CN103204497A - Method for preparing graphene material and application thereof in chemical energy storage and/or conversion - Google Patents
Method for preparing graphene material and application thereof in chemical energy storage and/or conversion Download PDFInfo
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- CN103204497A CN103204497A CN2013101310142A CN201310131014A CN103204497A CN 103204497 A CN103204497 A CN 103204497A CN 2013101310142 A CN2013101310142 A CN 2013101310142A CN 201310131014 A CN201310131014 A CN 201310131014A CN 103204497 A CN103204497 A CN 103204497A
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Abstract
The invention provides a method for preparing graphene material and an application thereof in chemical energy storage and/or conversion. The method comprises the following steps: 1, adding graphene oxide into a dispersion medium so as to obtain a graphene oxide suspension liquid; 2, spraying and drying the suspension liquid so as to obtain graphene oxide particles; and 3, reducing the graphene oxide particles through atmospheric reduction. The obtained material can be applied to super capacitor electrode materials, and the capacity of the electrode materials can reach 120F/g. A macro amount of porous graphene oxide particles can be produced through utilizing the method. The graphene material can be used as super capacitor electrode materials, catalyst carriers or infrared optical materials.
Description
Technical field
The present invention relates to the grapheme material field, especially relate to and a kind ofly prepare the method for grapheme material and in chemical energy storage and/or conversion field, the especially purposes in ultracapacitor.
Background technology
Since the strong K of the peace moral of Univ Manchester UK sea nurse (Andre K.Geim) has waited since preparing grapheme material in 2004, because its particular structure and photoelectric property, grapheme material has been subjected to attention widely.Mono-layer graphite is because its big specific surface area, good conduction, heat conductivility and low thermal expansivity and be considered to desirable material.It for example has following performance: 1. high strength, Young's modulus (1,100GPa), breaking tenacity (125GPa); 2. high heat conductance (5,000W/mK); 3. high conductivity, high carrier transmission rate (200,000cm
2/ Vs); 4. high-specific surface area (calculated value: 2,630m
2/ g).Especially because its high conductivity, the textural property of the two-dimensional nano yardstick of big specific surface area and unimolecular layer thereof, grapheme material can be used as electrode materials in ultracapacitor and lithium ion battery.Up to the present, the method for preparing Graphene has many kinds, wherein oxidation-reduction method is a kind ofly can prepare Graphene and the higher method of productive rate in a large number, whole process relates to graphite oxidation is become graphite oxide, graphite oxide is further peeling off the generation graphene oxide under external force, and chemistry or thermal reduction are Graphene again.Chemical reduction is a kind of method of comparatively simply reducing Graphene, and it is conducive to the compound of Graphene and other materials.But the Graphene after the reduction is easy to reunite, and causes the forfeiture of some performances, also is difficult to processing simultaneously, is unfavorable for industrialization.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of method for preparing grapheme material is provided, described method is based on the graphite oxide aqueous solution of oxidation style preparation, its spraying drying is gone forward side by side the reduction of promoting the circulation of qi atmosphere and obtains to have the Graphene microballoon of vesicular structure.
The present invention adopts following technical scheme:
1) graphene oxide is added in the dispersion medium to obtain the suspension of graphene oxide;
2) with described spray dried, thereby obtain the graphene oxide particle;
3) by the atmosphere method of reducing described graphene oxide particle is reduced.
Used graphene oxide can pass through oxidation style (for example hummers improved method) preparation in the step 1).In described oxidation style, Graphite Powder 99 and oxygenant are reacted at a certain temperature, thereby make graphite oxide.Described graphite oxide is further peeling off the generation graphene oxide under external force.Used oxygenant for example can be Potassium Persulphate, the vitriol oil, potassium permanganate etc.Oxidation style is known in those skilled in the art, for example referring to JACS, and 1958,80,1339.
In embodiments of the invention, used dispersion medium is water, ethanol, acetone, NMP, ionic liquid or its mixture in the step 1), is preferably water.Positively charged ion in the described ionic liquid for example is positively charged ions such as imidazoles, quaternary ammonium, carbazole, pyridine; Negatively charged ion wherein for example is fluoroboric acid root, hexafluorophosphoric acid root, two (fluoroform sulphonyl) imido negatively charged ion, two (fluorine sulphonyl) imido negatively charged ion, fluoroform sulfonic acid fluoride sulphonyl imido negatively charged ion etc.
In a preferred embodiment of the invention, in step 1), graphene oxide is added in the described dispersion medium with additive.Used additive is for can be in step 2) the spraying drying temperature or the reduction temperature of step 3) under and physics or chemical reaction take place between the graphene oxide for example to form those of new chemical structure, for example contain amino organic compound such as amino acid, urea, thiocarbamide, aromatic amine compounds (as Ursol D) etc., the organic compound of hydroxyl such as ethylene glycol, glycerine, cyclodextrin, glucose etc.; And formaldehyde etc.Described additive also can be can be in step 2) the spraying drying temperature under polymerization reaction take place, thereby form mixture with graphene oxide or cause the compound of described polyreaction, for example polymer monomer such as vinylbenzene, methacrylic acid, aniline etc. and initiator such as radical polymerization initiator, cationic polymerization initiators, anionic polymerization initiator etc.Described additive also can be and can decompose those that produce gas under the reduction temperature of step 3), as: amino acid, ammonium acetate, bicarbonate of ammonia etc.Wherein, the consumption of additive is 0.0001-30 weight % based on described dispersion medium weight, is preferably 0.001-20 weight %, 0.01-15 weight % more preferably, and more preferably 0.01-10 weight % most preferably is 0.01-5 weight %.
The applicant unexpectedly finds through studying for a long period of time, use above-mentionedly can and above-mentionedly can under the spraying drying temperature, help to form new structure as amino, hydroxyl etc. at the Graphene microballoon by the additive of polymerization reaction take place at the additive that physics or chemical reaction take place under spraying drying or the reduction temperature and between the graphene oxide, thereby obtain stable Graphene microballoon; Secondly, in the spraying drying or reduction process of graphene oxide, use and above-mentionedly can under spraying drying or reduction temperature, decompose the additive that produces gas and help to form vesicular structure at the Graphene microsphere surface.
In preferred embodiments, the graphene oxide concentration in the graphene oxide suspension in the step 1) is 0.01mg/ml to 10g/ml, is preferably 1mg/ml to 1g/ml.
In preferred embodiments, in step 1), by for example stir, mode such as ultrasonic, microwave is scattered in described graphene oxide in the dispersion medium.
In embodiments of the invention, in step 2) in, with described spray dried, thereby obtain the graphene oxide particle.Described spray drying technology can be centrifugal spraying, one or several in ullrasonic spraying, air-stream spraying or the press atomization technology.Spray drying device is known in those skilled in the art.The preferred press atomization technology that adopts.The size of described graphene oxide particle can be subjected to the isoparametric influence of concentration, intake air temperature, air outlet temperature and centrifugal speed (perhaps pressure) of raw material.Therefore, in step 2) in, preferably concentration, spray pressure, inlet temperature, air outlet temperature and the centrifugal speed parameters such as (perhaps pressure) to raw material is optimized, to obtain to have the oxyalkylene graphite granule of desired size, structure and required electrical property.Material concentration is described to the graphene oxide concentration in the suspension of step 1) as mentioned.The inventor is surprised to find that through studying for a long period of time, implementing the oxyalkylene graphite granule that spraying drying can obtain to have desired size, structure and required electrical property under the following processing condition: in the press atomization technology, spray pressure can be 1-10MPa, preferred 4-6MPa; Inlet temperature can be 120-200 ° of C, preferred 140-160 ° of C; Air outlet temperature can be 80-120 ° of C, preferred 90-100 ° of C.In the centrifugal spraying technology, centrifugal speed can be 50-10000 rev/min, preferred 2000-5000 rev/min.The diameter of gained oxyalkylene graphite granule is 100nm to 100 μ m, is preferably 500nm to 5 μ m.
In step 3), will be available from step 2 by atmosphere reduction) the reduction of graphene oxide particle.Described reduction is carried out under reducing atmosphere.Described reducing atmosphere can be H
2, NH
3, BH
3, PH
3, H
2Among the S etc. one or more, the wherein optional N that adds
2Reduction temperature is 60-1000 ° of C, preferred 60-800 ° of C, more preferably 60-600 ° of C, more preferably 60-400 ° of C, more preferably 60-200 ° of C, more preferably 60-150 ° of C still, still more preferably 80-120 ° of C, most preferably 90-100 ° of C.Described reduction reaction can be carried out in the preferred tube furnace at the high-temperature atmosphere Reaktionsofen.Described reduction can be by placing tube furnace with gained graphene oxide particle, and sealing feeds one or more H
2, NH
3, BH
3, PH
3, H
2The gas of S etc. (is wherein chosen wantonly and is added N
2), be warming up to required reduction temperature and carry out.Recovery time is 10 minutes to 10 hours, is preferably 30 minutes to 2 hours.
Surprisingly, the inventor finds to adopt the method for the invention described above can obtain the stable porous graphite alkene particle with micro nano structure through studying for a long period of time.In this article, " micro nano structure " means gained porous graphite alkene particle and has micron order or nano level primary particle diameter, and has micron order and nano grade pore on each particle.
More surprisingly, the inventor is through studying for a long period of time, if find earlier available from step 2) the graphene oxide particle carry out subzero treatment, subsequently it is carried out pyroprocessing, can obtain to have the porous graphite alkene particle of better properties and micro nano structure.
Above-mentioned low temperature and pyroprocessing are carried out in the following way: the graphene oxide particle that obtains is placed tube furnace, and sealing feeds one or more H
2, NH
3, BH
3, PH
3, H
2The gas of S etc. (is wherein chosen wantonly and is added N
2), carry out earlier subzero treatment at a lower temperature, form the graphene oxide micron particle of porous, subsequently at comparatively high temps and one or more H
2, NH
3, BH
3, PH
3, H
2The atmosphere of S (is wherein chosen wantonly and is added N
2) under carry out pyroreaction and handle, cooling obtains the Graphene particle of stable porous.
Therefore, in a preferred embodiment of the invention, the present invention relates to a kind of method for preparing grapheme material, described method comprises the steps:
1) graphene oxide is added in the dispersion medium to obtain the suspension of graphene oxide;
2) with described spray dried, thereby obtain the graphene oxide particle;
3) at first under lower-temperature atmosphere the reduction described oxyalkylene graphite granule, under high-temperature atmosphere, reduce subsequently, obtain stable porous graphite alkene microballoon thus.
Relating in the preferred embodiment that lower-temperature atmosphere reduction and high-temperature atmosphere reduce, above to step 1) and 2 above-mentioned) description and the preferred embodiment thereof done be applicable to this preferred embodiment too.Particularly, relate in the preferred embodiment that lower-temperature atmosphere is reduced and high-temperature atmosphere reduces above-mentioned:
(1) used graphene oxide can pass through oxidation style (for example hummers improved method) preparation in the step 1).
(2) used dispersion medium is water, ethanol, acetone, NMP, ionic liquid or its mixture in the step 1), is preferably water.Positively charged ion in the described ionic liquid for example is positively charged ions such as imidazoles, quaternary ammonium, carbazole, pyridine; Negatively charged ion wherein for example is fluoroboric acid root, hexafluorophosphoric acid root, two (fluoroform sulphonyl) imido negatively charged ion, two (fluorine sulphonyl) imido negatively charged ion, fluoroform sulfonic acid fluoride sulphonyl imido negatively charged ion etc.
(3) in this preferred embodiment, in step 1), graphene oxide is added in the described dispersion medium with additive.Used additive is for can be in step 2) the spraying drying temperature or the reduction temperature of step 3) under and physics or chemical reaction take place between the graphene oxide for example to form those of new chemical structure, for example contain amino organic compound such as amino acid, urea, thiocarbamide, aromatic amine compounds (as Ursol D) etc., the organic compound of hydroxyl such as ethylene glycol, glycerine, cyclodextrin, glucose etc.; And formaldehyde etc.Described additive also can be can be in step 2) the spraying drying temperature under polymerization reaction take place, thereby form mixture with graphene oxide or cause the compound of described polyreaction, for example polymer monomer such as vinylbenzene, methacrylic acid, aniline etc. and initiator such as radical polymerization initiator, cationic polymerization initiators, anionic polymerization initiator etc.Described additive also can be and can decompose those that produce gas under the reduction temperature of step 3), as: amino acid, ammonium acetate, bicarbonate of ammonia etc.Wherein, the consumption of additive is 0.0001-30 weight % based on described dispersion medium weight, is preferably 0.001-20 weight %, 0.01-15 weight % more preferably, and more preferably 0.01-10 weight % most preferably is 0.01-5 weight %.
(4) the graphene oxide concentration in the graphene oxide suspension in the step 1) is 0.01mg/ml to 10g/ml, is preferably 1mg/ml to 1g/ml.
(5) in step 1), by for example stir, mode such as ultrasonic, microwave is scattered in described graphene oxide in the dispersion medium.
(6) in step 2) in, with described spray dried, thereby obtain the graphene oxide particle.Described spray drying technology can be centrifugal spraying, one or several in ullrasonic spraying, air-stream spraying or the press atomization technology.Spray drying device is known in those skilled in the art.The preferred press atomization technology that adopts.The size of described graphene oxide particle can be subjected to the isoparametric influence of concentration, intake air temperature, air outlet temperature and centrifugal speed (perhaps pressure) of raw material.Therefore, in step 2) in, preferably concentration, spray pressure, inlet temperature, air outlet temperature and the centrifugal speed parameters such as (perhaps pressure) to raw material is optimized, to obtain to have the oxyalkylene graphite granule of desired size, structure and required electrical property.Material concentration is described to the graphene oxide concentration in the described suspension as mentioned.The inventor is surprised to find that through studying for a long period of time, implementing the oxyalkylene graphite granule that spraying drying can obtain to have desired size, structure and required electrical property under the following processing condition: in the press atomization technology, spray pressure can be 1-10MPa, preferred 4-6MPa; Inlet temperature can be 120-200 ° of C, preferred 140-160 ° of C; Air outlet temperature can be 80-120 ° of C, preferred 90-100 ° of C.In the centrifugal spraying technology, centrifugal speed can be 50-10000 rev/min, preferred 2000-5000 rev/min.The diameter of gained oxyalkylene graphite granule is 100nm to 100 μ m, is preferably 500nm-5 μ m.
The contriver finds unexpectedly that through long-term further investigation described lower-temperature atmosphere reduction helps further to remove moisture and the unsettled Sauerstoffatom that adsorbs on the described graphene oxide particle surface, forms vesicular structure thus; And high-temperature atmosphere subsequently also proper energy make Graphene further crosslinked, thereby form stable porous graphite alkene microballoon.
Described lower-temperature atmosphere reduction is carried out under the temperature of 80-200 ° of C usually, preferably at 100-180 ° of C, more preferably carries out under 150 ° of C.Described high-temperature atmosphere reduction is carried out under the temperature that is higher than 200 ° of C to 1000 ° of C usually, preferably at 400-800 ° of C, more preferably carries out under 600 ° of C.The low-temperature reduction time is 10 minutes to 5 hours, is preferably 30 minutes to 2 hours; The high temperature reduction time is 10 minutes to 5 hours, is preferably 30 minutes to 2 hours.
Relate in this preferred embodiment that lower-temperature atmosphere is reduced and high-temperature atmosphere reduces above-mentioned, used atmosphere is H in the step 3)
2, NH
3, BH
3, PH
3, H
2Among the S etc. one or more, the wherein optional N that adds
2Wherein, the reducing atmosphere in described lower-temperature atmosphere reduction and the high-temperature atmosphere reduction can be identical or different, and is preferably identical.
The porous graphite alkene microballoon that obtains by the inventive method has micron order or nano-grade size, has been covered with micron and nano grade pore on the described microballoon.
Therefore, in one embodiment of the invention, the present invention relates to a kind of porous graphite alkene microballoon, it has micron order or nano-grade size, it is characterized in that, has micron and nano grade pore on the described microballoon.Described porous graphite alkene microballoon can obtain by method of the present invention.
Porous graphite alkene microballoon of the present invention is very suitable for preparing the electrode materials of ultracapacitor, and electrical condenser prepared therefrom has electrical properties such as excellent charging and discharging, cyclic voltammetric, life-span.
The method that is prepared electrical condenser by the Graphene microballoon is that those skilled in the art are known, and it for example can comprise the steps: that batch mixing, stirring, coating, compressing tablet, cut-parts, assembling are to form the button electrical condenser.Electrical condenser by porous graphite alkene microballoon preparation of the present invention has chemical properties such as excellent charging and discharging, cyclic voltammetric, life-span.Especially, greater than 80F/g, resistance to pressure is greater than 3.5V by the capacity of the organic electrolyte system of the electrical condenser of porous graphite alkene microballoon of the present invention preparation, and high rate performance is greater than 10A/g, the long lifetime 1000 times〉80%.
Porous graphite alkene microballoon of the present invention is the useful as catalysts carrier also, for example is used in the reaction of fuel cell or lithium-air battery cathode catalysis redox oxygen molecule; And as infrared optical material, for example be used for the instrument of electromagnetic shielding object.
Therefore, in one embodiment of the invention, the present invention relates to the purposes of porous graphite alkene microballoon of the present invention, wherein used as the electrode materials of ultracapacitor, be used as support of the catalyst or infrared optical material.
The advantage of porous graphite alkene method for preparing microsphere of the present invention is: this Graphene microballoon possesses the stable vesicular structure of micro/nano level simultaneously, the grapheme material (simple nano level Graphene is assembled easily, causes the forfeiture of various performances) that is different from nanostructure and macrostructure again.By spray drying technology and atmosphere reduction technique can magnanimity preparation, be convenient to suitability for industrialized production, the powder body material of micro nano structure of the present invention both can retention stable, the size that obtains the Graphene particle is similar with the physical properties of the ultracapacitor absorbent charcoal material that uses in the market with monodispersity, can be dispersed in preferably in the solvent, directly replace existing product, can mate existing production technique preferably, be convenient to technology and be connected.
Therefore, the present invention relates to following technical scheme:
1. method for preparing grapheme material, it comprises the steps:
1) graphene oxide is added in the dispersion medium to obtain the suspension of graphene oxide;
2) with described spray dried, thereby obtain the graphene oxide particle;
3) by the atmosphere reduction described graphene oxide particle is reduced.
2. according to the 1st method, wherein in step 1), also in described suspension, adding additive; Wherein said additive is for can be in step 2) the spraying drying temperature or the reduction temperature of step 3) under and physics or chemical reaction take place between graphite oxide or the Graphene to form those of new chemical structure, for example contain amino organic compound such as amino acid, urea, thiocarbamide, aromatic amine compound such as Ursol D, the organic compound of hydroxyl such as ethylene glycol, glycerine, cyclodextrin, glucose; And formaldehyde; Can be in step 2) the spraying drying temperature under polymerization reaction take place, thereby form mixture with graphene oxide or cause the compound of described polyreaction, for example polymer monomer such as vinylbenzene, methacrylic acid, aniline and initiator such as radical polymerization initiator, cationic polymerization initiators, anionic polymerization initiator; Can under the reduction temperature of step 3), decompose those that produce gas, as amino acid, ammonium acetate, bicarbonate of ammonia.
3. according to the 2nd method, the consumption of wherein said additive is 0.0001-30 weight % based on described dispersion medium weight, is preferably 0.001-20 weight %, 0.01-15 weight % more preferably, and more preferably 0.01-10 weight % most preferably is 0.01-5 weight %.
4. according to each method of 1-3, wherein step 2) in spraying drying be centrifugal spraying, one or several in ullrasonic spraying, air-stream spraying or the press atomization; Be preferably centrifugal spraying or press atomization.
5. according to the 4th method, wherein in the press atomization technology, spray pressure is 1-10MPa, preferred 4-6MPa, and inlet temperature is 120-200 ° of C, preferred 140-160 ° of C, air outlet temperature is 80-120 ° of C, preferred 90-100 ° of C; In the centrifugal spraying technology, centrifugal speed is 50-10000 rev/min, preferred 2000-5000 rev/min.
6. according to each method among the 1-5, wherein the reduction of the atmosphere in the step 3) is carried out under reducing atmosphere, and described reducing atmosphere is H
2, NH
3, BH
3, PH
3, H
2Among the S one or more, the wherein optional N that adds
2
7. according to each method among the 1-6, wherein reduction temperature is 60-1000 ° of C in the step 3), preferred 60-800 ° of C, more preferably 60-600 ° of C, more preferably 60-400 ° of C, more preferably 60-200 ° of C, more preferably 60-150 ° of C still, still more preferably 80-120 ° of C, most preferably 90-100 ° of C; Recovery time is 10 minutes to 10 hours, is preferably 30 minutes to 2 hours.
8. method for preparing grapheme material, it comprises the steps:
1) graphene oxide is added in the dispersion medium to obtain the suspension of graphene oxide;
2) with described spray dried, thereby obtain the graphene oxide particle;
3) at first under lower-temperature atmosphere the reduction described oxyalkylene graphite granule, under high-temperature atmosphere, reduce subsequently, obtain porous graphite alkene microballoon thus.
9. according to the 8th method, wherein the temperature of lower-temperature atmosphere reduction is 80-200 ° of C, is preferably 100-180 ° of C, more preferably 150 ° of C; The temperature of high-temperature atmosphere reduction is preferably 400-800 ° of C, more preferably 600 ° of C for being higher than 200 ° of C to 1000 ° of C.
10. according to the 8th or 9 method, wherein the time of lower-temperature atmosphere reduction and high-temperature atmosphere reduction is 10 minutes to 5 hours, is preferably 30 minutes to 2 hours.
11. according to each method among the 8-10, wherein in step 1), also in described suspension, adding additive; Wherein said additive is for can be in step 2) the spraying drying temperature or the reduction temperature of step 3) under and physics or chemical reaction take place between graphite oxide or the Graphene to form those of new chemical structure, for example contain amino organic compound such as amino acid, urea, thiocarbamide, aromatic amine compound such as Ursol D, the organic compound of hydroxyl such as ethylene glycol, glycerine, cyclodextrin, glucose; And formaldehyde; Can be in step 2) the spraying drying temperature under polymerization reaction take place, thereby form mixture with graphene oxide or cause the compound of described polyreaction, for example polymer monomer such as vinylbenzene, methacrylic acid, aniline and initiator such as radical polymerization initiator, cationic polymerization initiators, anionic polymerization initiator; Can under the reduction temperature of step 3), decompose those that produce gas, as amino acid, ammonium acetate, bicarbonate of ammonia.
12. according to the 11st method, wherein the consumption of additive is 0.0001-30 weight % based on described dispersion medium weight, is preferably 0.001-20 weight %, 0.01-15 weight % more preferably, and more preferably 0.01-10 weight % most preferably is 0.01-5 weight %.
13. according to each method among the 8-12, wherein step 2) in spraying drying be centrifugal spraying, one or several in ullrasonic spraying, air-stream spraying or the press atomization; Be preferably centrifugal spraying or press atomization.
14. according to the 13rd method, wherein in the press atomization technology, spray pressure is 1-10MPa, preferred 4-6MPa, and inlet temperature is 120-200 ° of C, preferred 140-160 ° of C, air outlet temperature is 80-120 ° of C, preferred 90-100 ° of C; In the centrifugal spraying technology, centrifugal speed is 50-10000 rev/min, preferred 2000-5000 rev/min.
15. according to each method among the 8-14, wherein the reduction of the low temperature in the step 3) and high-temperature atmosphere is carried out under reducing atmosphere, described reducing atmosphere is H
2, NH
3, BH
3, PH
3, H
2Among the S one or more, the wherein optional N that adds
2
16. grapheme material that obtains by each method among the 1-15.
17. obtain or according to the purposes of the 16th grapheme material by each method among the 1-15, wherein used as the electrode materials of ultracapacitor, as support of the catalyst or infrared optical material.
Description of drawings
Fig. 1 is according to the stereoscan photograph of embodiment 1 by the porous graphite alkene particle of spraying drying and the acquisition of atmosphere reduction reaction.
Fig. 2 be followed successively by with the charging and discharging curve of the ultracapacitor of the porous graphite alkene granules preparation of embodiment 1 (3.5V, 2.7V), cyclic voltammetry curve and cycle life curve.Wherein the little figure among last figure of Fig. 2 is the partial enlarged drawing of big figure wherein.
Embodiment
But further elaborating the present invention those skilled in the art below by embodiment understands; embodiments of the invention are not construed as limiting the scope of the present invention; any improvement and variation of making on basis of the present invention is all within protection scope of the present invention.
Among the embodiment, described particle diameter is taken pictures by SEM hereinafter, obtains by the SEM photo is measured then.
1) obtains graphene oxide (referring to JACS, 1958,80,1339) by oxidation reduction process (hummers improved method).
Its concrete steps are that 20g50 order Graphite Powder 99,10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 80 ° of C, stir, and cooling 6h, washing is to neutrality, drying.Dried sample is added in the vitriol oil of 0 ° of C, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on 20 ° below the C, behind the maintenance 2h, slowly adds the 920mL deionized water then in the oil bath of 35 ° of C.After 15 minutes, add 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide) again, the mixture color becomes glassy yellow afterwards, suction filtration while hot, be that 10% hydrochloric acid washs with 5L concentration again, suction filtration, vacuum-drying 48h namely obtains graphene oxide under 60 ° of C.
2) prepare the graphene oxide microballoon by spraying drying
10 grams are added in the deionized water of 500 grams ultra-sonic dispersion, thereby the unit for uniform suspension of acquisition Graphene by the graphene oxide that step 1) obtains with 2 gram additive urea.Spray pressure at 1MPa, the inlet temperature of 120 ° of C is under the air outlet temperature of 80 ° of C, by spray-drier (model SY-600, Shanghai generation biological company limited far away) with described spray dried, obtaining particle diameter thus is the graphene oxide microballoon of 2-10 μ m.
3) by atmosphere reduction preparation porous graphite alkene microballoon
With 2 grams by step 2) the graphite oxide microballoon that obtains places tube furnace, sealing.At first, temperature is risen to 150 ° of C, and feed H with 0.5L/ minute flow velocity
2/ N
2Thereby, carry out low-temperature reduction.H wherein
2With N
2Volume ratio be 1:9, the time of low-temperature reduction is 30 minutes.Subsequently, keeping reducing atmosphere (that is, flow velocity, H
2With N
2Volume ratio) under the constant situation, temperature is risen to 600 ° of C, continue reaction 2 hours, obtain porous graphite alkene microballoon.Subsequently, make temperature be down to room temperature, take out described porous graphite alkene microballoon.
Use the porous graphite alkene microballoon of sem observation gained.Fig. 1 has shown the stereoscan photograph of gained porous graphite alkene microballoon.As seen from Figure 1, it is 5-15 μ m that described porous graphite alkene microballoon is of a size of particle diameter, and each microsphere surface has been covered with nano level pore structure.
4) prepare ultracapacitor by porous graphite alkene microballoon
To be the ratio of 85:5:10 according to mass ratio according to the porous graphite alkene microballoon of method for preparing as positive electrode material, described porous graphite alkene microballoon, polyvinylidene difluoride (PVDF) binding agent and conductive agent acetylene black will evenly be mixed to obtain slurry.Subsequently, described slurry scraper is coated on the aluminium foil, dry, roll film, cut edge and handle, thus make the ultracapacitor pole piece.Order lamination according to electrode slice, barrier film, electrode slice is assembled into electric core subsequently, use battery housing seal electricity core again, inject tetraethyl ammonium fluoroboric acid/acetonitrile electrolytic solution by the spout that is arranged on the battery container in battery container subsequently, the sealing spout obtains ultracapacitor.Test chemical properties such as it discharges and recharges, cyclic voltammetric, life-span.Gained the results are shown among Fig. 2.Capacitor produced capacity, resistance to pressure, high rate performance and life-span are summarized in the table 1.
Embodiment 2
1) obtains graphene oxide (selecting from JACS, 1958,80,1339) by oxidation reduction process (hummers improved method);
Obtain graphene oxide according to the method identical with embodiment 1.
2) prepare the graphene oxide microballoon by spraying drying
100 grams are added in the deionized water of 500 grams ultra-sonic dispersion, thereby the unit for uniform suspension of acquisition Graphene by the graphene oxide that step 1) obtains with 20 gram additive Ursol D.At the spray pressure of 10MPa, the inlet temperature of 200 ° of C under the air outlet temperature of 95 ° of C, with described spray dried, obtains to be of a size of the graphene oxide microballoon that particle diameter is 2-10 μ m by spray-drier (model SY-600) thus.
3) by atmosphere reduction preparation porous graphite alkene microballoon
With 2 grams by step 2) the graphite oxide microballoon that obtains places tube furnace, sealing.At first, temperature is risen to 120 ° of C, and feed NH with 0.5L/ minute flow velocity
3/ N
2Thereby, carry out low-temperature reduction.NH wherein
3With N
2Volume ratio be 1:9, the time of low-temperature reduction is 30 minutes.Subsequently, keeping reducing atmosphere (that is, flow velocity, NH
3With N
2Volume ratio) under the constant situation, temperature is risen to 1000 ° of C, continue reaction 2 hours, obtain porous graphite alkene microballoon.Subsequently, make temperature be down to room temperature, take out described porous graphite alkene microballoon.
Use the porous graphite alkene microballoon of sem observation gained.Electronic Speculum result shows that the particle diameter of described porous graphite alkene microballoon is 2-8 μ m, and each microsphere surface has been covered with nano level pore structure.
4) prepare ultracapacitor by porous graphite alkene microballoon
According to embodiment 1 described method, use the porous graphite alkene microballoon that is obtained by step 3) to prepare ultracapacitor.Measure capacity, resistance to pressure, high rate performance and the life-span of gained ultracapacitor, the results are summarized in the table 1.
Embodiment 3
1) obtains graphene oxide (selecting from JACS, 1958,80,1339) by oxidation reduction process (hummers improved method);
Obtain graphene oxide according to the method identical with embodiment 1.
2) prepare the graphene oxide microballoon by spraying drying
1 gram is added in the deionized water of 500 grams ultra-sonic dispersion, thereby the unit for uniform suspension of acquisition Graphene by the graphene oxide that step 1) obtains with 0.2 gram additive formaldehyde.Spray pressure at 2MPa, the inlet temperature of 160 ° of C is under the air outlet temperature of 80 ° of C, by spray-drier (model SY-600, Shanghai generation biological company limited far away) with described spray dried, obtaining particle diameter thus is the graphene oxide microballoon of 2-10 μ m.
3) by atmosphere reduction preparation porous graphite alkene microballoon
With 2 grams by step 2) the graphite oxide microballoon that obtains places tube furnace, sealing.At first, temperature is risen to 200 ° of C, and feed BH with 0.5L/ minute flow velocity
3/ N
2Thereby, carry out low-temperature reduction.BH wherein
3With N
2Volume ratio be 1:9, the time of low-temperature reduction is 30 minutes.Subsequently, keeping reducing atmosphere (that is, flow velocity, BH
3With N
2Volume ratio) under the constant situation, temperature is risen to 400 ° of C, continue reaction 2 hours, obtain porous graphite alkene microballoon.Subsequently, make temperature be down to room temperature, take out described porous graphite alkene microballoon.
Use the porous graphite alkene microballoon of sem observation gained.Electronic Speculum result shows that the particle diameter of described porous graphite alkene microballoon is 1-10 μ m, and each microsphere surface has been covered with micron and nano level pore structure.
4) prepare ultracapacitor by porous graphite alkene microballoon
According to embodiment 1 described method, use the porous graphite alkene microballoon that is obtained by step 3) to prepare ultracapacitor.Measure capacity, resistance to pressure, high rate performance and the life-span of gained ultracapacitor, the results are summarized in the table 1.
Embodiment 4
1) obtains graphene oxide (selecting from JACS, 1958,80,1339) by oxidation reduction process (hummers improved method);
Obtain graphene oxide according to the method identical with embodiment 1.
2) prepare the graphene oxide microballoon by spraying drying
10 grams are added in the deionized water of 500 grams ultra-sonic dispersion, thereby the unit for uniform suspension of acquisition Graphene by the graphene oxide that step 1) obtains with 2 gram additive bicarbonate of ammonia.At the spray pressure of 5MPa, the inlet temperature of 120 ° of C, under the air outlet temperature of 80 ° of C, with described spray dried, obtaining particle diameter thus is the graphene oxide microballoon of 2-10 μ m by spray-drier (model SY-600).
3) by atmosphere reduction preparation porous graphite alkene microballoon
With 2 grams by step 2) the graphite oxide microballoon that obtains places tube furnace, sealing.At first, temperature is risen to 80 ° of C, and feed PH with 0.5L/ minute flow velocity
3/ N
2Thereby, carry out low-temperature reduction.PH wherein
3With N
2Volume ratio be 1:9, the time of low-temperature reduction is 30 minutes.Subsequently, keeping reducing atmosphere (that is, flow velocity, BH
3With N
2Volume ratio) under the constant situation, temperature is risen to 250 ° of C, continue reaction 1 hour, obtain porous graphite alkene microballoon.Subsequently, make temperature be down to room temperature, take out described porous graphite alkene microballoon.
Use the porous graphite alkene microballoon of sem observation gained.Electronic Speculum result shows that the particle diameter of described Graphene microballoon is 1-15 μ m, and each microsphere surface has been covered with micron and nano level pore structure.
4) prepare ultracapacitor by porous graphite alkene microballoon
According to embodiment 1 described method, use the porous graphite alkene microballoon that is obtained by step 3) to prepare ultracapacitor.Measure capacity, resistance to pressure, high rate performance and the life-span of gained ultracapacitor, the results are summarized in the table 1.
The method that is similar to embodiment 1 prepares the Graphene microballoon, and difference is, with step 2) the graphite oxide microballoon that obtains reductase 12 hour under 400 ° of C.Use the thus obtained porous graphite alkene of sem observation microballoon.Electronic Speculum result shows that the particle diameter of described porous graphite alkene microballoon is 2-10 μ m, and each microsphere surface has been covered with nano level pore structure.
According to embodiment 1 described method, use described porous graphite alkene microballoon to prepare ultracapacitor.Measure capacity, resistance to pressure, high rate performance and the life-span of gained ultracapacitor, the results are summarized in the table 1.
The method that is similar to embodiment 5 prepares the Graphene microballoon, and difference is, with step 2) the graphite oxide microballoon that obtains reductase 12 hour under 1000 ° of C.Use the thus obtained porous graphite alkene of sem observation microballoon.Electronic Speculum result shows that the particle diameter of described porous graphite alkene microballoon is 2-15 μ m, and each microsphere surface has been covered with nano level pore structure.
According to embodiment 1 described method, use described porous graphite alkene microballoon to prepare ultracapacitor.Measure capacity, resistance to pressure, high rate performance and the life-span of gained ultracapacitor, the results are summarized in the table 1.
Embodiment 7
The method that is similar to embodiment 1 prepares the Graphene microballoon, and difference is that used reducing atmosphere is H
2Use the thus obtained porous graphite alkene of sem observation microballoon.Electronic Speculum result shows that the particle diameter of described porous graphite alkene microballoon is 2-10 μ m, and each microsphere surface has been covered with micron and nano level pore structure.
According to embodiment 1 described method, use described porous graphite alkene microballoon to prepare ultracapacitor.Measure capacity, resistance to pressure, high rate performance and the life-span of gained ultracapacitor, the results are summarized in the table 1.
Embodiment 8
The method that is similar to embodiment 1 prepares the Graphene microballoon, and difference is that used reducing atmosphere is H
2/ NH
3, H wherein
2With NH
3Volume ratio be 2:8.Use the thus obtained porous graphite alkene of sem observation microballoon.Electronic Speculum result shows that the particle diameter of described porous graphite alkene microballoon is 5-15 μ m, and each microsphere surface has been covered with micron and nano level pore structure.
According to embodiment 1 described method, use described porous graphite alkene microballoon to prepare ultracapacitor.Measure capacity, resistance to pressure, high rate performance and the life-span of gained ultracapacitor, the results are summarized in the table 1.
The comparative example 1
The method that is similar to embodiment 1 prepares the Graphene microballoon, and difference is not use any additives in the process of preparation graphite oxide suspension.Use thus obtained Graphene microballoon to prepare electrical condenser, measure capacitor produced capacity, resistance to pressure, high rate performance and life-span, the results are summarized in the table 1.
The comparative example 2
The method that is similar to embodiment 1 prepares the Graphene microballoon, and difference is that at spray pressure be 20MPa, and inlet temperature is 300 ° of C, and air outlet temperature is 200 ° of C.Use thus obtained Graphene microballoon to prepare electrical condenser, measure capacitor produced capacity, resistance to pressure, high rate performance and life-span, the results are summarized in the table 1.
Table 1 is by the electrical property of the electrical condenser of Graphene microballoon preparation
| The embodiment numbering | Capacity (F/g) | Voltage (V) | High rate performance (A/g) | Life-span (1000 times) |
| 1 | 105 | 3.5V | 10A/g | 85 |
| 2 | 122 | 3.5V | 10A/g | 86 |
| 3 | 145 | 3.5V | 10A/g | 89 |
| 4 | 150 | 3.5V | 10A/g | 80 |
| 5 | 86 | 3.5V | 10A/g | 82 |
| 6 | 80 | 3.5V | 10A/g | 83 |
| 7 | 96 | 3.5V | 10A/g | 90 |
| 8 | 106 | 3.5V | 10A/g | 88 |
| The comparative example 1 | 70 | 3.5V | 10A/g | 82 |
| The comparative example 2 | 70 | 3.5V | 10A/g | 80 |
As can be seen from the above table, compare with the comparative example 1 who does not add any additives, adopt the embodiment of the invention 1-8 of additive to have higher capacity; Secondly, compare with the comparative example 2 who does not adopt preferably spray drying processing parameter of the present invention, adopt the embodiment 1-8 of preferably spray drying processing parameter of the present invention can obtain better electrical property; At last, compare with the embodiment 5-6 that under single temperature, reduces, adopt embodiment 1-4 and the 7-8 of the combination of low-temperature reduction and high temperature reduction can obtain better electrical property.
Be it can also be seen that to have good electrical properties by the ultracapacitor of porous graphite alkene microballoon of the present invention preparation by last table, capacity is greater than 80F/g, and resistance to pressure is greater than 3.5V, and high rate performance is greater than 10A/g, the long lifetime 1000 times〉80%.
Porous graphite alkene microballoon by the inventive method preparation has micron order to nano level size, and each microsphere surface has been covered with nano level pore structure.And, porous graphite alkene microballoon by the inventive method preparation can retention stable, the size that obtains the Graphene particle is similar with the physical properties of the ultracapacitor absorbent charcoal material that uses in the market with monodispersity, can be dispersed in preferably and directly replace existing product in the solvent, can mate existing production technique preferably, be convenient to technology and be connected.
Should be understood that above-mentioned statement at preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
1. method for preparing grapheme material, it comprises the steps:
1) graphene oxide is added in the dispersion medium to obtain the suspension of graphene oxide;
2) with described spray dried, thereby obtain the graphene oxide particle;
3) by the atmosphere reduction described graphene oxide particle is reduced.
2. according to the process of claim 1 wherein in step 1), also in described suspension, adding additive; Wherein said additive is for can be in step 2) the spraying drying temperature or the reduction temperature of step 3) under and physics or chemical reaction take place between graphite oxide or the Graphene to form those of new chemical structure, for example contain amino organic compound such as amino acid, urea, thiocarbamide, aromatic amine compound such as Ursol D, the organic compound of hydroxyl such as ethylene glycol, glycerine, cyclodextrin, glucose; And formaldehyde; Can be in step 2) the spraying drying temperature under polymerization reaction take place, thereby form mixture with graphene oxide or cause the compound of described polyreaction, for example polymer monomer such as vinylbenzene, methacrylic acid, aniline and initiator such as radical polymerization initiator, cationic polymerization initiators, anionic polymerization initiator; Can under the reduction temperature of step 3), decompose those that produce gas, as amino acid, ammonium acetate, bicarbonate of ammonia.
3. according to the method for claim 2, the consumption of wherein said additive is 0.0001-30 weight % based on described dispersion medium weight, is preferably 0.001-20 weight %, more preferably 0.01-15 weight %, more preferably 0.01-10 weight % most preferably is 0.01-5 weight %.
4. according to each method among the claim 1-3, wherein step 2) in spraying drying be centrifugal spraying, one or several in ullrasonic spraying, air-stream spraying or the press atomization; Be preferably centrifugal spraying or press atomization.
5. according to the method for claim 4, wherein in the press atomization technology, spray pressure is 1-10MPa, preferred 4-6MPa, and inlet temperature is 120-200 ° of C, preferred 140-160 ° of C, air outlet temperature is 80-120 ° of C, preferred 90-100 ° of C; In the centrifugal spraying technology, centrifugal speed is 50-10000 rev/min, preferred 2000-5000 rev/min.
6. according to each method among the claim 1-5, wherein the reduction of the atmosphere in the step 3) is carried out under reducing atmosphere, and described reducing atmosphere is H
2, NH
3, BH
3, PH
3, H
2Among the S one or more, the wherein optional N that adds
2
7. according to each method among the claim 1-6, wherein reduction temperature is 60-1000 ° of C in the step 3), preferred 60-800 ° of C, more preferably 60-600 ° of C, more preferably 60-400 ° of C, more preferably 60-200 ° of C, still more preferably 60-150 ° of C, still more preferably 80-120 ° of C, most preferably 90-100 ° of C; Recovery time is 10 minutes to 10 hours, is preferably 30 minutes to 2 hours.
8. method for preparing grapheme material, it comprises the steps:
1) graphene oxide is added in the dispersion medium to obtain the suspension of graphene oxide;
2) with described spray dried, thereby obtain the graphene oxide particle;
3) at first under lower-temperature atmosphere the reduction described oxyalkylene graphite granule, under high-temperature atmosphere, reduce subsequently, obtain porous graphite alkene microballoon thus.
9. method according to Claim 8, wherein the temperature of lower-temperature atmosphere reduction is 80-200 ° of C, is preferably 100-180 ° of C, more preferably 150 ° of C; The temperature of high-temperature atmosphere reduction is preferably 400-800 ° of C, more preferably 600 ° of C for being higher than 200 ° of C to 1000 ° of C.
10. according to Claim 8 or 9 method, wherein lower-temperature atmosphere reduction and high-temperature atmosphere time of reducing is 10 minutes to 5 hours, is preferably 30 minutes to 2 hours.
11. each method according to Claim 8-10 is wherein in step 1), also to add additive in described suspension; Wherein said additive is for can be in step 2) the spraying drying temperature or the reduction temperature of step 3) under and physics or chemical reaction take place between graphite oxide or the Graphene to form those of new chemical structure, for example contain amino organic compound such as amino acid, urea, thiocarbamide, aromatic amine compound such as Ursol D, the organic compound of hydroxyl such as ethylene glycol, glycerine, cyclodextrin, glucose; And formaldehyde; Can be in step 2) the spraying drying temperature under polymerization reaction take place, thereby form mixture with graphene oxide or cause the compound of described polyreaction, for example polymer monomer such as vinylbenzene, methacrylic acid, aniline and initiator such as radical polymerization initiator, cationic polymerization initiators, anionic polymerization initiator; Can under the reduction temperature of step 3), decompose those that produce gas, as amino acid, ammonium acetate, bicarbonate of ammonia.
12. the method according to claim 11, wherein the consumption of additive is 0.0001-30 weight % based on described dispersion medium weight, is preferably 0.001-20 weight %, more preferably 0.01-15 weight %, more preferably 0.01-10 weight % most preferably is 0.01-5 weight %.
13. each method, wherein step 2 according to Claim 8-12) in spraying drying be centrifugal spraying, one or several in ullrasonic spraying, air-stream spraying or the press atomization; Be preferably centrifugal spraying or press atomization.
14. according to the method for claim 13, wherein in the press atomization technology, spray pressure is 1-10MPa, preferred 4-6MPa, and inlet temperature is 120-200 ° of C, preferred 140-160 ° of C, air outlet temperature is 80-120 ° of C, preferred 90-100 ° of C; In the centrifugal spraying technology, centrifugal speed is 50-10000 rev/min, preferred 2000-5000 rev/min.
15. each method according to Claim 8-14, wherein the reduction of the low temperature in the step 3) and high-temperature atmosphere is carried out under reducing atmosphere, and described reducing atmosphere is H
2, NH
3, BH
3, PH
3, H
2Among the S one or more, the wherein optional N that adds
2
16. grapheme material that obtains by each method among the claim 1-15.
17. obtain or according to the purposes of the grapheme material of claim 16 by each method among the claim 1-15, wherein used as the electrode materials of ultracapacitor, as support of the catalyst or infrared optical material.
Claims (10)
1. method for preparing grapheme material, it comprises the steps:
1) graphene oxide is added in the dispersion medium to obtain the suspension of graphene oxide;
2) with described spray dried, thereby obtain the graphene oxide particle;
3) by the atmosphere reduction described graphene oxide particle is reduced.
2. according to the process of claim 1 wherein in step 1), also in described suspension, adding additive; Wherein said additive is for can be in step 2) the spraying drying temperature or the reduction temperature of step 3) under and physics or chemical reaction take place between graphite oxide or the Graphene to form those of new chemical structure, for example contain amino organic compound such as amino acid, urea, thiocarbamide, aromatic amine compound such as Ursol D, the organic compound of hydroxyl such as ethylene glycol, glycerine, cyclodextrin, glucose; And formaldehyde; Can be in step 2) the spraying drying temperature under polymerization reaction take place, thereby form mixture with graphene oxide or cause the compound of described polyreaction, for example polymer monomer such as vinylbenzene, methacrylic acid, aniline and initiator such as radical polymerization initiator, cationic polymerization initiators, anionic polymerization initiator; Can under the reduction temperature of step 3), decompose those that produce gas, as amino acid, ammonium acetate, bicarbonate of ammonia.
3. according to the method for claim 2, the consumption of wherein said additive is 0.0001-30 weight % based on described dispersion medium weight, is preferably 0.001-20 weight %, more preferably 0.01-15 weight %, more preferably 0.01-10 weight % most preferably is 0.01-5 weight %.
4. according to each method among the claim 1-3, wherein in the press atomization technology, spray pressure is 1-10MPa, preferred 4-6MPa, and inlet temperature is 120-200 ° of C, preferred 140-160 ° of C, air outlet temperature is 80-120 ° of C, preferred 90-100 ° of C; In the centrifugal spraying technology, centrifugal speed is 50-10000 rev/min, preferred 2000-5000 rev/min.
5. method for preparing grapheme material, it comprises the steps:
1) graphene oxide is added in the dispersion medium to obtain the suspension of graphene oxide;
2) with described spray dried, thereby obtain the graphene oxide particle;
3) at first under lower-temperature atmosphere the reduction described oxyalkylene graphite granule, under high-temperature atmosphere, reduce subsequently, obtain porous graphite alkene microballoon thus.
6. according to the method for claim 5, wherein the temperature of lower-temperature atmosphere reduction is 80-200 ° of C, is preferably 100-180 ° of C, more preferably 150 ° of C; The temperature of high-temperature atmosphere reduction is preferably 400-800 ° of C, more preferably 600 ° of C for being higher than 200 ° of C to 1000 ° of C.
7. according to each method among the claim 5-6, wherein in step 1), also in described suspension, adding additive; Wherein said additive is for can be in step 2) the spraying drying temperature or the reduction temperature of step 3) under and physics or chemical reaction take place between graphite oxide or the Graphene to form those of new chemical structure, for example contain amino organic compound such as amino acid, urea, thiocarbamide, aromatic amine compound such as Ursol D, the organic compound of hydroxyl such as ethylene glycol, glycerine, cyclodextrin, glucose; And formaldehyde; Can be in step 2) the spraying drying temperature under polymerization reaction take place, thereby form mixture with graphene oxide or cause the compound of described polyreaction, for example polymer monomer such as vinylbenzene, methacrylic acid, aniline and initiator such as radical polymerization initiator, cationic polymerization initiators, anionic polymerization initiator; Can under the reduction temperature of step 3), decompose those that produce gas, as amino acid, ammonium acetate, bicarbonate of ammonia.
8. according to each method of claim 5-7, wherein the reduction of the low temperature in the step 3) and high-temperature atmosphere is carried out under reducing atmosphere, and described reducing atmosphere is H
2, NH
3, BH
3, PH
3, H
2Among the S one or more, the wherein optional N that adds
2
9. grapheme material that obtains by each method of claim 1-8.
10. obtain by each method of claim 1-8 or according to the purposes of the grapheme material of claim 9, wherein used as the electrode materials of ultracapacitor, as support of the catalyst or infrared optical material.
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| CN110093032B (en) * | 2019-04-28 | 2021-09-24 | 中科广化（重庆）新材料研究院有限公司 | Nitrogen-sulfur co-doped graphene/polyaniline aerogel and preparation method and application thereof |
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