CN104393254A - Nitrogen-doped graphene/molybdenum disulfide composite material, and preparation method and application thereof - Google Patents
Nitrogen-doped graphene/molybdenum disulfide composite material, and preparation method and application thereof Download PDFInfo
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- 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
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- 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
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Abstract
The invention discloses a nitrogen-doped graphene/molybdenum disulfide composite material, and a preparation method and application thereof. The nitrogen-doped graphene/molybdenum disulfide composite material is obtained by mixing a graphite oxide solution, a nitrogen-containing precursor, a sulfur-containing precursor and a molybdenum-containing precursor in a solution, removing the solvent or hetero-ion to obtain a precursor material, performing heat treatment on the precursor material under the protection of an inert gas, and performing nitrogen doping and crystallization. The nitrogen-doped graphene/molybdenum disulfide composite material is applicable to lithium ion batteries, sodium cells, magnesium cells, hydrogen generation under electrocatalysis, hydrogen generation under photocatalysis and super capacitors, and is capable of improving the capacity of an anode material and also enhancing the cycling performance and the rate performance of the anode material when being used as a lithium ion battery anode material.
Description
Technical field
The present invention relates to a kind of composite material and preparation method thereof, particularly relate to a kind of nitrogen-doped graphene/molybdenum bisuphide composite material and preparation method thereof, present invention also offers the nitrogen-doped graphene/application of molybdenum bisuphide composite material in lithium ion battery, the invention belongs to materialogy and technical field of electrochemistry.
Background technology
Lithium ion battery has been widely used in the portable electric appts such as mobile phone, notebook computer as a kind of mechanism of new electrochemical power sources, is also one of power supply of Development of EV.Electrode material is the key determining lithium ion battery combination property quality, and current business-like carbon negative pole material theoretical capacity is only 372mAh/g, is more and more difficult to meet the demand of market to high cycle performance, high-energy-density and high power density lithium ion battery.Therefore, high-performance storage lithium titanate cathode material 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, and Large ratio surface sum brute force learns performance.Nitrogen heteroatom is introduced in Graphene skeleton, electric conductivity and the band structure of Graphene can be regulated and controled further, affect spin density and the CHARGE DISTRIBUTION of carbon atom around, cause the distortion of graphene sheet layer topological structure, and introduce active defects site (graphite mould nitrogen, pyridine type nitrogen and pyrroles's type nitrogen) on surface, improve Graphene reactivity in electrochemical reaction; Nitrogen-doped graphene in conjunction with other functional material, can have important application prospect in scene effect transistor, catalysis, sensing, energy storage and conversion in addition.At present, the method preparing nitrogen-doped carbon mainly contains vapour deposition process, plasma treatment, solvent-thermal method, high temperature pyrolysis nitrogenous precursor, hydrazine hydrate process etc., but, these methods mostly need high temperature or condition of high voltage, equipment relative complex, production cost is high, is difficult to realize suitability for industrialized production; The nitrogen-atoms amount of adulterating in addition is generally all less than 10%, N doping form poor controllability and be difficult to the nitrogen forming stable doping.Therefore the method for seeking more rationally effective nitrogen-doped graphene is needed.
On the other hand, molybdenum bisuphide has and layer structure like graphite-phase, belongs to hexagonal crystal system.Having good catalytic activity, is a kind of traditional Hydrobon catalyst, also has excellent catalytic activity in photoelectricity hydrogen evolution reaction.It is very strong covalent bond (S-Mo-S) in curing molybdenum layer, interlaminar action is then more weak Van der Waals force, interlayer easily introduces foreign atom or molecule, and at lithium ion battery, sode cell, ultracapacitor equal energy source stores and conversion art has important application.But the electronics that molybdenum sulfide adjacent S-Mo-S interlayer is weak and ionic conductivity still limit their activity as electrode material.Therefore by grapheme material and molybdenum bisuphide combined structure novel nano structure, be expected to the chemical property significantly improving composite material, have great importance in fields such as the energy, catalysis, electronics.
Summary of the invention
Because the above-mentioned defect of prior art, it is large and can control the method for the nitrogen-doped graphene of N doping form that technical problem to be solved by this invention is to provide a kind of more rationally effective N doping amount, and can effectively Graphene and molybdenum bisuphide be combined and 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 material, its structure comprises nitrogen-doped graphene and molybdenum bisuphide, and described molybdenum bisuphide vertical-growth is in the surface of described nitrogen-doped graphene; In described nitrogen-doped graphene, described doping nitrogen mainly comprises pyridine type nitrogen and graphite mould nitrogen; Described molybdenum bisuphide is nano-lamellar structure.
Present invention also offers the preparation method of above-mentioned nitrogen-doped graphene/molybdenum bisuphide composite material, comprise the following steps:
Step one, by graphene oxide solution, nitrogenous precursor, sulfur-bearing with mix in a solvent containing molybdenum presoma, then obtain persursor material;
Step 2, the described persursor material obtained in step one to be heat-treated under inert gas shielding.
Further, the preparation process of the described graphene oxide solution in described step one is: mixed by stirring with 2 ~ 6g sodium nitrate by 1 ~ 5g graphite flake, and add 100 ~ 200mL concentrated sulfuric acid while stirring, after stirring half an hour, add 10 ~ 30g potassium permanganate, then stir one day, and place one week, add 500mL water and 20 ~ 50mL H afterwards successively
2o
2, finally product spin dialysis is obtained described graphene oxide solution.
Further, in described step one, described solvent is one or more the mixing in deionized water, ethanol, methyl alcohol, ethylene glycol, glycerol, oxolane, acetone, dimethyl formamide.
Further, described sulfur-bearing and be ammonium molybdate, sulphur ammonium molybdate or ammonium sulfide containing molybdenum presoma, described step one also comprises removes the process of solvent, thus obtains described persursor material.
Further, described sulfur-bearing and containing molybdenum presoma be sodium molybdate and vulcanized sodium, described step one also comprises described graphene oxide solution, described nitrogenous precursor, described sulfur-bearing and in described solvent, forms sediment containing molybdenum presoma in acid condition, then remove the process of solvent and heteroion, thus obtain described persursor material; Described heteroion comprises sodium ion and chloride ion.
Further, the described nitrogenous precursor in described step one is cyanamide, dicyandiamide, urea, thiocarbamide, melamine, graphitized carbon three nitrogen four; Described sulfur-bearing and comprise sodium molybdate, ammonium molybdate, sulphur ammonium molybdate, vulcanized sodium, ammonium sulfide containing molybdenum presoma.
Further, described graphene oxide solution in described step one, described nitrogenous precursor and the described mass ratio containing molybdenum presoma are 1:(1 ~ 50): (5 ~ 30), described sulfur-bearing presoma and the described mol ratio containing sulphur in molybdenum presoma and molybdenum are greater than 2:1.
Further, graphene oxide solution described in described step one, described nitrogenous precursor, described sulfur-bearing and mix at the temperature of the boiling point lower than water containing molybdenum presoma, described temperature is preferably 40 ~ 90 DEG C.
Further, in described step one, be successively by described nitrogenous precursor, described sulfur-bearing with disperse in described graphene oxide solution containing molybdenum presoma or the process of load by described graphene oxide solution, described nitrogenous precursor, described sulfur-bearing and the process that mixes in the solution containing molybdenum presoma.
Further, the described inert gas in described step 2 is the mist of nitrogen, argon gas or nitrogen and argon gas.
Further, the described heat treated temperature in described step 2 is 500 ~ 700 DEG C, and the time is 0.5 ~ 5h.
Further, in the nitrogen-doped graphene obtained by described preparation method/molybdenum bisuphide composite material, the atomic percentage of doping nitrogen and carbon can be greater than 10at%.
In nitrogen-doped graphene of the present invention/molybdenum bisuphide composite material, the nitrogen adulterated is mainly the pyridine type nitrogen and graphite mould nitrogen with electro-chemical activity, considerably increases electro-chemical activity site and the conductivity of material.These N doping sites more contribute to the combination with molybdenum bisuphide crystalline sheets, can improve the stability of material in electrochemical applications.
The preparation method of nitrogen-doped graphene of the present invention/molybdenum bisuphide composite material prepares persursor material by one kettle way, and carry out N doping by a step heat treatment method and crystallization obtains product, achieve the molybdenum bisuphide lamella being compounded with crystallization while N doping at graphenic surface.The existence of molybdenum sulfide facilitates the decomposition of the nitrogenous precursor of electron rich and the N doping of Graphene, thus achieves the N doping of high-load (>10at%) at a lower temperature.Preparation method of the present invention does not need to use complicated equipment, and simple to operate, cost is low.
Present invention also offers a kind of application of above-mentioned nitrogen-doped graphene/molybdenum bisuphide composite material, be preferably the application in lithium ion battery negative material, also can be applied to sode cell, magnesium cell, hydrogen is produced in electro-catalysis, in Photocatalyzed Hydrogen Production, ultracapacitor.
In a particular embodiment of the present invention, lithium ion battery negative material performance characterization carries out packaging and testing by button-shaped half-cell, negative pole is nitrogen-doped graphene/molybdenum bisuphide composite material, activated carbon black, Kynoar (mass ratio is 8:1:1) mixture, be metal lithium sheet to electrode, electrolyte is the ethyl carbonate/dimethyl carbonate solution of lithium hexafluorophosphate solution.
Nitrogen-doped graphene of the present invention/molybdenum bisuphide composite material, as lithium ion battery negative material, while raising negative material capacity, can strengthen its cycle performance and high rate performance
Be described further below with reference to the technique effect of accompanying drawing to design of the present invention, concrete structure and generation, to understand object of the present invention, characteristic sum effect fully.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of nitrogen-doped graphene/molybdenum bisuphide composite material prepared by embodiment 1;
Fig. 2 is the high-resolution-ration transmission electric-lens figure of nitrogen-doped graphene/molybdenum bisuphide composite material prepared by embodiment 1;
Fig. 3 is the X-ray diffractogram of nitrogen-doped graphene/molybdenum bisuphide composite material prepared by embodiment 1;
Fig. 4 is nitrogen element X-ray energy spectrum figure in the nitrogen-doped graphene/molybdenum bisuphide composite material of embodiment 1 preparation;
Fig. 5 is the cycle performance figure of nitrogen-doped graphene/molybdenum bisuphide composite material as lithium ion battery negative material of embodiment 1 preparation;
Fig. 6 is the high rate performance figure of nitrogen-doped graphene/molybdenum bisuphide composite material as lithium ion battery negative material of embodiment 1 preparation.
Embodiment
Preferred embodiment of the present invention provides the preparation method of a kind of nitrogen-doped graphene/molybdenum bisuphide composite material, specifically comprises the following steps:
(1) preparation of graphene oxide solution
1 ~ 5g graphite flake is mixed by stirring with 2 ~ 6g sodium nitrate, and adds 100 ~ 200mL concentrated sulfuric acid while stirring, after stirring half an hour, add 10 ~ 30g potassium permanganate, then stir one day, and place one week, add 500mL water and 20 ~ 50mL H afterwards successively
2o
2, finally product spin dialysis is obtained graphene oxide solution.
(2) preparation of nitrogen-doped graphene/molybdenum bisuphide composite material
Step one, by graphene oxide solution, nitrogenous precursor, sulfur-bearing and be 1:(1 ~ 50 containing molybdenum presoma according to mass ratio): (5 ~ 30) in a solvent, temperature be 40 ~ 90 DEG C at mixing, and wherein sulfur-bearing presoma is greater than 2:1 with the mol ratio containing molybdenum presoma.Then removal solvent or heteroion obtain persursor material.
Wherein, solvent is preferably deionized water, also can be ethanol, methyl alcohol, ethylene glycol, glycerol, oxolane, acetone, dimethyl formamide or mixed solvent.Nitrogenous precursor can be cyanamide, dicyandiamide, urea, thiocarbamide, melamine, graphitized carbon three nitrogen four.Sulfur-bearing and containing molybdenum presoma can be sodium molybdate, ammonium molybdate, sulphur ammonium molybdate, vulcanized sodium, ammonium sulfide.By graphene oxide solution, nitrogenous precursor, sulfur-bearing and the process that mixes in the solution containing molybdenum presoma actual in successively by nitrogenous precursor, sulfur-bearing with contain molybdenum presoma and disperse in graphene oxide solution or the process of load.
Step 2, heat-treated under inert gas shielding by the persursor material obtained in step one, heat treatment temperature is 500 ~ 700 DEG C, and heat treatment time is 0.5 ~ 5h.
Wherein, inert gas is the mist of nitrogen, argon gas or nitrogen and argon gas.
Embodiment 1:
The present embodiment 1 provides the preparation method of a kind of nitrogen-doped graphene/molybdenum bisuphide composite material, specifically comprises the following steps:
(1) preparation of graphene oxide solution
5g graphite flake is mixed by stirring with 5g sodium nitrate, and slowly adds the 200mL concentrated sulfuric acid while stirring, after stirring half an hour, slowly add 20g potassium permanganate, then stir one day, and place one week, slowly add 500mL water afterwards, then add 20 ~ 50mL H
2o
2, finally product spin dialysis is obtained graphene oxide solution.
(2) preparation of nitrogen-doped graphene/molybdenum bisuphide composite material
Step one, measure 50mg graphene oxide solution, and be dispersed in 200mL deionized water, then add 100mg graphitized carbon three nitrogen four wherein and obtain mixed liquor, by ultrasonic for this mixed liquor process to Homogeneous phase mixing, and by mixed liquor agitating heating in 90 DEG C of oil bath pans, then in mixed liquor, add 300mg sodium molybdate and 1.5g vulcanized sodium, and the pH value hydrochloric acid solution of whole system is adjusted to 3, obtain brown precipitate after removing heteroion (as sodium ion, chloride ion) and solvent, collect this brown precipitate and be dried and obtain persursor material.
Step 2, persursor material is placed in quartz boat, and is placed on and is connected with in the tube furnace of nitrogen, at 550 DEG C, heat treated obtains nitrogen-doped graphene/molybdenum bisuphide composite material after 3 hours.
As shown in Figures 1 to 3, nitrogen-doped graphene/molybdenum bisuphide composite material prepared by the present embodiment has laminated structure, and wherein molybdenum sulfide nanoscale twins vertical-growth is in graphene-based basal surface.As shown in Figure 4, doped with nitrogen element, its doping (atomic percentage of namely adulterate nitrogen and carbon) is 13at%, and this doping nitrogen mainly comprises pyridine type nitrogen and graphite mould nitrogen at graphene-based the end.
Embodiment 2:
The present embodiment 2 provides the preparation method of a kind of nitrogen-doped graphene/molybdenum bisuphide composite material, specifically comprises the following steps:
(1) preparation of graphene oxide solution
5g graphite flake is mixed by stirring with 5g sodium nitrate, and slowly adds the 200mL concentrated sulfuric acid while stirring, after stirring half an hour, slowly add 20g potassium permanganate, then stir one day, and place one week, slowly add 500mL water afterwards, then add 50mL H
2o
2, finally product spin dialysis is obtained graphene oxide solution.
(2) preparation of nitrogen-doped graphene/molybdenum bisuphide composite material
Step one, measure 50mg graphene oxide solution, and be dispersed in 200mL deionized water, then add 2g urea wherein and obtain mixed liquor, by this mixed liquor agitating heating in 90 DEG C of oil bath pans, then in mixed liquor, add 400mg sulphur ammonium molybdate, evaporating the water under 90 DEG C of conditions obtains persursor material.
Step 2, persursor material is placed in quartz boat, and is placed on and is connected with in the tube furnace of nitrogen, at 550 DEG C, heat treated obtains nitrogen-doped graphene/molybdenum bisuphide composite material after 5 hours.
Embodiment 3:
The present embodiment 3 provides the preparation method of a kind of nitrogen-doped graphene/molybdenum bisuphide composite material, specifically comprises the following steps:
(1) preparation of graphene oxide solution
5g graphite flake is mixed by stirring with 5g sodium nitrate, and slowly adds the 200mL concentrated sulfuric acid while stirring, after stirring half an hour, slowly add 20g potassium permanganate, then stir one day, and place one week, slowly add 500mL water afterwards, then add 50mL H
2o
2, finally product spin dialysis is obtained graphene oxide solution.
(2) preparation of nitrogen-doped graphene/molybdenum bisuphide composite material
Step one, measure 30mg graphene oxide solution, and be dispersed in 200mL deionized water, and in 90 DEG C of oil bath pans agitating heating, then 600mg sodium molybdate and 5g vulcanized sodium is added wherein, and the pH value hydrochloric acid solution of whole system is adjusted to 3, obtain brown precipitate after removing heteroion (as sodium ion, chloride ion) and solvent, collect this brown precipitate and this brown precipitate and 2g urea Homogeneous phase mixing are obtained persursor material.
Step 2, persursor material is placed in quartz boat, and is placed on and is connected with in the tube furnace of nitrogen, at 650 DEG C, heat treated obtains nitrogen-doped graphene/molybdenum bisuphide composite material after 1 hour.
Embodiment 4:
The present embodiment 4 provides the preparation method of a kind of nitrogen-doped graphene/molybdenum bisuphide composite material, specifically comprises the following steps:
(1) preparation of graphene oxide solution
5g graphite flake is mixed by stirring with 5g sodium nitrate, and slowly adds the 200mL concentrated sulfuric acid while stirring, after stirring half an hour, slowly add 20g potassium permanganate, then stir one day, and place one week, slowly add 500mL water afterwards, then add 50mL H
2o
2, finally product spin dialysis is obtained graphene oxide solution.
(2) preparation of nitrogen-doped graphene/molybdenum bisuphide composite material
Step one, measure 30mg graphene oxide solution, and be dispersed in 200mL deionized water, then add 2g thiocarbamide wherein and obtain mixed liquor, by this mixed liquor agitating heating in 90 DEG C of oil bath pans, then in mixed liquor, add 300mg ammonium molybdate, evaporating the water under 90 DEG C of conditions obtains persursor material.
Step 2, persursor material is placed in quartz boat, and is placed on and is connected with in the tube furnace of nitrogen, at 600 DEG C, heat treated obtains nitrogen-doped graphene/molybdenum bisuphide composite material after 2 hours.
Embodiment 5:
Nitrogen-doped graphene/molybdenum bisuphide composite material that embodiment 1 is prepared by the present embodiment 5 is applied in the negative material of lithium ion battery, and detailed process is:
With the nitrogen-doped graphene obtained by embodiment 1/molybdenum bisuphide composite material for active material, acetylene black is conductive agent, Kynoar is binding agent, 1-METHYLPYRROLIDONE is solvent, by active material, conductive agent, binding agent mass ratio 8:1:1 makes slurry and is coated on Copper Foil and makes negative plate, be to electrode with lithium metal, ethyl carbonate/dimethyl carbonate the solution of lithium hexafluorophosphate solution is electrolyte, by cathode pole piece, electrolyte, barrier film, lithium metal is assembled into button battery and tests, its cycle performance and high rate performance figure are respectively as shown in Figure 5 and Figure 6.As 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 material demonstrates higher capacity (1400mAh/g), and still can stablize under 200 charge and discharges circulation.As shown in Figure 6, nitrogen-doped graphene/molybdenum bisuphide composite material keeps 1200mAh/g under the large current density of 1A/g, still keeps the capacity of 830mAh/g under the large current density of 10A/g, shows excellent high rate performance.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technical staff in the art, all should by the determined protection range of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. nitrogen-doped graphene/molybdenum bisuphide composite material, is characterized in that, described nitrogen-doped graphene/molybdenum bisuphide composite material comprises nitrogen-doped graphene and molybdenum bisuphide, and described molybdenum bisuphide vertical-growth is in the surface of described nitrogen-doped graphene; In described nitrogen-doped graphene, described doping nitrogen mainly comprises pyridine type nitrogen and graphite mould nitrogen; Described molybdenum bisuphide is nano-lamellar structure.
2. an application for nitrogen-doped graphene/molybdenum bisuphide composite material as claimed in claim 1, is characterized in that, described in be applied as the application of to produce in lithium ion battery, sode cell, magnesium cell, electro-catalysis in hydrogen, Photocatalyzed Hydrogen Production, ultracapacitor.
3. a preparation method for nitrogen-doped graphene as claimed in claim 1/molybdenum bisuphide composite material, is characterized in that, comprise the following steps:
Step one, by graphene oxide solution, nitrogenous precursor, sulfur-bearing with mix in a solvent containing molybdenum presoma, then obtain persursor material;
Step 2, the described persursor material obtained in step one to be heat-treated under inert gas shielding.
4. preparation method as claimed in claim 3, it is characterized in that, the preparation process of the described graphene oxide solution in described step one is: mixed by stirring with 2 ~ 6g sodium nitrate by 1 ~ 5g graphite flake, and add 100 ~ 200mL concentrated sulfuric acid while stirring, after stirring half an hour, add 10 ~ 30g potassium permanganate, then stir one day, and place one week, add 500mL water and 20 ~ 50mL H afterwards successively
2o
2, finally product spin dialysis is obtained described graphene oxide solution.
5. preparation method as claimed in claim 3, it is characterized in that, the described nitrogenous precursor in described step one is cyanamide, dicyandiamide, urea, thiocarbamide, melamine, graphitized carbon three nitrogen four; Described sulfur-bearing and be ammonium molybdate, sulphur ammonium molybdate or ammonium sulfide containing molybdenum presoma, described step one also comprises removes the process of solvent, thus obtains described persursor material.
6. preparation method as claimed in claim 3, it is characterized in that, the described nitrogenous precursor in described step one is cyanamide, dicyandiamide, urea, thiocarbamide, melamine, graphitized carbon three nitrogen four; Described sulfur-bearing and containing molybdenum presoma be sodium molybdate and vulcanized sodium, described step one also comprises described graphene oxide solution, described nitrogenous precursor, described sulfur-bearing and in described solvent, forms sediment containing molybdenum presoma in acid condition, then remove the process of solvent and heteroion, thus obtain described persursor material; Described heteroion comprises sodium ion and chloride ion.
7. preparation method as claimed in claim 3, it is characterized in that, described graphene oxide solution in described step one, described nitrogenous precursor and the described mass ratio containing molybdenum presoma are 1:(1 ~ 50): (5 ~ 30), described sulfur-bearing presoma and the described mol ratio containing sulphur in molybdenum presoma and molybdenum are greater than 2:1.
8. preparation method as claimed in claim 3, is characterized in that, graphene oxide solution described in described step one, described nitrogenous precursor, described sulfur-bearing and mix at the temperature of the boiling point lower than water containing molybdenum presoma; Be successively by described nitrogenous precursor, described sulfur-bearing with disperse in described graphene oxide solution containing molybdenum presoma or the process of load by described graphene oxide solution, described nitrogenous precursor, described sulfur-bearing and the process that mixes in the solution containing molybdenum presoma.
9. preparation method as claimed in claim 3, it is characterized in that, the described heat treated temperature in described step 2 is 500 ~ 700 DEG C, and the time is 0.5 ~ 5h.
10. preparation method as claimed in claim 3, is characterized in that, in the nitrogen-doped graphene obtained by described preparation method/molybdenum bisuphide composite material, the atomic percentage of doping nitrogen and carbon can be greater than 10at%.
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