CN105060287A - Preparation method of connected and wound mesh-shaped graphene materials used for supercapacitors - Google Patents
Preparation method of connected and wound mesh-shaped graphene materials used for supercapacitors Download PDFInfo
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Abstract
The invention discloses a preparation method of connected and wound mesh-shaped graphene materials used for supercapacitors, and belongs to the technical field of novel carbon materials. According to the method, anthracene oil serves as a carbon source, nanometer calcium carbonate serves as a template, potassium hydroxide serves as an activating agent, N,N-dimethylformamide is added to make anthracene oil, nanometer calcium carbonate and potassium hydroxide evenly mixed, the mixture is then placed in a tubular furnace and heated under the argon atmosphere, and the target product is directly prepared. Low-price calcium carbonate serves as the template, anthracene oil serves as the carbon source, and the prepared connected and wound mesh-shaped graphene materials have the advantages of being high in capacity, large in available energy density, and the like. The materials are used as electrode materials of the symmetrical type supercapacitors; in BMIMPF6 ionic liquid electrolyte and under the current density of 0.05 A/g, the specific volume of the materials is 256 F/g, and the available energy density reaches up to 143 Wh/kg and can compared favorably with the energy density of lithium ion batteries.
Description
Technical field
The invention belongs to novel charcoal material technical field, be specifically related to a kind of ultracapacitor preparation method that is interconnective and the graphene net material rolled.
Background technology
Ultracapacitor is also known as double layer capacitor, it is a kind of novel energy-storing element between traditional capacitor and battery, have charge-discharge velocity fast, have extended cycle life, the advantage such as environmentally friendly, obtain applying more and more widely in fields such as industry, consumer electronics, communication, medicine equipment, national defence, military equipment, traffic.The significant parameter of ultracapacitor has capacity, power density and energy density etc., its specific storage C=KS/d, power density P=V
2/ 4R
2, energy density E=1/2CV
2.Therefore, preparation has the electrode materials of reasonable pore structure and selects the electrolytic solution of wider electromotive force window to be of great significance the chemical property tool improving ultracapacitor.
Graphene is a kind of novel Two-dimensional Carbon nano material, and its basic structure is with sp by carbon atom
2the six-ring that hydridization is formed.Single-layer graphene only has the thickness of an atom, and the monoatomic layer structure of its uniqueness gives the physical and chemical performance of its excellence.Grapheme material at room temperature has high carrier mobility (10000cm
2/ V/s), the theoretical specific surface area (2630m of superelevation
2/ g) and excellent thermal conductivity (3000-5000W/m/K).In addition, also there is stable chemical property, therefore, be widely used on the energy storage devices such as field emission device, sun power and wind energy.Current, commercial graphite alkene is prepared primarily of graphite oxide, and the price of graphite oxide is up to 1000 yuan/gram, causes holding at high price of Graphene.The performance of Graphene and price are primarily of decisions such as carbon source used and preparation technologies.Except being that raw material is prepared except Graphene with graphite or graphite oxide, grapheme material can also be prepared with the high molecular polymer of coal raw materials, biomass material, carbon containing and Organometallic complexes etc.
China is coal production big country, and carbolineum is cut the cut of 280 ~ 360 DEG C, and the price of carbolineum is only at about 0.005 yuan/gram.Carbolineum has cheapness, is easy to get, low ash and be rich in the advantages such as many cyclophanes fragrance structural unit.At present, wherein anthracene, phenanthrene, carbazole three kinds of components are mainly extracted to the processing of carbolineum both at home and abroad.These three kinds of components very easily form some two-pack eutectic mixtures and a series of sosoloid in the separation course of processing, separation difficulty and sepn process energy consumption is high, it is large to pollute.Explore the novel method directly being prepared High-performance graphene material by the carbolineum of cheapness, significant to industries such as biological medicine, material, metallurgy, also can realize the high value added utilization of carbolineum.
Calcium carbonate is the natural mineral of earth shell.Compared with expensive nano-metal-oxide, calcium carbonate has inexhaustible advantage.The distribution area of carbonatite reaches 5,340,000 square kilometres in the world, take up an area ball top long-pending 4%.China's carbonatite distribution area reaches 3,440,000 square kilometres, accounts for 64% of the world.Calcium carbonate has the advantages such as chemical purity high, thermally-stabilised good (can not decompose at 400 DEG C), hardness are low, nontoxic, tasteless, good dispersity, has been widely used in the fields such as papermaking, coating, pottery, food.If using calcium carbonate as original position template, be expected to the preparation realizing Authracene oil-based Graphene.Wherein, calcium carbonate obtains after carbonic acid gas and calcium oxide through pyrolytic decomposition, and it is physically activated that carbonic acid gas original position can occur, and has reaming effect to Carbon Materials, can realize the cheapness preparation of High-performance graphene material.Wherein, calcium oxide not only can adjustment aperture distribute, and can also promote that bases activator activates pore-creating.Finally, can wash away calcium oxide with dilute hydrochloric acid, this technique has pollutes little, simple operation and other advantages.
Ionic liquid refers to does not have electriccenter molecule, and 100% by a kind of nitrogenous or form containing the organic cation of phosphorus heterocycle and a kind of inorganic anion, be the material of liquid state under room temperature.Ionic liquid, owing to having extremely low vapour pressure, higher thermostability and adjustable dissolving power, can be used as green medium and is applied to organic synthesis, separating-purifying field; The electromotive force window wider due to it and adjustable acid-basicity, can be used as novel electrolytes and effective catalyst and be applied to catalytic chemistry and electrochemical research field.The energy density of ultracapacitor can be improved, so the present invention selects electromotive force window to reach the BMIMPF of 4V by the electromotive force window improving electrolytic solution
6ionic liquid is as the electrolytic solution of ultracapacitor.
Summary of the invention
The present invention with cheap and easy to get, be rich in the carbolineum of aromaticity structural unit for carbon source, DMF is solvent, and cheap nano-calcium carbonate is template, and potassium hydroxide is activator, prepares electrode for super capacitor material.
Preparation method's concrete steps of the present invention are as follows:
(1) mixing of reactant: by after nano-calcium carbonate and potassium hydroxide ground and mixed mixture, gained mixture adds and is equipped with in the beaker of carbolineum, and adds DMF, stirs said mixture and obtain reactant after evenly;
Wherein, the ratio of the quality of nano-calcium carbonate and carbolineum, nano-calcium carbonate and potassium hydroxide total mass is 1/3, and the quality of carbolineum and the mass ratio of potassium hydroxide are 1/2, and the mass ratio of DMF and nano-calcium carbonate is 17/90;
(2) the interconnective and preparation of the graphene net material rolled: the reactant that step (1) obtains is moved in corundum porcelain boat, corundum porcelain boat is placed in tube furnace, under an argon atmosphere, be warming up to 550 DEG C, after constant temperature 30min, continue the final temperature heated up diamond heating to 850 ~ 1000 DEG C, after constant temperature 60min, naturally cool to room temperature, products therefrom, after overpickling, washing and drying, obtains the interconnective and graphene net material rolled.
As one optimization, in step (1), nano-calcium carbonate is 9g, and carbolineum is 6g, and DMF is 1.7g, and potassium hydroxide is 12g; In step (2), diamond heating final temperature is 950 DEG C; Resulting materials is used as symmetric form electrode material for super capacitor, at BMIMPF
6in electrolytic solution, under the current density of 0.05A/g, its specific volume reaches 256F/g, and available energy density is up to 143Wh/kg.
Compared with prior art, the present invention has the following advantages:
1. carbolineum and nano-calcium carbonate all there is cheapness, be easy to get, low cost and other advantages, carbolineum also has low ash and is rich in the advantages such as many cyclophanes fragrance structural unit.
2. the effect of nano-calcium carbonate not only rapping plate, and after nano-calcium carbonate pyrolytic decomposition obtains calcium oxide and carbonic acid gas, carbonic acid gas also will play the physically activated effect of original position.
3. what the present invention prepared is interconnected and the electrochemical performance of the graphene net electrode materials rolled, at BMIMPF
6in electrolytic solution, its specific volume can reach 256F/g, and the available energy density of ultracapacitor, up to 143Wh/kg, can compare favourably with the energy density of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the interconnective of the embodiment of the present invention 1 preparation and the graphene net material IRGN rolled
850tEM figure.
Fig. 2 is the interconnective of the embodiment of the present invention 2 preparation and the graphene net material IRGN rolled
900tEM figure.
Fig. 3 is the interconnective of the embodiment of the present invention 3 preparation and the graphene net material IRGN rolled
950tEM figure.
Fig. 4 is the interconnective of the embodiment of the present invention 4 preparation and the graphene net material IRGN rolled
1000tEM figure.
Fig. 5 is that the interconnective and graphene net material rolled prepared of the embodiment of the present invention 1,2,3,4 is at BMIMPF
6in ionic liquid, specific volume is with the variation diagram of current density.
Fig. 6 is that the interconnective and graphene net material rolled prepared of the embodiment of the present invention 1,2,3,4 is at BMIMPF
6in ionic liquid, available energy density is with the variation diagram of power density.
Embodiment
Below in conjunction with specific embodiment in detail the present invention is described in detail, but the present invention is not limited to following embodiment, should be understood to example, those skilled in the art can carry out changing and revising on the basis of spirit and scope of the invention, and all such changes and modifications are included in the scope of the present invention.
Embodiment 1
Interconnective and the graphene net material IRGN rolled
850concrete preparation process is as follows:
(1) mixing of reactant: the nano-calcium carbonate taking 9g, the carbolineum of 6g, the potassium hydroxide of 12g.By nano-calcium carbonate and potassium hydroxide ground and mixed, gained mixture adds and is equipped with in the beaker of carbolineum, and adds 1.7gN, N-dimethylformamide, stirs said mixture and obtain reactant after evenly.
(2) the interconnective and preparation of the graphene net material rolled: the reactant that step (1) obtains is moved in corundum porcelain boat, then corundum porcelain boat is placed in tube furnace, under an argon atmosphere, 550 DEG C are warming up to 3 DEG C/min, after constant temperature 30min, continuation by diamond heating to 850 DEG C, after constant temperature 60min, naturally cools to room temperature with 3 DEG C/min temperature rise rate.The product obtained is ground, be transferred in beaker, the stirring of 40mL dilute hydrochloric acid, ultrasonic vibration is added in beaker, magnetic agitation, extremely neutral with hot distilled water washing after at room temperature leaving standstill, be placed in loft drier dry, ground 325 mesh standard sieves, obtained interconnective and the graphene net material designation rolled is IRGN
850.IRGN
850as symmetric form electrode material for super capacitor, at BMIMPF
6in electrolytic solution, under 0.05A/g current density, IRGN
850specific volume be 236F/g, available energy density reaches 128Wh/kg, and power density is 116W/kg.
Embodiment 2
Interconnective and the graphene net material IRGN rolled
900concrete preparation process is as follows:
(1) mixing of reactant: implement according to the method same with the step (1) in embodiment 1.
(2) the interconnective and preparation of the graphene net material rolled: implement according to the method same with the step (2) in embodiment 1, difference is tube furnace to be added to final temperature 900 DEG C.Obtained interconnective and the graphene net material designation rolled is IRGN
900.RGN
900as symmetric form electrode material for super capacitor, at BMIMPF
6in electrolytic solution, under 0.05A/g current density, IRGN
900specific volume be 247F/g, available energy density reaches 136Wh/kg, and power density is 111W/kg.
Embodiment 3
Interconnective and the graphene net material IRGN rolled
950concrete preparation process is as follows:
(1) mixing of reactant: implement according to the method same with the step (1) in embodiment 1.
(2) the interconnective and preparation of the graphene net material rolled: implement according to the method same with the step (2) in embodiment 1, difference is diamond heating to final temperature 950 DEG C.Obtained interconnective and the graphene net material designation rolled is IRGN
950.IRGN
950material is used as symmetric form electrode material for super capacitor, at BMIMPF
6in electrolytic solution, under 0.05A/g current density, its specific volume is 256F/g, and available energy density reaches 143Wh/kg, and power density is 107W/kg.
Embodiment 4
Interconnective and the graphene net material IRGN rolled
1000concrete preparation process is as follows:
(1) mixing of reactant: implement according to the method same with the step (1) in embodiment 1.
(2) the interconnective and preparation of the graphene net material rolled: implement according to the method same with the step (2) in embodiment 1, difference is diamond heating to final temperature 1000 DEG C.Obtained interconnective and the graphene net material designation rolled is IRGN
1000.IRGN
1000material is used as symmetric form electrode material for super capacitor, at BMIMPF
6in electrolytic solution, under 0.05A/g current density, its specific volume is 220F/g, and available energy density reaches 120Wh/kg, and power density is 116W/kg.
Claims (2)
1. ultracapacitor is with being interconnected and a preparation method for the graphene net material rolled, it is characterized in that the method processing step is as follows:
(1) mixing of reactant: by nano-calcium carbonate and potassium hydroxide ground and mixed, gained mixture adds and is equipped with in the beaker of carbolineum, adds DMF, stirs said mixture and obtain reactant after evenly;
Wherein: the ratio of the quality of nano-calcium carbonate and carbolineum, nano-calcium carbonate and potassium hydroxide total mass is 1/3, and the quality of carbolineum and the mass ratio of potassium hydroxide are 1/2, the mass ratio of DMF and nano-calcium carbonate is 17/90;
(2) to be interconnected and the preparation of the graphene net material rolled: the reactant that step (1) obtains is moved in corundum porcelain boat, corundum porcelain boat is placed in tube furnace, under an argon atmosphere, intensification is heated to 550 DEG C, after constant temperature 30min, continues the final temperature heated up diamond heating to 850 ~ 1000 DEG C, after constant temperature 60min, naturally cool to room temperature, products therefrom, after overpickling, washing and drying, obtains the interconnective and graphene net material rolled.
2. a kind of ultracapacitor as claimed in claim 1 is with being interconnected and the preparation method of the graphene net material rolled, it is characterized in that, in step (1), the quality of nano-calcium carbonate is 9g, the quality of carbolineum is 6g, the quality of DMF is 1.7g, and the quality of potassium hydroxide is 12g; In step (2), by diamond heating to final temperature 950 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105366661A (en) * | 2015-12-15 | 2016-03-02 | 安徽工业大学 | Preparation method of curled porous carbon nanometer sheet for supercapacitor |
| CN106430148A (en) * | 2016-09-05 | 2017-02-22 | 安徽工业大学 | Preparation method of washing-oil-based porous carbon nanosheet for supercapacitor |
| CN108117059A (en) * | 2018-01-17 | 2018-06-05 | 安徽工业大学 | It is a kind of to prepare method of the ultracapacitor with porous class graphene nanometer sheet |
| CN109133050A (en) * | 2018-09-25 | 2019-01-04 | 安徽工业大学 | The preparation method of acid dyes indyl porous charcoal nanometer sheet in a kind of absorption waste water |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641111A (en) * | 2013-12-26 | 2014-03-19 | 安徽工业大学 | Preparation method of graded porous graphene material for super-capacitor |
| CN103787327A (en) * | 2014-03-06 | 2014-05-14 | 安徽工业大学 | One-step preparation method of hollow spherical porous graphite for supercapacitor |
| CN104098091A (en) * | 2014-07-31 | 2014-10-15 | 安徽工业大学 | Method for preparing ultracapacitor-used porous grapheme material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641111A (en) * | 2013-12-26 | 2014-03-19 | 安徽工业大学 | Preparation method of graded porous graphene material for super-capacitor |
| CN103787327A (en) * | 2014-03-06 | 2014-05-14 | 安徽工业大学 | One-step preparation method of hollow spherical porous graphite for supercapacitor |
| CN104098091A (en) * | 2014-07-31 | 2014-10-15 | 安徽工业大学 | Method for preparing ultracapacitor-used porous grapheme material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105366661A (en) * | 2015-12-15 | 2016-03-02 | 安徽工业大学 | Preparation method of curled porous carbon nanometer sheet for supercapacitor |
| CN106430148A (en) * | 2016-09-05 | 2017-02-22 | 安徽工业大学 | Preparation method of washing-oil-based porous carbon nanosheet for supercapacitor |
| CN108117059A (en) * | 2018-01-17 | 2018-06-05 | 安徽工业大学 | It is a kind of to prepare method of the ultracapacitor with porous class graphene nanometer sheet |
| CN109133050A (en) * | 2018-09-25 | 2019-01-04 | 安徽工业大学 | The preparation method of acid dyes indyl porous charcoal nanometer sheet in a kind of absorption waste water |
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