CN102515144A - Method for preparing porous carbon microspheres converted from graphene - Google Patents
Method for preparing porous carbon microspheres converted from graphene Download PDFInfo
- Publication number
- CN102515144A CN102515144A CN2011104388154A CN201110438815A CN102515144A CN 102515144 A CN102515144 A CN 102515144A CN 2011104388154 A CN2011104388154 A CN 2011104388154A CN 201110438815 A CN201110438815 A CN 201110438815A CN 102515144 A CN102515144 A CN 102515144A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- graphene
- carbon microsphere
- preparation
- transforms
- 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
Relating to preparation methods of porous carbon microspheres, the invention provides a method for preparing porous carbon microspheres converted from graphene. The invention solves the technical problems of focus on template method, complex process, high cost, low yield, difficult realization of batch production as well as popularization and application in current preparation methods of porous carbon microspheres. The method comprises: adding graphite oxide into deionized water for ultrasonic stripping so as to obtain a graphite oxide dispersion solution, then adding an initiator mixing them uniformly, and placing the mixture in a steel reaction kettle with a polytetrafluoroethylene inner liner, sealing the kettle, then conducting hydrothermal treatment, carrying out natural cooling to room temperature, then performing washing with deionized water, and implementing drying, thus obtaining porous carbon microspheres. With the advantages of simple synthesis process, low cost, and short production cycle, etc., the method of the invention is easy to realize mass production as well as popularization and application. And the prepared carbon microspheres converted from graphene have a specific capacity of 306F.g<-1>, and excellent rate performance, thus boasting very good application prospects in the field of supercapacitors.
Description
Technical field
The present invention relates to the preparation method of porous carbon microsphere.
Background technology
Graphene with its unique physicochemical property, has become the focus that scientist pays close attention to since finding.Graphene is with sp by carbon atom
2The monoatomic layer that hydridization connects constitutes, and its theoretic throat is merely 0.35nm, is the thinnest two-dimensional material of being found at present.Graphene has low density, and the characteristics of high conductivity and high-specific surface area have important application prospects in fields such as ultracapacitor, lithium ion battery, solar cell and Hydrogen Energy storages.At present, people still concentrate on like other carbon material how to the research of Graphene to be raw material, to obtain high-quality Graphene through different physico-chemical processes, for example mechanically peel method and graphite oxide reduction method.And it is still less for the research that with the Graphene is other carbon material of raw material acquisition.Reported in literature is not also seen in the research that self-assembly prepares porous carbon microsphere about Graphene.
The porous spherical structure with uniqueness of porous carbon microsphere, at ultracapacitor, fields such as lithium ion battery and support of the catalyst have wide practical use.Yet the method for preparing porous carbon microsphere at present is main with the masterplate method mainly, complex process, and cost is high, yields poorly, and is difficult to produce in batches and apply.
Summary of the invention
It is main with the masterplate method mainly that the present invention will solve the present method for preparing porous carbon microsphere, complex process, and cost is high, yields poorly, and is difficult to the technical problem of producing in batches and applying; And provide Graphene to transform the preparation method of porous carbon microsphere.
The preparation method that Graphene of the present invention transforms porous carbon microsphere is undertaken by following step: graphite oxide is added obtain the graphene oxide dispersion liquid after deionized water for ultrasonic is peeled off 30～300min; Add the initiator mixing then, initiator is acid or alkali, and the concentration of initiator in the graphite oxide dispersion liquid is 0.01～5mol/L; Place the reaction kettle of steel band polytetrafluoroethylliner liner then; Airtight, at 100～250 ℃ of hydrothermal treatment consists 2～40h, naturally cool to room temperature then; Use deionized water wash again 3～6 times, drying; Make porous carbon microsphere.
Acid in the initiator is protonic acid or Lewis acid.Protonic acid such as HCl, HBr, H
2SO
4, HClO
4Or H
3PO
4Deng, Lewis acid is like BF
3, AlCl
3, AlBr
3, TiCl
4, SnCl
4, SbCl
4, PCl
5, ZnCl
2Deng metal halide or POCl
3, CrO
2Cl, SOCl
2, VOCl
3Deng the metal oxyhalogenide.
Alkali in the initiator is ammoniacal liquor, NaOH or KOH.
The diameter that Graphene transforms porous carbon microsphere is 0.5～3 μ m, like 600nm, 1 μ m, 2 μ m or 2.5 μ m.
The present invention has utilized the self-assembly effect of graphite oxide under hydrothermal condition to prepare Graphene and has transformed porous carbon microsphere; Adopt sem to characterize the pattern of Graphene conversion porous carbon microsphere, the method for employing cyclic voltammetric and constant current charge-discharge has been estimated the super capacitor performance of Graphene conversion porous carbon microsphere.The result finds; The inventive method has synthesis technique simple (synthetic through the one step self-assembly of graphene oxide dispersion liquid), and (raw material is business-like cheap products) with low cost, it is with short production cycle that (the hydro-thermal reaction time is merely 2～40h; And the masterplate method time relates to the synthetic of masterplate and removes; Cycle is long, is generally 2～5 days) etc. advantage, be prone to produce in batches and apply; And the Graphene for preparing conversion carbosphere specific storage reaches 306Fg
-1More than., and high rate performance is excellent, in the ultracapacitor field good application prospects is arranged.
Description of drawings
Fig. 1 transforms the electron scanning micrograph of porous carbon microsphere for the Graphene of test one preparation; Fig. 2 transforms the electron scanning micrograph of porous carbon microsphere for the Graphene of test two preparations; Fig. 3 transforms the constant current charge-discharge graphic representation of porous carbon microsphere for the Graphene of test one preparation.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method that Graphene transforms porous carbon microsphere in this embodiment is undertaken by following step: graphite oxide is added deionized water for ultrasonic peel off 30～300min and obtain the graphene oxide dispersion liquid; The back adds the initiator mixing, and initiator is acid or alkali, and the concentration of initiator in the graphite oxide dispersion liquid is 0.01～5mol/L; Place the reaction kettle of steel band polytetrafluoroethylliner liner then; Airtight, at 100～250 ℃ of hydrothermal treatment consists 2～40h, naturally cool to room temperature then; Use deionized water wash again 3～6 times, drying; Make porous carbon microsphere.
The diameter of porous carbon microsphere is 0.5～3 μ m, like 600nm, 1 μ m, 2 μ m or 2.5 μ m.Specific storage reaches 306Fg
-1More than.
Embodiment two: what this embodiment and embodiment one were different is: described graphite oxide is to be raw material with the natural flake graphite, prepares through improving the hummers method that (concrete operation method is referring to 1.N.I.Kovtyukhova, P.J.Ollivier; B.R.Martin; T.E.Mallouk, S.A.Chizhik, E.V.Buzaneva; | A.D.Gorchinskiy.Layer-by-Layer Assembly of Ultrathin Composite Films from Micron-Sized Graphite OxideSheets and Polycations|.Chem.Mater.1999; 11,771-778. and 2.W.S.Hummers, R.E.Offeman.Preparation of Graphitic Oxide.J.Am.Chem.Soc.1958; 80,1339-1339.).Other step is identical with embodiment one with parameter.
Embodiment three: what this embodiment was different with embodiment one or two is: the concentration of said graphene oxide dispersion liquid is 0.05～50mg/ml.Other step is identical with embodiment one or two with parameter.
Embodiment four: what this embodiment was different with one of embodiment one to three is: the power of said ultra-sonic dispersion is 50～500W.Other step is identical with one of embodiment one to three with parameter.
Embodiment five: what this embodiment was different with one of embodiment one to four is: the acid in the initiator is protonic acid or Lewis acid.Other step is identical with one of embodiment one to four with parameter.
Embodiment six: what this embodiment and embodiment five were different is: protonic acid is HCl, HBr, H
2SO
4, HClO
4Or H
3PO
4Lewis acid is BF
3, AlCl
3, AlBr
3, TiCl
4, SnCl
4, SbCl
4, PCl
5, ZnCl
2, POCl
3, CrO
2Cl, SOCl
2, or VOCl
3。Other step is identical with embodiment five with parameter.
Embodiment seven: what this embodiment was different with one of embodiment one to six is: the alkali in the initiator is ammoniacal liquor, NaOH or KOH.Other step is identical with one of embodiment one to six with parameter.
Embodiment eight: what this embodiment was different with one of embodiment one to seven is: drying temperature is 40～150 ℃, and be 5～30h time of drying.Other step is identical with one of embodiment one to seven with parameter.
This embodiment drying can be carried out under can be for air, inert gas atmosphere, also can adopt vacuum-drying, and rare gas element can be nitrogen or argon gas.
Embodiment nine: what this embodiment was different with one of embodiment one to eight is: the hydrothermal treatment consists temperature is 100～250 ℃, and the time is 2～40h.Other step is identical with one of embodiment one to eight with parameter.
Embodiment ten: what this embodiment was different with one of embodiment one to nine is: the concentration of initiator in the graphite oxide dispersion liquid is 0.01～5mol/L.Other step is identical with one of embodiment one to nine with parameter.
Adopt following verification experimental verification invention effect:
The test one: under the room temperature with the graphite oxide ultra-sonic dispersion in deionized water, ultrasonic power 100W, time 1h, the concentration of graphite oxide is 0.5mgmL
-1In the graphite oxide dispersion liquid, add initiator 85% SPA, the concentration of adjustment phosphoric acid in the graphite oxide dispersion liquid is 0.01molL
-1After mixing, airtight in the reaction kettle of mixing solutions with graphite oxide and phosphoric acid as for steel band polytetrafluoroethylliner liner, at 200 ℃ of following hydrothermal treatment consists 10h.Naturally cool to after the room temperature the product that generates with deionized water wash 5 times, place 80 ℃ the dry 10h of baking oven to obtain Graphene conversion porous carbon microsphere.
Graphene transforms the porous carbon microsphere electrode at 2mAcm
-2(0.4Ag
-1) discharging current under specific storage reach 306Fg
-1, current density is increased to 50mAcm
-2(10Ag
-1) time, capacity still remains 265Fg
-1
The testing method of super capacitor performance is following:
The preparation of electrode: Graphene is transformed porous carbon microsphere, acetylene black and PTFE emulsion join in a small amount of absolute ethyl alcohol, evenly be coated to 1 * 1cm with scraper in 80: 15: 5 ratio
2The nickel foam collector on, coated weight is controlled at 5mgcm
-2About, remove solvent and moisture in the electrode in 80 ℃ of dry 10h, use the pressure compression moulding of 5MPa then.
Adopt three-electrode system to study the super capacitor performance of Graphene conversion porous carbon microsphere, counter electrode is the Pt sheet of 2cm * 2cm, and reference electrode is a SCE, and electrolytic solution is 6molL
-1KOH.
Cyclic voltammetry curve is tested on CHI604C type electrochemical workstation.Potential region is [1 ,-0.2V], surface sweeping speed 5mVs
-1
The constant current charge-discharge curve is tested on Land 2001A type battery test system.Potential region [1 ,-0.2V], charging and discharging currents get 2,5,10,20,30,40 and 50mAcm respectively
-2
Method by the specific storage of constant current charge-discharge curve calculation active material is following:
C in the formula---specific storage (F/g);
I---discharging current (A cm
-2);
Δ t---discharge time (s);
The WV of Δ V---potential region or cell capaciator (V);
The quality of M---active material (g).
Fig. 1 is the electron scanning micrograph of the porous carbon microsphere of method for preparing, on scheming, can find out that the diameter of carbon ball is that the carbon ball has vesicular structure about 1 μ m.
Fig. 3 is the constant current charge-discharge curve of the porous carbon microsphere of method for preparing, on scheming, can find out that charging and discharging curve has typical super capacitor characteristic, is 304Fg by calculating loading capacity discharge time
-1
Test two:
Under the room temperature with the graphite oxide ultra-sonic dispersion in deionized water, ultrasonic power 100W, time 1h, the concentration of graphite oxide is 0.5mgmL
-1In the graphite oxide dispersion liquid, add initiator KOH, the concentration of adjustment KOH in the graphite oxide dispersion liquid is 0.1molL
-1After mixing, with the mixing solutions of graphite oxide and phosphoric acid as in the reaction kettle, at 160 ℃ of following hydrothermal treatment consists 5h.Naturally cool to after the room temperature the product that generates with deionized water wash 3 times, place 80 ℃ the dry 10h of baking oven to obtain Graphene conversion porous carbon microsphere.
Fig. 2 is the electron scanning micrograph that the Graphene of method for preparing transforms porous carbon microsphere, and the diameter that can find out the carbon ball on scheme is between 1～2 μ m, and the carbon ball has vesicular structure.
Claims (10)
1. Graphene transforms the preparation method of porous carbon microsphere, it is characterized in that the preparation method that Graphene transforms porous carbon microsphere is undertaken by following step: graphite oxide is added deionized water for ultrasonic peel off 30～300min and obtain the graphene oxide dispersion liquid, the back adds the initiator mixing; Initiator is acid or alkali; The concentration of initiator in the graphite oxide dispersion liquid is 0.01～5mol/L, places the reaction kettle of steel band polytetrafluoroethylliner liner then, and is airtight; Then at 100～250 ℃ of hydrothermal treatment consists 2～40h; Naturally cool to room temperature, use deionized water wash again 3～6 times, drying; Make porous carbon microsphere.
2. Graphene according to claim 1 transforms the preparation method of porous carbon microsphere, it is characterized in that described graphite oxide is is raw material with the natural flake graphite, prepares through improving the hummers method.
3. Graphene according to claim 2 transforms the preparation method of porous carbon microsphere, and the concentration that it is characterized in that described graphene oxide dispersion liquid is 0.05～50mg/mL.
4. Graphene according to claim 3 transforms the preparation method of porous carbon microsphere, and the power that it is characterized in that said ultra-sonic dispersion is 50～500W.
5. Graphene according to claim 4 transforms the preparation method of porous carbon microsphere, it is characterized in that the acid in the initiator is protonic acid or Lewis acid.
6. Graphene according to claim 5 transforms the preparation method of porous carbon microsphere, it is characterized in that said protonic acid is HCl, HBr, H
2SO
4, HClO
4Or H
3PO
4Said Lewis acid is BF
3, AlCl
3, AlBr
3, TiCl
4, SnCl
4, SbCl
4, PCl
5, ZnCl
2, POCl
3, CrO
2Cl, SOCl
2, or VOCl
3
7. Graphene according to claim 6 transforms the preparation method of porous carbon microsphere, it is characterized in that the alkali in the initiator is ammoniacal liquor, NaOH or KOH.
8. transform the preparation method of porous carbon microsphere according to the described Graphene of claim 7 claim, it is characterized in that drying temperature is 40～150 ℃, be 5～30h time of drying.
9. transform the preparation method of porous carbon microsphere according to each described Graphene in the claim 1～8, it is characterized in that the hydrothermal treatment consists temperature is 100～250 ℃, the time is 2～40h.
10. Graphene according to claim 9 transforms the preparation method of porous carbon microsphere, it is characterized in that the concentration of initiator in the graphite oxide dispersion liquid is 0.01～5mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110438815.4A CN102515144B (en) | 2011-12-23 | 2011-12-23 | Method for preparing porous carbon microspheres converted from graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110438815.4A CN102515144B (en) | 2011-12-23 | 2011-12-23 | Method for preparing porous carbon microspheres converted from graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102515144A true CN102515144A (en) | 2012-06-27 |
| CN102515144B CN102515144B (en) | 2014-04-02 |
Family
ID=46286297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110438815.4A Active CN102515144B (en) | 2011-12-23 | 2011-12-23 | Method for preparing porous carbon microspheres converted from graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102515144B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826542A (en) * | 2012-09-14 | 2012-12-19 | 常州第六元素材料科技股份有限公司 | High-specific surface active graphene with mesoporous and preparation method and application thereof |
| CN106082178A (en) * | 2016-06-01 | 2016-11-09 | 华东理工大学 | A kind of method preparing graphene film on insulating body |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001048508A (en) * | 1999-05-27 | 2001-02-20 | Eiji Osawa | Production of nanosize truely spherical graphite |
| CN101538034A (en) * | 2009-04-24 | 2009-09-23 | 江苏大学 | Preparation method of one-step synthesis carbon ball |
| CN101804978A (en) * | 2010-04-15 | 2010-08-18 | 山东大学 | Preparation method of micro nano graphite nodule |
| CN101817520A (en) * | 2010-04-27 | 2010-09-01 | 中国科学技术大学 | Method for manufacturing carbon microspheres by using waste macromolecules |
| CN101857222A (en) * | 2010-05-28 | 2010-10-13 | 常州大学 | Preparation method of large-area and continuous graphen/zinc oxide composite structure |
| CN101912777A (en) * | 2010-07-30 | 2010-12-15 | 清华大学 | Three-dimensional self-assembly of graphene oxide and preparation method and application thereof |
| CN101993056A (en) * | 2010-12-01 | 2011-03-30 | 天津大学 | Graphene-based porous macroscopic carbon material and preparation method thereof |
| CN102145888A (en) * | 2011-04-12 | 2011-08-10 | 东南大学 | Preparation method of grapheme three-dimensional entity |
-
2011
- 2011-12-23 CN CN201110438815.4A patent/CN102515144B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001048508A (en) * | 1999-05-27 | 2001-02-20 | Eiji Osawa | Production of nanosize truely spherical graphite |
| CN101538034A (en) * | 2009-04-24 | 2009-09-23 | 江苏大学 | Preparation method of one-step synthesis carbon ball |
| CN101804978A (en) * | 2010-04-15 | 2010-08-18 | 山东大学 | Preparation method of micro nano graphite nodule |
| CN101817520A (en) * | 2010-04-27 | 2010-09-01 | 中国科学技术大学 | Method for manufacturing carbon microspheres by using waste macromolecules |
| CN101857222A (en) * | 2010-05-28 | 2010-10-13 | 常州大学 | Preparation method of large-area and continuous graphen/zinc oxide composite structure |
| CN101912777A (en) * | 2010-07-30 | 2010-12-15 | 清华大学 | Three-dimensional self-assembly of graphene oxide and preparation method and application thereof |
| CN101993056A (en) * | 2010-12-01 | 2011-03-30 | 天津大学 | Graphene-based porous macroscopic carbon material and preparation method thereof |
| CN102145888A (en) * | 2011-04-12 | 2011-08-10 | 东南大学 | Preparation method of grapheme three-dimensional entity |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826542A (en) * | 2012-09-14 | 2012-12-19 | 常州第六元素材料科技股份有限公司 | High-specific surface active graphene with mesoporous and preparation method and application thereof |
| CN102826542B (en) * | 2012-09-14 | 2016-01-20 | 常州第六元素材料科技股份有限公司 | A kind of graphene with high specific surface activity, Its Preparation Method And Use with mesopore |
| CN106082178A (en) * | 2016-06-01 | 2016-11-09 | 华东理工大学 | A kind of method preparing graphene film on insulating body |
| CN106082178B (en) * | 2016-06-01 | 2019-04-26 | 华东理工大学 | A method of preparing graphene film on insulating body |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102515144B (en) | 2014-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Miller et al. | Graphene electric double layer capacitor with ultra-high-power performance | |
| Kundu et al. | Direct growth of mesoporous MnO2 nanosheet arrays on nickel foam current collectors for high-performance pseudocapacitors | |
| CN102468057B (en) | Preparation method for composite electrode material composed of graphite and manganese dioxide | |
| Zhang et al. | Biosorption-directed integration of hierarchical CoO/C composite with nickel foam for high-performance supercapacitor | |
| WO2016078509A1 (en) | Electrode applied to electrochemical energy storage apparatus and method for preparing same | |
| Liu et al. | Spontaneous exfoliation and tailoring derived oxygen-riched porous carbon nanosheets for superior Li+ storage performance | |
| CN102437314B (en) | Foam metal/lithium iron phosphate integral electrode with three-dimensional structure, preparation method thereof and lithium ion battery using integral electrode as positive pole piece | |
| CN106340401A (en) | Preparing method of composite electrode material and application thereof | |
| CN102682928A (en) | Preparation method of mesoporous carbon nanosheet and application of mesoporous carbon nanosheet as electrode material of super capacitor | |
| CN102800432A (en) | Method for preparing oxidized graphene/conductive polypyrrole nano wire composite material | |
| CN108133831B (en) | Ni3S2Preparation method of @ rGO @ LDHs | |
| CN107910513A (en) | Compound negative electrode of lithium ion battery of a kind of graphene/silicon and preparation method thereof | |
| CN102516764B (en) | Polyaniline nanowire/ graded porous carbon composite material as well as preparation method and application thereof | |
| CN104466134A (en) | Preparation method of self-supported graphene/carbon nano tube hybrid foam-loaded amino-anthraquinone polymer | |
| CN103839683A (en) | Graphene electrode plate and preparation method thereof | |
| CN104466110B (en) | Preparation method of high-performance lithium ion battery negative electrode material | |
| CN109524247A (en) | 3D- graphene/nickel foam and its preparation method and application | |
| CN110697782A (en) | Co3S4@MoS2Preparation method and application of core-shell structure nanosheet array material | |
| CN103137942B (en) | The preparation method of a kind of ferric phosphate lithium cell collector and positive plate | |
| CN102915844A (en) | Method for preparing different-electrode composite materials of carbon plate/manganese dioxide nanometer sheet and application thereof | |
| Zhang et al. | Synthesis of three-dimensional graphene@ Ni (OH) 2 nanoflakes on Ni foam by RF magnetron sputtering for application in supercapacitor | |
| CN110416539A (en) | Polypyrrole coats three-dimensional grapheme cobaltosic oxide lithium cell negative pole material preparation method | |
| CN110010875A (en) | A kind of preparation method of flake cobalt sulfide composite and flexible carbon cloth electrode material | |
| CN104167298A (en) | Graphene-protein derived carbon supercapcaitor material and preparation method thereof | |
| CN110415986B (en) | Ni-doped CoO/C composite material and preparation method thereof |
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 |