CN104821240B - 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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- 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, more particularly to a kind of step Hydrothermal Synthesiss SnS2/MoS2
The method of composite and its application.
Background technology
Contemporary society, energy problem undoubtedly has become one of global significant problem, causes extensive concern, finds new
Section bar material can have special effect to have become one of vital task of scientific worker in energy storage and use.It is super
Level capacitor, as a kind of new energy storage device, with advantages such as long service life, energy density height, causes people
Huge research interest.The active electrode material of ultracapacitor, have impact on to a great extent the electrification of energy storage device
Performance is learned, so find becoming the key issue of ultracapacitor development with novel structure electrode material.At present, two-dimensional nano
Piece crystal has the physics and the performance such as chemistry of many uniquenesses with its unique structure, with important scientific research meaning and latent
Wide application prospect, the particularly synthesis of transient metal sulfide two-dimensional nano piece and photoelectric properties research obtained people
Extensive concern.Stannic disulfide (SnS2) it is one of important semiconductor of IV-VI main groups, the PbI with hexagonal phase elementary cell2
Layer structure, has 2.2～2.35 eV band-gap energies under room temperature.The particularly SnS with two-dimensional structure2Nanometer sheet, because it has
Larger specific surface area, shorter diffusion length, so as to have good air-sensitive, optically and electrically characteristic, can be used as air-sensitive biography
Sense material, solar cell material, holographic recording system and power conversion system, the negative material of lithium ion battery and photocatalysis
Agent material.SnS is prepared at present2The method of nanometer sheet mainly has gas solid method and hydro-thermal and solvent-thermal method etc..Molybdenum bisuphide (MoS2)
With the layer structure similar to graphite, compared with body phase material, molybdenum bisuphide (MoS2) nanometer sheet specific surface area it is bigger,
Adsorption capacity is higher, reactivity also can be improved, catalytic performance is higher, and this also determines it in electrochemical field (lithium-ion electric
Pond negative material, electric chemical super capacitor), lubricating area (super kollag), catalytic field (light, electrochemical catalysis
Liberation of hydrogen) and intercalation chemistry field there is good application prospect.Current MoS2The preparation method of nanometer sheet is mainly hydro-thermal and molten
Hot method of agent etc..
Recently, the New Two Dimensional composite heterogenous junction structure for being formed is piled up by two different kinds of two-dimensional nano piece, it is novel
Property and photoelectronic device, clean energy resource conversion and store on potential application and cause the great research interest of people,
So as to be subject to people more and more to pay close attention to.For example, by the MoS of two-dimentional class graphene-structured2Or SnS2Nanometer sheet and two-dimentional graphite
Alkene combination is prepared into class Graphene/graphene composite material and is applied to the research of lithium ion cell electrode, in this preparation skill
In art, complete typically by multiple steps.As prepared graphene oxide by Hummers methods first, then will
Graphene oxide ultrasonic disperse, adds molybdenum source and sulphur source, and hydro-thermal reaction is passed through after being sufficiently stirred for；Finally by hydro-thermal product in height
Heat treatment is carried out under warm inert atmosphere and obtains MoS2/ Graphene or SnS2/ graphene product.But two kinds are tied with class Graphene
The MoS of structure2Nanometer sheet and SnS2Nanometer sheet is mutually piled up and to form the compound two-dimensional structure of new class Graphene and have not been reported.
The content of the invention
The present invention is directed to the deficiencies in the prior art, there is provided a kind of step Hydrothermal Synthesiss SnS2/MoS2The side of composite
Method.The inventive method have the advantages that process is simple, low cost, can rapid, high volume synthesis and product yield is high, prepare
SnS2/MoS2Composite pattern is more uniform.
It is a further object of the present invention to provide the SnS2/MoS2The application of composite.
It is a further object of the present invention to provide the method for the application.
The above-mentioned purpose of the present invention is achieved by the following technical programs.
One step Hydrothermal Synthesiss SnS of one kind2/MoS2The method of composite, comprises the steps：
S1. it is Xi Yuan and sulphur source is soluble in water, settled solution is formed, sulphur and the mol ratio of tin are 6.0 ~ 10.0 in solution:
1；
S2. add molybdenum source toward S1 solution, produce precipitation, be uniformly mixed so as to obtain mixture, make tin and molybdenum in mixture mole
Than for 4 ~ 19:1；
S3. the mixture for S2 being obtained carries out hydro-thermal reaction, cooling, and rinsing precipitation, centrifugation is dried to obtain product；
Wherein, the Xi Yuan and molybdenum source oppositely charged in the solution.
When as electrode material, SnS2The poor problem of cycle performance is frequently encountered, this is primarily due in discharge and recharge
When caused big bulk effect, cause the efflorescence of electrode material.Inventor is had found by studying, due to SnS2And MoS2Tool
There is similar layer structure, molybdenum is also very close with the atomic radius of tin, by SnS2And MoS2During synthetic composite material, introducing
MoS2With SnS2Pattern and structure there is preferable matching effect, make the two contact good, to SnS2Play certain protection to make
With；Secondly as SnS2And MoS2With similar layer structure, MoS is introduced in the preparation2Layer structure can mutually be suppressed
Stacking, be conducive to each self-forming that there is few number of plies structure of class graphene-structured, this few number of plies structure has more preferably electrification
Learn performance.
In addition, it has also been found that, only when sulphur and tin mol ratio are 6.0 ~ 10.0:1, the mol ratio of tin and molybdenum is 4 ~
19:When 1, SnS2And MoS2The composite for preparing could produce preferable cooperative effect, and experiment finds, with curing
The increase of molybdenum content, the number of plies of molybdenum bisuphide is in increase, and the number of plies of stannic disulfide is declining, so will be in a suitable ratio
Under example scope, chemical property is best when making both numbers of plies all not many；Further, since the specific capacitance of stannic disulfide compares
It is low, molybdenum bisuphide it is more relatively large, so there is also a suitable ratio, make SnS2And MoS2Between produce cooperative effect, i.e.,
So that the chemical property of composite had both been more than stannic disulfide, also greater than molybdenum bisuphide.
The present invention employs first raw material cheap and easy to get and gentle hydro-thermal method one-step synthesis SnS2/MoS2Composite,
And by the mol ratio of sulphur and tin, tin and molybdenum in control raw material, can rapid, high volume synthesis SnS2/MoS2Composite, product yield
Height, and the product pattern prepared is more uniform.
Preferably, the concentration of Xi Yuan described in S1 is 0.01 ~ 0.1 mol/L.
Preferably, the concentration of molybdenum source described in S2 is 0.001～0.05mol/L.
Preferably, the Xi Yuan is butter of tin or STANNOUS SULPHATE CRYSTALLINE.
Preferably, the molybdenum source is sodium molybdate or potassium molybdate
Preferably, the sulphur source is Cys or thiocarbamide.
Preferably, the Xi Yuan be butter of tin, molybdenum source is sodium molybdate, the sulphur source be Cys, sodium molybdate and
Butter of tin is cheap and easy to get, and Cys more have due to containing carboxyl, sulfydryl, there is certain complexing to metal ion
Beneficial to generation SnS2/MoS2Composite material nanometer piece.
Preferably, the condition of hydro-thermal reaction described in S3 is 220 ~ 240 DEG C of reaction 24h.Hydrothermal temperature is too high to cause reaction
Pressure too conference in kettle produces danger, too low to cause that molybdenum disulfide nano sheet can not be generated.Overlong time can cause material chi
It is very little to become big, it is too short, product cannot be generated or products collection efficiency is too low.
Preferably, comprise the steps：
S1. butter of tin is dissolved in into water, the concentration of tin ion is 0.01 ~ 0.1 mol/L, adds Cys,
Settled solution is formed, Cys and the mol ratio of tin ion are 6.0 ~ 10.0 in solution:1；
S2. the sodium molybdate solution of 0.001～0.05mol/L is added toward S1 solution, molybdic acid tin precipitation is produced, stirring is mixed
Tin and the mol ratio of molybdenum are 4 ~ 19 in compound:1；
S3. the mixture for S2 being obtained reacts 24h under 220 ~ 240 DEG C of hydrothermal conditions, cooling, with water and absolute ethyl alcohol
Rinsing respectively is precipitated three times, and centrifugation is dried to obtain product.
Preferably, stirring described in S2 is stirring 30min, solution is fully precipitated.
In order that raw material preferably dissolves during addition, it is preferable that the Xi Yuan, sulphur source and molybdenum source are in stirring
Under conditions of add solution in.
Preferably, the S3 is dried as 60 DEG C of vacuum drying 12h.Vacuum drying can avoid the sulfide for preparing compared with
It is oxidized under high-temperature.
The present invention also provides application of the above-mentioned composite in electrode material is prepared.
Preferably, the electrode material is the electrode material of ultracapacitor.
The method that the present invention also provides above-mentioned application, the composite is coated in conductive substrates.
Preferably, the composite 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 employs first raw material cheap and easy to get and temperature
Hydro-thermal method one-step synthesis SnS of sum2/MoS2Composite, and by sulphur in control raw material and the mol ratio of tin, tin and molybdenum, make
SnS2And MoS2Between produce cooperative effect, can rapid, high volume synthesis SnS2/MoS2Composite, and the product pattern prepared
It is more uniform, free from admixture.The inventive method has the advantages that the SnS that process is simple, low cost, yield are high, prepare2/MoS2
The bouquet that composite products are nanometer sheet or are made up of nanometer sheet, can be applicable to electrode material for super capacitor, be expected to
It is widely applied in fields such as lithium ion battery electrode material, photochemical catalysts.
Description of the drawings
Fig. 1 is SnS obtained in embodiment 12/MoS2The X-ray diffractogram of composite.
Fig. 2 is SnS obtained in embodiment 12/MoS2The scanning electron microscope (SEM) photograph and transmission electron microscope picture of composite；Wherein（A）、
（B）For scanning electron microscope (SEM) photograph,（C）For transmission electron microscope picture.
Fig. 3 is SnS obtained in embodiment 22/MoS2The X-ray diffractogram and scanning electron microscope (SEM) photograph of composite；Wherein（A）For
X-ray diffractogram,（B）For scanning electron microscope (SEM) photograph.
Fig. 4 is SnS obtained in embodiment 32/MoS2The X-ray diffractogram and scanning electron microscope (SEM) photograph of composite；Wherein（A）For
X-ray diffractogram,（B）For scanning electron microscope (SEM) photograph.
Specific embodiment
The present invention is described in further details with reference to Figure of description and specific embodiment, but embodiment is not right
The present invention is limited in any form.Unless stated otherwise, the reagent for adopting of the invention, method and apparatus are normal for the art
Rule reagent, method and apparatus.
Embodiment 1
One step Hydrothermal Synthesiss SnS of one kind2/MoS2The method of composite, comprises the steps：
S1. the Cys of the butter of tin of 1.2mmol and 9mmol are dissolved in 50mL deionized waters under agitation,
Solution A is formed, the concentration of Xi Yuan is 0.024 mol/L in solution, Cys are 7.5 with the mol ratio of tin ion:1.
S2. the sodium molybdate of 0.3mmol is dissolved in 10ml deionized waters and forms solution B, the concentration of sodium molybdate solution is
0.03 mol/L, is then under vigorous stirring added dropwise to solution B in solution A, generates greenish precipitate, drips follow-up
Continuous strong agitation 30 minutes, tin and the mol ratio of molybdenum are 4 in mixture:1.
S3. the mixture that S2 is obtained is transferred in the stainless steel cauldron that 100ml liners are polytetrafluoroethylene (PTFE), is placed in
In baking oven, in 240 DEG C of hydro-thermal reactions 24h, room temperature is naturally cooled to, gained precipitate with deionized water and absolute ethyl alcohol are floated respectively
Wash three times, centrifugation, 60 DEG C are dried 12h in vacuum drying chamber, obtain SnS2/MoS2Composite nano plate.
Obtained SnS2/MoS2The X-ray diffractogram of product is shown in Fig. 1, and each diffraction maximum position of stannic disulfide and intensity are equal in figure
It is consistent with standard diffraction card (JCPDS23-0677), each diffraction maximum position of molybdenum bisuphide and intensity with standard diffraction card
(JCPDS37-1492) it is consistent, illustrate that composite is made up of stannic disulfide and molybdenum bisuphide.
Obtained SnS2/MoS2The scanning electron microscope (SEM) photograph of product is shown in that Fig. 2, Fig. 2 (A) show SnS2/MoS2Joint product is size
With the more uniform micro-flowers of pattern.Fig. 2 (B) shows the surface texture of micro-flowers, and Fig. 2 (C) shows the internal structure of micro-flowers,
It can be seen that the nanometer sheet that this micro-flowers is staggered by many is constituted.
Weigh 40mg SnS2/MoS2Grind after joint product and the mixing of 5mg acetylene blacks, add 5mg polytetrafluoroethylene (PTFE), plus
A small amount of 1-METHYLPYRROLIDONE (NMP) ultrasonic disperse 30min, is coated in foam nickel surface, the vacuum at 60 DEG C after dispersion
It is dried after 12h and obtains required electrode slice.With resulting SnS2/MoS2Electrode as working electrode, platinum plate electrode be to electrode,
Saturated calomel electrode is reference electrode, and 3.5mol/L potassium hydroxide solutions are that electrolyte assembles super capacitor.Chemical property is surveyed
Take temperature bright, in 1Ag-1The specific capacitance of the lower ultracapacitor is 145F/g.
Embodiment 2
One step Hydrothermal Synthesiss SnS of one kind2/MoS2The method of composite, comprises the steps：
S1. under agitation the Cys of the butter of tin of 1.35mmol and 9mmol are dissolved in into 50mL deionized waters
In, solution A is formed, the concentration of Xi Yuan is 0.027 mol/L in solution, and Cys are 20 with the mol ratio of tin ion:3；
S2. the sodium molybdate of 0.15mmol is dissolved in 10ml deionized waters and forms solution B, the concentration of sodium molybdate solution is
0.015 mol/L, is then under vigorous stirring added dropwise to solution B in solution A, greenish precipitate is generated, after dripping
Continue strong agitation 30 minutes, tin and the mol ratio of molybdenum are 9 in mixture:1；
S3. the mixture that S2 is obtained is transferred in the stainless steel cauldron that 100ml liners are polytetrafluoroethylene (PTFE), is placed in
In baking oven, in 240 DEG C of hydro-thermal reactions 24h, room temperature is naturally cooled to, gained precipitate with deionized water and absolute ethyl alcohol are floated respectively
Wash three times, centrifugation, 60 DEG C are dried 12h in vacuum drying chamber, obtain SnS2/MoS2Composite nano plate.
Obtained SnS2/MoS2The X-ray diffractogram of product is shown in Fig. 3 (A), each diffraction maximum position of stannic disulfide and strong in figure
Degree is consistent with standard diffraction card (JCPDS23-0677), each diffraction maximum position of molybdenum bisuphide and intensity with standard diffraction card
Piece (JCPDS37-1492) is consistent, illustrates that composite is made up of stannic disulfide and molybdenum bisuphide.
Obtained SnS2/MoS2The scanning electron microscope (SEM) photograph of product is shown in that Fig. 3 (B), Fig. 3 (B) show SnS2/MoS2Joint product is
The micro-flowers that the nanometer sheet being staggered by many is constituted.
Weigh 40mg SnS2/MoS2Grind after joint product and the mixing of 5mg acetylene blacks, add 5mg polytetrafluoroethylene (PTFE), plus
A small amount of 1-METHYLPYRROLIDONE (NMP) ultrasonic disperse 30min, is coated in foam nickel surface, the vacuum at 60 DEG C after dispersion
It is dried after 12h and obtains required electrode slice.With resulting SnS2/MoS2Electrode as working electrode, platinum plate electrode be to electrode,
Saturated calomel electrode is reference electrode, and 3.5mol/L potassium hydroxide solutions are that electrolyte assembles super capacitor.Chemical property is surveyed
Take temperature bright, in 1Ag-1The specific capacitance of the lower ultracapacitor is 234F/g.
Embodiment 3
One step Hydrothermal Synthesiss SnS of one kind2/MoS2The method of composite, comprises the steps：
S1. under agitation the Cys of the butter of tin of 1.275mmol and 9mmol are dissolved in into 50mL deionized waters
In, solution A is formed, the concentration of Xi Yuan is 0.0255mol/L in solution, and Cys are 7 with the mol ratio of tin ion:1；
S2. the sodium molybdate of 0.225mmol is dissolved in 10ml deionized waters and forms solution B, the concentration of sodium molybdate solution is
0.0225 mol/L, is then under vigorous stirring added dropwise to solution B in solution A, greenish precipitate is generated, after dripping
Continue strong agitation 30 minutes, tin and the mol ratio of molybdenum are 17 in mixture:3；
S3. the mixture that S2 is obtained is transferred in the stainless steel cauldron that 100ml liners are polytetrafluoroethylene (PTFE), is placed in
In drying box, in 220 DEG C of hydro-thermal reactions 24h, room temperature is naturally cooled to, gained precipitate with deionized water and absolute ethyl alcohol are distinguished
Rinsing three times, centrifugation, 60 DEG C are dried 12h in vacuum drying chamber, obtain SnS2/MoS2Composite nano plate.
Obtained SnS2/MoS2The X-ray diffractogram of product is shown in Fig. 4 (A), each diffraction maximum position of stannic disulfide and strong in figure
Degree is consistent with standard diffraction card (JCPDS23-0677), each diffraction maximum position of molybdenum bisuphide and intensity with standard diffraction card
Piece (JCPDS37-1492) is consistent, illustrates that composite is made up of stannic disulfide and molybdenum bisuphide.
Obtained SnS2/MoS2The scanning electron microscope (SEM) photograph of product is shown in Fig. 4 (B), shows SnS2/MoS2Joint product is by many
The micro-flowers of the nanometer sheet composition being staggered.
Weigh 40mg SnS2/MoS2Grind after joint product and the mixing of 5mg acetylene blacks, add 5mg polytetrafluoroethylene (PTFE), plus
A small amount of 1-METHYLPYRROLIDONE (NMP) ultrasonic disperse 30min, is coated in foam nickel surface, the vacuum at 60 DEG C after dispersion
It is dried after 12h and obtains required electrode slice.With resulting SnS2/MoS2Electrode as working electrode, platinum plate electrode be to electrode,
Saturated calomel electrode is reference electrode, and 3.5mol/L potassium hydroxide solutions are that electrolyte assembles super capacitor.Chemical property is surveyed
Take temperature bright, in 1Ag-1The specific capacitance of the lower ultracapacitor is 183F/g.
Comparative example 1
This comparative example adopts following two tin molybdenum ratios：Process 1. 3:1；Process 2. 24:1 preparing SnS2/MoS2Composite wood
Material, concrete grammar is as follows：
Process 1.：One step Hydrothermal Synthesiss SnS2/MoS2The method of composite, comprises the steps：
S1. under agitation the Cys of the butter of tin of 1.125mmol and 9mmol are dissolved in into 50mL deionized waters
In, solution A is formed, the concentration of Xi Yuan is 0.0225mol/L in solution, and Cys are 8 with the mol ratio of tin ion:1；
S2. the sodium molybdate of 0.375mmol is dissolved in 10ml deionized waters and forms solution B, the concentration of sodium molybdate solution is
0.0375 mol/L, is then under vigorous stirring added dropwise to solution B in solution A, greenish precipitate is generated, after dripping
Continue strong agitation 30 minutes, tin and the mol ratio of molybdenum are 3 in mixture:1；
S3. the mixture that S2 is obtained is transferred in the stainless steel cauldron that 100ml liners are polytetrafluoroethylene (PTFE), is placed in
In drying box, in 220 DEG C of hydro-thermal reactions 24h, room temperature is naturally cooled to, gained precipitate with deionized water and absolute ethyl alcohol are distinguished
Rinsing three times, centrifugation, 60 DEG C are dried 12h in vacuum drying chamber, obtain SnS2/MoS2Composite nano plate.
Obtained SnS2/MoS2Product Jing X-ray diffractions are characterized, each diffraction maximum position of stannic disulfide and strong in composite
Degree is consistent with standard diffraction card (JCPDS23-0677), each diffraction maximum position of molybdenum bisuphide and intensity with standard diffraction card
Piece (JCPDS37-1492) is consistent, illustrates that composite is made up of stannic disulfide and molybdenum bisuphide.
Obtained SnS2/MoS2Product scanning electron microscopic observation, its pattern is the irregular micron of pattern of nanometer sheet composition
Flower.
Weigh 40mg SnS2/MoS2Grind after joint product and the mixing of 5mg acetylene blacks, add 5mg polytetrafluoroethylene (PTFE), plus
A small amount of 1-METHYLPYRROLIDONE (NMP) ultrasonic disperse 30min, is coated in foam nickel surface, the vacuum at 60 DEG C after dispersion
It is dried after 12h and obtains required electrode slice.With resulting SnS2/MoS2Electrode as working electrode, platinum plate electrode be to electrode,
Saturated calomel electrode is reference electrode, and 3.5mol/L potassium hydroxide solutions are that electrolyte assembles super capacitor.Chemical property is surveyed
Take temperature bright, in 1Ag-1The specific capacitance of the lower ultracapacitor is only 126F/g.This is because the content of molybdenum bisuphide is excessive
Cause well be combined the decline for causing capacity with stannic disulfide.
Process 2.：One step Hydrothermal Synthesiss SnS2/MoS2The method of composite, comprises the steps：
S1. under agitation the Cys of the butter of tin of 1.44mmol and 14.4mmol are dissolved in into 50mL deionizations
In water, solution A is formed, the concentration of Xi Yuan is 0.0288mol/L in solution, Cys are 10 with the mol ratio of tin ion:
1；
S2. the sodium molybdate of 0.06mmol is dissolved in 10ml deionized waters and forms solution B, the concentration of sodium molybdate solution is
0.006 mol/L, is then under vigorous stirring added dropwise to solution B in solution A, greenish precipitate is generated, after dripping
Continue strong agitation 30 minutes, tin and the mol ratio of molybdenum are 24 in mixture:1；
S3. the mixture that S2 is obtained is transferred in the stainless steel cauldron that 100ml liners are polytetrafluoroethylene (PTFE), is placed in
In drying box, in 220 DEG C of hydro-thermal reactions 24h, room temperature is naturally cooled to, gained precipitate with deionized water and absolute ethyl alcohol are distinguished
Rinsing three times, centrifugation, 60 DEG C are dried 12h in vacuum drying chamber, obtain SnS2/MoS2Composite nano plate.
Obtained SnS2/MoS2Product Jing X-ray diffractions are characterized, each diffraction maximum position of stannic disulfide and strong in composite
Degree is consistent with standard diffraction card (JCPDS23-0677), each diffraction maximum position of molybdenum bisuphide and intensity with standard diffraction card
Piece (JCPDS37-1492) is consistent, illustrates that composite is made up of stannic disulfide and molybdenum bisuphide.
Obtained SnS2/MoS2Product scanning electron microscopic observation, its pattern is nanometer sheet.
Weigh 40mg SnS2/MoS2Grind after joint product and the mixing of 5mg acetylene blacks, add 5mg polytetrafluoroethylene (PTFE), plus
A small amount of 1-METHYLPYRROLIDONE (NMP) ultrasonic disperse 30min, is coated in foam nickel surface, the vacuum at 60 DEG C after dispersion
It is dried after 12h and obtains required electrode slice.With resulting SnS2/MoS2Electrode as working electrode, platinum plate electrode be to electrode,
Saturated calomel electrode is reference electrode, and 3.5mol/L potassium hydroxide solutions are that electrolyte assembles super capacitor.Chemical property is surveyed
Take temperature bright, in 1Ag-1The specific capacitance of the lower ultracapacitor is only 98F/g.This mainly due to molybdenum bisuphide content compared with
Few, the capacity contribution to lifting whole composite is little.
Comparative example 2
The sulphur tin ratio adopted in this comparative example step S1 is for 3:1, prepare SnS2/MoS2The method of composite is as follows：
One step Hydrothermal Synthesiss SnS of one kind2/MoS2The method of composite, comprises the steps：
S1. under agitation the Cys of the butter of tin of 1.35mmol and 4.05mmol are dissolved in into 50mL deionizations
In water, solution A is formed, the concentration of Xi Yuan is 0.027 mol/L in solution, Cys are 3 with the mol ratio of tin ion:1；
S2. the sodium molybdate of 0.15mmol is dissolved in 10ml deionized waters and forms solution B, the concentration of sodium molybdate solution is
0.015 mol/L, is then under vigorous stirring added dropwise to solution B in solution A, greenish precipitate is generated, after dripping
Continue strong agitation 30 minutes, tin and the mol ratio of molybdenum are 9 in mixture:1；
S3. the mixture that S2 is obtained is transferred in the stainless steel cauldron that 100ml liners are polytetrafluoroethylene (PTFE), is placed in
In baking oven, in 240 DEG C of hydro-thermal reactions 24h, room temperature is naturally cooled to, gained precipitate with deionized water and absolute ethyl alcohol are floated respectively
Wash three times, centrifugation, 60 DEG C are dried 12h in vacuum drying chamber, obtain SnS2/MoS2Composite nano plate.
Obtained product learnt with X-ray diffraction analysis, each diffraction maximum position of stannic disulfide and intensity in X-ray diffractogram
It is consistent with standard diffraction card (JCPDS23-0677), each diffraction maximum position of molybdenum bisuphide and intensity with standard diffraction card
(JCPDS37-1492) it is consistent, in addition, have also appeared the diffraction maximum of a small amount of tin ash and molybdenum trioxide, when sulphur source it is inadequate
When, it is impossible to by its complete cure into stannic disulfide and molybdenum bisuphide.
Obtained product with scanning electron microscopic observation find, in addition to the nanometer sheet that there is bidimensional, also some are fragmentary
Nano-particle, tin ash or molybdenum trioxide nano particle that this nano-particle is not possibly fully vulcanized.
Comparative example 3
This comparative example prepares SnS2/MoS2The method of composite is substantially same as Example 3, except S3 hydro-thermal reactions
Condition is different.This comparative example adopts following hydrothermal reaction condition：The mixture that 1. process obtains S2 is in 150 DEG C of hydro-thermal reactions
24h；The mixture that 2. process obtains S2 is in 220 DEG C of hydro-thermal reactions 12h.
Obtained product under the conditions of above two is learnt into that stannic disulfide is each in X-ray diffractogram with X-ray diffraction analysis
Diffraction maximum position and intensity are consistent with standard diffraction card (JCPDS23-0677), each diffraction maximum position of molybdenum bisuphide and intensity
It is consistent with standard diffraction card (JCPDS37-1492), in addition, the diffraction maximum of a small amount of molybdenum trioxide is have also appeared, and
The degree of crystallinity of product is bad, illustrates when temperature is too low or during the too short reaction time, not only the crystallinity of product is bad, and can not
Completely sodium molybdate is sulfided into into molybdenum bisuphide.
Comparative example 4
One step Hydrothermal Synthesiss SnS of one kind2/MoS2The method of composite, comprises the steps：
S1. under agitation the Cys of the butter of tin of 0.75mmol and 10.5mmol are dissolved in into 50mL deionizations
In water, solution A is formed, the concentration of Xi Yuan is 0.015 mol/L in solution, Cys are 14 with the mol ratio of tin ion:
1；
S2. the sodium molybdate of 0.75mmol is dissolved in 10ml deionized waters and forms solution B, the concentration of sodium molybdate solution is
0.075 mol/L, is then under vigorous stirring added dropwise to solution B in solution A, greenish precipitate is generated, after dripping
Continue strong agitation 30 minutes, tin and the mol ratio of molybdenum are 1 in mixture:1；
S3. the mixture that S2 is obtained is transferred in the stainless steel cauldron that 100ml liners are polytetrafluoroethylene (PTFE), is placed in
In drying box, in 220 DEG C of hydro-thermal reactions 24h, room temperature is naturally cooled to, gained precipitate with deionized water and absolute ethyl alcohol are distinguished
Rinsing three times, centrifugation, 60 DEG C are dried 12h in vacuum drying chamber, obtain SnS2/MoS2Composite nano plate.
Obtained product under above-mentioned condition is learnt with X-ray diffraction analysis, each diffraction of stannic disulfide in X-ray diffractogram
Peak position and intensity are consistent with standard diffraction card (JCPDS23-0677), each diffraction maximum position of molybdenum bisuphide and intensity with
Standard diffraction card (JCPDS37-1492) is consistent, but each diffraction maximum is very weak, illustrates that the degree of crystallinity of product is bad.ESEM
It is the irregular micro-flowers being made up of nanometer sheet to observe its pattern.
The said goods are made into electrode by method above, electrochemical property test is carried out.As a result show, in 1Ag-1Down should
The specific capacitance of ultracapacitor is only 65F/g.This excessively causes and two mainly due to the content of one side molybdenum bisuphide
Artificial gold can not be combined well；On the other hand excessive sulphur source can introduce relatively low compared with multicapacity amorphous to composite
Carbon, the degree of crystallinity of the product for not only reducing, and the capacity of composite can be caused to decline.
Claims (10)
1. a kind of step Hydrothermal Synthesiss SnS2/MoS2The method of composite, it is characterised in that comprise the steps：
S1. it is Xi Yuan and sulphur source is soluble in water, settled solution is formed, sulphur and the mol ratio of tin are 6.0 ~ 10.0 in solution:1；
S2. add molybdenum source toward S1 solution, produce precipitation, be uniformly mixed so as to obtain mixture, make the tin in mixture be with the mol ratio of molybdenum
4~19:1；
S3. the mixture for S2 being obtained carries out hydro-thermal reaction, cooling, and rinsing precipitation, centrifugation is dried to obtain product；
Wherein, the Xi Yuan and molybdenum source oppositely charged in the solution.
2. method according to claim 1, it is characterised in that the concentration of Xi Yuan described in S1 is 0.01 ~ 0.1 mol/L.
3. method according to claim 1, it is characterised in that the concentration of molybdenum source described in S2 is 0.001～0.05mol/L.
4. method according to claim 1, it is characterised in that the Xi Yuan is butter of tin or STANNOUS SULPHATE CRYSTALLINE.
5. method according to claim 1, it is characterised in that the molybdenum source is sodium molybdate or potassium molybdate.
6. method according to claim 1, it is characterised in that the sulphur source is Cys or thiocarbamide.
7. method according to claim 1, it is characterised in that the condition of hydro-thermal reaction described in S3 is 220 ~ 240 DEG C of reactions
24h。
8. the method according to any one of claim 1 ~ 7, it is characterised in that comprise the steps：
S1. butter of tin is dissolved in into water, the concentration of tin ion is 0.01 ~ 0.1 mol/L, adds Cys, is formed clear
Clear solution, Cys and the mol ratio of tin ion are 6.0 ~ 10.0 in solution:1；
S2. the sodium molybdate solution of 0.001～0.05mol/L is added toward S1 solution, molybdic acid tin precipitation, stirring, mixture is produced
Middle tin is 4 ~ 19 with the mol ratio of molybdenum:1；
S3. the mixture for S2 being obtained reacts 24h under 220 ~ 240 DEG C of hydrothermal conditions, cooling, is distinguished with water and absolute ethyl alcohol
Rinsing precipitation three times, centrifugation is dried to obtain product.
9. application of the composite described in claim 1 in electrode material is prepared.
10. the method applied described in claim 9, it is characterised in that the composite is coated in conductive substrates.
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