CN108511201A

CN108511201A - A kind of ultra-thin MoS2Nanometer sheet/CNT composite material and preparation methods

Info

Publication number: CN108511201A
Application number: CN201711489880.3A
Authority: CN
Inventors: 张松利; 梁智萍; 关创
Original assignee: Zhenjiang Powerise Special Alloy Technology Development Co Ltd
Current assignee: Zhenjiang Powerise Special Alloy Technology Development Co Ltd
Priority date: 2017-12-29
Filing date: 2017-12-29
Publication date: 2018-09-07

Abstract

The invention discloses a kind of ultra-thin MoS₂Nanometer sheet/carbon nanotube（CNT）Composite material and preparation method.The present invention is prepared using hydro-thermal method, this method has many advantages, such as simple for process, flexible to operation, morphology controllable, which uses inorganic sulphur source, keeps the sulphur source utilization rate in the reaction larger, and environmentally harmful hydrogen sulfide gas is not will produce, it is a kind of environmentally friendly preparation method.The MoS of two-dimensional ultrathin structure₂With larger specific surface area, the contact area with electrolyte can be increased, more surface-active sites are provided, the reactivity of material surface is improved.And the CNT of one-dimensional perforation keeps being used as MoS in the case of complete structure in the reaction₂Growh framework；On the other hand, one-dimensional CNT pipelines can improve the power density of material as the quick transmission path of ion and electronics, make its cycle charge-discharge under high current density, can significantly improve the chemical property of material.

Description

A kind of ultra-thin MoS2Nanometer sheet/CNT composite material and preparation methods

Technical field

The present invention relates to a kind of MoS₂The functional composite material and preparation method of/CNT.It is prepared by one step hydro thermal method MoS₂The functional composite material of/CNT.The material has good chemical property, and preparation process is environmentally protective, as accumulator The electrode material of part, it will there is great application in electronic device fields such as ultracapacitor, lithium ion batteries.

Background technology

As the decaying of world's crude oil energy storage and Global Greenhouse Effect aggravate, people are to large power long time stable power-supplying Energy storage device more stringent requirements are proposed.Therefore to the performance of ultracapacitor, higher requirements are also raised, super capacitor Device has larger power density and good stable circulation performance as a kind of Utopian electrochemical energy storing device, makees An important factor for influence performance of the supercapacitor, electrode material has been obtained for the extensive research of people.

MoS₂As the two-dimensional layer material of a type graphene, there is the lattice symmetry structure and electricity similar with graphene Energy subband structure, MoS₂Unique texture with S-Mo-S " sandwich ", MoS₂Pass through weaker Van der Waals force between atomic layer It links together, is inserted into the methods of stripping by liquid phase stripping or ion, the 1T metal phase structures of single layer, the knot can be prepared There is structure good electric conductivity, band gap can be reduced after stripping, and two-dimensional layered structure can promote the quick of electronics Transfer and transmission, while it also has larger specific surface area, good flexibility and chemical stability, to make it in energy storage The fields such as field, biologic medical, photocatalysis and water electrolysis hydrogen production have a wide range of applications.

Carbon material is used as a kind of electrode material for super capacitor the most widely used now, has larger specific surface Product, the physical and chemical properties stablized and abundance are cheap, receive much attention.The carbon of one-dimensional perforation is received Mitron, on the one hand can be as the Growh framework of material, in the continuous of electrode material as a kind of carbon material with good conductivity In cyclic process, the stabilization of material can be kept, its broken and dusting is prevented, improves material structure stability；Another aspect CNT As good conductive material, the electric conductivity of composite material can also be enhanced, improve the power density of material.

Invention content

The invention aims to provide a kind of compound patterns of the 1D/2D of stabilization, and MoS can be significantly improved₂Monomer The MoS of specific capacitance₂/ CNT composite materials.The stable structure of products obtained therefrom, and the functionality with good chemical property is compound Material.

MoS in the present invention₂/ CNT have it is stable equal and compound pattern, MoS₂It is one-dimensional with ultra-thin lamellar structure The carbon nanotube of perforation is uniformly through MoS₂Between nanometer sheet, as illustrated in fig. 1 and 2.

The MoS of the present invention₂/ CNT composite materials have good chemical property, in MoS₂The basis of monomer has certain Raising.In test voltage range -0.8-0.2 V, sweep speed is in the CV loop tests of 10 to 50 mV/s, MoS₂/CNT Functional composite material shows outstanding chemical property.As shown in Figure 3.

Realize that the technical solution adopted in the present invention is：A kind of MoS₂/ CNT functional composite materials, pass through one step hydro thermal method From growing, have technique environmentally protective, the advantages of operation is simple and feasible, the carbon nanotube of gained is uniformly applied in two dimension MoS₂Nanometer sheet surface, and excellent chemical property is shown, preparation process is as follows：

（1）Utilize the HNO of debita spissitudo₃Solution carries out moditied processing to carbon nano tube surface, weighs the CNT of 100 mg A concentration of 60% HNO is added₃In solution, under conditions of being heated to boiling, continuing magnetic force stirs 2 h, then 1 h of sonic oscillation, To make CNT be uniformly dispersed.The mixed solution that will be prepared is transferred in 60 DEG C of vacuum drying chamber, is ground with agate after drying Alms bowl grinds 30 min, and collection is used as carbon source；

（2）Weigh step（1）In 10 mg of surface treated CNT, be added in 100 ml deionized waters, further 2 h of sonic oscillation makes CNT full and uniform dispersions, and 0.241 g Na are added₂MoO₄·2H₂In O to CNT solution, and stir at room temperature 1 h is mixed, 0.291 g KSCN are added, stirs 30 min.Acquired solution is transferred in the reaction kettle of 150 ml, at 180 DEG C Under reaction temperature, 12 h are reacted, MoS is made₂It is fully compound to be preferably grown in CNT.Room temperature is naturally cooled to after reaction, is used Deionized water and absolute ethyl alcohol repeatedly wash centrifugation, and dry in vacuum drying chamber；

Step（1）In 60% HNO₃Concentration refers to the volume ratio of concentrated nitric acid and deionized water；

Step（2）Middle Na₂MoO₄·2H₂O:KSCN=1:3（Molar ratio）；

Step（3）Middle centrifuge washing process is first to be cleaned 2 times with deionized water, then with washes of absolute alcohol 2 times, centrifuge Rotating speed be 5000rpm, time 5min.

Description of the drawings

Fig. 1 is MoS₂The SEM of/CNT composite materials.

Fig. 2 is MoS₂The TEM of/CNT composite materials.

Fig. 3 is MoS₂The CV curve graph of/CNT composite materials under different surface sweeping rates.

Specific embodiment

（1）Utilize the HNO of debita spissitudo₃Solution carries out moditied processing to carbon nano tube surface, weighs the CNT of 100 mg A concentration of 60% HNO is added₃In solution, under conditions of being heated to boiling, continuing magnetic force stirs 2 h, then 1 h of sonic oscillation, To make CNT be uniformly dispersed.The mixed solution that will be prepared is transferred in 60 DEG C of vacuum drying chamber, is ground with agate after drying Alms bowl grinds 30 min, and collection is used as carbon source.

（2）Weigh step（1）In 10 mg of surface treated CNT, be added in 100 ml deionized waters, further 2 h of sonic oscillation makes CNT full and uniform dispersions, and 0.241 g Na are added₂MoO₄·2H₂In O to CNT solution, and stir at room temperature 1 h is mixed, 0.291 g KSCN are added, stirs 30 min.Acquired solution is transferred in the reaction kettle of 150 ml, at 180 DEG C Under reaction temperature, 12 h are reacted, MoS is made₂It is fully compound to be preferably grown in CNT.Room temperature is naturally cooled to after reaction, is used Deionized water and absolute ethyl alcohol repeatedly wash centrifugation, and dry in vacuum drying chamber.

Claims

1. a kind of ultra-thin MoS₂Nanometer sheet/CNT composite materials, it is characterised in that：The composite material is by ultra-thin MoS₂Nanometer sheet It is formed with two kinds of Material claddings of CNT of one-dimensional perforation, there is two dimensional surface shape characteristic.

2. a kind of ultra-thin MoS₂The preparation method of nanometer sheet/CNT composite materials, it is characterised in that including following preparation process：

（1）Utilize the HNO of debita spissitudo₃Solution carries out moditied processing to carbon nano tube surface, and the CNT additions for weighing 100 mg are dense The HNO that degree is 60%₃In solution, under conditions of being heated to boiling, continuing magnetic force stirs 2h, then sonic oscillation 1h, to make CNT is uniformly dispersed；The mixed solution that will be prepared is transferred in 60 DEG C of vacuum drying chamber, is ground with agate mortar after drying 30min, collection are used as carbon source；

（2）Weigh step（1）In surface treated CNT10mg, be added in 100ml deionized waters, further ultrasound is shaken Swinging 2h makes CNT full and uniform dispersions, and 0.241 g Na are added₂MoO₄·2H₂In O to CNT solution, and 1h is stirred at room temperature, then 0.291 g KSCN are added, stir 30min；Acquired solution is transferred in the reaction kettle of 150ml, under 180 DEG C of reaction temperature, 12h is reacted, MoS is made₂It is fully compound to be preferably grown in CNT；

（3）Room temperature is naturally cooled to after reaction, repeatedly washs centrifugation with deionized water and absolute ethyl alcohol, and be dried in vacuo It is dry in case.

3. a kind of ultra-thin MoS as described in claim 1₂The preparation method of nanometer sheet/CNT composite materials, it is characterised in that：Institute State step step（1）In 60% HNO₃Concentration refers to the volume ratio of concentrated nitric acid and deionized water.

4. a kind of ultra-thin MoS as described in claim 1₂The preparation method step of nanometer sheet/CNT composite materials（2）In Na₂MoO₄·2H₂O:KSCN=1:3（Molar ratio）.

5. a kind of ultra-thin MoS as described in claim 1₂The preparation method step of nanometer sheet/CNT composite materials（3）Middle centrifugation is washed It is first clean 2 times with deionized water, then with washes of absolute alcohol 2 times, the rotating speed of centrifuge is 5000rpm to wash process, and the time is 5min。