CN104944419A

CN104944419A - Graphitized carbon material and preparation method thereof, and supercapacitor

Info

Publication number: CN104944419A
Application number: CN201510367813.9A
Authority: CN
Inventors: 郑超; 姜萍; 吕彬彬; 王国华; 周旭峰; 刘兆平
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Graphene Innovation Center Co Ltd
Priority date: 2015-06-29
Filing date: 2015-06-29
Publication date: 2015-09-30
Anticipated expiration: 2035-06-29
Also published as: CN104944419B

Abstract

The invention belongs to the field of carbon materials, and particularly relates to a graphitized carbon material and a preparation method thereof, and a supercapacitor. The graphitized carbon material provided by the invention can implement bulk phase graphitization, the degree of graphitization is 20-90%, the average pore size is 2-5nm, the porosity is 1.0-1.6 cm<3>/g, and the tap density is 0.2-0.5 g/ml. The supercapacitor prepared from the graphitized carbon material has higher energy density, and thus, has high practical application value. The experimental result indicates that the energy density of the supercapacitor prepared from the graphitized carbon material is greater than 10Wh/kg, the power density is greater than 20 kW/kg, and the capacity attenuation after 10000 loops under 10C magnification is less than 5%.

Description

A kind of graphitized carbon material and preparation method thereof and super capacitor

Technical field

The invention belongs to carbon material field, particularly relate to a kind of graphitized carbon material and preparation method thereof and super capacitor.

Background technology

Current, the energy and becoming increasingly conspicuous of environmental problem make the efficient storage of electric energy, clean energy and are converted into the problem concentrated and pay close attention to.Gac due to have cheap, wide material sources, volume and capacity ratio are higher, prepare the advantages such as simple.Be used widely in commercial ultracapacitor at present, its principle mainly by electrostatic ionic on the interface of gac high-specific surface area and electrolytic solution adsorb/desorption realizes the storage of electric energy, have high power density, can fast charging and discharging, 1,000,000 rank long circulation lifes and the characteristic such as safe and reliable.

Commercial gac specific surface area is up to 1000 ~ 2000m ²/ g, but the commercial super capacitor energy density using gac to prepare at present is only 5 ~ 7Wh/kg, far below expected value.A wherein very important reason is that the electroconductibility of gac is poor, and poorly conductive not only affects the utilization ratio of gac unit surface, affects its power density and high rate performance etc. simultaneously.Now widely used mode improves the electroconductibility of gac, adds a certain proportion of super carbon black, carbon nanotube and Graphene etc. in such as activated carbon electrodes.But the interpolation due to conductive agent just reduces the contact resistance between activated carbon granule, improve ion/electronics in the outside rate of diffusion of activated carbon granule, therefore adopt the mode of adding conductive agent can not significantly promote gac conductivity, the energy density of the commercial ultracapacitor adopting the gac being added with conductive agent to obtain is still lower.

Summary of the invention

In view of this, the object of the present invention is to provide a kind of graphitized carbon material and preparation method thereof and super capacitor, the super capacitor energy density adopting graphitized carbon material provided by the invention obtained is high.

The invention provides a kind of graphitized carbon material, the degree of graphitization of described graphitized carbon material is 20 ~ 90%, and mean pore size is 2 ~ 5nm, and porosity is 1.0 ~ 1.6cm ³/ g, tap density is 0.2 ~ 0.5g/mL.

Preferably, the degree of graphitization of described graphitized carbon material is 30% ~ 80%.

The invention provides the preparation method of the graphitized carbon material described in a kind of technique scheme, comprise the following steps:

A), carbon source mixes with metal catalyst, obtains the carbon source being adsorbed with metal catalyst;

Described metal catalyst comprise in nickel salt, molysite, molybdenum salt, cobalt salt and tungsten salt one or more;

The mass ratio of described carbon source and metal catalyst is 1:(0.001 ~ 2);

B), described in be adsorbed with carbon source and the activator mix of metal catalyst, obtain presoma;

Described activator comprise in water vapour, potassium hydroxide, phosphoric acid, zinc chloride and sodium hydroxide one or more;

Described activator and step a) described in the mass ratio of carbon source be (0.5 ~ 10): 1;

C), described presoma heats carbonization in inert gas atmosphere, obtains graphitized carbon material.

Preferably, the temperature of described heating carbonization is 600 ~ 1000 DEG C; The time of described heating carbonization is 0.1 ~ 24h.

Preferably, described carbon source is selected from one or more in decolorizing carbon, resin material and biological material.

Preferably, step a) in, before described carbon source mixes with metal catalyst, first use properties-correcting agent modification is carried out to carbon source;

Described properties-correcting agent comprise in ethanol, sodium hydroxide, potassium hydroxide, calcium hydroxide, phosphoric acid, oxalic acid, citric acid, nitric acid, potassium permanganate, hydrogen peroxide, calcium chloride, methyl acrylate, dithiocarbonic anhydride, mercaptoethanol, Repone K, magnesium chloride, ozone, chlorine and nitrogen peroxide one or more.

Preferably, step c) in, described presoma carries out heating carbonization under carbonization conditioning agent exists;

Described carbonization conditioning agent comprise in alkane, alkene, alkynes, Benzene and Homologues, condensed-nuclei aromatics, saturated halogenated hydrocarbon, unsaturated halohydrocarbon, halogenated aryl hydrocarbon, ether compound, alcohol compound, aldehyde compound, ketone compounds, carboxylic acid compound, nitrogen-containing organic compound and inorganic nitrogen-containing compound one or more.

Preferably, described alkane is C ₁~ C ₁₀alkane; Described alkene is C ₂~ C ₁₀alkene; Described alkynes is C ₂~ C ₁₀alkynes; Described condensed-nuclei aromatics comprise in naphthalene, anthracene and phenanthrene one or more; Described ether compound comprise in methyl ether, ether, n-butyl ether and oxyethane one or more; Described alcohol compound comprise in methyl alcohol, ethanol, propyl alcohol and furfuryl alcohol one or more; Described aldehyde compound comprise in formaldehyde, acetaldehyde, propenal and butyraldehyde one or more; Described ketone compounds comprise in acetone, butanone and pimelinketone one or more; Described carboxylic acid compound comprise in formic acid, acetic acid, propionic acid, terephthalic acid, phenylformic acid and citric acid one or more; Described nitrogen-containing organic compound comprise in aromatic nitro compound, aminated compounds, nitrile compounds, diazonium compound, azo-compound and amino acid one or more; Described inorganic nitrogen-containing compound comprises volatile salt and/or bicarbonate of ammonia.

Preferably, described carbonization conditioning agent comprise methane, ethane, ethene, acetylene, propylene, methyl alcohol, ethanol, propyl alcohol, furfuryl alcohol, trimeric cyanamide, Dyhard RU 100, urea, methylamine, ethamine, quadrol, aniline, Diisopropyl azodicarboxylate, nitrogen benzide, to one or more in methylaminoazobenzene, acetonitrile, butyronitrile, vinyl cyanide, cyanobenzene, bicarbonate of ammonia, glycine, L-Ala, leucine, Serine, Gelucystine, L-glutamic acid, arginine, Histidine and tryptophane.

Preferably, described carbonization conditioning agent is one or more in gas carburization conditioning agent, liquid phase carbonation conditioning agent and solid phase carbonization conditioning agent;

Described step c) be: lead to gas carburization conditioning agent to described presoma, described presoma heats carbonization in gas carburization conditioning agent atmosphere, obtains graphitized carbon material;

The air flow of described gas carburization conditioning agent is 1 ~ 5000mL/h;

Or

Described step c) be: lead to liquid phase carbonation conditioning agent to described presoma, described presoma heats carbonization in the liquid phase carbonation conditioning agent atmosphere of vaporization, obtains graphitized carbon material;

The air flow of described gas carburization conditioning agent is 10 ~ 4000mL/h;

Or

Described step c) be: described presoma mixes with solid phase carbonization conditioning agent, is mixed to get mixture heating carbonization, obtains graphitized carbon material;

Described solid-state carbonization conditioning agent and step a) described in the mass ratio of carbon source be (0.05 ~ 100): 1.

The invention provides a kind of ultracapacitor, comprise electrode, barrier film and electrolytic solution;

Described electrode comprises the obtained graphitized carbon material of the graphitized carbon material described in technique scheme or the method described in technique scheme.

Compared with prior art, the invention provides a kind of graphitized carbon material and preparation method thereof and super capacitor.Graphitized stephanoporate material with carbon element provided by the invention can realize body phase greying, and degree of graphitization is 20 ~ 90%, and mean pore size is 2 ~ 5nm, and porosity is 1.0 ~ 1.6cm ³/ g, tap density is 0.2 ~ 0.5g/mL.The ultracapacitor prepared by this graphitized carbon material shows higher energy density, has very strong actual application value.Experimental result shows, the energy density of the ultracapacitor adopting graphitized carbon material provided by the invention to obtain is greater than 10Wh/kg, and power density is greater than 20kW/kg, and after lower 10000 circulations of 10C multiplying power, capacity attenuation is less than 5%.

Accompanying drawing explanation

In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.

Fig. 1 is the SEM figure of the graphitized carbon material that the embodiment of the present invention 1 obtains;

Fig. 2 is the SEM figure of the graphitized carbon material that the embodiment of the present invention 2 obtains;

Fig. 3 is the SEM figure of the graphitized carbon material that the embodiment of the present invention 10 obtains;

Fig. 4 is the TEM figure of the graphitized carbon material that the embodiment of the present invention 10 obtains;

Fig. 5 is the SEM figure of the graphitized carbon material that the embodiment of the present invention 19 obtains.

Embodiment

Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.

The invention provides a kind of graphitized carbon material, the degree of graphitization of described graphitized carbon material is 20% ~ 90%, and the mean pore size of described graphitized carbon material is 2 ~ 5nm, and the porosity of described graphitized carbon material is 1.0 ~ 1.6cm ³/ g, tap density is 0.2 ~ 0.5g/mL.In an embodiment provided by the invention, the degree of graphitization of described graphitized carbon material is 40% ~ 80%; In another embodiment provided by the invention, the degree of graphitization of described graphitized carbon material is 50% ~ 70%.In an embodiment provided by the invention, the mean pore size of described graphitized carbon material is 3 ~ 4nm; In another embodiment provided by the invention, the mean pore size of described graphitized carbon material is 3.3 ~ 3.6nm.In an embodiment provided by the invention, the porosity of described graphitized carbon material is 1.1 ~ 1.2cm ³/ g; In another embodiment provided by the invention, the porosity of described graphitized carbon material is 1.11 ~ 1.15cm ³/ g.In an embodiment provided by the invention, the tap density of described graphitized carbon material is 0.2 ~ 0.5g/mL; In another embodiment provided by the invention, the tap density of described graphitized carbon material is 0.3 ~ 0.4g/mL; In other embodiments provided by the invention, the tap density of described graphitized carbon material is 0.31 ~ 0.37g/mL.In an embodiment provided by the invention, the specific surface area of described graphitized carbon material is 1000 ~ 2500m ²/ g; In another embodiment provided by the invention, the specific surface area of described graphitized carbon material is 1200 ~ 1500m ²/ g; In other embodiments provided by the invention, the specific surface area of described graphitized carbon material is 1230 ~ 1245m ²/ g.

The invention provides the porous carbon materials that a class degree of graphitization is different, achieve the body phase greying of porous carbon materials.Graphitized carbon material provided by the invention has carbon nanotube, carbon fiber, Graphene, class Graphene etc. at the hole wall surface growth in situ of porous carbon materials, is a kind of graphitized carbon material with multidimensional conductive path.The degree of graphitization of graphitized carbon material provided by the invention is 20 ~ 90%, and mean pore size is 2 ~ 5nm, and porosity is 1.0 ~ 1.6cm ³/ g, tap density is 0.2 ~ 0.5g/mL.When this graphitized carbon material is used for electrode material for super capacitor, show higher energy density, there is very strong actual application value.Experimental result shows, the energy density of the super capacitor adopting graphitized carbon material provided by the invention to obtain is greater than 10Wh/kg, and power density is greater than 20kW/kg, and after lower 10000 circulations of 10C multiplying power, capacity attenuation is less than 5%.

The mass ratio of described carbon source and metal catalyst is 1:(0.001 ~ 2);

Described activator comprise in water vapour, potassium hydroxide, phosphoric acid, zinc chloride, sodium hydroxide one or more;

In the preparation method of graphitized carbon material provided by the invention, first carry out step a): carbon source and metal catalyst are mixed, obtain the carbon source being adsorbed with metal catalyst.Wherein, described carbon source preferably includes one or more in decolorizing carbon, resin material and biological material.

In the present invention, described decolorizing carbon preferably includes one or more in gac, carbon black, pitch, mud coal, brown coal and weathered coal, more preferably comprises one or more in gac, carbon black and pitch.

In the present invention, described resin material preferably includes one or more in resol, styrene resin, acrylic resin, epoxy resin, aminoresin, Synolac and urea-formaldehyde resin.In an embodiment provided by the invention, the resol of the models such as D122, D125 that described resol can adopt Liaoyuan, Bengbu novel material company limited to produce; The styrene resin of the models such as D301, D320, BSD-92, BS-66, BS-67-7 that described styrene resin can adopt Liaoyuan, Bengbu novel material company limited to produce.

In the present invention, described biological material preferably includes one or more in xylogen, modified-cellulose, treated starch, maize straw, husk, nut-shell, tealeaves, bagasse, orange peel, rice husk, tree bits, chlorella, bladder wrack, sea-tangle, black wrack and sargassun, more preferably comprises one or more in nut-shell, chlorella, bladder wrack, black wrack and sargassun.

In the present invention, described metal catalyst comprise in nickel salt, molysite, molybdenum salt, cobalt salt and tungsten salt one or more, preferably include one or more in iron(ic) chloride, nickelous chloride, nickel acetate, iron acetate, ferric sulfate, single nickel salt, the Tripotassium iron hexacyanide and yellow prussiate of potash, more preferably comprise one or more in nickelous chloride, iron(ic) chloride, the Tripotassium iron hexacyanide and nickel acetate.In the present invention, the mass ratio of described carbon source and metal catalyst is 1:(0.001 ~ 2), be preferably 1:(0.001 ~ 1), be more preferably 1:(0.01 ~ 0.8), most preferably be 1:(0.1 ~ 0.5).

In the present invention, preferably adopt the carbon source being adsorbed with metal catalyst described in the preparation of the solution of described metal catalyst, this process is specially:

First described carbon source is impregnated in the solution of metal catalyst, then drying is carried out to the carbon source after dipping, obtain the carbon source being adsorbed with metal catalyst.Wherein, the concentration of the solution of described metal catalyst is preferably 0.001 ~ 1g/mL, is more preferably 0.005 ~ 0.5g/mL, most preferably is 0.05 ~ 0.5g/mL.The mode of described drying is preferably dries.

In the present invention, before described carbon source mixes with metal catalyst, first use properties-correcting agent to carry out modification to carbon source, described properties-correcting agent comprises one or more in ethanol, sodium hydroxide, potassium hydroxide, calcium hydroxide, phosphoric acid, oxalic acid, citric acid, nitric acid, potassium permanganate, hydrogen peroxide, calcium chloride, methyl acrylate, dithiocarbonic anhydride, mercaptoethanol, Repone K, magnesium chloride, ozone, chlorine and nitrogen peroxide.In the present invention, the object of carbon source being carried out to modification is the adsorption group changing carbon source, thus improves carbon source to the adsorptivity of metal catalyst, and then improves the chemical property of final obtained graphitized carbon material.

In the present invention, when the state of the properties-correcting agent adopted is solid-state and/or liquid, the solution of the described properties-correcting agent of preferred employing carries out modification to described carbon source, this process is specially: first described carbon source be immersed in the solution of described properties-correcting agent, then the carbon source after dipping is filtered successively, dry, obtain modification carbon source.Wherein, the concentration of the solution of described properties-correcting agent is preferably 0.5 ~ 20wt%, is more preferably 0.5 ~ 15wt%, most preferably is 0.8 ~ 10wt%.The time of described dipping is preferably 5 ~ 36h, is more preferably 6 ~ 24h; The temperature of described dipping is preferably 30 ~ 80 DEG C.The mode of described drying is preferably dries.

In the present invention, when the state of the properties-correcting agent adopted is gaseous state, the mode directly described carbon source being placed in described properties-correcting agent atmosphere is preferably adopted to carry out modification to described carbon source.In described properties-correcting agent atmosphere, the content of properties-correcting agent is preferably 10 ~ 20wt%.The time that described carbon source is placed in described properties-correcting agent atmosphere is preferably 5 ~ 36h, is more preferably 6 ~ 12h; The temperature that described carbon source is placed in described properties-correcting agent atmosphere is preferably room temperature.

Obtained be adsorbed with the carbon source of metal catalyst after, carry out step b): described in be adsorbed with carbon source and the activator mix of metal catalyst, obtain presoma.Wherein, described activator comprises one or more in water vapour, potassium hydroxide, phosphoric acid, zinc chloride, Repone K, sodium hydroxide.Described activator and step a) described in the mass ratio of carbon source be (0.5 ~ 10): 1, be preferably (1 ~ 8): 1, be more preferably (2 ~ 5): 1.In the present invention, preferably first described activator is mixed with solution, then the solution of activator is mixed with the described metal catalyst that is adsorbed with, finally carry out drying to containing the activator solution being adsorbed with metal catalyst, obtain described presoma.

After obtained described presoma, carry out step c): described presoma heats carbonization in inert gas atmosphere.In the present invention, described rare gas element is preferably one or more in nitrogen, carbonic acid gas and rare gas element.The temperature of described presoma heating carbonization is preferably 600 ~ 1000 DEG C, is more preferably 800 ~ 950 DEG C, most preferably is 850 ~ 900 DEG C.In the present invention, the temperature of described presoma heating carbonization controls to realize by heating up, and the speed of described intensification is preferably 1 ~ 10 DEG C/min, is more preferably 2 ~ 9 DEG C/min, most preferably is 4 ~ 6 DEG C/min.In the present invention, the time of described presoma heating carbonization is preferably 0.1 ~ 24h, is more preferably 0.5 ~ 8h, most preferably is 1 ~ 7h, be the most preferably 3 ~ 6h.In the present invention, the time of described presoma heating carbonization does not comprise the time that described temperature-rise period consumes.

In the present invention, described presoma preferably carries out heating carbonization under carbonization conditioning agent exists, described carbonization conditioning agent comprise in alkane, alkene, alkynes, Benzene and Homologues, condensed-nuclei aromatics, saturated halogenated hydrocarbon, unsaturated halohydrocarbon, halogenated aryl hydrocarbon, ether compound, alcohol compound, aldehyde compound, ketone compounds, carboxylic acid compound, nitrogen-containing organic compound and inorganic carbon nitrogen compound one or more.Wherein, described alkane is preferably C ₁~ C ₁₀alkane, be more preferably in methane, ethane, propane, butane and pentane one or more; Described alkene is preferably C ₂~ C ₁₀alkene, be more preferably in ethene, propylene, butylene and amylene one or more; Described alkynes is preferably C ₂~ C ₁₀alkynes, be more preferably in acetylene, propine, butine and pentyne one or more; Described condensed-nuclei aromatics preferably include in naphthalene, anthracene and phenanthrene one or more; Described ether compound preferably include in methyl ether, ether, n-butyl ether and oxyethane one or more; Described alcohol compound preferably include in methyl alcohol, ethanol, propyl alcohol and furfuryl alcohol one or more; Described aldehyde compound preferably include in formaldehyde, acetaldehyde, propenal and butyraldehyde one or more; Described ketone compounds preferably include in acetone, butanone and pimelinketone one or more; Described carboxylic acid compound preferably include in formic acid, acetic acid, propionic acid, terephthalic acid, phenylformic acid and citric acid one or more; Described nitrogen-containing organic compound preferably include in aromatic nitro compound, aminated compounds, nitrile compounds, diazonium compound, azo-compound and amino acid one or more; Described aminated compounds preferably include in methylamine, ethamine, aniline, quadrol, trimeric cyanamide, Dyhard RU 100 and urea one or more; Described nitrile compounds preferably include in acetonitrile, isopropyl cyanide and vinyl cyanide one or more; Described amino acid preferably include in glycine, L-Ala, leucine, Serine and Methionin one or more; Described inorganic carbon nitrogen compound preferably includes volatile salt and/or bicarbonate of ammonia.

In the present invention, the carbonization conditioning agent adopted preferably include methane, ethane, ethene, acetylene, propylene, methyl alcohol, ethanol, propyl alcohol, furfuryl alcohol, trimeric cyanamide, Dyhard RU 100, urea, methylamine, ethamine, quadrol, aniline, Diisopropyl azodicarboxylate, nitrogen benzide, to one or more in methylaminoazobenzene, acetonitrile, butyronitrile, vinyl cyanide, cyanobenzene, bicarbonate of ammonia, glycine, L-Ala, leucine, Serine, Gelucystine, L-glutamic acid, arginine, Histidine and tryptophane.

In the present invention, different according to the state of described carbonization conditioning agent, be divided into gas carburization conditioning agent, liquid phase carbonation conditioning agent and solid phase carbonization conditioning agent.In an embodiment provided by the invention, described carbonization conditioning agent is one or more in gas carburization conditioning agent, liquid phase carbonation conditioning agent and solid phase carbonization conditioning agent.

Comprise in the embodiment of gas carburization conditioning agent at a described carbonization conditioning agent provided by the invention, the process that described presoma carries out heating carbonization under gas carburization conditioning agent exists is specially:

Lead to gas carburization conditioning agent to described presoma, described presoma heats carbonization in gas carburization conditioning agent atmosphere, obtains graphitized carbon material; The air flow of described gas carburization conditioning agent is 1 ~ 5000mL/h.

In above-described embodiment provided by the invention, the gas carburization conditioning agent adopted be preferably in methane, ethane, ethene, acetylene and propylene one or more.The air flow of described gas carburization conditioning agent is preferably 1 ~ 5000mL/h, is more preferably 50 ~ 1000mL/h, most preferably is 100 ~ 500mL/h.Described presoma heats carbonization and preferably carries out in tube furnace in gas carburization conditioning agent atmosphere.

The described carbonization conditioning agent carried in the present invention comprises in the embodiment of liquid phase carbonation conditioning agent, and the process that described presoma carries out heating carbonization under liquid phase carbonation conditioning agent exists is specially:

Lead to liquid phase carbonation conditioning agent to described presoma, described presoma heats carbonization in the liquid phase carbonation conditioning agent atmosphere of vaporization, obtains graphitized carbon material; The air flow of described gas carburization conditioning agent is 10 ~ 4000mL/h.

In above-described embodiment provided by the invention, the liquid phase carbonation conditioning agent adopted be preferably in methyl alcohol, ethanol, furfuryl alcohol and quadrol one or more.The air flow of described gas carburization conditioning agent is preferably 10 ~ 4000mL/h, is more preferably 15 ~ 1000mL/h, most preferably is 100 ~ 400mL/h.Described presoma heats carbonization and preferably carries out in tube furnace in gas carburization conditioning agent atmosphere.

The described carbonization conditioning agent carried in the present invention comprises in the embodiment of solid phase carbonization conditioning agent, and the process that described presoma carries out heating carbonization under solid phase carbonization conditioning agent exists is specially:

Described presoma mixes with solid-state carbonization conditioning agent, is mixed to get mixture heating carbonization, obtains graphitized carbon material; Described solid-state carbonization conditioning agent and step a) described in the mass ratio of carbon source be (0.05 ~ 100): 1.

In above-described embodiment provided by the invention, the solid phase carbonization conditioning agent adopted is one or more in trimeric cyanamide, Dyhard RU 100 and urea.Described solid-state carbonization conditioning agent and step a) described in carbon source mass ratio be preferably (0.05 ~ 100): 1, be more preferably (0.1 ~ 20): 1, most preferably be (1 ~ 10): 1.

Presoma, after heating carbonization terminates, carries out aftertreatment to the product that heating carbonization obtains.The detailed process of described aftertreatment preferably includes: the product that described heating carbonization obtains carries out washing, filtering and drying successively.The mode of described washing is preferably pickling.The washings of described pickling preferably include in hydrochloric acid, sulfuric acid and nitric acid one or more.The mode of described drying is preferably dries.After aftertreatment terminates, obtain graphitized carbon material.

Preparation method provided by the invention obtains graphitized carbon material by single step situ catalytic greying carbon source, and the method technique is simple, productive rate is high, available carbon source wide material sources, with low cost, be easy to industrialization.

In a preferred embodiment of the invention, presoma carries out heating carbonization under carbonization conditioning agent exists, the degree of graphitization that can regulate graphitized carbon material of carbonization conditioning agent, improves the apparent form of graphitized carbon material, and then improves the electric property of final obtained graphitized carbon material.

Described electrode comprises graphitized carbon material that method described in technique scheme obtains or the graphitized carbon material described in technique scheme.

Super capacitor provided by the invention comprises electrode, barrier film and electrolytic solution.Wherein, described electrode comprises described graphitized carbon material.In an embodiment provided by the invention, described electrode also comprises binding agent, conductive agent and metal pole piece.Described binding agent is preferably polyvinylidene difluoride (PVDF) (PVDF) and/or tetrafluoroethylene (PTFE); Described conductive agent be preferably in graphitized carbon black, carbon nanotube, Graphene and carbon nanofiber pipe (VGCF) one or more; Described metal pole piece is preferably aluminium foil.The mass ratio of graphitized carbon material described in electrode, binding agent and conductive agent is preferably 8:1:1.

In the present invention, described electrode is preferably prepared in accordance with the following methods:

First graphitized carbon material, binding agent and conductive agent are mixed in a solvent, obtain electrode slurry; Then electrode slurry is coated on metal pole piece, dry, obtain electrode.

In the present invention, described solvent is preferably one or more in N-Methyl pyrrolidone, dehydrated alcohol and aqueous ethanolic solution.The thickness of described electrode slurry coating is preferably 50 ~ 200 μm, is more preferably 100 ~ 150 μm.The mode of described drying is preferably dries; The temperature of described drying is preferably 100 ~ 150 DEG C, is more preferably 120 ~ 130 DEG C.

In the present invention, described barrier film is preferably Japanese NKK barrier film (TF4030) and/or Celgard2400.Described electrolytic solution is preferably the carbonic allyl ester solution (Et of tetraethylammonium tetrafluoroborate ₄nBF ₄/ PC).Tetraethylammonium tetrafluoroborate (Et in the carbonic allyl ester solution of described tetraethylammonium tetrafluoroborate ₄nBF ₄) concentration be preferably 1 ~ 2mol/L.

In the present invention, according to electric capacity assembling mode well known to those skilled in the art, above-mentioned electrode, barrier film and electrolytic solution are assembled, super capacitor provided by the invention can be obtained.

Super capacitor provided by the invention has higher energy density.Experimental result shows, the energy density of the specific capacitance of super capacitor provided by the invention is greater than 10Wh/kg, and power density is greater than 20kW/kg, and after lower 10000 circulations of 10C multiplying power, capacity attenuation is less than 5%.

For the purpose of clearer, be described in detail below by following examples.

Embodiment 1

Get 100g resol (4169, Changchun, Taiwan), be immersed in 200ml and contain in the aqueous solution of 50g single nickel salt, dry, obtain the resol of adsorbing metal ions catalyzer; Afterwards the resol of adsorbing metal ions catalyzer is added in the solution containing 200g KOH, dry and pulverize, obtain presoma.

Presoma is placed in tube furnace, in nitrogen atmosphere, passes into methane gas according to the flow of 5000mL/h, be warming up to 900 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 1h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Join in 25mL graduated cylinder by the above-mentioned obtained graphitized carbon material of 0.3g, through shaking up and down, finally estimating the tap density obtained is 0.4g/mL.

Detect the specific surface area of above-mentioned graphitized carbon material, porosity and mean pore size, result is: specific surface area is 1500m ²/ g, porosity is 1.12cm ³/ g, mean pore size is 3.2nm.

Calculate the degree of graphitization of above-mentioned graphitized carbon material, its calculation formula is such as formula shown in (I):

G=(0.3440-d002)/(0.3440-0.3354) formula (I);

In formula (I): g is degree of graphitization; 0.3440 is the interlamellar spacing of completely non-graphitized charcoal; 0.3354 is the interlamellar spacing of ideal graphite crystal; D002 is the interlamellar spacing in carbon material (002) face, and d002 detects acquisition by carrying out XRD to described graphitized carbon material.

Degree of graphitization calculation result is: the degree of graphitization of this graphitized carbon material is 81.9%.

Carry out scanning electron microscope (SEM) test to above-mentioned obtained graphitized carbon material, result as shown in Figure 1.Fig. 1 is the SEM figure of the graphitized carbon material that the embodiment of the present invention 1 obtains, as seen in Figure 1, graphitized carbon material is the grainy texture of 10 ~ 20 μm, and its surface metal catalysis and in situ grown the Graphene of accordion, and this material has higher degree of graphitization.

The ratio of above-mentioned obtained graphitized carbon material, caking agent (PVDF) and conductive agent (graphitized carbon black) 8:1:1 is in mass ratio mixed, add appropriate N-Methyl pyrrolidone to stir formation slurry, be coated on aluminium foil, coating thickness is 100 μm, dry under 120 DEG C of conditions, be then cut into the electrode slice of Φ 13.In glove box, by electrode slice and barrier film and electrolytic solution (1M Et ₄nBF ₄/ PC) be assembled into 2032 type button super capacitors.

Carry out electrochemical property test to obtained button super capacitor, its specific storage is 75F/g, and corresponding energy density is 13Wh/kg, lower 10000 the recycle ratio capacity attenuations 3.5% of power density 25kW/kg, 10C multiplying power.

Embodiment 2

Get 1000g trimeric cyanamide to mix with precursor and be placed in tube furnace, in nitrogen atmosphere, be warming up to 850 DEG C according to the temperature rise rate of 4 DEG C/min, after keeping 6h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Carry out scanning electron microscope (SEM) test to above-mentioned obtained graphitized carbon material, result as shown in Figure 2.Fig. 2 is the SEM figure of the graphitized carbon material that the embodiment of the present invention 2 obtains, and as seen in Figure 2, the surface in situ of granular graphite carbon material grown one dimension caliber 20 ~ 100nm carbon nanotube, is a kind of matrix material of graphitized carbon/carbon nanotube.

Calculate with reference to the degree of graphitization of method to above-mentioned obtained graphitized carbon material described in embodiment 1, result is: the degree of graphitization of this graphitized carbon material is 81.9%.

Embodiment 3

Presoma is placed in tube furnace, in nitrogen atmosphere, passes into ethanol according to the flow of 400mL/h, be warming up to 850 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 6h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 4

Get 100g resol (4169, Changchun, Taiwan), be immersed in 200ml and contain in the aqueous solution of 10g single nickel salt, dry, obtain the resol of adsorbing metal ions catalyzer; Afterwards the resol of adsorbing metal ions catalyzer is added in the solution containing 300g KOH, dry and pulverize, obtain presoma.

Get 10000g trimeric cyanamide to mix with precursor and be placed in tube furnace, in nitrogen atmosphere, be warming up to 900 DEG C according to the temperature rise rate of 4 DEG C/min, after keeping 1h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Join in 25mL graduated cylinder by the above-mentioned obtained graphitized carbon material of 0.3g, through shaking up and down, finally estimating the tap density obtained is 0.2g/mL.

Detect the specific surface area of above-mentioned graphitized carbon material, porosity and mean pore size, result is: specific surface area is 2500m ²/ g, porosity is 1.15cm ³/ g, mean pore size is 3.3nm.

According to the method described in embodiment 1, the graphitized carbon material that the present embodiment obtains is carried out to the calculating of degree of graphitization, calculation result is: the degree of graphitization of this graphitized carbon material is 73.3%.

Carry out electrochemical property test to obtained button super capacitor, its specific storage is 85F/g, and corresponding energy density is 15Wh/kg, lower 10000 the recycle ratio capacity attenuations 4% of power density 21KW/kg, 10C multiplying power.

Embodiment 5

Embodiment 6

Presoma is placed in tube furnace, in nitrogen atmosphere, passes into ethanol according to the flow of 4000mL/h, be warming up to 900 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 1h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 7

Get 100g resol (4169, Changchun, Taiwan), be immersed in 100ml and contain in the aqueous solution of 0.1g single nickel salt, dry, obtain the resol of adsorbing metal ions catalyzer; Afterwards the resol of adsorbing metal ions catalyzer is added in the solution containing 50g KOH, dry and pulverize, obtain presoma.

Get 5g trimeric cyanamide to mix with precursor and be placed in tube furnace, in argon atmosphere, be warming up to 800 DEG C according to the temperature rise rate of 4 DEG C/min, after keeping 24h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Join in 25mL graduated cylinder by the above-mentioned obtained graphitized carbon material of 0.3g, through shaking up and down, finally estimating the tap density obtained is 0.5g/mL.

Detect the specific surface area of above-mentioned graphitized carbon material, porosity and mean pore size, result is: specific surface area is 1000m ²/ g, porosity is 1.10cm ³/ g, mean pore size is 3.1nm.

According to the method described in embodiment 1, the graphitized carbon material that the present embodiment obtains is carried out to the calculating of degree of graphitization, calculation result is: the degree of graphitization of this graphitized carbon material is 20%.

Carry out electrochemical property test to obtained button super capacitor, its specific storage is 70F/g, and corresponding energy density is 12Wh/kg, lower 10000 the recycle ratio capacity attenuations 4.5% of power density 20KW/kg, 10C multiplying power.

Embodiment 8

Presoma is placed in tube furnace, in argon atmosphere, passes into methane gas according to the flow of 50mL/h, be warming up to 800 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 24h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 9

Presoma is placed in tube furnace, in argon atmosphere, passes into ethanol according to the flow of 15mL/h, be warming up to 800 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 24h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 10

Get 100g nut-shell, joined the KMnO of 10wt% ₄in solution, 80 DEG C of water-bath 6h, filtering drying; Then being immersed in 200ml contains in the aqueous solution of the 80g Tripotassium iron hexacyanide, dries, obtains the nut-shell being adsorbed with metal catalyst; Afterwards the nut-shell of adsorbing metal ions catalyzer is added in the solution containing 400g KOH, dry and pulverize, obtain presoma.

Get 2000g urea to mix with precursor and be placed in tube furnace, in nitrogen atmosphere, be warming up to 1000 DEG C according to the temperature rise rate of 4 DEG C/min, after keeping 4h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Detect the specific surface area of above-mentioned graphitized carbon material, porosity and mean pore size, result is: specific surface area is 1350m ²/ g, porosity is 1.10cm ³/ g, mean pore size is 3nm.

According to the method described in embodiment 1, the graphitized carbon material that the present embodiment obtains is carried out to the calculating of degree of graphitization, calculation result is: the degree of graphitization of this graphitized carbon material is 90%.

Carry out scanning electron microscope (SEM) and transmission electron microscope (TEM) observation to above-mentioned graphitized carbon material, result as shown in Figure 3 and Figure 4.Fig. 3 is the SEM figure of the graphitized carbon material that the embodiment of the present invention 10 obtains, and can observe the flake that graphitized carbon material provided by the invention is into 5 ~ 20 μm from Fig. 3.Fig. 4 is the TEM figure of the graphitized carbon material that the embodiment of the present invention 10 obtains, and as seen in Figure 4, the edge of graphitized carbon material has good graphite linings structure, and interlamellar spacing is 0.35nm, and this material has higher degree of graphitization.

Carry out electrochemical property test to obtained button super capacitor, its specific storage is 75F/g, and corresponding energy density is 13Wh/kg, lower 10000 the recycle ratio capacity attenuations 3% of power density 30KW/kg, 10C multiplying power.

Embodiment 11

Presoma is placed in tube furnace, in nitrogen atmosphere, passes into ethane gas according to the flow of 300mL/h, be warming up to 1000 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 4h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 12

Presoma is placed in tube furnace, in nitrogen atmosphere, passes into furfuryl alcohol according to the flow of 250mL/h, be warming up to 1000 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 4h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 13

Get 100g nut-shell, joined the KMnO of 10wt% ₄in solution, 80 DEG C of water-bath 6h, filtering drying; Then being immersed in 200ml contains in the aqueous solution of the 30g Tripotassium iron hexacyanide, dries, obtains the nut-shell being adsorbed with metal catalyst; Afterwards the nut-shell of adsorbing metal ions catalyzer is added in the solution containing 500g KOH, dry and pulverize, obtain presoma.

Get 8000g urea to mix with precursor and be placed in tube furnace, in nitrogen atmosphere, be warming up to 1100 DEG C according to the temperature rise rate of 4 DEG C/min, after keeping 24h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Join in 25mL graduated cylinder by the above-mentioned obtained graphitized carbon material of 0.3g, through shaking up and down, finally estimating the tap density obtained is 0.31g/mL.

Detect the specific surface area of above-mentioned graphitized carbon material, porosity and mean pore size, result is: specific surface area is 2000m ²/ g, porosity is 1.2cm ³/ g, mean pore size is 4nm.

According to the method described in embodiment 1, the graphitized carbon material that the present embodiment obtains is carried out to the calculating of degree of graphitization, calculation result is: the degree of graphitization of this graphitized carbon material is 70.5%.

Carry out electrochemical property test to obtained button super capacitor, its specific storage is 78F/g, and corresponding energy density is 14Wh/kg, lower 10000 the recycle ratio capacity attenuations 4% of power density 26KW/kg, 10C multiplying power.

Embodiment 14

Presoma is placed in tube furnace, in nitrogen atmosphere, passes into ethane gas according to the flow of 1mL/h, be warming up to 1100 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 24h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 15

Presoma is placed in tube furnace, in nitrogen atmosphere, passes into furfuryl alcohol according to the flow of 10mL/h, be warming up to 1100 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 24h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 16

Get 100g nut-shell, added the KMnO of 10wt% ₄in solution, 80 DEG C of water-bath 6h, filtering drying; Then being immersed in 100ml contains in the aqueous solution of the 1g Tripotassium iron hexacyanide, dries, obtains the nut-shell being adsorbed with metal catalyst; Afterwards the nut-shell of adsorbing metal ions catalyzer is added in the solution containing 100g KOH, dry and pulverize, obtain presoma.

Get 100g urea to mix with precursor and be placed in tube furnace, in argon atmosphere, be warming up to 900 DEG C according to the temperature rise rate of 4 DEG C/min, after keeping 2h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Join in 25mL graduated cylinder by the above-mentioned obtained graphitized carbon material of 0.3g, through shaking up and down, finally estimating the tap density obtained is 0.34g/mL.

Detect the specific surface area of above-mentioned graphitized carbon material, porosity and mean pore size, result is: specific surface area is 1250m ²/ g, porosity is 1.12cm ³/ g, mean pore size is 3.2nm.

According to the method described in embodiment 1, the graphitized carbon material that the present embodiment obtains is carried out to the calculating of degree of graphitization, calculation result is: the degree of graphitization of this graphitized carbon material is 52.3%.

Embodiment 17

Presoma is placed in tube furnace, in argon atmosphere, passes into ethane gas according to the flow of 100mL/h, be warming up to 900 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 2h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 18

Presoma is placed in tube furnace, in argon atmosphere, passes into furfuryl alcohol according to the flow of 150mL/h, be warming up to 900 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 2h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 19

Get 100g gac, joined the KMnO of 10wt% ₄in solution, 80 DEG C of water-bath 6h, filtering drying; Then being immersed in 200ml contains in the aqueous solution of 100g nickelous chloride, dries, obtains the gac being adsorbed with metal catalyst; Afterwards the gac of adsorbing metal ions catalyzer is added in the solution containing 600g KOH, dry and pulverize, obtain presoma.

Get 3000g trimeric cyanamide to mix with precursor and be placed in tube furnace, in argon atmosphere, be warming up to 850 DEG C according to the temperature rise rate of 4 DEG C/min, after keeping 6h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Detect the specific surface area of above-mentioned graphitized carbon material, porosity and mean pore size, result is: specific surface area is 1500m ²/ g, porosity is 1.15cm ³/ g, mean pore size is 3.4nm.

According to the method described in embodiment 1, the graphitized carbon material that the present embodiment obtains is carried out to the calculating of degree of graphitization, calculation result is: the degree of graphitization of this graphitized carbon material is 75.8%.

Carry out scanning electron microscope (SEM) test to above-mentioned obtained graphitized carbon material, result as shown in Figure 5.Fig. 5 is the SEM figure of the graphitized carbon material that the embodiment of the present invention 19 obtains, as seen in Figure 5, the graphite alkylene carbon material that the present embodiment provides still keeps the block grain pattern of gac, but its surface becomes more coarse, the coated Graphene that grown fold of surface in situ.

Carry out electrochemical property test to obtained button super capacitor, its specific storage is 75F/g, and corresponding energy density is 14Wh/kg, special capacity fade 3.5% after 10000 circulations under power density 25KW/kg, 10C multiplying power.

Embodiment 20

Presoma is placed in tube furnace, in argon atmosphere, passes into methane gas according to the flow of 400mL/h, be warming up to 850 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 6h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 21

Presoma is placed in tube furnace, in argon atmosphere, passes into quadrol according to the flow of 300mL/h, be warming up to 850 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 6h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 22

Get 100g gac, joined the KMnO of 10wt% ₄in solution, 80 DEG C of water-bath 6h, filtering drying; Then being immersed in 200ml contains in the aqueous solution of 200g nickelous chloride, dries, obtains the gac being adsorbed with metal catalyst; Afterwards the gac of adsorbing metal ions catalyzer is added in the solution containing 800g KOH, dry and pulverize, obtain presoma;

Get 5000g trimeric cyanamide to mix with precursor and be placed in tube furnace, in argon atmosphere, be warming up to 900 DEG C according to the temperature rise rate of 4 DEG C/min, after keeping 3h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Join in 25mL graduated cylinder by the above-mentioned obtained graphitized carbon material of 0.3g, through shaking up and down, finally estimating the tap density obtained is 0.32g/mL.

Detect the specific surface area of above-mentioned graphitized carbon material, porosity and mean pore size, result is: specific surface area is 2000m ²/ g, porosity is 1.16cm ³/ g, mean pore size is 3.5nm.

According to the method described in embodiment 1, the graphitized carbon material that the present embodiment obtains is carried out to the calculating of degree of graphitization, calculation result is: the degree of graphitization of this graphitized carbon material is 78.5%.

Carry out electrochemical property test to obtained button super capacitor, its specific storage is 80F/g, and corresponding energy density is 15Wh/kg, special capacity fade 4% after 10000 circulations under power density 23KW/kg, 10C multiplying power.

Embodiment 23

Presoma is placed in tube furnace, in argon atmosphere, passes into methane gas according to the flow of 1000mL/h, be warming up to 900 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 3h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 24

Presoma is placed in tube furnace, in argon atmosphere, passes into quadrol according to the flow of 200mL/h, be warming up to 900 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 3h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 25

Get 100g gac, joined the KMnO of 10wt% ₄in solution, 80 DEG C of water-bath 6h, filtering drying; Then being immersed in 100ml contains in the aqueous solution of 5g nickelous chloride, dries, obtains the gac being adsorbed with metal catalyst; Afterwards the gac of adsorbing metal ions catalyzer is added in the solution containing 200g KOH, dry and pulverize, obtain presoma.

Get 10g trimeric cyanamide to mix with precursor and be placed in tube furnace, in argon atmosphere, be warming up to 800 DEG C according to the temperature rise rate of 4 DEG C/min, after keeping 20h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Join in 25mL graduated cylinder by the above-mentioned obtained graphitized carbon material of 0.3g, through shaking up and down, finally estimating the tap density obtained is 0.36g/mL.

Detect the specific surface area of above-mentioned graphitized carbon material, porosity and mean pore size, result is: specific surface area is 1380m ²/ g, porosity is 1.13cm ³/ g, mean pore size is 3.2nm.

According to the method described in embodiment 1, the graphitized carbon material that the present embodiment obtains is carried out to the detection of degree of graphitization, detected result is: the degree of graphitization of this graphitized carbon material is 65.5%.

Carry out electrochemical property test to obtained button super capacitor, its specific storage is 70F/g, and corresponding energy density is 11Wh/kg, special capacity fade 4.5% after 10000 circulations under power density 20KW/kg, 10C multiplying power.

Embodiment 26

Presoma is placed in tube furnace, in argon atmosphere, passes into methane gas according to the flow of 500mL/h, be warming up to 800 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 20h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

Embodiment 27

Presoma is placed in tube furnace, in argon atmosphere, passes into quadrol according to the flow of 100mL/h, be warming up to 800 DEG C according to the temperature rise rate of 4 DEG C/min simultaneously, after keeping 20h, take out after Temperature fall, carry out pickling, filtration, drying successively, obtain graphitized carbon material.

The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims

1. a graphitized carbon material, the degree of graphitization of described graphitized carbon material is 20 ~ 90%, and mean pore size is 2 ~ 5nm, and porosity is 1.0 ~ 1.6cm ³/ g, tap density is 0.2 ~ 0.5g/mL.

2. graphitized carbon material according to claim 1, is characterized in that, the degree of graphitization of described graphitized carbon material is 30% ~ 80%.

3. a preparation method for graphitized carbon material according to claim 1, comprises the following steps:

The mass ratio of described carbon source and metal catalyst is 1:(0.001 ~ 2);

4. preparation method according to claim 3, is characterized in that, the temperature of described heating carbonization is 600 ~ 1000 DEG C; The time of described heating carbonization is 0.1 ~ 24h.

5. preparation method according to claim 3, is characterized in that, described carbon source be selected from decolorizing carbon, resin material and biological material one or more.

6. preparation method according to claim 3, is characterized in that, step a) in, before described carbon source mixes with metal catalyst, first use properties-correcting agent modification is carried out to carbon source;

7. preparation method according to claim 3, is characterized in that, step c) in, described presoma carries out heating carbonization under carbonization conditioning agent exists;

8. preparation method according to claim 7, is characterized in that, described alkane is C ₁~ C ₁₀alkane; Described alkene is C ₂~ C ₁₀alkene; Described alkynes is C ₂~ C ₁₀alkynes; Described condensed-nuclei aromatics comprise in naphthalene, anthracene and phenanthrene one or more; Described ether compound comprise in methyl ether, ether, n-butyl ether and oxyethane one or more; Described alcohol compound comprise in methyl alcohol, ethanol, propyl alcohol and furfuryl alcohol one or more; Described aldehyde compound comprise in formaldehyde, acetaldehyde, propenal and butyraldehyde one or more; Described ketone compounds comprise in acetone, butanone and pimelinketone one or more; Described carboxylic acid compound comprise in formic acid, acetic acid, propionic acid, terephthalic acid, phenylformic acid and citric acid one or more; Described nitrogen-containing organic compound comprise in aromatic nitro compound, aminated compounds, nitrile compounds, diazonium compound, azo-compound and amino acid one or more; Described inorganic nitrogen-containing compound comprises volatile salt and/or bicarbonate of ammonia.

9. preparation method according to claim 8, it is characterized in that, described carbonization conditioning agent comprise methane, ethane, ethene, acetylene, propylene, methyl alcohol, ethanol, propyl alcohol, furfuryl alcohol, trimeric cyanamide, Dyhard RU 100, urea, methylamine, ethamine, quadrol, aniline, Diisopropyl azodicarboxylate, nitrogen benzide, to one or more in methylaminoazobenzene, acetonitrile, butyronitrile, vinyl cyanide, cyanobenzene, bicarbonate of ammonia, glycine, L-Ala, leucine, Serine, Gelucystine, L-glutamic acid, arginine, Histidine and tryptophane.

10. preparation method according to claim 7, is characterized in that, described carbonization conditioning agent is one or more in gas carburization conditioning agent, liquid phase carbonation conditioning agent and solid phase carbonization conditioning agent;

The air flow of described gas carburization conditioning agent is 1 ~ 5000mL/h;

Or

11. 1 kinds of ultracapacitors, comprise electrode, barrier film and electrolytic solution;

Described electrode comprises the obtained graphitized carbon material of the graphitized carbon material described in any one of claim 1 ~ 2 or the method described in any one of claim 3 ~ 10.