CN105293590B - Vulcanized cobalt-nickel/graphene/carbon nano fiber composite material and preparation method thereof - Google Patents
Vulcanized cobalt-nickel/graphene/carbon nano fiber composite material and preparation method thereof Download PDFInfo
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- CN105293590B CN105293590B CN201510669559.8A CN201510669559A CN105293590B CN 105293590 B CN105293590 B CN 105293590B CN 201510669559 A CN201510669559 A CN 201510669559A CN 105293590 B CN105293590 B CN 105293590B
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Abstract
The invention belongs to the technical field of transition metal sulfide-carbon materials, and particularly relates to a vulcanized cobalt-nickel/graphene/carbon nano fiber composite material and a preparation method thereof. The preparation method includes the steps that polyacrylonitrile nano fibers are prepared through electrostatic spinning, oxidized graphene/polyacrylonitrile nano fiber aerogel is prepared through mechanical stirring and freezing drying, then graphene/carbon nano fiber aerogel is prepared through high-temperature carbonization, and finally, vulcanized cobalt-nickel nanosheets grow in situ on the graphene/carbon nano fiber aerogel through the one-step hydrothermal method. The vulcanized cobalt-nickel/graphene/carbon nano fiber composite material prepared through the method has the advantages that the material has a three-dimensional porous space structure, conductivity is good and chemical properties are stable, and can serve as an ideal high-performance electro-catalysis material and electrode materials of new energy devices such as lithium ion batteries and solar batteries.
Description
Technical field
The invention belongs to transient metal sulfide-material with carbon element technical field, and in particular to a kind of cobalt sulfide nickel/Graphene/
Carbon nano-fiber composite material and preparation method thereof.
Technical background
Graphene has excellent physical and chemical performance, such as higher electric conductivity, excellent mechanical property, high-ratio surface
Low and good chemical stability of product, light weight density etc..These special natures make it be widely used in catalyst carrier, macromolecule
The fields such as the flexible base material of nano composite material, energy conversion and memory device, it is considered to be following ten is big most potential
One of new material.However, graphene sheet layer is easy to stacking, the excellent properties for making Graphene are not fully utilized.This patent
Using electrostatic spinning process, mechanical agitation and freeze-drying are mutual by graphene oxide and Static Spinning polyacrylonitrile nanofiber
With reference to, the graphene oxide with three-dimensional net structure/polyacrylonitrile carbon nano-fiber aeroge is prepared, then by high temperature
Carbonization can prepare graphene/carbon nanofiber aeroge.Carbon nano-fiber and Graphene are connected with each other, and can effectively suppress stone
The stacking of black alkene, improves overall electric conductivity and specific surface area, so as to reach the association between Graphene and carbon nano-fiber
Same effect.As base material, can further prepare with high performance composite.
Cobalt sulfide nickel is a kind of typical bimetallic sulfide, with nontoxic, environmental friendliness, easily prepared, self-conductive
Property good and theoretical capacity value it is high the advantages of.Compared with monometallic nickel sulfide or cobalt sulfide, cobalt sulfide nickel has higher conduction
Performance and theoretical lithium storage content value, are widely closed in fields such as catalysis, ultracapacitor and lithium ion battery electrode materials
Note and application.But, pure sulfuration cobalt granule nickel is easy to reunite so as to which avtive spot cannot fully be exposed, and be had a strong impact on
The cyclical stability of its catalysis characteristics and energy stores.Therefore, cobalt sulfide nickel is entered with the carbon nanomaterial of excellent in stability
Row is effectively combined significant.
The present invention prepares a kind of new cobalt sulfide nickel/graphene/carbon nanofiber by simple technological design
Composite.The composite has following advantage：Graphene/carbon nanofiber aeroge has unique three-dimensional net structure
And high-specific surface area, more growth sites can be provided for cobalt sulfide nickel；Cobalt sulfide nickel nano film is equably grown in graphite
On alkene/carbon nano-fiber aeroge, the reunion of cobalt sulfide nickel is restrained effectively, the avtive spot for making cobalt sulfide nickel is obtained fully
Exposure；Graphene/carbon nanofiber aeroge possesses excellent electric conductivity, is conducive to the quick transmission of electronics, improves compound
The overall electric conductivity of material；Cobalt sulfide nickel nano film possesses in itself higher catalysis activity and theoretical stored energy capacitance value, can improve
The overall catalytic performance of composite and energy stores performance.Therefore, by graphene/carbon nanofiber aeroge and cobalt sulfide nickel
Nanometer sheet is effectively combined, it is possible to achieve good synergy between three, to prepare the composite of excellent performance.
The content of the invention
It is an object of the invention to provide a kind of preparation process is environmentally friendly, with low cost, electrochemical performance cobalt sulfide
Nickel/graphene/carbon nano-fiber composite material and preparation method thereof.
Cobalt sulfide nickel/graphene/carbon nano-fiber composite material provided by the present invention, its preparing raw material includes：Poly- third
Alkene nitrile,N,N-Dimethylformamide, graphene oxide, cobalt salt, nickel salt, thiocarbamide, ethylenediamine etc..
Cobalt sulfide nickel/graphene/carbon nano-fiber composite material provided by the present invention, its preparation process includes：Pass through
Electrostatic spinning prepares polyacrylonitrile nanofiber, and through mechanical agitation and freeze-drying graphene oxide/poly- is prepared
Propylene nitrile nanofibre aeroge, then graphene/carbon nanofiber aeroge is prepared by high temperature cabonization, finally by one
One-step hydrothermal growth in situ cobalt sulfide nickel nano film on graphene/carbon nanofiber aeroge.Comprise the following steps that：
（1）Polyacrylonitrile powder is added toN,N-In solvent dimethylformamide, persistently stir, prepare homogeneous
Sticky dispersion liquid；
（2）The polyacrylonitrile dispersion liquid for obtaining is carried out into electrostatic spinning, polyacrylonitrile nanofiber film is prepared；
（3）Polyacrylonitrile nanofiber film is pre-oxidized in air atmosphere, poly- third after pre-oxidation is prepared
Alkene nitrile nanofibre film；
（4）Polyacrylonitrile nanofiber film after pre-oxidation is shredded, and is put in graphene oxide solution and is carried out machinery
Stirring, prepares uniform graphene oxide/polyacrylonitrile nanofiber pastel；
（5）The graphene oxide for obtaining/polyacrylonitrile nanofiber viscous pastes are carried out into freeze-drying, is prepared
Graphene oxide/polyacrylonitrile nanofiber aeroge；
（6）Graphene oxide/polyacrylonitrile nanofiber aeroge is carried out into high temperature cabonization under inert gas shielding, is made
It is standby to obtain graphene/carbon nanofiber aeroge；
（7）Cobalt salt, nickel salt, thiocarbamide and ethylenediamine are dissolved in deionized water, are persistently stirred, prepare homogeneous salt molten
Liquid；
（8）Graphene/carbon nanofiber aeroge is added to into salting liquid and is transferred in water heating kettle, at a certain temperature
By hydro-thermal reaction for a period of time, cobalt sulfide nickel/graphene/carbon nano-fiber composite material is prepared；
（9）The cobalt sulfide for preparing nickel/graphene/carbon nano-fiber composite material is carried out under inert gas shielding
Heat treatment, to improve the crystal structure of cobalt sulfide nickel.
In the present invention, step（2）Described electrostatic spinning process, its technological parameter is：The kV of electrostatic field voltage 15 ~ 25, spins
The silk mm min of speed 0.2 ~ 0.4-1, receive the cm of distance 15 ~ 25.
In the present invention, step（3）Described preoxidation process, temperature is 250 ~ 300 DEG C, and heating rate is 1 ~ 2 DEG C of min-1, preoxidation time is 1 ~ 2 h.
In the present invention, step（4）Described mechanical agitation process, graphene oxide concentration is 1 ~ 3 mg mL-1。
In the present invention, step（6）Described high temperature cabonization process, the inert gas is high-purity argon gas or high pure nitrogen,
High temperature cabonization temperature is 800 ~ 1500 DEG C, and the high temperature cabonization time is 1 ~ 3 h.
In the present invention, step（7）Described salting liquid preparation process, cobalt salt includes cobalt nitrate, cobaltous sulfate, cobalt chloride, vinegar
Sour cobalt；Nickel salt includes nickel nitrate, nickel sulfate, nickel chloride, nickel acetate；The mass range of nickel salt is 5 ~ 25 mg mL-1, preferably 10 ~
15 mg mL-1；The mass range of cobalt salt is 10 ~ 50 mg mL-1, preferably 20 ~ 30 mg mL-1；The mass concentration of thiocarbamide be 10 ~
40 mg mL-1, preferably 20 ~ 30 mg mL-1；The consumption of ethylenediamine is 1 ~ 5 mL, preferably 2 ~ 3 mL.Cobalt and nickel salt in cobalt salt
In nickel mol ratio be 2 ~ 2.5, preferably 2.
In the present invention, step（8）Described hydrothermal reaction process, hydrothermal temperature scope is 160 ~ 220 DEG C, preferably
180 ~ 200 DEG C, the reaction time is 10 ~ 24 h, preferably 12 ~ 15 h.
In the present invention, step（9）Described heat treatment process, inert gas is high-purity argon gas or high pure nitrogen, is heat-treated
Temperature range is 250 ~ 400 DEG C, and preferably 300 ~ 350 DEG C, heat treatment time is 1 ~ 4 h.
Using SEM（SEM）And X-ray diffractometer（XRD）To characterize preparation-obtained sulfuration of the invention
The pattern and structure of cobalt nickel/graphene/carbon nano-fiber composite material, its result is as follows：
（1）SEM test results show：Graphene/carbon nanofiber aeroge prepared in the present invention has three-dimensional space
Between structure, carbon nano-fiber and Graphene be coupled to each other, and restrained effectively the stacking of Graphene, and its high specific surface area is sulphur
Change cobalt nickel and provide more growth sites.Prepared cobalt sulfide nickel/graphene/carbon nano-fiber composite material has uniqueness
Multilevel hierarchy, cobalt sulfide nickel nano film is equably grown on graphene/carbon nanofiber aeroge, restrained effectively sulphur
Change the reunion of cobalt nickel itself, the cobalt sulfide nickel nano film with high electrochemical activity is fully exposed.Referring to accompanying drawing 1 and attached
Fig. 2；
（2）XRD test results show：There is a feature diffraction in 2 θ=17 ° in prepared Static Spinning polyacrylonitrile film
Peak；There is diffraction maximum 2 θ=10 ° and 17 ° in prepared graphene oxide/polyacrylonitrile nanofiber aeroge, right respectively
Should be in graphene oxide and polyacrylonitrile.Prepared graphene/carbon nanofiber aeroge 2 θ=25 ° occur one compared with
Wide diffraction maximum, corresponding to Graphene and carbon nano-fiber（002）Crystal face.Prepared cobalt sulfide nickel/graphene/carbon nanometer
Fibrous composite is in 2 θ=16 °, 14 °, 27 °, 32 °, 39 °, 48 °, 55 °, 65 °, the 69 ° and 79 ° spies for occurring in that cobalt sulfide nickel
Peak is levied, corresponding to cobalt sulfide nickel（111）,（220）,（311）,（400）,（422）,（511）,（440）,（533）,（444）With
（731）Crystal face.Prepared cobalt sulfide nickel/graphene/carbon nano-fiber composite material diffraction maximum embodies graphene/carbon nanometer
The characteristic peak of fiber aeroge and cobalt sulfide nickel, it was confirmed that Graphene, carbon nano-fiber and cobalt sulfide nickel three in composite
Effective combination.Referring to accompanying drawing 3.
It is an advantage of the current invention that：
（1）Preparation process is simple, it is easy to operate；
（2）Experimental design is ingenious.Graphene oxide and carbon nano-fiber are passed through into mechanical agitation, freeze-drying and pyrocarbon
The method of change prepares the graphene/carbon nanofiber aeroge with three-dimensional net structure and high-specific surface area, and with this
For base material, by one step hydro thermal method on graphene/carbon nanofiber aeroge growth in situ cobalt sulfide nickel nano film, have
The reunion of cobalt sulfide nickel is inhibited to effect, the nickel of the cobalt sulfide with multilevel hierarchy/graphene/carbon nanofiber three has successfully been constructed
First composite；
（3）Prepared cobalt sulfide nickel/graphene/carbon nano-fiber composite material has the three-dimensional network knot being coupled to each other
Structure, preferable electric conductivity and higher specific surface area, make the cobalt sulfide nickel with high electrochemical activity and high theoretical capacity receive
Rice piece is evenly distributed on graphene/carbon nanofiber aeroge, and the avtive spot for making cobalt sulfide nickel nano film is obtained fully
Exposure, is the ideal electrode material of the new energy devices such as ultracapacitor, lithium ion battery.
Description of the drawings
Fig. 1 is the SEM figures of graphene/carbon nanofiber aeroge in the present invention.
Fig. 2 is the SEM figures of cobalt sulfide nickel/graphene/carbon nano-fiber composite material in the present invention.
Fig. 3 is Static Spinning polyacrylonitrile nanofiber in the present invention, graphene oxide/polyacrylonitrile aeroge, Graphene/
The XRD of carbon nano-fiber aeroge and cobalt sulfide nickel/graphene/carbon nano-fiber composite material.
Specific embodiment
With reference to instantiation, the present invention is expanded on further, it should be appreciated that these embodiments be merely to illustrate the present invention and
It is not used in restriction the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, those skilled in the art
Various changes or modification can be made to the present invention, these equivalent form of values equally fall within what the application appended claims were limited
Scope.
Embodiment 1, the present embodiment is comprised the following steps：
（1）1 g polyacrylonitrile powders are added to into 5 mLN,N-In solvent dimethylformamide, persistently stir, be prepared into
To homogeneous sticky dispersion liquid.
（2）The polyacrylonitrile dispersion liquid for obtaining is carried out into electrostatic spinning, its regulation technological parameter is：Electrostatic field voltage 20
KV, the mm min of spinning speed 0.3-1, the cm of distance 20 is received, prepare polyacrylonitrile nanofiber film.
（3）The polyacrylonitrile spinning film for obtaining is pre-oxidized in air atmosphere, the temperature of pre-oxidation is 250 DEG C,
Heating rate is 1 DEG C of min-1, preoxidation time is 1.5 h, prepares the polyacrylonitrile nanofiber film after pre-oxidation.
（4）100 mg polyacrylonitrile nanofibers films chopping after by pre-oxidation, and it is put into the 1 mg mL of 20 mL-1Oxidation
Mechanical agitation is carried out in graphene solution, uniform graphene oxide/polyacrylonitrile nanofiber pastel is prepared.
（5）The graphene oxide for obtaining/polyacrylonitrile nanofiber viscous pastes are carried out into freeze-drying, is prepared
Graphene oxide/polyacrylonitrile nanofiber aeroge.
（6）The graphene oxide for obtaining/polyacrylonitrile nanofiber aeroge is carried out into high temperature cabonization in high pure nitrogen,
High temperature cabonization temperature is 1200 DEG C, and the high temperature cabonization time is 2 h, prepares graphene/carbon nanofiber aeroge.
（7）By 232 mg cobalt nitrates, 116 mg nickel nitrates, 200 mg thiocarbamides and 2 mL ethylenediamines are dissolved in 10mL deionized waters
In, 5 min are stirred, prepare homogeneous salting liquid.
（8）20 mg graphene/carbon nanofiber aeroges are added to salting liquid and are transferred in water heating kettle, at 200 DEG C
Middle reaction 15h, after Temperature fall, takes out sediment and deionized water is cleaned multiple and is dried repeatedly, prepares sulfuration
Cobalt nickel/graphene/carbon nano-fiber composite material, is designated as NiCo2S4/GNS/CNF-1。
（9）The cobalt sulfide for preparing nickel/graphene/carbon nano-fiber composite material is carried out into hot place in high pure nitrogen
Reason, to improve the crystal structure of cobalt sulfide nickel nano film.Heat treatment temperature is 350 DEG C, and heat treatment time is 3 h.
Embodiment 2, by the quality of the cobalt nitrate in embodiment 1 116 mg are changed into, and the quality of nickel nitrate is changed into 58 mg, sulphur
The quality of urea is changed into 100 mg, and, with embodiment 1, the composite for finally being obtained is designated as NiCo for remaining2S4/GNS/CNF-2。
Result of implementation：Cobalt sulfide nickel nano film is equably grown on graphene/carbon nanofiber aeroge；With NiCo2S4/GNS/
CNF-1 is compared, and is designated as NiCo2S4The lamella of the cobalt sulfide nickel nano film in/GNS/CNF-2 is less, and content is also less.
Embodiment 3, by the quality of the cobalt nitrate in embodiment 1 464 mg are changed into, and the quality of nickel nitrate is changed into 232 mg, sulphur
The quality of urea is changed into 400 mg, and, with embodiment 1, the composite for finally being obtained is designated as NiCo for remaining2S4/GNS/CNF-3。
Result of implementation：Cobalt sulfide nickel nano film is equably grown on graphene/carbon nanofiber aeroge；With NiCo2S4/GNS/
CNF-1 is compared, and is designated as NiCo2S4The lamella of the cobalt sulfide nickel nano film in/GNS/CNF-3 is larger, and content is also more.
Embodiment 4, by the hydrothermal temperature in embodiment 1 220 DEG C are changed into, and the reaction time is changed into 24h, and remaining is with real
Example 1 is applied, the composite for finally being obtained is designated as NiCo2S4/GNS/CNF-4.Result of implementation：Cobalt sulfide nickel nano film is equably
It is grown on graphene/carbon nanofiber aeroge；With NiCo2S4/ GNS/CNF-1 is compared, NiCo2S4In/GNS/CNF-4
The lamella of cobalt sulfide nickel nano film is larger, and crystallization degree is higher.
Embodiment 5, elects the graphene oxide concentration in embodiment 1 as 3mg mL-1, remaining is with embodiment 1, final institute
The composite of acquisition is designated as NiCo2S4/GNS/CNF-5.Result of implementation：With NiCo2S4/ GNS/CNF-1 is compared, NiCo2S4/
Graphene content in GNS/CNF-5 is more, and Graphene is cross-linked with each other into three-dimensional net structure, cobalt sulfide nickel with carbon nano-fiber
Nanometer sheet is equably grown in graphene/carbon nanofiber aeroge.
Claims (10)
1. a kind of preparation method of cobalt sulfide nickel/graphene/carbon nano-fiber composite material, it is characterised in that concrete steps are such as
Under：
（1）Polyacrylonitrile powder is added toN,N-In solvent dimethylformamide, persistently stir, prepare homogeneous sticky
Dispersion liquid；
（2）The polyacrylonitrile dispersion liquid for obtaining is carried out into electrostatic spinning, polyacrylonitrile nanofiber film is prepared；
（3）Polyacrylonitrile nanofiber film is pre-oxidized in air atmosphere, the polyacrylonitrile after pre-oxidation is prepared
Nano fibrous membrane；
（4）Polyacrylonitrile nanofiber film after pre-oxidation is shredded, and is put in graphene oxide solution and is carried out mechanical agitation,
Prepare uniform graphene oxide/polyacrylonitrile nanofiber pastel；
（5）The graphene oxide for obtaining/polyacrylonitrile nanofiber viscous pastes are carried out into freeze-drying, oxidation is prepared
Graphene/polyacrylonitrile nanofiber aeroge；
（6）Graphene oxide/polyacrylonitrile nanofiber aeroge is carried out into high temperature cabonization under inert gas shielding, is prepared into
To graphene/carbon nanofiber aeroge；
（7）Cobalt salt, nickel salt, thiocarbamide and ethylenediamine are dissolved in deionized water, are persistently stirred, prepare homogeneous salting liquid；
（8）Graphene/carbon nanofiber aeroge is added to into salting liquid and is transferred in water heating kettle, by hydro-thermal reaction, system
It is standby to obtain cobalt sulfide nickel/graphene/carbon nano-fiber composite material；
（9）The cobalt sulfide for preparing nickel/graphene/carbon nano-fiber composite material is carried out into hot place under inert gas shielding
Reason, to improve the crystal structure of cobalt sulfide nickel.
2. the preparation method of cobalt sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, its feature exists
In step（2）Described electrostatic spinning, its technological parameter is：The kV of electrostatic field voltage 15 ~ 25, the mm of spinning speed 0.2 ~ 0.4
min-1, receive the cm of distance 15 ~ 25.
3. the preparation method of cobalt sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, its feature exists
In step（3）Described pre-oxidation, temperature is 250 ~ 300 DEG C, and heating rate is 1 ~ 2 DEG C of min-1, preoxidation time is 1 ~ 2 h.
4. the preparation method of cobalt sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, its feature exists
In step（4）In, described graphene oxide concentration is 1 ~ 3 mg mL-1。
5. the preparation method of cobalt sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, its feature exists
In step（6）Described high temperature cabonization, inert gas used is high-purity argon gas or high pure nitrogen, high temperature cabonization temperature is 800 ~
1500 DEG C, the high temperature cabonization time is 1 ~ 3 h.
6. the preparation method of cobalt sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, its feature exists
In step（7）In, described cobalt salt is selected from cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt acetate；Nickel salt selected from nickel nitrate, nickel sulfate,
Nickel chloride, nickel acetate；The mass concentration scope of nickel salt is 5 ~ 25 mg mL-1；The mass concentration scope of cobalt salt is 10 ~ 50 mg
mL-1；The mass concentration of thiocarbamide is 10 ~ 40 mg mL-1；The consumption of ethylenediamine is 1 ~ 5 mL；The nickel in cobalt and nickel salt in cobalt salt
Mol ratio be 2 ~ 2.5.
7. the preparation method of cobalt sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, its feature exists
In step（8）Described hydro-thermal reaction, range of reaction temperature is 160 ~ 220 DEG C, and the reaction time is 10 ~ 24 h.
8. the preparation method of cobalt sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, its feature exists
In step（9）Described heat treatment, inert gas used is high-purity argon gas or high pure nitrogen, heat-treatment temperature range is 250 ~
400 DEG C, heat treatment time is 1 ~ 4 h.
9. a kind of cobalt sulfide nickel/graphene/carbon nanofiber prepared by one of claim 1-8 preparation method is answered
Condensation material.
10. cobalt sulfide nickel/graphene/carbon nano-fiber composite material as claimed in claim 9 is catalyzed material as high-performance electric
Material, and the application of the electrode material of lithium ion battery and solar cell.
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| CN104401977A (en) * | 2014-10-28 | 2015-03-11 | 同济大学 | Preparation method of graphene aerogel and graphene-carbon nanotube aerogel |
| CN104299797B (en) * | 2014-11-06 | 2017-10-17 | 中南大学 | One kind is based on NiCo2S4And its water system asymmetrical type ultracapacitor of composite |
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