阅读说明：本技术 一种Ag支撑MnS嵌入式柔性电极材料的制备方法及应用 (Preparation method and application of Ag-supported MnS embedded flexible electrode material ) 是由 尤俊华 王璐 赵耀 鲍婉婷 孟庆宇 于 2019-11-05 设计创作，主要内容包括：本发明属于能源材料领域,具体涉及一种Ag支撑MnS嵌入式柔性电极材料制备方法,通过电沉积时间、次数的的控制,形成单层及多层的纳米Ag/MnS结构,使其产生所需的电催化效果、比表面积、电容量。本发明制备工艺简单,制备出的材料具有多孔孔道,比表面积大,形貌新颖,通过正负电压的调节,可制备出具有不同纳米尺度及形貌、催化性能各异的催化材料,并且电极选用可折叠多次的碳布,可推广为柔性可穿戴电极材料,并广泛应用于能源转化与存储、全解水产氢、产氧等领域。(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.)

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.

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.