CN109904400A - A kind of molybdenum disulfide/three-dimensional graphene composite material - Google Patents

A kind of molybdenum disulfide/three-dimensional graphene composite material Download PDF

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CN109904400A
CN109904400A CN201711296630.8A CN201711296630A CN109904400A CN 109904400 A CN109904400 A CN 109904400A CN 201711296630 A CN201711296630 A CN 201711296630A CN 109904400 A CN109904400 A CN 109904400A
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graphene
preparation
dimensional
composite material
molybdenum disulfide
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郭金
张会成
王少军
凌凤香
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy 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, four thio ammonium molybdate and the grinding of three-dimensional grapheme aeroge are placed in microwave reaction chamber, with the heats 1-20min 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 heated decompose rapidly of single-source precursor generates MoS2, growth in situ is directly gone up on the surface of graphene, and 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

A kind of molybdenum disulfide/three-dimensional graphene composite material
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 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/ 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 four thio ammonium molybdate and is ground;
C. the material after grinding in step b is placed in microwave reaction chamber, with the heats 1-20min of 300-1000W, Obtain molybdenum disulfide/three-dimensional graphene composite material.
In the above preparation method, as a further preference, microwave reaction preferably heats 3 ~ 15min in 500 ~ 1000W, More preferably 6 ~ 15min of heating.
In the above preparation method, as a further preference, graphene oxide described in step a and L-cysteine are mixed Conjunction mass ratio is 1:1-20, preferably 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, four thio ammonium molybdate and three-dimensional grapheme airsetting in step b The mixing mass ratio of glue is 1-20:1.The mass ratio that feeds intake of mill ball and mixture is 1-20:1, revolution in ball mill when grinding For 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, 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 rapidly to be heat-treated graphene oxide for graphene by microwave heating, while single-source precursor tetrathio molybdenum Heated decompose rapidly of sour ammonium generates MoS2, so that MoS2Nanometer sheet growth in situ directly on three-dimensional structure graphene surface, due to Microwave heating speed is fast, and homogeneous heating makes MoS2Nanometer sheet is firmly combined with graphene, and does not easily cause particle packing, pole Time needed for shortening synthetic material greatly, and alleviate graphene and MoS2The problem of reuniting in long-term heated situation. Meanwhile the graphene of three-dimensional structure prepared by the present invention is not easy to send out in recombination process compared to two-dimensional structure grapheme material It is raw to stack and reunite again, it preferably ensure that the performance of graphene excellent properties, facilitate lithium ion and charge in combination electrode Transmission in material.
The technical purpose of third aspect 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, stone is effectively relieved in graphene reduction Black alkene and MoS2It is firmly combined and does not significantly build up, molybdenum disulfide nano sheet is uniformly dispersed on the surface of graphene.Meanwhile this hair The graphene of the three-dimensional structure of bright preparation compared to two-dimensional structure grapheme material, be not susceptible to stack again in recombination process and Reunite, preferably ensure that the performance of graphene excellent properties, facilitate the biography of lithium ion and charge in combination electrode material It is defeated.Stability of material is good, in air not mutability, is easy storage, large specific surface area, as lithium ion battery negative material, Good channel is provided 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/graphene composite material in current density is 100mAg in embodiment 9-1When charge and discharge cycles it is bent Line.
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-cysteine mass ratio is that 1:4 is added into above-mentioned suspension L-cysteine, ultrasonic dissolution obtain uniform suspension, place it in hydrothermal synthesis kettle, hydro-thermal reaction 12h at 180 DEG C, Hydrogel is obtained, three-dimensional structure graphene aerogel is obtained after freeze-drying.Obtained three-dimensional grapheme aeroge be it is cylindric, Its 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 four thio ammonium molybdate and three-dimensional grapheme aeroge 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, is set In microwave reaction chamber, 1h is purged with the argon gas of 100mL/min.3min is heated with the power microwave of 400W.It is cold under an ar atmosphere But 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
Molybdenum disulfide/three-dimensional graphene composite material preparation: by four thio ammonium molybdate and three-dimensional grapheme aeroge with 2:1's 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, revolving speed After 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, microwave is placed in In reaction chamber, 1h is purged with the argon gas of 100mL/min.6min is heated with the power microwave of 400W.It is cooled to room under an ar atmosphere Temperature is 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
Molybdenum disulfide/three-dimensional graphene composite material preparation: by four thio ammonium molybdate and three-dimensional grapheme aeroge with 3:1's 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, revolving speed After 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, microwave is placed in In reaction chamber, 1h is purged with the argon gas of 100mL/min.9min is heated with the power microwave of 600W.It is cooled to room under an ar atmosphere Temperature is 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
Molybdenum disulfide/three-dimensional graphene composite material preparation: by four thio ammonium molybdate and three-dimensional grapheme aeroge with 3:1's 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, revolving speed After 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, microwave is placed in In reaction chamber, 1h is purged with the argon gas of 100mL/min.9min is heated with the power microwave of 800W.It is cooled to room under an ar atmosphere Temperature is 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
Molybdenum disulfide/three-dimensional graphene composite material preparation: by four thio ammonium molybdate and three-dimensional grapheme aeroge with 3:1's 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, revolving speed After 400rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, microwave is placed in In reaction chamber, 1h is purged with the argon gas of 100mL/min.12min is heated with the power microwave of 600W.It is cooled to room under an ar atmosphere Temperature is 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
Molybdenum disulfide/three-dimensional graphene composite material preparation: by four thio ammonium molybdate and three-dimensional grapheme aeroge with 3:1's 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, revolving speed After 600rpm ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, it then will reaction Pipe is placed in microwave reaction chamber, purges 1h with the argon gas of 100mL/min.3min is heated with the power microwave of 600W.In Ar atmosphere Under be cooled to room temperature 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
Molybdenum disulfide/three-dimensional graphene composite material preparation: by four thio ammonium molybdate and three-dimensional grapheme aeroge with 3:1's 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, revolving speed After 800rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, microwave is placed in In reaction chamber, 1h is purged with the argon gas of 100mL/min.6min is heated with the power microwave of 800W.It is cooled to room under an ar atmosphere Temperature is 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
Molybdenum disulfide/three-dimensional graphene composite material preparation: by four thio ammonium molybdate and three-dimensional grapheme aeroge with 3:1's 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, revolving speed After 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.3min is heated with the power microwave of 800W.? It is cooled to room temperature under 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
Molybdenum disulfide/three-dimensional graphene composite material preparation: by four thio ammonium molybdate and three-dimensional grapheme aeroge with 3:1's 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, revolving speed After 800rpm, ball milling 1h, cooled to room temperature collects product.Material after ball milling is encased in reaction tube, microwave is placed in In reaction chamber, 1h is purged with the argon gas of 100mL/min.3min is heated with the power microwave of 1000W.It is cooled to room under an ar atmosphere Temperature is to get molybdenum disulfide/three-dimensional graphene composite material.
Molybdenum disulfide/three-dimensional graphene composite material of embodiment 1 ~ 9 is used for lithium ion battery negative material.With synthesis Molybdenum disulfide/three-dimensional grapheme be active component, select 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, The poly- third coal film of Celgard2300 micropore is as battery diaphragm.The above material is assembled into button in the glove box full of Ar gas Formula battery is tested again after waiting working electrodes sufficiently to be 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 9 is in 0.01-3.0V voltage In range, 100mAg-1Current density under cyclical stability test result it is as shown in Fig. 3.The charge and discharge for the first time of embodiment 1 ~ 9 Capacitance and the discharge capacity after 100 charge-discharge tests are shown in Table 1.
Table 1
Comparative example 1
Using preparation method same as Example 9, the difference is that not using microwave heating, it is exchanged with conventional Muffle furnace 800 DEG C roasting 3min.Four thio ammonium molybdate does not decompose completely as the result is shown, causes molybdenum disulfide/three-dimensional grapheme yield less, will Resulting materials are used for lithium cell cathode material, and initial discharge capacity only has 426mAhg-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 four thio ammonium molybdate and is ground;
C. the material after grinding in step b is placed in microwave reaction chamber, with the heats 1-20min 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- Sour mixing mass ratio 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 four thio ammonium molybdate and three-dimensional grapheme in step b The mixing mass ratio of aeroge is 1-20:1.
5. 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.
6. preparation method according to claim 1, which is characterized in that with nitrogen or lazy before microwave reaction and in reaction process Property gas purge microwave reaction chamber.
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.
CN201711296630.8A 2017-12-08 2017-12-08 A kind of molybdenum disulfide/three-dimensional graphene composite material Pending CN109904400A (en)

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CN112447954A (en) * 2019-09-03 2021-03-05 王宝辉 Graphene-modified ferrate material and preparation method and application thereof
CN112744859A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Fibrous graphene doped TiO2Composite material
CN112751013A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Nitrogen-doped TiO2/GRA composite material

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NING LIU 等: "Microwave-assisted synthesis of MoS2/graphene nanocomposites for efficient hydrodesuldurization", 《FUEL》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112447954A (en) * 2019-09-03 2021-03-05 王宝辉 Graphene-modified ferrate material and preparation method and application thereof
CN112447954B (en) * 2019-09-03 2022-02-08 王宝辉 Graphene-modified ferrate material and preparation method and application thereof
CN112744859A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Fibrous graphene doped TiO2Composite material
CN112751013A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Nitrogen-doped TiO2/GRA composite material
CN112751013B (en) * 2019-10-31 2022-07-12 中国石油化工股份有限公司 Nitrogen-doped TiO2/GRA composite material
CN112023952A (en) * 2020-08-25 2020-12-04 辽宁大学 Cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material and preparation method and application thereof

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Application publication date: 20190618