CN105060287B - A kind of preparation method of graphene net material that is that ultracapacitor is connected with each other and rolling - Google Patents
A kind of preparation method of graphene net material that is that ultracapacitor is connected with each other and rolling Download PDFInfo
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- CN105060287B CN105060287B CN201510532535.8A CN201510532535A CN105060287B CN 105060287 B CN105060287 B CN 105060287B CN 201510532535 A CN201510532535 A CN 201510532535A CN 105060287 B CN105060287 B CN 105060287B
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Abstract
The present invention discloses a kind of preparation method of the graphene net material that ultracapacitor is connected with each other and rolls, and belongs to novel charcoal material technical field.The method is that, with carbolineum as carbon source, nano-calcium carbonate is template, and potassium hydroxide is activator, after adding N, N dimethylformamides to make three well mixed, is placed in tube furnace, is heated under an argon atmosphere, directly prepares target product.With cheap calcium carbonate as template, carbolineum is carbon source to the present invention, and the interconnection of preparation and the ultracapacitor graphene net electrode material rolled have the advantages that capacity is high, utilisable energy density is big.The material is used as symmetric form electrode material for super capacitor, in BMIMPF6In il electrolyte, under 0.05A/g current densities, its specific volume is 256F/g, and utilisable energy density is up to 143Wh/kg, can be compared favourably with the energy density of lithium ion battery.
Description
Technical field
The invention belongs to novel charcoal material technical field, and in particular to that a kind of ultracapacitor is connected with each other and roll
Graphene net material preparation method.
Background technology
Ultracapacitor, also known as double layer capacitor, is a kind of novel energy-storing unit between traditional capacitor and battery
Part, has the advantages that charge-discharge velocity is fast, has extended cycle life, environmentally friendly, in industry, consumer electronics, communication, Medical treatment device
The fields such as tool, national defence, military equipment, traffic are increasingly widely applied.The major parameter of ultracapacitor has capacity, work(
Rate density and energy density etc., its specific capacity C=KS/d, power density P=V2/4R2, energy density E=1/2CV2.Therefore, make
Electrochemistry of the electrolyte of standby electrode material and selection potential window wider with reasonable pore structure to improvement ultracapacitor
Performance tool is of great significance.
Graphene is a kind of new two-dimentional carbon nanomaterial, and its basic structure is with sp by carbon atom2What hydridization was formed
Hexatomic ring.The thickness of single-layer graphene only one of which atom, its unique monoatomic layer structure assigns its excellent physical chemistry
Performance.Grapheme material has carrier mobility (10000cm high at room temperature2/ V/s), the theoretical specific surface area of superelevation
(2630m2/ g) and excellent thermal conductivity factor (3000-5000W/m/K).Additionally, also there is the chemical property of stabilization, therefore, quilt
It is widely applied on the energy storage devices such as field emission device, solar energy and wind energy.Currently, commercial graphite alkene is main by graphite oxide system
It is standby, and the price of graphite oxide is up to 1000 yuan/gram, causes holding at high price for Graphene.The performance and price of Graphene
Mainly determined by carbon source and preparation technology used etc..Except that can be that raw material prepares Graphene with graphite or graphite oxide
Outward, can also be prepared with coal raw materials, biomass material, carbon containing high molecular polymer and Organometallic complexes etc.
Grapheme material.
China is coal production big country, and carbolineum is that 280~360 DEG C of cut is cut by Doak Tar Oil, the valency of carbolineum
Lattice are only in 0.005 yuan/gram or so.Carbolineum have the advantages that inexpensively, be easy to get, it is low ash and rich in polycyclic armaticity construction unit.Mesh
Before, the processing to carbolineum both at home and abroad is mainly extraction wherein anthracene, phenanthrene, three kinds of components of carbazole.These three components are processed in separation
Some bi-component eutectics and a series of solid solution are easily formed in journey, difficult and separation process high energy consumption, pollution is separated greatly.
Exploration is directly prepared the new method of High-performance graphene material by cheap carbolineum, is had to industries such as biological medicine, material, metallurgy
It is significant, it is also possible to realize the high value added utilization of carbolineum.
Calcium carbonate is the natural minerals of earth shell.Compared with expensive nano-metal-oxide, calcium carbonate has
Inexhaustible advantage.The distribution area of carbonatite accounts for earth top up to 5,340,000 square kilometres in the world
Long-pending 4%.Chinese carbonatite distribution area accounts for the 64% of the world up to 3,440,000 square kilometres.Calcium carbonate has chemical purity
The advantages of high, thermally-stabilised good (will not be decomposed at 400 DEG C), low, nontoxic, tasteless hardness, good dispersion, it is widely used to make
The fields such as paper, coating, ceramics, food.If using calcium carbonate as template in situ, being expected to realize the preparation of Authracene oil-based Graphene.Its
In, calcium carbonate after pyrolytic obtains carbon dioxide and calcium oxide, carbon dioxide can occur it is in situ physically activated, to charcoal
There is material reaming to act on, it is possible to achieve the cheap preparation of High-performance graphene material.Wherein, calcium oxide not only can be with adjustment hole
Footpath is distributed, and bases activator can also be promoted to activate pore-creating.Finally, calcium oxide can be washed away with watery hydrochloric acid, the technique has dirt
Contaminate small, simple operation and other advantages.
Ionic liquid refers to do not have electrfic centre molecule, and 100% by a kind of nitrogenous or organic cation containing phosphorus heterocycle and
A kind of inorganic anion composition, is at room temperature the material of liquid.Ionic liquid is due to steady with extremely low vapour pressure, heat higher
Qualitative and adjustable solvability, can be applied to organic synthesis, separating-purifying field as green medium；Due to its electricity wider
Gesture window and adjustable acid-base property, can be applied to catalytic chemistry and electrochemical research as novel electrolytes and effective catalyst
Field.The energy density of ultracapacitor can be improved by the potential window for improving electrolyte, so the present invention selects potential
BMIMPF of the window up to 4V6Ionic liquid as ultracapacitor electrolyte.
The content of the invention
With carbolineum cheap and easy to get, rich in armaticity construction unit as carbon source, DMF is molten to the present invention
Agent, cheap nano-calcium carbonate is template, and potassium hydroxide is activator, prepares electrode for super capacitor material.
Preparation method of the present invention is comprised the following steps that：
(1) mixing of reactant：Mixture will be obtained after nano-calcium carbonate and potassium hydroxide ground and mixed, gained mixture adds
In entering the beaker equipped with carbolineum, and DMF is added, stirring said mixture is to obtaining reactant after uniform；
Wherein, the ratio of the quality and carbolineum, nano-calcium carbonate and potassium hydroxide gross mass of nano-calcium carbonate is 1/3, anthracene
The quality of oil is 1/2 with the mass ratio of potassium hydroxide, and DMF is 17/90 with the mass ratio of nano-calcium carbonate；
(2) preparation of graphene net material that is being connected with each other and rolling：The reactant that step (1) is obtained is moved to just
In beautiful porcelain boat, corundum porcelain boat is placed in tube furnace, under an argon atmosphere, is warming up to 550 DEG C, after constant temperature 30min, continue to heat up
By the final temperature of diamond heating to 850~1000 DEG C, after constant temperature 60min, naturally cool to room temperature, products therefrom through overpickling,
After washing and drying, graphene net material that is being connected with each other and rolling.
Optimize as one kind, in step (1), nano-calcium carbonate is 9g, and carbolineum is 6g, and DMF is
1.7g, potassium hydroxide is 12g；In step (2), diamond heating final temperature is 950 DEG C；Resulting materials are used as the super electricity of symmetric form
Container electrode material, in BMIMPF6In electrolyte, under the current density of 0.05A/g, its specific volume reaches 256F/g, and utilisable energy is close
Degree is up to 143Wh/kg.
Compared with prior art, the present invention has advantages below：
1. carbolineum and nano-calcium carbonate be respectively provided with inexpensively, be easy to get, low cost and other advantages, carbolineum also have it is low ash and rich in many
The advantages of cyclophane fragrance construction unit.
2. the effect of nano-calcium carbonate not only lifting plate, and, nano-calcium carbonate pyrolytic obtains calcium oxide and dioxy
After changing carbon, carbon dioxide will also play physically activated effect in situ.
3. the present invention interconnection prepared and the electrochemical performance of graphene net electrode material rolled,
BMIMPF6In electrolyte, its specific volume is up to 143Wh/kg, Ke Yihe up to 256F/g, the utilisable energy density of ultracapacitor
The energy density of lithium ion battery compares favourably.
Brief description of the drawings
Fig. 1 is graphene net material IRGN that is interconnection and rolling prepared by the embodiment of the present invention 1850TEM
Figure.
Fig. 2 is graphene net material IRGN that is interconnection and rolling prepared by the embodiment of the present invention 2900TEM
Figure.
Fig. 3 is graphene net material IRGN that is interconnection and rolling prepared by the embodiment of the present invention 3950TEM
Figure.
Fig. 4 is graphene net material IRGN that is interconnection and rolling prepared by the embodiment of the present invention 41000TEM
Figure.
Fig. 5 is that graphene net material that is interconnection and rolling prepared by the embodiment of the present invention 1,2,3,4 exists
BMIMPF6In ionic liquid specific volume with current density variation diagram.
Fig. 6 is that graphene net material that is interconnection and rolling prepared by the embodiment of the present invention 1,2,3,4 exists
BMIMPF6In ionic liquid utilisable energy density with power density variation diagram.
Specific 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 embodiments, it should be understood that succeed
Example property, those skilled in the art can be changed and modified on the basis of without prejudice to spirit and scope of the invention, institute
There are these changes and modification to be included in the scope of the present invention.
Embodiment 1
Graphene net material IRGN that is being connected with each other and rolling850Specific preparation process is as follows：
(1) mixing of reactant：Weigh the nano-calcium carbonate of 9g, the carbolineum of 6g, the potassium hydroxide of 12g.By nano-calcium carbonate
Calcium and potassium hydroxide ground and mixed, gained mixture is added in the beaker equipped with carbolineum, and adds 1.7g N, N dimethyl formyl
Amine, stirring said mixture is to obtaining reactant after uniform.
(2) preparation of graphene net material that is being connected with each other and rolling：The reactant that step (1) is obtained is moved to just
In beautiful porcelain boat, then corundum porcelain boat is placed in tube furnace, under an argon atmosphere, 550 DEG C, constant temperature is warming up to 3 DEG C/min
After 30min, continue diamond heating to 850 DEG C with 3 DEG C/min heating rates, after constant temperature 60min, naturally cool to room temperature.
The product that will be obtained grinds, and is transferred in beaker, to adding the stirring of 40mL watery hydrochloric acid, ultrasonic vibration in beaker, magnetic agitation,
Washed to neutrality with hot distilled water after standing at room temperature, be placed in drying box and dry, ground 325 mesh standard sieve is obtained mutual
Graphene net material designation that is connecting and rolling is IRGN850。IRGN850As symmetric form electrode material for super capacitor,
In BMIMPF6In electrolyte, under 0.05A/g current densities, IRGN850Specific volume be 236F/g, utilisable energy density reach 128Wh/
Kg, power density is 116W/kg.
Embodiment 2
Graphene net material IRGN that is being connected with each other and rolling900Specific preparation process is as follows：
(1) mixing of reactant：Implement according to the method same with the step (1) in embodiment 1.
(2) preparation of graphene net material that is being connected with each other and rolling：According to same with step (2) in embodiment 1
The method of sample is implemented, and difference is that tube furnace is added into 900 DEG C of final temperature.Netted graphite that is being connected with each other and rolling is obtained
Alkene material designation is IRGN900。RGN900As symmetric form electrode material for super capacitor, in BMIMPF6In electrolyte, 0.05A/
Under g current densities, IRGN900Specific volume be 247F/g, utilisable energy density reach 136Wh/kg, power density is 111W/kg.
Embodiment 3
Graphene net material IRGN that is being connected with each other and rolling950Specific preparation process is as follows：
(1) mixing of reactant：Implement according to the method same with the step (1) in embodiment 1.
(2) preparation of graphene net material that is being connected with each other and rolling：According to same with step (2) in embodiment 1
The method of sample is implemented, and difference is by diamond heating to 950 DEG C of final temperature.Netted stone that is being connected with each other and rolling is obtained
Black alkene material designation is IRGN950。IRGN950Material is used as symmetric form electrode material for super capacitor, in BMIMPF6Electrolyte
In, under 0.05A/g current densities, its specific volume is 256F/g, and utilisable energy density reaches 143Wh/kg, and power density is 107W/kg.
Embodiment 4
Graphene net material IRGN that is being connected with each other and rolling1000Specific preparation process is as follows：
(1) mixing of reactant：Implement according to the method same with the step (1) in embodiment 1.
(2) preparation of graphene net material that is being connected with each other and rolling：According to same with step (2) in embodiment 1
The method of sample is implemented, and difference is by diamond heating to 1000 DEG C of final temperature.Be obtained be connected with each other and roll it is netted
Grapheme material is named as IRGN1000。IRGN1000Material is used as symmetric form electrode material for super capacitor, in BMIMPF6Electrolysis
In liquid, under 0.05A/g current densities, its specific volume is 220F/g, and utilisable energy density reaches 120Wh/kg, and power density is 116W/
kg。
Claims (2)
1. a kind of preparation method of the graphene net material that ultracapacitor is connected with each other and rolls, it is characterised in that the party
Method processing step is as follows：
(1) mixing of reactant：Nano-calcium carbonate and potassium hydroxide ground and mixed, gained mixture are added into the burning equipped with carbolineum
In cup, DMF is added, stirring said mixture is to obtaining reactant after uniform；
Wherein：The ratio of the quality and carbolineum, nano-calcium carbonate and potassium hydroxide gross mass of nano-calcium carbonate is 1/3, carbolineum
Quality is 1/2 with the mass ratio of potassium hydroxide, and DMF is 17/90 with the mass ratio of nano-calcium carbonate；
(2) preparation of the graphene net material for being connected with each other and rolling：The reactant that step (1) is obtained is moved to corundum porcelain boat
In, corundum porcelain boat is placed in tube furnace, under an argon atmosphere, intensification is heated to 550 DEG C, after constant temperature 30min, and continuing intensification will
The final temperature of diamond heating to 850~1000 DEG C, after constant temperature 60min, naturally cools to room temperature, and products therefrom is through overpickling, water
After washing and drying, graphene net material that is being connected with each other and rolling.
2. the preparation of the graphene net material that a kind of ultracapacitor is connected with each other and rolls as claimed in claim 1
Method, it is characterised in that in step (1), the quality of nano-calcium carbonate is 9g, and the quality of carbolineum is 6g, N, N dimethyl formyl
The quality of amine is 1.7g, and the quality of potassium hydroxide is 12g；In step (2), by diamond heating to 950 DEG C of final temperature.
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| 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 |
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