CN105280896A - Cobalt-nickel sulfide/carbon nanofiber composite material and preparation method and application thereof - Google Patents
Cobalt-nickel sulfide/carbon nanofiber composite material and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- 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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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
- Y02E60/10—Energy storage using batteries
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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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to the technical field of transition metal sulfide-carbon materials, and particularly discloses a cobalt-nickel sulfide/carbon nanofiber composite material and a preparation method and an application thereof. The method comprises the following preparation processes: preparing a carbon nanofiber through electrostatic spinning and high-temperature carbonization methods; and carrying out in-situ growth of a cobalt-nickel sulfide nanorod on the carbon nanofiber through a one-step hydrothermal method. The carbon nanofiber prepared by the method has the advantages of stable chemical property, good conductivity, good mechanical property and the like; the final cobalt-nickel sulfide/carbon nanofiber composite material is controllable in morphology; the cobalt-nickel sulfide nanorod uniformly grows on the carbon nanofiber; and a unique base structure and high specific surface area of the carbon nanofiber are fully utilized. The cobalt-nickel sulfide/carbon nanofiber composite material prepared by the method can be used as an ideal high-property electrocatalytic 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/carbon nano-fiber composite material and its preparation method and application.
Background technology
Carbon nano-fiber has acted on the physical and chemical performance of carbon nanomaterial excellence, 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.Electrostatic spinning is a kind of technology simply and effectively preparing carbon nano-fiber, by high-pressure electrostatic, polymer solution is carried out spinning, then carry out pre-oxidation and high temperature cabonization can prepare the carbon nano-fiber spinning film with three-dimensional porous structure, high-ratio surface sum high conductivity.This patent adopts electrostatic spinning process, polyacrylonitrile solution is carried out spinning, then prepares carbon nano-fiber by pre-oxidation and high temperature cabonization, and prepare high performance composite material further as base material.
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 nickel particle 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 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/carbon nano-fiber composite material.This composite material has following advantage: Static Spinning carbon nano-fiber has unique three-dimensional porous 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 carbon nano-fiber is conducive to the transmission of electronics, improves the conductivity of composites; The mechanical property of carbon nano-fiber excellence makes composite material can be used as flexible electrode material and is applied to catalysis and energy storage device; Cobalt sulfide nanosized nickel rods itself possesses higher theoretical lithium storage content value, can improve the specific capacity of composites.Therefore, carbon nano-fiber and cobalt sulfide nanosized nickel rods are carried out effective compound, good synergy can be realized, to prepare the composite material of excellent performance.
Summary of the invention
The object of the present invention is to provide the cobalt sulfide nickel/carbon nano-fiber composite material and its preparation method and application of a kind of preparation process environmental protection, with low cost, electrochemical performance.
Cobalt sulfide nickel/carbon nano-fiber composite material provided by the present invention, its raw materials comprises: polyacrylonitrile,
n, N-dimethyl formamide, cobalt salt, nickel salt, thiocarbamide, urea etc.
Cobalt sulfide nickel/carbon nano-fiber composite material provided by the present invention, its preparation process comprises: prepare carbon nano-fiber by electrostatic spinning, pre-oxidation and high temperature cabonization technology, then by one step hydro thermal method growth in situ cobalt sulfide nanosized nickel rods on carbon nano-fiber.Concrete steps are as follows:
(1) polyacrylonitrile powder is joined
n, N-in solvent dimethylformamide, Keep agitation, obtains homogeneous thickness dispersion liquid;
(2) the polyacrylonitrile dispersion liquid obtained is carried out electrostatic spinning, obtain polyacrylonitrile nanofiber film;
(3) the polyacrylonitrile spinning film obtained is carried out pre-oxidation in air atmosphere, obtain the polyacrylonitrile nanofiber film after pre-oxidation;
(4) the polyacrylonitrile nanofiber film after gained pre-oxidation is carried out high temperature cabonization under inert gas shielding, obtain carbon nanofiber membrane;
(5) cobalt salt, nickel salt, thiocarbamide and urea are dissolved in deionized water, obtain homogeneous salting liquid;
(6) obtained salting liquid and carbon nanofiber membrane are carried out hydro-thermal reaction, obtain cobalt sulfide nanosized nickel rods/carbon nano-fiber composite material;
(7) cobalt sulfide obtained nickel/carbon nano-fiber composite material is heat-treated under inert gas shielding, to improve the crystal structure of cobalt sulfide nanosized nickel rods.
In the present invention, the electrostatic spinning described in step (2), its technological parameter is: electrostatic field voltage 15 ~ 25kV, spinning speed 0.2 ~ 0.4mmmin
-1, receiving range 15 ~ 25cm.
In the present invention, the pre-oxidation described in step (3), the temperature of pre-oxidation is 250 ~ 300 DEG C, and heating rate is 1 ~ 2 DEG C of min
-1, preoxidation time is 1 ~ 2h, and the preferred time is 1.5h.
In the present invention, the high temperature cabonization process described in step (4), inert gas is high-purity argon gas or high pure nitrogen, and high temperature cabonization temperature is 1000 ~ 1500 DEG C, and the high temperature cabonization time is 1 ~ 3h, preferred 2h.
In the present invention, the salting liquid preparation process described in step (5), 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 cobalt salt is 10 ~ 50mgmL
-1, preferably 20 ~ 30mgmL
-1; The mass range of nickel salt is 5 ~ 25mgmL
-1, preferably 10 ~ 15mgmL
-1; The mass concentration of thiocarbamide is 10 ~ 50mgmL
-1, preferably 20 ~ 30mgmL
-1; The mass concentration of urea is 10 ~ 30mgmL
-1, preferably 15 ~ 25mgmL
-1.
In the present invention, the hydro-thermal reaction described in step (6), reaction temperature 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 described in step (7), inert gas is high-purity argon gas or high pure nitrogen, and heat treatment temperature 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), pattern that X-ray diffractometer (XRD), battery test system characterize the preparation-obtained cobalt sulfide nickel/carbon nano-fiber composite material of the present invention and structure and be used as the chemical property of lithium ion battery negative material, its result is as follows:
(1) SEM test result shows: carbon nanofiber membrane prepared in the present invention has three-dimensional porous structure, and the diameter of fiber is about 100-200 nanometer, and its high specific area is that cobalt sulfide nickel provides and more grows site.Prepared cobalt sulfide nickel/carbon nano-fiber composite material has unique multilevel hierarchy, cobalt sulfide nanosized nickel rods grows equably on carbon nano-fiber, restrained effectively the reunion of cobalt sulfide nickel self, the cobalt sulfide nanosized nickel rods with high electrochemical activity is fully exposed.See accompanying drawing 1.
(2) XRD test result shows: prepared carbon nano-fiber has a wider diffraction maximum in 2 θ=26 °, corresponding to its (002) crystal face.Prepared cobalt sulfide nickel/carbon nano-fiber composite material 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.See accompanying drawing 2.
(3) Electrochemical results shows: the performance of pure carbon nano-fiber is very stable, but its capability value only has 260mAhg
-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 350mAhg
-1.By contrast, prepared cobalt sulfide nickel/carbon nano-fiber 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 1060mAhg
-1.The raising of the structure this demonstrating cobalt sulfide nickel/carbon nano-fiber composite material to its reversible capacity value and cyclical stability has and acts on very significantly.See accompanying drawing 3.
The invention has the advantages that:
(1) simple, the environmental protection of preparation process, being easy to operation, is a kind of Green Chemistry preparation method;
(2) experimental design is ingenious.By electrostatic spinning and high temperature cabonization technology, prepare the carbon nanofiber membrane with three-dimensional porous structure and high-specific surface area simply and effectively, and as base material, by one step hydro thermal method growth in situ cobalt sulfide nanosized nickel rods on carbon nano-fiber, restrained effectively the reunion of cobalt sulfide nickel and successfully constructed the composite material with multilevel hierarchy;
(3) the cobalt sulfide nickel/carbon nano-fiber composite material prepared by has good pliability, and higher reversible capacity value and good cyclical stability can be used as the ideal electrode material of the new energy devices such as ultracapacitor, lithium ion battery.
Accompanying drawing explanation
Fig. 1 is (A) carbon nano-fiber in the present invention, the SEM figure of (B) cobalt sulfide nickel/carbon nano-fiber composite material.
Fig. 2 is the XRD figure of cobalt sulfide nickel/carbon nano-fiber composite material in the present invention.
Fig. 3 is that in the present invention, cobalt sulfide nickel/carbon nano-fiber 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) 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 pre-oxidation in air atmosphere, the temperature of pre-oxidation is 250 DEG C, and heating rate is 1 DEG C of min
-1, preoxidation time is 1.5h, prepares the polyacrylonitrile nanofiber film after pre-oxidation;
(4) the polyacrylonitrile nanofiber film after gained pre-oxidation is carried out high temperature cabonization in high pure nitrogen, high temperature cabonization temperature is 1500 DEG C, and the high temperature cabonization time is 2h, prepares carbon nanofiber membrane;
(5) by 580mg cobalt nitrate, 290mg nickel nitrate, 600mg thiocarbamide and 500mg urea are dissolved in 25mL deionized water, and ultrasonic 5min prepares homogeneous salting liquid;
(6) salting liquid prepared and carbon nanofiber membrane are put into water heating kettle, in 200 DEG C, react 12h, after Temperature fall, take out tunica fibrosa and repeatedly clean repeatedly and drying with deionized water and ethanol, prepare cobalt sulfide nanosized nickel rods/carbon nano-fiber composite material, be designated as NiCo
2s
4cNF;
(7) cobalt sulfide prepared nickel/carbon nano-fiber composite material is heat-treated in high pure nitrogen, to improve the crystal structure of cobalt sulfide nanosized nickel rods.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 290mg, and the quality of nickel nitrate becomes 145mg, and the quality of thiocarbamide becomes 300mg, and all the other are all with embodiment 1, and final obtained composite material is designated as NiCo
2s
4cNF-1.
embodiment 3
The quality of the cobalt nitrate in embodiment 1 is become 1160mg, and the quality of nickel nitrate becomes 580mg, and the quality of thiocarbamide becomes 1200mg, and all the other are all with embodiment 1, and final obtained composite material is designated as NiCo
2s
4cNF-2.
Claims (9)
1. a preparation method for cobalt sulfide nickel/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, obtains homogeneous thickness dispersion liquid;
(2) the polyacrylonitrile dispersion liquid obtained is carried out electrostatic spinning, obtain polyacrylonitrile nanofiber film;
(3) the polyacrylonitrile spinning film obtained is carried out pre-oxidation in air atmosphere, obtain the polyacrylonitrile nanofiber film after pre-oxidation;
(4) the polyacrylonitrile nanofiber film after gained pre-oxidation is carried out high temperature cabonization under inert gas shielding, obtain carbon nanofiber membrane;
(5) cobalt salt, nickel salt, thiocarbamide and urea are dissolved in deionized water, obtain homogeneous salting liquid;
(6) obtained salting liquid and carbon nanofiber membrane are carried out hydro-thermal reaction, obtain cobalt sulfide nanosized nickel rods/carbon nano-fiber composite material;
(7) cobalt sulfide obtained nickel/carbon nano-fiber composite material is heat-treated under inert gas shielding, to improve the crystal structure of cobalt sulfide nanosized nickel rods.
2. the preparation method of cobalt sulfide nickel/carbon nano-fiber composite material according to claim 1, it is characterized in that the electrostatic spinning described in step (2), its technological parameter is: electrostatic field voltage 15 ~ 25kV, spinning speed 0.2 ~ 0.4mmmin
-1, receiving range 15 ~ 25cm.
3. the preparation method of cobalt sulfide nickel/carbon nano-fiber composite material according to claim 1 or 2, it is characterized in that the pre-oxidation described in step (3), temperature is 250 ~ 300 DEG C, and heating rate is 1 ~ 2 DEG C of min
-1, preoxidation time is 1 ~ 2h.
4. the preparation method of cobalt sulfide nickel/carbon nano-fiber composite material according to claim 3, it is characterized in that the high temperature cabonization process described in step (4), inert gas is high-purity argon gas or high pure nitrogen, and high temperature cabonization temperature is 1000 ~ 1500 DEG C, and the high temperature cabonization time is 1 ~ 3h.
5. the preparation method of cobalt sulfide nickel/carbon nano-fiber composite material according to claim 1,2 or 4, is characterized in that the cobalt salt described in step (5) 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 cobalt salt is 10 ~ 50mgmL
-1, the mass range of nickel salt is 5 ~ 25mgmL
-1, the mass concentration of thiocarbamide is 10 ~ 50mgmL
-1, the mass concentration of urea is 10 ~ 30mgmL
-1.
6. the preparation method of cobalt sulfide nickel/carbon nano-fiber composite material according to claim 1,2 or 4, it is characterized in that the hydro-thermal reaction described in step (6), reaction temperature is 160 ~ 220 DEG C, and the reaction time is 10 ~ 24h.
7. the preparation method of cobalt sulfide nickel/carbon nano-fiber composite material according to claim 6, it is characterized in that the heat treatment process described in step (7), 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 ~ 4hh.
8. the cobalt sulfide nickel/carbon nano-fiber composite material prepared by preparation method described in claim 1-7.
9. as cobalt sulfide nickel/carbon nano-fiber composite material according to claim 8 as high-performance electric catalysis material, and lithium ion battery, electrode material for super capacitor purposes.
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