CN101404211A - Production method of high-performance framework carbon material for super capacitor - Google Patents

Production method of high-performance framework carbon material for super capacitor Download PDF

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Publication number
CN101404211A
CN101404211A CNA2008101436366A CN200810143636A CN101404211A CN 101404211 A CN101404211 A CN 101404211A CN A2008101436366 A CNA2008101436366 A CN A2008101436366A CN 200810143636 A CN200810143636 A CN 200810143636A CN 101404211 A CN101404211 A CN 101404211A
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carbon
carbon material
tube furnace
chlorine
carbide
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王先友
杨顺毅
李娜
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Xiangtan University
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Xiangtan University
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    • 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 preparation method of carbon skeleton material used for a super-capacitor; the carbon skeleton material used for the super-capacitor can obviously improve the electrical conductivity of the skeleton material and regulate the microstructure of the carbon material in atomic level, and has high specific area; the particle size distribution range of the carbon skeleton material is narrow; the aperture distribution range is precisely adjustable, most of which is in middle hole range; the carbon material has good hydrophilicity and excellent conductivity and is an excellent super-capacitor electrode material. The method is simple, and has high yield and good performance.

Description

A kind of preparation method of high-performance framework carbon material for super capacitor
Technical field
The present invention relates to a kind of preparation method of framework carbon material.
Background technology
Ultracapacitor is a kind of novel energy accumulating device, claims electrochemical capacitor or double electric layer capacitor again, and its capacity can reach farad level even tens thousand of farad, and specific energy is 20～200 times of traditional capacitor.Have in addition that power density is big, temperature range is wide (20-60 ℃) concurrently, good characteristic such as pollution-free, long-life, be a kind of mechanism of new electrochemical power sources between rechargeable battery and traditional capacitor, have broad application prospects.
Carbide skeleton carbon (carbide derived-carbon) is called for short skeleton carbon, is a kind of novel porous framework carbon material of rising in recent years, the existing century-old research history of this material, but just made a breakthrough in nearly ten years.Along with going deep into of investigative technique, find that microstructure, surface area, aperture and the surface chemical structure etc. of control material can prepare the carbon skeleton material of different purposes, as the electrode material of ultracapacitor etc.In recent years, along with going deep into of research work, the application of carbide skeleton carbon has been extended to numerous areas such as gas storage, water purification and desalination, bioengineering technology, medicine.
The initial of carbide skeleton carbon is that research work starts from 1918, has obtained material with carbon element when preparing silicon tetrachloride at that time, but does not consider its application as accessory substance.Preparation principle is:
SiC+2Cl 2＝SiCl 4+C
Under 1000 ℃ or higher temperature, dry chlorine and carborundum react in high temperature resistance furnace, and the silicon tetrachloride gas of generation enters the condenser from outlet, and remaining carbon is converted into graphite.
Boehm and Warnecke found the molecular sieve character of carbide skeleton carbon in 1975.Preparation condition, character and the application etc. of carbide skeleton carbon have systematically been studied by U.S. Drexel university over past ten years; The skeleton carbon seminar of Switzerland is applied to ultracapacitor for carbide skeleton carbon and does a lot of work.
Present carbide skeleton carbon is to be presoma with the carbide, under low pressure or vacuum, the non-carbon atom in the carbide is being shifted out regulation and control carbide skeleton carbon structure on atomic level between 600-1650 ℃ with halogen, supercritical water steam or other etching agent.This material has that cost is low, specific area is big, pore-size distribution is narrow and advantage such as accurately adjustable.In addition the carbon structure that contains variform in the carbide skeleton carbon, for example: amorphous carbon, graphite, many walls nanotube, fullerene carbon, onion carbon, diamond-like-carbon etc.
With different carbide is presoma, adopts different etching agents such as halogen, halogen compounds, supercritical water steam, at high temperature with the nanometer framework carbon material of carbide prepared in reaction porous, wherein uses at most as etching agent with chlorine.Carbide skeleton carbon preparation principle institute is shown in Figure 1, and its reaction is:
M aC b+(ac/2)Cl 2(g)＝bC(s)+aMCl c(g)
M wherein aC bFor: SiC, TiC, ZrC, V 2C, NbC, Nb 2C, TaC, Ta 2C, Cr 3C 2, Mo 2C, MoC, W 2C, WC, BaC 2, CaC 2, SrC 2, Al 4C 3, B 4C, Fe 3C etc.Etching agent is: F 2, Cl 2, Br 2, I 2, HF, CCl 4, CHCl 3, Cl 2-H 2, Cl 2-HCl, H 2O etc.
In material with carbon element, carbon-based materials such as activated carbon, carbon aerogels, xerogel, template carbon, carbon nano-tube, carbide skeleton carbon all can be used as electrode material for super capacitor, but except that carbide skeleton carbon, the difficult control of other material with carbon elements aperture.And carbide skeleton carbon can be prepared the framework carbon material in different apertures, and can regulate and control the microstructure of material with carbon element from atomic level by changing technological parameters such as presoma, etching agent, reaction temperature, and the skeleton carbon that is obtained has bigger specific area.
The method for preparing skeleton carbon with carbide is more, and the traditional preparation process method has two step method and one-step method.As use CaC 2Preparation skeleton carbon has MgCl 2Method and NaCl method:
MgCl 2Method: CaC 2+ MgCl 2=MgC 2+ CaCl 2
2MgC 2＝Mg 2C 3+C
Mg 2C 3＝2Mg+3C
NaCl method: CaC 2+ 2NaCl=2C+2Na+CaCl 2
MgCl 2Method needs the reaction of two steps, and temperature range is at 600-1275 ℃, and reaction time 1-5 hour, the skeleton carbon of best in quality will just can make at 950-1200 ℃.Although and the NaCl method is a single step reaction, need be 400-900 ℃ of reaction, and reaction is not exclusively, and the skeleton carbon accessory substance that makes is many, and properties of product are with control.
More above-mentioned two kinds of methods can find that traditional method prepares framework carbon material, the reaction temperature height, and the aperture is difficult to accurate control, and the quality of product and performance are difficult to be fit to the requirement of electrode material for super capacitor.
Summary of the invention
The purpose of this invention is to provide a kind of method by gas-solid phase reaction efficient production high-performance framework carbon material for super capacitor.
The objective of the invention is to realize in the following way: a kind of preparation method of high-performance framework carbon material for super capacitor:
(1) with the carbide ball mill crushing, cross the 100-400 mesh sieve, getting particle diameter is 1-40 μ m powder;
(2) add the metal halide that accounts for total weight 0.1-20% in powder and make catalyst, ball milling mixes, and gets presoma;
(3) presoma being added in the tube furnace, feed inert gas in the pipe of tube furnace removing air, is that the HCl of 5-35% is added drop-wise to MnO with concentration 2In the powder, get the etching agent of the high activity chlorine of prepared fresh as metal or non-metallic atom in the removal carbide; Tube furnace is heated to 150-600 ℃, and the high activity chlorine of prepared fresh feeds dense H 2SO 4In to remove the moisture content in the chlorine, then chlorine is directly imported in the tube furnace and the presoma reaction, mixture of reaction products, unnecessary chlorine absorbs with alkaline absorption solution;
(4) with the mixture of reaction products acid elution, remove unreacted matters, wash to pH=7 ± 0.5 with pure water or distilled water, obtain skeleton carbon at 60-100 ℃ of dry 6-48h.
(5) gained skeleton carbon is added in the solution of the aniline, pyrroles, thiophene or their derivative that contain 1-20g/L, pass through polymerization reaction, in skeleton carbon surface and hole, form the finishing coat of polyaniline, polypyrrole, polythiophene or their derivative polymer, get high-performance framework carbon material for super capacitor.
Carbide commonly used is SiC, TiC, ZrC, V 2C, NbC, Nb 2C, TaC, Ta 2C, Cr 3C 2, Mo 2C, MoC, W 2C, WC, BaC 2, CaC 2, SrC 2, Al 4C 3, B 4C or Fe 3A kind of among the C.
Metal halide catalyst can be NaCl, KCl, CaCl 2, MgCl 2, CuCl 2, NaBr, KBr, CaBr 2, MgBr 2, CuBr 2, NaI, KI, CaI 2, MgI 2Or CuI 2In a kind of.
The present invention has following beneficial effect, and the one, with metal or non-metallic carbide, as CaC, SiC etc. reduce the reactant particle diameter by ball milling, increase the area that gas contacts with solid reactant, to increase gas-solid phase reaction speed; The 2nd, reactant behind the ball milling and metal halide catalyst are mixed by ball milling, reduce the temperature of gas-solid phase reaction, improve reaction rate; The 3rd, the etching agent chlorine of prepared fresh contains a large amount of chlorine radicals, has high reactivity, the chlorine and the solid reactant of prepared fresh are directly reacted, both can significantly improve reaction speed, can increase substantially productive rate again, also can effectively adjust the pore-size distribution of framework carbon material simultaneously; The 4th, the framework carbon material of gained is carried out finishing, can adjust the hydrophily in framework carbon material surface and the hole, improve electrolyte wetting to material, help forming effective electric double layer.Simultaneously, modify and be the conductive polymer polymer, can obviously improve the conductivity of framework material with macromolecular material; The 6th, the inventive method has made can be from atom level level regulation and control material with carbon element microstructure, framework carbon material with high specific surface area, the product cut size narrow distribution range, pore size distribution range is accurately adjustable, mostly in the mesopore scope, the material with carbon element good hydrophilic property, excellent conductivity is a kind of good electrode material for super capacitor.One-step method of the present invention prepares framework carbon material, and method is simple, productive rate is high, and performance is good, is a kind of method that ultracapacitor is used framework carbon material for preparing of novelty.
Description of drawings
Fig. 1 the present invention prepares the Experimental equipment of ultracapacitor with framework carbon material;
The ultracapacitor of Fig. 2 the present invention preparation transmission electron microscope photo of framework carbon material;
The ultracapacitor of Fig. 3 the present invention preparation pore size distribution curve of framework carbon material;
The ultracapacitor of Fig. 4 the present invention preparation cyclic voltammetry curve of framework carbon material;
The ultracapacitor of Fig. 5 the present invention preparation charge-discharge test curve of framework carbon material.
Embodiment
The present invention will be further described below in conjunction with embodiment:
Fig. 1 is that the present invention prepares the Experimental equipment of ultracapacitor with framework carbon material.The dense H of (1) splendid attire wherein 2SO 4Wide-mouth bottle, (2) quartz ampoule, (3) precursor samples, (4) tube furnace, (5) tail gas absorption bottle.
Embodiment 1:
Take by weighing 10g CaC 2With 4000rpm rotating speed ball milling 4h, cross 300 mesh sieves, getting particle diameter is the powder of 40 μ m; With carrying powder and 1g MgCl 2Ball milling 2h is even, gets presoma; Presoma is placed tube furnace; With MnO 2Powder places wide-mouth bottle, inserts dropping funel with rubber stopper sealing back, adds 12mol/L HCl in dropping funel; Experimental provision is warming up to 400 ℃ with tube furnace after pressing Fig. 1 connection, opens the switch of dropping funel, and HCl begins to drop to MnO 2On, fresh Cl 2Begin to produce, use dense H 2SO 4After the absorption, import in the tube furnace and CaC by conduit 2Reaction, unnecessary Cl 2Absorb with 6mol/L NaOH; 0.5h afterreaction finishes, and gets black powder shape product; The black product is soaked 1h with 2mol/L HCl, be washed with distilled water to pH=7, suction filtration, dry 4h gets the skeleton carbon products under 100 ℃ in vacuum drying chamber.The skeleton carbon products is added in the 1g/L aniline solution, add ammonium persulfate, reaction 0.5h, washing, suction filtration, dry 6h gets the high-performance framework carbon products under 80 ℃ in vacuum drying chamber.
Embodiment 2:
Take by weighing 10g SiC with 4000rpm rotating speed ball milling 4h, cross 300 mesh sieves, getting particle diameter is the powder of 40 μ m; With carrying powder and 1g CaCl 2Ball milling 2h is even, gets presoma; Presoma is placed tube furnace; With MnO 2Powder places wide-mouth bottle, inserts dropping funel with rubber stopper sealing back, adds 12mol/L HCl in dropping funel; Experimental provision is warming up to 400 ℃ with tube furnace after pressing Fig. 1 connection, opens the switch of dropping funel, and HCl begins to drop to MnO 2On, fresh Cl 2Begin to produce, use dense H 2SO 4After the absorption, import in the tube furnace and CaC by conduit 2Reaction, unnecessary Cl 2Absorb with 6mol/L NaOH; 0.5h afterreaction finishes, and gets black powder shape product; The black product is soaked 1h with 6mol/L HF, be washed with distilled water to pH=7, suction filtration, dry 4h gets the skeleton carbon products under 100 ℃ in vacuum drying chamber.The skeleton carbon products is added in the 1g/L aniline solution, add ammonium persulfate, reaction 0.5h, washing, suction filtration, dry 6h gets the high-performance framework carbon products under 80 ℃ in vacuum drying chamber.
Embodiment 3:
Take by weighing 10g CaC 2With 4000rpm rotating speed ball milling 4h, cross 300 mesh sieves, getting particle diameter is the powder of 40 μ m; With carrying powder and 1g CuCl 2Ball milling 2h is even, gets presoma; Presoma is placed tube furnace; With MnO 2Powder places wide-mouth bottle, inserts dropping funel with rubber stopper sealing back, and bucket adds 12mol/L HCl in leaking toward dropping liquid; Experimental provision is warming up to 400 ℃ with tube furnace after pressing Fig. 1 connection, opens the switch of dropping funel, and HCl begins to drop to MnO 2On, fresh Cl 2Begin to produce, use dense H 2SO 4After the absorption, import in the tube furnace and CaC by conduit 2Reaction, unnecessary Cl 2Absorb with 6mol/L NaOH; 0.5h afterreaction finishes, and gets black powder shape product; The black product is soaked 1h with 2mol/L HCl, be washed with distilled water to pH=7, suction filtration, dry 4h gets the skeleton carbon products under 100 ℃ in vacuum drying chamber.The skeleton carbon products is added in the 1g/L aniline solution, add ammonium persulfate, reaction 0.5h, washing, suction filtration, dry 6h gets the high-performance framework carbon products under 80 ℃ in vacuum drying chamber.
Embodiment 4:
Take by weighing 10g CaC 2With 4000rpm rotating speed ball milling 4h, cross 300 mesh sieves, getting particle diameter is the powder of 40 μ m; With carrying powder and 1g MgCl 2Ball milling 2h is even, gets presoma; Presoma is placed tube furnace; With MnO 2Powder places wide-mouth bottle, inserts dropping funel with rubber stopper sealing back, adds 12mol/L HCl in dropping funel; Experimental provision is warming up to 400 ℃ with tube furnace after pressing Fig. 1 connection, opens the switch of dropping funel, and HCl begins to drop to MnO 2On, fresh Cl 2Begin to produce, use dense H 2SO 4After the absorption, import in the tube furnace and CaC by conduit 2Reaction, unnecessary Cl 2Absorb with 6mol/L NaOH; 0.5h afterreaction finishes, and gets black powder shape product; The black product is soaked 1h with 2mol/L HCl, be washed with distilled water to pH=7, suction filtration, dry 4h gets the skeleton carbon products under 100 ℃ in vacuum drying chamber.The skeleton carbon products is added in 0.5g/L pyrroles's solution, add several sulfuric acid solutions again and transfer to pH=1, add ammonium persulfate, reaction 0.5h, washing, suction filtration, dry 6h gets the high-performance framework carbon products under 80 ℃ in vacuum drying chamber.
Embodiment 5:
Take by weighing 10g CaC 2With 4000rpm rotating speed ball milling 4h, cross 300 mesh sieves, getting particle diameter is the powder of 40 μ m; With carrying powder and 1g MgCl 2Ball milling 2h is even, gets presoma; Presoma is placed tube furnace; With MnO 2Powder places wide-mouth bottle, inserts dropping funel with rubber stopper sealing back, and bucket adds 12mol/L HCl in leaking toward dropping liquid; Experimental provision is warming up to 400 ℃ with tube furnace after pressing Fig. 1 connection, opens the switch of dropping funel, and HCl begins to drop to MnO 2On, fresh Cl 2Begin to produce, use dense H 2SO 4After the absorption, import in the tube furnace and CaC by conduit 2Reaction, unnecessary Cl 2Absorb with 6mol/L NaOH; 0.5h afterreaction finishes, and gets black powder shape product; The black product is soaked 1h with 2mol/L HCl, be washed with distilled water to pH=7, suction filtration, dry 4h gets the skeleton carbon products under 100 ℃ in vacuum drying chamber.The skeleton carbon products is added 1mol/L FeCl 3The aqueous solution in, ultrasonic dispersion 15min adds the 0.75g/L thiophene, stir while adding, reaction 3h, washing, suction filtration, in vacuum drying chamber 80 ℃ down dry 6h get the high-performance framework carbon products.
The foregoing description all can obtain high performance ultracapacitor framework carbon material, and Fig. 2 is the transmission electron microscope photo of framework carbon material.From Fig. 2 as seen, skeleton carbon is the nano-porous structure of tangible amorphous substance, and hole enriches and is interconnected, and helps the diffusion of electrolyte.Fig. 3 is a pore size distribution curve, narrower uni-modal pore size distribution, and most probable is distributed as 3.32nm, shows that framework carbon material is the mesoporous carbon material.Sweep speed is the cyclic voltammetry curve of 5mV/s among Fig. 4, and curve is regular rectangle.Fig. 5 charges and discharge curve for constant current, and curve presents tangible triangular symmetry.By Fig. 4 and Fig. 5 as seen, the prepared high-performance framework carbon material of the present invention is bigger than electric capacity, has good invertibity.Therefore, the high-performance framework carbon material of the present invention's preparation is a kind of electrode material for super capacitor of good child-rearing.

Claims (3)

1, a kind of preparation method of high-performance framework carbon material for super capacitor is characterized in that:
(1) with the carbide ball mill crushing, cross the 100-400 mesh sieve, getting particle diameter is 1-40 μ m powder;
(2) add the metal halide that accounts for total weight 0.1-20% in powder and make catalyst, ball milling mixes, and gets presoma;
(3) presoma being added in the tube furnace, feed inert gas in the pipe of tube furnace removing air, is that the HCl of 5-35% is added drop-wise to MnO with concentration 2In the powder, get the etching agent of the high activity chlorine of prepared fresh as metal or non-metallic atom in the removal carbide; Tube furnace is heated to 150-600 ℃, and the high activity chlorine of prepared fresh feeds dense H 2SO 4In to remove the moisture content in the chlorine, then chlorine is directly imported in the tube furnace and the presoma reaction, mixture of reaction products, unnecessary chlorine absorbs with alkaline absorption solution;
(4) with the mixture of reaction products acid elution, remove unreacted matters, wash to pH=7 ± 0.5 with pure water or distilled water, obtain skeleton carbon at 60-100 ℃ of dry 6-48h;
(5) gained skeleton carbon is added in the solution of the aniline, pyrroles, thiophene or their derivative that contain 1-20g/L, pass through polymerization reaction, in skeleton carbon surface and hole, form the finishing coat of polyaniline, polypyrrole, polythiophene or their derivative polymer, get high-performance framework carbon material for super capacitor.
2, a kind of ultracapacitor according to claim 1 one one step preparation method of framework carbon material, it is characterized in that: carbide is SiC, TiC, ZrC, V 2C, NbC, Nb 2C, TaC, Ta 2C, Cr 3C 2, Mo 2C, MoC, W 2C, WC, BaC 2, CaC 2, SrC 2, Al 4C 3, B 4C or Fe 3A kind of among the C.
3. a kind of ultracapacitor according to claim 1 one one step preparation method of framework carbon material, it is characterized in that: metal halide catalyst is NaCl, KCl, CaCl 2, MgCl 2, CuCl 2, NaBr, KBr, CaBr 2, MgBr 2, CuBr 2, NaI, KI, CaI 2, MgI 2Or CuI 2In a kind of.
CNA2008101436366A 2008-11-18 2008-11-18 Production method of high-performance framework carbon material for super capacitor Pending CN101404211A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102583317A (en) * 2012-02-22 2012-07-18 燕山大学 Method for enhancing structural order of carbide derived carbon
CN102786043A (en) * 2012-07-04 2012-11-21 燕山大学 Method for regulating pore structure of carbide derived carbon
CN102786044A (en) * 2012-07-04 2012-11-21 燕山大学 Method for enhancing structural order of carbide derived carbon
CN103771392A (en) * 2014-02-09 2014-05-07 湘潭大学 Preparation method of shape-controllable ordered layer porous chromium carbide skeleton carbon material for supercapacitor
CN104768870A (en) * 2012-10-16 2015-07-08 住友电气工业株式会社 Method for manufacturing porous carbon material
CN105948015A (en) * 2016-04-27 2016-09-21 北京化工大学 Method for synthesizing carbyne nano-material from calcium carbide and polyhalohydrocarbon as raw materials through ball-milling
CN108101021A (en) * 2017-12-22 2018-06-01 安徽工业大学 Using calcium carbide and chain polyhalohydrocarbon as the method for Material synthesis carbon nanomaterial under the conditions of solvent heat
CN113860285A (en) * 2021-10-27 2021-12-31 燕山大学 Nano-diamond structure carbon material prepared massively at normal pressure and preparation method and application thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102583317A (en) * 2012-02-22 2012-07-18 燕山大学 Method for enhancing structural order of carbide derived carbon
CN102786043A (en) * 2012-07-04 2012-11-21 燕山大学 Method for regulating pore structure of carbide derived carbon
CN102786044A (en) * 2012-07-04 2012-11-21 燕山大学 Method for enhancing structural order of carbide derived carbon
CN104768870A (en) * 2012-10-16 2015-07-08 住友电气工业株式会社 Method for manufacturing porous carbon material
CN103771392A (en) * 2014-02-09 2014-05-07 湘潭大学 Preparation method of shape-controllable ordered layer porous chromium carbide skeleton carbon material for supercapacitor
CN105948015A (en) * 2016-04-27 2016-09-21 北京化工大学 Method for synthesizing carbyne nano-material from calcium carbide and polyhalohydrocarbon as raw materials through ball-milling
CN105948015B (en) * 2016-04-27 2018-03-30 北京化工大学 It is a kind of in method of the calcium carbide with polyhalohydrocarbon as raw material ball break-in into alkynes carbon nanomaterial
CN108101021A (en) * 2017-12-22 2018-06-01 安徽工业大学 Using calcium carbide and chain polyhalohydrocarbon as the method for Material synthesis carbon nanomaterial under the conditions of solvent heat
CN113860285A (en) * 2021-10-27 2021-12-31 燕山大学 Nano-diamond structure carbon material prepared massively at normal pressure and preparation method and application thereof

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