CN105293590A - 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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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-carbon material technical field, be specifically related to a kind of cobaltous sulfide nickel/graphene/carbon nano-fiber composite material and preparation method thereof.
Technical background
Graphene has excellent physical and chemical performance, chemical stability etc. as low and good in higher electroconductibility, excellent mechanical property, high-specific surface area, light weight density.These special propertys make it be widely used in the fields such as the flexible base material of support of the catalyst, high molecule nano composite material, energy transformation and memory device, are considered to one of novel material of the large most potentiality of Future Ten.But graphene sheet layer is easy to stacking, the excellent properties of Graphene is not fully utilized.This patent adopts electrostatic spinning process, graphene oxide and Static Spinning polyacrylonitrile nanofiber be combined with each other by mechanical stirring and freeze-drying, prepare the graphene oxide/polyacrylonitrile carbon nanofiber aerogel with three-dimensional net structure, then graphene/carbon nanofiber aerogel can be prepared by high temperature cabonization.Carbon nanofiber and Graphene are interconnected, and can effectively suppress the stacking of Graphene, improve overall electroconductibility and specific surface area, thus reach the synergistic effect between Graphene and carbon nanofiber.As base material, can prepare further and there is high performance matrix material.
Cobaltous sulfide nickel is a kind of typical bimetal sulfide, has nontoxic, environmental friendliness, is easy to preparation, the good and theoretical capacity value advantages of higher of self-conductive.Compared with monometallic nickelous sulfide or cobaltous sulfide, cobaltous sulfide nickel has higher conductivity and theoretical lithium storage content value, is paid close attention to widely in fields such as catalysis, ultracapacitor and lithium ion battery electrode materials and applies.But pure cobaltous sulfide particle nickel is easy to reunite, and makes its avtive spot fully be exposed, has had a strong impact on the cyclical stability of its catalysis characteristics and stored energy.Therefore, the carbon nanomaterial of cobaltous sulfide nickel and excellent in stability is carried out effective compound significant.
The present invention, by simple technological design, prepares a kind of novel cobaltous sulfide nickel/graphene/carbon nano-fiber composite material.This matrix material has following advantage: graphene/carbon nanofiber aerogel has unique three-dimensional net structure and high-specific surface area, more can grow site for cobaltous sulfide nickel provides; Cobaltous sulfide nickel nano film grows equably on graphene/carbon nanofiber aerogel, restrained effectively the reunion of cobaltous sulfide nickel, and the avtive spot of cobaltous sulfide nickel is fully exposed; Graphene/carbon nanofiber aerogel possesses excellent electroconductibility, is conducive to the fast transport of electronics, improves the electroconductibility of composites; Cobaltous sulfide nickel nano film itself possesses higher catalytic activity and theoretical stored energy capacitance value, can improve catalytic performance and the stored energy performance of composites.Therefore, graphene/carbon nanofiber aerogel and cobaltous sulfide nickel nano film are carried out effective compound, synergy good between three can be realized, to prepare the matrix material of excellent performance.
Summary of the invention
The object of the present invention is to provide the cobaltous sulfide nickel/graphene/carbon nano-fiber composite material and preparation method thereof of a kind of preparation process environmental protection, with low cost, electrochemical performance.
Cobaltous sulfide nickel/graphene/carbon nano-fiber composite material provided by the present invention, its raw materials comprises: polyacrylonitrile,
n, N-dimethyl formamide, graphene oxide, cobalt salt, nickel salt, thiocarbamide, quadrol etc.
Cobaltous sulfide nickel/graphene/carbon nano-fiber composite material provided by the present invention, its preparation process comprises: prepare polyacrylonitrile nanofiber by electrostatic spinning, graphene oxide/polyacrylonitrile nanofiber aerogel is prepared through mechanical stirring and lyophilize, graphene/carbon nanofiber aerogel is prepared again, finally by one step hydro thermal method growth in situ cobaltous sulfide nickel nano film on graphene/carbon nanofiber aerogel by high temperature cabonization.Concrete steps are as follows:
(1) polyacrylonitrile powder is joined
n, N-in solvent dimethylformamide, Keep agitation, prepares homogeneous thickness dispersion liquid;
(2) the polyacrylonitrile dispersion liquid obtained is carried out electrostatic spinning, prepare polyacrylonitrile nanofiber film;
(3) polyacrylonitrile nanofiber film is carried out preoxidation in air atmosphere, prepare the polyacrylonitrile nanofiber film after preoxidation;
(4) by the polyacrylonitrile nanofiber film chopping after preoxidation, and put in graphene oxide solution and carry out mechanical stirring, prepare uniform graphene oxide/polyacrylonitrile nanofiber mashed prod;
(5) graphene oxide obtained/polyacrylonitrile nanofiber viscous pastes is carried out lyophilize, prepare graphene oxide/polyacrylonitrile nanofiber aerogel;
(6) graphene oxide/polyacrylonitrile nanofiber aerogel is carried out high temperature cabonization under protection of inert gas, prepare graphene/carbon nanofiber aerogel;
(7) cobalt salt, nickel salt, thiocarbamide and quadrol are dissolved in deionized water, Keep agitation, prepare homogeneous salts solution;
(8) graphene/carbon nanofiber aerogel joined salts solution and be transferred in water heating kettle, at a certain temperature by hydro-thermal reaction for some time, preparing cobaltous sulfide nickel/graphene/carbon nano-fiber composite material;
(9) cobaltous sulfide prepared nickel/graphene/carbon nano-fiber composite material is heat-treated under protection of inert gas, to improve the crystalline structure of cobaltous sulfide nickel.
In the present invention, the electrostatic spinning process described in step (2), its processing parameter is: electrostatic field voltage 15 ~ 25kV, spinning speed 0.2 ~ 0.4mmmin
-1, receiving range 15 ~ 25cm.
In the present invention, the preoxidation process described in step (3), temperature is 250 ~ 300 DEG C, and temperature rise rate is 1 ~ 2 DEG C of min
-1, preoxidation time is 1 ~ 2h.
In the present invention, the mechanical agitation process described in step (4), graphene oxide concentration is 1 ~ 3mgmL
-1.
In the present invention, the high temperature cabonization process described in step (6), described rare gas element is high-purity argon gas or high pure nitrogen, and high temperature cabonization temperature is 800 ~ 1500 DEG C, and the high temperature cabonization time is 1 ~ 3h.
In the present invention, the salts solution preparation process described in step (7), cobalt salt comprises Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobalt chloride, Cobaltous diacetate; Nickel salt comprises nickelous nitrate, single nickel salt, nickelous chloride, nickel acetate; The mass range of nickel salt is 5 ~ 25mgmL
-1, preferably 10 ~ 15mgmL
-1; The mass range of cobalt salt is 10 ~ 50mgmL
-1, preferably 20 ~ 30mgmL
-1; The mass concentration of thiocarbamide is 10 ~ 40mgmL
-1, preferably 20 ~ 30mgmL
-1; The consumption of quadrol is 1 ~ 5mL, preferably 2 ~ 3mL.The mol ratio of the cobalt in cobalt salt and the nickel in nickel salt is 2 ~ 2.5, preferably 2.
In the present invention, the hydrothermal reaction process described in step (8), hydrothermal temperature scope is 160 ~ 220 DEG C, preferably 180 ~ 200 DEG C, and the reaction times is 10 ~ 24h, preferably 12 ~ 15h.
In the present invention, the heat treatment process described in step (9), rare gas element is high-purity argon gas or high pure nitrogen, and heat-treatment temperature range is 250 ~ 400 DEG C, preferably 300 ~ 350 DEG C, and heat treatment time is 1 ~ 4h.
Use scanning electronic microscope (SEM) and X-ray diffractometer (XRD) to characterize pattern and the structure of the preparation-obtained cobaltous sulfide nickel/graphene/carbon nano-fiber composite material of the present invention, its result is as follows:
(1) SEM test result shows: graphene/carbon nanofiber aerogel prepared in the present invention has three-D space structure, carbon nanofiber and Graphene are coupled to each other, restrained effectively the stacking of Graphene, its high specific surface area is that cobaltous sulfide nickel provides and more grows site.Prepared cobaltous sulfide nickel/graphene/carbon nano-fiber composite material has unique multilevel hierarchy, cobaltous sulfide nickel nano film grows equably on graphene/carbon nanofiber aerogel, restrained effectively the reunion of cobaltous sulfide nickel self, the cobaltous sulfide nickel nano film with high electrochemical activity is fully exposed.See accompanying drawing 1 and accompanying drawing 2;
(2) XRD test result shows: prepared Static Spinning polyacrylonitrile film is a ° appearance characteristic diffraction peak in 2 θ=17; Prepared graphene oxide/polyacrylonitrile nanofiber aerogel in 2 θ=10 ° and 17 ° there is diffraction peak, correspond respectively to graphene oxide and polyacrylonitrile.° to there is a wider diffraction peak in prepared graphene/carbon nanofiber aerogel, corresponding to (002) crystal face of Graphene and carbon nanofiber in 2 θ=25.Prepared cobaltous sulfide nickel/graphene/carbon nano-fiber composite material in 2 θ=16 °, 14 °, 27 °, 32 °, 39 °, 48 °, 55 °, 65 °, 69 ° and the 79 ° characteristic peaks having occurred cobaltous sulfide nickel, corresponding to (111) of cobaltous sulfide nickel, (220), (311), (400), (422), (511), (440), (533), (444) and (731) crystal face.Prepared cobaltous sulfide nickel/graphene/carbon nano-fiber composite material diffraction peak embodies the characteristic peak of graphene/carbon nanofiber aerogel and cobaltous sulfide nickel, confirms effective combination of Graphene in matrix material, carbon nanofiber and cobaltous sulfide nickel three.See accompanying drawing 3.
The invention has the advantages that:
(1) preparation process is simple, easy handling;
(2) experimental design is ingenious.Graphene oxide and carbon nanofiber are prepared the graphene/carbon nanofiber aerogel with three-dimensional net structure and high-specific surface area by the method for mechanical stirring, lyophilize and high temperature cabonization, and as base material, by one step hydro thermal method growth in situ cobaltous sulfide nickel nano film on graphene/carbon nanofiber aerogel, restrained effectively the reunion of cobaltous sulfide nickel, successfully construct the cobaltous sulfide nickel/graphene/carbon nanofiber trielement composite material with multilevel hierarchy;
(3) the cobaltous sulfide nickel/graphene/carbon nano-fiber composite material prepared by has the three-dimensional net structure be coupled to each other, good conductivity and higher specific surface area, the cobaltous sulfide nickel nano film with high electrochemical activity and high theoretical capacity is made to be evenly distributed on graphene/carbon nanofiber aerogel, the avtive spot of cobaltous sulfide nickel nano film is fully exposed, and is the ideal electrode material of the new energy devices such as ultracapacitor, lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the SEM figure of graphene/carbon nanofiber aerogel in the present invention.
Fig. 2 is the SEM figure of cobaltous 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 aerogel, the XRD figure of graphene/carbon nanofiber aerogel and cobaltous sulfide nickel/graphene/carbon nano-fiber composite material.
Embodiment
Below in conjunction with specific examples, set forth the present invention further, should be understood that these embodiments are only not used in for illustration of the present invention and limit the scope of the invention.In addition should be understood that those skilled in the art can make various change or amendment to the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
embodiment 1,the present embodiment comprises the following steps:
(1) 1g polyacrylonitrile powder is joined 5mL
n, N-in solvent dimethylformamide, Keep agitation, prepares homogeneous thickness dispersion liquid.
(2) the polyacrylonitrile dispersion liquid obtained is carried out electrostatic spinning, its adjusting process parameter is: electrostatic field voltage 20kV, spinning speed 0.3mmmin
-1, receiving range 20cm, prepares polyacrylonitrile nanofiber film.
(3) the polyacrylonitrile spinning film obtained is carried out preoxidation in air atmosphere, the temperature of preoxidation is 250 DEG C, and temperature rise rate is 1 DEG C of min
-1, preoxidation time is 1.5h, prepares the polyacrylonitrile nanofiber film after preoxidation.
(4) by the 100mg polyacrylonitrile nanofiber film chopping after preoxidation, and the 1mgmL of 20mL is put into
-1carry out mechanical stirring in graphene oxide solution, prepare uniform graphene oxide/polyacrylonitrile nanofiber mashed prod.
(5) graphene oxide obtained/polyacrylonitrile nanofiber viscous pastes is carried out lyophilize, prepare graphene oxide/polyacrylonitrile nanofiber aerogel.
(6) graphene oxide obtained/polyacrylonitrile nanofiber aerogel is carried out high temperature cabonization in high pure nitrogen, high temperature cabonization temperature is 1200 DEG C, and the high temperature cabonization time is 2h, prepares graphene/carbon nanofiber aerogel.
(7) by 232mg Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, 116mg nickelous nitrate, 200mg thiocarbamide and 2mL quadrol are dissolved in 10mL deionized water, stir 5min, prepare homogeneous salts solution.
(8) 20mg graphene/carbon nanofiber aerogel is joined salts solution and is transferred in water heating kettle, 15h is reacted in 200 DEG C, after Temperature fall, take out throw out and repeatedly clean repeatedly and drying with deionized water, prepare cobaltous sulfide nickel/graphene/carbon nano-fiber composite material, be designated as NiCo
2s
4/ GNS/CNF-1.
(9) cobaltous sulfide prepared nickel/graphene/carbon nano-fiber composite material is heat-treated in high pure nitrogen, to improve the crystalline structure of cobaltous sulfide nickel nano film.Thermal treatment temp is 350 DEG C, and heat treatment time is 3h.
embodiment 2,the quality of the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in embodiment 1 is become 116mg, and the quality of nickelous nitrate becomes 58mg, and the quality of thiocarbamide becomes 100mg, and all the other are all with embodiment 1, and final obtained matrix material is designated as NiCo
2s
4/ GNS/CNF-2.Result of implementation: cobaltous sulfide nickel nano film grows equably on graphene/carbon nanofiber aerogel; With NiCo
2s
4/ GNS/CNF-1 compares, and is designated as NiCo
2s
4the lamella of the cobaltous sulfide nickel nano film in/GNS/CNF-2 is less, and content is also less.
embodiment 3,the quality of the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in embodiment 1 is become 464mg, and the quality of nickelous nitrate becomes 232mg, and the quality of thiocarbamide becomes 400mg, and all the other are all with embodiment 1, and final obtained matrix material is designated as NiCo
2s
4/ GNS/CNF-3.Result of implementation: cobaltous sulfide nickel nano film grows equably on graphene/carbon nanofiber aerogel; With NiCo
2s
4/ GNS/CNF-1 compares, and is designated as NiCo
2s
4the lamella of the cobaltous sulfide nickel nano film in/GNS/CNF-3 is comparatively large, and content is also more.
embodiment 4,hydrothermal temperature in embodiment 1 is become 220 DEG C, and the reaction times becomes 24h, and all the other are all with embodiment 1, and final obtained matrix material is designated as NiCo
2s
4/ GNS/CNF-4.Result of implementation: cobaltous sulfide nickel nano film grows equably on graphene/carbon nanofiber aerogel; With NiCo
2s
4/ GNS/CNF-1 compares, NiCo
2s
4the lamella of the cobaltous sulfide nickel nano film in/GNS/CNF-4 is comparatively large, and crystallization degree is higher.
embodiment 5,elect the graphene oxide concentration in embodiment 1 as 3mgmL
-1, all the other are all with embodiment 1, and final obtained matrix material is designated as NiCo
2s
4/ GNS/CNF-5.Result of implementation: with NiCo
2s
4/ GNS/CNF-1 compares, NiCo
2s
4graphene content in/GNS/CNF-5 is more, and Graphene is cross-linked with each other into three-dimensional net structure with carbon nanofiber, and cobaltous sulfide nickel nano film grows equably at graphene/carbon nanofiber aerogel.
Claims (10)
1. a preparation method for cobaltous sulfide nickel/graphene/carbon nano-fiber composite material, is characterized in that concrete steps are as follows:
(1) polyacrylonitrile powder is joined
n, N-in solvent dimethylformamide, Keep agitation, prepares homogeneous thickness dispersion liquid;
(2) the polyacrylonitrile dispersion liquid obtained is carried out electrostatic spinning, prepare polyacrylonitrile nanofiber film;
(3) polyacrylonitrile nanofiber film is carried out preoxidation in air atmosphere, prepare the polyacrylonitrile nanofiber film after preoxidation;
(4) by the polyacrylonitrile nanofiber film chopping after preoxidation, and put in graphene oxide solution and carry out mechanical stirring, prepare uniform graphene oxide/polyacrylonitrile nanofiber mashed prod;
(5) graphene oxide obtained/polyacrylonitrile nanofiber viscous pastes is carried out lyophilize, prepare graphene oxide/polyacrylonitrile nanofiber aerogel;
(6) graphene oxide/polyacrylonitrile nanofiber aerogel is carried out high temperature cabonization under protection of inert gas, prepare graphene/carbon nanofiber aerogel;
(7) cobalt salt, nickel salt, thiocarbamide and quadrol are dissolved in deionized water, Keep agitation, prepare homogeneous salts solution;
(8) graphene/carbon nanofiber aerogel joined salts solution and be transferred in water heating kettle, by hydro-thermal reaction, preparing cobaltous sulfide nickel/graphene/carbon nano-fiber composite material;
(9) cobaltous sulfide prepared nickel/graphene/carbon nano-fiber composite material is heat-treated under protection of inert gas, to improve the crystalline structure of cobaltous sulfide nickel.
2. the preparation method of cobaltous sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, it is characterized in that the electrostatic spinning described in step (2), its processing parameter is: electrostatic field voltage 15 ~ 25kV, spinning speed 0.2 ~ 0.4mmmin
-1, receiving range 15 ~ 25cm.
3. the preparation method of cobaltous sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, it is characterized in that the preoxidation described in step (3), temperature is 250 ~ 300 DEG C, and temperature rise rate is 1 ~ 2 DEG C of min
-1, preoxidation time is 1 ~ 2h.
4. the preparation method of cobaltous sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, is characterized in that, in step (4), described graphene oxide concentration is 1 ~ 3mgmL
-1.
5. the preparation method of cobaltous sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, it is characterized in that the high temperature cabonization described in step (6), rare gas element used is high-purity argon gas or high pure nitrogen, and high temperature cabonization temperature is 800 ~ 1500 DEG C, and the high temperature cabonization time is 1 ~ 3h.
6. the preparation method of cobaltous sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, is characterized in that in step (7), described cobalt salt is selected from Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobalt chloride, Cobaltous diacetate; Nickel salt is selected from nickelous nitrate, single nickel salt, nickelous chloride, nickel acetate; The mass range of nickel salt is 5 ~ 25mgmL
-1; The mass range of cobalt salt is 10 ~ 50mgmL
-1; The mass concentration of thiocarbamide is 10 ~ 40mgmL
-1; The consumption of quadrol is 1 ~ 5mL; The mol ratio of the cobalt in cobalt salt and the nickel in nickel salt is 2 ~ 2.5.
7. the preparation method of cobaltous sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, it is characterized in that the hydro-thermal reaction described in step (8), range of reaction temperature is 160 ~ 220 DEG C, and the reaction times is 10 ~ 24h.
8. the preparation method of cobaltous sulfide nickel/graphene/carbon nano-fiber composite material according to claim 1, it is characterized in that the thermal treatment described in step (9), rare gas element used is high-purity argon gas or high pure nitrogen, and heat-treatment temperature range is 250 ~ 400 DEG C, and heat treatment time is 1 ~ 4h.
9. the cobaltous sulfide nickel/graphene/carbon nano-fiber composite material prepared by the described preparation method of one of claim 1-8.
10. cobaltous sulfide nickel/graphene/carbon nano-fiber composite material as claimed in claim 9 is as high-performance electric catalytic material, and the application of the electrode materials of lithium ion battery and solar cell.
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