CN109904396A - A kind of molybdenum disulfide-three-dimensional graphene composite material - Google Patents
A kind of molybdenum disulfide-three-dimensional graphene composite material Download PDFInfo
- Publication number
- CN109904396A CN109904396A CN201711295375.5A CN201711295375A CN109904396A CN 109904396 A CN109904396 A CN 109904396A CN 201711295375 A CN201711295375 A CN 201711295375A CN 109904396 A CN109904396 A CN 109904396A
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- dimensional
- composite material
- molybdenum disulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
A kind of molybdenum disulfide-three-dimensional graphene composite material, it is prepared by the following method: preparing three-dimensional grapheme aeroge using graphene oxide and L-cysteine, the grinding of molybdenum salt, sulphur powder and three-dimensional grapheme aeroge is placed in microwave reaction chamber, with the heats 10-60min of 300-1000W, molybdenum disulfide-three-dimensional graphene composite material is obtained.Material of the invention is under microwave heating condition, and graphene oxide is heat-treated as graphene, while the MoS generated2Direct growth in situ upper on the surface of graphene, microwave heating speed is fast, and homogeneous heating makes MoS2Nanometer sheet is firmly combined with graphene, does not easily cause particle packing, the time needed for greatly shortening synthetic material and alleviates graphene and MoS2The problem of reuniting in long-term heated situation；And the graphene of three-dimensional structure is not susceptible to stack and reunite again in recombination process compared to two-dimensional structure, it preferably ensure that the performance of graphene excellent properties, above-mentioned composite material shows good cyclical stability and high rate performance as lithium ion battery negative material.
Description
Technical field
The present invention relates to a kind of molybdenum disulfide-three-dimensional grapheme structure lithium cell cathode materials, and provide preparation method,
Belong 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
For black alkene in conjunction with the problem of unstable, charge and discharge easily lead to electrode breakages, the present invention provides a kind of solventless method synthesis of carbon/molybdenum disulfide-
It is negative to be directly available in lithium battery without the processes such as washing, separation, dry for the method for three-dimensional graphene composite material, products obtained therefrom
Pole material, application performance are good.
To realize the above-mentioned technical purpose, first aspect present invention provides a kind of molybdenum disulfide-three-dimensional grapheme composite wood
The preparation method of material, comprising the following steps:
A. in deionized water by graphene oxide and L-cysteine ultrasonic disperse, it is placed in hydrothermal synthesis kettle, carries out hydro-thermal
Reaction, obtains hydrogel, three-dimensional grapheme aeroge is obtained after being dried；
B. three-dimensional grapheme aeroge prepared by step a is mixed to be placed in ball mill with molybdenum salt, sulphur powder and is ground；
C. the material after grinding in step b is placed in microwave reaction chamber, with the heats 10-60min of 300-1000W,
Obtain molybdenum disulfide-three-dimensional graphene composite material.
In the above preparation method, as a further preference, graphene oxide described in step a and L-cysteine are mixed
The ratio of conjunction is 1:1-20, preferably are as follows: 1:3-8；The temperature of the hydro-thermal reaction be 80-220 DEG C, preferably 150-200 DEG C, when
Between be 8-20h.
In the above preparation method, as a further preference, molybdenum salt described in step b is selected from molybdenum pentachloride, para-molybdic acid
At least one of ammonium and sodium molybdate, preferably ammonium paramolybdate.Sulphur powder, molybdenum salt and three-dimensional grapheme aeroge mixing mass ratio be
1:1-10:1-10, preferably 1:1-5:1-5；The mass ratio that feeds intake of mill ball and mixture is 1-20:1 in ball mill when grinding,
Revolution is 300-3000r/min, milling time 0.5-3h.The grinding is to carry out under an inert atmosphere.
In the above preparation method, as a further preference, the microwave reaction preferably 500 ~ 1000W react 10 ~
40min。
In the above preparation method, as a further preference, before microwave reaction and in reaction process with nitrogen or inertia
Gas purges microwave reaction chamber, it is preferred to use argon gas purging.
In the above preparation method, as a further preference, the graphene oxide, which is especially selected from, has the following properties that
Graphene oxide: lamella area be 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-three-dimensional grapheme composite wood of above method preparation
Material, the material are by microwave heating rapidly heat-treat three-dimensional graphene oxide for three-dimensional grapheme, while generation
MoS2Nanometer sheet growth in situ directly on three-dimensional structure graphene surface, since microwave heating speed is fast, homogeneous heating, so that
MoS2Nanometer sheet is firmly combined with graphene, and does not easily cause particle packing, the time needed for greatly shortening synthetic material,
And alleviate graphene and MoS2The problem of reuniting in long-term heated situation.Meanwhile three-dimensional structure prepared by the present invention
Graphene is not susceptible to stack and reunite again in recombination process, preferably ensure that compared to two-dimensional structure grapheme material
The performance of graphene excellent properties facilitates the transmission of lithium ion and charge in combination electrode material.
The technical purpose of third invention of the present invention is to provide the application of above-mentioned molybdenum disulfide-three-dimensional graphene composite material,
The 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-three-dimensional graphene composite material, solvent-free place using solvent-free microwave heating method
The last handling processes such as the washing, separation and drying of product are omitted in reason mode, and obtained product can be used directly；Microwave heating speed
Degree is fast, homogeneous heating, and thoroughly, and the aggregately stacked of nano particle in long-term heat treatment process is effectively relieved in graphene reduction, and three
Tie up graphene and MoS2It is firmly combined and does not significantly build up, molybdenum disulfide nano sheet is uniformly dispersed on the surface of graphene.Meanwhile
The graphene of three-dimensional structure prepared by the present invention is not susceptible to weight heap compared to two-dimensional structure grapheme material in recombination process
Folded and reunion, preferably ensure that the performance of graphene excellent properties, facilitates lithium ion and charge in combination electrode material
Transmission.Stability of material is good, in air not mutability, is easy storage, large specific surface area, as negative electrode of lithium ion battery material
Material, provides good channel for lithium ion transport, 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；
Fig. 2 is the TEM figure of three-dimensional grapheme prepared in embodiment 1；
Fig. 3 is that molybdenum disulfide-three-dimensional graphene composite material in current density is 100mAg in embodiment 11-1When 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
The 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, Jiang Sankou
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 temperature
When degree 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.
The preparation of three-dimensional grapheme aeroge: first by the graphene oxide ultrasonic disperse of above-mentioned preparation in deionized water
In, graphene oxide suspension is prepared, by graphene oxide: L- is added into above-mentioned suspension in L-cysteine mass ratio 1:4
Cysteine, ultrasonic dissolution obtain uniform suspension, place it in hydrothermal synthesis kettle, and hydro-thermal reaction 12h, obtains at 180 DEG C
To hydrogel, three-dimensional structure graphene aerogel is obtained after freeze-drying.Obtained three-dimensional grapheme aeroge be it is cylindric,
TEM schemes as shown in Fig. 2, can clearly find out the layer structure of graphene aerogel, and there are some folds on surface.
The preparation of molybdenum disulfide-three-dimensional graphene composite material: by sulphur powder, ammonium paramolybdate and three-dimensional grapheme aeroge with
The mass ratio of 1:3:4 mixes, and mixture is placed in the agate pot full of nitrogen, using ball mill ball milling, ball material mass ratio is
After 3:1, revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube,
It is placed in microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.10min is heated with the power microwave of 600W.Under an ar atmosphere
It is cooled to room temperature to get molybdenum disulfide-three-dimensional graphene composite material.
Embodiment 2
The preparation method is the same as that of Example 1 for graphene oxide and three-dimensional grapheme aeroge
The preparation of molybdenum disulfide-three-dimensional graphene composite material: by sulphur powder, ammonium paramolybdate and three-dimensional grapheme aeroge with 1:1:
4 mass ratio mixing, mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 3:1,
After revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, is placed in
In microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.10min is heated with the power microwave of 600W.It cools down under an ar atmosphere
To room temperature to get molybdenum disulfide-three-dimensional graphene composite material.
Embodiment 3
The preparation method is the same as that of Example 1 for graphene oxide and three-dimensional grapheme aeroge
The preparation of molybdenum disulfide-three-dimensional graphene composite material: by sulphur powder, ammonium paramolybdate and three-dimensional grapheme aeroge with 1:2:
4 mass ratio mixing, mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 3:1,
After revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, is placed in
In microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.10min is heated with the power microwave of 600W.It cools down under an ar atmosphere
To room temperature to get molybdenum disulfide-three-dimensional graphene composite material.
Embodiment 4
The preparation method is the same as that of Example 1 for graphene oxide and three-dimensional grapheme aeroge
The preparation of molybdenum disulfide-three-dimensional graphene composite material: by sulphur powder, ammonium paramolybdate and three-dimensional grapheme aeroge with 1:2:
4 mass ratio mixing, mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 4:1,
After revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, is placed in
In microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.20min is heated with the power microwave of 600W.It cools down under an ar atmosphere
To room temperature to get molybdenum disulfide-three-dimensional graphene composite material.
Embodiment 5
The preparation method is the same as that of Example 1 for graphene oxide and three-dimensional grapheme aeroge
The preparation of molybdenum disulfide-three-dimensional graphene composite material: by sulphur powder, ammonium paramolybdate and three-dimensional grapheme aeroge with 1:2:
4 mass ratio mixing, mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 5:1,
After revolving speed 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, is placed in
In microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.30min is heated with the power microwave of 600W.It cools down under an ar atmosphere
To room temperature to get molybdenum disulfide-three-dimensional graphene composite material.
Embodiment 6
The preparation method is the same as that of Example 1 for graphene oxide and three-dimensional grapheme aeroge
The preparation of molybdenum disulfide-three-dimensional graphene composite material: by sulphur powder, ammonium paramolybdate and three-dimensional grapheme aeroge with 1:2:
4 mass ratio mixing, mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 5:1,
After revolving speed 600rpm ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, then will
Reaction tube is placed in microwave reaction chamber, purges 1h with the argon gas of 100mL/min.10min is heated with the power microwave of 800W.In Ar
It is cooled to room temperature under atmosphere to get molybdenum disulfide-three-dimensional graphene composite material.
Embodiment 7
The preparation method is the same as that of Example 1 for graphene oxide and three-dimensional grapheme aeroge
The preparation of molybdenum disulfide-three-dimensional graphene composite material: by sulphur powder, ammonium paramolybdate and three-dimensional grapheme aeroge with 1:2:
4 mass ratio mixing, mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 5:1,
After revolving speed 800rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, is placed in
In microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.20min is heated with the power microwave of 800W.It cools down under an ar atmosphere
To room temperature to get molybdenum disulfide-three-dimensional graphene composite material.
Embodiment 8
The preparation method is the same as that of Example 1 for graphene oxide and three-dimensional grapheme aeroge
The preparation of molybdenum disulfide-three-dimensional graphene composite material: by sulphur powder, ammonium paramolybdate and three-dimensional grapheme aeroge with 1:2:
4 mass ratio mixing, mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 5:1,
After revolving speed 800rpm ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in fluidizing type reaction tube,
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 800W
30min.It is cooled to room temperature under an ar atmosphere to get molybdenum disulfide-three-dimensional graphene composite material.
Embodiment 9
The preparation method is the same as that of Example 1 for graphene oxide and three-dimensional grapheme aeroge
The preparation of molybdenum disulfide-three-dimensional graphene composite material: by sulphur powder, ammonium paramolybdate and three-dimensional grapheme aeroge with 1:2:
4 mass ratio mixing, mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 5:1,
After revolving speed 800rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, is placed in
In microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.10min is heated with the power microwave of 1000W.It is cold under an ar atmosphere
But to room temperature to get molybdenum disulfide-three-dimensional graphene composite material.
Embodiment 10
The preparation method is the same as that of Example 1 for graphene oxide and three-dimensional grapheme aeroge
The preparation of molybdenum disulfide-three-dimensional graphene composite material: by sulphur powder, ammonium paramolybdate and three-dimensional grapheme aeroge with 1:2:
4 mass ratio mixing, mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 5:1,
After revolving speed 800rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, is placed in
In microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.20min is heated with the power microwave of 1000W.It is cold under an ar atmosphere
But to room temperature to get molybdenum disulfide-three-dimensional graphene composite material.
Embodiment 11
The preparation method is the same as that of Example 1 for graphene oxide and three-dimensional grapheme aeroge
The preparation of molybdenum disulfide-three-dimensional graphene composite material: by sulphur powder, ammonium paramolybdate and three-dimensional grapheme aeroge with 1:2:
4 mass ratio mixing, mixture is placed in the agate pot full of nitrogen, and using ball mill ball milling, ball material mass ratio is 5:1,
After revolving speed 800rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, is placed in
In microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.30min is heated with the power microwave of 1000W.It is cold under an ar atmosphere
But to room temperature to get molybdenum disulfide-three-dimensional graphene composite material.
Molybdenum disulfide-three-dimensional graphene composite material of embodiment 1 ~ 11 is used for lithium ion battery negative material.With synthesis
Molybdenum disulfide-three-dimensional grapheme is active component, selects 2016 type battery cases, metal lithium sheet (16 mm of Φ × 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 11 is in 0.01-3.0V voltage
In range, 100mAg-1Current density under cyclical stability test result it is as shown in Fig. 3.Embodiment 1 ~ 11 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 11, the difference is that not using microwave heating, it is exchanged with conventional Muffle furnace 800
DEG C roasting 3min.Ammonium paramolybdate does not react completely as the result is shown, causes molybdenum disulfide-three-dimensional grapheme yield less, by gained
Material is used for lithium cell cathode material, and initial discharge capacity only has 373mAhg-1。
Claims (12)
1. a kind of preparation method of molybdenum disulfide-three-dimensional graphene composite material, comprising the following steps:
A. in deionized water by graphene oxide and L-cysteine ultrasonic disperse, it is placed in hydrothermal synthesis kettle, carries out hydro-thermal
Reaction, obtains hydrogel, three-dimensional grapheme aeroge is obtained after being dried；
B. three-dimensional grapheme aeroge prepared by step a is mixed to be placed in ball mill with molybdenum salt, sulphur powder and is ground；
C. the material after grinding in step b is placed in microwave reaction chamber, with the heats 10-60min of 300-1000W,
Obtain molybdenum disulfide-three-dimensional graphene composite material.
2. preparation method according to claim 1, which is characterized in that half Guang ammonia of graphene oxide described in step a and L-
The mass ratio that acid-mixed is closed is 1:1-20.
3. preparation method according to claim 1, which is characterized in that the temperature of hydro-thermal reaction described in step a is 80-
220 DEG C, time 8-20h.
4. preparation method according to claim 1, which is characterized in that molybdenum salt described in step b is selected from molybdenum pentachloride, secondary molybdenum
At least one of sour ammonium and sodium molybdate, preferably ammonium paramolybdate.
5. preparation method according to claim 1, which is characterized in that sulphur powder, molybdenum salt and three-dimensional grapheme airsetting in step b
The mass ratio of glue mixing is 1:1-10:1-10.
6. preparation method according to claim 1, which is characterized in that mill ball and mixed in ball mill when being ground in step b
The mass ratio that feeds intake for closing material is 1-20:1, milling time 0.5-3h.
7. 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.
8. preparation method according to claim 1, which is characterized in that the graphene oxide is that graphite is obtained through oxidation.
9. preparation method according to claim 8, which is characterized in that the graphene oxide is synthesized using Hummers method,
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 solution becomes
For glassy yellow, hydrogen peroxide is added thereto, is stirred to react, cools down, washs, is dried to obtain graphene oxide, pulverize spare.
10. preparation method according to claim 9, which is characterized in that the specification of the natural flake graphite is 100-500
Mesh.
11. molybdenum disulfide-three-dimensional graphene composite material of the preparation of method described in claim 1 ~ 10 any one.
12. molybdenum disulfide-three-dimensional graphene composite material answering as lithium ion battery negative material described in claim 11
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711295375.5A CN109904396A (en) | 2017-12-08 | 2017-12-08 | A kind of molybdenum disulfide-three-dimensional graphene composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711295375.5A CN109904396A (en) | 2017-12-08 | 2017-12-08 | A kind of molybdenum disulfide-three-dimensional graphene composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109904396A true CN109904396A (en) | 2019-06-18 |
Family
ID=66940465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711295375.5A Pending CN109904396A (en) | 2017-12-08 | 2017-12-08 | A kind of molybdenum disulfide-three-dimensional graphene composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109904396A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110600734A (en) * | 2019-09-11 | 2019-12-20 | 三峡大学 | Ternary WxMo1-xS2Sodium ion battery negative electrode material and preparation method thereof |
| CN110850301A (en) * | 2019-11-20 | 2020-02-28 | 仰恩大学 | MoS2/graphene/MoS2Sandwich structure and Na-ion battery capacity prediction method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102074681A (en) * | 2010-12-03 | 2011-05-25 | 广东工业大学 | Method for preparing carbon nano tube doped lithium titanate composite electrode material |
| CN103840158A (en) * | 2014-03-21 | 2014-06-04 | 新疆大学 | Preparation method for graphene/molybdenum disulfide composite material |
| US20150280217A1 (en) * | 2013-03-11 | 2015-10-01 | William Marsh Rice University | Three-dimensional graphene-backboned architectures and methods of making the same |
| US20160181596A1 (en) * | 2013-08-05 | 2016-06-23 | Kansas State University Research Foundation | ROBUST MoS2/GRAPHENE COMPOSITE ELECTRODES FOR NA+ BATTERY APPLICATIONS |
| CN106057471A (en) * | 2016-05-27 | 2016-10-26 | 同济大学 | Preparation method and application of three-dimensional graphene aerogel load molybdenum disulfide nano-sheet hybridization material |
-
2017
- 2017-12-08 CN CN201711295375.5A patent/CN109904396A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102074681A (en) * | 2010-12-03 | 2011-05-25 | 广东工业大学 | Method for preparing carbon nano tube doped lithium titanate composite electrode material |
| US20150280217A1 (en) * | 2013-03-11 | 2015-10-01 | William Marsh Rice University | Three-dimensional graphene-backboned architectures and methods of making the same |
| US20160181596A1 (en) * | 2013-08-05 | 2016-06-23 | Kansas State University Research Foundation | ROBUST MoS2/GRAPHENE COMPOSITE ELECTRODES FOR NA+ BATTERY APPLICATIONS |
| CN103840158A (en) * | 2014-03-21 | 2014-06-04 | 新疆大学 | Preparation method for graphene/molybdenum disulfide composite material |
| CN106057471A (en) * | 2016-05-27 | 2016-10-26 | 同济大学 | Preparation method and application of three-dimensional graphene aerogel load molybdenum disulfide nano-sheet hybridization material |
Non-Patent Citations (1)
| Title |
|---|
| NING LIU 等: "Microwave-assisted synthesis of MoS2/grapheme nanocomposites for efficient hydrodesuldurization", 《FUEL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110600734A (en) * | 2019-09-11 | 2019-12-20 | 三峡大学 | Ternary WxMo1-xS2Sodium ion battery negative electrode material and preparation method thereof |
| CN110850301A (en) * | 2019-11-20 | 2020-02-28 | 仰恩大学 | MoS2/graphene/MoS2Sandwich structure and Na-ion battery capacity prediction method |
| CN110850301B (en) * | 2019-11-20 | 2021-09-07 | 仰恩大学 | MoS2/graphene/MoS2Sandwich structure and Na-ion battery capacity prediction method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105895886B (en) | A kind of sodium-ion battery transition metal phosphide/porous anode composite and preparation method thereof | |
| CN105336958B (en) | Graphene/CNTs/Super P combined conductive agents, combined conductive agent slurry and preparation method thereof | |
| CN106410199B (en) | A kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method | |
| Shen et al. | Ionic liquid assist to prepare Si@ N-doped carbon nanoparticles and its high performance in lithium ion batteries | |
| Zhou et al. | Enhanced rate performance and high potential as well as decreased strain of LiNi0. 6Co0. 2Mn0. 2O2 by facile fluorine modification | |
| CN104393272A (en) | Lithium titanate cathode composite material and preparation method | |
| CN109904400A (en) | A kind of molybdenum disulfide/three-dimensional graphene composite material | |
| CN109904395A (en) | A kind of molybdenum disulfide-graphene composite material | |
| CN107611425B (en) | Fusiform zinc ferrite/carbon lithium ion battery nano composite negative electrode material and preparation method and application thereof | |
| CN107611374A (en) | A kind of preparation method of new lithium sulfur battery anode material | |
| Kim et al. | V4P7@ C nanocomposite as a high performance anode material for lithium-ion batteries | |
| Liu et al. | Rheological phase synthesis of nanosized α-LiFeO2 with higher crystallinity degree for cathode material of lithium-ion batteries | |
| CN107658461B (en) | Method for preparing ferric fluoride/carbon composite material by taking organic iron compound as raw material | |
| Tang et al. | Fabrication of a highly stable Nb 2 O 5@ C/CNTs based anolyte for lithium slurry flow batteries | |
| Cheng et al. | Synthesis and structural stability of Cr-doped Li2MnSiO4/C cathode materials by solid-state method | |
| CN109904398A (en) | A kind of molybdenum disulfide/graphene composite material | |
| Tang et al. | Spray-drying synthesis of Na2Fe1-xMnxPO4F/C cathodes: a facile synergetic strategy harvesting superior sodium storage | |
| Rahman et al. | Clusters of α-LiFeO 2 nanoparticles incorporated into multi-walled carbon nanotubes: a lithium-ion battery cathode with enhanced lithium storage properties | |
| CN114242961A (en) | Graphene/silicon oxide-coated nano-silicon composite material, and preparation method and application thereof | |
| CN109904396A (en) | A kind of molybdenum disulfide-three-dimensional graphene composite material | |
| Yang et al. | Preparation of LiNi1/3Co1/3Mn1/3O2/polytriphenylamine cathode composites with enhanced electrochemical performances towards reversible lithium storage | |
| Wu et al. | Cobalt phthalocyanine derived bifunctional carbon decorated CoSe with enhanced lithium storage capability | |
| Cao et al. | Size effect on the electrochemical reaction path and performance of nano size phosphorus rich skutterudite nickle phosphide | |
| Dai et al. | Fabrication of MnO@ C-CNTs composite by CVD for enhanced performance of lithium ion batteries | |
| Sun et al. | Scale-up synthesis, structure characterization and electrochemical characteristics of C-LiFePO4 nanocomposites for lithium ion rechargeable batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190618 |