CN104934233B - Porous, electrically conductive graphene/carbon nanometer angle composite material, preparation method and applications - Google Patents
Porous, electrically conductive graphene/carbon nanometer angle composite material, preparation method and applications Download PDFInfo
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- H—ELECTRICITY
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- 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
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- 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
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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
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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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- H01M4/58—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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- H—ELECTRICITY
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- H—ELECTRICITY
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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
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- 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
- Y02E60/10—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
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention provides a kind of with porous conductive graphene/carbon nanohorn composite material, which is characterized in that the carbon nanohorn is distributed in graphene film interlayer or graphene film layer surface.The composite material effectively prevents or reduces the stacking of graphene sheet layer, reunites, and forms a large amount of hierarchical structure hole (including micropore and mesoporous) and bigger serface；Meanwhile graphene plays bridging effect between carbon nanohorn, forms conductive network structure, increases its electric conductivity.The present invention also provides the preparation methods of the composite material, and the material is for electrode materials or the applications as additive such as supercapacitor, lithium ion battery, fuel cells, the capacitance of the electrode material is big, charge/discharge speed is fast, and number is recycled and increases.
Description
Technical field
The present invention relates to a kind of porous, electrically conductive graphene/carbon nanometer angle composite material and preparation methods, belong to material, electricity
Chemistry, energy storage, environment protection field.
Background technique
In the past few decades, carbon material is due to itself good conductivity, large specific surface area, chemistry and mechanical stability
Good, in fields such as electronics, chemical industry, machinery, environmental protection, especially in cleaning energy storage, such as electrochemical energy storage, (such as lithium ion battery surpasses
Grade capacitor) etc. attract wide attention.Wherein, the carbon materials such as carbon fiber (CNFs), carbon nanotube (CNTs), graphene
Have broad application prospects in terms of electrode or as the important additives in high-performance electric chemistry energy storage device.For example,
Although the theoretical specific surface area of graphene and carbon nanotube is very big, reunion, graphene film stacking or the carbon nanometer of graphene
Pipe bundle structure accumulation is reunited and (is caused by the Van der Waals force interaction of adjacent level), these carbon materials are greatly reduced
Specific surface area and micropore volume make the reduced performance in terms of its electrochemical energy storage (such as lithium ion battery, supercapacitor).This
Outside, in terms of practical application, the load capacity of graphene is low, and there is also more problems for stability etc..According to the literature, in order to subtract
Few graphene film stacking, agglomeration, researcher develops the graphene of fold or graphene sol, gel, capacitor reach
180F/g；Graphene film interlayer is supported on carbon nanotube or carbon nanotube is placed between graphene sheet layer, can be up to
The capacitance of 187F/g.Also it has been reported that by metal and metal oxide insertion graphene film with fake capacitance performance
Interlayer can prevent the stacking of graphene sheet layer, increase its specific surface area and pore volume, achieve the purpose that improve its capacitance.
But the capacitor containing metal and metal oxide, not only have that performance is unstable, cycle-index is low, service life is short
The problem of disadvantage, there is also toxic and environmental pollution aspects.According to another document report, received using chemicals dispersed graphite alkene and carbon
Mitron and use chemicals (such as hydrazine hydrate) redox graphene, not only synthesis cost is high, there is also toxicity and environment
Pollution problem.
Summary of the invention
Present invention seek to address that the foregoing problems of the prior art, provide the production technology that a kind of method is simple, environmental-friendly
And technology, synthesis have porous conductive graphene/carbon nanohorn sandwich.The composite material is characterized in that carbon
Nanometer angle is distributed in graphene film interlayer or graphene film layer surface, the stacking and reunion of effective prevention graphene sheet layer,
Form a large amount of hierarchical structure hole (including micropore and mesoporous) and bigger serface；Meanwhile graphene plays between carbon nanohorn
Bridging effect forms conductive network structure, increases its electric conductivity.The material is for supercapacitor, lithium ion battery, fuel electricity
On the electrode materials such as pond or electrochemical energy storing device, capacitance is big, charge/discharge speed is fast, and number is recycled and increases.
The present invention is achieved through the following technical solutions:
One kind having porous conductive graphene/carbon nanohorn composite material, which is characterized in that the carbon nanohorn distribution
In on graphene film interlayer and/or graphene film layer surface.
According to the present invention, the graphene is selected from graphene oxide, redox graphene, graphene or thin layer graphite.
According to the present invention, the carbon nanohorn is selected from carbon nanohorn, carbon nanohorn particle, carbon nanohorn micelle, carbon nanometer
Angle aggregation or carbon nanohorn, carbon nanohorn particle, carbon nanohorn micelle, carbon nanohorn assembly containing nano-pore；It is described
Carbon nanohorn is single angle or multi-wall carbon nano-tube angle, preferably single angle.
According to the present invention, the mass ratio of the graphene and carbon nanohorn is 20:1-1:1, preferably 5:1-5:2.
According to the present invention, the porosity (pore volume) of the composite material is greater than 0.08cm3/ g, preferably greater than
0.1cm3/g。
According to the present invention, the composite material has hierarchical pore structure, the pore structure preferred microporous and mesoporous.
The mesoporous aperture is in 2-50nm, preferably in 2-20nm, more preferably 2-5nm.
According to the present invention, the aperture of the micropore is between 0.4-2nm, preferably 0.5-1nm.
According to the present invention, the composite material is similar gels structure or porous structure.
According to the present invention, the specific surface area of the composite material is greater than 100m2/ g, preferably greater than 180m2/g。
According to the present invention, the composite material is conductive network structure.
The present invention also provides a kind of preparation methods of above-mentioned composite material, which is characterized in that by graphene oxide (or reduction
Graphene oxide or graphene or thin layer graphite) and single angle (or through the processed single angle of concentrated nitric acid)
It is first dispersed in solvent or water, then passes through hydro-thermal reaction, synthesizing graphite alkene/single angle composite material.
According to the present invention, the solvent is selected from organic solvent, acid, water and its mixture, preferred acid, water, and its mixing
Liquid.
According to the present invention, the organic solvent is selected from toluene, phenol or dimethylbenzene.
According to the present invention, the sour solvent is selected from concentrated nitric acid.Preferably, at first with concentrated nitric acid to single angle
Reason.
According to the present invention, ultrasonic wave dispersion is carried out to the material being dispersed in solvent or water or is dispersed with stirring processing.It is preferred that
Ground, treated graphene oxide and single angle form uniform colloid or suspended matter.
The present invention also provides the applications of above-mentioned composite material, which is characterized in that it is described using for supercapacitor, lithium from
The electrode materials such as sub- battery, fuel cell or additive application as supercapacitor, lithium ion battery, fuel cell etc..
The capacitance of the material is big, charge/discharge speed is fast, and number is recycled and increases.
Due to current graphene (or synthesizing graphite alkene) be two layers or more structures, thus single angle or
Single angle particle, single angle micelle, single angle aggregation are distributed in graphene oxide (or graphite
Alkene) on interlayer or its surface, effectively prevents or reduce its stacking, reunites, keep its large specific surface area, voidage (pore volume) high.
Conductive network structure is formed since graphene and single angle are in close contact, which there is porosity and height to lead
Electrical property.The porous, electrically conductive graphene synthesized by the technical solution/single angle composite material, is suitable for ion
Adsorption-desorption, ion quickly spread and migrate, the quick diffusion and migration of electrolyte, can be with to improve its chemical property
It is applied in the energy storage devices such as high-performance super capacitor, lithium ion battery, fuel cell well.The nanometer of technology synthesis
Carbon composite is tried without toxic and harmful chemistry is not added in metal, nano metal or metal oxide, synthesis process yet
Agent, therefore be nontoxic an environmentally friendly technology and technology.
Detailed description of the invention:
Fig. 1 graphene/single angle composite material scanning electron microscope (SEM) figure
Fig. 2 graphene/single angle composite material 77K nitrogen adsorption isotherm
The electrochemistry cyclic voltammetry curve that Fig. 3 graphene/single angle composite material measures in 1M KOH solution
(CV) curve.
Specific embodiment
Below in conjunction with drawings and examples, the present invention is described in further detail.But skilled in the art realises that
Protection scope of the present invention is not limited only to following embodiment.According to the present disclosure, those skilled in the art will recognize that
To in the case where not departing from technical characteristic given by technical solution of the present invention and range, embodiment described above is made perhaps
More change and modification belong to protection scope of the present invention.
Embodiment 1
50mg single angle (Single wall carbon nanohorns) is added in 50mL concentrated nitric acid, 60
It at a temperature of DEG C after stir process 12 hours, separates, be washed with water, then separate, be washed with water and wash, after repetition 2,3 times or more times,
It is stand-by after drying in 70 DEG C of baking ovens.
It gets out graphene oxide (or powdered graphite or graphite oxide first synthesize graphene oxide) or reduction-oxidation in advance
Graphene is stand-by.
By above-mentioned ready 50mg graphene oxide and 10mg single angle, that is, the weight ratio of 5:1 is pressed, is dispersed in
In 30mL water, ultrasonic wave decentralized processing 3 hours, make graphene oxide and single angle formed in water uniform colloid or
Suspended matter.The colloidal solution or suspension are transferred in hydrothermal reactor again, it is small that hydro-thermal reaction 18 is carried out at a temperature of 180 DEG C
When.After reaction, room temperature is naturally cooled to.The product for the similar hydrogel (hydrogel) that reaction generates is immersed in water
In, and every after five minutes, moisture is sucked, the product for impregnating the similar gels is added water, it is after being repeated several times, this is similar solidifying
The product of glue places a whole night at room temperature, allows it to spontaneously dry, obtains reaction product-stone of similar gels (frozen glue)
Black alkene/single angle composite material.Finally, flowing down it in tube furnace in nitrogen (or argon gas) with 5 DEG C per minute
Heating rate is heated to 800 DEG C, and is kept for 2 hours to get porous, electrically conductive graphene/single angle composite material is arrived.
Porous, electrically conductive graphene/single angle composite material that we are synthesized by hydro-thermal method, passes through a series of knots
Structure characterization and Electrochemical Properties, the results showed that, which has about 0.6nm micropore and about 2-12nm is mesoporous
Similar gels structure or porous structure, and its nanometer of pore volume is about 0.2cm3/g.At room temperature, in 1M KOH solution, fastly
Under fast charge and discharge, the graphene/single angle composite material capacitor for measuring synthesis is up to 244F/g, and the composite material
With good high rate performance, chemical property especially electrochemical energy storage performance is better than graphene oxide, oxygen reduction fossil
Black alkene, single angle and other single angles composite material.Constant current charge and discharge is carried out under the current density of 10A/g
Electricity, circulation are also able to maintain 99% capacitance for 1000 times, therefore, high-energy density energy storage device (such as supercapacitor),
It has broad application prospects in the application such as lithium ion battery, fuel cell.
Embodiment 2
50mg single angle (Single wall carbon nanohorns) is added in 50mL concentrated nitric acid, 60
It at a temperature of DEG C after stir process 12 hours, separates, be washed with water, then separate, be washed with water and wash, after repetition 2,3 times or more times,
It is stand-by after drying in 70 DEG C of baking ovens.
It gets out graphene oxide (or powdered graphite or graphite oxide first synthesize graphene oxide) or reduction-oxidation in advance
Graphene is stand-by.
By above-mentioned ready 50mg graphene oxide and 20mg single angle, that is, press the weight ratio of 2.5:1, dispersion
In 30mL water, ultrasonic wave decentralized processing 3 hours, graphene oxide and single angle is made to form uniform colloid in water
Or suspended matter.The colloidal solution or suspension are transferred in hydrothermal reactor again, it is small that hydro-thermal reaction 18 is carried out at a temperature of 180 DEG C
When.After reaction, room temperature is naturally cooled to.The product for the similar hydrogel (hydrogel) that reaction generates is immersed in water
In, and every after five minutes, moisture is sucked, the reaction product for impregnating this similar to hydrogel is added water, after being repeated several times, by this
Reaction product places a whole night at room temperature, it is allowed to spontaneously dry, and the graphene/single wall carbon for obtaining similar gels (frozen glue) is received
Rice angle composite material.Finally, flowing down it in tube furnace in nitrogen (or argon gas) with 5 DEG C of heating rate per minute, heating
To 800 DEG C, and kept for 2 hours to get porous, electrically conductive graphene/single angle composite material is arrived.
Porous, electrically conductive graphene/single angle composite material that we are synthesized by hydro-thermal method, passes through a series of knots
Structure characterization and Electrochemical Properties, the results showed that, at room temperature, in 1M KOH solution, under fast charging and discharging, measure synthesis
The composite material of graphene/single angle composite wood capacitance ratio 1 is low, about 133F/g, which has good
Good high rate performance, chemical property such as electrochemical energy storage performance are better than graphene oxide, redox graphene, single wall carbon
The composite material at nanometer angle and other single angles.
Embodiment 3
By 50mg graphene oxide (or powdered graphite or graphite oxide first synthesize graphene oxide) or reduction-oxidation graphite
Alkene and 10-20mg single angle are pressed the weight ratio of 5:1-2.5:1, are dispersed in 30mL water, ultrasonic wave decentralized processing,
Graphene oxide or redox graphene and single angle is set to form uniform colloid or suspended matter in water.Again should
Colloidal solution or suspension are transferred in hydrothermal reactor, are carried out hydro-thermal reaction 18 hours at a temperature of 180 DEG C.After reaction,
Naturally cool to room temperature.The product for the similar hydrogel (hydrogel) that reaction is generated impregnated in water, and every 5 minutes
Afterwards, moisture is sucked, the reaction product for impregnating this similar to hydrogel is added water, after being repeated several times, by the reaction of similar hydrogel
Product places a whole night at room temperature, it is allowed to spontaneously dry, and the graphene/single angle for obtaining similar gels (frozen glue) is multiple
Condensation material.Finally, flowing down it in tube furnace in nitrogen (or argon gas) with 5 DEG C of heating rate per minute, it is heated to 800
DEG C, and kept for 2 hours to get porous, electrically conductive graphene/single angle composite material is arrived.
Graphene/single angle composite material that we synthesize hydro-thermal method, passes through a series of structural characterizations and electricity
Chemical property research, the results showed that, at room temperature, in 1M KOH solution, under fast charging and discharging, measure the graphene of synthesis/mono-
The composite material of the capacitance ratio 1 of wall carbon nano-tube angle composite wood is low, but the composite material has good high rate performance, electricity
Chemical property such as electrochemical energy storage performance is better than graphene oxide, redox graphene, single angle and other single walls
The composite material of carbon nanohorn.
Claims (14)
1. one kind has porous conductive graphene/carbon nanohorn composite material, which is characterized in that
The carbon nanohorn is distributed in graphene film interlayer or graphene film layer surface, and the composite material tape has levels structure
Hole, the structure hole are selected from micropore and mesoporous, and the composite material is conductive network structure, and the carbon nanohorn is selected from carbon nanometer
Angle particle, carbon nanohorn micelle, carbon nanohorn assembly,
The porosity of the composite material is greater than 0.08cm3/ g, the specific surface area of the composite material are greater than 100 m2/ g,
The mesoporous aperture is in 2-20nm, and the aperture of the micropore is in 0.5-1nm.
2. composite material according to claim 1, which is characterized in that the carbon nanohorn is single angle or multi wall
Carbon nanohorn.
3. composite material according to claim 1 or 2, wherein the mass ratio of the graphene and carbon nanohorn is 20:1-1:1.
4. composite material according to claim 3, wherein the mass ratio of the graphene and carbon nanohorn is 5:1-5:2.
5. composite material according to claim 1 or 2, which is characterized in that the porosity of the composite material is greater than 0.1cm3/
g；The specific surface area of the composite material is greater than 180 m2/g。
6. composite material according to claim 1 or 2, wherein the micropore size of the composite material is 0.6 nm, mesoporous hole
Diameter is 2-12 nm.
7. composite material according to claim 1 or 2, which is characterized in that the mesoporous aperture is in 2-5nm.
8. composite material according to claim 1 or 2, which is characterized in that the carbon nanohorn is selected from the carbon containing nano-pore and receives
Rice angle.
9. a kind of preparation method of the described in any item composite materials of claim 1-8, which is characterized in that by graphene oxide,
Graphene, thin layer graphite or oxide thin layer graphite and single angle first disperse through the processed carbon nanohorn of concentrated nitric acid
In a solvent, ultrasonic wave dispersion is carried out to the material of dispersion in a solvent or is dispersed with stirring processing, then pass through hydro-thermal reaction, synthesis
The composite material, the carbon nanohorn are selected from carbon nanohorn particle, carbon nanohorn micelle, carbon nanohorn assembly；
The composite material tape has levels structure hole, and the structure hole is selected from micropore and mesoporous,
The solvent is selected from organic solvent, acid and its mixture, alternatively, the solvent is selected from water.
10. preparation method according to claim 9, which is characterized in that the organic solvent is selected from toluene, phenol, dimethylbenzene.
11. preparation method according to claim 9, which is characterized in that the acid is selected from concentrated nitric acid.
12. according to the preparation method of any one of claim 9-11, which is characterized in that graphene oxide, graphene and single wall carbon
Nanometer angle forms uniform colloid or suspended matter through the processed carbon nanohorn of concentrated nitric acid in a solvent.
13. preparation method according to claim 9, which is characterized in that the carbon nanohorn is selected from the carbon nanometer containing nano-pore
Angle.
14. the application of the described in any item composite materials of claim 1-8, which is characterized in that be used for supercapacitor, lithium ion
Battery, fuel cell electrode material in or as supercapacitor, lithium ion battery, fuel cell additive.
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