CN104409706B - A kind of molybdenum bisuphide/sulphur, nitrogen-doped graphene nanosheet composite material and its preparation method and application - Google Patents

A kind of molybdenum bisuphide/sulphur, nitrogen-doped graphene nanosheet composite material and its preparation method and application Download PDF

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CN104409706B
CN104409706B CN201410798090.3A CN201410798090A CN104409706B CN 104409706 B CN104409706 B CN 104409706B CN 201410798090 A CN201410798090 A CN 201410798090A CN 104409706 B CN104409706 B CN 104409706B
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sulphur
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molybdenum bisuphide
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CN104409706A (en
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王双印
刘秋红
吴振军
吴江红
马兆玲
窦烁
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Hunan University
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Abstract

The invention discloses a kind of molybdenum bisuphide/sulphur, nitrogen-doped graphene nanosheet composite material and its preparation method and application, in the composite, molybdenum bisuphide is supported on the graphene nanometer sheet of sulphur, N doping.The preparation method of the composite is comprised the following steps：Four thio ammonium molybdate, graphene oxide, thiocarbamide are dissolved in into N, in N dimethylformamides, are well mixed, obtained mixed solution, be then dried, be finally sintered in protective gas；Wherein four thio ammonium molybdate, graphene oxide, the mass ratio of thiocarbamide are 1 ~ 500：15：10~1000.Molybdenum bisuphide/the sulphur of the present invention, nitrogen-doped graphene nanosheet composite material applied range, can be applicable in fields such as lithium ion battery, ultracapacitor, hydrogen precipitation, photocatalysis, nano-devices.

Description

A kind of molybdenum bisuphide/sulphur, nitrogen-doped graphene nanosheet composite material and its preparation side Method and application
Technical field
The present invention relates to inorganic nano material, more particularly to a kind of nano composite material and its preparation method and application.
Background technology
At present lithium ion battery is used as a kind of free of contamination electrochmical power source of novel high-energy, by global energy chemical research The favor of person, with traditional one-shot battery compared with secondary cell, lithium ion battery has that discharge voltage is high, self discharge is little, nothing The advantages of memory effect, it is widely used in the fields such as information, electronics, traffic, national defense and military. in many transition metal materials In, MoS2As the stratified material of a species Graphene, except lubricating and being catalyzed in addition to the domains such as neck tool is widely used, in recent years Scientific research personnel has found which also has huge application prospect in lithium cell cathode material field.MoS2As lithium ion battery negative material The theoretical capacity of material reaches 670mAh/g（There are four mole electrons to participate in reaction per moles of active species in assuming course of reaction）. Research show the electrode material of bulky grain size in charge and discharge process easily polarization so that capacity attenuation is fast, nano material has Big specific surface area can increase the contact area with electrolyte, can reduce relatively the diffusion length of electronics and ion, so as to The decay of capacity is reduced, but, big specific surface is easily caused nano material reunion, reduces the contact area with electrode solution； Nano material is grown in certain substrate being effectively to reduce one of method of nano material reunion.
Recently, the grapheme material for developing rapidly, have that surface area is big, conduct electricity very well due to which, pliability it is good, electrochemical The advantages of performance is steady, has been widely used in the fields such as chemistry, biology, electronics.In terms of lithium ion battery negative material, Graphene has more superior removal lithium embedded performance compared with other material with carbon elements.In addition, Graphene can also prevent nanometer as cushion Particle is reunited in cyclic process.The compound of generally molybdenum bisuphide and Graphene is all using sulphur such as thioacetamide, thiocarbamides Source, adopting ammonium molybdate or sodium molybdate a certain amount of graphene oxide is added for molybdenum source to be well mixed carries out hydro-thermal reaction and obtains two The compound of molybdenum sulfide and Graphene.Molybdenum bisuphide is poor as a kind of semiconducting electrical conductivity, compound with Graphene to increase really Plus the electric conductivity of material is conducive to electric transmission, but the graphene conductive that hydro-thermal reaction is obtained not is highly desirable, Er Qieshui The molybdenum bisuphide that thermal response is obtained be not growth in situ on Graphene be it is mixed together, the molybdenum bisuphide of lamella Contact defective tightness with Graphene, can so increase electric transmission path, and the sample that another aspect hydro-thermal reaction is obtained is produced Amount is less, is unfavorable for large-scale production.
The content of the invention
The technical problem to be solved be overcome the shortcomings of background above technology in mention and defect, there is provided one Specific surface area is big, chemical property is good molybdenum bisuphide/sulphur, the composite of nitrogen-doped graphene nanometer sheet are planted, is correspondingly provided A kind of preparation method is simple, the molybdenum bisuphide/sulphur that can be mass produced, the composite of nitrogen-doped graphene nanometer sheet Preparation method and the application in prepared by lithium ion battery.
To solve above-mentioned technical problem, technical scheme proposed by the present invention is a kind of molybdenum bisuphide/sulphur, nitrogen-doped graphene Nanosheet composite material, in the composite, molybdenum bisuphide is supported on the graphene nanometer sheet of sulphur, N doping.By MoS2 The transmission of electronics in electrochemical reaction process can not only be promoted after compound is compounded to form with Graphene, while electrode can be slowed down Volume Changes problem during embedding and removing, prevents MoS2Accumulation and efflorescence.
In above-mentioned molybdenum bisuphide/sulphur, nitrogen-doped graphene nanosheet composite material, it is preferred that the composite is The disk of a diameter of 40 ~ 100nm.
Used as a total technology design, the present invention also provides a kind of above-mentioned molybdenum bisuphide/sulphur, nitrogen-doped graphene and receives The preparation method of rice piece composite, comprises the following steps：Four thio ammonium molybdate, graphene oxide, thiocarbamide are dissolved in into N, N- bis- NMF（DMF）In, ultrasound is well mixed, obtains mixed solution, is then dried above-mentioned mixed solution, is finally protecting It is sintered in shield gas；
The four thio ammonium molybdate, graphene oxide, the mass ratio of thiocarbamide are 1 ~ 500：15：10~1000.
In above-mentioned preparation method, it is preferred that the DMF（DMF）Volume and the graphite oxide The corresponding relation of alkene quality is 1mL/mg ~ 1000 mL/mg.
In above-mentioned preparation method, it is preferred that the drying is concretely comprised the following steps：At 90 ~ 110 DEG C, rotary evaporation is carried out Preliminarily dried, is then further vacuum dried at 80 ~ 120 DEG C.
In above-mentioned preparation method, it is preferred that characterized in that, the sintering is divided into three phases, first stage：By 1 ~ The ramp of 10 DEG C/min is incubated 1 ~ 3h to 450 DEG C；Second stage：By the ramp of 1 ~ 10 DEG C/min to 800 DEG C, protect 1 ~ 3h of temperature；Phase III is temperature-fall period：300 DEG C are cooled to by the speed of 5 DEG C/min, room temperature is then naturally cooling to.
In above-mentioned preparation method, it is preferred that in the first stage, protective gas is Ar/H2, the wherein volume of hydrogen Fraction is 10%；In described second and third stage, protective gas is argon gas.
Used as a total technology design, the present invention also provides a kind of above-mentioned molybdenum bisuphide/sulphur, nitrogen-doped graphene and receives Rice application of the piece composite in lithium ion battery is prepared.
Inventive conception is that：Four thio ammonium molybdate, graphene oxide, thiocarbamide are dissolved according to certain ratio It is well mixed which in DMF, is placed in tube furnace after being dried and first passes through Ar/H2（10%）450 DEG C process a period of time, make MoS2's Presoma four thio ammonium molybdate is decomposed thermally to form MoS2And be laid on graphene oxide, then through 800 DEG C in argon gas protection Under the conditions of high temperature sintering process, allow thiocarbamide to decompose and produce hydrogen sulfide and ammonia, serving as sulphur source and nitrogen source has scarce to graphene oxide Adulterate where falling into, while making graphene oxide reduce under the high temperature conditions, and make larger-size graphene oxide originally exist Due to the fracture and formation of some chemical bonds while doping, cause the broken so as to reduce Graphene size of Graphene, finally Obtain molybdenum bisuphide/sulphur, nitrogen-doped graphene nanosheet composite material, the material is modified, compares table with atom doped The features such as area is big.
Compared with prior art, it is an advantage of the current invention that：
（1）In the present invention, molybdenum bisuphide is supported on the Graphene of sulphur, nitrogen-doping, not only reduces Graphene Particle diameter, and make composite that there is the big characteristic of atom doped modified, specific surface area；
（2）Molybdenum bisuphide/the sulphur of the present invention, nitrogen-doped graphene nanosheet composite material preparation method are simple, can carry out Large-scale production；
（3）Molybdenum bisuphide/the sulphur of the present invention, nitrogen-doped graphene nanosheet composite material applied range, can be applicable to In fields such as lithium ion battery, ultracapacitor, hydrogen precipitation, photocatalysis, nano-devices.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing Accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are the present invention Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can be with basis These accompanying drawings obtain other accompanying drawings.
Fig. 1 is the molybdenum bisuphide/sulphur of the preparation of the embodiment of the present invention 1, the transmission of nitrogen-doped graphene nanosheet composite material Electromicroscopic photograph（TEM）.
Fig. 2 is the molybdenum bisuphide/sulphur of the preparation of the embodiment of the present invention 1, the x-ray of nitrogen-doped graphene nanosheet composite material XPS Analysis figure（XPS）.
Specific embodiment
For the ease of understanding the present invention, more complete is made to the present invention below in conjunction with Figure of description and preferred embodiment Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art It is identical.Technical term used herein is intended merely to the purpose for describing specific embodiment, is not intended to limit the present invention Protection domain.
Unless otherwise specified, the various raw material used in the present invention, reagent, instrument and equipment etc. can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1
A kind of molybdenum bisuphide/sulphur of the present invention, nitrogen-doped graphene nanosheet composite material, in the composite, two sulphur Change molybdenum to be supported on the graphene nanometer sheet of sulphur, N doping；Disk of the composite for a diameter of 40 ~ 100nm.
Molybdenum bisuphide/the sulphur of the present embodiment, the preparation method of nitrogen-doped graphene nanosheet composite material, including following step Suddenly：0.22g four thio ammonium molybdates, 0.15g graphene oxides, 1.5g thiocarbamides are weighed respectively, and in being dissolved in 150mL DMF, ultrasound is mixed After closing uniformly, with Rotary Evaporators, in oil bath, 110 DEG C of rotary evaporations are removed after most of solvents, and taking-up sample is in surface plate 120 DEG C of vacuum drying, are placed in quartz boat with mortar is finely ground afterwards after taking out, are placed in tube furnace, use threeway after being completely dried Connection argon gas/hydrogen (10%) and argon gas, then hunted leak with suds, checks each interface whether there is gas leak phenomenon, it is ensured that everywhere without After gas leak phenomenon, first lead to 20min argon gas, then change argon gas/hydrogen (10%) into, and heating schedule is set to 5 DEG C/min intensifications To 450 DEG C, 3h is incubated, recycles threeway that gas is changed into argon gas, be continuously heating to 800 DEG C by 450 DEG C with 5 DEG C/min, be incubated 1h, then be cooled to 300 DEG C with 5 DEG C/min, then be naturally cooling to room temperature, turns off gas, collects the sample in quartz boat, and as two Molybdenum sulfide/sulphur, nitrogen-doped graphene nanosheet composite material.
Molybdenum bisuphide/the sulphur of the present embodiment, nitrogen-doped graphene nanosheet composite material can be applicable to lithium ion battery, surpass The fields such as level capacitor, hydrogen precipitation, photocatalysis, nano-device.
Fig. 1 is the transmission electron microscope photograph of molybdenum bisuphide/sulphur manufactured in the present embodiment, nitrogen-doped graphene nanosheet composite material Piece（TEM）；As seen from Figure 1, molybdenum bisuphide is supported on the nanometer sheet of formed 40 ~ 100nm on the Graphene of sulphur, N doping. Fig. 2 is the x-ray photoelectron spectroscopy point of molybdenum bisuphide/sulphur manufactured in the present embodiment, nitrogen-doped graphene nanosheet composite material Analysis figure（XPS）.As shown in Figure 2, Graphene is doped with sulphur, nitrogen-atoms.
Embodiment 2
A kind of molybdenum bisuphide/sulphur of the present invention, nitrogen-doped graphene nanosheet composite material, in the composite, two sulphur Change molybdenum to be supported on the graphene nanometer sheet of sulphur, N doping；Disk of the composite for a diameter of 40 ~ 100nm.
Molybdenum bisuphide/the sulphur of the present embodiment, the preparation method of nitrogen-doped graphene nanosheet composite material, including following step Suddenly：0.3g four thio ammonium molybdates, 0.15g graphene oxides, 2g thiocarbamides are weighed respectively, are dissolved in ultrasonic mixing in 500mL DMF After uniform, with Rotary Evaporators, in oil bath, 90 DEG C of rotary evaporations are removed after most of solvent, and taking-up sample is 100 in surface plate DEG C vacuum drying, after being completely dried take out after with mortar it is finely ground after be placed in quartz boat, be placed in tube furnace, connected with threeway Argon gas/hydrogen (10%) and argon gas, then hunted leak with suds, check each interface whether there is gas leak phenomenon, it is ensured that everywhere without gas leakage After phenomenon, first lead to 20min argon gas, then change argon gas/hydrogen (10%) into, and heating schedule is set to 10 DEG C/min and be warming up to 450 DEG C, 2h is incubated, recycles threeway that gas is changed into argon gas, be continuously heating to 800 DEG C by 450 DEG C with 10 DEG C/min, be incubated 2h, then be cooled to 300 DEG C with 5 DEG C/min, then be naturally cooling to room temperature, turns off gas, collects the sample in quartz boat, and as two Molybdenum sulfide/sulphur, nitrogen-doped graphene nanosheet composite material.
Molybdenum bisuphide/the sulphur of the present embodiment, nitrogen-doped graphene nanosheet composite material can be applicable to lithium ion battery, surpass The fields such as level capacitor, hydrogen precipitation, photocatalysis, nano-device.
Embodiment 3
A kind of molybdenum bisuphide/sulphur of the present invention, nitrogen-doped graphene nanosheet composite material, in the composite, two sulphur Change molybdenum to be supported on the graphene nanometer sheet of sulphur, N doping；Disk of the composite for a diameter of 40 ~ 100nm.
Molybdenum bisuphide/the sulphur of the present embodiment, the preparation method of nitrogen-doped graphene nanosheet composite material, including following step Suddenly：0.2g four thio ammonium molybdates, 0.2g graphene oxides, 2.5g thiocarbamides are weighed respectively, and in being dissolved in 1000mL DMF, ultrasound is mixed After closing uniformly, with Rotary Evaporators, in oil bath, 100 DEG C of rotary evaporations are removed after most of solvents, and taking-up sample is in surface plate 80 DEG C of vacuum drying, are placed in quartz boat with mortar is finely ground afterwards after taking out, are placed in tube furnace, are led to three after being completely dried Argon gas/hydrogen (10%) and argon gas are connect, then is hunted leak with suds, check each interface whether there is gas leak phenomenon, it is ensured that everywhere without leakage After gas phenomenon, first lead to 20min argon gas, then change argon gas/hydrogen (10%) into, and heating schedule is set to 5 DEG C/min and be warming up to 450 DEG C, 3h is incubated, recycles threeway that gas is changed into argon gas, be continuously heating to 800 DEG C by 450 DEG C with 5 DEG C/min, be incubated 2h, 300 DEG C are cooled to 5 DEG C/min again, then are naturally cooling to room temperature, turn off gas, collect the sample in quartz boat, as two sulphur Change molybdenum/sulphur, nitrogen-doped graphene nanosheet composite material.
Molybdenum bisuphide/the sulphur of the present embodiment, nitrogen-doped graphene nanosheet composite material can be applicable to lithium ion battery, surpass The fields such as level capacitor, hydrogen precipitation, photocatalysis, nano-device.
Embodiment 4
A kind of molybdenum bisuphide/sulphur of the present invention, nitrogen-doped graphene nanosheet composite material, in the composite, two sulphur Change molybdenum to be supported on the graphene nanometer sheet of sulphur, N doping；Disk of the composite for a diameter of 40 ~ 100nm.
Molybdenum bisuphide/the sulphur of the present embodiment, the preparation method of nitrogen-doped graphene nanosheet composite material, including following step Suddenly：0.3g four thio ammonium molybdates, 0.15g graphene oxides, 2.0g thiocarbamides are weighed respectively, and in being dissolved in 1200mL DMF, ultrasound is mixed After closing uniformly, with Rotary Evaporators, in oil bath, 110 DEG C of rotary evaporations are removed after most of solvents, and taking-up sample is in surface plate 120 DEG C of vacuum drying, are placed in quartz boat with mortar is finely ground afterwards after taking out, are placed in tube furnace, use threeway after being completely dried Connection argon gas/hydrogen (10%) and argon gas, then hunted leak with suds, checks each interface whether there is gas leak phenomenon, it is ensured that everywhere without After gas leak phenomenon, first lead to 20min argon gas, then change argon gas/hydrogen (10%) into, and heating schedule is set to 5 DEG C/min intensifications To 450 DEG C, 2h is incubated, recycles threeway that gas is changed into argon gas, be continuously heating to 800 DEG C by 450 DEG C with 5 DEG C/min, be incubated 1h, then be cooled to 300 DEG C with 5 DEG C/min, then be naturally cooling to room temperature, turns off gas, collects the sample in quartz boat, and as two Molybdenum sulfide/sulphur, nitrogen-doped graphene nanosheet composite material.
Molybdenum bisuphide/the sulphur of the present embodiment, nitrogen-doped graphene nanosheet composite material can be applicable to lithium ion battery, surpass The fields such as level capacitor, hydrogen precipitation, photocatalysis, nano-device.
The case study on implementation of the present invention is the foregoing is only, the scope of the claims of the present invention is not thereby limited, it is every using this Description of the invention and the made equivalent structure of accompanying drawing content or equivalent flow conversion, or directly or indirectly it is used in other related skills Art field, is included in protection scope of the present invention.

Claims (3)

1. a kind of molybdenum bisuphide/sulphur, the preparation method of nitrogen-doped graphene nanosheet composite material, it is characterised in that described multiple Disk of the condensation material for a diameter of 40 ~ 100nm, molybdenum bisuphide therein are supported on the graphene nanometer sheet of sulphur, N doping；Its Preparation is comprised the following steps：Four thio ammonium molybdate, graphene oxide, thiocarbamide are dissolved in DMF, mixing is equal It is even, mixed solution is obtained, then above-mentioned mixed solution is dried, is finally sintered in protective gas；The sintering is divided into Three phases, first stage：By the ramp of 1 ~ 10 DEG C/min to 450 DEG C, 1 ~ 3h is incubated；Second stage：By 1 ~ 10 DEG C/ The ramp of min is incubated 1 ~ 3h to 800 DEG C；Phase III is temperature-fall period：300 DEG C are cooled to by the speed of 5 DEG C/min, Then it is naturally cooling to room temperature；In the first stage, protective gas is argon gas and hydrogen, and the volume fraction of wherein hydrogen is 10%；In described second and third stage, protective gas is argon gas；
The four thio ammonium molybdate, graphene oxide, the mass ratio of thiocarbamide are 1 ~ 500：15：10~1000.
2. preparation method according to claim 1, it is characterised in that the volume of the DMF with it is described The corresponding relation of graphene oxide quality is 1mL/mg ~ 1000 mL/mg.
3. preparation method according to claim 1, it is characterised in that the drying is concretely comprised the following steps：At 90 ~ 110 DEG C Lower rotary evaporation carries out preliminarily dried, is then further vacuum dried at 80 ~ 120 DEG C.
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