CN103787327B - The ultracapacitor one-step preppn process of hollow sphere porous graphene - Google Patents
The ultracapacitor one-step preppn process of hollow sphere porous graphene Download PDFInfo
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Abstract
The present invention discloses a kind of one-step preppn process of ultracapacitor hollow sphere porous graphene, belongs to technical field of carbon material preparation.The method with plastic coal-tar pitch for carbon source, nano magnesia is guiding die plate, potassium hydroxide is activator, the mixed mixture of three's dry grinding is transferred in corundum boat, be placed in tube furnace and heat under the condition of normal pressure or negative pressure, single stage method obtains ultracapacitor hollow sphere porous graphene material.The present invention directly to be rich in aromatic ring, cheap coal-tar pitch for raw material, to enormously simplify preparation technology, adds processing safety.The present invention has the advantages such as simple, the with low cost and applicable suitability for industrialized production of technique, hollow sphere porous graphene prepared by the present invention is as electrode of super capacitor, in 6MKOH electrolytic solution, under 20A/g high current density, its specific volume reaches 194 ~ 244F/g, shows fabulous rate capability and very high specific volume.
Description
Technical field:
The invention belongs to technical field of carbon material preparation, be specifically related to a kind of one-step preppn process of ultracapacitor hollow sphere porous graphene.
Background technology:
Ultracapacitor, as a kind of novel energy-storage travelling wave tube, causes the extensive concern of people.Graphene is a kind of flat film material, and having the advantage such as specific surface area of high strength, good electroconductibility, thermal conductivity, super large, is desirable electrode material for super capacitor.But, the specific volume of current Graphene electrodes material is not high, its major cause is in electrode production process, owing to having stronger Van der Waals force between graphene sheet layer, Graphene synusia is heaped again, form effective electric double layer capacitance in the small space causing electrolyte ion to be difficult between Graphene synusia, thus cause the utilization ratio of its specific surface area very low.Porous graphene, owing to having large electronic conduction network and abundant electrolyte ion transmission path and active sites, is expected to have larger specific volume and good rate capability.At present, the method for synthesizing graphite alkene mainly comprises method (top-down) (Science, 332(2011) 1537 from top to bottom) and method (bottom-up) (J.Am.Chem.Soc.135(2013) 9590 from bottom to top).Wherein, from top to bottom during the synthesizing porous Graphene of method, be all with the graphite of compact structure for raw material, to need graphite oxidation under the condition of strong acid and Strong oxdiative and obtain layered graphite oxide after dispersion, then being reduced by the process such as heat or microwave heating and obtain Graphene.And legal system is very high to the requirement of equipment for porous graphene technology from bottom to top, yield poorly, operational condition is harsh, causes the Graphene complex process prepared by the method and cost is very high.
Chinese patent CN102543483A discloses a kind of preparation method of grapheme material, and namely first rapid heating graphite oxide prepares expanded graphite alkene; Re-use ZnCl
2as activator, be uniformly mixed 6-24h with gained expanded graphite alkene, then with acid with deionized water repeatedly washs, after drying, at high temperature pass into CO in chemical gas-phase deposition system
2gas carries out activation pore-creating, is down to room temperature after reaction 1-6h, obtained porous graphene material.Porous graphene obtained by the method is as electrode material for super capacitor, and in organic electrolyte, its specific volume reaches 200F/g.But the method requires high to starting material, and complicated process of preparation, energy consumption is high.Chinese patent CN103258658A discloses a kind of preparation method based on functional type electrode material for super capacitor, first the method uses Hummers legal system for graphite oxide slurry, again graphite oxide slurry is evenly coated in nickel foam, graphite oxide is made to enter into the silk screen micropore of nickel foam, and use microwave heating nickel foam, make the graphite oxide in foam nickel screen be reduced into the Graphene be embedded in nickel foam silk screen; The nickel foam being inlaid with functional type Graphene is pressed into sheet, obtains electrode material for super capacitor after cropped.Although the method has obtained grapheme material, the method preparation technology is loaded down with trivial details, and preparation condition is harsh, and require high to starting material, production cost is high.
On the whole, the equal more complicated of aforesaid method preparation process, production cost is very high.Therefore, a kind of method preparing porous graphene material of simple, efficient, low cost is needed badly.
Coal-tar pitch is the by product in coal tar processing process, and China's coal-tar pitch output is huge, and coal-tar pitch has inexpensive, low ash, is rich in the advantages such as the aromatic shape structure unit of similar Graphene.If coal-tar pitch direct production porous graphene material can be utilized, then not only can realize the high value added utilization of coal-tar pitch, and the preparation technology of porous graphene can be simplified, reduce the production cost of porous graphene.
Summary of the invention:
The present invention is directed to the technical problem existed in the preparation of existing porous graphene material, propose a kind of one-step preppn process of ultracapacitor hollow sphere porous graphene.The method concrete steps are as follows:
(1) pre-treatment of reactant: take normal hexane solvend as the coal-tar pitch of 26.2% be raw material, after coal-tar pitch is ground, take the coal-tar pitch that a certain amount of particle diameter is less than 74 μm and put into mortar, add a certain amount of nano magnesia, add a certain amount of solid potassium hydroxide again, obtain reactant by after gained three kinds of raw mill 1-2; The quality that described particle diameter is less than the coal-tar pitch of 74 μm accounts for 11.1% ~ 15.6% of mixture total mass, and described nano level magnesian quality accounts for 62.2% ~ 66.7% of mixture total mass.
(2) preparation of hollow sphere porous graphene material: the reactant that step (1) obtains is put into corundum boat, again described corundum boat is placed in tube furnace, rare gas element 5 ~ 15min is passed into by the air emptying in described tube furnace with the flow velocity of 60 ~ 80mL/min, make the pressure of described tubular type furnace gas under the condition of normal pressure or negative pressure with the temperature rise rate of 5 DEG C/min by described diamond heating to 150 DEG C, constant temperature 0.5h, continuation by described diamond heating to 800 DEG C, makes described tube furnace Temperature fall to room temperature with the temperature rise rate of 5 DEG C/min after constant temperature 1h.Finally by the product obtained take out, grind after put into beaker, after pickling, distilled water wash and drying, obtain ultracapacitor hollow sphere porous graphene material.
Described rare gas element is argon gas or nitrogen, and described normal pressure is 1 normal atmosphere, and described negative pressure is taken out by pump to make the pressure of described tubular type furnace gas between-0.05MPa ~-0.1MPa.
The inventive method is directly to be rich in the coal-tar pitch of aromatic ring for carbon source, nano magnesia is guiding die plate, potassium hydroxide is activator, under normal pressure or condition of negative pressure, prepare ultracapacitor hollow sphere porous graphene by conventional heating, the specific surface area of gained hollow sphere porous graphene material is between 1832 ~ 1947m
2between/g, total hole pore volume is between 1.08 ~ 1.16cm
3between/g, mean pore size is between 2.31 ~ 2.48nm, and the productive rate of hollow sphere porous graphene is between 47.7 ~ 67.3%.The present invention directly with the coal-tar pitch of cheapness for raw material, technique is very simple; And the raw material of routine mainly graphite, namely pre-oxidation graphite material is adopted to obtain graphite oxide, then graphene oxide is obtained by the step such as mechanically peel or intercalation, porous graphene material could be prepared by physically activated or chemical activation again, use the preparation process of convenient source very loaded down with trivial details.The present invention enormously simplify preparation process, adds processing safety, the advantage such as simple, with low cost and applicable suitability for industrialized production of the method that possesses skills novelty, technique.Obtained hollow sphere porous graphene is as electrode material for super capacitor, and in 6MKOH electrolytic solution, under 20A/g high current density, its specific volume reaches 194 ~ 244F/g, shows fabulous rate capability and very high specific volume.
The present invention has the following advantages:
1, coal-tar pitch is as the by product of coking of coal, have inexpensive, be easy to get, low ash, be rich in the advantages such as the aromatic ring structure unit similar with graphene-structured.
2, the commercial common dilute acid soln of nano magnesia with guiding die plate effect used can be easy to removing.
3, raw materials used is all by dry mixed, and need evaporation superfluous water to grade complex process after eliminating wet-mixed, energy-saving effect is obvious.What is more important, compared with the raw materials such as graphite oxide, the present invention directly with cheap, be rich in the coal-tar pitch of aromatic ring structure for carbon source, the single stage method achieving hollow sphere porous graphene is efficiently prepared, simplify the preparation process of hollow sphere porous graphene, significantly reduce the preparation cost of hollow sphere porous graphene, be applicable to suitability for industrialized production.
Accompanying drawing illustrates:
Fig. 1 is N2 adsorption and the desorption isotherm of hollow sphere porous graphene prepared by the embodiment of the present invention 1,2,3,4;
Fig. 2 is the transmission electron microscope picture of hollow sphere porous graphene prepared by the embodiment of the present invention 1;
Fig. 3 is the transmission electron microscope picture of hollow sphere porous graphene prepared by the embodiment of the present invention 2;
Fig. 4 is the transmission electron microscope picture of hollow sphere porous graphene prepared by the embodiment of the present invention 3;
Fig. 5 is the variation diagram of specific volume with current density of hollow sphere porous graphene electrode materials prepared by the embodiment of the present invention 1,2,3,4.
Embodiment:
Embodiment 1: hollow sphere porous graphene HSPG
3-18-6-Arconcrete preparation process is as follows:
(1) pre-treatment of reactant: take normal hexane solvend as the coal-tar pitch of 26.2% be raw material, after coal-tar pitch is ground, take the coal-tar pitch that 3g particle diameter is less than 74 μm and put into mortar, add 18g nano magnesia, add 6g solid potassium hydroxide again, obtain reactant by after gained three kinds of raw material mixed grinding 1h;
(2) preparation of hollow sphere porous graphene: the reactant that step (1) obtains is put into corundum boat, again corundum boat is placed in tube furnace, argon gas 10min is passed into by the air emptying in described tube furnace with the flow velocity of 60mL/min, under making the gas in described tube furnace be in normal pressure 1 normal atmosphere, then with the temperature rise rate heated Tube-furnace to 150 DEG C of 5 DEG C/min, after constant temperature 0.5h, continue to be heated to 800 DEG C with the temperature rise rate of 5 DEG C/min, after constant temperature 1h, Temperature fall is to room temperature.Taken out by the product obtained after grinding and put into beaker, the 2M dilute hydrochloric acid adding certain volume stirs rear ultrasonic vibration 1h.Then, after at room temperature leaving standstill 24h, be obtain hollow sphere porous graphene after 6 ~ 7 by the distilled water washs of 70 ~ 90 DEG C to the pH value of filtrate, hollow sphere porous graphene after washing to be placed in loft drier ground 325 mesh sieves after 110 DEG C of freeze-day with constant temperature 24h, to obtain ultracapacitor hollow sphere Graphene.Gained hollow sphere porous graphene is labeled as HSPG
3-18-6-Ar.
Embodiment 2: hollow sphere porous graphene HSPG
3-18-6-N2concrete preparation process is as follows:
(1) pre-treatment of reactant: implement according to the method same with the step (1) in embodiment 1.
(2) preparation of hollow sphere porous graphene: implement according to the method same with the step (2) in embodiment 1, difference is, the rare gas element passed into is nitrogen.Gained hollow sphere porous graphene is labeled as HSPG
3-18-6-N2.
Embodiment 3: hollow sphere porous graphene HSPG
3-18-6concrete preparation process is as follows:
(1) pre-treatment of reactant: implement according to the method same with the step (1) in embodiment 1.
(2) preparation of hollow sphere porous graphene: implement according to the method same with the step (2) in embodiment 1, difference is, the rare gas element passed into is nitrogen, and in heat-processed, use vacuum pump to extract a part of gas in described tube furnace out, make gaseous tension in described tube furnace between-0.05MPa ~-0.1MPa.Gained hollow sphere porous graphene is labeled as HSPG
3-18-6.
Embodiment 4: hollow sphere porous graphene HSPG
4.2-16.8-6concrete preparation process is as follows:
(1) pre-treatment of reactant: implement according to the method same with the step (1) in embodiment 1, difference is, what take is 4.2g coal-tar pitch, what add is 16.8g nano magnesia.
(2) preparation of hollow sphere porous graphene: implement according to the method same with the step (2) in embodiment 3.Gained hollow sphere porous graphene is labeled as HSPG
4.2-16.8-6.
The pore structure analysis result of embodiment 1-4 gained hollow sphere porous graphene is listed in table 1.
The pore structure analysis result of table 1 embodiment 1-4 gained hollow sphere porous graphene
Claims (2)
1. the ultracapacitor one-step preppn process of hollow sphere porous graphene, is characterized in that the method concrete steps are as follows:
(1) pre-treatment of reactant: the coal-tar pitch being 26.2wt% with normal hexane solvend is raw material, after coal-tar pitch is ground, take the coal-tar pitch that a certain amount of particle diameter is less than 74 μm and put into mortar, add a certain amount of nano level magnesium oxide, add a certain amount of solid potassium hydroxide again, by gained three kinds of reactant mixed grinding 1 ~ 2h, the quality that described particle diameter is less than the coal-tar pitch of 74 μm accounts for 11.1% ~ 15.6% of mixture total mass, and described nano level magnesian quality accounts for 62.2% ~ 66.7% of mixture total mass;
(2) preparation of hollow sphere porous graphene: the reactant that step (1) obtains is put into corundum boat, again described corundum boat is placed in tube furnace, rare gas element 5 ~ 10min is passed into by after the air emptying in described tube furnace with the flow velocity of 60 ~ 80mL/min, make the pressure of described tubular type furnace gas under the condition of normal pressure or negative pressure with the temperature rise rate of 5 DEG C/min by described diamond heating to 150 DEG C, constant temperature 0.5h, continue described diamond heating to 800 DEG C with the temperature rise rate of 5 DEG C/min, after constant temperature 1h, Temperature fall is to room temperature, finally the product obtained is taken out, beaker is put into after grinding, through pickling, ultracapacitor hollow sphere porous graphene is obtained after distilled water wash and drying.
2. the one-step preppn process of a kind of ultracapacitor hollow sphere porous graphene according to claim 1, is characterized in that described in step (2), rare gas element is argon gas or nitrogen; Described normal pressure is 1 normal atmosphere, and described negative pressure is taken out by pump to make the pressure of described tubular type furnace gas between-0.05MPa ~-0.1MPa.
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104009205B (en) * | 2014-06-12 | 2016-08-24 | 上海中聚佳华电池科技有限公司 | A kind of hollow graphite alkene ball and its production and use |
| CN104591127B (en) * | 2015-01-09 | 2016-11-09 | 中山大学 | A kind of superhigh specific surface area Carbon Hollow nanosphere and preparation method and application |
| CN105060287B (en) * | 2015-08-25 | 2017-06-06 | 安徽工业大学 | A kind of preparation method of graphene net material that is that ultracapacitor is connected with each other and rolling |
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| CN105236394A (en) * | 2015-08-31 | 2016-01-13 | 安徽工业大学 | Method of preparing mutually-connected graphene nano sheet used for supercapacitor |
| CN105331999B (en) * | 2015-10-13 | 2017-10-24 | 湖南农业大学 | The preparation method of hollow plumbago alkene |
| CN105502363B (en) * | 2015-12-25 | 2018-02-09 | 安徽工业大学 | A kind of preparation method of the graphene nanometer sheet of ultracapacitor fold |
| CN105417521B (en) * | 2015-12-28 | 2018-03-09 | 安徽工业大学 | A kind of method for preparing the classifying porous charcoal nanometer sheet of ultracapacitor fluorenyl |
| CN106185890B (en) * | 2016-07-04 | 2019-02-15 | 石河子大学 | A kind of preparation method of porous class graphene |
| CN109081323B (en) * | 2017-06-14 | 2020-10-27 | 中国石油化工股份有限公司 | Hollow carbon nanosphere and preparation method thereof |
| CN107902644A (en) * | 2017-12-12 | 2018-04-13 | 四川聚创石墨烯科技有限公司 | A kind of open-type alkylene micro-nano cryptomere material three-dimensional structure and preparation method thereof |
| CN108358200B (en) * | 2018-02-12 | 2020-05-22 | 黑龙江省牡丹江农垦奥宇石墨深加工有限公司 | Integrated spherical graphite processing device and processing method thereof |
| CN108584949A (en) * | 2018-05-24 | 2018-09-28 | 安徽工业大学 | A kind of preparation and application of coal tar pitch substrate shape mesoporous carbon |
| CN109437160B (en) * | 2018-11-22 | 2022-05-06 | 陕西延长石油（集团）有限责任公司 | Graphene/carbon composite material for supercapacitor and preparation method thereof |
| CN109305669A (en) * | 2018-11-22 | 2019-02-05 | 陕西延长石油（集团）有限责任公司 | It is a kind of to utilize the clay standby three-dimensional porous graphene and preparation method thereof of coal base oil |
| CN113184847A (en) * | 2021-04-15 | 2021-07-30 | 安徽工业大学 | Porous carbon material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367516A (en) * | 2008-09-26 | 2009-02-18 | 天津大学 | High electrochemistry capacitance oxidization plumbago alkene, low-temperature preparation method and uses |
| CN102515151A (en) * | 2011-12-22 | 2012-06-27 | 哈尔滨工程大学 | Porous graphene with stratified columnar support structure and its preparation method |
-
2014
- 2014-03-06 CN CN201410081975.1A patent/CN103787327B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367516A (en) * | 2008-09-26 | 2009-02-18 | 天津大学 | High electrochemistry capacitance oxidization plumbago alkene, low-temperature preparation method and uses |
| CN102515151A (en) * | 2011-12-22 | 2012-06-27 | 哈尔滨工程大学 | Porous graphene with stratified columnar support structure and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of mesoporous carbons for supercapacitors from coal tar pitch by coupling microwave-assisted KOH activation with a MgO template;Xiaojun He et al.;《Carbon》;20120618;第50卷;4911-4921 * |
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