CN105551829A - Sandwich structured porous carbon/graphene composite material and application in supercapacitor - Google Patents

Sandwich structured porous carbon/graphene composite material and application in supercapacitor Download PDF

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Publication number
CN105551829A
CN105551829A CN201510938992.7A CN201510938992A CN105551829A CN 105551829 A CN105551829 A CN 105551829A CN 201510938992 A CN201510938992 A CN 201510938992A CN 105551829 A CN105551829 A CN 105551829A
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CN
China
Prior art keywords
composite material
graphene
graphene composite
porous charcoal
porous carbon
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Pending
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CN201510938992.7A
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Chinese (zh)
Inventor
解勤兴
周姝雯
解超
张宇峰
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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Priority to CN201510938992.7A priority Critical patent/CN105551829A/en
Publication of CN105551829A publication Critical patent/CN105551829A/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a sandwich structured porous carbon/graphene composite material, a preparation method thereof and application in a supercapacitor. The porous carbon/graphene composite material is prepared by carrying out surface coating on polyacrylonitrile nanofiber cloth with a graphene solution, carrying out pre-oxidation for 1 to 2 hours at a condition of 200-300 DEG C, carrying out carbonization and activation at 600-1,000 DEG C, and washing and drying the nanofiber cloth. The supercapacitor assembled by taking the porous carbon/graphene composite material prepared according to the technical scheme as an electrode has the characteristics of excellent performance, high energy density, high specific power, high rate capability, long cycle lifetime and the like.

Description

A kind of sandwich structure porous charcoal/graphene composite material and super capacitor application
Technical field
The present invention relates to technical field of inorganic nonmetallic materials, particularly relate to a kind of Novel super capacitor porous carbon/graphene composite material and preparation method thereof.
Background technology
Active carbon has the features such as high-specific surface area, high stability and aperture be controlled, is thus extensively used as electrode material for super capacitor.But absorbent charcoal based ultracapacitor has the low shortcoming of energy density, it is promoted and use is very restricted.Graphene has high-specific surface area, and (theoretical value is 2650m 2/ g), the feature such as high conductivity, in super capacitor energy-storage, have very strong application prospect, its theoretical specific capacity is up to 550F/g (Small, 2014,10 (17): 3480-3498; Chemistry, 2014,20 (43): 13838-13852).But should see, the preparation technology of Graphene is loaded down with trivial details, with high costs, easily cause the overlapping again of graphene film in extensive preparation process simultaneously, thus causing property loss of energy, therefore the single graphene-based ultracapacitor of bibliographical information is not only expensive, and its ratio capacitance is well below theoretical value (ChemSusChem, 2010,3 (2): 136-168).
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the present invention for carbon source, prepares a kind of novel class sandwich structure N doping porous carbon/graphene composite material with polyacrylonitrile nanofiber cloth, and as electrode assembling ultracapacitor.Because institute's prepared material has special sandwich loose structure, high-specific surface area, the simultaneously fake capacitance characteristic that has of nitrogen-atoms, the ultracapacitor assembled has high specific capacitance, high magnification and high cycle performance, and energy density improves greatly simultaneously.
The technical solution adopted in the present invention is:
Can adulterate in 0 ~ 2wt.% Graphene and carbon nano-tube in the polyacrylonitrile nanofiber adopted one or both;
The Graphene adopted is one or both in graphene oxide, reduced graphene;
Polyacrylonitrile nanofiber cloth graphene solution is carried out pre-oxidation 1 ~ 3 hour after surface coating, drying under 200 ~ 300 degree of conditions, then carry out carbonization and activation at 600 ~ 1000 degree, after washing, drying, obtain porous charcoal/graphene composite material.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment 1 product.
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 2 product
Fig. 3 is the charging and discharging curve of aqueous super capacitor when current density is 1A/g.
Fig. 4 is the relation curve between the ratio capacitance of aqueous super capacitor and current density.
Fig. 5 is the charging and discharging curve of organic system ultracapacitor under different current density.
Fig. 6 is the relation curve between the power density of water system and organic system ultracapacitor and energy density.
Embodiment
Embodiment 1: the preparation of porous charcoal/graphene composite material
Method of electrostatic spinning is utilized to prepare polyacrylonitrile nanofiber cloth.By polyacrylonitrile nanofiber cloth dip coated in 0.1% graphene oxide solution, and dry.By the 300 degree of insulations 1 hour in atmosphere of the composite fibre that obtains, then 750 degree of carbonizations 1 hour in blanket of nitrogen.By product and KOH with 1: 4 mass ratio mix, and 700 degree of activation 2 hours under nitrogen atmosphere.Product is obtained, as shown in Figure 1 with after distilled water washing, forced air drying.
Embodiment 2: the preparation of porous charcoal/graphene composite material
Method of electrostatic spinning is utilized to prepare the polyacrylonitrile composite nano fiber cloth containing 0.5% graphene oxide.By polyacrylonitrile nanofiber cloth dip coated in 0.1% graphene oxide solution, and dry.By the 300 degree of insulations 1 hour in atmosphere of the composite fibre that obtains, then 750 degree of carbonizations 1 hour in blanket of nitrogen.By product and KOH with 1: 4 mass ratio mix, and 700 activation 2 hours under nitrogen atmosphere.Product is obtained, as shown in Figure 2 with after distilled water washing, forced air drying
Embodiment 3: the electrochemical property test of material
Adopt the electrochemical properties of two electrode super capacitor systems at room temperature test material, wherein electrolyte is 6M potassium hydroxide aqueous solution and 1M tetrafluoro boric acid tetraethyl amine (TEABF 4) acetonitrile (AN) solution, adopt Shanghai CHI660E electrochemical workstation to carry out charge-discharge test to ultracapacitor, voltage range is 0-1.0V (KOH) and 0-2.5V (TEABF 4/ AN).Result is as follows:
(1) as seen from Figure 3, present typical isosceles triangle charging and discharging curve with the aqueous super capacitor that electrode material prepared by the technical program is assembled, internal resistance is very little not have obvious pressure drop to illustrate.As seen from Figure 4, ratio capacitance when embodiment 1 and the composite material 0.1A/g prepared by embodiment 2 still remains 216.0F/g and 257.0F/g up to when 362.0F/g and 381.6F/g, 20A/g respectively, presents good high rate performance.
(2) as seen from Figure 5, the organic system ultracapacitor assembled with electrode material prepared by the technical program presents typical isosceles triangle charging and discharging curve, and internal resistance is very little not have obvious pressure drop to illustrate.When current density is 1A/g, ratio capacitance still keeps 143.2F/g up to when 156.0F/g, 5A/g, presents good high rate performance.
(3) water system of as seen from Figure 6, assembling with electrode material prepared by the technical program and organic system ultracapacitor all have high-energy-density and high power density.Wherein with the energy density of the aqueous super capacitor that is electrode of composite material prepared by embodiment 1 and embodiment 2 when 0.1A/g respectively up to 12.6Wh/kg and 13.2Wh/kg, far above bibliographical information numerical value (JournalofPowerSources, 2013,240:109-113; JournalofPowerSources, 2012,209:152-157), even be better than the carbon nano-fiber, carbon nano-tube and graphene-based ultracapacitor (the ACSSustainableChemistry & Engineering that report, 2014,2,1525-1533; ElectrochemistryCommunications, 2011,13:355-358).With the organic system ultracapacitor that composite material prepared by embodiment 2 is electrode, there is higher energy density and power density.

Claims (6)

1. the preparation method of porous charcoal/graphene composite material, its concrete steps are: polyacrylonitrile nanofiber cloth graphene aqueous solution be coated with, under 200 ~ 300 degree of conditions, pre-oxidation 1 ~ 3 hour is carried out after drying, then carry out carbonization and activation at 600 ~ 1000 degree, after washing, drying, obtain porous charcoal/graphene composite material.
2. the preparation method of a kind of porous charcoal/graphene composite material according to claim 1, it is characterized in that can adulterating in described polyacrylonitrile nanofiber in 0 ~ 2wt.% Graphene and carbon nano-tube one or both.
3. a kind of preparation method of porous charcoal/graphene composite material according to claim 1,2, it is characterized in that described Graphene be in graphene oxide and reduced graphene one or both.
4. porous charcoal/graphene composite material, described composite material is by the method preparation according to any one of right 1 ~ 3.
5. porous charcoal/graphene composite material, described composite material has class sandwich loose structure.
6. porous charcoal/the graphene composite material described in Claims 1 to 5 can be used as electrode of super capacitor.
CN201510938992.7A 2015-12-16 2015-12-16 Sandwich structured porous carbon/graphene composite material and application in supercapacitor Pending CN105551829A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106952738A (en) * 2017-03-09 2017-07-14 安徽大学 A kind of electrode with flexible self-supporting structure and preparation method and application
CN108711520A (en) * 2018-05-22 2018-10-26 青岛大学 A kind of preparation method and applications of the oxidation carbon cloth based on polyacrylonitrile

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104167298A (en) * 2014-07-28 2014-11-26 复旦大学 Graphene-protein derived carbon supercapcaitor material and preparation method thereof
CN104477878A (en) * 2014-12-04 2015-04-01 中国科学院山西煤炭化学研究所 Graphene-based hierarchical porous carbon material as well as preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104167298A (en) * 2014-07-28 2014-11-26 复旦大学 Graphene-protein derived carbon supercapcaitor material and preparation method thereof
CN104477878A (en) * 2014-12-04 2015-04-01 中国科学院山西煤炭化学研究所 Graphene-based hierarchical porous carbon material as well as preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QINXING XIE等: "Sandwich-like nitrogen-enriched porous carbon/graphene composites as electrodes for aqueous symmetric supercapacitors with high energy density", 《ELECTROCHIMICA ACTA》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106952738A (en) * 2017-03-09 2017-07-14 安徽大学 A kind of electrode with flexible self-supporting structure and preparation method and application
CN106952738B (en) * 2017-03-09 2019-04-09 安徽大学 A kind of electrode and the preparation method and application thereof with flexible self-supporting structure
CN108711520A (en) * 2018-05-22 2018-10-26 青岛大学 A kind of preparation method and applications of the oxidation carbon cloth based on polyacrylonitrile

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Application publication date: 20160504