CN104821240A - SnS2/MoS2 composite material one-step hydrothermal synthesizing method and application thereof - Google Patents
SnS2/MoS2 composite material one-step hydrothermal synthesizing method and application thereof Download PDFInfo
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- CN104821240A CN104821240A CN201510211189.3A CN201510211189A CN104821240A CN 104821240 A CN104821240 A CN 104821240A CN 201510211189 A CN201510211189 A CN 201510211189A CN 104821240 A CN104821240 A CN 104821240A
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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
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a SnS2/MoS2 composite material one-step hydrothermal synthesizing method. The method comprises the following steps that S1. a tin source and a sulfur source are dissolved in water to form settled solution, and mole ratio of sulfur to tin in the solution is 6/0-10.0:1; S2. a molybdenum source is added in the solution of step S1 to generate precipitation, and the obtained mixture is uniformly mixed so that mole ratio of tin to molybdenum in the mixture is enabled to be 4-19:1; S3. and hydrothermal reaction is performed on the obtained mixture in the step S2, then cooling is performed, the precipitation is rinsed, and centrifugal separation is performed so that the product is obtained through drying. Mole ratio of sulfur to tin and tin to molybdenum in the raw material is controlled so that the synergistic effect is enabled to be generated between SnS2 and MoS2, large amount of SnS2/MoS2 composite material can be rapidly synthesized, and the prepared product is relatively uniform in morphology without impurity. The method has advantages of being simple in technology, low in cost and high in productivity and can be applied to super-capacitor electrode material and can also be widely applied to the fields of lithium ion battery electrode material and photocatalyst.
Description
Technical field
The present invention relates to inorganic technical field of micro nano material preparation, particularly relate to an a kind of step Hydrothermal Synthesis SnS
2/ MoS
2the method of composite material and application thereof.
Background technology
Contemporary society, energy problem has become one of global significant problem undoubtedly, causes and pays close attention to widely, and finding new material can have special effect one of vital task becoming scientific worker at energy storage and use.Ultracapacitor, as a kind of new energy storage device, has the advantage such as long service life, energy density height, causes the research interest that people are huge.The active electrode material of ultracapacitor, have impact on the chemical property of energy storage device to a great extent, has so find the key issue that novel structure electrode material becomes ultracapacitor development.At present, two-dimensional nano sheet crystal has the performances such as the physics and chemistry of many uniquenesses with the structure of its uniqueness, there is the extensive concern that the synthesis of important scientific research meaning and potential wide application prospect, particularly transient metal sulfide two-dimensional nano sheet and photoelectric properties research obtain people.Stannic disulfide (SnS
2) be one of important semiconductor of IV-VI main group, there is the PbI of six side's phase elementary cells
2layer structure, has 2.2 ~ 2.35 eV band-gap energies under room temperature.Particularly there is the SnS of two-dimensional structure
2nanometer sheet, because it has larger specific area, shorter diffusion length, thus there is good air-sensitive, optics and electrology characteristic, can be used as gas sensing materials, solar cell material, holographic recording system and power conversion system, the negative material of lithium ion battery and photocatalyst material.Current preparation SnS
2the method of nanometer sheet mainly contains gas solid method and hydro-thermal and solvent-thermal method etc.Molybdenum bisuphide (MoS
2) there is the layer structure being similar to graphite, compared with body phase material, molybdenum bisuphide (MoS
2) specific area of nanometer sheet is larger, adsorption capacity is stronger, reactivity also can improve, catalytic performance is stronger, this also determines it and has good application prospect in electrochemical field (lithium ion battery negative material, electric chemical super capacitor), lubricating area (super kollag), catalytic field (optical, electrical chemical catalysis liberation of hydrogen) and intercalation chemistry field.Current MoS
2preparation method's mainly hydro-thermal and solvent-thermal method etc. of nanometer sheet.
Recently, the New Two Dimensional composite heterogenous junction structure formed is piled up by two kinds of different types of two-dimensional nano sheets, its novel character and the potential application on photoelectronic device, clean energy resource transform and store and cause people to study interest greatly, thus be subject to people and more and more pay close attention to.Such as, by the MoS of two-dimentional class graphene-structured
2or SnS
2nanometer sheet and two-dimensional graphene combine and are prepared into class Graphene/graphene composite material and the research being applied to lithium ion cell electrode, in this technology of preparing, have normally been come by multiple step.As first prepared graphene oxide by Hummers method, then by graphene oxide ultrasonic disperse, then adding molybdenum source and sulphur source, after fully stirring, passing through hydro-thermal reaction; Finally hydro-thermal product is heat-treated under high temperature inert atmosphere and obtain MoS
2/ Graphene or SnS
2/ graphene product.But two kinds are had the MoS of class graphene-structured
2nanometer sheet and SnS
2nanometer sheet is mutually piled up the new class Graphene compound two-dimensional structure of formation and be have not been reported.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide an a kind of step Hydrothermal Synthesis SnS
2/ MoS
2the method of composite material.The inventive method has that technique is simple, cost is low, can rapid, high volume synthesis and the high advantage of product yield, the SnS prepared
2/ MoS
2composite material pattern is comparatively even.
Another object of the present invention is to provide described SnS
2/ MoS
2the application of composite material.
Another object of the present invention is to provide the method for described application.
Above-mentioned purpose of the present invention is achieved by the following technical programs.
An a kind of step Hydrothermal Synthesis SnS
2/ MoS
2the method of composite material, comprises the steps:
S1. by Xi Yuan and sulphur source soluble in water, formed settled solution, in solution, the mol ratio of sulphur and tin is 6.0 ~ 10.0:1;
S2. in S1 solution, add molybdenum source, produce precipitation, mixing obtains mixture, makes the mol ratio of tin and molybdenum in mixture be 4 ~ 19:1;
S3. the mixture obtained by S2 carries out hydro-thermal reaction, cooling, and rinsing precipitates, centrifugation, and drying obtains product;
Wherein, described Xi Yuan and molybdenum source oppositely charged in the solution.
When as electrode material, SnS
2often run into the problem that cycle performance is poor, this mainly because the large bulk effect caused when discharge and recharge, causes the efflorescence of electrode material.Inventor is found, due to SnS by research
2and MoS
2have similar layer structure, the atomic radius of molybdenum and tin is also very close, by SnS
2and MoS
2during synthetic composite material, the MoS of introducing
2with SnS
2pattern and structure there is good matching effect, make the two contact good, to SnS
2play certain protective effect; Secondly, due to SnS
2and MoS
2there is similar layer structure, introduce MoS in the preparation
2mutually can suppress the stacking of layer structure, be conducive to few number of plies structure that each self-forming has class graphene-structured, this few number of plies structure has better chemical property.
In addition, the present invention also finds, only has when sulphur and tin mol ratio are 6.0 ~ 10.0:1, when the mol ratio of tin and molybdenum is 4 ~ 19:1, and SnS
2and MoS
2the composite material prepared could produce good cooperative effect, experiment finds, along with the increase of molybdenum disulfide content, the number of plies of molybdenum bisuphide is in increase, and the number of plies of stannic disulfide is in decline, so will under a suitable proportion, when making both numbers of plies all not many, chemical property be best; In addition, because the ratio capacitance of stannic disulfide is lower, molybdenum bisuphide relatively large, so the ratio that also existence one is suitable, makes SnS
2and MoS
2between produce cooperative effect, namely make the chemical property of composite material both be greater than stannic disulfide, be also greater than molybdenum bisuphide.
The present invention have employed raw material cheap and easy to get and gentle hydro thermal method one-step synthesis SnS first
2/ MoS
2composite material, and by controlling the mol ratio of sulphur and tin, tin and molybdenum in raw material, can rapid, high volume synthesis SnS
2/ MoS
2composite material, product yield is high, and the product pattern prepared is comparatively even.
Preferably, the concentration of Xi Yuan described in S1 is 0.01 ~ 0.1 mol/L.
Preferably, described in S2, the concentration in molybdenum source is 0.001 ~ 0.05mol/L.
Preferably, described Xi Yuan is butter of tin or STANNOUS SULPHATE CRYSTALLINE.
Preferably, described molybdenum source is sodium molybdate or potassium molybdate
Preferably, described sulphur source is Cys or thiocarbamide.
Preferably, described Xi Yuan is butter of tin, and molybdenum source is sodium molybdate, and described sulphur source is Cys, sodium molybdate and butter of tin cheap and easy to get, Cys, due to containing carboxyl, sulfydryl, has certain complexing to metal ion, be more conducive to generate SnS
2/ MoS
2composite material nanometer sheet.
Preferably, the condition of hydro-thermal reaction described in S3 is 220 ~ 240 DEG C of reaction 24h.The too high meeting of hydrothermal temperature causes reacting kettle inner pressure, and too conference generation is dangerous, and too low meeting causes generating molybdenum disulfide nano sheet.Overlong time can cause scantling to become large, too short, cannot generate product or products collection efficiency is too low.
Preferably, comprise the steps:
S1. butter of tin is water-soluble, tin ion concentration be 0.01 ~ 0.1 mol/L, then add Cys, form settled solution, in solution, the mol ratio of Cys and tin ion is 6.0 ~ 10.0:1;
S2. in S1 solution, add the sodium molybdate solution of 0.001 ~ 0.05mol/L, produce molybdic acid tin precipitation, stir, in mixture, the mol ratio of tin and molybdenum is 4 ~ 19:1;
S3. the mixture obtained by S2 reacts 24h under 220 ~ 240 DEG C of hydrothermal conditions, cooling, with water and absolute ethyl alcohol respectively rinsing precipitate three times, centrifugation, drying obtains product.
Preferably, stir described in S2 as stirring 30min, solution is fully precipitated.
In order to make raw material dissolve better in the process added, preferably, described Xi Yuan, sulphur source and molybdenum source add in solution under the condition stirred.
Preferably, described S3 drying is 60 DEG C of vacuumize 12h.Vacuumize can avoid the sulfide for preparing oxidized at relatively high temperatures.
The present invention also provides above-mentioned composite material preparing the application in electrode material.
Preferably, described electrode material is the electrode material of ultracapacitor.
The present invention also provides the method for above-mentioned application, is coated in conductive substrates by described composite material.
Preferably, described composite material is coated in as in the nickel foam of conductive substrates.
Compared with prior art, beneficial effect of the present invention is: the present invention have employed raw material cheap and easy to get and gentle hydro thermal method one-step synthesis SnS first
2/ MoS
2composite material, and by controlling the mol ratio of sulphur and tin, tin and molybdenum in raw material, make SnS
2and MoS
2between produce cooperative effect, can rapid, high volume synthesis SnS
2/ MoS
2composite material, and the product pattern prepared is comparatively even, free from admixture.The inventive method has the advantage that technique is simple, cost is low, productive rate is high, the SnS prepared
2/ MoS
2the bouquet that composite products is nanometer sheet or is made up of nanometer sheet, can be applicable to electrode material for super capacitor, is also expected to obtain in the field such as lithium ion battery electrode material, photochemical catalyst apply widely.
Accompanying drawing explanation
Fig. 1 is the SnS that embodiment 1 obtains
2/ MoS
2the X-ray diffractogram of composite material.
Fig. 2 is the SnS that embodiment 1 obtains
2/ MoS
2the scanning electron microscope (SEM) photograph of composite material and transmission electron microscope picture; Wherein (A), (B) are scanning electron microscope (SEM) photograph, and (C) is transmission electron microscope picture.
Fig. 3 is the SnS that embodiment 2 obtains
2/ MoS
2the X-ray diffractogram of composite material and scanning electron microscope (SEM) photograph; Wherein (A) is X-ray diffractogram, and (B) is scanning electron microscope (SEM) photograph.
Fig. 4 is the SnS that embodiment 3 obtains
2/ MoS
2the X-ray diffractogram of composite material and scanning electron microscope (SEM) photograph; Wherein (A) is X-ray diffractogram, and (B) is scanning electron microscope (SEM) photograph.
Embodiment
Below in conjunction with Figure of description and specific embodiment, the present invention is described in further details, but embodiment does not limit in any form the present invention.Unless stated otherwise, the present invention adopts reagent, method and apparatus are the art conventional reagent, method and apparatus.
embodiment
1
An a kind of step Hydrothermal Synthesis SnS
2/ MoS
2the method of composite material, comprises the steps:
S1. be under agitation dissolved in 50mL deionized water by the butter of tin of 1.2mmol and the Cys of 9mmol, form solution A, in solution, the concentration of Xi Yuan is 0.024 mol/L, and the mol ratio of Cys and tin ion is 7.5:1.
S2. the sodium molybdate of 0.3mmol is dissolved in 10ml deionized water and forms solution B, the concentration of sodium molybdate solution is 0.03 mol/L, then under vigorous stirring solution B is dropwise joined in solution A, generate greenish precipitate, drip rear continuation strong agitation 30 minutes, in mixture, the mol ratio of tin and molybdenum is 4:1.
S3. the mixture that S2 obtains being transferred to 100ml liner is in the stainless steel cauldron of polytetrafluoroethylene, be placed in baking oven, in 240 DEG C of hydro-thermal reaction 24h, naturally cool to room temperature, gained precipitate with deionized water and absolute ethyl alcohol are distinguished rinsing three times, centrifugation, in vacuum drying chamber, 60 DEG C of dry 12h, obtain SnS
2/ MoS
2composite nano plate.
Obtained SnS
2/ MoS
2the X-ray diffractogram of product is shown in Fig. 1, in figure, stannic disulfide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS23-0677), molybdenum bisuphide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS37-1492), illustrate that composite material is made up of stannic disulfide and molybdenum bisuphide.
Obtained SnS
2/ MoS
2the scanning electron microscope (SEM) photograph of product is shown in Fig. 2, and Fig. 2 (A) shows SnS
2/ MoS
2joint product is the comparatively uniform micro-flowers of size and pattern.Fig. 2 (B) shows the surface texture of micro-flowers, and Fig. 2 (C) shows the internal structure of micro-flowers, therefrom can find out that this micro-flowers is made up of many nanometer sheet be staggered.
Weigh 40mg SnS
2/ MoS
2grind after joint product and the mixing of 5mg acetylene black, add 5mg polytetrafluoroethylene, add a small amount of 1-METHYLPYRROLIDONE (NMP) ultrasonic disperse 30min, be coated in nickel foam surface after dispersion, at 60 DEG C, obtain required electrode slice after vacuumize 12h.With obtained SnS
2/ MoS
2electrode is as work electrode, and platinum plate electrode is to electrode, and saturated calomel electrode is reference electrode, and 3.5mol/L potassium hydroxide solution is electrolyte assembling super capacitor.Electrochemical property test shows, at 1Ag
-1the specific capacitance of this ultracapacitor lower is 145F/g.
embodiment
2
An a kind of step Hydrothermal Synthesis SnS
2/ MoS
2the method of composite material, comprises the steps:
S1. be under agitation dissolved in 50mL deionized water by the butter of tin of 1.35mmol and the Cys of 9mmol, form solution A, in solution, the concentration of Xi Yuan is 0.027 mol/L, and the mol ratio of Cys and tin ion is 20:3;
S2. the sodium molybdate of 0.15mmol is dissolved in 10ml deionized water and forms solution B, the concentration of sodium molybdate solution is 0.015 mol/L, then under vigorous stirring solution B is dropwise joined in solution A, generate greenish precipitate, drip rear continuation strong agitation 30 minutes, in mixture, the mol ratio of tin and molybdenum is 9:1;
S3. the mixture that S2 obtains being transferred to 100ml liner is in the stainless steel cauldron of polytetrafluoroethylene, be placed in baking oven, in 240 DEG C of hydro-thermal reaction 24h, naturally cool to room temperature, gained precipitate with deionized water and absolute ethyl alcohol are distinguished rinsing three times, centrifugation, in vacuum drying chamber, 60 DEG C of dry 12h, obtain SnS
2/ MoS
2composite nano plate.
Obtained SnS
2/ MoS
2the X-ray diffractogram of product is shown in Fig. 3 (A), in figure, stannic disulfide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS23-0677), molybdenum bisuphide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS37-1492), illustrate that composite material is made up of stannic disulfide and molybdenum bisuphide.
Obtained SnS
2/ MoS
2the scanning electron microscope (SEM) photograph of product is shown in Fig. 3 (B), and Fig. 3 (B) shows SnS
2/ MoS
2joint product is the micro-flowers be made up of many nanometer sheet be staggered.
Weigh 40mg SnS
2/ MoS
2grind after joint product and the mixing of 5mg acetylene black, add 5mg polytetrafluoroethylene, add a small amount of 1-METHYLPYRROLIDONE (NMP) ultrasonic disperse 30min, be coated in nickel foam surface after dispersion, at 60 DEG C, obtain required electrode slice after vacuumize 12h.With obtained SnS
2/ MoS
2electrode is as work electrode, and platinum plate electrode is to electrode, and saturated calomel electrode is reference electrode, and 3.5mol/L potassium hydroxide solution is electrolyte assembling super capacitor.Electrochemical property test shows, at 1Ag
-1the specific capacitance of this ultracapacitor lower is 234F/g.
embodiment
3
An a kind of step Hydrothermal Synthesis SnS
2/ MoS
2the method of composite material, comprises the steps:
S1. be under agitation dissolved in 50mL deionized water by the butter of tin of 1.275mmol and the Cys of 9mmol, form solution A, in solution, the concentration of Xi Yuan is 0.0255mol/L, and the mol ratio of Cys and tin ion is 7:1;
S2. the sodium molybdate of 0.225mmol is dissolved in 10ml deionized water and forms solution B, the concentration of sodium molybdate solution is 0.0225 mol/L, then under vigorous stirring solution B is dropwise joined in solution A, generate greenish precipitate, drip rear continuation strong agitation 30 minutes, in mixture, the mol ratio of tin and molybdenum is 17:3;
S3. the mixture that S2 obtains being transferred to 100ml liner is in the stainless steel cauldron of polytetrafluoroethylene, be placed in drying box, in 220 DEG C of hydro-thermal reaction 24h, naturally cool to room temperature, gained precipitate with deionized water and absolute ethyl alcohol are distinguished rinsing three times, centrifugation, in vacuum drying chamber, 60 DEG C of dry 12h, obtain SnS
2/ MoS
2composite nano plate.
Obtained SnS
2/ MoS
2the X-ray diffractogram of product is shown in Fig. 4 (A), in figure, stannic disulfide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS23-0677), molybdenum bisuphide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS37-1492), illustrate that composite material is made up of stannic disulfide and molybdenum bisuphide.
Obtained SnS
2/ MoS
2the scanning electron microscope (SEM) photograph of product is shown in Fig. 4 (B), display SnS
2/ MoS
2joint product is the micro-flowers be made up of many nanometer sheet be staggered.
Weigh 40mg SnS
2/ MoS
2grind after joint product and the mixing of 5mg acetylene black, add 5mg polytetrafluoroethylene, add a small amount of 1-METHYLPYRROLIDONE (NMP) ultrasonic disperse 30min, be coated in nickel foam surface after dispersion, at 60 DEG C, obtain required electrode slice after vacuumize 12h.With obtained SnS
2/ MoS
2electrode is as work electrode, and platinum plate electrode is to electrode, and saturated calomel electrode is reference electrode, and 3.5mol/L potassium hydroxide solution is electrolyte assembling super capacitor.Electrochemical property test shows, at 1Ag
-1the specific capacitance of this ultracapacitor lower is 183F/g.
comparative example
1
This comparative example adopts following two kinds of tin molybdenums ratio: process 1. 3:1; Process 2. 24:1 to prepare SnS
2/ MoS
2composite material, concrete grammar is as follows:
Process 1.: a step Hydrothermal Synthesis SnS
2/ MoS
2the method of composite material, comprises the steps:
S1. be under agitation dissolved in 50mL deionized water by the butter of tin of 1.125mmol and the Cys of 9mmol, form solution A, in solution, the concentration of Xi Yuan is 0.0225mol/L, and the mol ratio of Cys and tin ion is 8:1;
S2. the sodium molybdate of 0.375mmol is dissolved in 10ml deionized water and forms solution B, the concentration of sodium molybdate solution is 0.0375 mol/L, then under vigorous stirring solution B is dropwise joined in solution A, generate greenish precipitate, drip rear continuation strong agitation 30 minutes, in mixture, the mol ratio of tin and molybdenum is 3:1;
S3. the mixture that S2 obtains being transferred to 100ml liner is in the stainless steel cauldron of polytetrafluoroethylene, be placed in drying box, in 220 DEG C of hydro-thermal reaction 24h, naturally cool to room temperature, gained precipitate with deionized water and absolute ethyl alcohol are distinguished rinsing three times, centrifugation, in vacuum drying chamber, 60 DEG C of dry 12h, obtain SnS
2/ MoS
2composite nano plate.
Obtained SnS
2/ MoS
2product characterizes through X-ray diffraction, in composite material, stannic disulfide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS23-0677), molybdenum bisuphide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS37-1492), illustrate that composite material is made up of stannic disulfide and molybdenum bisuphide.
Obtained SnS
2/ MoS
2product scanning electron microscopic observation, its pattern is the irregular micro-flowers of pattern of nanometer sheet composition.
Weigh 40mg SnS
2/ MoS
2grind after joint product and the mixing of 5mg acetylene black, add 5mg polytetrafluoroethylene, add a small amount of 1-METHYLPYRROLIDONE (NMP) ultrasonic disperse 30min, be coated in nickel foam surface after dispersion, at 60 DEG C, obtain required electrode slice after vacuumize 12h.With obtained SnS
2/ MoS
2electrode is as work electrode, and platinum plate electrode is to electrode, and saturated calomel electrode is reference electrode, and 3.5mol/L potassium hydroxide solution is electrolyte assembling super capacitor.Electrochemical property test shows, at 1Ag
-1the specific capacitance of this ultracapacitor lower is only 126F/g.This is because the content of molybdenum bisuphide too much causes compound to cause the decline of capacity well with stannic disulfide.
Process 2.: a step Hydrothermal Synthesis SnS
2/ MoS
2the method of composite material, comprises the steps:
S1. be under agitation dissolved in 50mL deionized water by the butter of tin of 1.44mmol and the Cys of 14.4mmol, form solution A, in solution, the concentration of Xi Yuan is 0.0288mol/L, and the mol ratio of Cys and tin ion is 10:1;
S2. the sodium molybdate of 0.06mmol is dissolved in 10ml deionized water and forms solution B, the concentration of sodium molybdate solution is 0.006 mol/L, then under vigorous stirring solution B is dropwise joined in solution A, generate greenish precipitate, drip rear continuation strong agitation 30 minutes, in mixture, the mol ratio of tin and molybdenum is 24:1;
S3. the mixture that S2 obtains being transferred to 100ml liner is in the stainless steel cauldron of polytetrafluoroethylene, be placed in drying box, in 220 DEG C of hydro-thermal reaction 24h, naturally cool to room temperature, gained precipitate with deionized water and absolute ethyl alcohol are distinguished rinsing three times, centrifugation, in vacuum drying chamber, 60 DEG C of dry 12h, obtain SnS
2/ MoS
2composite nano plate.
Obtained SnS
2/ MoS
2product characterizes through X-ray diffraction, in composite material, stannic disulfide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS23-0677), molybdenum bisuphide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS37-1492), illustrate that composite material is made up of stannic disulfide and molybdenum bisuphide.
Obtained SnS
2/ MoS
2product scanning electron microscopic observation, its pattern is nanometer sheet.
Weigh 40mg SnS
2/ MoS
2grind after joint product and the mixing of 5mg acetylene black, add 5mg polytetrafluoroethylene, add a small amount of 1-METHYLPYRROLIDONE (NMP) ultrasonic disperse 30min, be coated in nickel foam surface after dispersion, at 60 DEG C, obtain required electrode slice after vacuumize 12h.With obtained SnS
2/ MoS
2electrode is as work electrode, and platinum plate electrode is to electrode, and saturated calomel electrode is reference electrode, and 3.5mol/L potassium hydroxide solution is electrolyte assembling super capacitor.Electrochemical property test shows, at 1Ag
-1the specific capacitance of this ultracapacitor lower is only 98F/g.This content mainly due to molybdenum bisuphide is less, little to the capacity contribution promoting whole composite material.
comparative example
2
The sulphur tin adopted in this comparative example step S1 is than being 3:1, preparation SnS
2/ MoS
2the method of composite material is as follows:
An a kind of step Hydrothermal Synthesis SnS
2/ MoS
2the method of composite material, comprises the steps:
S1. be under agitation dissolved in 50mL deionized water by the butter of tin of 1.35mmol and the Cys of 4.05mmol, form solution A, in solution, the concentration of Xi Yuan is 0.027 mol/L, and the mol ratio of Cys and tin ion is 3:1;
S2. the sodium molybdate of 0.15mmol is dissolved in 10ml deionized water and forms solution B, the concentration of sodium molybdate solution is 0.015 mol/L, then under vigorous stirring solution B is dropwise joined in solution A, generate greenish precipitate, drip rear continuation strong agitation 30 minutes, in mixture, the mol ratio of tin and molybdenum is 9:1;
S3. the mixture that S2 obtains being transferred to 100ml liner is in the stainless steel cauldron of polytetrafluoroethylene, be placed in baking oven, in 240 DEG C of hydro-thermal reaction 24h, naturally cool to room temperature, gained precipitate with deionized water and absolute ethyl alcohol are distinguished rinsing three times, centrifugation, in vacuum drying chamber, 60 DEG C of dry 12h, obtain SnS
2/ MoS
2composite nano plate.
Obtained product X-ray diffraction analysis is learnt, in X-ray diffractogram, stannic disulfide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS23-0677), molybdenum bisuphide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS37-1492), in addition, have also appeared the diffraction maximum of a small amount of tin ash and molybdenum trioxide, when sulphur source is inadequate, its complete cure can not be become stannic disulfide and molybdenum bisuphide.
Finding with scanning electron microscopic observation of obtained product, except the nanometer sheet that there is bidimensional, also have some fragmentary nano particles, this nano particle may be the tin ash or molybdenum trioxide nano particle that are not fully vulcanized.
comparative example
3
This comparative example prepares SnS
2/ MoS
2the method of composite material is basic identical with embodiment 3, except the condition of S3 hydro-thermal reaction is different.This comparative example adopts following hydrothermal reaction condition: the mixture that 1. S2 obtains by process is at 150 DEG C of hydro-thermal reaction 24h; The mixture that 2. S2 obtains by process is at 220 DEG C of hydro-thermal reaction 12h.
Product X-ray diffraction analysis obtained under above-mentioned two kinds of conditions is learnt, in X-ray diffractogram, stannic disulfide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS23-0677), molybdenum bisuphide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS37-1492), in addition, have also appeared the diffraction maximum of a small amount of molybdenum trioxide, and the degree of crystallinity of product is bad, illustrate when temperature is too low or the reaction time is too short, not only the crystallinity of product is bad, and completely sodium molybdate can not be sulfided into molybdenum bisuphide.
comparative example 4
An a kind of step Hydrothermal Synthesis SnS
2/ MoS
2the method of composite material, comprises the steps:
S1. be under agitation dissolved in 50mL deionized water by the butter of tin of 0.75mmol and the Cys of 10.5mmol, form solution A, in solution, the concentration of Xi Yuan is 0.015 mol/L, and the mol ratio of Cys and tin ion is 14:1;
S2. the sodium molybdate of 0.75mmol is dissolved in 10ml deionized water and forms solution B, the concentration of sodium molybdate solution is 0.075 mol/L, then under vigorous stirring solution B is dropwise joined in solution A, generate greenish precipitate, drip rear continuation strong agitation 30 minutes, in mixture, the mol ratio of tin and molybdenum is 1:1;
S3. the mixture that S2 obtains being transferred to 100ml liner is in the stainless steel cauldron of polytetrafluoroethylene, be placed in drying box, in 220 DEG C of hydro-thermal reaction 24h, naturally cool to room temperature, gained precipitate with deionized water and absolute ethyl alcohol are distinguished rinsing three times, centrifugation, in vacuum drying chamber, 60 DEG C of dry 12h, obtain SnS
2/ MoS
2composite nano plate.
Product X-ray diffraction analysis obtained under above-mentioned condition is learnt, in X-ray diffractogram, stannic disulfide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS23-0677), molybdenum bisuphide each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS37-1492), but each diffraction maximum is very weak, illustrate that the degree of crystallinity of product is bad.Its pattern of scanning electron microscopic observation is the irregular micro-flowers be made up of nanometer sheet.
The said goods is made electrode by method above, carries out electrochemical property test.Result shows, at 1Ag
-1the specific capacitance of this ultracapacitor lower is only 65F/g.Mainly due to the content of one side molybdenum bisuphide, too much cause can not compound well with stannic disulfide for this; The amorphous carbon lower compared with multicapacity can be introduced to composite material, the degree of crystallinity of the product not only reduced in sulphur source excessive on the other hand, and the capacity of composite material can be caused to decline.
Claims (10)
1. a step Hydrothermal Synthesis SnS
2/ MoS
2the method of composite material, is characterized in that, comprises the steps:
S1. by Xi Yuan and sulphur source soluble in water, formed settled solution, in solution, the mol ratio of sulphur and tin is 6.0 ~ 10.0:1;
S2. in S1 solution, add molybdenum source, produce precipitation, mixing obtains mixture, makes the mol ratio of tin and molybdenum in mixture be 4 ~ 19:1;
S3. the mixture obtained by S2 carries out hydro-thermal reaction, cooling, and rinsing precipitates, centrifugation, and drying obtains product;
Wherein, described Xi Yuan and molybdenum source oppositely charged in the solution.
2. method according to claim 1, it is characterized in that, the concentration of Xi Yuan described in S1 is 0.01 ~ 0.1 mol/L.
3. method according to claim 1, is characterized in that, described in S2, the concentration in molybdenum source is 0.001 ~ 0.05mol/L.
4. method according to claim 1, is characterized in that, described Xi Yuan is butter of tin or STANNOUS SULPHATE CRYSTALLINE.
5. method according to claim 1, is characterized in that, described molybdenum source is sodium molybdate or potassium molybdate.
6. method according to claim 1, is characterized in that, described sulphur source is Cys or thiocarbamide.
7. method according to claim 1, is characterized in that, the condition of hydro-thermal reaction described in S3 is 220 ~ 240 DEG C of reaction 24h.
8. the method according to any one of claim 1 ~ 7, is characterized in that, comprises the steps:
S1. butter of tin is water-soluble, tin ion concentration be 0.01 ~ 0.1 mol/L, then add Cys, form settled solution, in solution, the mol ratio of Cys and tin ion is 6.0 ~ 10.0:1;
S2. in S1 solution, add the sodium molybdate solution of 0.001 ~ 0.05mol/L, produce molybdic acid tin precipitation, stir, in mixture, the mol ratio of tin and molybdenum is 4 ~ 19:1;
S3. the mixture obtained by S2 reacts 24h under 220 ~ 240 DEG C of hydrothermal conditions, cooling, with water and absolute ethyl alcohol respectively rinsing precipitate three times, centrifugation, drying obtains product.
9. the application in electrode material prepared by composite material described in claim 1.
10. the method for application described in claim 9, is characterized in that, be coated in conductive substrates by described composite material.
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