CN104393254B - Nitrogen-doped graphene/molybdenum bisuphide composite and its preparation method and application - Google Patents
Nitrogen-doped graphene/molybdenum bisuphide composite and its preparation method and application Download PDFInfo
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- CN104393254B CN104393254B CN201410519794.2A CN201410519794A CN104393254B CN 104393254 B CN104393254 B CN 104393254B CN 201410519794 A CN201410519794 A CN 201410519794A CN 104393254 B CN104393254 B CN 104393254B
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- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- 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
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Abstract
The invention discloses a kind of nitrogen-doped graphene/molybdenum bisuphide composite and preparation thereof and application.Graphene oxide solution, nitrogenous precursor, sulfur-bearing and the presoma Han molybdenum are mixed by the present invention in the solution; obtain persursor material after removing solvent or heteroion, this persursor material heat treatment under inert gas shielding is carried out N doping and crystallization thus obtains nitrogen-doped graphene/molybdenum bisuphide composite.The nitrogen-doped graphene of the present invention/molybdenum bisuphide composite can apply to lithium ion battery, sode cell, magnesium cell, hydrogen is produced in electro-catalysis, Photocatalyzed Hydrogen Production, ultracapacitor, during as lithium ion battery negative material, its cycle performance and high rate performance can be strengthened while improving negative material capacity.
Description
Technical field
The present invention relates to a kind of composite and preparation method thereof, particularly relate to a kind of nitrogen-doped graphene/molybdenum bisuphide multiple
Condensation material and preparation method thereof, present invention also offers nitrogen-doped graphene/molybdenum bisuphide composite at lithium ion battery
In application, the invention belongs to materialogy and technical field of electrochemistry.
Background technology
Lithium ion battery has been widely used in the portable electric such as mobile phone, notebook computer as a kind of mechanism of new electrochemical power sources
Subset, is also one of the power supply of Development of EV.Electrode material is to determine that lithium ion battery combination property is good and bad
Key, current business-like carbon negative pole material theoretical capacity is only 372mAh/g, is increasingly difficult to meet market to height
Cycle performance, high-energy-density and the demand of high power density lithium ion battery.Therefore, high-performance storage lithium titanate cathode material
It is difficult point and the focus of Study on Li-ion batteries.
Graphene, as a kind of Two-dimensional Carbon material, has electric-conductivity heat-conductivity high, bigger serface and strong mechanical property.?
Graphene skeleton introduces nitrogen heteroatom, electric conductivity and the band structure of Graphene, impact week can be regulated and controled further
Enclose spin density and the CHARGE DISTRIBUTION of carbon atom, cause the distortion of graphene sheet layer topological structure, and introduce on surface
Active defects site (graphite mould nitrogen, pyridine type nitrogen and pyrroles's type nitrogen), improves the Graphene middle reaction in electrochemical reaction
Activity；Additionally nitrogen-doped graphene can in conjunction with other functional material, scene effect transistor, be catalyzed, sense, the energy
Storage and conversion has important application prospect.At present, prepare the method for nitrogen-doped carbon mainly have vapour deposition process, etc.
Ion processing, solvent-thermal method, high temperature pyrolysis nitrogenous precursor, hydrazine hydrate process etc., but, these methods mostly need
Wanting high temperature or condition of high voltage, equipment is relative complex, and production cost is high, it is difficult to realize industrialized production；Additionally adulterate
Nitrogen-atoms amount typically less than 10%, N doping form poor controllability and be hardly formed the nitrogen of stable doping.Therefore need
The method seeking more rationally effective nitrogen-doped graphene.
On the other hand, molybdenum bisuphide have with graphite-phase as layer structure, belong to hexagonal crystal system.There is good catalysis
Activity, is a kind of traditional Hydrobon catalyst, also has the catalysis activity of excellence in photoelectricity hydrogen evolution reaction.
Being the strongest covalent bond (S-Mo-S) in layer of molybdenum-disulfide, interlaminar action is then more weak Van der Waals force, and interlayer is easy
Introduce foreign atom or molecule, have with conversion art in lithium ion battery, sode cell, the storage of ultracapacitor equal energy source
There is important application.But the electronics that molybdenum sulfide adjacent S-Mo-S interlayer is weak and ionic conductivity still limit them to be made
Activity for electrode material.Therefore by grapheme material and molybdenum bisuphide combined structure novel nano structure, it is expected to notable
Improve the chemical property of composite, have great importance in fields such as the energy, catalysis, electronics.
Summary of the invention
Because the drawbacks described above of prior art, the technical problem to be solved is to provide one more rationally effectively
N doping amount big and can control the method for nitrogen-doped graphene of N doping form, and can effectively by Graphene and
Molybdenum bisuphide combines and the advanced composite material (ACM) improving chemical property and preparation method thereof.
For achieving the above object, the invention provides a kind of nitrogen-doped graphene/molybdenum bisuphide composite, in its structure
Including nitrogen-doped graphene and molybdenum bisuphide, described molybdenum bisuphide vertical-growth is in the surface of described nitrogen-doped graphene；
In described nitrogen-doped graphene, described doping nitrogen mainly includes pyridine type nitrogen and graphite mould nitrogen；Described molybdenum bisuphide is for receiving
Rice lamellar structure.
Present invention also offers the preparation method of above-mentioned nitrogen-doped graphene/molybdenum bisuphide composite, including following step
Rapid:
Step one, graphene oxide solution, nitrogenous precursor, sulfur-bearing and the presoma Han molybdenum are mixed, so in a solvent
After obtain persursor material；
Step 2, the described persursor material obtained in step one is carried out heat treatment under inert gas shielding.
Further, the preparation process of the described graphene oxide solution in described step one is: by 1～5g graphite flake
Mixed by stirring with 2～6g sodium nitrates, and add 100～200mL concentrated sulphuric acids while stirring, stir half an hour
After, add 10～30g potassium permanganate, then stirring one day, and places one week, be sequentially added into afterwards 500mL water with
20～50mL H2O2, finally product spin dialysis is obtained described graphene oxide solution.
Further, in described step one, described solvent be deionized water, ethanol, methanol, ethylene glycol, glycerol,
One or more mixing in oxolane, acetone, dimethylformamide.
Further, described sulfur-bearing and be ammonium molybdate, sulfur ammonium molybdate or ammonium sulfide containing molybdenum presoma, described step one is also
Including the process of removal solvent, thus obtain described persursor material.
Further, described sulfur-bearing and containing molybdenum presoma be sodium molybdate and sodium sulfide, described step one also includes described oxygen
Functionalized graphene solution, described nitrogenous precursor, described sulfur-bearing and containing molybdenum presoma in described solvent in acid condition
Form precipitate, then remove solvent and the process of heteroion, thus obtain described persursor material；Described heteroion
Comprise sodium ion and chloride ion.
Further, the described nitrogenous precursor in described step one is cyanamide, dicyandiamide, carbamide, thiourea, trimerization
Cyanamide, graphitized carbon three nitrogen four；Described sulfur-bearing and the presoma Han molybdenum include sodium molybdate, ammonium molybdate, sulfur ammonium molybdate,
Sodium sulfide, ammonium sulfide.
Further, the described graphene oxide solution in described step one, described nitrogenous precursor and described containing molybdenum before
The mass ratio driving body is 1:(1～50): (5～30), described sulfur-bearing presoma with described containing sulfur in molybdenum presoma and molybdenum
Mol ratio is more than 2:1.
Further, graphene oxide solution described in described step one, described nitrogenous precursor, described sulfur-bearing and contain
Molybdenum presoma is mixing less than at a temperature of the boiling point of water, and described temperature is preferably 40～90 DEG C.
Further, in described step one, by described graphene oxide solution, described nitrogenous precursor, described sulfur-bearing
The process mixed in the solution with the presoma containing molybdenum is successively by described nitrogenous precursor, described sulfur-bearing and the presoma Han molybdenum
The process disperseed in described graphene oxide solution or load.
Further, the mixed gas that described noble gas is nitrogen, argon or nitrogen and argon in described step 2.
Further, the temperature of the described heat treatment in described step 2 is 500～700 DEG C, and the time is 0.5～5h.
Further, by nitrogen-doped graphene/molybdenum bisuphide composite that described preparation method obtains, adulterate nitrogen
10at% can be more than with the atomic percentage of carbon.
In the nitrogen-doped graphene of the present invention/molybdenum bisuphide composite, the nitrogen adulterated predominantly has electro-chemical activity
Pyridine type nitrogen and graphite mould nitrogen, considerably increase electro-chemical activity site and the electric conductivity of material.These N doping positions
Point is more conducive to and the combination of molybdenum bisuphide crystalline sheets, can improve the stability of material in electrochemical applications.
The preparation method of the nitrogen-doped graphene of the present invention/molybdenum bisuphide composite prepares presoma material by one kettle way
Material, and carry out N doping by a step heat treatment method and crystallization obtains product, it is achieved that same at N doping
Time be compounded with the molybdenum bisuphide lamella of crystallization at graphenic surface.The existence of molybdenum sulfide promote electron rich nitrogenous before
Drive the decomposition of body and the N doping of Graphene, it is achieved thereby that high-load (> 10at% at a lower temperature) N doping.
The preparation method of the present invention need not use the equipment of complexity, simple to operate, low cost.
Present invention also offers the application of a kind of above-mentioned nitrogen-doped graphene/molybdenum bisuphide composite, be preferably lithium from
Application in sub-cell negative electrode material, it is also possible to be applied to sode cell, magnesium cell, electro-catalysis produces hydrogen, Photocatalyzed Hydrogen Production,
In ultracapacitor.
In a particular embodiment of the present invention, lithium ion battery negative material performance characterization is carried out by button-shaped half-cell
Packaging and testing, negative pole is nitrogen-doped graphene/molybdenum bisuphide composite, activated carbon black, Kynoar (quality
Ratio is 8:1:1) mixture, it is metal lithium sheet to electrode, electrolyte is the ethyl carbonate/carbon of lithium hexafluorophosphate solution
Dimethyl phthalate solution.
The nitrogen-doped graphene of the present invention/molybdenum bisuphide composite, as lithium ion battery negative material, can improve
While negative material capacity, strengthen its cycle performance and high rate performance
Below with reference to accompanying drawing, the technique effect of design, concrete structure and the generation of the present invention is described further, with
It is fully understood from the purpose of the present invention, feature and effect.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the nitrogen-doped graphene/molybdenum bisuphide composite of embodiment 1 preparation；
Fig. 2 is the high-resolution-ration transmission electric-lens figure of the nitrogen-doped graphene/molybdenum bisuphide composite of embodiment 1 preparation；
Fig. 3 is the X-ray diffractogram of the nitrogen-doped graphene/molybdenum bisuphide composite of embodiment 1 preparation；
Fig. 4 is nitrogen element X-ray energy spectrogram in nitrogen-doped graphene/molybdenum bisuphide composite prepared by embodiment 1；
Fig. 5 is that the nitrogen-doped graphene/molybdenum bisuphide composite of embodiment 1 preparation is as lithium ion battery negative material
Cycle performance figure；
Fig. 6 is that the nitrogen-doped graphene/molybdenum bisuphide composite of embodiment 1 preparation is as lithium ion battery negative material
High rate performance figure.
Detailed description of the invention
Presently preferred embodiments of the present invention provides the preparation method of a kind of nitrogen-doped graphene/molybdenum bisuphide composite, tool
Body comprises the following steps:
(1) preparation of graphene oxide solution
1～5g graphite flake and 2～6g sodium nitrates are mixed by stirring, and adds 100～200mL while stirring
Concentrated sulphuric acid, after stirring half an hour, adds 10～30g potassium permanganate, then stirring one day, and places one week, afterwards
It is sequentially added into 500mL water and 20～50mL H2O2, finally product spin dialysis is obtained graphene oxide solution.
(2) preparation of nitrogen-doped graphene/molybdenum bisuphide composite
Step one, by graphene oxide solution, nitrogenous precursor, sulfur-bearing be 1 containing molybdenum presoma according to mass ratio:
(1～50): (5～30) in a solvent, temperature be at 40～90 DEG C mix, and wherein sulfur-bearing presoma with containing molybdenum forerunner
The mol ratio of body is more than 2:1.Then remove solvent or heteroion obtains persursor material.
Wherein, solvent is preferably deionized water, it is also possible to for ethanol, methanol, ethylene glycol, glycerol, oxolane,
Acetone, dimethylformamide or mixed solvent.Nitrogenous precursor can be cyanamide, dicyandiamide, carbamide, thiourea, three
Poly cyanamid, graphitized carbon three nitrogen four.Sulfur-bearing and containing molybdenum presoma can be sodium molybdate, ammonium molybdate, sulfur ammonium molybdate, sulfur
Change sodium, ammonium sulfide.Graphene oxide solution, nitrogenous precursor, sulfur-bearing and the presoma Han molybdenum are mixed in the solution
Process is actual is nitrogenous precursor, sulfur-bearing and the presoma Han molybdenum to be disperseed in graphene oxide solution successively or load
Process.
Step 2, the persursor material obtained in step one is carried out heat treatment, heat treatment temperature under inert gas shielding
Degree is 500～700 DEG C, and heat treatment time is 0.5～5h.
Wherein, noble gas is the mixed gas of nitrogen, argon or nitrogen and argon.
Embodiment 1:
The present embodiment 1 provides the preparation method of a kind of nitrogen-doped graphene/molybdenum bisuphide composite, specifically include with
Lower step:
(1) preparation of graphene oxide solution
5g graphite flake is mixed by stirring with 5g sodium nitrate, and is slowly added to the dense sulfur of 200mL while stirring
Acid, after stirring half an hour, is slowly added to 20g potassium permanganate, then stirring one day, and places one week, the most slowly
Add 500mL water, be subsequently adding 20～50mL H2O2, finally product spin dialysis is obtained graphene oxide
Solution.
(2) preparation of nitrogen-doped graphene/molybdenum bisuphide composite
Step one, measure 50mg graphene oxide solution, and be dispersed in 200mL deionized water, then exist
Wherein add 100mg graphitized carbon three nitrogen four and obtain mixed liquor, by this mixed liquor supersound process to uniformly mixing, and will
Mixed liquor is agitating heating in 90 DEG C of oil bath pans, then adds 300mg sodium molybdate and 1.5g sodium sulfide in mixed liquor,
And the pH value hydrochloric acid solution of whole system is adjusted to 3, after removing heteroion (such as sodium ion, chloride ion) and solvent
Obtain brown precipitate, collect this brown precipitate and be dried and obtain persursor material.
Step 2, persursor material is placed in quartz boat, and is placed in the tube furnace being connected with nitrogen, at 550 DEG C
Lower heat treated obtains nitrogen-doped graphene/molybdenum bisuphide composite after 3 hours.
As shown in Figures 1 to 3, nitrogen-doped graphene prepared by the present embodiment/molybdenum bisuphide composite has laminated structure,
Wherein molybdenum sulfide nanoscale twins vertical-growth is in graphene-based basal surface.As shown in Figure 4, at graphene-based the end doped with
Nitrogen element, its doping (i.e. doping nitrogen and the atomic percentage of carbon) is 13at%, and this doping nitrogen mainly includes pyridine
Type nitrogen and graphite mould nitrogen.
Embodiment 2:
The present embodiment 2 provides the preparation method of a kind of nitrogen-doped graphene/molybdenum bisuphide composite, specifically include with
Lower step:
(1) preparation of graphene oxide solution
5g graphite flake is mixed by stirring with 5g sodium nitrate, and is slowly added to the dense sulfur of 200mL while stirring
Acid, after stirring half an hour, is slowly added to 20g potassium permanganate, then stirring one day, and places one week, the most slowly
Add 500mL water, be subsequently adding 50mL H2O2, finally product spin dialysis is obtained graphene oxide molten
Liquid.
(2) preparation of nitrogen-doped graphene/molybdenum bisuphide composite
Step one, measure 50mg graphene oxide solution, and be dispersed in 200mL deionized water, then
Add 2g carbamide wherein and obtain mixed liquor, by this mixed liquor agitating heating in 90 DEG C of oil bath pans, then in mixing
Liquid adds 400mg sulfur ammonium molybdate, evaporates the water under the conditions of 90 DEG C and obtain persursor material.
Step 2, persursor material is placed in quartz boat, and is placed in the tube furnace being connected with nitrogen, at 550 DEG C
Lower heat treated obtains nitrogen-doped graphene/molybdenum bisuphide composite after 5 hours.
Embodiment 3:
The present embodiment 3 provides the preparation method of a kind of nitrogen-doped graphene/molybdenum bisuphide composite, specifically include with
Lower step:
(1) preparation of graphene oxide solution
5g graphite flake is mixed by stirring with 5g sodium nitrate, and is slowly added to the dense sulfur of 200mL while stirring
Acid, after stirring half an hour, is slowly added to 20g potassium permanganate, then stirring one day, and places one week, the most slowly
Add 500mL water, be subsequently adding 50mL H2O2, finally product spin dialysis is obtained graphene oxide molten
Liquid.
(2) preparation of nitrogen-doped graphene/molybdenum bisuphide composite
Step one, measure 30mg graphene oxide solution, and be dispersed in 200mL deionized water, and 90
Agitating heating in DEG C oil bath pan, adds 600mg sodium molybdate and 5g sodium sulfide the most wherein, and by whole system
PH value hydrochloric acid solution is adjusted to 3, obtains brown precipitate after removing heteroion (such as sodium ion, chloride ion) and solvent,
Collect this brown precipitate and this brown precipitate and 2g carbamide are uniformly mixed to get persursor material.
Step 2, persursor material is placed in quartz boat, and is placed in the tube furnace being connected with nitrogen, at 650 DEG C
Lower heat treated obtains nitrogen-doped graphene/molybdenum bisuphide composite after 1 hour.
Embodiment 4:
The present embodiment 4 provides the preparation method of a kind of nitrogen-doped graphene/molybdenum bisuphide composite, specifically include with
Lower step:
(1) preparation of graphene oxide solution
5g graphite flake is mixed by stirring with 5g sodium nitrate, and is slowly added to the dense sulfur of 200mL while stirring
Acid, after stirring half an hour, is slowly added to 20g potassium permanganate, then stirring one day, and places one week, the most slowly
Add 500mL water, be subsequently adding 50mL H2O2, finally product spin dialysis is obtained graphene oxide molten
Liquid.
(2) preparation of nitrogen-doped graphene/molybdenum bisuphide composite
Step one, measure 30mg graphene oxide solution, and be dispersed in 200mL deionized water, then exist
Wherein add 2g thiourea and obtain mixed liquor, by this mixed liquor agitating heating in 90 DEG C of oil bath pans, then at mixed liquor
Middle addition 300mg ammonium molybdate, evaporates the water under the conditions of 90 DEG C and obtains persursor material.
Step 2, persursor material is placed in quartz boat, and is placed in the tube furnace being connected with nitrogen, at 600 DEG C
Lower heat treated obtains nitrogen-doped graphene/molybdenum bisuphide composite after 2 hours.
Embodiment 5:
The nitrogen-doped graphene that embodiment 1 is prepared by the present embodiment 5/molybdenum bisuphide composite is applied to lithium ion battery
Negative material in, detailed process is:
With the nitrogen-doped graphene obtained by embodiment 1/molybdenum bisuphide composite as active substance, acetylene black is conduction
Agent, Kynoar is binding agent, and N-Methyl pyrrolidone is solvent, by active substance, conductive agent, binding agent matter
Measuring and make slurry than 8:1:1 and be coated on Copper Foil and make negative plate, with lithium metal for electrode, lithium hexafluoro phosphate is molten
The ethyl carbonate of liquid/dimethyl carbonate solution is electrolyte, cathode pole piece, electrolyte, barrier film, lithium metal is assembled into
Button battery is tested, and its cycle performance and high rate performance figure are the most as shown in Figure 5 and Figure 6.As it is shown in figure 5,
In 0-3.0V voltage range, with under the charging and discharging currents of 0.1A/g, nitrogen-doped graphene/molybdenum bisuphide composite
Demonstrate and remain to stablize under higher capacity (1400mAh/g), and 200 charge and discharges circulation.As shown in Figure 6, nitrogen is mixed
Miscellaneous Graphene/molybdenum bisuphide composite keeps 1200mAh/g under the large current density of 1A/g, big at 10A/g
Still keep the capacity of 830mAh/g under current charge-discharge, show the high rate performance of excellence.
The preferred embodiment of the present invention described in detail above.Should be appreciated that those of ordinary skill in the art without
Need creative work just can make many modifications and variations according to the design of the present invention.Therefore, all in the art
Technical staff the most on the basis of existing technology can by logical analysis, reasoning, or a limited experiment
With the technical scheme obtained, all should be in the protection domain being defined in the patent claims.
Claims (4)
1. the preparation method of nitrogen-doped graphene/molybdenum bisuphide composite, it is characterised in that described N doping
Graphene/molybdenum bisuphide composite includes nitrogen-doped graphene and molybdenum bisuphide, described molybdenum bisuphide vertical-growth in
The surface of described nitrogen-doped graphene；In described nitrogen-doped graphene, described doping nitrogen mainly includes pyridine type nitrogen and stone
Ink type nitrogen；Described molybdenum bisuphide is nano-lamellar structure；
The preparation method of described nitrogen-doped graphene/molybdenum bisuphide composite comprises the following steps:
Step one, graphene oxide solution, nitrogenous precursor, sulfur-bearing and the presoma Han molybdenum are mixed, so in a solvent
After obtain persursor material；
Described nitrogenous precursor in described step one is cyanamide, dicyandiamide, carbamide, thiourea, tripolycyanamide, graphite
Change carbon three nitrogen four；Described sulfur-bearing and be ammonium molybdate, sulfur ammonium molybdate or ammonium sulfide containing molybdenum presoma, or is sodium sulfide and molybdenum
Acid sodium；
When described sulfur-bearing and containing molybdenum presoma be ammonium molybdate, sulfur ammonium molybdate or ammonium sulfide time, described step one include oxidation
Graphene solution, described nitrogenous precursor, described sulfur-bearing and mix in described solvent and evaporate containing molybdenum presoma
Solvent forms the persursor material of mixing；When described sulfur-bearing and containing molybdenum presoma be sodium sulfide and sodium molybdate time, described
Step one also includes described graphene oxide solution, described nitrogenous precursor, described sulfur-bearing and contains molybdenum presoma described
Solvent is formed precipitate in acid condition, then removes solvent and the process of heteroion, thus obtain described forerunner
Body material；Described heteroion comprises sodium ion and chloride ion；
Described graphene oxide solution in described step one, described nitrogenous precursor and the described quality containing molybdenum presoma
Ratio is 1:(1～50): (5～30), described sulfur-bearing presoma is more than with the described mol ratio containing sulfur in molybdenum presoma with molybdenum
2:1；
Step 2, the described persursor material obtained in step one is carried out heat treatment under inert gas shielding；
By in nitrogen-doped graphene/molybdenum bisuphide composite that described preparation method obtains, adulterate the nitrogen atom with carbon
Percent can be more than 10at%.
2. preparation method as claimed in claim 1, it is characterised in that the described graphene oxide in described step one
The preparation process of solution is: 1～5g graphite flake and 2～6g sodium nitrates are mixed by stirring, and while stirring
Add 100～200mL concentrated sulphuric acids, after stirring half an hour, add 10～30g potassium permanganate, then stirring one day, and
Place one week, be sequentially added into 500mL water and 20～50mL H afterwards2O2, finally product spin dialysis is obtained
Described graphene oxide solution.
3. preparation method as claimed in claim 1, it is characterised in that described in described step one, graphene oxide is molten
Liquid, described nitrogenous precursor, described sulfur-bearing and mixing less than at a temperature of the boiling point of water containing molybdenum presoma；Will
The process that described graphene oxide solution, described nitrogenous precursor, described sulfur-bearing and the presoma Han molybdenum mix in the solution
For by described nitrogenous precursor, described sulfur-bearing and disperseing in described graphene oxide solution or negative containing molybdenum presoma successively
The process carried.
4. preparation method as claimed in claim 1, it is characterised in that the temperature of the described heat treatment in described step 2
Degree is 500～700 DEG C, and the time is 0.5～5h.
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| CN104835654B (en) * | 2015-05-29 | 2016-03-30 | 青岛大学 | A kind of three-dimensional nitrogen-doped graphene/molybendum disulfide complexes and preparation method thereof |
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