CN108101030B - Preparation method of three-dimensional porous graphene material - Google Patents
Preparation method of three-dimensional porous graphene material Download PDFInfo
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- CN108101030B CN108101030B CN201810131171.6A CN201810131171A CN108101030B CN 108101030 B CN108101030 B CN 108101030B CN 201810131171 A CN201810131171 A CN 201810131171A CN 108101030 B CN108101030 B CN 108101030B
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- C01B2204/00—Structure or properties of graphene
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- C01B2204/32—Size or surface area
Abstract
The invention discloses a preparation method of a three-dimensional porous graphene material, which comprises the steps of mixing hot-melt resin powder, a template agent and deionized waterAfter uniformly stirring, transferring into a reaction kettle, treating at a certain temperature and for a certain time, cooling to room temperature along with the furnace temperature, drying moisture, finally transferring into a heating furnace for pyrolysis in a vacuum or atmosphere protection environment, washing a pyrolysis product to be neutral by deionized water, and drying to obtain the three-dimensional porous graphene material; the specific surface area of the obtained three-dimensional porous graphene material is more than 800m2The material has excellent electrochemical energy storage performance when being used as a negative electrode material of a lithium ion battery, and can be expanded to be used in a super capacitor.
Description
Technical Field
The invention belongs to the technical field of porous material preparation, and particularly relates to a preparation method of a three-dimensional (3D) graphene material with a porous structure.
Background
The carbon material with a porous structure has a better spatial configuration, and can be widely applied to the fields of energy, environment and catalysis, so that research on the carbon material with the porous structure becomes a current research hotspot. At present, a carbon material with a porous structure is usually constructed by a self-assembly method, a hydrothermal method or a template method by using a precursor of a carbon nanotube, graphene or other types of carbon, and can be directly used for an electrode of a battery or a capacitor, or a carrier of a catalyst to improve catalytic performance, and can also be assembled into an adsorbing material of harmful substances in the environment. Zishou Zhang, et al, a carbon material with a Three-dimensional structure is prepared by selecting a carbon nano tube, an ethylene vinyl acetate copolymer and polyacrylamide, and the prepared material is used in an electrode of a super capacitor, and the result shows that the specific capacity performance maintaining efficiency of the carbon material with the Three-dimensional structure after charging and discharging reach 45000 times reaches more than 95% (Zhang, Z.S. et al, Three-dimensional carbon nanotube/ethylene acetate/polyanaline a high performance electron for supercapacitors, J Mater Chem A2015, 3 (5), 1884 1889.); hui Mao et al polypropylene and acrylic acid and NaHCO3Preparing carbon spheres (-COOH-PS) containing carboxylate radical by using deionized water to act together to prepare template method, making said carbon spheres react with platinum chloride and glucose in hydrochloric acid and aqueous solution, washing, drying and protectingThe Carbon material with three-dimensional platinum (Pt) particles is obtained by atmosphere sintering and is used for the oxidation process of Carbon monoxide (CO), and the result shows that the Carbon material with the three-dimensional structure has higher catalytic activity (Mao, H. et al, high hly active and stable heterologous catalysts based on the experimental method of non-metallic nanoparticles in 3D ordered porous Carbon n.Carbon 2016, 96, 75-82.); kyoungso kim.et al, synthesizes porous three-dimensional graphene carbon material on a zeolite template by employing lanthanide catalysis, which is removed using a mixed acid of hydrofluoric acid and hydrochloric acid (Kim, k. et al, Lanthanum-catalyzed synthesis of microporosius 3D graphene-like carbon in zeolite template Nature 2016, 535 (7610), 131).
Therefore, in the preparation process of the 3D porous carbon material, the preparation by adopting the self-assembly method usually needs multi-step reactions, and the template removal method for preparing the porous structure carbon material usually needs template removal, and the template removal usually needs inorganic strong acid or strong base, which inevitably needs some special requirements on experimental equipment, especially the preparation of large-batch materials. Meanwhile, strong acid and strong base inevitably bring environmental problems, and the development direction of modern green chemical industry is not met. Therefore, how to realize simple and large-scale process and green preparation of the porous structure carbon material has important significance.
Disclosure of Invention
The invention aims to provide a green, environment-friendly and efficient preparation method of a three-dimensional porous graphene material aiming at the defects of the prior art.
The technical scheme adopted by the invention is as follows:
a preparation method of a three-dimensional porous graphene material comprises the following steps: stirring hot-melt resin powder, a template agent and deionized water uniformly, transferring the mixture into a reaction kettle, treating the mixture at a certain temperature for a certain time, cooling the mixture to room temperature along with the furnace temperature, drying the water, transferring the dried mixture into a heating furnace for pyrolysis in a vacuum or atmosphere protection environment, washing the pyrolysis product to be neutral by the deionized water, and drying the product to obtain the three-dimensional porous graphene material; the hot-melt resin is one or a mixture of polyethylene, polycarbonate, polyamide, polymethyl methacrylate and polyethylene terephthalate; the template agent is one or a mixture of any more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and the total addition amount of the template agent is 10-400% of the mass of the hot-melt resin.
Preferably, in the preparation method of the three-dimensional porous graphene material, the temperature in the reaction hot kettle is 100-200 ℃ and the time is 1-20 hours.
Preferably, in the preparation method of the three-dimensional porous graphene material, the drying is performed in a hot oven, the temperature is controlled to be 40-120 ℃, and the time is 6-20 hours.
Preferably, in the preparation method of the three-dimensional porous graphene material, the atmosphere is nitrogen, argon or helium.
Preferably, in the preparation method of the three-dimensional porous graphene material, the pyrolysis temperature is 500-1000 ℃.
Preferably, in the preparation method of the three-dimensional porous graphene material, the drying is freeze drying or vacuum drying, wherein the freeze drying temperature is-50 to-10 ℃, and the vacuum drying temperature is 50 to 120 ℃.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, through a large number of experiments, a specific resin and a template matched with the resin are screened, and the selected template has good water solubility and catalytic property, so that the template can be removed through pyrolysis and washing after preparation, and inorganic strong acid or alkali is not required. And the specific surface area of the prepared three-dimensional porous graphene-like material is more than 800m2And the material is used as a negative electrode material of a lithium ion battery and has excellent electrochemical energy storage performance.
Drawings
Fig. 1 is an X-ray diffraction pattern (XRD) of a 3D porous graphene material prepared from PC;
fig. 2 is a Scanning Electron Microscope (SEM) image of a 3D porous graphene material prepared from PC;
FIG. 3 is a Transmission Electron Microscope (TEM) image of a 3D porous graphene material prepared from PC;
fig. 4 is a specific surface area diagram (BET) of a 3D porous graphene material prepared from PC;
FIG. 5 shows that the amount of the 3D porous graphene material prepared from PC is 100 mA g-1Capacity plot at current;
fig. 6 is an SEM image of a 3D porous graphene material prepared from PET and PE;
fig. 7 is an SEM image of a 3D porous graphene material prepared from PMMA.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention in any way.
Example 1
10 grams (g) of polycarbonate, 10g of sodium bicarbonate and 8 milliliters (ml) of deionized water were stirred together to form a homogeneous mixture. And then transferring the uniformly mixed substance into a PTFE reaction kettle (a stainless steel sleeve is arranged outside the PTFE reaction kettle), putting the reaction kettle into an oven, heating to 160 ℃, keeping the temperature for 5 hours (h), cooling to room temperature along with the temperature of the oven, taking out the reaction kettle, drying in the oven, putting the reaction kettle into a ceramic crucible, heating to 700 ℃ at the rate of 5 ℃ per minute (DEG C/min) in a vacuum atmosphere furnace, keeping the temperature for 5 hours, naturally cooling along with the temperature of the oven, and taking out. Washing the reaction product with deionized water until the pH value of the filtrate is 7, and drying in a vacuum drying oven at 65 ℃ (DEG C) for 12h to obtain a product with a specific surface area of 1150 m2The graphene material is a 3D porous graphene-like material. The prepared material is used as a negative electrode material of a lithium ion battery and is tested at 100 mA g-1When the battery is charged and discharged for 60 circles under current, the specific capacity can reach 705 mAh g-1. In which fig. 1 is an X-ray diffraction pattern (XRD) of a 3D porous graphene material prepared using PC as a raw material, fig. 2 is an SEM of the 3D porous graphene material prepared using PC as a raw material, fig. 3 is a TEM of the 3D porous graphene material prepared using PC as a raw material, fig. 4 is a BET of the 3D porous graphene material prepared using PC as a raw material, and fig. 5 is a BET of the 3D porous graphene material prepared using PC as a raw material at 100 mA g-1Capacity graph at current.
Example 2
15 g of polyethylene terephthalate (PET) and 5g of polyethylene were stirred together with 15 g of sodium carbonate and 10 ml of deionized water to form a homogeneous mixture. Then transferring the uniformly mixed substance into a PTFE reaction kettle (a stainless steel sleeve is arranged outside the PTFE reaction kettle), putting the reaction kettle into an oven, heating to 180 ℃, keeping the temperature for 4 hours, cooling to room temperature along with the temperature of the oven, taking out the reaction kettle, drying the reaction kettle in the oven, and putting the reaction kettle into a ceramic crucible in nitrogen (N)2) And (3) heating the furnace to 800 ℃ at the speed of 6 ℃/min in a protective atmosphere furnace, keeping the temperature for 3 hours, naturally cooling along with the furnace temperature, and taking out. Washing the reaction product with deionized water until the pH value of the filtrate is 7, and then drying in a freeze drying device at-40 ℃ for 12h to obtain the product with the specific surface area of 1100 m2The prepared material is used as a negative electrode material of a lithium ion battery, and the prepared material is tested at 500 mA g-1When the battery is charged and discharged for 100 circles under current, the specific capacity can reach 605 mAh g-1。
Example 3
15 g of polymethyl methacrylate (PMMA) and 10g of potassium carbonate are taken, mixed powder of 10g of potassium bicarbonate and 10 ml of deionized water are stirred together to form a uniform mixture. And then transferring the uniformly mixed substances into a PTFE reaction kettle (a stainless steel sleeve is arranged outside the PTFE reaction kettle), putting the reaction kettle into an oven, heating to 200 ℃, keeping the temperature for 3 hours, cooling to room temperature along with the temperature of the oven, taking out the reaction kettle, drying in the oven, putting the reaction kettle into a ceramic crucible, heating to 850 ℃ at the speed of 6 ℃/min in an argon (Ar) protective atmosphere furnace, keeping the temperature for 2 hours, and naturally cooling along with the temperature of the oven, and taking out. Washing the reaction product with deionized water until the pH value of the filtrate is 7, and drying the filtrate in a vacuum drying oven at 80 ℃ for 10 hours to obtain the product with the specific surface area of 1050 m2The prepared material is used as a negative electrode material of a lithium ion battery, and the prepared material is tested at 1000 mA g of a 3D porous graphene-like material (see figure 7)-1When the battery is charged and discharged for 100 circles under current, the specific capacity can reach 496 mAh g-1。
Example 4
In the examples1, replacing polycarbonate with polyamide and replacing sodium bicarbonate with potassium carbonate, and obtaining the product with the specific surface area of 1200 m under the same conditions2The graphene material is a 3D porous graphene-like material. Test it at 100 mA g-1When the battery is charged and discharged for 60 circles under current, the specific capacity can reach 710 mAh g-1The performance is substantially equivalent to that of example 1.
Claims (1)
1. A preparation method of a three-dimensional porous graphene material is characterized by comprising the following steps:
taking 10g of polycarbonate, 10g of sodium bicarbonate and 8 ml of deionized water, and stirring the polycarbonate, the sodium bicarbonate and the deionized water together to form a uniform mixture; then transferring the uniformly mixed substances into a PTFE reaction kettle, arranging a stainless steel sleeve outside, putting the reaction kettle into an oven, heating to 160 ℃, keeping the temperature for 5 hours, cooling to room temperature along with the temperature of the oven, taking out the reaction kettle, drying the reaction kettle in the oven, putting the reaction kettle into a ceramic crucible, heating to 700 ℃ at the rate of 5 ℃ per minute in a vacuum atmosphere furnace, keeping the temperature for 5 hours, naturally cooling along with the temperature of the furnace, and taking out; washing the reaction product with deionized water until the pH value of the filtrate is 7, and drying the filtrate in a vacuum drying oven at 65 ℃ for 12 hours to obtain a 3D porous graphene material; the prepared material is used as a negative electrode material of a lithium ion battery and is tested at 100 mA g-1When the battery is charged and discharged for 60 circles under current, the specific capacity can reach 705 mAh g-1。
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| CN103663448A (en) * | 2012-09-19 | 2014-03-26 | 天津普兰纳米科技有限公司 | Preparation method of carbon material, obtained carbon material and application thereof |
| CN105502359A (en) * | 2015-12-22 | 2016-04-20 | 福州大学 | Preparation method of low-cost porous graphene |
| CN106058173A (en) * | 2016-06-14 | 2016-10-26 | 中南大学 | Graphene-like carbon material/sulphur composite cathode material for lithium-sulphur battery, and preparation method and application thereof |
| CN106744859A (en) * | 2017-01-22 | 2017-05-31 | 广西大学 | Graphene three-dimensional multistage pore structure powder prepared by a kind of low temperature polymer cracking |
| CN107301922A (en) * | 2017-06-07 | 2017-10-27 | 中国人民解放军国防科学技术大学 | Three-dimensional porous graphene nano material and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103663448A (en) * | 2012-09-19 | 2014-03-26 | 天津普兰纳米科技有限公司 | Preparation method of carbon material, obtained carbon material and application thereof |
| CN105502359A (en) * | 2015-12-22 | 2016-04-20 | 福州大学 | Preparation method of low-cost porous graphene |
| CN106058173A (en) * | 2016-06-14 | 2016-10-26 | 中南大学 | Graphene-like carbon material/sulphur composite cathode material for lithium-sulphur battery, and preparation method and application thereof |
| CN106744859A (en) * | 2017-01-22 | 2017-05-31 | 广西大学 | Graphene three-dimensional multistage pore structure powder prepared by a kind of low temperature polymer cracking |
| CN107301922A (en) * | 2017-06-07 | 2017-10-27 | 中国人民解放军国防科学技术大学 | Three-dimensional porous graphene nano material and its preparation method and application |
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