CN105244482A - Nickel cobalt sulfide/graphene/carbon nanotube composite material and preparation method and application thereof - Google Patents
Nickel cobalt sulfide/graphene/carbon nanotube composite material and preparation method and application thereof Download PDFInfo
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- CN105244482A CN105244482A CN201510577445.0A CN201510577445A CN105244482A CN 105244482 A CN105244482 A CN 105244482A CN 201510577445 A CN201510577445 A CN 201510577445A CN 105244482 A CN105244482 A CN 105244482A
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to the technical field of transition metal sulfides, namely carbon materials, and particularly discloses a nickel cobalt sulfide/graphene/carbon nanotube composite material and a preparation method and an application thereof. The method comprises the following preparation processes: mixing graphene oxide with a carbon nanotube, and preparing a graphene oxide/carbon nanotube hybrid material through ultrasound; and carrying out in-situ growth of a nickel cobalt sulfide nanosheet on the graphene oxide/carbon nanotube hybrid material through a one-step hydrothermal process. The graphene oxide/carbon nanotube hybrid material prepared by the method has the advantages of a three-dimension porous space structure, excellent conductivity, large specific surface area, stable chemical property and the like; the final nickel cobalt sulfide/graphene/carbon nanotube composite material is controllable in morphology; the nickel cobalt sulfide nanosheet evenly grows on the graphene oxide/carbon nanotube hybrid material; and a unique base structure and high specific surface area of the graphene oxide/carbon nanotube hybrid material are fully utilized. The material disclosed by the invention can be used as an ideal high-performance electric catalytic material, and an electrode material for new energy devices of a lithium-ion battery, a super capacitor and the like.
Description
Technical field
The invention belongs to transient metal sulfide-material with carbon element technical field, be specifically related to a kind of cobalt sulfide nickel/Graphene/carbon nanotube composite material and its preparation method and application.
Background technology
Graphene has excellent physical and chemical performance, chemical stability etc. as low and good in higher conductivity, excellent mechanical property, high specific area, light weight density.These special natures make it be widely used in the fields such as the flexible base material of catalyst carrier, high molecule nano composite material, power conversion and memory device, are considered to one of new 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.Research shows, by adding carbon nano-tube between graphene sheet layer, can effectively suppress the stacking of Graphene, also can suppress the reunion of carbon nano-tube simultaneously.Carbon nano-tube and Graphene are interconnected, and can construct the graphene/carbon nano-tube hybrid material with three-dimensional net structure, substantially increase its conductivity and specific area, thus reach the cooperative effect between Graphene and carbon nano-tube.Graphene and carbon nano-tube by ultrasonic method, are prepared graphene/carbon nano-tube hybrid material, and prepare high-performance composite materials further as base material by this patent.
Cobalt sulfide nickel is a kind of typical bimetallic sulfide, has nontoxic, environmental friendliness, is easy to preparation, the good and theoretical capacity value advantages of higher of self-conductive.Compared with monometallic nickel sulfide or cobalt sulfide, cobalt sulfide nickel has higher electric 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 cobalt sulfide particle nickel is easy to reunite, and makes its avtive spot fully be exposed, has a strong impact on the cyclical stability of its catalysis characteristics and stored energy.Therefore, the carbon nanomaterial of cobalt sulfide nickel and excellent in stability is carried out effective compound significant.The present invention, by simple technological design, prepares a kind of novel cobalt sulfide nickel/graphene/carbon nano-tube trielement composite material.This composite material has following advantage: graphene/carbon nano-tube hybrid material has unique three-dimensional net structure and high-specific surface area, more site can be grown for cobalt sulfide nickel provides, restrained effectively the reunion of cobalt sulfide nickel, the avtive spot of cobalt sulfide nickel is fully exposed; The excellent electric conductivity of graphene/carbon nano-tube hybrid material is conducive to the transmission of electronics, improves the conductivity of composites; Cobalt sulfide nickel nano film itself possesses higher theoretical lithium storage content value, can improve the specific capacity of composites.Therefore, carried out compound, good synergy can be realized, prepared the combination electrode material of excellent performance.
Summary of the invention
The object of the present invention is to provide the cobalt sulfide nickel/Graphene/carbon nanotube composite material and its preparation method and application of a kind of preparation process environmental protection, with low cost, electrochemical performance.
Cobalt sulfide nickel/Graphene/carbon nanotube composite material provided by the present invention, its raw materials comprises: graphene oxide, carbon nano-tube, cobalt salt, nickel salt, thiocarbamide, ethylenediamine etc.
Cobalt sulfide nickel/Graphene/carbon nanotube composite material provided by the present invention, its preparation process comprises: graphene oxide and carbon nano-tube are mixed merga pass ultrasonic preparation and obtains graphene oxide/carbon nano-tube hybridization material, then by one step hydro thermal method growth in situ cobalt sulfide nickel nano film on graphene oxide/carbon nano-tube hybridization material.Concrete steps are as follows:
(1) graphene oxide is joined in deionized water, ultrasonic disperse, obtain the graphene oxide dispersion of stable dispersion;
(2) carbon nano-tube is joined in graphene oxide dispersion, continue ultrasonic, and by centrifuging and taking upper strata black liquor, obtain the graphene/carbon nano-tube dispersion liquid of stable homogeneous;
(3) cobalt salt, nickel salt, thiocarbamide and ethylenediamine are dissolved in deionized water, obtain homogeneous salting liquid;
(4) by salting liquid, join in graphene/carbon nano-tube dispersion liquid, ultrasonic disperse, obtain the mixed solution of uniform salting liquid and graphene/carbon nano-tube dispersion liquid;
(5) mixed solution of the salting liquid prepared and graphene/carbon nano-tube dispersion liquid is transferred in water heating kettle, carries out hydro-thermal reaction, obtain cobalt sulfide nickel/Graphene/carbon nanotube composite material;
(6) cobalt sulfide obtained nickel/Graphene/carbon nanotube composite material is heat-treated under inert gas shielding, to improve the crystal structure of cobalt sulfide nickel and further reduced graphene.
In the present invention, in step (2), the mass ratio of graphene oxide and carbon nano-tube is 5:1 ~ 1:3, preferred 2:1; Ultrasonic time is 1 ~ 3h, preferred 2h; Centrifugation rate is 6000 ~ 12000rpm, preferably 8000 ~ 10000rpm; Centrifugation time is 10 ~ 40min, preferably 20 ~ 30min.
In the present invention, the salting liquid preparation process of step (3), described cobalt salt is selected from cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt acetate; Nickel salt is selected from nickel nitrate, nickelous sulfate, nickel 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 ethylenediamine 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 ultrasonic disperse process described in step (4), the concentration of graphene/carbon nano-tube dispersion liquid is 0.5 ~ 3mgmL
-1, preferably 1 ~ 2mgmL
-1; The concentration ratio of graphene/carbon nano-tube hybrid material and cobalt salt is 1:2 ~ 1:15, preferred 1:5 ~ 1:10.
In the present invention, the hydrothermal reaction process described in step (5), hydrothermal temperature scope is 160 ~ 220 DEG C, preferably 180 ~ 200 DEG C, and the reaction time is 10 ~ 24h, preferably 12 ~ 15h.
In the present invention, the heat treatment process described in step (6), inert gas 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, preferably 2 ~ 3h.
Use scanning electron microscopy (SEM), transmission electron microscope (TEM), pattern that X-ray diffractometer (XRD) and battery test system characterize the preparation-obtained cobalt sulfide nickel/Graphene/carbon nanotube composite material of the present invention and structure and the chemical property as lithium ion battery negative material, its result is as follows:
(1) SEM test result shows: graphene/carbon nano-tube hybrid material prepared in the present invention has three-dimensional net structure, and its high specific area is that cobalt sulfide nickel provides and more grows site.Carbon nano-tube and Graphene interact, and restrained effectively the stacking of Graphene, also inhibits the reunion of carbon nano-tube simultaneously.Prepared cobalt sulfide nickel/Graphene/carbon nanotube composite material has unique multilevel hierarchy, cobalt sulfide nickel nano film grows equably on graphene/carbon nano-tube hybrid material, restrained effectively the reunion of cobalt sulfide nickel self, the cobalt sulfide nickel nano film with high electrochemical activity is fully exposed.See Fig. 1.
(2) TEM test result shows: in cobalt sulfide nickel/Graphene/carbon nanotube composite material prepared in the present invention, the diameter of carbon nano-tube is 50-100nm, is distributed between Graphene two dimension lamella, restrained effectively the stacking of graphene sheet layer; Cobalt sulfide nickel nano film is 20-50nm, grows equably on graphene/carbon nano-tube hybrid material, restrained effectively the reunion of cobalt sulfide nickel nano film.See accompanying drawing 2.
(3) XRD test result shows: prepared graphene/carbon nano-tube hybrid material has a diffraction maximum in 2 θ=26.4 °, corresponding to (002) crystal face of carbon nano-tube.Prepared pure cobalt sulfide nickel in 2 θ=16.5 °, 14.2 °, 27.1 °, 31.8 °, 38.6 °, 47.6 °, 55.5 °, 65.4 °, 69.7 ° and the 78.4 ° characteristic peaks having occurred cobalt sulfide nickel, corresponding to (111) of cobalt sulfide nickel, (220), (311), (400), (422), (511), (440), (533), (444) and (731) crystal face.Prepared cobalt sulfide nickel/Graphene/carbon nanotube composite material diffraction maximum embodies the characteristic peak of graphene/carbon nano-tube hybrid material and cobalt sulfide nickel, confirms effective combination of Graphene in composite material, carbon nano-tube and cobalt sulfide nickel three.See accompanying drawing 3.
(4) Electrochemical results shows: the performance of graphene/carbon nano-tube hybrid material is very stable, but its capability value only has 190mAhg
-1.And the capability value of pure cobalt sulfide nickel can up to 1300mAhg
-1, but its cycle performance is poor, after discharge and recharge 100 is enclosed, only have 260mAhg
-1.By contrast, prepared cobalt sulfide nickel/Graphene/carbon nanotube composite material has higher reversible capacity value and good cyclical stability.After 100 circle charge and discharge cycles, its reversible capacity value still can up to 1050mAhg
-1.The appropriate design and the structure that this demonstrate composite material have remarkable effect to the raising of its reversible capacity value and cyclical stability.See accompanying drawing 4.
The invention has the advantages that:
(1) preparation process is simple, is easy to operation;
(2) experimental design is ingenious.Graphene oxide and carbon nano-tube are mixed graphene oxide/carbon nano-tube hybridization material that the ultrasonic method of merga pass prepares three-dimensional net structure and high-specific surface area, and as base material, by one step hydro thermal method growth in situ cobalt sulfide nickel nano film on graphene oxide/carbon nano-tube hybridization material, restrained effectively the reunion of cobalt sulfide nickel and successfully constructed the composite material with multilevel hierarchy;
(3) the cobalt sulfide nickel/Graphene/carbon nanotube composite material prepared by has the three-dimensional net structure be coupled to each other, good electric conductivity and higher specific area, the cobalt sulfide nickel nano film with high electrochemical activity and high theoretical capacity is made to be evenly distributed in graphene/carbon nano-tube hybrid material, the avtive spot of cobalt 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 (A) graphene/carbon nano-tube hybrid material in the present invention, the SEM figure of (B) cobalt sulfide nickel/Graphene/carbon nanotube composite material.
Fig. 2 is the TEM figure of cobalt sulfide nickel/Graphene/carbon nanotube composite material in the present invention.
Fig. 3 is the XRD figure of cobalt sulfide nickel/Graphene/carbon nanotube composite material in the present invention.
Fig. 4 is that in the present invention, cobalt sulfide nickel/Graphene/carbon nanotube composite material is 0.2Ag in current density
-1under cycle performance figure.
Embodiment
Below in conjunction with instantiation, 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) 100mg graphene oxide is scattered in 100mL deionized water, is obtained the graphene oxide dispersion of stable dispersion by ultrasonic preparation.
(2) 50mg carbon nano-tube is joined in graphene oxide dispersion, continue ultrasonic 2h, and by centrifuging and taking upper strata black liquor, centrifugation rate is 8000rpm, and centrifugation time is 20min, prepares the graphene/carbon nano-tube dispersion liquid of stable homogeneous.
(3) by 232mg cobalt nitrate, 116mg nickel nitrate, 200mg thiocarbamide and 2mL ethylenediamine are dissolved in 10mL deionized water, and ultrasonic 5min prepares homogeneous salting liquid.
(4) salting liquid will prepared, add in the graphene/carbon nano-tube dispersion liquid of 20mL, ultrasonic 20min prepares the mixed solution of uniform salting liquid and graphene/carbon nano-tube dispersion liquid.
(5) mixed solution of the salting liquid prepared and graphene/carbon nano-tube dispersion liquid is transferred in water heating kettle, 12h is reacted in 200 DEG C, after Temperature fall, take out black precipitate and repeatedly clean repeatedly and drying with deionized water and ethanol, prepare cobalt sulfide nickel/Graphene/carbon nanotube composite material, be designated as NiCo
2s
4/ CNT/graphene.
(6) cobalt sulfide prepared nickel/Graphene/carbon nanotube composite material is heat-treated in high pure nitrogen, to improve the crystal structure of cobalt sulfide nickel nano film.Heat treatment temperature is 350 DEG C, and heat treatment time is 3h.
embodiment 2
The quality of the cobalt nitrate in embodiment 1 is become 116mg, and the quality of nickel nitrate becomes 58mg, and the quality of thiocarbamide becomes 100mg, and all the other are all with embodiment 1, and final obtained composite material is designated as NiCo
2s
4/ CNT/graphene-1.
embodiment 3
The quality of the cobalt nitrate in embodiment 1 is become 464mg, and the quality of nickel nitrate becomes 232mg, and the quality of thiocarbamide becomes 400mg, and all the other are all with embodiment 1, and final obtained composite material is designated as NiCo
2s
4/ CNT/graphene-2.
Claims (8)
1. a preparation method for cobalt sulfide nickel/Graphene/carbon nanotube composite material, is characterized in that concrete steps are as follows:
(1) graphene oxide is joined in deionized water, ultrasonic disperse, obtain the graphene oxide dispersion of stable dispersion;
(2) carbon nano-tube is joined in graphene oxide dispersion, continue ultrasonic, and by centrifuging and taking upper strata black liquor, obtain the graphene/carbon nano-tube dispersion liquid of stable homogeneous;
(3) cobalt salt, nickel salt, thiocarbamide and ethylenediamine are dissolved in deionized water, obtain homogeneous salting liquid;
(4) joined by salting liquid in graphene/carbon nano-tube dispersion liquid, ultrasonic disperse, obtains the mixed solution of uniform salting liquid and graphene/carbon nano-tube dispersion liquid;
(5) mixed solution of the salting liquid obtained and graphene/carbon nano-tube dispersion liquid is transferred in water heating kettle, carries out hydro-thermal reaction, obtain cobalt sulfide nickel/Graphene/carbon nanotube composite material;
(6) cobalt sulfide obtained nickel/Graphene/carbon nanotube composite material is heat-treated under inert gas shielding, to improve the crystal structure of cobalt sulfide nickel and further reduced graphene.
2. the preparation method of cobalt sulfide nickel/Graphene/carbon nanotube composite material according to claim 1, is characterized in that in step (2), and the mass ratio of described graphene oxide and carbon nano-tube is 5:1 ~ 1:3; Ultrasonic time is 1 ~ 3h; Centrifugation rate is 6000 ~ 12000rpm, and centrifugation time is 10 ~ 40min.
3. the preparation method of cobalt sulfide nickel/Graphene/carbon nanotube composite material according to claim 1 and 2, is characterized in that in step (3), described cobalt salt is selected from cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt acetate; Nickel salt is selected from nickel nitrate, nickelous sulfate, nickel 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 ethylenediamine is 1 ~ 5mL; The mol ratio of the cobalt in cobalt salt and the nickel in nickel salt is 2 ~ 2.5.
4. the preparation method of cobalt sulfide nickel/Graphene/carbon nanotube composite material according to claim 3, is characterized in that in step (4), and the concentration of described graphene/carbon nano-tube dispersion liquid is 0.5 ~ 3mgmL
-1; The concentration ratio of graphene/carbon nano-tube hybrid material and cobalt salt is 1:2 ~ 1:15.
5. the preparation method of the cobalt sulfide nickel/Graphene/carbon nanotube composite material according to claim 1,2 or 4, is characterized in that in step (5), and the reaction temperature of described hydro-thermal reaction is 160 ~ 220 DEG C, and the reaction time is 10 ~ 24h.
6. the preparation method of the cobalt sulfide nickel/Graphene/carbon nanotube composite material according to claim 1,2 or 4, it is characterized in that in step (6), described inert gas is high-purity argon gas or high pure nitrogen, and heat treatment temperature is 250 ~ 400 DEG C, and heat treatment time is 1 ~ 4h.
7. the cobalt sulfide nickel/Graphene/carbon nanotube composite material prepared by the described preparation method of one of claim 1-6.
8. cobalt sulfide nickel/Graphene/carbon nanotube composite material according to claim 7 is as high-performance electric catalysis material, and lithium ion battery, electrode material for super capacitor purposes.
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