CN102515144B - Method for preparing porous carbon microspheres converted from graphene - Google Patents
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- CN102515144B CN102515144B CN201110438815.4A CN201110438815A CN102515144B CN 102515144 B CN102515144 B CN 102515144B CN 201110438815 A CN201110438815 A CN 201110438815A CN 102515144 B CN102515144 B CN 102515144B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 239000004005 microsphere Substances 0.000 title claims abstract description 37
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 6
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000010959 steel Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- -1 polytetrafluoroethylene Polymers 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
Relating to preparation methods of porous carbon microspheres, the invention provides a method for preparing porous carbon microspheres using strong phosphoric acid as the initiator. The invention solves the technical problems of low specific capacity and poor rate capability 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
Since Graphene self-discovery, with its unique physicochemical property, become the focus that scientist pays close attention to.Graphene is with sp by carbon atom
2the monoatomic layer that hydridization connects forms, and its theoretic throat is only 0.35nm, is the thinnest two-dimensional material of finding at present.Graphene has low density, and the feature of high conductivity and high-specific surface area has important application prospect in fields such as ultracapacitor, lithium ion battery, solar cell and Hydrogen Energy storages.At present, people to the research of Graphene still concentrate on as other carbon material be how raw material, by different physico-chemical processes, obtain high-quality Graphene.
In the research of preparing porous carbon microsphere, application number is 201110090764.0, the patent of invention that name is called " a kind of preparation method of grapheme three-dimensional entity " is directed to take alkali and prepares the method for grapheme three-dimensional entity as initiator, its main process is: graphene oxide is mixed with water, stir or ultrasonic dispersion, form the graphene oxide solution that mass body volume concentrations is 1mg/ml~10mg/ml, then add basic solution, and make pH in 8~13 scope, this solution is poured in hydrothermal reaction kettle, be placed in loft drier and be warming up to 100~400 ℃ of reactions, continue 3~48h, then cooling, take out and dry, obtain grapheme three-dimensional entity.The method only be take basic solution as initiator, and it is low to prepare the specific storage of grapheme three-dimensional entity, and high rate performance is poor.
Porous carbon microsphere there is unique porous spherical structure, at ultracapacitor, the fields such as lithium ion battery and support of the catalyst have wide practical use.Yet the method for preparing at present porous carbon microsphere mainly be take masterplate method as main, complex process, cost is high, yields poorly, and is difficult to batch production and applies.
Summary of the invention
The present invention will solve that to prepare at present the specific storage of porous carbon microsphere low, and the poor technical problem of high rate performance; And provide, take strong phosphoric acid and prepare the method for porous carbon microsphere as initiator.
The present invention be take the method that strong phosphoric acid prepares porous carbon microsphere as initiator and is carried out in the steps below: after adding deionized water for ultrasonic to peel off 30~300min graphite oxide, obtain graphene oxide dispersion liquid, then add initiator to mix, initiator is acid, the concentration of initiator in graphene oxide dispersion liquid is 0.01~5mol/L, then be placed in the reactor of steel band polytetrafluoroethylliner liner, airtight, then at 100~250 ℃ of hydrothermal treatment consists 2~40h, naturally cool to room temperature, use again deionized water wash 3~6 times, dry; Make porous carbon microsphere.
Acid in initiator is protonic acid or Lewis acid.Protonic acid is as HCl, HBr, H
2sO
4, HClO
4or H
3pO
4deng, Lewis acid, as 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 metal oxyhalogenide.
The diameter of porous carbon microspheres converted from graphene is 0.5~3 μ m, as 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 porous carbon microspheres converted from graphene, adopt scanning electronic microscope to characterize the pattern of porous carbon microspheres converted from graphene, adopt cyclic voltammetric and constant current charge-discharge method evaluation the super capacitor performance of porous carbon microspheres converted from graphene.Found that, the inventive method has synthesis technique simple (by graphene oxide dispersion liquid one step self assembly), (raw material is business-like cheap products) with low cost, it is with short production cycle that (the hydro-thermal reaction time is only 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, easily produce in batches and apply; And the Graphene preparing conversion carbosphere specific storage reaches 306Fg
-1above, and high rate performance excellence, in ultracapacitor field, there is good application prospect.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of the porous carbon microspheres converted from graphene of test one preparation; Fig. 2 is the constant current charge-discharge graphic representation of the porous carbon microspheres converted from graphene of test one preparation.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method that the strong phosphoric acid of take in present embodiment is prepared porous carbon microsphere as initiator is carried out in the steps below: add deionized water for ultrasonic to peel off 30~300min graphite oxide and obtain graphene oxide dispersion liquid, after add initiator to mix, initiator is acid, the concentration of initiator in graphene oxide dispersion liquid is 0.01~5mol/L, then be placed in the reactor of steel band polytetrafluoroethylliner liner, airtight, then at 100~250 ℃ of hydrothermal treatment consists 2~40h, naturally cool to room temperature, use again deionized water wash 3~6 times, dry, make porous carbon microsphere.
The diameter of porous carbon microsphere is 0.5~3 μ m, as 600nm, 1 μ m, 2 μ m or 2.5 μ m.Specific storage reaches 306Fg
-1above.
Embodiment two: present embodiment is different from embodiment one: described graphite oxide is to take natural flake graphite as raw material, by improving hummers method, prepare 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 Oxide Sheets 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 and parameter are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: the concentration of described graphene oxide dispersion liquid is 0.05~50mg/ml.Other step and parameter are identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: the power of described ultrasonic dispersion is 50~500W.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: the acid in initiator is protonic acid or Lewis acid.Other step and parameter are identical with one of embodiment one to four.
Embodiment six: present embodiment is different from embodiment five: protonic acid is HCl, HBr, H
2sO
4, HClO
4or H
3pO
4; 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.Other step and parameter are identical with embodiment five.
Embodiment seven: present embodiment is different from one of embodiment one to six: drying temperature is 40~150 ℃, and be 5~30h time of drying.Other step and parameter are identical with one of embodiment one to six.
Present embodiment is dry can carry 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 eight: present embodiment is different from one of embodiment one to seven: hydrothermal treatment consists temperature is 100~250 ℃, and the time is 2~40h.Other step and parameter are identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: the concentration of initiator in graphene oxide dispersion liquid is 0.01~5mol/L.Other step and parameter are identical with one of embodiment one to eight.
Adopt following verification experimental verification invention effect:
Test one: under room temperature, be distributed in deionized water graphite oxide is ultrasonic, ultrasonic power 100W, time 1h, the concentration of graphite oxide is 0.5mgmL
-1.In graphene oxide dispersion liquid, add initiator 85% strong phosphoric acid, adjusting the concentration of phosphoric acid in graphene oxide dispersion liquid is 0.01molL
-1.After mixing, in the reactor by the mixing solutions of graphite oxide and phosphoric acid as for steel band polytetrafluoroethylliner liner, airtight, hydrothermal treatment consists 10h at 200 ℃.Naturally cool to after room temperature deionized water wash 5 times for the product generating, the dry 10h of baking oven that is placed in 80 ℃ obtains porous carbon microspheres converted from graphene.
Porous carbon microspheres converted from graphene electrode is 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 as follows:
The preparation of electrode: porous carbon microspheres converted from graphene, acetylene black and PTFE emulsion are joined in a small amount of dehydrated alcohol in the ratio of 80:15:5, be evenly coated to 1 * 1cm with scraper
2nickel foam collector on, coated weight is controlled at 5mgcm
-2left and right, removes solvent and the moisture in electrode in 80 ℃ of dry 10h, then uses the pressure compression moulding of 5MPa.
Adopt three-electrode system to study the super capacitor performance of porous carbon microspheres converted from graphene, the Pt sheet that is 2cm * 2cm to electrode, reference electrode is saturated calomel electrode, 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.
Constant current charge-discharge curve is tested on Land2001A type battery test system.Potential region [1 ,-0.2V], charging and discharging currents gets respectively 2,5,10,20,30,40 and 50mAcm
-2.
Method by the specific storage of constant current charge-discharge curve calculation active material is as follows:
C in formula---specific storage (F/g);
I---discharging current (A cm
-2);
Δ t---discharge time (s);
The operating voltage 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 prepared of aforesaid method, and the diameter that can find out carbon ball from scheming is 1 μ m left and right, and carbon ball has vesicular structure.
Fig. 2 is the constant current charge-discharge curve of the porous carbon microsphere prepared of aforesaid method, can find out that charging and discharging curve has typical supercapacitor properties from scheming, and by calculating loading capacity discharge time, is 304Fg
-1.
Claims (5)
1. the strong phosphoric acid of take is prepared the method for porous carbon microsphere as initiator, it is characterized in that take that the method that strong phosphoric acid is prepared porous carbon microsphere as initiator carries out in the steps below: add deionized water for ultrasonic to peel off 30-300min graphite oxide and obtain graphene oxide dispersion liquid, after add initiator to mix, initiator is strong phosphoric acid, the concentration of initiator in graphene oxide dispersion liquid is 0.01-5mol/L, then be placed in the reactor of steel band polytetrafluoroethylliner liner, airtight, then at 100~250 ° of C hydrothermal treatment consists 2~40h, naturally cool to room temperature, use again deionized water wash 3~6 times, dry, make porous carbon microsphere.
2. according to claim 1ly take strong phosphoric acid and prepare the method for porous carbon microsphere as initiator, it is characterized in that described graphite oxide is to take natural flake graphite as raw material, by improving hummers method, prepare.
3. according to claim 2ly take strong phosphoric acid and prepare the method for porous carbon microsphere as initiator, it is characterized in that the concentration of described graphene oxide dispersion liquid is 0.05~50mg/mL.
4. according to claim 3ly take strong phosphoric acid and prepare the method for porous carbon microsphere as initiator, the power that it is characterized in that described ultrasonic dispersion is 50~500W.
5. according to claim 4ly take strong phosphoric acid and prepare the method for porous carbon microsphere as initiator, it is characterized in that drying temperature is 40~150 ° of C, be 5~30h time of drying.
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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 |
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CN101912777B (en) * | 2010-07-30 | 2012-10-10 | 清华大学 | Three-dimensional self-assembly of graphene oxide and preparation method and application thereof |
CN101993056B (en) * | 2010-12-01 | 2012-05-30 | 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 |
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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 |
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