CN109256546A - A kind of molybdenum disulfide/graphene composite material and its preparation method and application - Google Patents
A kind of molybdenum disulfide/graphene composite material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of molybdenum disulfide/graphene composite materials and its preparation method and application, belong to electrochemistry and new energy materials field, and preparation method of the invention is the following steps are included: (1) prepares four thio ammonium molybdate；(2) electrochemical process prepares graphene slurry；(3) graphene surface is modified；(4) molybdenum disulfide/graphene composite material preparation.Present invention process is simple to operation, and mild condition, repeatability are high, yield is high, is suitable for batch production.The composite material of preparation both improves MoS2Electric conductivity, and inhibit MoS2With the reunion of graphene, when being applied to lithium ion battery negative material, high specific capacity and excellent cyclical stability are shown.First discharge specific capacity reaches 700~1200mAh/g at 0.01~3.0V, 200 mA/g current densities, maintains 550~850 mAh/g by 200 circulation specific discharge capacities.
Description
Technical field
The present invention relates to a kind of molybdenum disulfide/graphene composite materials and its preparation method and application, belong to new energy electricity
Pond field of material technology.
Background technique
Due to the protrusion of the energy and environmental crisis problem, the chemistry storage of safe and efficient, environmental-friendly secondary cell system
Energy technology receives significant attention and Innovation Input.Wherein lithium ion battery is green energy most competitive in secondary cell system
Source.Lithium ion battery has energy density height, stable operating voltage, has a safety feature, has extended cycle life, the spies such as memory-less effect
Property advantage, is widely used in the fields such as communications and transportation, household electrical appliances, office, mobile communication.However, the specific volume of conventional graphite cathode
Amount (372 mAh/g) is lower, significantly limits the application of lithium ion battery.Therefore, research and development have more preferable performance
Novel anode material oneself through at lithium ion battery material research aspect heat subject.
Molybdenum disulfide (MoS2), as a kind of stratified material with similar graphene two-dimensional structure, there is theoretical ratio
Capacity height (670 mAh/g), it is low in cost the advantages that, caused the very big concern of numerous scientific research personnel, be considered as a kind of
The lithium ion battery negative material of great prospect.However, MoS2There are still some inevitable defects, such as electric conductivity for itself
The problems such as being easy to happen reunion in difference, cyclic process, greatly reduces its cycle performance, is unable to satisfy requirement.Currently, often
MoS2Method of modifying has two classes: first, preparing the MoS of special nanostructure2, such as MoS2Nanotube, MoS2Nano flower etc.,
But the MoS of such methods preparation2The problems such as there are complex process uncontrollable, easy to reunite and poorly conductive；Second, by MoS2
It is compound with Carbon Materials, such as graphene, carbon nanotube, amorphous carbon, prepare combination electrode material.
Summary of the invention
The present invention is intended to provide a kind of molybdenum disulfide/graphene composite material and its preparation method and application, solves existing
Have when preparing complicated molybdenum disulfide composite technology, poor controllability in technology and being used as lithium ion battery negative material, follows
The problem of ring low efficiency and stability difference.This method simple process is easy to operate, and mild condition, reproducible, yield is high, is suitable for
Batch production.
The present invention is by MoS2It is compound with Carbon Materials graphene, combination electrode material has been prepared, MoS is not only increased2Lead
Electrically, and MoS is inhibited2With the reunion of graphene sheet layer, when being applied to lithium ion battery negative material, show high
Specific capacity and excellent cyclical stability.First discharge specific capacity reaches 700 at 0.01~3.0V, 200mA/g current density
~1200mAh/g maintains 550~850 mAh/g by 200 circulation specific discharge capacities.
The present invention provides a kind of preparation methods of molybdenum disulfide/graphene composite material, comprising the following steps: (1) makes
Standby four thio ammonium molybdate；(2) electrochemical process prepares graphene slurry；(3) graphene surface is modified；(4) molybdenum disulfide/stone is prepared
Black alkene composite material.
Specifically, above-mentioned preparation method the following steps are included:
(1) four thio ammonium molybdate is prepared:
Ammonium Molybdate Tetrahydrate is dissolved in deionized water, pH is adjusted with ammonium hydroxide, ammonium sulfide solution is added, in 75 ~ 95 DEG C of water-bath items
1 ~ 3h of reaction is stirred at reflux under part, cooled to room temperature stands still for crystals 24 ~ 48h, and filtering washes crystal with dehydrated alcohol
It washs, drying at room temperature, finally obtains four thio ammonium molybdate crystal；
(2) electrochemical process prepares graphene slurry:
Using graphite rod as working electrode, controlling DC voltage in the electrolytic solution is 5 ~ 10V, and electrolysis time is 12 ~ 36h, is then passed through
Separation of solid and liquid, ultrasonic disperse, washing are crossed, graphene slurry is finally obtained；
(3) graphene surface is modified:
Cetyl trimethylammonium bromide ultrasonic wave added is dissolved in deionized water, the solution that concentration is 0.1M is configured to, by it
Be added in the made graphene slurry of step (2), 0.5 ~ 2h of ultrasonic disperse, at room temperature with the speed of 150 r/min stirring 24 ~
48h；
(4) molybdenum disulfide/graphene composite material is prepared:
Four thio ammonium molybdate is dissolved in the in the mixed solvent of n,N-Dimethylformamide and deionized water, is added to step (3) institute
In the modified graphene slurry of system, 0.5 ~ 2h of ultrasonic disperse reacts 2~4h under 50~70 DEG C of water bath conditions, freeze-drying for 24 hours,
Gained sample obtains molybdenum disulfide/graphene composite material by the high temperature anneal.
Above-mentioned preparation method in step (1), adjusts pH to 9 ~ 12 with ammonium hydroxide, and Ammonium Molybdate Tetrahydrate and ammonium sulfide rub
You are than being 1:(28~42)；The mass concentration of ammonium sulfide solution is 25%.
Above-mentioned preparation method, in step (2), the electrolyte is N- butyl-pyridinium tetrafluoroborate, 1- octyl -3- first
One of base imidazoles bromide, 1- hexyl -3- methylimidazole hexafluorophosphate, 1- butyl -3- methyl imidazolium tetrafluoroborate or
Several mixtures (various substances can be mixed in mixture with arbitrary proportion).
Above-mentioned preparation method, in step (2), the mass concentration of the graphene slurry is 1 ~ 3.5%.
Above-mentioned preparation method, in step (3), the solution of the cetyl trimethylammonium bromide and graphene slurry
Volume ratio is 1:(5~30).
Above-mentioned preparation method, in step (4), the volume ratio of the n,N-Dimethylformamide and deionized water be 1:5 ~
The molal volume ratio of 3:1, four thio ammonium molybdate and mixed solvent is 1:3(mol/L), i.e., 1mol four thio ammonium molybdate uses mixing
Solvent 3L；The mass ratio of four thio ammonium molybdate and graphene is 1:(0.1~1.5).
Above-mentioned preparation method, in step (4), the annealing treating process parameter are as follows: temperature is 400~700 DEG C, heat preservation
Time is 1 ~ 3h, and heating rate is 5 ~ 15 DEG C/min, and protection gas is nitrogen.
The present invention provides using molybdenum disulfide/graphene composite material made from above-mentioned preparation method.
It is described the present invention provides application of the above-mentioned molybdenum disulfide/graphene composite material in lithium cell cathode material
Molybdenum disulfide/graphene composite material can be used as active constituent and be used to prepare negative electrode of lithium ion battery.
The preparation method of the negative electrode of lithium ion battery specifically: by active material molybdenum disulfide/graphene composite material,
Conductive agent acetylene black and binder Kynoar are uniformly mixed according to mass ratio for 8:1:1, and N-Methyl pyrrolidone is solvent,
Prepare electrode slurry；Then the slurry is uniformly coated on copper foil, working electrode is pressed into after vacuum drying；With metallic lithium foil
For to electrode and reference electrode, diaphragm is polypropylene film (Celgard-2400), electrolyte is 1.0 M LiPF6Carbonic acid second
Enester (EC)/dimethyl carbonate (DMC) solution (volume ratio 1:1) carries out battery assembly in the glove box full of argon gas.
At room temperature, using the capacity and cycle performance of LAND 2001A series battery controlled testing instrument test simulation battery
Test.Charging and discharging currents are 200 mA/g, and voltage cut-off section is 3.0V ~ 0.01V.It is close in 0.01~3.0V, 200mA/g electric current
It spends lower first discharge specific capacity and reaches 700~1200mAh/g, maintain 550~850 by 200 circulation specific discharge capacities
MAh/g,
Beneficial effects of the present invention:
(1) present invention solve it is existing prepare molybdenum disulfide/graphene composite material complex process, preparation poor controllability is asked
Topic.Present invention process is simple to operation, and mild condition, reproducible, yield is high, is suitable for batch production；
(2) present invention prepares graphene slurry using electrochemical process, and graphene product can be obtained in a step, is easy manipulation, environmental protection
It is pollution-free, and a large amount of defects will not be introduced on the surface of graphene；
(3) invention introduces cationic surfactants, not only obtain evenly dispersed MoS2Nano particle, and very big journey
Inhibit MoS to degree2With the reunion of graphene；
(4) molybdenum disulfide/graphene nanocomposite material obtained by the present invention directly applies to lithium ion battery negative material
When, show high specific capacity and excellent cyclical stability.It discharges for the first time at 0.01~3.0V, 200mA/g current density
Specific capacity reaches 700~1200mAh/g, maintains 550~850 mAh/g by 200 circulation specific discharge capacities.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) photo of 1 gained graphene of the embodiment of the present invention.
Fig. 2 is 2 gained molybdenum disulfide of the embodiment of the present invention/graphene composite material scanning electron microscope (SEM) photo.
Fig. 3 is molybdenum disulfide/graphene composite material X-ray diffraction (XRD) figure prepared by the embodiment of the present invention 3.
Fig. 4 is the X-ray diffraction (XRD) figure of four thio ammonium molybdate prepared by the embodiment of the present invention 4.
Fig. 5 is molybdenum disulfide/graphene composite material of the preparation of the embodiment of the present invention 5 as lithium ion battery negative material
?
Stable circulation performance test chart under 200mA/g current density.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following embodiment.
Embodiment 1:
S1. prepare four thio ammonium molybdate: 5g Ammonium Molybdate Tetrahydrate be dissolved in 30 mL deionized waters, with ammonium hydroxide adjust pH to
11,70mL ammonium sulfide solution is added, reaction 2.5h is stirred at reflux at 80 DEG C, is cooled to room temperature, stands still for crystals 42h, by crystal mistake
Filter, is washed with dehydrated alcohol, and drying for 24 hours, obtains four thio ammonium molybdate crystallization at room temperature.
S2. electrochemical process prepares graphene slurry: being the N- butyl pyrrole of 1:1 with volume ratio using graphite rod as working electrode
The mixture of pyridine tetrafluoroborate and 1- hexyl -3- methylimidazole hexafluorophosphate is electric under the voltage of 8.5V as electrolyte
18h is solved, separation of solid and liquid, ultrasonic disperse, washing are then passed through, finally obtains the graphene slurry that mass concentration is 1.5%.
S3. graphene surface is modified: accurately weighing 3.644g(0.01mol) cetyl trimethylammonium bromide ultrasound is auxiliary
Then hydrotropy is settled to 100 mL in 50 mL deionized waters, obtain the solution that concentration is 0.1M.By volume for 1:20's
Ratio is added in graphene slurry, and ultrasonic disperse 1h is vigorously stirred for 24 hours at room temperature.
S4. molybdenum disulfide/graphene composite lithium ion battery negative electrode material preparation, specifically by 2.6g four thio ammonium molybdate
It is dissolved in the in the mixed solvent of n,N-Dimethylformamide and deionized water that 30 mL volume ratios are 1:1, it is modified to be added to 43.3g
In graphene slurry, ultrasonic disperse 0.5h reacts 2h under 60 DEG C of water bath conditions, freeze-drying for 24 hours, finally in a nitrogen atmosphere
500 DEG C of the high temperature anneals, soaking time 1.5h, heating rate are 10 DEG C/min, obtain molybdenum disulfide/graphene composite lithium ion battery
Negative electrode material.
By resulting active material molybdenum disulfide/graphene composite material, conductive agent acetylene black and binder polyvinylidene fluoride
Alkene is uniformly mixed according to mass ratio for 8:1:1, and N-Methyl pyrrolidone is solvent, prepares electrode slurry.Then the slurry is equal
It is coated on copper foil evenly, working electrode is pressed into after vacuum drying.Metallic lithium foil is to electrode and reference electrode, and diaphragm is poly- third
Alkene film (Celgard-2400), electrolyte are 1.0 M LiPF6Ethylene carbonate (EC)/dimethyl carbonate (DMC) solution
(volume ratio 1:1) carries out battery assembly in the glove box full of argon gas.At room temperature, using LAND 2001A series battery
The capacity and cycle performance of controlled testing instrument test simulation battery are tested.
Material first discharge specific capacity at 0.01~3.0V, 200mA/g current density reaches 782mAh/g, passes through
200 times circulation specific discharge capacity maintains 571mAh/g.
Fig. 1 is scanning electron microscope (SEM) photo of 1 gained graphene of the embodiment of the present invention.Found out by Fig. 1 and successfully prepares slice
Layer graphene.
Embodiment 2
S1. prepare four thio ammonium molybdate: 5g Ammonium Molybdate Tetrahydrate be dissolved in 30 mL deionized waters, with ammonium hydroxide adjust pH to
12,90mL ammonium sulfide solution is added, reaction 1.5h is stirred at reflux at 90 DEG C, is cooled to room temperature, stands still for crystals 36h, by crystal mistake
Filter, is washed with dehydrated alcohol, and drying for 24 hours, obtains four thio ammonium molybdate crystallization at room temperature.
S2. electrochemical process prepares graphene slurry: being the N- butyl of 1:1:1 with volume ratio using graphite rod as working electrode
The mixture of pyridinium tetrafluoroborate salt, 1- octyl -3- methylimidazole bromide and 1- hexyl -3- methylimidazole hexafluorophosphate is made
It for electrolyte, is electrolysed under the voltage of 7V for 24 hours, then passes through separation of solid and liquid, ultrasonic disperse, washing, finally obtain mass concentration
For 2.0% graphene slurry.
S3. graphene surface is modified: accurately weighing 3.644g(0.01mol) cetyl trimethylammonium bromide ultrasound is auxiliary
Then hydrotropy is settled to 100 mL in 50 mL deionized waters, obtain the solution that concentration is 0.1M.By volume for 1:10's
Ratio is added in graphene slurry, and ultrasonic disperse 0.5h is vigorously stirred 36h at room temperature.
S4. molybdenum disulfide/graphene composite lithium ion battery negative electrode material preparation, specifically by 2.6g four thio ammonium molybdate
It is dissolved in the in the mixed solvent of n,N-Dimethylformamide and deionized water that 30 mL volume ratios are 2:1, is added to the modified stone of 130g
In black alkene slurry, ultrasonic disperse 0.5h reacts 2.5h under 65 DEG C of water bath conditions, freeze-drying for 24 hours, finally in a nitrogen atmosphere
500 DEG C of the high temperature anneals, soaking time 1h, heating rate are 10 DEG C/min, and it is negative to obtain molybdenum disulfide/graphene composite lithium ion battery
Pole material.Material first discharge specific capacity at 0.01~3.0V, 200mA/g current density reaches 1063mAh/g, passes through
200 times circulation specific discharge capacity maintains 818mAh/g.
Fig. 2 is 2 gained molybdenum disulfide of the embodiment of the present invention/graphene composite material scanning electron microscope (SEM) photo.It can by figure
To find out that molybdenum disulfide disperses on the surface of graphene well, it is suppressed that the reunion of molybdenum disulfide and graphene.
Embodiment 3
S1. prepare four thio ammonium molybdate: 5g Ammonium Molybdate Tetrahydrate be dissolved in 30 mL deionized waters, with ammonium hydroxide adjust pH to
9.5,85mL ammonium sulfide solution is added, reaction 2h is stirred at reflux at 85 DEG C, is cooled to room temperature, stands still for crystals 30h, by crystal mistake
Filter, is washed with dehydrated alcohol, and drying for 24 hours, obtains four thio ammonium molybdate crystallization at room temperature.
S2. electrochemical process prepares graphene slurry: being the N- butyl pyrrole of 1:1 with volume ratio using graphite rod as working electrode
Pyridine tetrafluoroborate and the mixture of 1- octyl -3- methylimidazole bromide are electrolysed 36h, so as electrolyte under the voltage of 6V
Afterwards by separation of solid and liquid, ultrasonic disperse, washing, the graphene slurry that mass concentration is 2.5% is finally obtained.
S3. graphene surface is modified: accurately weighing 3.644g(0.01mol) cetyl trimethylammonium bromide ultrasound is auxiliary
Then hydrotropy is settled to 100 mL in 50 mL deionized waters, obtain the solution that concentration is 0.1M.By volume for 1:15's
Ratio is added in graphene slurry, and ultrasonic disperse 2h is vigorously stirred 42h at room temperature.
S4. molybdenum disulfide/graphene composite lithium ion battery negative electrode material preparation, specifically by 2.6g four thio ammonium molybdate
It is dissolved in the in the mixed solvent of n,N-Dimethylformamide and deionized water that 30 mL volume ratios are 1:2, is added to the modified stone of 12g
In black alkene slurry, ultrasonic disperse 0.5h reacts 4h under 50 DEG C of water bath conditions, freeze-drying for 24 hours, finally in a nitrogen atmosphere 600
DEG C the high temperature anneal, soaking time 2h, heating rate are 15 DEG C/min, obtain molybdenum disulfide/graphene composite lithium ion battery cathode
Material.Material first discharge specific capacity at 0.01~3.0V, 200mA/g current density reaches 715mAh/g, by 200 times
Circulation specific discharge capacity maintains 608mAh/g.
Fig. 3 is molybdenum disulfide/graphene composite material X-ray diffraction (XRD) figure prepared by the embodiment of the present invention 3.By
Figure can be seen that the characteristic diffraction peak of molybdenum disulfide and graphene, illustrate successfully to prepare molybdenum disulfide/graphene composite material.
Embodiment 4
S1. prepare four thio ammonium molybdate: 5g Ammonium Molybdate Tetrahydrate be dissolved in 30 mL deionized waters, with ammonium hydroxide adjust pH to
10,80mL ammonium sulfide solution is added, reaction 3h is stirred at reflux at 75 DEG C, is cooled to room temperature, stands still for crystals 48h, crystal is filtered,
It is washed with dehydrated alcohol, drying for 24 hours, obtains four thio ammonium molybdate crystallization at room temperature.
S2. electrochemical process prepares graphene slurry: being the N- butyl pyrrole of 1:1 with volume ratio using graphite rod as working electrode
The mixture of pyridine tetrafluoroborate and 1- hexyl -3- methylimidazole hexafluorophosphate is electric under the voltage of 9.5V as electrolyte
12h is solved, separation of solid and liquid, ultrasonic disperse, washing are then passed through, finally obtains the graphene slurry that mass concentration is 3.0%.
S3. graphene surface is modified: accurately weighing 3.644g(0.01mol) cetyl trimethylammonium bromide ultrasound is auxiliary
Then hydrotropy is settled to 100 mL in 50 mL deionized waters, obtain the solution that concentration is 0.1M.By volume for 1:25's
Ratio is added in graphene slurry, and ultrasonic disperse 0.5h is vigorously stirred 30h at room temperature.
S4. molybdenum disulfide/graphene composite lithium ion battery negative electrode material preparation, specifically by 2.6g four thio ammonium molybdate
It is dissolved in the in the mixed solvent of n,N-Dimethylformamide and deionized water that 30 mL volume ratios are 1:4, is added to the modified stone of 65g
In black alkene slurry, ultrasonic disperse 0.5h reacts 2.5h under 65 DEG C of water bath conditions, freeze-drying for 24 hours, finally in a nitrogen atmosphere
700 DEG C of the high temperature anneals, soaking time 1h, heating rate are 10 DEG C/min, and it is negative to obtain molybdenum disulfide/graphene composite lithium ion battery
Pole material.Material first discharge specific capacity at 0.01~3.0V, 200mA/g current density reaches 834mAh/g, by 200
Secondary circulation specific discharge capacity maintains 716mAh/g.
Fig. 4 is the X-ray diffraction (XRD) figure of four thio ammonium molybdate prepared by the embodiment of the present invention 4.It makes as can be seen from Figure
For the four thio ammonium molybdate crystallization for going out fine purity.
Embodiment 5
S1. it prepares four thio ammonium molybdate: 5g Ammonium Molybdate Tetrahydrate is dissolved in 30 mL deionized waters, adjust pH to 9 with ammonium hydroxide,
75mL ammonium sulfide solution is added, reaction 1h is stirred at reflux at 95 DEG C, is cooled to room temperature, stands still for crystals for 24 hours, crystal is filtered, is used
Dehydrated alcohol washing, drying for 24 hours, obtains four thio ammonium molybdate crystallization at room temperature.
S2. electrochemical process prepares graphene slurry: being the N- butyl of 1:1:1 with volume ratio using graphite rod as working electrode
The mixture of pyridinium tetrafluoroborate salt, 1- octyl -3- methylimidazole bromide and 1- hexyl -3- methylimidazole hexafluorophosphate is made
For electrolyte, it is electrolysed 36h under the voltage of 5.5V, then passes through separation of solid and liquid, ultrasonic disperse, washing, it is dense to finally obtain quality
The graphene slurry that degree is 2.5%.
S3. graphene surface is modified: accurately weighing 3.644g(0.01mol) cetyl trimethylammonium bromide ultrasound is auxiliary
Then hydrotropy is settled to 100 mL in 50 mL deionized waters, obtain the solution that concentration is 0.1M.It is by volume the ratio of 1:5
Example is added in graphene slurry, and ultrasonic disperse 2h is vigorously stirred 48h at room temperature.
S4. molybdenum disulfide/graphene composite lithium ion battery negative electrode material preparation, specifically by 2.6g four thio ammonium molybdate
It is dissolved in the in the mixed solvent of n,N-Dimethylformamide and deionized water that 30 mL volume ratios are 3:1, is added to the modified stone of 60g
In black alkene slurry, ultrasonic disperse 0.5h reacts 3h under 50 DEG C of water bath conditions, freeze-drying for 24 hours, finally in a nitrogen atmosphere 450
DEG C the high temperature anneal, soaking time 2.5h, heating rate are 5 DEG C/min, obtain molybdenum disulfide/graphene composite lithium ion battery cathode
Material.Material first discharge specific capacity at 0.01~3.0V, 200mA/g current density reaches 936mAh/g, by 200 times
Circulation specific discharge capacity maintains 742mAh/g.
Fig. 5 is molybdenum disulfide/graphene composite material of the preparation of the embodiment of the present invention 5 as lithium ion battery negative material
Stable circulation performance test chart under 200mA/g current density.It is recycled under 200mA/g current density as can be seen from Figure
The specific capacity that 742mAh/g is still kept after 200 circles, shows good cyclical stability.
Claims (10)
1. a kind of preparation method of molybdenum disulfide/graphene composite material, it is characterised in that the following steps are included: (1) preparation four
Ammonium thiomolybdate；(2) electrochemical process prepares graphene slurry；(3) graphene surface is modified；(4) molybdenum disulfide/graphene is compound
The preparation of material.
2. the preparation method of molybdenum disulfide/graphene composite material according to claim 1, it is characterised in that including following
Step:
(1) four thio ammonium molybdate is prepared:
Ammonium Molybdate Tetrahydrate is dissolved in deionized water, pH is adjusted with ammonium hydroxide, ammonium sulfide solution is added, in 75 ~ 95 DEG C of water-bath items
1 ~ 3h of reaction is stirred at reflux under part, cooled to room temperature stands still for crystals 24 ~ 48h, and filtering washes crystal with dehydrated alcohol
It washs, drying at room temperature, finally obtains four thio ammonium molybdate crystal；
(2) electrochemical process prepares graphene slurry:
Using graphite rod as working electrode, controlling DC voltage in the electrolytic solution is 5 ~ 10V, and electrolysis time is 12 ~ 36h, is then passed through
Separation of solid and liquid, ultrasonic disperse, washing are crossed, graphene slurry is finally obtained；
(3) graphene surface is modified:
Cetyl trimethylammonium bromide ultrasonic wave added is dissolved in deionized water, the solution that concentration is 0.1M is configured to, by it
Be added in the made graphene slurry of step (2), 0.5 ~ 2h of ultrasonic disperse, at room temperature with the speed of 150 r/min stirring 24 ~
48h；
(4) molybdenum disulfide/graphene composite material is prepared:
Four thio ammonium molybdate is dissolved in the in the mixed solvent of n,N-Dimethylformamide and deionized water, is added to step (3) institute
In the modified graphene slurry of system, 0.5 ~ 2h of ultrasonic disperse reacts 2~4h under 50~70 DEG C of water bath conditions, is then freeze-dried
For 24 hours, gained sample obtains molybdenum disulfide/graphene composite material by the high temperature anneal.
3. the preparation method of molybdenum disulfide/graphene composite material according to claim 2, it is characterised in that: step (1)
In, with ammonium hydroxide adjusting pH to 9 ~ 12, the molar ratio of Ammonium Molybdate Tetrahydrate and ammonium sulfide is 1:(28~42), the matter of ammonium sulfide solution
Measuring concentration is 25%.
4. the preparation method of molybdenum disulfide/graphene composite material according to claim 2, it is characterised in that: step (2)
In, the electrolyte is N- butyl-pyridinium tetrafluoroborate, 1- octyl -3- methylimidazole bromide, 1- hexyl -3- methylimidazole six
The mixture of one or more of fluorophosphate, 1- butyl -3- methyl imidazolium tetrafluoroborate；The matter of the graphene slurry
Measuring concentration is 1 ~ 3.5%.
5. the preparation method of molybdenum disulfide/graphene composite material according to claim 2, it is characterised in that: step (3)
In, the solution of the cetyl trimethylammonium bromide and the volume ratio of graphene slurry are 1:(5~30).
6. the preparation method of molybdenum disulfide/graphene composite material according to claim 2, it is characterised in that: step (4)
In, the volume ratio of the n,N-Dimethylformamide and deionized water is 1:5 ~ 3:1, and four thio ammonium molybdate and mixed solvent rub
Your volume ratio is 1:3(mol/L), the mass ratio of four thio ammonium molybdate and graphene is 1:(0.1~1.5).
7. the preparation method of molybdenum disulfide/graphene composite material according to claim 2, it is characterised in that: step (4)
In, the annealing treating process parameter are as follows: temperature be 400~700 DEG C, soaking time be 1 ~ 3h, heating rate be 5 ~ 15 DEG C/
Min, protection gas are nitrogen.
8. a kind of existed using molybdenum disulfide/graphene composite material made from the described in any item preparation methods of claim 1 ~ 7
Application in lithium cell cathode material.
9. application according to claim 8, it is characterised in that: by active material molybdenum disulfide/graphene composite material, lead
Electric agent acetylene black and binder Kynoar are uniformly mixed according to mass ratio for 8:1:1, and N-Methyl pyrrolidone is solvent, system
Standby electrode slurry；Then the slurry is uniformly coated on copper foil, working electrode is pressed into after vacuum drying；It is with metallic lithium foil
To electrode and reference electrode, diaphragm is polypropylene film, and electrolyte is 1.0 M LiPF6Ethylene carbonate/dimethyl carbonate
Solution carries out battery assembly in the glove box full of argon gas.
10. application according to claim 9, it is characterised in that: under 0.01~3.0V, 200mA/g current density for the first time
Specific discharge capacity reaches 700~1200mAh/g, maintains 550~850 mAh/g by 200 circulation specific discharge capacities.
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