CN111847514B - Metal phase molybdenum disulfide, self-supporting electrode, preparation method and application - Google Patents

Metal phase molybdenum disulfide, self-supporting electrode, preparation method and application Download PDF

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CN111847514B
CN111847514B CN202010732763.0A CN202010732763A CN111847514B CN 111847514 B CN111847514 B CN 111847514B CN 202010732763 A CN202010732763 A CN 202010732763A CN 111847514 B CN111847514 B CN 111847514B
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molybdenum
self
molybdenum disulfide
supporting electrode
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CN111847514A (en
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李楠
刘志鹏
苑世盛
王凯雯
向丽娟
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Jilin University
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Abstract

The invention relates to the field of materials, and particularly discloses a metal phase molybdenum disulfide, a self-supporting electrode, a preparation method and application, wherein the metal phase molybdenum disulfide comprises the following raw materials: molybdenum trioxide (as a molybdenum source), a sulfur source, and an amount of a reducing agent and an amount of water; wherein the ratio of the number of molybdenum atoms in the molybdenum trioxide to the number of sulfur atoms in the sulfur source is 1: 5-40. According to the metal phase molybdenum disulfide provided by the embodiment of the invention, molybdenum trioxide is used as a molybdenum source, and a proper amount of sulfur source, reducing agent and water are used for hydrothermal synthesis to prepare the metal phase molybdenum disulfide, so that the content of the metal phase molybdenum disulfide in the product is high; the preparation method has the advantages of simple and safe operation, short preparation period and suitability for large-scale production, solves the problems of long preparation period and low safety of the existing method for synthesizing the metal phase molybdenum disulfide mostly by lithium ion stripping, and has wide market prospect.

Description

Metal phase molybdenum disulfide, self-supporting electrode, preparation method and application
Technical Field
The invention relates to the field of materials, in particular to a metal phase molybdenum disulfide, a self-supporting electrode, a preparation method and application.
Background
Molybdenum disulfide (MoS)2) Having a graphite-like layered structure, molybdenum disulfide can be divided into different crystal phases, i.e., a 1T phase and a 2H phase, depending on the coordination between S — Mo, the 2H phase being a typical semiconductor, and the 1T phase having a conductive ability similar to a conductor, and thus is also referred to as metallic phase molybdenum disulfide. From the perspective of practical application, the 1T phase has obvious advantages, and particularly has wide application prospects in the fields of electrocatalysis, battery electrodes, supercapacitors and the like, which relate to electron transfer. Generally, the metallic phase molybdenum disulfide is synthesized only artificially.
At present, the traditional method for synthesizing metal phase molybdenum disulfide is realized by lithium ion delamination, and specifically, the method is implemented by immersing 2H phase molybdenum disulfide powder in hexane solution of tert-butyl lithium, inserting lithium ions into a molybdenum disulfide layer, stirring or even heating is generally required in the process to accelerate the diffusion of a lithium ion intercalator between the molybdenum disulfide layers, and then ultrasonically dispersing the obtained molybdenum disulfide solid in water to form single-layer 1T phase molybdenum disulfide. However, the above method has the following disadvantages in practical use: 1) although under the action of heating and stirring, the diffusion rate of lithium ions between the molybdenum disulfide layers is still slow, so that the preparation period is long, and is generally 3 to 5 days; 2) because n-butyllithium is adopted as a raw material and some intermediate products involved in the lithium intercalation process are extremely flammable, the reaction has certain danger; 3) the reaction yield is small, and the product is dispersed in water, so that the practical application requirement is difficult to meet; 4) the reaction is carried out under an inert atmosphere, and a glove box or the like is required.
Disclosure of Invention
An embodiment of the present invention provides a metal phase molybdenum disulfide, so as to solve the problems that synthesis of the existing metal phase molybdenum disulfide proposed in the background art is mostly realized by lithium ion stripping, and the preparation period is long and the safety is low.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a metallic phase molybdenum disulfide comprising the following raw materials: molybdenum trioxide (as a molybdenum source), a sulfur source, and an amount of a reducing agent and an amount of water; wherein the ratio of the number of molybdenum atoms in the molybdenum trioxide to the number of sulfur atoms in the sulfur source is 1: 5-40.
As a further scheme of the invention: the concentration of the molybdenum trioxide in the first solution is 0.008-1 mmol.L-1The first solution is a mixed solution obtained by uniformly mixing the molybdenum trioxide, the sulfur source, the reducing agent and water.
As a still further scheme of the invention: the concentration of the molybdenum trioxide in the first solution is 0.008-0.32 mmol.L-1Or the concentration of the molybdenum trioxide in the first solution is 0.5-1 mmol.L-1。
As a still further scheme of the invention: the sulfur source is selected from one or more of thioacetamide or sodium sulfide.
As a still further scheme of the invention: the reducing agent is selected from any one or more of urea or hydrazine hydrate.
As a still further scheme of the invention: the water may be any one selected from purified water, mineral water, distilled water, deionized water, and soft water, and is not limited thereto and may be selected as needed.
Preferably, the water is deionized water.
Another object of an embodiment of the present invention is to provide a method for preparing molybdenum disulfide as a metal phase, including the following steps:
1) weighing molybdenum trioxide, a sulfur source and a reducing agent according to a proportion, adding the molybdenum trioxide, the sulfur source and the reducing agent into water, dissolving and uniformly mixing, and stirring to form a uniform mixed solution to obtain a first solution;
2) and placing the first solution in a closed environment for hydrothermal reaction, cooling, centrifugally separating, washing and drying to obtain the metal phase molybdenum disulfide.
As a still further scheme of the invention: the reaction temperature of the hydrothermal reaction is 160-240 ℃, and the reaction time is 4-24 hours.
Preferably, the reaction temperature of the hydrothermal reaction is 180 to 220 ℃ and the reaction time is 8 to 12 hours.
As a still further scheme of the invention: the concentration of molybdenum trioxide in the first solution is 0.008-1 mmol.L in terms of molybdenum atom-1。
As a still further scheme of the invention: the concentration of molybdenum trioxide in the first solution is 0.5-1 mmol.L in terms of molybdenum atom-1。
As a still further scheme of the invention: in the method for preparing the metal phase molybdenum disulfide, the washing may be performed by a method in the prior art, as long as impurities in the solid product can be removed, and for example, the solid phase molybdenum disulfide may be washed several times with ethanol, or washed several times with water and ethanol repeatedly, and the washing is not limited herein and may be selected as needed.
As a still further scheme of the invention: the preparation method of the metal phase molybdenum disulfide specifically comprises the following steps:
1) weighing molybdenum trioxide, a sulfur source and a reducing agent according to a proportion, adding the molybdenum trioxide, the sulfur source and the reducing agent into water, dissolving and uniformly mixing, and stirring to form a uniform mixed solution to obtain a first solution;
2) and transferring the first solution into a reaction kettle, sealing and then carrying out hydrothermal reaction at the temperature of 160-240 ℃ for 4-24 hours, after the reaction is finished, naturally cooling the reaction kettle, centrifugally separating a solid product, repeatedly cleaning the solid product with water and ethanol, and drying the solid product at the temperature of below 60 ℃ under a vacuum condition to obtain the metal phase molybdenum disulfide.
Another object of an embodiment of the present invention is to provide a metal phase molybdenum disulfide prepared by the above method for preparing metal phase molybdenum disulfide.
Another object of an embodiment of the present invention is to provide a self-supporting electrode (self-supporting structure electrode), in particular, a self-supporting electrode having a nano-array structure, wherein the self-supporting electrode is prepared by the above method for preparing metal phase molybdenum disulfide, and the method for preparing the self-supporting electrode further includes a step of immersing a conductive substrate containing a transition metal basic carbonate nano-array in the first solution based on the above method for preparing metal phase molybdenum disulfide.
As a still further scheme of the invention: the preparation method of the conductive substrate containing the transition metal carbonate hydroxide nano array can comprise the following steps: dissolving transition metal salt and a proper amount of nucleating agent in a mixed solution of water and ethanol, and preparing the basic carbonate array structure on the conductive substrate through hydrothermal/solvothermal synthesis.
As a still further scheme of the invention: the transition metal salt comprises cobalt nitrate (Co (NO)3)2·6H2O), cobalt chloride (CoCl)2·12H2O), the nucleating agent comprises urea and ammonium fluoride, and the conductive substrate comprises a titanium sheet and a carbon cloth.
Of course, the conductive substrate of the transition metal-containing basic carbonate nano-array can also adopt a synthesis method in the prior art or directly adopt the existing carbon cloth-loaded basic cobalt carbonate nano-array.
As a still further scheme of the invention: in the preparation method of the self-supporting electrode, the micro-morphology of the product can be controllably adjusted by changing the reaction time, the reactant concentration and the species.
As a still further scheme of the invention: in the preparation method of the self-supporting electrode, the molybdenum source is adjustedAmount of outer layer MoS can be changed2The thickness of the nanosheet. Wherein the concentration of molybdenum trioxide in terms of molybdenum atom in the first solution is 0.01 to 0.05 mmol.L-1More preferably, the concentration of molybdenum trioxide in terms of molybdenum atoms in the first solution is 0.008 to 0.32 mmol.L-1。
As a still further scheme of the invention: the micro-morphology of the product can be adjusted by changing the type and the dosage of the sulfur source, particularly, the effective regulation and control of the nano structure can be realized by changing the type and the dosage of the sulfur source, and the composite structure self-supporting electrode with a solid or hollow nano-wire structure is respectively prepared. Specifically, when the concentration of sodium sulfide is higher, the product is a solid nanorod consisting of 1T-MoS2And nano sheets are constructed. When the concentration of thioacetamide is higher, the product is a hollow nano rod, the inner layer is a hollow tube formed by cobalt sulfide, and the outer layer is 1T-MoS2And constructing the product. Wherein, preferably, the first structure (solid nanorods) is realized, the concentration of sodium sulfide is 15 mmol.L-1To 30 mmol. L-1Realizing the second structure (hollow nano rod), the dosage of the sodium sulfide is less than 2.5 mmol.L-1And the dosage of thioacetamide is more than 1.5 mmol.L-1。
Another object of the embodiments of the present invention is to provide an application of the above self-supporting electrode in hydrogen evolution by water electrolysis and/or preparation of a negative electrode material of a lithium ion battery.
As a still further scheme of the invention: the self-supporting electrode can be used as a lithium ion battery cathode material to prepare a flexible electronic device and can also be used for preparing an electrolytic water hydrogen evolution catalyst.
Compared with the prior art, the invention has the beneficial effects that:
according to the metal phase molybdenum disulfide provided by the invention, molybdenum trioxide is used as a molybdenum source, and a proper amount of sulfur source, reducing agent and water are used for carrying out hydrothermal synthesis to prepare the metal phase molybdenum disulfide, so that the content of the metal phase molybdenum disulfide in the product is high; the preparation method has the advantages of simple and safe operation, short preparation period and suitability for large-scale production, solves the problems of long preparation period and low safety of the existing method for synthesizing the metal phase molybdenum disulfide mostly by lithium ion stripping, and has wide market prospect.
Drawings
FIG. 1 shows a CoS according to an embodiment of the present invention2@1T-MoS2Scanning electron microscopy of nanowires.
FIG. 2 shows a CoS according to an embodiment of the present invention2@1T-MoS2Transmission electron microscopy of nanowires.
FIG. 3 shows a CoS according to an embodiment of the present invention2@1T-MoS2Linear sweep voltammogram of nanowires.
FIG. 4 shows a CoS according to an embodiment of the present invention2@1T-MoS2Scanning electron microscopy of hollow nanowires.
FIG. 5 shows a CoS according to an embodiment of the present invention2@1T-MoS2Transmission electron microscopy of hollow nanowires.
FIG. 6 shows a CoS according to an embodiment of the present invention2@1T-MoS2A charge-discharge cycle stability performance curve diagram of the hollow nanowire.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
A metal phase molybdenum disulfide is prepared by the following specific preparation method:
1) weighing 12mg of molybdenum trioxide, 500 mg of sodium sulfide, 14 mg of thioacetamide and 0.12 g of urea, dissolving in water, and stirring to form a uniform mixed solution to obtain a first solution;
2) transferring the first solution into a 50mL reaction kettle, sealing the reaction kettle, and placing the reaction kettle in an oven for hydrothermal reaction at 200 ℃ for 8 hours;
3) and naturally cooling to room temperature after the hydrothermal reaction is finished, centrifugally separating the obtained solid product, respectively washing the solid product with deionized water and ethanol for a plurality of times, collecting the solid product, and drying in vacuum to obtain the metal phase molybdenum disulfide powder.
Example 2
A metal phase molybdenum disulfide is prepared by the following specific preparation method:
1) weighing 14.4mg of molybdenum trioxide, 39mg of sodium sulfide and 0.12 g of urea, dissolving in water, and stirring to form a uniform mixed solution to obtain a first solution;
2) transferring the first solution into a 50mL reaction kettle, sealing the reaction kettle, and placing the reaction kettle in an oven for hydrothermal reaction at 160 ℃ for 4 hours;
3) and naturally cooling to room temperature after the hydrothermal reaction is finished, centrifugally separating the obtained solid product, respectively washing the solid product with deionized water and ethanol for a plurality of times, collecting the solid product, and drying in vacuum to obtain the metal phase molybdenum disulfide powder.
Example 3
A metal phase molybdenum disulfide is prepared by the following specific preparation method:
1) weighing 14.4mg of molybdenum trioxide, 312mg of sodium sulfide and 0.12 g of urea, dissolving in water, and stirring to form a uniform mixed solution to obtain a first solution;
2) transferring the first solution into a 50mL reaction kettle, sealing the reaction kettle, and placing the reaction kettle in an oven for hydrothermal reaction at 240 ℃ for 24 hours;
3) and naturally cooling to room temperature after the hydrothermal reaction is finished, centrifugally separating the obtained solid product, respectively washing the solid product with deionized water and ethanol for a plurality of times, collecting the solid product, and drying in vacuum to obtain the metal phase molybdenum disulfide powder.
Example 4
Compared with example 1, except that the concentration of the molybdenum trioxide in the first solution is 0.008 mmol.L-1Otherwise, the procedure was as in example 1.
Example 5
Compared with example 1, except that the concentration of the molybdenum trioxide in the first solution is 1 mmol.L-1Otherwise, the procedure was as in example 1.
Example 6
Compared with example 1, except that the concentration of the molybdenum trioxide in the first solution is 0.01 mmol.L-1Otherwise, the procedure was as in example 1.
Example 7
Compared with example 1, except that the concentration of the molybdenum trioxide in the first solution is 0.32 mmol.L-1Otherwise, the procedure was as in example 1.
Example 8
Compared with example 1, except that the concentration of the molybdenum trioxide in the first solution is 0.5 mmol.L-1Otherwise, the procedure was as in example 1.
Example 9
Compared with example 1, except that the concentration of the molybdenum trioxide in the first solution is 0.05 mmol.L-1Otherwise, the procedure was as in example 1.
Example 10
The same procedure as in example 1 was repeated, except that the hydrothermal reaction was carried out at a reaction temperature of 180 ℃ and a reaction time of 8 hours, as compared with example 1.
Example 11
The hydrothermal reaction was carried out at 220 ℃ for 12 hours as compared with example 1, and the reaction was carried out in the same manner as in example 1.
Example 12
The same procedure as in example 1 was repeated, except that the hydrothermal reaction was carried out at a reaction temperature of 200 ℃ and a reaction time of 10 hours, as compared with example 1.
Example 13
Same as example 1 except that urea was replaced with hydrazine hydrate as compared with example 1.
Example 14
The same as example 1 was repeated, except that urea was replaced with hydrazine hydrate to urea (the mass ratio of hydrazine hydrate to urea was 1: 1) as compared with example 1.
Example 15
The procedure of example 3 was followed, except that sodium sulfide was replaced with thioacetamide, in comparison with example 3.
Example 16
Dissolving transition metal salt and a proper amount of nucleating agent in a mixed solution of water and ethanol, and preparing a basic carbonate array structure on a conductive substrate by hydrothermal/solvothermal synthesis, wherein the transition metal salt comprises cobalt nitrate (Co (NO)3)2·6H2O), cobalt chloride (CoCl)2·12H2O), the nucleating agent comprises urea and ammonium fluoride, and the conductive substrate comprises a titanium sheet and carbon cloth.
Example 17
Dissolving transition metal salt and a proper amount of nucleating agent in a mixed solution of water and ethanol by adopting the existing method, and preparing the basic carbonate array structure on the conductive substrate by hydrothermal/solvothermal synthesis, wherein the transition metal salt is cobalt nitrate (Co (NO)3)2·6H2O), the nucleating agent is urea, and the conductive substrate is a carbon cloth.
Example 18
The method comprises the steps of dissolving transition metal salt and a proper amount of nucleating agent in a mixed solution of water and ethanol by adopting the existing method, and preparing the basic carbonate array structure on the conductive substrate through hydrothermal/solvothermal synthesis, wherein the transition metal salt is cobalt chloride, the nucleating agent is urea, and the conductive substrate is carbon cloth.
Example 19
Dissolving transition metal salt and a proper amount of nucleating agent in a mixed solution of water and ethanol by adopting the existing method, and preparing the basic carbonate array structure on the conductive substrate by hydrothermal/solvothermal synthesis, wherein the transition metal salt is cobalt nitrate (Co (NO)3)2·6H2O), the nucleating agent is ammonium fluoride and the conductive substrate is a carbon cloth.
Example 20
Dissolving transition metal salt and a proper amount of nucleating agent in a mixed solution of water and ethanol by adopting the existing method, and preparing the basic carbonate array structure on the conductive substrate by hydrothermal/solvothermal synthesis, wherein the transition metal salt is cobalt nitrate (Co (NO)3)2·6H2O), the nucleating agent is urea, and the conductive substrate is a titanium sheet.
Example 21
A self-supporting electrode is prepared by the following specific steps:
1) weighing 12mg of molybdenum trioxide, 500 mg of sodium sulfide, 14 mg of thioacetamide and 0.12 g of urea, dissolving in water, and stirring to form a uniform mixed solution to obtain a first solution;
2) transferring the first solution into a 50mL reaction kettle, immersing the prepared carbon cloth loaded with basic cobalt carbonate nanowires into the first solution, sealing the reaction kettle, and respectively placing the reaction kettle in an oven for hydrothermal reaction at 200 ℃ for 2, 4, 6 and 8 hours;
3) naturally cooling to room temperature after the hydrothermal reaction is finished, taking out the carbon cloth, respectively cleaning the carbon cloth with deionized water and ethanol for a plurality of times, and drying in vacuum to obtain a self-supporting electrode which is marked as CoS2@1T-MoS2Nanowires, i.e. CoS2@1T-MoS2The nanowire array-carbon cloth substrate self-supporting electrode can be used as a catalyst for electrolyzing water to generate hydrogen.
Example 22
A self-supporting electrode is prepared by the following specific steps:
1) weighing 5mg of molybdenum trioxide, 10 mg of sodium sulfide, 30 mg of thioacetamide and 0.12 g of urea, dissolving in water, and stirring to form a uniform mixed solution to obtain a first solution;
2) transferring the first solution into a 50mL reaction kettle, immersing the prepared carbon cloth loaded with basic cobalt carbonate nanowires into the first solution, sealing the reaction kettle, and placing the reaction kettle in an oven for hydrothermal reaction at 220 ℃ for 4-12 hours at 180-;
3) naturally cooling to room temperature after the hydrothermal reaction is finished, taking out the carbon cloth, respectively cleaning the carbon cloth with deionized water and ethanol for a plurality of times, and drying in vacuum to obtain a self-supporting electrode which is marked as CoS2@1T-MoS2Hollow nanowires, i.e. CoS2@1T-MoS2The hollow nanowire array-carbon cloth substrate self-supporting electrode can be used as a lithium ion battery cathode material.
Example 23
CoS prepared in example 212@1T-MoS2Scanning Electron Microscope (SEM) characterization is carried out on the nanowires, the obtained SEM pictures are shown in figure 1, and figure 1 shows CoS obtained in different hydrothermal reaction times2@1T-MoS2SEM pictures of nanowires in FIG. 1, wherein the graphs (a), (b), (c) and (d) correspond to CoS obtained by hydrothermal reaction for 2, 4, 6 and 8 hours2@1T-MoS2The nanowires, and the corresponding lower image of each image in the first row of images is an SEM image of the same at different magnifications, for example, the (a) image in the first row of images in fig. 1, and the corresponding lower two images are SEM images of the (a) image at different magnifications.
The micro-morphology of the nanowire array structure is changed along with the change of the reaction time, CoS2@1T-MoS2Outer layer 1T-MoS of nanowire2The size of the nano-sheets gradually increases.
Example 24
Referring to the method of example 23, except that, preferably, the hydrothermal reaction is set to proceed for between 8 and 16 hours, the product CoS2@1T-MoS2The core of the nanowire was completely dissolved to form a hollow structure, and the corresponding Transmission Electron Microscope (TEM) picture is shown in fig. 2.
Example 25
The self-supporting electrode prepared under the preferred conditions in the above example 24 is directly applied to hydrogen production catalysis by electrolysis of water under acidic conditions, and FIG. 3 is the corresponding CoS2@1T-MoS2Linear sweep voltammogram of nanowires, CoS, as can be seen in FIG. 32@1T-MoS2Nanowire in H2SO4The catalyst shows excellent catalytic activity. At a rate of 10 mA cm-2Overpotential (Overpotential) corresponding to Current Density (Current Density) is an evaluation parameter, CoS2@1T-MoS2The corresponding overpotential of the nanowire is 69 mV, which is different from that of the current 20wt% Pt/C noble metal catalyst with the best catalytic performance by only 20 mV. The performance is superior to most of the electrolytic water hydrogen evolution catalysts reported internationally at present.
Among the samples shown in FIG. 3, Pt/C represents a 20wt% Pt/C noble metal catalyst, which is an existing product, manufactured by Shanghai Chenghua electric Co., Ltd, and the rest is a self-made sample. Wherein, CoS2No MoO is added on the basis of the prior basic carbonate3The preparation method comprises the steps of (1) preparing,MoS2the preparation is carried out without changing the other conditions for not adding basic cobaltous carbonate.
Example 26
CoS prepared in example 222@1T-MoS2Scanning Electron Microscopy (SEM) characterization of the hollow nanowires was performed to obtain SEM pictures as shown in FIG. 4, and CoS prepared in example 22 was used2@1T-MoS2The hollow nanowires were characterized by Transmission Electron Microscopy (TEM), and the resulting TEM images are shown in fig. 5. Comparing the structures of fig. 1 and 2, it can be seen that the microstructure of the product can be adjusted by changing the type and concentration of the sulfur source in the reactants. The CoS obtained above is subjected to2@1T-MoS2The hollow nanowire is used for the lithium ion battery anode material, the cycle stability performance curve of the hollow nanowire is shown in FIG. 6, and CoS can be seen from 62@1T-MoS2The hollow nanowire has excellent cycle stability and a current density of 1 A.g-1The lithium ion battery can stably cycle for more than 150 times under high-rate charge-discharge cycle, and can be used for preparing a lithium ion battery cathode material.
Example 27
High-purity 1T-MoS2The preparation process comprises the following steps: by using MoO3The high-purity 1T-MoS is prepared in the hydrothermal synthesis process by using an octahedral coordination structure between Mo and O in a molecular structure as a sulfur source and selecting a proper sulfur source2(the phase purity is more than 90%).
In this embodiment, the specific method includes:
taking molybdenum trioxide as a molybdenum source, wherein the ratio of the sulfur source to the molybdenum source is 1:5 to 1: 40;
the problem that the molybdenum trioxide is insoluble in water is solved by using the sodium sulfide and the molybdenum trioxide to dissolve together;
excessive urea or hydrazine hydrate is used as a reducing agent to provide reducing conditions in the hydrothermal process to promote 1T-MoS2Generating; preferably, the hydrothermal synthesis temperature is 180 to 220 ℃ and the hydrothermal synthesis time is 4 to 16 hours.
In this example, it should be noted that 1T phase MoS2Can only be synthesized artificially, and the synthesis method commonly used at present is mainly lithiumIon stripping, the method essentially comprising the steps of: first, 2H phase powder was immersed in n-hexane solution of n-butyllithium to insert lithium ions into MoS2Interlaminar, this process typically requires agitation and even heating to accelerate the lithium ion intercalating agent in the MoS2Diffusion between layers. Subsequently, the intercalated MoS2Taking out, cleaning with a large amount of n-hexane, placing in ultrapure water for ultrasonic treatment, wherein lithium ions inserted between layers react with water to generate a large amount of H2Further to MoS2Delaminating the layers to form a single layer of MoS2Dispersion in water. The above process has several problems: first, the lithium ions are in the MoS despite the effect of heating and stirring2The diffusion rate between the layers is still slow and the preparation cycle is therefore long, typically 3 to 5 days. Secondly, the n-butyllithium used for intercalation is very natural in air, so the whole reaction process needs to be carried out in a glove box under argon atmosphere. Thirdly, 1T phase MoS prepared by lithium ion intercalation2The 2H phase is generally associated with the 1T phase, and the purity of the 1T phase is generally about 80 percent. Fourth, 1T phase MoS ultrasonically dispersed in water2The collection and application are difficult with a single layer structure. And the yield of the reaction process is low, so that the requirement of large-scale application is difficult to meet.
The metal phase molybdenum disulfide provided by the invention has the beneficial effects that molybdenum trioxide is used as a molybdenum source, and hydrothermal synthesis is carried out through a proper amount of sulfur source, reducing agent and water to prepare the metal phase molybdenum disulfide, the content of the metal phase molybdenum disulfide in the product can reach 80%, the metal phase molybdenum disulfide has the advantages of simple and safe operation, short preparation period and suitability for large-scale production, and the problems of long preparation period and low safety caused by the fact that most of the existing synthesis of the metal phase molybdenum disulfide is realized through lithium ion stripping are solved.
It should be noted that the traditional metallic phase molybdenum disulfide is mainly obtained by a lithium ion stripping mode, the required reaction time is long, the reaction conditions are harsh, extremely flammable medicines need to be involved, and the product is generally a monolayer MoS dispersed in water2The collection and application process is cumbersome. The method selects molybdenum trioxide as a molybdenum source through hydrothermal synthesis,dissolving in water together with sodium sulfide, and preparing 1T phase MoS with high phase purity under reducing solution condition2To prepare 1T-MoS2Provides a new synthesis way with simple operation, high yield and uniform phase. On the basis, CoS with a nanowire array structure is prepared2@1T-MoS2The array and the self-supporting structure can avoid steric effect caused by particle accumulation, effectively improve electron transfer rate, accelerate mass transfer rate in the electrode reaction process, improve the mechanical stability of the material due to the substrate, and can be applied to flexible electronic devices.
The self-supporting electrode prepared by the invention adopts a self-supporting structure, the nano structure is directly compounded with the current collector, and the nano structure and the current collector form tight electronic combination, so that the electronic transmission capability can be effectively improved, and the array structure can avoid mutual shielding among nano materials; the unique array structure can also enhance mass transport during the reaction process. For example, in the hydrogen evolution reaction process, the nanowire array can improve the desorption efficiency of hydrogen and avoid the influence of hydrogen adsorption on further reaction; in the lithium ion battery electrode, the nanowire array structure can shorten the lithium ion diffusion distance, and the one-dimensional structure of the nanowire array structure is also favorable for relieving the structural pulverization effect caused by volume expansion after lithium embedding.
The invention provides a simple and feasible hydrothermal synthesis method aiming at the defects of the metal phase molybdenum disulfide synthesis method, and MoO is adopted3As a molybdenum source, urea is added to adjust the reducibility of an aqueous hot solution system, so that the coordination atom coordination structure of a product is influenced, and the 1T-phase MoS is promoted2The method has the advantages of short production period, simple raw materials, safe experiment and suitability for industrial production of the high-purity 1T-phase molybdenum disulfide. Based on the method, 1T-phase MoS is constructed by a self-sacrifice template method2And the fourth phase transition metal cobalt sulfide (CoS)2) The nanowire array structure of (1). Based on the above, by self-sacrifice template method, molybdenum disulfide and CoS in metal phase2Construction of nanowire arrays, in comparison with lithium ion productionThe preparation method of the layer, the hydrothermal synthesis process has the advantages of simple equipment, safe operation and suitability for large-scale production, and in addition, the product is an electrode with a self-supporting structure, so that the application is more convenient and the performance is more outstanding.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.

Claims (4)

1. A self-supporting electrode is characterized in that the preparation method of the self-supporting electrode comprises the following steps: immersing a conductive substrate containing a basic carbonate nano array of transition metal in the first solution, wherein the first solution is a mixed solution obtained by uniformly mixing molybdenum trioxide, a sulfur source, a reducing agent and water, and the concentration of the molybdenum trioxide in the first solution is 0.008-1 mmol.L-1The reducing agent is selected from any one or more of urea or hydrazine hydrate, the first solution is placed in a closed environment for hydrothermal reaction, the reaction temperature of the hydrothermal reaction is 160-240 ℃, the reaction time is 4-24 hours, then separation, washing and drying are carried out to obtain the metal phase molybdenum disulfide, the sulfur source is selected from any one or more of thioacetamide or sodium sulfide, and the ratio of the number of molybdenum atoms in the molybdenum trioxide to the number of sulfur atoms in the sulfur source is 1: 5-40; when the dosage of the sodium sulfide is less than 2.5 mmol.L-1And the dosage of thioacetamide is more than 1.5 mmol.L-1Then, obtaining a composite structure self-supporting electrode with a hollow nanowire structure of metal phase molybdenum disulfide and cobalt sulfide; when the concentration of sodium sulfide is 15 mmol.L-1To 30 mmol. L-1And then, the reaction time of the hydrothermal reaction is 2 or 4-8 hours, and the self-supporting electrode with the composite structure of the solid nanowire structure of the metal phase molybdenum disulfide and cobalt sulfide is obtained.
2. The self-supporting electrode according to claim 1, wherein, in the method of preparing the self-supporting electrode,
the concentration of molybdenum trioxide in the first solution is 0.008-0.32 mmol.L in terms of molybdenum atom-1。
3. The self-supporting electrode according to claim 1, wherein, in the method of preparing the self-supporting electrode,
the concentration of molybdenum trioxide in the first solution is 0.01-0.05 mmol.L in terms of molybdenum atom-1。
4. Use of the self-supporting electrode of claim 1 for the electrolysis of water for hydrogen evolution and/or for the preparation of negative electrode materials for lithium ion batteries.
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