CN109904397A - A kind of molybdenum disulfide/C/ graphene composite material - Google Patents
A kind of molybdenum disulfide/C/ graphene composite material Download PDFInfo
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- CN109904397A CN109904397A CN201711295387.8A CN201711295387A CN109904397A CN 109904397 A CN109904397 A CN 109904397A CN 201711295387 A CN201711295387 A CN 201711295387A CN 109904397 A CN109904397 A CN 109904397A
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Abstract
A kind of molybdenum disulfide/C/ graphene composite material is prepared by following steps: first using molybdenum salt, ammonium hydroxide and quaternary ammonium salt as raw material, preparing thio metal salt precursor；It is placed in graphene oxide and thio metal salt precursor mixed grinding in microwave reaction chamber, with the heats 1-15min of 300-1000W, obtains the molybdenum disulfide/C/ graphene composite material.The present invention prepares composite material using solvent-free microwave heating method, the last handling processes such as the washing, separation and drying of product are omitted in solvent-free mode, molybdenum disulfide nano sheet is uniformly dispersed on the surface of graphene, agraphitic carbon is effectively relieved graphene and stacks again in recombination process, and obtained product can be used directly；Since microwave heating speed is fast, thoroughly, the aggregately stacked of nano particle in long-term heat treatment process, graphene and MoS can also be effectively relieved in homogeneous heating, graphene reduction2It is firmly combined.Stability of material is good, in air not mutability, is easy storage；Large specific surface area provides good channel for lithium ion transport, shows biggish specific capacity and preferable stable circulation performance as lithium ion battery negative material.
Description
Technical field
The present invention relates to a kind of molybdenum disulfide/C/ graphene hierarchical structure lithium cell cathode materials, and provide its preparation side
Method belongs to nanocomposite and its applied technical field.
Background technique
Lithium ion battery is widely used in hand due to its high-energy density, high working voltage and longer service life
Machine, the modern times such as electric car power storage system.The electrochemical properties of negative electrode material directly affect the entirety of lithium ion battery
Performance.Due to high coulombic efficiency, the advantages that good cyclical stability, nature rich reserves, is widely used in graphite
Lithium ion battery negative material.However its lower specific capacity (372mAh g-1) and poor high rate performance be unable to satisfy future
The demand of portable equipment and electric car, therefore, urgent need develop the lithium cell cathode material of novel high-performance.
Transient metal chalcogenide compound is an important component in Material Field, due to its special physics, chemistry
Property and extensive concern and dense research interest are caused in the application value that every field is dived, and increasingly shown
Many unique performances, such as photoelectricity performance, magnetic force performance and superconductivity.Section transitions metal chalcogenides have only
Special layer structure, interlayer can introduce otheralkali metal or other atoms.Wherein, MoS2As a kind of typical transition gold
Belong to chalcogen compound, there is the layer structure and high theoretical capacity (670 mAh g of similar graphene-1), and it is cheap, surely
It is qualitative good, therefore attracted wide attention as a kind of potential high-performance lithium cell negative electrode material.
However MoS2The defects of electric conductivity is poor and cyclical stability is poor hinders its large-scale application.Two-dimensional structure
Graphene there is high-specific surface area and excellent electric conductivity, and electrochemical stability is good, so that MoS2/ graphene nano
Composite material becomes research hotspot.
CN106207171A, which is provided, a kind of prepares MoS2The method of/graphene nanocomposite material, mainly passes through hydro-thermal
Recombination process, the product after hydro-thermal obtain MoS after washing is dry2/ graphene nanocomposite material, by resulting MoS2/ stone
Black alkene nanocomposite applications are in lithium cell cathode material, it is shown that more excellent chemical property.But hydro-thermal and molten
The hot recombination process of agent generally requires reaction 20h or more there are some problems, such as reaction time are long, be difficult in reaction process by
Graphene oxide restores completely, and MoS2It is unstable in conjunction with graphene, the destruction of electrode is easily led in charge and discharge process,
Furthermore the product that hydro-thermal obtains also need to be easy to cause by processes such as washing, separation, dryings the accumulation again of graphene to
Transmission of the lithium ion in graphene is influenced, and then influences MoS2The chemical property of/graphene nanocomposite material.
Summary of the invention
It is mostly to use hydro-thermal method, or synthesizing to solve molybdenum disulfide/graphene nanocomposite material in the prior art
Solvent is needed in journey, the reaction time is generally longer, and product needs complicated separation last handling process, MoS in synthetic material2With stone
Black alkene combines unstable, the problem of charge and discharge easily lead to electrode breakages, the present invention provide a kind of solventless method synthesis of carbon/molybdenum disulfide/
The method of C/ graphene composite material, products obtained therefrom are directly available in cathode of lithium battery without the processes such as washing, separation, dry
Material, application performance are good.
To realize the above-mentioned technical purpose, first aspect present invention provides a kind of molybdenum disulfide/C/ graphene composite material
Preparation method, comprising the following steps:
(1) preparation of thio metal salt precursor: molybdenum salt and ammonium hydroxide being mixed, ammonium sulfide is added after being heated to 40-70 DEG C, reacted
0.5-2h, then quaternary ammonium salt is added into solution, precipitating is generated, cooling and standings wait for that crystal is precipitated, wash, are dried to obtain thio metal
Salt precursor；
(2) it prepares composite material: thio metal salt precursor prepared by graphene oxide and step (1) being mixed, ball mill is placed in
Inside ground；Material after ball milling is placed in microwave reaction chamber, with the heats 1-15min of 300-1000W, is obtained
The molybdenum disulfide/C/ graphene composite material.
In the above preparation method, the molybdenum salt is selected from ammonium molybdate and/or sodium molybdate.
In the above preparation method, the quaternary ammonium salt is the ammonium halide containing 4 ~ 30 carbon, preferably carbon chain length contain 4 ~
The ammonium halide of 25 carbon, as more specific embodiment, the quaternary ammonium salt be selected from tetramethyl ammonium chloride, 4 bromide,
Etamon chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, hexadecyltrimethylammonium chloride, 16
At least one of alkyl trimethyl ammonium bromide, octadecyltrimethylammonium chloride and Cetyltrimethylammonium bromide.
In the above preparation method, the mixing molar ratio of molybdenum salt, ammonium sulfide and alkylammonium salt is 1:1-20:0.1-5, ammonium hydroxide
Additional amount be completely dissolved molybdenum salt and the pH value of mixed solution made to maintain 7.5-11, preferably make the pH value of mixed solution
8-10。
In the above preparation method, the mixing mass ratio of graphene oxide and thio metal salt precursor is 1 in step (2):
1-20。
In the above preparation method, the mass ratio that feeds intake of mill ball and mixture is 1-20:1 in ball mill when grinding, is turned
Speed is 300-3000r/min, milling time 0.5-3h.Mill ball and feed ratio are greater than 1, are conducive to feed intake abundant with mill ball
Contact, grinding effect are more preferable.
In the above preparation method, grinding is to carry out under an inert atmosphere.
In the above preparation method, microwave reaction is preferable over 500 ~ 1000W and heats 3 ~ 10min in step (2).
In the above preparation method, before microwave reaction and in reaction process with nitrogen or inert gas purge microwave reaction
Chamber, it is preferred to use argon gas purging.
In the above preparation method, the graphene oxide is especially selected from the graphene oxide having the following properties that: lamella
Area is 100 μm2More than, conductivity is 3500S/m or more.
In the above preparation method, the graphene oxide is that graphite is obtained through oxidation, and graphene oxide of the invention is adopted
It is synthesized with Hummers method, as more specific embodiment, the present invention discloses the specific preparation method of the graphite oxide such as
Under: natural flake graphite is added under agitation into the concentrated sulfuric acid of ice bath, temperature is down to 0-10 DEG C, and sodium nitrate, height is added
Potassium manganate is stirred to react, and adds deionized water, is warming up to 50-100 DEG C, isothermal reaction to reaction solution becomes glassy yellow, Xiang Qi
Middle addition hydrogen peroxide, is stirred to react, and cooling washs, is dried to obtain graphene oxide, pulverizes spare.
The specification of the natural flake graphite is 100-500 mesh.After completion of the reaction, when post-processing first with deionized water repeatedly
Sedimentation removes unreacted graphite particle, then with salt acid centrifuging, cleaning removes the Cl ion in reaction solution, is washed with deionized water
To pH value close to neutrality, drying is ground.
Above-mentioned Hummers method charge stripping efficiency is 93% or more, and yield is 90% or more, and gained graphene oxide layer structure is complete
Whole degree is high, and lattice is complete after thermal reduction.
The technical purpose of second aspect of the present invention is to provide molybdenum disulfide/C/ graphene composite wood of above method preparation
Material, the material is to make the pyrogenous origin MoS of thio metal salt precursor under solvent-free microwave heating condition2Nanometer sheet is straight
Upper growth in situ on the surface of graphene is connect, while the agraphitic carbon that the alkyl pyrolysis in thio metal salt precursor generates can be effective
Alleviate the stacking again in graphene recombination process, further enhances the stability of composite material.Due to microwave heating speed is fast,
Homogeneous heating, so that MoS2Nanometer sheet is firmly combined with graphene, and does not easily cause particle packing, greatly shortens synthesis material
Expect the required time and alleviates graphene and MoS2The problem of reuniting in long-term heated situation.
The technical purpose of third aspect present invention is to provide the application of above-mentioned molybdenum disulfide/C/ graphene composite material, institute
Stating material can be used as lithium ion battery negative material, show good cyclical stability and high rate performance.
Compared with the prior art, the present invention has the following advantages:
The present invention prepares molybdenum disulfide/C/ graphene composite material, solvent-free processing using solvent-free microwave heating method
The last handling processes such as the washing, separation and drying of product are omitted in mode, and molybdenum disulfide nano sheet disperses on the surface of graphene
Even, agraphitic carbon is effectively relieved graphene and stacks again in recombination process, and obtained product can be used directly；In addition, due to micro-
Wave heating speed is fast, homogeneous heating, and thoroughly, the poly- of nano particle in long-term heat treatment process can also be effectively relieved in graphene reduction
Collection accumulation, graphene and MoS2It is firmly combined and does not significantly build up, molybdenum disulfide nano sheet is uniformly dispersed on the surface of graphene.
Stability of material is good, in air not mutability, is easy storage；Large specific surface area is lithium as lithium ion battery negative material
Ion transmission provides good channel, shows biggish specific capacity and preferable stable circulation performance.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the XRD diagram of graphene oxide prepared in embodiment 1；
It in current density is 100mAg that Fig. 2, which is molybdenum disulfide/C/ graphene composite material in embodiment 12,-1When charge and discharge
Cyclic curve.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Embodiment 1
(1) preparation of graphene oxide: the concentrated sulfuric acid of 100mL 98% is taken to be slowly added into the dry there-necked flask of 500mL, by three
Mouth bottle ice bath cooling is placed on magnetic stirring apparatus.It quickly is added with stirring 2.0g natural flake graphite (180 mesh), to reaction solution
When temperature is down to about 0 DEG C, it is slowly added to 4.0g sodium nitrate, continues to stir 2h.Then 10g permanganic acid is slowly added portionwise in 1h
Potassium, persistently stirs 2h, and reaction temperature is controlled at 10 DEG C or less.There-necked flask is moved into 40 DEG C of water-baths again, continues to be stirred to react
2h.Then, it is slowly added to 200mL temperature deionized water, reacting liquid temperature is maintained within 100 DEG C.98 DEG C of constant temperature reactions, until anti-
Liquid is answered to become glassy yellow.The hydrogen peroxide of 20mL 30% is added into reaction solution, lasting stirring reacts it sufficiently.It, will after cooling
Acquired solution replacement deionized water settles repeatedly, removes unreacted graphite particle, with hydrochloric acid eccentric cleaning, removes in reaction solution
Cl ion, then be washed with deionized water to pH value close to neutrality.Last 80 DEG C of vacuum drying 12h, obtains graphene oxide, grinding
At powdered spare.Its XRD diagram is as shown in Figure 1, be located at 11oLeft and right is typical 001 diffraction maximum of graphene oxide, peak master
If caused by being intercalation between graphene sheet layer due to a large amount of oxygen-containing functional groups.Oxidation can be calculated by Scherrer formula
Distance is 0.7nm between graphite flake layer, hence it is evident that greater than the interlamellar spacing 0.3254nm of graphite.Increased interlamellar spacing is mainly due to inserting
Layer is to caused by the oxygen-containing functional group between graphene sheet layer.
(2) 1.00g ammonium molybdate and 30mL concentrated ammonia liquor (NH the preparation of tetramethyl four thio ammonium molybdate: are taken3·H2O it) is added to
In three-necked flask.8g ammonium sulfide ((NH is added when temperature is increased to 60 DEG C for agitating and heating4)2S), in the state of magnetic agitation
Lower reaction 0.5h.Then 4 bromide is added into the solution, continues there is precipitating to generate with reaction.Subsequent ice bath is quiet
2h is set, gradually there is crystal precipitation, then obtains tetramethyl by reaction solution filtering, with dehydrated alcohol and deionized water rinsing, drying
Four thio ammonium molybdate.
(3) molybdenum disulfide/C/ graphene composite material preparation: by tetramethyl four thio ammonium molybdate and graphene oxide with
The mass ratio of 1:1 mixes, and mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 3:
After 1, revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is fitted into reaction tube, then
Reaction tube is placed in microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.3min is heated with the power microwave of 600W.?
It is cooled to room temperature under Ar atmosphere to get molybdenum disulfide/C/ graphene nanocomposite material.
Embodiment 2
(1) the preparation method is the same as that of Example 1 for graphene oxide.
(2) the preparation method is the same as that of Example 1 for tetramethyl four thio ammonium molybdate.
(3) molybdenum disulfide/C/ graphene composite material preparation: by tetramethyl four thio ammonium molybdate and graphene oxide with
The mass ratio of 2:1 mixes, and mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 3:
After 1, revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is fitted into reaction tube, then
Reaction tube is placed in microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.5min is heated with the power microwave of 600W.?
It is cooled to room temperature under Ar atmosphere to get molybdenum disulfide/C/ graphene nanocomposite material.
Embodiment 3
(1) the preparation method is the same as that of Example 1 for graphene oxide.
(2) the preparation method is the same as that of Example 1 for tetramethyl four thio ammonium molybdate.
(3) molybdenum disulfide/C/ graphene composite material preparation: by tetramethyl four thio ammonium molybdate and graphene oxide with
The mass ratio of 2:1 mixes, and mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 3:
After 1,400 rpm of revolving speed, 1 h of ball milling, cooled to room temperature collects product.Material after ball milling is encased in reaction tube,
Then reaction tube is placed in microwave reaction chamber, 1 h is purged with the argon gas of 100 mL/min.It is heated with the power microwave of 1000 W
10 min.It is cooled to room temperature under an ar atmosphere to get MoS2/ C/ graphene nanocomposite material.
Embodiment 4
(1) the preparation method is the same as that of Example 1 for graphene oxide.
(2) 1.00g ammonium molybdate and 30mL concentrated ammonia liquor (NH the preparation of tetraethyl four thio ammonium molybdate: are taken3·H2O it) is added to
In three-necked flask.8g ammonium sulfide ((NH is added when temperature is increased to 60 DEG C for agitating and heating4)2S), in the state of magnetic agitation
Lower reaction 0.5h.Then tetraethylammonium bromide is added into the solution, continues there is precipitating to generate with reaction.Subsequent ice bath is quiet
2h is set, gradually there is crystal precipitation, then obtains tetraethyl by reaction solution filtering, with dehydrated alcohol and deionized water rinsing, drying
Four thio ammonium molybdate.
(3) molybdenum disulfide/C/ graphene composite material preparation: by the tetraethyl four thio ammonium molybdate and oxygen of step (2)
Graphite alkene is mixed with the mass ratio of 1:1, and mixture is placed in the agate pot full of nitrogen, ball mill ball milling, ball material are used
Mass ratio is 3:1, and after revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in instead
Reaction tube is then placed in microwave reaction chamber by Ying Guanzhong, purges 1h with the argon gas of 100mL/min.With the power microwave of 600W
Heat 5min.It is cooled to room temperature under an ar atmosphere to get molybdenum disulfide/C/ graphene nanocomposite material.
Embodiment 5
(1) the preparation method is the same as that of Example 1 for graphene oxide.
(2) preparation of tetraethyl four thio ammonium molybdate is the same as embodiment 4.
(3) molybdenum disulfide/C/ graphene composite material preparation: by tetraethyl four thio ammonium molybdate and graphene oxide with
The mass ratio of 2:1 mixes, and mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 3:
After 1, revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in fluidizing type reaction tube
In, then reaction tube is placed in microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.It is heated with the power microwave of 600W
8min.It is cooled to room temperature under an ar atmosphere to get molybdenum disulfide/C/ graphene nanocomposite material.
Embodiment 6
(1) the preparation method is the same as that of Example 1 for graphene oxide.
(2) preparation of tetraethyl four thio ammonium molybdate is the same as embodiment 4.
(3) molybdenum disulfide/C/ graphene composite material preparation: by tetraethyl four thio ammonium molybdate and graphene oxide with
The mass ratio of 2:1 mixes, and mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 3:
After 1, revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in fluidizing type reaction tube
In, then reaction tube is placed in microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.It is heated with the power microwave of 1000W
10min.It is cooled to room temperature under an ar atmosphere to get molybdenum disulfide/C/ graphene nanocomposite material.
Embodiment 7
(1) the preparation method is the same as that of Example 1 for graphene oxide.
(2) 1.00g ammonium molybdate and 30mL concentrated ammonia liquor (NH the preparation of tetrabutyl four thio ammonium molybdate: are taken3·H2O it) is added to
In three-necked flask.8g ammonium sulfide ((NH is added when temperature is increased to 60 DEG C for agitating and heating4)2S), in the state of magnetic agitation
Lower reaction 0.5h.Then tetrabutylammonium bromide is added into the solution, continues there is precipitating to generate with reaction.Subsequent ice bath is quiet
2h is set, gradually there is crystal precipitation, then obtains tetraethyl by reaction solution filtering, with dehydrated alcohol and deionized water rinsing, drying
Four thio ammonium molybdate.
(3) molybdenum disulfide/C/ graphene composite material preparation: by tetrabutyl four thio ammonium molybdate and graphene oxide with
The mass ratio of 1:1 mixes, and mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 3:
After 1, revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, with
Reaction tube is placed in microwave reaction chamber afterwards, 1h is purged with the argon gas of 100mL/min.3min is heated with the power microwave of 600W.
It is cooled to room temperature under an ar atmosphere to get molybdenum disulfide/C/ graphene nanocomposite material.
Embodiment 8
(1) the preparation method is the same as that of Example 1 for graphene oxide.
(2) preparation of tetrabutyl four thio ammonium molybdate is the same as embodiment 7.
(3) molybdenum disulfide/C/ graphene composite material preparation: by tetrabutyl four thio ammonium molybdate and graphene oxide with
The mass ratio of 2:1 mixes, and mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 3:
After 1, revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, with
Reaction tube is placed in microwave reaction chamber afterwards, 1h is purged with the argon gas of 100mL/min.5min is heated with the power microwave of 600W.
It is cooled to room temperature under an ar atmosphere to get MoS2/ C/ graphene nanocomposite material.
Embodiment 9
(1) the preparation method is the same as that of Example 1 for graphene oxide.
(2) preparation of tetrabutyl four thio ammonium molybdate is the same as embodiment 7.
(3) molybdenum disulfide/C/ graphene composite material preparation: by tetraethyl four thio ammonium molybdate and graphene oxide with
The mass ratio of 2:1 mixes, and mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 3:
After 1, revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, with
Reaction tube is placed in microwave reaction chamber afterwards, 1h is purged with the argon gas of 100mL/min.10 are heated with the power microwave of 1000W
min.It is cooled to room temperature under an ar atmosphere to get MoS2/ C/ graphene nanocomposite material.
Embodiment 10
(1) the preparation method is the same as that of Example 1 for graphene oxide.
(2) 1.00g ammonium molybdate and 30mL concentrated ammonia liquor (NH the preparation of cetyl trimethyl four thio ammonium molybdate: are taken3·
H2O it) is added in three-necked flask.8g ammonium sulfide ((NH is added when temperature is increased to 60 DEG C for agitating and heating4)2S), in magnetic force
0.5h is reacted in the state of stirring.Then cetyl trimethylammonium bromide is added into the solution, continues to have with reaction
Precipitating generates.Subsequent ice bath stands 2h, gradually there is crystal precipitation, then by reaction solution filtering, with dehydrated alcohol and deionized water
Rinsing, drying obtains tetraethyl four thio ammonium molybdate.
(3) molybdenum disulfide/C/ graphene composite material preparation: by the cetyl trimethyl tetrathio molybdenum of step (2)
Sour ammonium and graphene oxide are mixed with the mass ratio of 1:1, and mixture is placed in the agate pot full of nitrogen, ball mill ball is used
Mill, ball material mass ratio is 3:1, and after revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.By the material after ball milling
It is encased in reaction tube, then reaction tube is placed in microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.With 600W's
Power microwave heats 3min.It is cooled to room temperature under an ar atmosphere to get molybdenum disulfide/C/ graphene nanocomposite material.
Embodiment 11
(1) the preparation method is the same as that of Example 1 for graphene oxide.
(2) preparation of cetyl trimethyl four thio ammonium molybdate is the same as embodiment 10.
(3) molybdenum disulfide/C/ graphene composite material preparation: by cetyl trimethyl four thio ammonium molybdate and oxidation
Graphene is mixed with the mass ratio of 2:1, and mixture is placed in the agate pot full of nitrogen, ball mill ball milling, ball material matter are used
Ratio is measured as 3:1, after revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction
Reaction tube is then placed in microwave reaction chamber by Guan Zhong, purges 1h with the argon gas of 100mL/min.Added with the power microwave of 600W
Hot 5min.It is cooled to room temperature under an ar atmosphere to get molybdenum disulfide/C/ graphene nanocomposite material.
Embodiment 12
(1) the preparation method is the same as that of Example 1 for graphene oxide.
(2) preparation of cetyl trimethyl four thio ammonium molybdate is the same as embodiment 10.
(3) molybdenum disulfide/C/ graphene composite material preparation: by cetyl trimethyl four thio ammonium molybdate and oxidation
Graphene is mixed with the mass ratio of 2:1, and mixture is placed in the agate pot full of nitrogen, ball mill ball milling, ball material matter are used
Ratio is measured as 3:1, after revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction
Reaction tube is then placed in microwave reaction chamber by Guan Zhong, purges 1h with the argon gas of 100mL/min.Added with the power microwave of 1000W
Hot 10min.It is cooled to room temperature under an ar atmosphere to get molybdenum disulfide/C/ graphene nanocomposite material.
The molybdenum disulfide that embodiment 1 ~ 12 is obtained/C/ graphene composite material is used for lithium ion battery negative material.With synthesis
Molybdenum disulfide/C/ graphene be active component, select 2016 type battery cases, metal lithium sheet (Φ 16mm × 1mm), with 1.0M
LiPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) mixed liquor (volume ratio 1:1) be electrolyte, Celgard2300
The poly- third coal film of micropore is as battery diaphragm.The above material is assembled into button battery in the glove box full of Ar gas, etc. works
Make to be tested again after electrode is sufficiently infiltrated by electrolyte.It is specifically divided into following five steps:
(1) it sizes mixing
Material used is since specific surface is larger, the moisture being easy in absorption air, so first having to prepare the material of electrode
It is sufficiently dry in 120 DEG C of vacuum oven, remove surface moisture.Then by active material, conductive additive (acetylene black)
Dispersing agent is added to according to the proportion of mass percent 80:10:10 with binder (PVDF)NMethyl pyrrolidone (NMP) mixing
Grinding, mixes material uniformly, viscous paste is made.
(2) film
Obtained viscous paste is uniformly coated on copper foil (thickness is about 100 μm).Concrete operations are as follows: 1) shearing is good big
Small moderate copper foil, and tiled on the table.2) copper foil surface spot is removed.3) slurry is dispersed on copper foil, is used
Slurry is uniformly laid on copper foil by mold.4) copper foil for being coated with slurry is dried into 12h in 120 DEG C of vacuum ovens.
(3) it rolls
After drying completely, the copper foil for being coated with slurry is rolled with small-sized roller, to prevent electrode material from copper foil surface
It falls off.
(4) tabletting
The film after rolling is cut into several circular electric pole pieces, diameter 12mm with hand microtome.Film is filling in order to prevent
It falls off during discharge cycles, tabletting is carried out to it with hydraulic press.Weighing is taken out after drying, to packed battery.
(5) assembled battery
The process for assembling button cell carries out in the glove box full of Ar gas.According to negative battery shell/electrolyte/working electrode
Piece/electrolyte/diaphragm/lithium piece/positive battery shell sequence is assembled into battery.It places for 24 hours, liquid to be electrolysed carries out after sufficiently infiltrating
Electro-chemical test.
By assembled button-shaped simulated battery, charge-discharge test is carried out.The material of embodiment 12 is in 0.01-3.0V voltage
In range, 100mAg-1Current density under cyclical stability test result it is as shown in Fig. 2.Embodiment 1 ~ 12 is filled for the first time
Discharge capacity and the discharge capacity after 100 charge-discharge tests are shown in Table 1.
Table 1
Comparative example 1
Using preparation method identical with embodiment 12, the difference is that not using microwave heating, it is exchanged with conventional Muffle furnace 800
DEG C roasting 10min.Ammonium paramolybdate does not react completely as the result is shown, causes molybdenum disulfide/C/ graphene yield less, by gained material
Material is used for lithium cell cathode material, and initial discharge capacity only has 405.6mAhg-1。
Claims (13)
1. a kind of molybdenum disulfide/C/ graphene composite material preparation method, comprising the following steps:
(1) preparation of thio metal salt precursor: molybdenum salt and ammonium hydroxide being mixed, ammonium sulfide is added after being heated to 40-70 DEG C, reacted
0.5-2h, then quaternary ammonium salt is added into solution, precipitating is generated, cooling and standings wait for that crystal is precipitated, wash, are dried to obtain thio metal
Salt precursor；
(2) it prepares composite material: thio metal salt precursor prepared by graphene oxide and step (1) being mixed, ball mill is placed in
Inside ground；Material after ball milling is placed in microwave reaction chamber, with the heats 1-15min of 300-1000W, is obtained
The molybdenum disulfide/C/ graphene composite material.
2. preparation method according to claim 1, which is characterized in that the molybdenum salt is selected from ammonium molybdate and/or sodium molybdate.
3. preparation method according to claim 1, which is characterized in that the quaternary ammonium salt is the halogenation containing 4 ~ 30 carbon
The a length of ammonium halide containing 4 ~ 25 carbon of ammonium, preferably carbochain.
4. preparation method according to claim 3, which is characterized in that the quaternary ammonium salt is selected from tetramethyl ammonium chloride, tetramethyl
Base ammonium bromide, etamon chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, cetyl trimethyl chlorine
Change in ammonium, cetyl trimethylammonium bromide, octadecyltrimethylammonium chloride and Cetyltrimethylammonium bromide at least
It is a kind of.
5. preparation method according to claim 1, which is characterized in that the mixing mole of molybdenum salt, ammonium sulfide and alkylammonium salt
Than for 1:1-20:0.1-5.
6. preparation method according to claim 1, which is characterized in that the additional amount of the ammonium hydroxide is completely dissolved molybdenum salt simultaneously
And the pH value of mixed solution is made to maintain 7.5-11, preferably make the pH value 8-10 of mixed solution.
7. preparation method according to claim 1, which is characterized in that graphene oxide and thio metal salt in step (2)
The mixing mass ratio of precursor is 1:1-20.
8. preparation method according to claim 1, which is characterized in that when grinding in ball mill mill ball and mixture throwing
Material mass ratio is 1-20:1, milling time 0.5-3h.
9. preparation method according to claim 1, which is characterized in that the graphene oxide is selected from and has the following properties that
Graphene oxide: lamella area is 100 μm2More than, conductivity is 3500S/m or more.
10. preparation method according to claim 1, which is characterized in that the graphene oxide is that graphite is obtained through oxidation.
11. preparation method according to claim 9, which is characterized in that the graphene oxide is closed using Hummers method
At specifically the preparation method is as follows: natural flake graphite is added under agitation into the concentrated sulfuric acid of ice bath, temperature is down to 0-10
DEG C, sodium nitrate, potassium permanganate is added, is stirred to react, adds deionized water, is warming up to 50-100 DEG C, isothermal reaction to reaction
Liquid becomes glassy yellow, and hydrogen peroxide is added thereto, is stirred to react, and cooling washs, is dried to obtain graphene oxide, pulverizes
It is spare.
12. molybdenum disulfide/C/ graphene composite material of the preparation of method described in claim 1 ~ 10 any one.
13. molybdenum disulfide described in claim 11/application of the C/ graphene composite material as lithium ion battery negative material.
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