CN107004518B - Composite material and preparation method - Google Patents
Composite material and preparation method Download PDFInfo
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- CN107004518B CN107004518B CN201580064957.5A CN201580064957A CN107004518B CN 107004518 B CN107004518 B CN 107004518B CN 201580064957 A CN201580064957 A CN 201580064957A CN 107004518 B CN107004518 B CN 107004518B
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- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 329
- 239000000463 material Substances 0.000 claims abstract description 235
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 209
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 110
- 239000002245 particle Substances 0.000 claims abstract description 78
- 229920000767 polyaniline Polymers 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 31
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 11
- 229920001940 conductive polymer Polymers 0.000 claims description 88
- 239000002322 conducting polymer Substances 0.000 claims description 83
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 23
- 150000001412 amines Chemical class 0.000 claims description 11
- 125000003368 amide group Chemical group 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 229910017709 Ni Co Inorganic materials 0.000 claims description 2
- 229910003310 Ni-Al Inorganic materials 0.000 claims description 2
- 229910003267 Ni-Co Inorganic materials 0.000 claims description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 2
- 239000001230 potassium iodate Substances 0.000 claims description 2
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 2
- 229940093930 potassium iodate Drugs 0.000 claims description 2
- 235000006666 potassium iodate Nutrition 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 description 16
- 125000000524 functional group Chemical group 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- 239000003638 chemical reducing agent Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 230000001976 improved effect Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
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- 235000019441 ethanol Nutrition 0.000 description 6
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- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- -1 phenylenevinylenes Chemical class 0.000 description 5
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/48—Conductive polymers
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a kind of composite materials, it includes multiple active carbon particles, first layer and the second layer, the first layer includes the graphene-based material being arranged on one or more active carbon particles, the second layer includes the pseudo-capacitance material being arranged on the first layer including graphene-based material, such as polyaniline and polypyrrole.The present invention also provides the methods for preparing composite material and the electrode including composite material.
Description
Cross reference to related applications
This application claims the priority of the Singapore patent application No.10201407656U submitted on November 17th, 2014
Equity, entire contents are incorporated herein by reference for all purposes.
Technical field
The method that each embodiment is related to composite material and prepares composite material.
Background technique
Supercapacitor has become a kind of cost efficient, environmental-friendly and reliable energy scheme, provides height
Power density simultaneously has extended service life.The application of supercapacitor includes consumer electronics, intermittent power generation machine (such as intelligence
Power grid, solar panel and windmill) energy storage and bulk transport system (such as electric rail gantry and hybrid vehicle).
Based on its energy storage mechanism, supercapacitor can be divided into two types: electrochemical double layer capacitor (EDLC)
Or pseudocapacitor.EDLC can be generated by the separation of charge of electrode/electrolyte interface, and effective table of electrode can be used
The dielectric constant of area and electrolyte determines.On the other hand, pseudocapacitor can be by fast between electrode material and electrolyte
Fast faraday's reaction generates.Therefore, pseudocapacitor combines the feature of capacitor and battery.
EDLC usually can have the gravimetric capacitance of about 80F/g to about 120F/g, and active carbon is mainly as application of electrode.It is quasi-
Capacitor usually can have the gravimetric capacitance of about 200F/g to about 2000F/g, wherein metal oxide such as RuO2、MnO2、NiO、
Co(OH)2And/or Co3O4And conducting polymer such as polyaniline, polypyrrole and/or polythiophene, it is mainly used as electrode.With quasi- electricity
Container is compared, and EDLC has longer cycle life, but specific capacitance value is lower.
Although supercapacitor shows the maximum power capability and about 10 of about 1kW/kg so far4It is a to be recycled to about 106It is a
The long life cycle in period, but they are subject to the low energy densities of about 0.5Wh/kg to about 5Wh/kg.It is ground in supercapacitor
Study carefully aspect and carried out many effort, it is therefore an objective to be made up between conventional capacitor and battery in terms of power and energy performance respectively
Gap.
For the large-scale application of supercapacitor commercial viability, needs bigger energy density and reduce cost.It is super
Equation E=0.5CV can be used in the energy density (E) of grade capacitor2It determines, wherein C indicates that capacitor, V indicate operating potential.Root
According to above-mentioned theory, since operating potential (V) depends primarily on used electrolyte, so for the plan for increasing capacitance (C)
Slightly for realizing that bigger energy density is particularly important.
Graphene is the two-dimentional allotrope of carbon, and carbon atom is with the sp of rule2The form of hexagons of bonding is densely filled out
It fills.Due to its special performance, such as big thermal conductivity, excellent mechanical performance, and by their a wide range of pi-conjugated production
The uncommon electrical property of raw about 100S/m, graphene-based material cause great interest.In addition, such as chemical stability
It is high, surface area is big, electrochemical window mouth width attribute applies graphene-based material to have in the electrode material of supercapacitor
It is attractive.The graphene of chemical derivatization for supercapacitor is shown respectively in nonaqueous electrolyte and aqueous electrolyte
The capacitance of 99F/g and 135F/g.Other attributes, such as high surface area, adjustable surface chemistry and unique two-dimentional (2D) structure,
Graphene has been set to become the ideal substrate for loading pseudo-capacitance material, the pseudo-capacitance material is used for high-energy/power
Supercapacitor applications.However, pure graphene has low mass density and Gao Chengben, so that it is not suitable for extensive work at present
Industry application.
Accordingly, there are the needs for the improvement material for overcoming or at least mitigating one or more above problems.
Summary of the invention
In a first aspect, providing a kind of composite material.Composite material includes multiple active carbon particles, first layer and second
Layer, first layer include the graphene-based material being arranged on one or more active carbon particles, the second layer include be arranged in including
Pseudo-capacitance material on the first layer of graphene-based material.
In second aspect, the method that composite material is prepared according to first aspect is provided.This method includes
A) graphene-based material is provided；
B) graphene-based material is added in dispersion to form first layer, which includes multiple active carbons
Grain, which includes the graphene-based material being arranged on one or more active carbon particles, and
C) deposition includes the second layer of pseudo-capacitance material to obtain composite wood on the first layer for including graphene-based material
Material.
In the third aspect, provide including the composite material according to first aspect or by the method system according to second aspect
The electrode of standby composite material.
Detailed description of the invention
It is described in detail in conjunction with non-limiting example and attached drawing, is better understood with the present invention, in which:
Fig. 1 shows the schematic diagram of materials synthesis: (a) active carbon/conducting polymer (AC/CP) composite material, and (b) living
Property charcoal/NH2Modified graphene/ conductive polymer (AC/NHG/CP) composite material.
Fig. 2 is the chart that the capacitivity performance of various composite materials compares: (i) AC/ graphene/CP, (ii) AC/CP,
(iii)AC。
Fig. 3 describes the electrochemistry of AC/NHG/CP composite material in symmetrical twin electrodes AC/NHG/CP supercapacitor
Can, it wherein (a) is cyclic voltammetry, and is (b) charge/discharge curve.(a) illustration in is advised according to embodiment laboratory
The photo of the AC/NHG/CP supercapacitor device of mould.
Specific embodiment
In a first aspect, each embodiment is related to composite material.The term as used herein " compound " refers to by two kinds or more
The material that kind different component is formed, and there is the function and/or structural property different from individual each component.
Composite material includes multiple active carbon particles, first layer and the second layer, and first layer includes being arranged in one or more
Graphene-based material on active carbon particle, the second layer include the pseudo-capacitance material being arranged on graphene-based material.
It, can be in graphene by forming the first layer including graphene-based material on one or more active carbon particles
Pseudo-capacitance material is arranged on the surface of sill to form the second layer, which includes the substantially uniform pseudo-capacitance material of thickness
Material, can be in nanometer scale.Therefore, composite material can contain the micro-structure there are many active carbon particle, active carbon particle
With the bilayer or multilayer encapsulated by structures including grapheme material layer and pseudo-capacitance material layer.The thickness of pseudo-capacitance material can be lower than
The thickness of graphene-based material.As a result, the energy density and capacitor of composite material can be greatly improved.Since active carbon particle can
To be inserted between graphene-based material layer the stacking again for preventing graphene, therefore this further improves graphene-based materials
Dispersibility in the composite.Herein it has been proved that the physicochemical properties of composite material and super electricity in the prior art
Container material is suitable, while cycle life that is light-weight and having length.In addition, the method for preparing composite material is low cost and peace
Full method, and can easily amplify for plant-scale manufacture.
As used herein, " active carbon " refers to the porous carbon with random or amorphous structure.In controlled atmosphere and temperature
Under degree, by physical modification and in the thermal decomposition of at least 600 DEG C temperature, carbon-based material or any organic material with high-carbon content
Material can be converted into active carbon.After processing, active carbon can have the network structure in sub- micro- hole, lead to big specific surface area
(surface area of per unit volume), can be in about 500m2/ g to about 3000m2In the range of/g.
Composite material includes multiple active carbon particles.Term " particle " refer to little particle, fiber, thin slice, sphere, powder,
Platelet-like and other forms and shape, can be regular or irregular.In various embodiments, active carbon particle can be with
It is at least substantially spherical.
The size of active carbon particle can be characterized by their average diameter.Although term " diameter " is commonly used in finger
Pass through center and connect the maximum length of the line segment of two points on sphere periphery, but is also used for referring to through center and company here
Connect the maximum length of the line segment of two points on the particle periphery of incomplete spherical shape.Term " average diameter " refers to being averaged for particle
Diameter, and can be by calculating the sum of diameter of each particle divided by the sum of particle.
In various embodiments, the size of active carbon particle is in the range of about 10nm to about 50nm.For example, active carbon
Grain can have the size within the scope of about 10nm to about 40nm, for example, about 10nm to about 30nm, about 10nm to about 20nm, about
20nm to about 50nm, about 30nm are to about 50nm, about 40nm to about 50nm, about 20nm to about 40nm, or about 30nm to about 40nm.Cause
This, active carbon particle is referred to as active carbon nano particle, wherein term " nano particle " refer to average diameter be 100nm or
Lower particle.
As described above, active carbon particle is formed and can be thermally decomposed at a high temperature of making carbon-based material in furnace.
Due to used high temperature, being formed by active carbon particle can be without on surface functional group or active carbon particle outer surface
Functional group.
Active carbon particle may be constructed the main component of composite material.In various embodiments, active carbon in composite material
The amount of particle is range of the about 40wt% to about 98wt%, for example, about 40wt% to about 90wt%, about 40wt% to about 80wt%,
About 40wt% to about 70wt%, about 40wt% to about 60wt%, about 40wt% to about 50wt%, about 50wt% to about 98wt%,
About 60wt% is to about 98wt% about 70wt% to about 98wt%, about 80wt% to about 98wt%, about 50wt% to about 90wt%, about
50wt% to about 80wt%, about 60wt% are to about 80wt%, or about 55wt% to about 75wt%.
Composite material disclosed herein further includes graphene-based material, wherein graphene-based material be arranged in one or
First layer on multiple active carbon particles exists.
The example of graphene-based material include but is not limited to graphene, graphene oxide, reduced form graphene oxide and its
Mixture.
Graphene typically refers to the form of graphitic carbon, and wherein carbon atom is covalently bonded to one another to form the two of bonding carbon atom
It ties up piece (sheet).Carbon atom can pass through sp2Key bonds together, and can form the repetitive unit of 6 member rings, and may be used also
To include 5 member rings and/or 7 member rings.In its crystal form, two panels or more graphene can be stacked to be formed
Multiple stack layers.In general, the side of graphene is saturated by hydrogen atom.
Graphene oxide refers to the oxidised form of graphene, and may include oxygen-containing group, for example, hydroxyl, epoxy group,
Carboxyl and/or ketone group.Reduced form graphene oxide refers to that graphene oxide has carried out reduction treatment, thus partially or substantially
Redox graphene.For example, some oxygen-containing groups, which can be retained in, to be formed after so that graphene oxide is carried out reduction treatment
On reduced form graphene oxide.Reduction treatment can be carried out by chemistry route or by heat treatment.Although can also be by also
Former graphene oxide obtains graphene, but the term as used herein " reduced form graphene oxide " does not refer to graphene.Pass through
At least partly redox graphene is to form reduced form graphene oxide, while not being reduced into graphene, Yi Xiehan
Oxygen groups can be removed from graphene oxide, to partly save the sp of graphene2Network.When doing so, this allows
Electric charge transfer occurs in the graphene network of preservation, to assign material conductivity.
In various embodiments, graphene-based material includes or mixtures thereof graphene oxide, reduced form graphene oxide.
For example, graphene-based material may include or be made of graphene oxide.In some embodiments, graphene-based material include or
It is made of reduced form graphene oxide.In a particular embodiment, graphene-based material is made of reduced form graphene oxide.
Graphene-based material can adulterate nitrogen, or can be grafted nitrogen substance on it.
In various embodiments, material doped there is nitrogen including in the composite graphene-based.The term as used herein
" doping " refers to that the carbon atom in graphene-based material is replaced by the atom of another element.For example, can will such as by doping
The hetero atom of nitrogen-atoms is introduced into the carbon lattice of graphene.
In various embodiments, there is nitrogen substance including graphene-based grafting materials in the composite.Nitrogen substance
Example include but is not limited to amide groups (- C (O) N), itrile group (- C ≡ N) and amido (- NH2).The term as used herein " grafting "
Refer to and forms one or more chemical bonds between two molecules.Compared with doping, nitrogen-atoms directly replaces stone in the doping
Carbon atom in mertenyl material, nitrogen substance are attached on graphene-based material and with bond with carbon, thus by one or
Multiple nitrogen-atoms are introduced into carbon material.In a particular embodiment, nitrogen substance is-NH2.Advantageously, because introducing pseudo-capacitance
Interaction and improved the wetability ,-NH of graphene2Modification is the effective ways for improving graphene capacitance.
The amount of graphene-based material can be in the range of about 1wt% to about 30wt% in composite material.For example, composite wood
The amount of graphene-based material can be in the range of about 1wt% to about 20wt% in material, for example, about 1wt% to about 15wt%, about
1wt% to about 10wt%, about 5wt% are to about 30wt%, about 10wt% to about 30wt%, about 15wt% to about 30wt%, about
20wt% to about 30wt%, about 10wt% are to about 25wt%, or about 5wt% to about 20wt%.
Graphene-based material can have the size in about 50nm to about 20 μ ms.In the content of graphene-based material
In, size refers to the full-size of graphene-based material in any direction.According to the size of graphene-based material, including graphite
The first layer of olefinic base material can be arranged on tens of, hundreds of, thousands of tens of thousands of or tens of thousands of a active carbon particles.
Therefore, the first layer including graphene-based material can cover one of one or more active carbon particle outer surfaces
Divide or most of.In various embodiments, the first layer including graphene-based material partly surrounds or surrounds one or more
Active carbon particle.For example, when two or more active carbon particles are assembled and/or are in contact with each other, due in two active carbons
There are lap between particle, graphene-based material may be cannot be introduced into, therefore the first layer including graphene-based material can
Each active carbon particle can be surrounded.In a particular embodiment, the first layer including graphene-based material encapsulates one or more
A active carbon particle.
As noted previously, as the high temperature involved in active carbon particle synthesis, active carbon particle can not contain surface function
Group, i.e. functional group on active carbon particle outer surface.Therefore, the first layer including graphene-based material may not be with active carbon
Particle chemical bonding.For example, graphene-based material may not be covalently bound on active carbon particle.On the contrary, active carbon particle can
It can be inserted between graphene-based material, which may exist with layer, to make graphene-based material separation to divide
It dissipates graphene-based material and them is avoided to stack again.
In various embodiments, the thickness of the first layer including graphene-based material can be in about 0.5nm to about 30nm's
In range.E.g., including the first layer of graphene-based material can have the thickness of about 0.5nm to about 25nm range, for example, about
5nm to about 25nm, about 10nm are to about 25nm, about 15nm to about 25nm, about 20nm to about 25nm, about 0.5nm to about 15nm, about
0.5nm to about 10nm, about 0.5nm are to about 5nm, about 5nm to about 20nm, about 5nm to about 15nm, or about 10nm to about 20nm.
When thickness is greater than 30nm, graphene-based material can be the form of thin slice or graphite flake, too thick and all
Such as cannot working well in for supercapacitor.On the contrary, include graphene-based material first layer preferably have it is several
To about 10nm or about 0.5nm to about 5nm, this can provide improved performance for the thickness of nanometer range, for example, about 0.5nm.
The second layer including pseudo-capacitance material is arranged on the first layer including graphene-based material.In each embodiment
In, pseudo-capacitance material is directly arranged on graphene-based material, for example, pseudo-capacitance material is contacted with graphene-based Material Physics,
And covalent bond and/or non-covalent bond can be formed with graphene-based material.In such an embodiment, in pseudo-capacitance material and graphene
Middle layer is not present between sill, and may be such when pseudo-capacitance material is directly formed on graphene-based material
Situation.
In various embodiments, pseudo-capacitance material is selected from by conducting polymer, metal oxide, metal sulfide, metal
The group of hydroxide and combinations thereof composition.
Conducting polymer is often referred to be able to carry out the polymer of electronics conduction.In various embodiments, conducting polymer has
There is the conjugated pi-skeleton for making polymer be able to carry out electron charge conduction.The example of conducting polymer includes but is not limited to polypyrrole
And its derivative and copolymer, polythiophene and its derivative and copolymer (including poly- (3- alkylthrophene) and poly- (3,4- ethylene two
Oxygen thiophene) (PEDOT)), Polyaniline and its derivative and copolymer, poly- (to phenylene vinylidene) and its derivative and copolymerization
Object；Polysulfones and its derivative and copolymer and polyacetylene and its derivative and copolymer.
In various embodiments, conducting polymer is selected from by polyaniline, polypyrrole, polythiophene, poly- (phenylenevinylenes
Base), poly- (diphenyl sulfide), poly- diphenylamines, poly- sub- thienyl ethenylidene, double thiophene, polyethylene dioxythiophene, poly- triazine, poly- second
The group of alkynes and its derivative and its mixture composition.
In a particular embodiment, conducting polymer is selected from by polyaniline, polypyrrole, polythiophene and its copolymer and combinations thereof
The group of composition.It due to its low cost, is readily synthesized, good electric conductivity, quick redox rate and high pseudo-capacitance, gathers
Aniline is denoted herein as PANi, is particularly advantageous.
In addition to conducting polymer beyond the region of objective existence, metal oxide, metal sulfide and/or metal hydroxides are also used as quasi- electricity
Capacity materials.In various embodiments, metal oxide choosing is by autoxidation nickel, ruthenium-oxide, manganese oxide, cobalt oxide (II), Co3O4, oxygen
Change the group of iron and combinations thereof composition.The example for the metal sulfide that can be used includes NiCo2S4.In the feelings of metal hydroxides
In condition, metal hydroxides can be selected from by cobalt hydroxide, Cu (OH)2、Ni(OH)2, Ni-Co hydroxide, Ni-Al hydroxide
The group of object and combinations thereof composition.
The amount of pseudo-capacitance material can be within the scope of about 1wt% to about 30wt% in composite material, and for example, about 1wt% is to about
20wt%, about 1wt% are to about 15wt%, and about 1wt% to about 10wt%, about 5wt% to about 30wt%, about 10wt% is to about
30wt%, about 20wt% are to about 30wt%, and about 10wt% to about 25wt%, about 5wt% to about 20wt%, about 10wt% is to about
20wt%, or about 1wt% to about 5wt%.
The second layer including pseudo-capacitance material can be covered in a part or major part of first layer, which includes
Graphene-based material.In various embodiments, the second layer including pseudo-capacitance material partly surrounds or surrounds one or more
Active carbon particle, active carbon particle have the first layer of the graphene-based material including being disposed thereon.In some embodiments,
Second layer encapsulating including pseudo-capacitance material has the active carbon particle of first layer, which includes arranging on the activated carbon
Graphene-based material.
Advantageously, pseudo-capacitance material can be with coating or layer arrangement on graphene-based material, and the coating or layer have extremely
Few substantially uniform thickness.In the case where graphene-based material is not present, pseudo-capacitance material, such as conducting polymer, in work
Property charcoal particle on do not form shallow layer because they tend between active carbon particle assemble and/or formed particle, this may
It is since surface functional group being not present on active carbon particle.When pseudo-capacitance material is applied directly on active carbon, this is converted into
Much lower capacitance.
Therefore, even if a part of of pseudo-capacitance material may be physically contacted with active carbon particle, pseudo-capacitance material tends to
The not forming layer on active carbon particle.Therefore, graphene-based material may be used as boundary layer, to allow the table in active carbon particle
Uniform pseudo-capacitance material layer is formed on face, this is important, because the capacitance contribution of pseudo-capacitance material is in 100nm and below
Thickness can be most preferably.In this respect, graphene-based material can provide surface functional group abundant, which can be with
With pseudo-capacitance material it is covalent and/or it is non-covalent be bonded, to allow pseudo-capacitance material with substantially uniform layer in active carbon particle
On be uniformly distributed.
In various embodiments, between pseudo-capacitance material and graphene-based material exist by electrostatic interaction and/
Or the combination of the covalent bond and non-covalent bond of hydrogen bond, to provide the stronger connection of pseudo-capacitance material Yu graphene-based material.
In this respect, noted herein, dispersion or material containing active carbon, graphene-based material and pseudo-capacitance material
(wherein graphene-based material and pseudo-capacitance material be not with the individual course presence on active carbon), does not constitute composite wood as described herein
Material.
In various embodiments, the second layer including pseudo-capacitance material and the first layer covalent bond including graphene-based material
It closes.In some embodiments, the second layer including pseudo-capacitance material is total to the first layer for including graphene-based material by amine key
Valence link closes.
The thickness of the second layer including pseudo-capacitance material can depend on following factor, such as (a) pseudo-capacitance material is negative
Loading capacity ratio (loading weight ratio), and (b) content of graphene-based material.
Load weight comparison in order to illustrate pseudo-capacitance material includes the influence of the thickness of the second layer of pseudo-capacitance material, is mentioned
Following exemplary embodiment is supplied.For example, polyaniline (PANi) is polyaniline/graphene/active carbon particle of 10wt%
(PANi/G/AC) composite material, wherein graphene content is 10wt%, can result in the second layer that thickness is less than 10nm.
On the other hand, PANi is the PANi/G/AC composite material of 50wt%, and wherein graphene content is 10wt%, can be resulted in
The second layer of the thickness within the scope of about 15nm to about 50nm.Therefore, the content for increasing pseudo-capacitance material, so that its load weight ratio
Increase, the thicker second layer can be resulted in.
As described previously for the influence of graphene-based material content, in polyaniline/stone that polyaniline (PANi) is 10wt%
In black alkene/active carbon particle (PANi/G/AC) composite material, wherein graphene content is 10wt%, can result in about 1nm
To the second layer of about 5nm thickness.However, PANi is the PANi/G/AC composite material of 10wt%, wherein the content of graphene is
1wt% can result in thickness greater than 3nm but be less than the second layer of 10nm.
In general, the content of the load weight ratio and/or the graphene-based material of reduction that increase pseudo-capacitance material can increase by second
The thickness of layer.
The thickness of pseudo-capacitance material can be about 100nm or smaller on graphene-based material.For example, the thickness of pseudo-capacitance material
Degree can be within the scope of about 1nm to about 100nm, for example, about 1nm to about 80nm, about 1nm to about 60nm, about 1nm to about 40nm, about
30nm to about 100nm, about 50nm are to about 100nm, about 70nm to about 100nm, about 30nm to about 80nm, about 30nm to about 60nm,
About 20nm to about 40nm, about 60nm are to about 80nm, about 10nm, about 20nm, about 30nm, about 40nm, about 50nm, about 60nm, about
70nm, about 80nm, about 90nm or about 100nm.
Advantageously, herein it is verified on graphene-based material with less than 100nm film existing for pseudo-capacitance material
(such as conducting polymer) is effectively that pseudo-capacitance material provides standard as a result, for completely reversibility and quick faraday's reaction
Capacitance charge storage.Graphene-based material can provide a platform, pseudo-capacitance material can be arranged in graphite on the platform
To form uniform coating on olefinic base material, and pseudo-capacitance material can contribute big capacitance.
In a particular embodiment, composite material includes multiple active carbon particles, first layer and the second layer, and first layer includes cloth
The graphene-based material on one or more active carbon particles is set, the second layer includes be arranged in including graphene-based material
Conducting polymer on one layer, wherein graphene-based material includes or by-NH2The reduced form graphene oxide of grafting forms, and
Conducting polymer includes polyaniline and/or polypyrrole.
Each embodiment is related to preparing the method according to first aspect composite material in second aspect.This method includes providing
Graphene-based material；Graphene-based material is added to form first layer in dispersion, which includes multiple active carbons
Particle, the first layer include the graphene-based material being arranged on one or more active carbon particles, and are including graphene-based
Deposition includes the second layer of pseudo-capacitance material to obtain composite material on the first layer of material.
The example that the graphene-based material that can be used is described above.In a particular embodiment, graphene substrate
Material includes or is made of reduced form graphene oxide.
There is provided graphene-based material may include grafting chemical linker, which is suitble to make graphene-based material
With the pseudo-capacitance material covalent bonding and/or electrostatic interaction on graphene-based material.As used herein, " chemistry is even for term
Junctor " refers to the chemical structure or atom group for connecting two entities.The example of chemical linker include functional group's such as amido,
Carboxyl, hydroxyl, carbonyl, amide groups, itrile group and epoxy group.
In various embodiments, graphene-based material can be with NH2The graphene of group, and pseudo-capacitance material can be with
It is with NH2The PANI of group.Graphene can occur chemical reaction with PANI and form graphene-NH-NH-PANi.Some
In embodiment, graphene-based material can be the graphene with COOH group, and pseudo-capacitance material can be with NH2Group
PANI.Graphene can occur chemical reaction with PANI and form graphene-C (O)-NH-PANi.
In the other embodiments that wherein pseudo-capacitance material includes PANI, for example, one or more above-mentioned is connected chemically
Body can be grafted on graphene-based material, and can be with the N functional group electrostatic interaction that is present on PANI, can be with
Using PANi-NH-PANi, PANi=N-PANi and NH2The form of-PANi.
In various embodiments, suitable for by the pseudo-capacitance material covalent bonding on graphene-based material and graphene-based material
Chemical linker be amido.The graphene-based material that offer is grafted with amido thereon can be for example, by following progress: by stone
Mertenyl material is dispersed in the solution including reducing agent to form the first suspension and come；Packet is added into first suspension
The solution of amino-contained substance is included to form the second suspension；And make the second suspension experience solvent heat treatment amido to be grafted
Onto graphene-based material.
As described above, graphene-based material can be dispersed in the solution including reducing agent to form the first suspension.This
Term used in text " reducing agent " refers to provides the reagent of electronics in redox reaction.In various embodiments, reducing agent
It is formed including polar organic solvent or by polar organic solvent.The example of polar organic solvent include but is not limited to alcohol (such as methanol,
Ethyl alcohol and propyl alcohol), ketone, amide, amine, nitrile, acetic acid esters, ether and aldehyde.The specific example for the reducing agent that can be used includes but unlimited
In ethylene glycol, hydrazine compound, hydrogen, formaldehyde and azanol.For example, reducing agent can be the hydrazine compound containing diazanyl.It can be used
The example of hydrazine compound includes hydrazine, hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrate, a hydrazine hydrate, phenylhydrazine, benzyl hydrazine and ethyl hydrazine.In a reality
It applies in example, reducing agent includes or is made of ethylene glycol.In the embodiment that graphene-based material is graphene oxide, for example, also
Former agent can be used for redox graphene (GO), to remove some oxygen-containing groups in GO, to form reduced form graphene oxide
(RGO).By doing so, the graphene oxide of insulation can be converted into conductive reduced form graphene oxide.
The liquid of solution can be formed according to the factors such as the electric conductivity of liquid medium and the type of reducing agent used, selection
Body medium.Suitable liquid medium can be with e.g. with the medium of high dielectric constant.In various embodiments, liquid medium
It is organic solvent.Usually polar organic solvent, such as pure and mild ketone can be used.The example packet for the organic solvent that can be used
Include dimethylformamide, ethyl alcohol, acetone and methyl ethyl ketone etc..Alternatively, liquid medium can be water-bearing media, such as water.
In various embodiments, graphene-based material can be evenly dispersed in solution.For example, when using graphite oxide
When alkene or reduced form graphene oxide, since there are oxygen-containing group, graphene oxide or reduced form graphene oxides can be parent
Aqueous, and individual graphene oxide sheet or reduced form oxidation stone can be easily dispersed into suitable liquid medium
Black alkene piece.Mechanical stirring or ultrasound can be optionally used, graphene-based material is dispersed in the solution including reducing agent.
The graphene-based material that offer is grafted with amido thereon may further include the solution including amino-contained substance
It is added in the first suspension to form the second suspension.In various embodiments, the solution of the substance including amino-contained can be with
It is inorganic amine, and can be selected from by ammonium hydroxide, urea, ethylenediamine, hydrazine, triethylamine, aniline, methylamine, ethanol amine, chloramines, dichloro
The group of amine, azanol, ammonia borine and combinations thereof composition.
It can be optionally using the stirring means such as mechanical stirring or ultrasound, so that first of the substance including amino-contained is molten
Mixing between liquid and the first suspension improves.
Then solvent heat treatment can be carried out to the second suspension to be grafted the substance of amino-contained on graphene-based material.
Solvent heat treatment typically refers to the heat treatment carried out in pressure vessel.By carrying out the processing in pressure vessel, this makes
It must react and be carried out under the raising pressure of about 1atm, 5atm, about 10atm, about 20atm, about 30atm, about can be up to about
40atm, about 50atm or higher.Raised pressure to react be higher than reagent respectively boiling point at a temperature of carry out.
In various embodiments, solvent heat treatment carries out at a temperature in the range of about 80 DEG C to about 250 DEG C, for example, about
100 DEG C to about 250 DEG C, 150 DEG C to about 250 DEG C, about 200 DEG C to about 250 DEG C, about 80 DEG C to about 200 DEG C, about 80 DEG C to about 150
DEG C, about 100 DEG C to about 200 DEG C, about 100 DEG C to about 150 DEG C, about 150 DEG C to about 200 DEG C, about 150 DEG C, about 180 DEG C or about 200
℃.In a particular embodiment, solvent heat treatment about 180 DEG C at a temperature of carry out.
In the embodiment that the substance of amino-contained is ammonium hydroxide, for example, the ammonium ion in ammonium hydroxide can attack graphene substrate
The oxide group of material, and primary amine group is generated on the surface of graphene-based material by nucleophilic displacement of fluorine, thus in graphene
Primary amine functional group is grafted on sill.
Method according to various embodiments includes that graphene-based material is added to the dispersion including multiple active carbon particles
To form first layer in body, which includes the graphene-based material being arranged on one or more active carbon particles.As above
Described, graphene-based material can be arranged in the surface of one or more active carbon particles, without with active carbon particle chemistry knot
It closes, because active carbon particle can not contain functional group on the surface thereof.
The second layer including pseudo-capacitance material is deposited on the first layer including graphene-based material to obtain composite material.
In various embodiments, pseudo-capacitance material is selected from by conducting polymer, metal oxide, metal sulfide, metal
The group of hydroxide and combinations thereof composition.
By growing (grow) metal oxide nanoparticles on the surface of graphene-based material, metal can be aoxidized
Object, such as nickel oxide, ruthenium-oxide, manganese oxide, cobalt oxide (II), Co3O4And/or iron oxide is deposited on including graphene-based material
First layer on.Metal ion, for example, the edge of graphene-based material, functional group and/or graphene-based material can be adsorbed on
Defect on, and can be there are reducing agent (such as NaBH4And/or citric acid) or coprecipitator (such as NaOH, KOH, urea
And/or ammonium hydroxide) under nucleation to form nano particle.It does so, packet can be formed on the first layer for including graphene-based material
Include the second layer using metal oxide as pseudo-capacitance material.
In a particular embodiment, pseudo-capacitance material includes conducting polymer.It in these embodiments, will include pseudo-capacitance material
The second layer of material is deposited on the first layer including graphene-based material, may include by the monomer and oxidant of conducting polymer
It is added in mixture, and the monomer of polymeric conductive polymer is to obtain the second layer.With other preparation methods such as electrochemistry formated
It compares, by carrying out chemical oxidising polymerisation, can easily amplify the formation of the second layer including pseudo-capacitance material.
The example of suitable conducting polymer already discussed above.Conducting polymer can be with, for example, selected from by polyaniline,
The group that the group of polypyrrole, polythiophene and its copolymer and these substances is combined into.Therefore, the monomer of these conducting polymers can
Respectively aniline, pyrroles, thiophene and combinations thereof.
Polymerization reaction can carry out in the presence of an oxidizer.The example for the oxidant that can be used includes iron (III) salt, copper
(II) salt, silver (I) salt, hydrogen peroxide, ammonium persulfate and combinations thereof.In various embodiments, oxidant is selected from by iron chloride
(III), the group of ammonium persulfate, silver nitrate, hydrogen peroxide, potassium bichromate, potassium permanganate, Potassiumiodate and its mixture composition.
It can be carried out in the case where light is not present in the monomer of polymeric conductive polymer on graphene-based material, and
It is carried out within the temperature range of about 0 DEG C to about 30 DEG C.In various embodiments, temperature model of the polymerization reaction at about 0 DEG C to about 30 DEG C
Interior progress is enclosed, for example, about 0 DEG C to about 20 DEG C, about 0 DEG C to about 15 DEG C, about 0 DEG C to about 10 DEG C, about 0 DEG C to about 5 DEG C, about 10 DEG C extremely
About 30 DEG C, about 15 DEG C to about 30 DEG C, about 20 DEG C to about 30 DEG C, about 10 DEG C to about 20 DEG C, about 25 DEG C, about 15 DEG C, about 10 DEG C, about 5
DEG C, about 1 DEG C or about 0 DEG C.
Advantageously, nitrogen-atoms is introduced in the graphene network of graphene-based material to promote conducting polymer equal on it
Even growth.Due to the conforming layer of the conducting polymer of formation, this is converted into pseudo-capacitance generation again.Graphene material sill electrical property
Improvement, it may be possible to pseudo-capacitance generate and improveds charge transfer effciency synergistic effect as a result, pseudo-capacitance generate be by
In forming the uniform layer of conducting polymer, improved charge transfer effciency is the graphene substrate of the amido due to being grafted on it
The improved electric conductivity of material.
Each embodiment is related to including according to the electrode of the composite material of first aspect, or by according on the other hand
The composite material of the method preparation of two aspects.
Composite material may be used as the electrode material of supercapacitor, lithium battery, biosensor and gas sensor.It is logical
It crosses to combine graphene and pseudo-capacitance material and active carbon particle and forms mixed electrode, may result in graphene-based super electricity
The potential breakthrough of container amplification application, because the presence of pseudo-capacitance material can significantly improve the capacitance of active carbon in electrode.
Other than the electrode material being used as in supercapacitor, battery and sensor, composite material can also be used to manufacture solar energy turn
Transparent or semitransparent membrane electrode in changing device, and the substrate (SERS) for surface enhanced resonant spectrometer.In each reality
It applies in example, electrode can be included in supercapacitor, sensor, hybrid electrochemical device, rechargeable battery or metal-air
Electrode in battery.
Hereinafter, the present invention will be described more fully hereinafter with reference to the accompanying drawings, exemplary reality the invention is shown in the accompanying drawings
Apply example.However, the present invention can be embodied in many different forms, and should not be construed as limited to set forth herein exemplary
Embodiment.And these embodiments are to provide, so that the disclosure will be thorough and complete, and will be to those skilled in the art
Fully communicate the scope of the present invention.In the accompanying drawings, for the sake of clarity, the length and size of layer and region may be exaggerated.
As it is used herein, term "and/or" includes any and all combinations of one or more projects listed.This
The invention that illustratively describes of text can suitably no any element or element, define or limit in the case where implement, this
In with no specific disclosure of.Thus, for example, term " includes ", "comprising", " containing " etc. should be read extensively and unlimitedly.
In addition, terms used herein and expression already function as the term illustrated and noted limit, and it is not intended to use these arts
Language and expression exclude any equivalent or part thereof of shown or described feature, it should be recognized that claimed
The scope of the present invention in various modifications be possible.It will thus be appreciated that although passing through preferred embodiment and optional feature
The present invention is specifically disclosed, but the modifications and variations of invention disclosed herein can be referred to by those skilled in the art, and
And these modifications and variations are considered as within the scope of the invention.
Widely and the present invention is generally described herein.Fall into the relatively narrow type of each of general disclosure
A part of the invention is also constituted with the combination of secondary category.This includes general description of the invention, has from the category and removes any theme
Collateral condition or negative limitation, but regardless of whether specifically describing the material left out herein.
Other embodiments are in appended claims and non-limiting embodiment.In addition, in features or aspect of the invention
In the case where being described according to marlcush group, those skilled in the art will appreciate that the present invention also by marlcush group it is any at
Member or subgroup member describe.
Experimental section
It has been disclosed herein and selectively coats tool controllable thickness on the absorbent charcoal composite material of graphene package
Conducting polymer.Combination electrode has shown excellent performance, such as high capacity, high conductivity and high-speed performance, this
Them are made to be suitable as electrode of super capacitor.
Each embodiment is related to the preparation of AC/ graphene/CP composite material, the verified electricity as supercapacitor
The advantageous characteristic of pole.Advantageous characteristic include the easy scalability of production process (scalability), production it is low at
Originally, high and reliable capacitance and required cycle characteristics.In various CP, such as polyaniline (PANi) and polypyrrole of test
(PPy) in, AC/NHG/PANi and AC/NHG/PPy have shown best as a result, compared with pure AC, NHG or CP, super electricity
Capacitive can significantly improve.
In various embodiments, use active carbon (AC) as the main component of composite material, and load pseudo-capacitance material
The graphene (NHG) of the modification of material is used as active coating, forms the AC-NHG-CP composite material of mixing.
In general, graphene oxide (G-O) is to peel off preparation by the chemistry of graphite by improved Hummers method.Then exist
In the presence of inorganic amine such as ammonium hydroxide or ethylenediamine, by a step solvothermal, with primary amine functional group (- NH2) it is modified G-O.It will
Pseudocapacitor is coated in the NH with controllable thickness2On modified graphene layer (NHG), wherein pseudocapacitor component be can be
Transition metal oxide or conducting polymer (CP) can improve capacitor by providing high pseudo-capacitance charging significantly
Value.
Other than conducting polymer (CP), the oxide of metal oxide (MO) such as Ni, Co and Fe are also used as quasi- electricity
Capacity materials.
NH between active carbon (AC) and conducting polymer active layer2Modified graphene layer component is not only conducting polymer
The growth of object provides many anchored sites, but also the electric charge transfer between active carbon and conductive polymer coating provide it is good
Good conductive network.Active carbon in composite material generates the double-deck charge, and additionally aids from graphene network to afflux
The electric charge transfer of device.
Cheap active carbon cluster-active carbon as carbon carrier is the first material that selection is used for EDLC electrode.It is usually
It is by with high-specific surface area (1000m2/ g to 3000m2/ g) it is tiny but " coarse particle " composition powder.Surface area is
About 1000m2The electrode of/g leads to about 10 μ F/cm2Typical double layer capacitor and 100F/g theoretical specific capacitance.In each embodiment
In, the weight ratio of the active carbon as main component is more than 40%.
Graphene active layer for pseudo-capacitance Material growth --- pseudo-capacitance material (such as conducting polymer) is in carbon substrate
On growth, two steps can be related to: adsorbing the oxidation polymerization of monomer and monomer, dopant/counter ion counterionsl gegenions in carbon surface
It is inserted into simultaneously, is further formed polymer chain.Due to only have conducting polymer coating on carbon surface can from electrolyte and
Reversible redox reaction on electrode interface promotes total capacitance value that it is best therefore to prepare conducting polymer/carbon composite
Method is the formation uniform shallow layer of conducting polymer on carbon surface.Therefore, the first step not only determines conducting polymer
Form, and also have apparent influence to the performance of final products.
Active carbon is made of the small carbon nano-particle of size about 10nm to 50nm, is being greater than 600 DEG C of height for burning or activating
The lower preparation of temperature.Due to the high-temperature process in synthesis, active carbon can lack surface functional group.Therefore, in the feelings of not graphene
Under condition, conducting polymer tends to assemble between active carbon particle, rather than shallow layer is generated in activated carbon granule surface.
NH2In the presence of modified graphene layer, there are surface functional groups abundant, it can be ensured that conductive polymer nanometer grade thin layer it is equal
The generation of even distribution and pseudo-capacitance charge.
Fig. 1 is provided and NH is not present2The AC/CP when graphene layer being modified is compared, for producing AC/NHG/CP's
Schematic process flow diagram.Use NH2For modified graphene layer as active layer, conducting polymer can effectively load to NH2Change
Property graphene layer surface, with controlled thickness and uniform distribution.
Embodiment 1: material
NH can be obtained by processing graphene oxide using a step solvothermal2Modified graphene layer.G-O modification
There are functional group containing O, such as carboxylic acid, phenol, lactone, carboxylic acid anhydrides, ketone, ether, pyranone or quinine.By nucleophilic displacement of fluorine, functional group exists
It can easily be reacted with small molecule inorganic amine during solvent heat.In the process, most of functional group's quilt containing O in G-O
It removes, and NH2It is introduced into graphene by covalent bond.
In general, in suitable solvent (for example, DI water, ethyl alcohol, methanol etc.), it will be at least one under solvent heat or reflux
The amine precursor of type is heated to 60 DEG C or more of temperature together with G-O and maintains certain time.After reaction, washed with ethyl alcohol and DI
It washs to handle product to remove excessive unreacted amine.
It can be used after active carbon purchase, without being further processed.Active carbon is dispersed under magnetic agitation or ultrasound
In DI water, until obtaining uniform solution.
By magnetic agitation by the NH of design weight ratio2Modified graphene layer is mixed with Actidose.
The monomer of conducting polymer such as pyrroles and aniline are added in AC/NHG solution in a manner of dropwise addition.Then, it is added
Oxidant such as FeCl3Or ammonium persulfate, and solution is maintained in ice bath under magnetic stirring to be polymerize completely.Then will
Product ethyl alcohol and DI water washing are to remove remaining oxidant.
Embodiment 2: electrical characterization
In order to compare the property of AC/NHG/CP Yu AC and AC/CP, electrode material is tested in 3 electrode systems.When scanning speed
When rate is 2mV/s, the specific capacitance of AC/NHG/CP, AC and AC/CP are respectively 330,120 and 80F/g.
It can be seen that from the result obtained when sweep speed increases to 100mV/s, the capacitor of AC/NHG/CP is kept still
So more than 200F/g, this is more considerably higher than the value of AC or AC/CP about 80F/g under identical measuring condition.The AC/CP composite wood of preparation
The capacitance of material is suitable with pure AC.The AC for lacking surface functional group cannot adhere to for CP provides anchored site.Therefore, CP and AC is real
Body only passes through physical contact assembling.During the preparation process, CP can be removed easily in washing step.However, AC/NHG is mixed
It closes object and shows that significant capacitance improves after load C P.AC/NHG/PANi composite material (80% AC) is shown almost
It is the specific capacitance of pure AC three times.It can be further improved capacitance by adjusting the weight ratio of AC, NHG and PANi.
Embodiment 3: the symmetrical supercapacitor device of model
In order to prove the property of AC/NHG/CP, AC/NHG/PANi is assembled into the symmetrical supercapacitor device of model.It will
The property to be proved includes capacitance and super capacitor behavior.
Fig. 3 shows the cyclic voltammetry (CV) and charge/discharge curve of supercapacitor device, two electrodes by
AC/NHG/PANi composition.The illustration of Fig. 3 (a) shows the AC/NHG/PANi supercapacitor of the laboratory scale for test
The photo of device.The CV of AC/NHG/PANi device shows big integral area (integration area), and rectangle is presented
Curve shape, this is the feature for the ideal hyper capacitor that there is good dynamic charge to propagate.AC/NHG/PANi device is various
Charge/discharge curve under electric current is symmetrically, to show that AC/NHG/PANi system has high conductivity and excellent electrochemical capacitance
Can, this give longer cycle life and less safety problems.
As disclosed herein, each embodiment is related to preparing active carbon, graphene and conducting polymer composite material
Method.This method may include that primary amine is introduced into graphene oxide, this is returned by solvent heat treatment and at least one amine
(G-O is in a solvent) is flowed to obtain NHG；And mechanically active carbon is mixed with NHG to obtain AC/NHG composite material.It can be with
At least a type of conducting polymer is equably loaded on AC/NHG by growth in situ, it is multiple to obtain AC/NHG/CP
Condensation material.
Active carbon, graphene and conducting polymer can be the form of three-decker.In various embodiments, graphene is
The modified reduced form graphene oxide (NHG) of amine.The weight ratio of active carbon can be in 40wt% to 98wt% tune in composite material
Section；NH2The weight ratio of graphene can change in 1wt% between 30wt%, and the weight ratio of conducting polymer can be
1wt% to 30wt%.
As disclosed herein, active carbon (AC) can be used as main component (more than 40wt%), the oxygen being modified by amine
Graphite alkene (NHG) package, is then coated with the conducting polymer (CP) of nano thickness.Cost can be significantly reduced using active carbon,
Enhance the electric conductivity of composite material, and ensures the compatibility that Novel super capacitor is produced with existing industrial process.Advantageously,
NHG layers can provide many anchored sites for the growth of CP, and N is modified and solvent heat treatment can assign that NHG is good to be led
Electrically, redox charge is transferred to AC from CP layers.
In some embodiments, very thin CP layer (nm scale) is grown on the surface NHG.As a result, can significantly improve
Charge generation/cumulative efficiency of CP.
AC/NHG/CP uses AC as main component；Therefore, this method can easily amplify.Advantageously, according to implementation
The AC/NHG/CP of example is compatible with existing supercapacitor production technology, which ensure that from present material (active carbon) to being based on
The seamless switching of the new electrode material of new A C/NHG/CP.This method is general, and can be easily extended to AC/G/
CP composite material uses Fe, Ni, Co, Ru and Mn oxide of other pseudo-capacitance material such as nanostructures.
Use AC at low cost as main component (more than 40wt%)；Novel structure design imparts composite material ratio
AC, graphene and the higher capacitor of CP；Compared with pure CP, G-O or NHG, cycle life is longer.Using 3 electrode measurement systems,
The material of verified AC/NHG/CP disclosed herein is greater than the capacitor of 380F/g.
Although specifically illustrating and describing the present invention by reference to exemplary embodiment of the present invention, this field
Those of ordinary skill will be appreciated that, not depart from the spirit and scope of the present invention being defined by the following claims, Ke Yi
Various changes are carried out in form and details.
Claims (25)
1. a kind of composite material comprising multiple active carbon particles, first layer and the second layer, the first layer include being arranged in
Graphene-based material on one or more active carbon particles, the second layer include being arranged in including graphene-based material
First layer on pseudo-capacitance material；Including the graphene-based material first layer thickness in 0.5nm to 30nm model
In enclosing；And it is lower than the first layer including the graphene-based material including the thickness of the second layer of the pseudo-capacitance material
Thickness.
2. composite material according to claim 1, wherein the size of the active carbon particle is within the scope of 10nm to 50nm.
3. composite material according to claim 1 or 2, wherein the amount of active carbon particle is in 40wt% in the composite material
To 98wt%.
4. composite material according to claim 1, wherein the graphene-based material includes or by reduced form graphite oxide
Alkene composition.
5. composite material according to claim 1, wherein in the composite material graphene-based material amount 1wt% extremely
Within the scope of 30wt%.
6. composite material according to claim 1 encapsulates the work including the first layer of the graphene-based material
Property charcoal particle.
7. composite material according to claim 1, including the graphene-based material first layer not with the work
Property charcoal particle covalent bonding.
8. composite material according to claim 1 is aoxidized wherein the pseudo-capacitance material is selected from by conducting polymer, metal
The group of object, metal sulfide, metal hydroxides and combinations thereof composition.
9. composite material according to claim 8, wherein the conducting polymer is selected from by polyaniline, polypyrrole, poly- thiophene
The group of pheno, its copolymer and combinations thereof composition.
10. composite material according to claim 8, wherein the metal oxide is selected from by nickel oxide, ruthenium-oxide, oxidation
Manganese, cobalt oxide (II), Co3O4, iron oxide and combinations thereof composition group.
11. composite material according to claim 8, wherein the metal sulfide includes or by NiCo2S4Composition.
12. composite material according to claim 8, wherein the metal hydroxides is selected from by cobalt hydroxide, Cu (OH)2、
Ni(OH)2, Ni-Co hydroxide, Ni-Al hydroxide and combinations thereof composition group.
13. composite material according to claim 1, wherein in the composite material pseudo-capacitance material amount 1wt% extremely
Within the scope of 30wt%.
14. composite material according to claim 1 encapsulates the activity including the second layer of the pseudo-capacitance material
Charcoal particle, the active carbon particle have first layer, and the first layer includes the graphene substrate being arranged on active carbon particle
Material.
15. composite material according to claim 1, including the pseudo-capacitance material the second layer with include the stone
The first layer covalent bonding of mertenyl material.
16. composite material according to claim 15, including the pseudo-capacitance material the second layer with include described
The first layer of graphene-based material passes through amine key covalent bonding.
17. the method for preparing composite material described in any one of -16 according to claim 1, the method includes
A) graphene-based material is provided；
B) graphene-based material is added in dispersion, the dispersion includes multiple active carbon particles, includes cloth to be formed
The first layer of the graphene-based material on one or more active carbon particles is set, and
C) deposition includes the second layer of pseudo-capacitance material to obtain composite material on the first layer for including graphene-based material.
18. according to the method for claim 17, wherein providing graphene-based material includes grafting chemical linker, described
Chemical linker be suitable for by graphene-based material on graphene-based material pseudo-capacitance material covalent bonding and/or electrostatic it is mutual
Effect.
19. according to the method for claim 18, wherein the chemical linker is amido.
20. method described in any one of 7-19 according to claim 1, wherein the active carbon particle is free of official on the surface thereof
It can group.
21. according to the method for claim 17, wherein the pseudo-capacitance material is selected from by conducting polymer, metal oxidation
The group of object, metal sulfide, metal hydroxides and combinations thereof composition.
22. according to the method for claim 17, wherein the pseudo-capacitance material includes conducting polymer.
23. according to the method for claim 22, wherein deposition includes quasi- electricity on the first layer for including graphene-based material
The second layer of capacity materials, including
A) monomer of conducting polymer and oxidant are added in mixture, and
B) it polymerize the monomer of the conducting polymer to obtain the second layer.
24. according to the method for claim 23, wherein the oxidant is selected from by iron chloride (III), ammonium persulfate, nitric acid
The group of silver, hydrogen peroxide, potassium bichromate, potassium permanganate, Potassiumiodate and combinations thereof composition.
25. a kind of electrode comprising composite material described in any one of -16 or by being wanted according to right according to claim 1
Composite material prepared by the method for seeking any one of 17-24.
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106128783B (en) * | 2016-08-11 | 2019-04-23 | 重庆中科超容科技有限公司 | A kind of pseudocapacitors electrode and preparation method thereof based on vulcanization nickel cobalt |
| CN106449144A (en) * | 2016-10-25 | 2017-02-22 | 嘉善蓝欣涂料有限公司 | An intercalated ketone aluminum hydrotalcite electrode material and a preparation method thereof |
| CN107217482B (en) * | 2017-07-10 | 2019-11-05 | 西安科技大学 | A kind of polyaniline hybridized electrode material of nitrogen-phosphor codoping porous carbon membrane@and preparation method thereof with interface covalent linkage |
| CN109384215A (en) * | 2017-08-14 | 2019-02-26 | 中国科学院山西煤炭化学研究所 | The method based on core-shell structure copolymer graphene/polyacrylonitrile Nano carbon balls of preparation |
| US11390527B2 (en) | 2017-12-28 | 2022-07-19 | Texas Instruments Incorporated | Multi-layered SP2-bonded carbon tubes |
| US11254775B2 (en) | 2017-12-28 | 2022-02-22 | Texas Instruments Incorporated | Filler particles for polymers |
| US11938715B2 (en) | 2017-12-28 | 2024-03-26 | Texas Instruments Incorporated | SP2-bonded carbon structures |
| US11370662B2 (en) | 2017-12-28 | 2022-06-28 | Texas Instruments Incorporated | Hexagonal boron nitride structures |
| US20190204252A1 (en) * | 2017-12-29 | 2019-07-04 | Texas Instruments Incorporated | Gas sensor with superlattice structure |
| CN110364682B (en) * | 2018-04-11 | 2022-06-24 | 广州墨羲科技有限公司 | Three-dimensional graphene microsphere composite material, and manufacturing method and application thereof |
| CN110364368B (en) * | 2018-04-11 | 2021-09-21 | 广州墨羲科技有限公司 | Nanoparticle three-dimensional graphene composite material, and manufacturing method and application thereof |
| US10748999B2 (en) | 2018-12-21 | 2020-08-18 | Texas Instruments Incorporated | Multi-super lattice for switchable arrays |
| CN109622056B (en) * | 2018-12-29 | 2020-10-30 | 武汉大学 | Composite efficient visible light photocatalyst and preparation method and application thereof |
| WO2020219530A1 (en) * | 2019-04-22 | 2020-10-29 | Uwm Research Foundation, Inc. | Capacitive deionization with zero wastewater |
| CN110517898A (en) * | 2019-08-14 | 2019-11-29 | 上海应用技术大学 | The preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867650A (en) * | 2012-09-03 | 2013-01-09 | 中国科学院大连化学物理研究所 | High-magnification supercapacitor composite electrode material and preparation method thereof |
| CN103295798A (en) * | 2013-05-16 | 2013-09-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Porous composite carbon material and application thereof |
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| CN103295798A (en) * | 2013-05-16 | 2013-09-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Porous composite carbon material and application thereof |
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|---|
| Fabrication of Free-Standing Hierarchical Carbon Nanofiber/Graphene Oxide/Polyaniline Films for Supercapacitors;Dongdong Xu等;《APPLIED MATERIALS & INTERFACES》;20131210;第6卷;第200-209页 * |
| 聚苯胺纳米材料的电化学性能研究;王峰;《万方数据》;20140925;第14-17页 * |
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