CN103787327A - One-step preparation method of hollow spherical porous graphite for supercapacitor - Google Patents
One-step preparation method of hollow spherical porous graphite for supercapacitor Download PDFInfo
- Publication number
- CN103787327A CN103787327A CN201410081975.1A CN201410081975A CN103787327A CN 103787327 A CN103787327 A CN 103787327A CN 201410081975 A CN201410081975 A CN 201410081975A CN 103787327 A CN103787327 A CN 103787327A
- Authority
- CN
- China
- Prior art keywords
- porous graphene
- hollow sphere
- coal
- preparation
- step preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a one-step preparation method of a hollow spherical porous graphite for a supercapacitor and belongs to the technical field of carbon material preparation. In the one-step preparation method, plastic coal pitch serves as a carbon source, nanometer magnesia serves as a guiding template, potassium hydroxide serves as an activating agent, and a mixture formed by grinding and mixing three raw materials by using a dry method is transferred to a corundum crucible, the corundum crucible is arranged in a tubular furnace to be heated under the condition of ordinary pressure or negative pressure, and the hollow spherical porous graphite material for the supercapacitor is prepared by using the one-step preparation method. The one-step preparation method directly uses the cheap aromatic-ring-rich coal pitch as a raw material, a preparation process is greatly simplified, and the operation safety is improved. The one-step preparation method has the advantages of being simple in process, low in cost, suitable for industrial production and the like. The prepared hollow spherical porous graphite is used as a supercapacitor electrode, the specific volume of the supercapacitor electrode in 6MKOH electrolyte under the condition of 20A/g large-current density reaches to 194-244F/g, and good rate performance and high specific volume are displayed.
Description
Technical field:
The invention belongs to Carbon Materials preparing technical field, be specifically related to the one-step preppn process of a kind of ultracapacitor hollow sphere porous graphene.
Background technology:
Ultracapacitor, as a kind of novel energy-storage travelling wave tube, has caused people's extensive concern.Graphene is a kind of flat film material, has the advantages such as the specific surface area of high strength, good electroconductibility, thermal conductivity, super large, is desirable electrode material for super capacitor.But, the specific volume of Graphene electrodes material is not high at present, its major cause is in electrode production process, owing to having between graphene sheet layer compared with strong Van der Waals force, Graphene synusia is heaped again, cause electrolyte ion to be difficult to form in the small space between Graphene synusia effective electric double layer capacitance, thereby 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 when the synthesizing porous Graphene of method, be all graphite take compact structure as raw material, need under the condition of strong acid and strong oxidation, obtain layered graphite oxide by graphite oxidation and after disperseing, then by the process such as heat or microwave heating, its reduction be obtained to Graphene.And legal system is very high to the requirement of equipment for porous graphene technology from bottom to top, yield poorly, operational condition harshness, causes Graphene complex process and the cost prepared by the method very high.
Chinese patent CN102543483A discloses a kind of preparation method of grapheme material, and first rapid heating graphite oxide is prepared expanded graphite alkene; Re-use ZnCl
2as activator, be uniformly mixed 6-24h with gained expanded graphite alkene, then with acid and deionized water repeatedly washs, be dried after, at high temperature in chemical gas-phase deposition system, pass into CO
2gas activates pore-creating, after reaction 1-6h, is down to room temperature, makes porous graphene material.The prepared porous graphene of the method is as electrode material for super capacitor, and in organic electrolyte, its specific volume reaches 200F/g.But it is high that the method requires starting material, 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 is used Hummers legal system for graphite oxide slurry, again graphite oxide slurry is evenly coated in nickel foam, make graphite oxide 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 being embedded in nickel foam silk screen; The nickel foam that is inlaid with functional type Graphene is pressed into sheet, obtains after cropped electrode material for super capacitor.Although the method has made grapheme material, the method preparation technology is loaded down with trivial details, preparation condition harshness, and high to starting material requirement, production cost is high.
On the whole, the equal more complicated of aforesaid method preparation process, production cost is very high.Therefore, need a kind of method of preparing simply, efficiently, cheaply porous graphene material badly.
Coal-tar pitch is the by product in coal tar processing process, and China's coal-tar pitch output is huge, coal-tar pitch has inexpensive, low ash, is rich in the advantages such as the aromatic shape structure unit of similar Graphene.If can utilize coal-tar pitch direct production porous graphene material, not only can realize the high value added utilization of coal-tar pitch, and can simplify the preparation technology of porous graphene, reduce the production cost of porous graphene.
Summary of the invention:
The present invention is directed to the technical problem existing in existing porous graphene material preparation, propose the one-step preppn process of a kind of ultracapacitor hollow sphere porous graphene.The method concrete steps are as follows:
(1) pre-treatment of reactant: the coal-tar pitch take normal hexane solvend as 26.2% is as raw material, after coal-tar pitch is ground, take the coal-tar pitch that a certain amount of particle diameter is less than 74 μ m and put into mortar, add a certain amount of nano magnesia, add again a certain amount of solid potassium hydroxide, will after three kinds of former abrasive lapping 1-2 of gained, obtain reactant; The quality that described particle diameter is less than the coal-tar pitch of 74 μ m 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) is obtained is put into corundum boat, again described corundum boat is placed in tube furnace, pass into rare gas element 5～15min by the air emptying in described tube furnace with the flow velocity of 60～80mL/min, the pressure that makes described tubular type furnace gas under the condition of normal pressure or negative pressure with the temperature rise rate of 5 ℃/min by described diamond heating to 150 ℃, constant temperature 0.5h, continue with the temperature rise rate of 5 ℃/min, by described diamond heating to 800 ℃, after constant temperature 1h, to make described tube furnace naturally be cooled to room temperature.After finally the product obtaining being taken out, ground, put into beaker, obtain ultracapacitor hollow sphere porous graphene material through pickling, distilled water wash with after being dried.
Described rare gas element is argon gas or nitrogen, and described normal pressure is 1 normal atmosphere, and described negative pressure is to take out the pressure that makes described tubular type furnace gas between between-0.05MPa～-0.1MPa by pump.
The inventive method is directly take the coal-tar pitch that is rich in aromatic ring as 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 is directly take cheap coal-tar pitch as raw material, and technique is very simple; And conventional raw material is mainly graphite, adopt pre-oxidation graphite material to obtain graphite oxide, then make graphene oxide by the step such as mechanically peel or intercalation, could prepare porous graphene material by physically activated or chemical activation again, use the preparation process of conventional raw material very loaded down with trivial details.The present invention has simplified preparation process greatly, has increased processing safety, the advantage such as simple, with low cost and applicable suitability for industrialized production of the method that possesses skills novelty, technique.The hollow sphere porous graphene making is as electrode material for super capacitor, and in 6M KOH electrolytic solution, under 20A/g high current density, its specific volume reaches 194～244F/g, has shown 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 coal tar, have inexpensive, be easy to get, low ash, be rich in and the advantages such as the similar aromatic ring structure of graphene-structured unit.
2, the commercial common dilute acid soln of nano magnesia with guiding die plate effect used can be easy to remove.
3, raw materials used is all by dry mixed, needs the complex processes such as evaporating surplus moisture after having saved wet-mixed, and energy-saving effect is obvious.What is more important, compared with the raw materials such as graphite oxide, the present invention is directly take cheap, to be rich in aromatic ring structure coal-tar pitch as carbon source, having realized the single stage method of hollow sphere porous graphene efficiently prepares, 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 explanation:
Fig. 1 is the nitrogen adsorption and desorption thermoisopleth of the hollow sphere porous graphene of the embodiment of the present invention 1,2,3,4 preparations;
Fig. 2 is the transmission electron microscope picture of the hollow sphere porous graphene prepared of the embodiment of the present invention 1;
Fig. 3 is the transmission electron microscope picture of the hollow sphere porous graphene prepared of the embodiment of the present invention 2;
Fig. 4 is the transmission electron microscope picture of the hollow sphere porous graphene prepared of the embodiment of the present invention 3;
Fig. 5 is that the specific volume of hollow sphere porous graphene electrode materials of the embodiment of the present invention 1,2,3,4 preparation is with the variation diagram of current density.
Embodiment:
Embodiment 1: hollow sphere porous graphene HSPG
3-18-6-Arconcrete preparation process is as follows:
(1) pre-treatment of reactant: the coal-tar pitch take normal hexane solvend as 26.2% is as raw material, after coal-tar pitch is ground, take the coal-tar pitch that 3g particle diameter is less than 74 μ m and put into mortar, add 18g nano magnesia, add again 6g solid potassium hydroxide, will after three kinds of raw material mixed grinding 1h of gained, obtain reactant;
(2) preparation of hollow sphere porous graphene: the reactant that step (1) is obtained is put into corundum boat, again corundum boat is placed in tube furnace, pass into argon gas 10min by the air emptying in described tube furnace with the flow velocity of 60mL/min, make gas in described tube furnace under 1 normal atmosphere of normal pressure, then with the temperature rise rate heated Tube-furnace to 150 ℃ of 5 ℃/min, after constant temperature 0.5h, continue to be heated to 800 ℃ with the temperature rise rate of 5 ℃/min, after constant temperature 1h, be naturally cooled to room temperature.After the product taking-up obtaining is ground, put into beaker, add the 2M dilute hydrochloric acid of certain volume to stir rear ultrasonic concussion 1h.Then, at room temperature leave standstill after 24h, be to obtain hollow sphere porous graphene after 6～7 by the distilled water washs of 70～90 ℃ to the pH value of filtrate, hollow sphere porous graphene after washing is placed in loft drier and after 110 ℃ of freeze-day with constant temperature 24h, ground 325 mesh sieves, 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 step (1) in embodiment 1.
(2) preparation of hollow sphere porous graphene: implement according to the method same with step (2) in embodiment 1, difference is, the rare gas element passing 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 step (1) in embodiment 1.
(2) preparation of hollow sphere porous graphene: implement according to the method same with step (2) in embodiment 1, difference is, the rare gas element passing 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 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 step (1) in embodiment 1, difference is, what take is 4.2g coal-tar pitch, and what add is 16.8g nano magnesia.
(2) preparation of hollow sphere porous graphene: implement according to the method same with 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 one-step preppn process of hollow sphere porous graphene for ultracapacitor, is characterized in that the method concrete steps are as follows:
(1) pre-treatment of reactant: the coal-tar pitch take normal hexane solvend as 26.2wt% 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 μ m and put into mortar, add a certain amount of nano level magnesium oxide, add again a certain amount of solid potassium hydroxide, by three kinds of reactant mixed grinding 1～2h of gained, the quality that described particle diameter is less than the coal-tar pitch of 74 μ m 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) is obtained is put into corundum boat, again described corundum boat is placed in tube furnace, pass into rare gas element 5～10min by after the air emptying in described tube furnace with the flow velocity of 60～80mL/min, the pressure that makes described tubular type furnace gas under the condition of normal pressure or negative pressure with the temperature rise rate of 5 ℃/min by described diamond heating to 150 ℃, constant temperature 0.5h, continue with the temperature rise rate of 5 ℃/min described diamond heating to 800 ℃, after constant temperature 1h, be naturally cooled to room temperature, finally the product obtaining is taken out, after grinding, put into beaker, through pickling, distilled water wash and dry after obtain ultracapacitor hollow sphere porous graphene.
2. the one-step preppn process of hollow sphere porous graphene for a kind of ultracapacitor 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 to take out the pressure that makes described tubular type furnace gas between between-0.05MPa～-0.1MPa by pump.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410081975.1A CN103787327B (en) | 2014-03-06 | 2014-03-06 | The ultracapacitor one-step preppn process of hollow sphere porous graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410081975.1A CN103787327B (en) | 2014-03-06 | 2014-03-06 | The ultracapacitor one-step preppn process of hollow sphere porous graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103787327A true CN103787327A (en) | 2014-05-14 |
| CN103787327B CN103787327B (en) | 2015-11-18 |
Family
ID=50663455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410081975.1A Active CN103787327B (en) | 2014-03-06 | 2014-03-06 | The ultracapacitor one-step preppn process of hollow sphere porous graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103787327B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104009205A (en) * | 2014-06-12 | 2014-08-27 | 上海中聚佳华电池科技有限公司 | Hollow graphene ball and preparation method and application thereof |
| CN104591127A (en) * | 2015-01-09 | 2015-05-06 | 中山大学 | Ultrahigh-specific-area hollow carbon nano-spheres as well as preparation method and application thereof |
| CN105060287A (en) * | 2015-08-25 | 2015-11-18 | 安徽工业大学 | Preparation method of connected and wound mesh-shaped graphene materials used for supercapacitors |
| CN105110325A (en) * | 2015-08-25 | 2015-12-02 | 安徽工业大学 | Method for preparing interconnected and folded graphene materials for super-capacitor |
| 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 |
| CN105331999A (en) * | 2015-10-13 | 2016-02-17 | 湖南农业大学 | Preparing method for hollow graphene |
| CN105417521A (en) * | 2015-12-28 | 2016-03-23 | 安徽工业大学 | Method for preparing fluorene-based hierarchical porous carbon nanosheets for super capacitors |
| CN105502363A (en) * | 2015-12-25 | 2016-04-20 | 安徽工业大学 | Method for preparing corrugated graphene nanosheets for supercapacitor |
| CN106185890A (en) * | 2016-07-04 | 2016-12-07 | 石河子大学 | A kind of preparation method of porous class Graphene |
| 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 |
| CN108358200A (en) * | 2018-02-12 | 2018-08-03 | 黑龙江省牡丹江农垦奥宇石墨深加工有限公司 | A kind of integration spherical machining graphite device and its processing method |
| 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 |
| CN109081323A (en) * | 2017-06-14 | 2018-12-25 | 中国石油化工股份有限公司 | A kind of hollow Nano carbon balls 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 |
| CN109437160A (en) * | 2018-11-22 | 2019-03-08 | 陕西延长石油（集团）有限责任公司 | A kind of supercapacitor graphene/carbon composite material and preparation method thereof |
| 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 |
|---|
| XIAOJUN HE ET AL.: "Synthesis of mesoporous carbons for supercapacitors from coal tar pitch by coupling microwave-assisted KOH activation with a MgO template", 《CARBON》, vol. 50, 18 June 2012 (2012-06-18), pages 4911 - 4921 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104009205A (en) * | 2014-06-12 | 2014-08-27 | 上海中聚佳华电池科技有限公司 | Hollow graphene ball and preparation method and application thereof |
| CN104591127A (en) * | 2015-01-09 | 2015-05-06 | 中山大学 | Ultrahigh-specific-area hollow carbon nano-spheres as well as preparation method and application thereof |
| CN105060287A (en) * | 2015-08-25 | 2015-11-18 | 安徽工业大学 | Preparation method of connected and wound mesh-shaped graphene materials used for supercapacitors |
| CN105110325A (en) * | 2015-08-25 | 2015-12-02 | 安徽工业大学 | Method for preparing interconnected and folded graphene materials for super-capacitor |
| 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 |
| CN105331999A (en) * | 2015-10-13 | 2016-02-17 | 湖南农业大学 | Preparing method for hollow graphene |
| 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 |
| CN105502363A (en) * | 2015-12-25 | 2016-04-20 | 安徽工业大学 | Method for preparing corrugated graphene nanosheets for supercapacitor |
| CN105417521A (en) * | 2015-12-28 | 2016-03-23 | 安徽工业大学 | Method for preparing fluorene-based hierarchical porous carbon nanosheets for super capacitors |
| CN106185890A (en) * | 2016-07-04 | 2016-12-07 | 石河子大学 | A kind of preparation method of porous class Graphene |
| CN109081323A (en) * | 2017-06-14 | 2018-12-25 | 中国石油化工股份有限公司 | A kind of hollow Nano carbon balls and preparation method thereof |
| 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 |
| CN108358200A (en) * | 2018-02-12 | 2018-08-03 | 黑龙江省牡丹江农垦奥宇石墨深加工有限公司 | A kind of integration spherical machining graphite device and its processing method |
| 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 |
| 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 |
| CN109437160A (en) * | 2018-11-22 | 2019-03-08 | 陕西延长石油（集团）有限责任公司 | A kind of supercapacitor graphene/carbon composite material and preparation method thereof |
| CN113184847A (en) * | 2021-04-15 | 2021-07-30 | 安徽工业大学 | Porous carbon material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103787327B (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103787327B (en) | The ultracapacitor one-step preppn process of hollow sphere porous graphene | |
| Luo et al. | Synthesis of 3D-interconnected hierarchical porous carbon from heavy fraction of bio-oil using crayfish shell as the biological template for high-performance supercapacitors | |
| CN103641111B (en) | A kind of ultracapacitor preparation method of classifying porous grapheme material | |
| He et al. | A layered-template-nanospace-confinement strategy for production of corrugated graphene nanosheets from petroleum pitch for supercapacitors | |
| JP6682557B2 (en) | Method for preparing graphene from coal | |
| CN106365142B (en) | A kind of preparation method of the compound carbon aerogels of high-specific surface area High conductivity graphene based on chemical crosslinking | |
| CN104098091B (en) | A kind of method preparing ultracapacitor porous graphene material | |
| CN102350357B (en) | Nano-nickel catalyst loaded on grapheme and preparation method thereof | |
| Wang et al. | Low-cost, green synthesis of highly porous carbons derived from lotus root shell as superior performance electrode materials in supercapacitor | |
| CN105417521B (en) | A kind of method for preparing the classifying porous charcoal nanometer sheet of ultracapacitor fluorenyl | |
| CN108772079B (en) | Preparation method of nano black phosphorus/graphene composite material | |
| CN104528720A (en) | Preparation method and product of multistage porous carbon material | |
| CN102838105B (en) | Preparation method of grading porous carbon material | |
| Wang et al. | Hydrothermal synthesis and electrochemical performance of NiO microspheres with different nanoscale building blocks | |
| CN103440995A (en) | Electrode material for super capacitor and preparing method thereof | |
| CN103663438A (en) | Preparation method of porous graphene | |
| CN103601913A (en) | Graphene/polypyrrole hybrid aerogel and preparation method thereof | |
| CN106024410A (en) | High-capacity graphene-based supercapacitor electrode material and preparation method thereof | |
| Venkateshalu et al. | Heterogeneous 3D graphene derivatives for supercapacitors | |
| CN106395802B (en) | Preparation method of graphene porous membrane | |
| CN106024424A (en) | Nickel hydroxide/graphene roll-carbon nano-tube composite carbon aerogel, preparation thereof and application thereof | |
| CN109378457A (en) | A kind of high compacted density porous silicon chip/carbon compound cathode materials and preparation method | |
| CN107161989A (en) | A kind of preparation method of cellular three-dimensional grapheme | |
| CN103833006A (en) | One-step preparation method of three-dimensional mesoporous nanometer cage-shaped carbon material for super capacitor | |
| CN106629722B (en) | A kind of supercapacitor rice husk/coal tar pitch Quito hole graphitized charcoal nanometer sheet preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |