CN106129407A - MoS2the synthetic method of@graphene composite nano material - Google Patents
MoS2the synthetic method of@graphene composite nano material Download PDFInfo
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- CN106129407A CN106129407A CN201610749509.5A CN201610749509A CN106129407A CN 106129407 A CN106129407 A CN 106129407A CN 201610749509 A CN201610749509 A CN 201610749509A CN 106129407 A CN106129407 A CN 106129407A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of MoS2The synthetic method of@graphene composite nano material.The present invention uses a step hydrothermal synthesis method, and with the graphene oxide of pyrolysis reduction, sodium molybdate, thiourea as raw material, Tris buffer is solvent, under dopamine assosting effect, is prepared for the uniform MoS of pattern2@graphene composite nano material.TEM/SEM result shows, substantial amounts of MoS2Ultrathin nanometer sheet homoepitaxial, on graphenic surface, forms the structure as net and is tightly wrapped in above Graphene.Knowable to XRD spectra, MoS2Well-crystallized, belongs to the 2H MoS of hexagonal crystal system2Crystalline phase.Present invention process is simple, and condition is controlled, and material load uniformity is high, the MoS of preparation2@graphene composite nano material is with a wide range of applications at new energy fields such as lithium ion battery negative materials.
Description
Technical field
The present invention relates to a kind of MoS2The synthetic method of@graphene composite nano material, belongs to the new energy such as lithium ion battery
Source material preparation field.
Background technology
The transient metal sulfide MS of two-dimensional layered structure2(M=Mo, Ti, V), generally have than zero dimension and one-dimensional more
Avtive spot, can show more active surface, and two-dimensional structure also has that weight is little, surface area big and is evenly distributed simultaneously
Feature, shows many excellent performances at aspects such as optical, electrical, magnetic.In these materials, there is the curing of graphite-like structure
Molybdenum nano material (MoS2), the theoretical capacity higher due to it and special structure are at new forms of energy such as lithium ion battery negative materials
Field causes the extensive concern of people.
But, MoS2When deep discharge, inevitably there is serious volumetric expansion, cause the microcosmic of material to be tied
Structure changes, and then affects multiplying power and the cycle performance of material；Plus the limitation of electric conductivity own, the most greatly limit
It is further applied.Therefore, simple MoS2Make electrode material to have met and be actually needed.Currently, improve
One effective ways of material property exactly with conduct electricity very well, constitutionally stable material with carbon element forms composite nanostructure.And stone
Two-dimensional structure, high specific surface and the electric conductivity of excellence that ink alkene is unique so that it is become load MoS2Ideal carrier.Very
Multi-method has been used to prepare MoS2@graphene composite material, as synthesized under the assosting effect of surfactant；Nitrating is modified
Graphene and MoS2It is combined.Although making some progress in this respect, but the building-up process of composite is the most multiple
Miscellaneous.Therefore, simple and effective preparation technology is developed, successfully by MoS2It is combined with Graphene, improves its chemical property, at new energy
There is important Research Significance in the fields such as source.
Summary of the invention
It is an object of the invention to provide a kind of MoS2The preparation method of@graphene lithium ion battery negative material.
For achieving the above object, the present invention is by the following technical solutions:
A kind of MoS2The preparation method of@graphene composite nano material, it is characterised in that concretely comprising the following steps of the method:
A. add graphene oxide in Tris buffer, be configured to concentration be 0.0350～
The mixed solution of 0.0450mol/L；Add dopamine, after continuing to stir, add sodium molybdate, continue to stir；?
Rear addition thiourea；Described graphene oxide, dopamine, sodium molybdate, the mol ratio of thiourea be: 1:0.075～0.235:0.33:
2.10；
B. step a gained mixed solution is reacted under the conditions of 180～240 DEG C 12～24h；After having reacted, by product
Centrifugation, and by deionized water and washing with alcohol, dry, obtain black powder；
C., by step b gained black powder in an inert atmosphere, under the conditions of 600～800 DEG C, 1～3h is calcined, i.e. get Ben Fa
The MoS of bright preparation2@graphene composite nano material.
The present invention is with sodium molybdate for molybdenum source, and thiourea is sulfur source, under the assosting effect of dopamine, carries out multiple with Graphene
Close, prepare and there is equally loaded sheet-like morphology MoS2@graphene composite nano material.During present invention process, DOPA
Amine first passes through electrostatic interaction and adsorbs on redox graphene surface, the molybdenum acid ion of the sodium molybdate hydrolysis being subsequently added
Absorption is on dopamine, and molybdate is reduced into MoS by the hydrogen sulfide that the thiourea being eventually adding at high temperature decomposites2, end form
The composite nano materials uniformly loaded.
Compared with existing synthetic technology, the technology of the present invention has following remarkable advantage: technique is simple, and condition is controlled, material
Material Load Balanced degree is high, has the application prospect in terms of potential field of lithium ion battery material.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention gained MoS2The XRD spectra of@graphene composite nano material.
Fig. 2 is embodiment of the present invention gained MoS2The TEM picture of@graphene composite nano material.
Fig. 3 is embodiment of the present invention gained MoS2The SEM picture of@graphene composite nano material.
Fig. 4 is the embodiment of the present invention and comparative example gained MoS2The electrochemistry cycle performance of@graphene composite nano material
Figure.
Detailed description of the invention
All embodiments are all operated by the operating procedure of technique scheme.Graphene oxide used in the present invention
Preparation method refer to J.Am.Chem.Soc., 2008,130,5856-5857.Specific as follows: first by potassium peroxydisulfate
(K2S2O8) and phosphorus pentoxide (P2O5) it being dissolved in concentrated sulphuric acid, ultrasonic agitation is uniform, after adding the most load weighted graphite powder, complete
Become preoxidation process.The most under cryogenic with potassium permanganate (KMnO4) and concentrated sulphuric acid sufficiently aoxidize.Pass through dilute hydrochloric acid again
Clean and i.e. can get graphene oxide with washing repeatedly.The graphene oxide of pyrolysis reduction is obtained finally by 500 DEG C of calcinings.
Embodiment one:
A. the graphene oxide of 30mg pyrolysis reduction is weighed, the trihydroxy methyl of the 10mM that ultrasonic disperse prepares in advance in 60ml
Aminomethane buffer agent；
B. in above-mentioned a mixed solution, add 90mg dopamine, stir 2h, fully dissolve；
C. 0.2g sodium molybdate is added in above-mentioned solution b, continue stirring 1h；Add the thiourea of 0.4g, be sufficiently stirred for 1h；
D. reacted mixed solution is poured in band teflon-lined autoclave, under the conditions of 200 DEG C
Reaction 24h；
E. after having reacted, product is taken out from reactor, centrifugation, and with deionized water and ethanol cyclic washing
After, by it at 60 DEG C of dried in vacuum overnight, and in nitrogen atmosphere, under the conditions of 600 DEG C, calcine 2h, obtain prepared by the present invention
MoS2@graphene composite nano material.
The sample of gained is carried out physical property sign, and its partial results is as shown in drawings.From result, gained MoS2@stone
The MoS that ink alkene composite pattern is homogeneous, ultra-thin2Nanometer sheet is supported on graphenic surface, forms the structure as net tightly
It is wrapped on Graphene.
Comparative example
Preparation process and the step of the present embodiment are essentially identical with embodiment, and difference is b step:
Do not add dopamine.
Acquired results is significantly different with embodiment, MoS2It is difficult to uniform load and part on Graphene and reunites serious.
Seeing accompanying drawing, Fig. 1 is embodiment of the present invention gained MoS2The XRD spectra of@graphene composite nano material.XRD divides
Analysis: carry out on Japan's RigaKu D/max-2550 type X-ray diffractometer；Use CuK α diffraction.It can be seen that, institute of the present invention
In composite, diffraction maximum go out peak position in 2 θ=14.5 °, 40.2 °, 50.3 °, 59.9 ° correspond respectively to MoS2's
(002), (103), (105), (110) crystal face, consistent with standard spectrogram (JCPDF No.37-1492), it is typical hexagonal crystal
It is 2H-MoS2Crystalline phase.And have no that other miscellaneous peaks occur, the highly purified MoS that products therefrom is well-crystallized is described2Nanometer sheet.
Seeing accompanying drawing, Fig. 2 is embodiment of the present invention gained MoS2The transmission electron microscope (TEM) of@graphene composite nano material
Picture.Tem analysis: use Jeol Ltd. JEOL-200CX type transmission electron microscope observation material morphology and knot
Structure.In gained composite of the present invention, lamellar MoS2Uniform load is on graphenic surface.
Seeing accompanying drawing, Fig. 3 is embodiment of the present invention gained MoS2The scanning electron microscope (SEM) of@graphene composite nano material
Picture.Sem analysis: use NEC company JSM-20CX type to launch sem observation material morphology.Tie from SEM
Fruit is it can be seen that substantial amounts of MoS2Ultrathin nanometer sheet homoepitaxial, on graphenic surface, forms the structure as net tightly
It is wrapped in above Graphene, consistent with TEM result.
Seeing accompanying drawing, Fig. 4 is the embodiment of the present invention and comparative example gained MoS2The electrochemistry of@graphene composite nano material
Cycle performance figure.Wherein, the method for testing of chemical property is as follows: prepare MoS2@graphene composite nano material and white carbon black,
PVDF (polyvinylidene fluoride, 2.5wt.% aqueous solution) mix homogeneously, makes the negative pole of battery；Using lithium metal as positive pole, micro-
Hole polypropylene material is as barrier film；Electrolyte is by LiPF6It is dissolved in ethylene carbonic ether (EC), propylene carbonate (DMC) and carbon
In acetoacetic ester (DEC) formulated (respective quality than for 1:1:1).In the glove box being assembled in full argon of simulated battery complete
Become.Figure 4, it is seen that embodiment gained composite nano materials discharges under conditions of electric current density is 100mA/g first
Capacity is 1732.3mAh/g, and after 50 circulations, capacity still reaches 1100.0mAh/g, and its capability retention still can reach
To 63.5%.And the electric discharge first under same electric current density of comparative example resulting materials is 1430.0mAh/g, after circulating at 50 times
Capacity only has 413.6mAh/g, and capability retention is the lowest.
Claims (1)
1. a MoS2The preparation method of@graphene composite nano material, it is characterised in that concretely comprising the following steps of the method:
A. adding graphene oxide in Tris buffer, being configured to concentration is 0.0350 ~ 0.0450
The mixed solution of mol/L；Add dopamine, after continuing to stir, add sodium molybdate, continue to stir；It is eventually adding
Thiourea；Described graphene oxide, dopamine, sodium molybdate, the mol ratio of thiourea be: 1:0.075～0.235:0.33:
2.10；
B. step a gained mixed solution is reacted under the conditions of 180～240 DEG C 12～24 h；After having reacted, by product from
The heart separates, and by deionized water and washing with alcohol, dries, obtain black powder；
C. the said goods is calcined under the conditions of 600～800 DEG C in nitrogen atmosphere 1～3 h, obtains MoS prepared by the present invention2@
Graphene composite nano material.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450336A (en) * | 2016-12-06 | 2017-02-22 | 先进储能材料国家工程研究中心有限责任公司 | Lithium ion battery negative electrode slurry and preparation method thereof |
| CN107275627A (en) * | 2017-06-27 | 2017-10-20 | 武汉理工大学 | Mn doping hollow porous classifying nano ball electrode materials of CuS and its preparation method and application |
| CN107492664A (en) * | 2017-07-14 | 2017-12-19 | 中国第汽车股份有限公司 | Electrodes of lithium-ion batteries coating with heat sinking function |
| CN109638230A (en) * | 2017-10-09 | 2019-04-16 | 中国科学院大连化学物理研究所 | The preparation method of graphene coated foam-like molybdenum sulfide anode material of lithium-ion battery |
| CN109686954A (en) * | 2018-12-27 | 2019-04-26 | 陕西科技大学 | A kind of C-O-Mo key bridge joint monolithic taper MoS2/ NG sodium ion negative electrode material and preparation method thereof |
| CN110773162A (en) * | 2019-11-04 | 2020-02-11 | 青岛大学 | Preparation method and application of carbon-coated two-dimensional layered molybdenum oxide compound-supported noble metal |
| CN111902975A (en) * | 2017-12-06 | 2020-11-06 | 汉阳大学校产学协力团 | Anode active material for lithium-sulfur secondary battery and method for preparing same |
| CN114324517A (en) * | 2021-12-08 | 2022-04-12 | 常州大学 | Electrode for detecting hydrogen peroxide, electrochemical sensor and detection method thereof |
| CN114507981A (en) * | 2022-01-28 | 2022-05-17 | 南京工业大学 | Preparation method of graphene/molybdenum disulfide composite fiber fabric |
| CN117712360A (en) * | 2024-02-06 | 2024-03-15 | 深圳市华明胜科技有限公司 | Preparation method of composite modified graphite anode material |
| CN117712360B (en) * | 2024-02-06 | 2024-04-23 | 深圳市华明胜科技有限公司 | Preparation method of composite modified graphite anode material |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106450336B (en) * | 2016-12-06 | 2019-07-02 | 先进储能材料国家工程研究中心有限责任公司 | A kind of lithium ion battery anode slurry and preparation method thereof |
| CN106450336A (en) * | 2016-12-06 | 2017-02-22 | 先进储能材料国家工程研究中心有限责任公司 | Lithium ion battery negative electrode slurry and preparation method thereof |
| CN107275627A (en) * | 2017-06-27 | 2017-10-20 | 武汉理工大学 | Mn doping hollow porous classifying nano ball electrode materials of CuS and its preparation method and application |
| CN107492664A (en) * | 2017-07-14 | 2017-12-19 | 中国第汽车股份有限公司 | Electrodes of lithium-ion batteries coating with heat sinking function |
| CN109638230B (en) * | 2017-10-09 | 2021-08-06 | 中国科学院大连化学物理研究所 | Preparation method of graphene-coated foamy molybdenum sulfide sodium-ion battery negative electrode material |
| CN109638230A (en) * | 2017-10-09 | 2019-04-16 | 中国科学院大连化学物理研究所 | The preparation method of graphene coated foam-like molybdenum sulfide anode material of lithium-ion battery |
| CN111902975A (en) * | 2017-12-06 | 2020-11-06 | 汉阳大学校产学协力团 | Anode active material for lithium-sulfur secondary battery and method for preparing same |
| CN109686954A (en) * | 2018-12-27 | 2019-04-26 | 陕西科技大学 | A kind of C-O-Mo key bridge joint monolithic taper MoS2/ NG sodium ion negative electrode material and preparation method thereof |
| CN110773162A (en) * | 2019-11-04 | 2020-02-11 | 青岛大学 | Preparation method and application of carbon-coated two-dimensional layered molybdenum oxide compound-supported noble metal |
| CN114324517A (en) * | 2021-12-08 | 2022-04-12 | 常州大学 | Electrode for detecting hydrogen peroxide, electrochemical sensor and detection method thereof |
| CN114507981A (en) * | 2022-01-28 | 2022-05-17 | 南京工业大学 | Preparation method of graphene/molybdenum disulfide composite fiber fabric |
| CN117712360A (en) * | 2024-02-06 | 2024-03-15 | 深圳市华明胜科技有限公司 | Preparation method of composite modified graphite anode material |
| CN117712360B (en) * | 2024-02-06 | 2024-04-23 | 深圳市华明胜科技有限公司 | Preparation method of composite modified graphite anode material |
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