CN102923689A - Method for preparing grapheme/carbon composite material - Google Patents
Method for preparing grapheme/carbon composite material Download PDFInfo
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- CN102923689A CN102923689A CN2012104395595A CN201210439559A CN102923689A CN 102923689 A CN102923689 A CN 102923689A CN 2012104395595 A CN2012104395595 A CN 2012104395595A CN 201210439559 A CN201210439559 A CN 201210439559A CN 102923689 A CN102923689 A CN 102923689A
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Abstract
The invention provides a method for preparing a grapheme/carbon composite material. The method comprises steps of mixing and reacting aniline monomer, an oxidant and mesomorphic grapheme oxide, obtaining a grapheme oxide/polyaniline compound, mixing and reacting the obtained grapheme oxide/polyaniline compound and an activating agent and obtaining the grapheme/carbon composite material. The aniline monomer and the mesomorphic grapheme oxide serve as raw materials and are mixed completely, polyaniline is produced among layers of grapheme oxide, the agglomeration phenomenon during the grapheme activating process can be avoided effectively, the polyaniline attached to grapheme surfaces forms a multi-hole carbon material through the activating treatment, and the prepared grapheme/carbon composite material has good capacitive and cycle performance.
Description
Technical field
The present invention relates to the Graphene technical field, relate in particular to a kind of graphene/carbon composite manufacture method.
Background technology
Ultracapacitor is a kind of novel energy-storing element between electrical condenser and battery, have the energy density height, the speed that discharges and recharges is fast, power density is high, have extended cycle life, safety performance is good, low-temperature performance is superior and the good characteristic such as pollution-free and non-maintaining, is widely used in the fields such as electromobile, electronic product.
At present, the electrode materials of ultracapacitor mainly is gac, it has that specific surface area is large, capacity is large, catalytic performance is superior, stability and the good advantage of chemical property, but the surface of gac mostly is microvoid structure, so that the surperficial shared proportion that can be used effectively is lower, limited the capacity performance of material, further developed thereby restricted it.Find after deliberation, Graphene has huge theoretical specific surface area and the specific conductivity of superelevation, can improve largely specific storage and the cycle performance of ultracapacitor, but Graphene is very easily reunited in the process of preparation, so that its specific surface area reduces, thereby affected the specific storage of material, existing grapheme material specific storage does not far reach the theoretical specific capacity of 500F/g.
Prior art generally with the additive of conductive polymers as grapheme material, is improved its chemical property.Polyaniline is the representative of conductive polymers, has good environmental stability and higher oxidation-reduction quality, and theoretical specific capacity is greater than 1000F.g
-1But the electric conductivity of polyaniline is not high, and in charge and discharge cycles, the volume of polyaniline expands/contraction change, causes macromolecular chain to destroy, and finally causes the electrical property of polyaniline electrode material to descend, and this has just limited the application of polyaniline material.Research is found, Graphene and polyaniline are compounded to form grapheme/polyaniline composite material, utilizes the synergistic effect of Graphene and polyaniline, not only can improve the cyclical stability of polyaniline, can also reduce the internal resistance of matrix material.The high congruence of stone has been reported a kind of preparation method of graphene/polyaniline combination electrode material, the method is filtered Graphene and is obtained the graphene/polyaniline combination electrode material with polyaniline nano fiber mixing final vacuum, but Graphene is very easily reunited in the method, and polyaniline can not be well and Graphene compound, adopt the very difficult matrix material that obtains even structure of above-mentioned technology, affected the chemical property of material.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of graphene/carbon composite manufacture method, and the graphene/carbon matrix material for preparing has good volumetric properties and cycle performance.
The invention provides a kind of graphene/carbon composite manufacture method, may further comprise the steps:
A) aniline monomer, oxygenant and mesomorphic graphene oxide are mixed, react, obtain graphene oxide/Polyaniline;
B) with steps A) obtain the graphene/carbon matrix material after graphene oxide/Polyaniline of obtaining and activator mix, the reaction.
Preferably, the described mesomorphic graphene oxide graphene oxide colloidal sol that is concentration 0.1mg/mL ~ 15mg/mL.
Preferably, the mass ratio of described graphene oxide and aniline monomer is 0.05 ~ 15:1.
Preferably, the mol ratio of described aniline monomer and oxygenant is 0.5 ~ 10:1.
Preferably, the mass ratio of described graphene oxide/Polyaniline and activator is 1:0.05 ~ 150.
Preferably, described steps A) be specially: aniline monomer, oxygenant, acid solution and mesomorphic graphene oxide are mixed, react, obtain graphene oxide/Polyaniline.
Preferably, described acid solution is selected from any one or a few in hydrochloric acid soln, sulphuric acid soln and the perchloric acid solution.
Preferably, the concentration of described acid solution is 0.05mol/L ~ 5mol/L.
Preferably, described oxygenant is selected from any one or a few in ammonium persulphate, iron(ic) chloride, Manganse Dioxide and the Potassium Iodate; Described activator is selected from any one or a few in potassium hydroxide, zinc chloride, nitric acid and the phosphoric acid.
Preferably, described steps A) in, the condition of described reaction is hydro-thermal reaction, temperature of reaction is 100 ℃ ~ 300 ℃.
Preferably, described step B) in, the temperature of described reaction is 300 ℃ ~ 1500 ℃, the time of described reaction is 2h ~ 48h.
Compared with prior art, the present invention at first mixes aniline monomer, oxygenant and mesomorphic graphene oxide, reaction, obtains graphene oxide/Polyaniline; Then will can obtain the graphene/carbon matrix material after graphene oxide/Polyaniline of obtaining and activator mix, the reaction.It is raw material that the present invention adopts aniline monomer and mesomorphic graphene oxide, it is fully mixed, generated polyaniline at the graphene oxide interlayer, can prevent effectively that agglomeration from appearring in Graphene in reactivation process, activation treatment can make the polyaniline that is attached to the Graphene surface form porous carbon materials simultaneously, thereby makes the graphene/carbon matrix material for preparing have good volumetric properties and cycle performance.
The graphene/carbon matrix material for preparing is carried out electro-chemical test, and the result shows graphene/carbon matrix material provided by the invention when current density is 5A/g, and specific storage is about 200F/g, circulates 10000 times, and its capability retention is more than 93%.
Description of drawings
Fig. 1 is the x-ray photoelectron energy spectrogram of the graphene/carbon matrix material of the embodiment of the invention 1 preparation;
Fig. 2 is the scanning electron microscope diagram of the graphene/carbon matrix material of the embodiment of the invention 1 preparation;
Fig. 3 is the constant current charge-discharge graphic representation of graphene/carbon matrix material when different current density of the embodiment of the invention 1 preparation;
Fig. 4 is the cyclic curve figure of graphene/carbon matrix material under current density 5A/g condition of the embodiment of the invention 1 preparation.
Embodiment
The invention provides a kind of graphene/carbon composite manufacture method, may further comprise the steps:
A) aniline monomer, oxygenant and mesomorphic graphene oxide are mixed, react, obtain graphene oxide/Polyaniline;
B) with steps A) obtain the graphene/carbon matrix material after graphene oxide/Polyaniline of obtaining and activator mix, the reaction.
It is raw material that the present invention adopts aniline monomer and mesomorphic graphene oxide, it is fully mixed, generated polyaniline at the graphene oxide interlayer, can prevent effectively that agglomeration from appearring in Graphene in reactivation process, activation treatment can make the polyaniline that is attached to the Graphene surface form porous carbon materials simultaneously, thereby makes the graphene/carbon matrix material for preparing have good volumetric properties and cycle performance.
The present invention at first mixes aniline monomer, oxygenant and mesomorphic graphene oxide, reaction, obtains graphene oxide/Polyaniline; Then will can obtain the graphene/carbon matrix material after graphene oxide/Polyaniline of obtaining and activator mix, the reaction.
The present invention is take aniline monomer as raw material, and the source of described aniline monomer is not had particular requirement, can be for generally commercially available.
Oxygenant of the present invention is preferably any one or a few in ammonium persulphate, iron(ic) chloride, Manganse Dioxide and the Potassium Iodate, more preferably any one in ammonium sulfate or the Potassium Iodate.The present invention there is no particular requirement to the source of described oxygenant, can be for generally commercially available.
The present invention is take mesomorphic graphene oxide as raw material, and described mesomorphic graphene oxide is preferably the graphene oxide colloidal sol of concentration 0.1mg/mL ~ 15mg/mL, more preferably the graphene oxide colloidal sol of concentration 1mg/mL ~ 10mg/mL.The present invention there is no particular requirement to the preparation method of described graphene oxide colloidal sol, can be preparation method well known to those skilled in the art, the present invention is in accordance with the following methods preparation preferably: graphene oxide solution is cleaned to sulfate radical-free repeatedly with deionized water, then the graphite oxide aqueous solution that obtains is processed 20min ~ 2h in whizzer, can obtain the mesomorphic graphene oxide water-sol.The present invention there is no particular requirement to the source of described graphene oxide solution, can be for general commercially available or obtain according to the Hummer legal system is standby.The present invention there is no particular requirement to described whizzer, can be general commercially available whizzer, and the present invention is preferably the whizzer of 5000r/min ~ 10000r/min.
The present invention at first mixes aniline monomer, oxygenant and mesomorphic graphene oxide, and the mass ratio of described graphene oxide and aniline monomer is preferably 0.05 ~ 15:1, more preferably 0.1 ~ 10:1.The mol ratio of described aniline monomer and oxygenant is preferably 0.5 ~ 10:1, more preferably 1 ~ 5:1.The present invention there is no particular restriction to the order by merging of described aniline monomer, oxygenant and mesomorphic graphene oxide, is preferably first aniline monomer and mesomorphic graphene oxide are mixed, and then it is mixed with aqueous oxidizing agent solution.
After aniline monomer, oxygenant and the mixing of mesomorphic graphene oxide, react, obtain graphene oxide/Polyaniline.The present invention does not have particular requirement to described reactive mode, can be reactive mode well known to those skilled in the art, and the present invention is preferably hydro-thermal reaction, and the temperature of described hydro-thermal reaction is preferably 100 ℃ ~ 300 ℃, more preferably 150 ℃ ~ 250 ℃; The time of described reaction is preferably 3h ~ 12h, more preferably 5h ~ 10h.
Further, the present invention preferably in the process of preparation graphene oxide/Polyaniline, adds acid solution, is about to aniline monomer, oxygenant, acid solution and mesomorphic graphene oxide and mixes.The present invention there is no particular restriction to the order of described mixing, is preferably oxygenant is dissolved in the acid solution, and is added drop-wise in the mixing solutions of aniline monomer and mesomorphic graphene oxide.Among the present invention, described acid solution is preferably any one or a few in hydrochloric acid soln, sulphuric acid soln and the perchloric acid solution, more preferably any one in hydrochloric acid soln or the sulphuric acid soln.The concentration of described acid solution is preferably 0.05mol/L ~ 5mol/L, more preferably 0.1mol/L ~ 2mol/L.The present invention there is no particular restriction to the consumption of described acid solution, oxygenant fully can be dissolved to get final product.
After obtaining graphene oxide/Polyaniline, with itself and activator mix, obtain the graphene/carbon matrix material after the reaction.The mass ratio of described graphene oxide/Polyaniline and activator is preferably 1:0.05 ~ 150, more preferably 1:1 ~ 100.The temperature of described reaction is preferably 300 ℃ ~ 1500 ℃, more preferably 500 ℃ ~ 1000 ℃.The time of described reaction is 2h ~ 48h, more preferably 3h ~ 24h.The present invention preferably reacts under nitrogen protection.Among the present invention, described activator is preferably any one or a few in potassium hydroxide, zinc chloride, nitric acid and the phosphoric acid, more preferably any one in potassium hydroxide or the phosphoric acid.The present invention there is no particular restriction to the source of described activator, can be for generally commercially available.
After preparing the graphene/carbon matrix material, it is carried out electro-chemical test, the result shows graphene/carbon matrix material provided by the invention when current density is 5A/g, and specific storage is about 200F/g, circulates 10000 times, and its capability retention is more than 93%.
The present invention at first mixes aniline monomer, oxygenant and mesomorphic graphene oxide, reaction, obtains graphene oxide/Polyaniline; Then will can obtain the graphene/carbon matrix material after graphene oxide/Polyaniline of obtaining and activator mix, the reaction.It is raw material that the present invention adopts aniline monomer and mesomorphic graphene oxide, it is fully mixed, generated polyaniline at the graphene oxide interlayer, can prevent effectively that agglomeration from appearring in Graphene in reactivation process, mesomorphic graphene oxide is because interlamellar spacing only is several nanometers simultaneously, so that Graphene and polyaniline can close contacts, the carbonization polyaniline that forms after the activation treatment can well be attached to the Graphene surface, thereby makes the graphene/carbon matrix material for preparing have good volumetric properties and cycle performance.
In order to further specify the present invention, below in conjunction with embodiment graphene/carbon composite manufacture method provided by the invention is described in detail.
Embodiment 1
With the standby graphene oxide solution of Hummer legal system, detect till occur without white precipitate with barium chloride solution after repeatedly cleaning with deionized water, then this graphite oxide aqueous solution is processed 30min in 5000 ~ 10000r/min whizzer, can obtain concentration range is the liquid crystal state graphene oxide colloidal sol of 0.1mg/mL ~ 15mg/mL.
Embodiment 2
Be that the graphene oxide water-sol of 1mg/mL mixes with 1g aniline monomer and 100mL concentration, the 2.33g ammonium persulphate fully is dissolved in the 20mL deionized water, then slowly drop in the mixed sols of aniline monomer and graphene oxide, then 200 ℃ of reaction 8h in the hydro-thermal tank obtain graphene oxide/polyaniline combination product with reaction product after with deionized water and washing with alcohol; Then graphene oxide/the Polyaniline that 1g is obtained mixes with 1g potassium hydroxide also fully puts into tube furnace after the grinding, and 500 ℃ of reaction 48h under nitrogen protection with deionized water wash and after drying, obtain the graphene/carbon matrix material with product.
The graphene/carbon matrix material for preparing is carried out x-ray photoelectron scanning, and the results are shown in Figure 1, Fig. 1 is the x-ray photoelectron energy spectrogram of the graphene/carbon matrix material of the embodiment of the invention 1 preparation.As shown in Figure 1, its x-ray photoelectron spectrum curve has obvious nitrogen element peak, and the nitrogen element derives from the polyaniline carbon material after the activation treatment, and this shows that method provided by the invention can successfully make the graphene/carbon matrix material.
The graphene/carbon matrix material for preparing is carried out scanning electronic microscope to be detected, the results are shown in Figure 2, Fig. 2 is the scanning electron microscope diagram of the graphene/carbon matrix material of the embodiment of the invention 1 preparation, and as shown in Figure 2, graphene/carbon matrix material provided by the invention is reunited.
Graphene/carbon matrix material provided by the invention is carried out electro-chemical test, and test result is seen Fig. 3 and Fig. 4.Fig. 3 is the constant current charge-discharge graphic representation of graphene/carbon matrix material when different current density of the embodiment of the invention 1 preparation, and Fig. 4 is the cyclic curve figure of graphene/carbon matrix material under current density 5A/g condition of the embodiment of the invention 1 preparation.As shown in Figure 3, this matrix material is under current density 5A/g condition, and initial specific storage can reach 210F/g.As shown in Figure 4, this matrix material circulates 10000 times under current density 5A/g condition, and capability retention is 98%.
Embodiment 3
Be that the graphene oxide water-sol of 10mg/mL mixes with 0.1g aniline monomer and 100mL concentration, 0.046g iron(ic) chloride fully is dissolved in the hydrochloric acid that 20mL concentration is 2mol/L, then slowly drop in the mixed sols of aniline monomer and graphene oxide, then 100 ℃ of reaction 10h in the hydro-thermal tank obtain graphene oxide/polyaniline combination product with reaction product after with deionized water and washing with alcohol; Then graphene oxide/the Polyaniline that 1g is obtained mixes with the 100g zinc chloride also fully puts into tube furnace after the grinding, and 1000 ℃ of reaction 2h under nitrogen protection with deionized water wash and after drying, obtain the graphene/carbon matrix material with product.
The graphene/carbon matrix material for preparing is carried out x-ray photoelectron scanning, and its x-ray photoelectron spectrum curve has obvious nitrogen element peak, shows successfully to have made the graphene/carbon matrix material.
The scanning electronic microscope detected result shows that the graphene/carbon matrix material of preparation is reunited.
Graphene/carbon matrix material provided by the invention is carried out electro-chemical test, and the result shows this matrix material under current density 5A/g condition, and initial specific storage can reach 200F/g, circulates 10000 times, and capability retention is 94%.
Embodiment 4
Be that the graphene oxide water-sol of 5mg/mL mixes with 0.1g aniline monomer and 100mL concentration, the 0.116g Potassium Iodate fully is dissolved in the sulfuric acid that 20mL concentration is 0.1mol/L, then slowly drop in the mixed sols of aniline monomer and graphene oxide, then 300 ℃ of reaction 5h in the hydro-thermal tank obtain graphene oxide/polyaniline combination product with reaction product after with deionized water and washing with alcohol; Then graphene oxide/the Polyaniline that 1g is obtained mixes with 50g phosphoric acid also fully puts into tube furnace after the grinding, and 800 ℃ of reaction 24h under nitrogen protection with deionized water wash and after drying, obtain the graphene/carbon matrix material with product.
The graphene/carbon matrix material for preparing is carried out x-ray photoelectron scanning, and its x-ray photoelectron spectrum curve has obvious nitrogen element peak, shows successfully to have made the graphene/carbon matrix material.
The scanning electronic microscope detected result shows that the graphene/carbon matrix material of preparation is reunited.
Graphene/carbon matrix material provided by the invention is carried out electro-chemical test, and the result shows this matrix material under current density 5A/g condition, and initial specific storage can reach 198F/g, circulates 10000 times, and capability retention is 93%.
Be that the graphene oxide water-sol of 8mg/mL mixes with 0.2g aniline monomer and 50mL concentration, the 0.232g Potassium Iodate fully is dissolved in the sulfuric acid that 20mL concentration is 0.5mol/L, then slowly drop in the mixed sols of aniline monomer and graphene oxide, then 250 ℃ of reaction 6h in the hydro-thermal tank obtain graphene oxide/polyaniline combination product with reaction product after with deionized water and washing with alcohol; Then graphene oxide/the Polyaniline that 2g is obtained mixes with 60g potassium hydroxide also fully puts into tube furnace after the grinding, and 900 ℃ of reaction 3h under nitrogen protection with deionized water wash and after drying, obtain the graphene/carbon matrix material with product.
The graphene/carbon matrix material for preparing is carried out x-ray photoelectron scanning, and its x-ray photoelectron spectrum curve has obvious nitrogen element peak, shows successfully to have made the graphene/carbon matrix material.
The scanning electronic microscope detected result shows that the graphene/carbon matrix material of preparation is reunited.
Graphene/carbon matrix material provided by the invention is carried out electro-chemical test, and the result shows this matrix material under current density 5A/g condition, and initial specific storage can reach 205F/g, circulates 10000 times, and capability retention is 96%.
By above-described embodiment and comparative example as can be known, graphene/carbon matrix material provided by the invention has good volumetric properties and cycle performance.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (11)
1. a graphene/carbon composite manufacture method is characterized in that, may further comprise the steps:
A) aniline monomer, oxygenant and mesomorphic graphene oxide are mixed, react, obtain graphene oxide/Polyaniline;
B) with steps A) obtain the graphene/carbon matrix material after graphene oxide/Polyaniline of obtaining and activator mix, the reaction.
2. preparation method according to claim 1 is characterized in that, described steps A) in, the graphene oxide colloidal sol that described mesomorphic graphene oxide is concentration 0.1mg/mL ~ 15mg/mL.
3. preparation method according to claim 1 is characterized in that, described steps A) in, the mass ratio of described graphene oxide and aniline monomer is 0.05 ~ 15:1.
4. preparation method according to claim 1 is characterized in that, described steps A) in, the mol ratio of described aniline monomer and oxygenant is 0.5 ~ 10:1.
5. preparation method according to claim 1 is characterized in that, described step B) in, the mass ratio of described graphene oxide/Polyaniline and activator is 1:0.05 ~ 150.
6. preparation method according to claim 1 is characterized in that, described steps A) be specially: aniline monomer, oxygenant, acid solution and mesomorphic graphene oxide are mixed, react, obtain graphene oxide/Polyaniline.
7. preparation method according to claim 6 is characterized in that, described acid solution is selected from any one or a few in hydrochloric acid soln, sulphuric acid soln and the perchloric acid solution.
8. preparation method according to claim 7 is characterized in that, the concentration of described acid solution is 0.05mol/L ~ 5mol/L.
9. described preparation method is characterized in that according to claim 1 ~ 6, and described oxygenant is selected from any one or a few in ammonium persulphate, iron(ic) chloride, Manganse Dioxide and the Potassium Iodate; Described activator is selected from any one or a few in potassium hydroxide, zinc chloride, nitric acid and the phosphoric acid.
10. preparation method according to claim 1 is characterized in that, described steps A) in, the condition of described reaction is hydro-thermal reaction, temperature of reaction is 100 ℃ ~ 300 ℃.
11. preparation method according to claim 1 is characterized in that, described step B) in, the temperature of described reaction is 300 ℃ ~ 1500 ℃, the time of described reaction is 2h ~ 48h.
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| CN112863893B (en) * | 2021-01-11 | 2022-05-27 | 扬州工业职业技术学院 | Composite biochar-based material, and preparation method and application thereof |
| CN114058155A (en) * | 2021-12-23 | 2022-02-18 | 广东格瑞新材料股份有限公司 | High-thermal-conductivity liquid crystal polymer material and preparation method thereof |
| CN114058155B (en) * | 2021-12-23 | 2024-02-06 | 广东格瑞新材料股份有限公司 | High-heat-conductivity liquid crystal polymer material and preparation method thereof |
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