to obtain solution A.
(2) Dissolving 1mmol of ammonia water in 20mmol of deionized water, magnetically stirring for 30min at the stirring speed of 700r/min, and mixing uniformly to obtain solution B.
(3) 0.5mmol of sodium dodecyl sulfate is dissolved in 5mmol of propanol solution, and after the sodium dodecyl sulfate is completely dissolved, solution C is prepared. Mixing A and B, slowly pouring the solution C, carrying out ultrasonic treatment for 30min, and standing to obtain a solution D.
(4) 2mmol of MnCl2·4H2O was dissolved in 40mmol of deionized water, and 1.2 times of MnCl was added2·4H2And (3) thiourea with the molar weight of O is magnetically stirred and uniformly mixed to prepare a solution E.
(5) And (2) preparing an original Ag support material in the solution D by using carbon cloth (1cm multiplied by 1cm) as a working electrode, a Pt electrode as a counter electrode and a saturated calomel electrode as a reference electrode through an electrodeposition method, applying a voltage of-5V of a direct current electric field for reaction for 30s, and carefully rinsing the carbon cloth electrode for 3 times by using deionized water and ethanol to obtain a product F.
(6) Putting the product F into the solution E, taking a Pt electrode as a counter electrode, after electrodeposition for 30s, carefully rinsing for several times by deionized water and ethanol, and blow-drying to form Ag/Mn embedded with silver3S2And an electrode.
Fig. 6 is a capacitance test curve of the material prepared in example 4, and it can be seen from the CV curve that the planar capacitance of the prepared electrode is small. Two oxidation-reduction peaks exist in the scanning range of the active substance, which respectively correspond to Ag+Ag and Mn3+/Mn2+An electrical pair. This greatly enhances the pseudocapacitance of the electrode, where the sample was deposited 2 times with Ag/MnS capacitance maximized.
Comparative example 1 (Nano Ag/Co)3O4Preparation of Flexible electrode Material
The patent of Qinhuangdai of northeast university Guo Rui et al, an electrochemical preparation method of nano Ag embedded electrode material (application number 201811236257.1), firstly obtaining original Co by electrodeposition method3O4Nanosheet array of virgin Co3O4Calcining the nano-sheet array at 400-500 ℃ for 1-2 hours to convert the nano-sheet array into Co3O4A nanosheet of (a); secondly, supporting Co by electrodepositing multi-layer nano Ag on the basis of the above3O4Nanosheets, multilayered Co3O4And supporting and fixing the nano sheets by virtue of nano Ag to prepare the nano Ag embedded electrode material. The patent adopts heating conditions in the process of preparing Co3O4, which leads Ag nano-rods to agglomerate at high temperature, and finally leads the conductivity of the nano-wires to be reduced.
The invention is different from the patent, firstly, the invention adopts the carbon cloth as the electrolyte carrier, has wider applicability, the prepared material has larger specific surface area and stronger single-loading capacity, and the carbon cloth is used as a flexible material, and has wider application space. Secondly, different from the above patents, the preparation method of the invention is completely prepared at normal temperature and normal pressure without any heating condition. Furthermore, the sulfides employed in the present invention have better activity than the oxides due to low coordination at the edges of the particles. And compared with an O atom, the S atom has stronger activity and better catalytic effect by adopting the S atom as an active site. The ORE over-potential of a sample prepared from Ag/Co3O4 is 366mV, while the ORE over-potential of a nano Ag/MnS flexible electrode material prepared from carbon cloth applied by the invention is 185 mV.
Comparative example 2
The patent of Gaoyu, et al, Jilin university, a flexible electrode material and a preparation method thereof, which are applied to the preparation of the flexible electrode by an electrostatic spinning method, are different from the method essentially. Electrospinning requires several steps through mixing, spinning, pre-oxidation and carbonization. The commercial application range of electrostatic spinning is limited in China and even all over the world, and the electrostatic spinning has the following points: 1. the production efficiency is low; 2. the control factors are complex and changeable; 3. the equipment cost is high; 4. the consistency of the product is relatively unstable. In comparative example 2, the diameter of the electrospun filament is generally about 150nm or more, and many factors affect the morphology and properties of the electrospun material, such as voltage, flow rate, spinning distance, and it is difficult to control the particle size of the filament, and the yield is low. In comparative example 2, the flexible material was prepared without a conductive support material inside, and the unit area monodispersity was small.
Compared with the comparative example 2, the invention introduces the nano Ag as the inter-particle conductive material, so as to improve the inter-particle conductivity, inhibit the particle growth and enable the material particles to be nano. The Ag rods are used as conductive materials among particles, so that the unit area single-loading capacity is more, the preparation method is more suitable for preparing large-current devices, and samples prepared by the electro-deposition method are short in period, strong in adhesive force and better in cycle stability.
In conclusion, the preparation method and the shape of the MnS powder reported in the present stage are different from those of the invention. The embedded electrode material prepared by the invention does not adopt higher temperature and pressure in the preparation process, well overcomes the defects of the existing material preparation, ensures the safety in the preparation process, and is a flexible electrode material. In addition, the embedded quasi-three-dimensional electrode material prepared by the invention can regulate and control the appearance and size of a product by regulating and controlling the electrodeposition time, and is beneficial to improving the electrochemical performance of the product. The material can be popularized as a flexible wearable electrode material and widely applied to energy conversion and storage, hydrogen production by full hydrolysis and oxygen production.

Claims (9)

1. A preparation method of an Ag-supported MnS embedded flexible electrode material comprises the following steps:
(1) dissolving silver nitrate in deionized water, wherein the using amount of the deionized water is 5-10 times of the molar weight of the silver nitrate, and uniformly mixing to obtain a solution A;
(2) dissolving ammonia water in deionized water, wherein the using amount of the deionized water is 10-20 times of the molar weight of the ammonia water, and uniformly stirring to obtain a solution B;
(3) dissolving sodium dodecyl sulfate in an alcohol solution, wherein the molar weight of the alcohol solution is 10-20 times of that of dodecylamine, and preparing a solution C; uniformly stirring the solution A and the solution B, slowly pouring the solution C, and performing ultrasonic treatment for 30-60 min; standing to obtain a solution D;
(4) mixing MnCl2·4H2Dissolving O in deionized water, wherein the dosage of the deionized water is MnCl2·4H2Adding 1.2 times of MnCl into the mixture 20-30 times of the molar weight of O2·4H2Thiourea with the molar weight of O is evenly stirred to obtain a solution E;
(5) preparing an original Ag support material in a D solution by an electrodeposition method by taking carbon cloth as a working electrode, a Pt electrode as a counter electrode and a saturated calomel electrode as a reference electrode, wherein the voltage of a positive direct current electric field and a negative direct current electric field is-10V to +10V, and the reaction time is 30s-90 s; rinsing and vacuum drying to obtain a product F;
(6) putting the product F into the solution E, taking the Pt electrode as a counter electrode, carrying out electrodeposition for 30-90 s, rinsing, and blow-drying to form an Ag/MnS electrode embedded with silver;
(7) and (5) repeating the steps (5) and (6) for 1-3 times to obtain the Ag-supported MnS embedded flexible electrode material.
2. The method according to claim 1, wherein the magnetic stirring is performed in steps (1), (2) and (4) at a rotation speed of 500-800 r/min.
3. The method according to claim 1, wherein the concentration of the ammonia water in the step (2) is 25%, and the ratio of the silver nitrate to the ammonia water is 1:1 to 1: 3.
4. The method according to claim 1, wherein the molar amount of sodium lauryl sulfate in the step (3) is 0.5 to 1 times the molar amount of silver nitrate.
5. The method according to claim 1, wherein the alcohol solution in step (3) is a small molecular weight alcohol such as methanol, ethanol, propanol, butanol, etc.
6. The method according to claim 1, wherein the MnCl is used in the step (4)2·4H2The molar weight of O is 2 to 5 times of the molar weight of silver nitrate.
7. The production method according to claim 1, wherein the carbon cloth in the step (5) is 1cm x 1 cm.
8. The method of claim 1, wherein the carbon cloth electrode is carefully rinsed 3 to 5 times with deionized water and ethanol in the steps (5) and (6).
9. An application of an Ag-supported MnS embedded flexible electrode material in flexible wearable electrode materials, full-hydrolysis hydrogen production catalysts, capacitor materials, energy conversion and storage.
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