CN105702473B

CN105702473B - Carbon-based electrode material and its combination electrode material with superelevation specific capacitance

Info

Publication number: CN105702473B
Application number: CN201410697163.XA
Authority: CN
Inventors: 黄富强; 林天全
Original assignee: Shanghai Institute of Ceramics of CAS
Current assignee: Shanghai Institute of Ceramics of CAS
Priority date: 2014-11-26
Filing date: 2014-11-26
Publication date: 2017-11-10
Anticipated expiration: 2034-11-26
Also published as: CN105702473A

Abstract

The present invention relates to a kind of carbon-based electrode material and its combination electrode material with superelevation specific capacitance, the electric capacity of the carbon-based electrode material is made up of electric double layer capacitance and Faraday pseudo-capacitance two parts, the electric double layer capacitance accounts for the 20~60% of the electric capacity of the carbon-based electrode material, carbon-based electrode material specific capacity under 1A/g current density is more than 400, volume and capacity ratio is at 300 farads more than every milliliter, the energy density of the symmetrical device of water based electrolyte is more than 20 watt-hour per kilograms, and volume energy density is more than 15 every liter of watt-hours.

Description

Carbon-based electrode material and its combination electrode material with superelevation specific capacitance

Technical field

The present invention relates to a kind of carbon-based electrode material and its combination electrode material of superelevation specific capacitance, belong to material, electrification Technical field.

Background technology

Ultracapacitor has the characteristics that power density is high, had extended cycle life and safe and reliable, can be widely applied to mix Electric automobile, high-power output equipment etc..Ultracapacitor has formed a considerable market rule in global range at present Mould, 2010 annual value of production keep nearly 20% growth rate in recent years up to 4.7 hundred million dollars.Although ultracapacitor industrial prospect protrudes, But being constrained to energy density, too low (regular activated charcoal super capacitor quality compares electric capacity<200F/g, volumetric capacitance<200F/ ML, energy density<10Wh/kg), far below lithium battery (>100Wh/kg), large-scale application is led to not.Activated carbon electrodes The reason for energy density is low is that a large amount of microcellular structures are unfavorable for the effective mobility of electric charge, causes a large amount of avtive spot energy storage to be lost Effect, while high fault of construction causes it stability is bad under high voltages, limits the lifting of energy density.Another major reason It is that the carbon atom of porous carbon materials is more with sp³Based on hydridization, sp²Hybridized atom ratio is low, and poorly conductive is (typical<100S/ cm).Obtain the Carbon Materials with high conductivity, it is necessary to improve the sp of carbon atom²Hybridization ratios.Although has document report at present Road has a high sp²The carbon material of hydridization, and the sp2 hydridization of this kind of material has locality, its local conductivity is good, but overall Electric conductivity still can not meet the requirement of electrode for capacitors.High sp²The graphene of hydridization can have concurrently high-specific surface area (2, 620m²/ g), high conductivity and high structural stability, the performance bottleneck of active carbon electrode material can be overcome.However, current carbon The specific capacity of electrode is less than 1000m still far below theoretical value (550F/g), key factor in the specific surface area of reality²/g；In addition The bulk density of graphene is low, can also reduce the volume energy density of device.

In order to obtain higher specific capacitance, doped chemical, such as nitrogen, oxygen, sulphur, boron are incorporated into more by existing document report In hole carbon or graphene, faraday's electric capacity is produced by the way that redox reaction occurs.However, this kind of material of document report has Two it is fatal the problem of：First, the doped chemical introduced can substantially reduce the electric conductivity of material；Second, caused by doped chemical Faraday's capacitance ratio is very low (typically less than 10%), and this is main reasons is that there is substantial amounts of doping activated centre can not be effective Utilization.

In addition, high sp²The carbon material of hydridization can also load as the carrier with high-specific surface area and high conductivity Other active materials with height ratio capacity, so as to further improve the specific energy density of electrode material.Faraday's capacitor is (such as Polymer, transition metal oxide etc.) although higher ratio electricity can be obtained by the redox reaction in charge and discharge process Hold, but because its stability is poor (capacity retention is less than 50% after 5,000 circulations), power density is relatively low (to be less than 1 kilowatt often Kilogram), limit the practical application of faraday's capacitor.Moreover, the electrode material with faraday's electric capacity be fabricated to it is super After capacitor element, because the voltage of positive and negative polarities is different, oxidation-reduction potential can not be reached simultaneously, it is impossible to show completely super The energy storage characteristic of electrode material.At present, the capacitor element based on metallic compound or conductive polymer surfaces redox reaction, Its specific capacitance have lost more than 15%.

Therefore, how a kind of C-base composte material is provided, combines high-specific surface area carbon material, High-conductivity carbon material and method The advantages of drawing electric capacity three, the shortcomings that respective is abandoned, so as to obtain the super capacitor with superelevation specific capacitance and energy density Equipment material, it is one of study hotspot of this area.

The content of the invention

It is contemplated that the defects of overcoming existing C-base composte material, the invention provides a kind of the carbon-based of superelevation specific capacitance Electrode material and its combination electrode material and preparation method.

The invention provides a kind of carbon-based electrode material with superelevation specific capacitance, it is characterised in that the carbon-based electrode The electric capacity of material is made up of electric double layer capacitance and Faraday pseudo-capacitance two parts, and the electric double layer capacitance accounts for the carbon-based electrode material The 20~60% of the electric capacity of material, carbon-based electrode material specific capacity under 1A/g current density is more than 400, volume specific volume Amount is at 300 farads more than every milliliter, and the energy density of the symmetrical device of water based electrolyte is more than 20 watt-hour per kilograms, volume Energy density is in more than every liter of 15- watt-hours.

The present invention basic ideas be：Activity is introduced by element doping in the highly conductive and carbon material of high-specific surface area Site, Faraday pseudo-capacitance is produced, doped chemical is that one or both of nitrogen, boron, phosphorus, sulphur combine, the atom of doped chemical Concentration is 0.5%-20%.After doping, the electric conductivity of carbon-based material is not decreased obviously, and the dispersiveness in water substantially carries Height, zeta current potentials are less than -15mV；

Carbon material provided by the invention also has another important except specific capacitance and energy density characteristics with superelevation Advantage, the oxidation-reduction potential of electrode material can be adjusted by controlling content and the doped structure of doped chemical, realized different Faraday's electric capacity.By taking the mesoporous graphene of the N doping obtained by the present invention as an example, the combination between nitrogen and carbon includes pyridine It is anti-that with hydrogen ion reversible redox can occur for three kinds of type, pyrroles's type and graphite mould, wherein pyridine type and pyrroles's type nitrogen-atoms Should, it is effective doping avtive spot, redox reaction current potential is influenceed by the ratio of pyridine type and pyrroles's type nitrogen-atoms, i.e., The oxidation-reduction potential of the mesoporous graphene of N doping can be regulated and controled by adjusting the ratio of pyridine type and pyrroles's type nitrogen-atoms.And root According to the tandem principle of two electrode capacitances, the total capacitance C=C of device₁C₂/(C₁+C₂), the doped carbon with different oxidation-reduction potentials After base electrode Material cladding, it may be such that positive and negative polarities under multiple voltages while are reaching oxidation-reduction potential, while obtain most Big faraday's electric capacity, i.e. C1=C2, it can now obtain maximum specific capacitance.The specific capacitance of thus obtained device and material sheet The specific capacitance of body is compared, within 5%.After the single material with faraday's electric capacity makes device, its capacitance loss More than 15%.

It is preferred that the sp of the carbon atom in the carbon-based electrode material²The ratio of hydridization is more than 60%, the carbon-based electricity The conductance of pole material is more than 200 Siemens per centimeters.

It is preferred that the specific surface area of the carbon-based electrode material is 1200 square metres more than every gram.

It is preferred that carbon-based electrode material zeta current potentials in water are less than -15mV.

The carbon-based electrode material, for structure, mainly by the carbon atom of sp2 hydridization form high-specific surface area, simultaneously Structure comprising defect, specific surface area are 1200 square metres more than every gram；Chemically for composition, the doping comprising non-carbon Atom；From in water for zeta current potentials, the carbon-based electrode material is less than -15mV.

It is preferred that the carbon-based electrode material Faraday pseudo-capacitance introduces avtive spot generation by adulterating doped chemical, The doped chemical is at least one of nitrogen, boron, phosphorus, sulphur, and the doping of doped chemical is 0.5%-20%.

It is preferred that being combined by the doped chemical with charged ion, redox reaction occurs and introduces the active sites Point.

It is preferred that the combination between the doped chemical and carbon atom includes doping in ring, border doping and height Spend defective bit doping.

It is preferred that the doped chemical is nitrogen, in the carbon-based electrode material combination of nitrogen and carbon include pyridine type, Three kinds of pyrroles's type and graphite mould, the wherein ratio shared by pyridine type and pyrroles's type are more than 70%.

It is preferred that mesoporous graphene of the carbon-based electrode material for the doping doped chemical high-ratio surface, the height Than the sp of carbon atom in the mesoporous graphene on surface²For the ratio of hydridization more than 80%, specific surface area is 1500 square metres every gram More than, for conductance more than 400 Siemens per centimeters, the number of plies of graphene is 3-5 layers.

It is preferred that doping high specific surface area three-dimensional graphene, has the conductive network of three-dimensional communication, its conductance is more than 300 Siemens per centimeters, specific surface area are more than 2000 square metres every gram, and its density is per cubic centimeter less than 0.1 gram.

It is preferred that the carbon-based electrode material one of preferably, include mesoporous and two kinds of pore passage structures of micropore, the micropore Pore diameter range be 0.5-2 nanometers, mesoporous pore diameter range be 2-20 nanometers.

In addition, present invention also offers a kind of combination electrode material for including above-mentioned carbon-based electrode material, it is described compound Material is combined by the carbon-based electrode material with different oxidation-reduction potentials, or by the carbon-based electrode material with Metallic compound and/or conducting polymer are combined.

It is preferred that the metallic compound includes manganese oxide, nickel oxide, cobalt oxide, niobium oxide, tantalum oxide, ruthenium-oxide, sulphur Change titanium, molybdenum sulfide, vanadic sulfide, vulcanization tantalum, selenizing vanadium, at least one of selenizing tantalum, the conducting polymer include polyaniline, Polypyrrole and/or polythiophene.

Following Summary, using the carbon-based electrode material as the stone doped with least one of nitrogen, boron, phosphorus, sulphur Exemplified by black alkene, preparation method is described.

In the preparation of carbon-based electrode material, in doped source, nitrogen source include melamine, aminoguanidine, ammonia, amino acid, At least one of ethylenediamine, boron source include at least one of Boron tribromide, boron trifluoride, boric acid, pure boron, and phosphorus source includes At least one of trioctylphosphine phosphorus, triphenyl phosphorus, phosphorus pentoxide, sulphur source are included in thiocarbamide, thiophene, benzyl disulfide at least It is a kind of；

Carbon source includes methane, ethene, acetylene, methanol and/or ethanol；

Metal form or metallic catalyst include Ni, Cu, Co and/or Fe；

In source metal, Ni sources include at least one of nickel nitrate, nickel acetate, nickel chloride, nickel sulfate；Cu sources include nitric acid At least one of copper, copper acetate, copper chloride, copper sulphate；Co sources are included in cobalt nitrate, cobalt acetate, cobalt chloride, cobaltous sulfate extremely Few one kind；Fe sources include at least one of ferric nitrate, ferric acetate, iron chloride, ferric sulfate.

The first also provided of the invention prepares a kind of preparation method of example carbon-based electrode material, the preparation method bag Include：

First, the metal form with three-dimensional continuous pore structure, organic carbon source, doped source are scattered in solvent, ultrasound It is scattered, prepare organic carbon source and doped source is filled in metal form/organic carbon source/doped source xerogel in metal form, so Afterwards, by metal form/organic carbon source/doped source xerogel successively through chemical vapor deposition, go the removal of impurity, the carbon is prepared Base electrode material；

Or

First, by porous oxide or porous ceramics with three-dimensional continuous pore structure, after being mixed with source metal solution, stir Mix, ultrasonic disperse, vacuumize and after solution evaporation or after drying, obtain the porous oxide or porous ceramics filled with source metal Colloidal sol；The porous oxide or porous ceramics colloidal sol that will be filled with source metal again are incubated at protective atmosphere, 300-500 DEG C To porous oxide or porous ceramics filled with metallic catalyst, the porous oxide or porous ceramics include but is not limited to Porous oxide includes silica, magnesia, titanium dioxide, strontium titanates, barium titanate, sodium metasilicate, calcium silicates, magnesium silicate etc.,

Secondly, will be filled with the porous oxide of metallic catalyst or porous ceramics, organic carbon source, doped source be scattered in it is molten In agent, ultrasonic disperse, drying, obtain organic carbon source, doped source is filled in porous oxide or porous ceramics in porous oxidation Thing or porous ceramics/metallic catalyst/organic carbon source/doped source xerogel；

Furthermore by porous oxide or porous ceramics/metallic catalyst/organic carbon source/doped source xerogel successively through changing Vapour deposition is learned, the removal of impurity is gone, the carbon-based electrode material is prepared；

Wherein, the temperature of chemical vapour deposition technique is 600-1100 DEG C, and chemical vapor deposition is gases used including hydrogen, gas State carbon source.

The present invention prepares the basic ideas of mesoporous graphene：Using mesoporous silicon oxide as template, with poly furfuryl alcohol, sucrose, One or more combination in glucose, phenolic resin, polymethyl methacrylate, polystyrene is carbon source, golden in duct Under the catalysis of category, using chemical vapour deposition technique, mesoporous graphene is grown into along the wall of mesoporous silicon oxide.Metal used Catalyst is Ni, Cu, Co, one or more of combinations in Fe.Ni sources are in nickel nitrate, nickel acetate, nickel chloride, nickel sulfate One or more combination；Cu sources are the one or more combination in copper nitrate, copper acetate, copper chloride, copper sulphate；Co sources are nitric acid One or more combination in cobalt, cobalt acetate, cobalt chloride, cobaltous sulfate；Fe sources are in ferric nitrate, ferric acetate, iron chloride, ferric sulfate One or more combination.The mass ratio of source metal and silica is 0.25-2.5.Load used in chemical vapour deposition technique Gas is nitrogen or argon gas, and reducibility gas is hydrogen, and gaseous carbon sources are one kind in methane, ethene, acetylene, methanol, ethanol etc. Or several combinations；Graphene growth temperature is 800-1100 DEG C.

It is preferred that organic carbon source includes poly furfuryl alcohol, sucrose, glucose, phenolic resin, polymethyl methacrylate, polyphenyl At least one of ethene.

It is preferred that the aperture of metal form, porous oxide and/or porous ceramics is 2-20 nanometers.

It is preferred that the concentration in source metal GOLD FROM PLATING SOLUTION category source is 0.1-2.0mol/L, source metal and porous oxide or more The mass ratio of hole ceramics is 0.25-2.5, and the mass ratio of doped source and carbon source is (0.1-2)：1, be preferably (0.5-1)：1, it is porous Oxide or porous ceramics and the mass ratio of carbon source are (0.2-2)：1.

It is preferred that it is 2-5 hours to prepare the porous oxide for being filled with metallic catalyst or porous ceramics soaking time, protect It is the inert gas doped with 1-20% hydrogen to protect atmosphere.

It is preferred that the mode of filling includes priming by vacuum method, injection pressure is 1-100Pa.

It is preferred that 800-1100 DEG C of chemical vapor deposition temperature, sedimentation time is 5-60 minutes, preferably 10-30 minutes, is changed Learn that vapour deposition is gases used also to include nitrogen or argon gas, ammonia, vapor and/or carbon dioxide, gas flow 50- 500sccm, including：The flow of nitrogen or argon gas is 50-400sccm, 5-100sccm of flow of hydrogen, the stream of gaseous carbon source Measure 1-20sccm, 0.5-20sccm of flow of ammonia, 0.5-10sccm of flow of vapor, the flow 0.5 of carbon dioxide- 10sccm。

The preparation method of another example carbon-based electrode material provided by the invention, methods described include：

1) add activator, doped source and source metal into graphite, after ball milling, at 600-1000 DEG C, include gaseous state Carbon source, hydrogen gas in, heat 0.5-10 hours, then cool down after go the removal of impurity, obtain the carbon-based electrode material, its In, activator is potassium hydroxide, sodium hydroxide, at least one of zinc chloride, graphite, activator, doped source and source metal Between mass ratio be 1：(0.5—2)：(0.01—1)：(0.5—2)；Or

A) activator is first added into graphene, then under 500-1000 DEG C, argon gas or nitrogen atmosphere, heating response 0.5-10 hours, defective graphene is prepared, wherein, the mass ratio of activator and graphene is (0.5-4)：1, activator For at least one of potassium hydroxide, sodium hydroxide, zinc chloride；

B) after the defective graphene, doped source and the source metal ball milling mixing that prepare step a), it is placed in chemical gas In phase cvd furnace, 800-1100 DEG C are warming up in argon gas or nitrogen, is passed through the gas including hydrogen, gaseous carbon source, is incubated 10-30 minutes, the removal of impurity is gone after then cooling down, obtains the carbon-based electrode material, wherein, defective graphene, doped source And the mass ratio between source metal is 1：(0.01—1)：(0.5—2).

It is preferred that in step 1) or step a), heated 2-10 hours at 600-900 DEG C, reaction atmosphere also include ammonia, Nitrogen, vapor and/or carbon dioxide, gas flow are 50-300sccm, including：2-20sccm of flow of gaseous carbon source, 5-20sccm of flow of hydrogen, 10-20sccm of flow of ammonia, 200-300sccm of flow of nitrogen, the flow of vapor 5-20sccm, 5-20sccm of flow of carbon dioxide.

It is preferred that in step b), 50-500sccm of gas flow, including：5-50sccm of flow of hydrogen, gaseous carbon source 2-10sccm of flow, 1-20sccm of flow of ammonia or borine, 50-450sccm of flow of nitrogen, the flow of vapor 2-20sccm, 2-20sccm of flow of carbon dioxide.

It is described present invention also offers also a kind of preparation method of example carbon-based electrode material except above-mentioned preparation method Method includes：

First, graphene oxide, doped source, source metal are dispersed in the alcohol solvent with nano-high molecule ball, led to Freeze-drying is crossed, obtains three-dimensional porous presoma, wherein, the mass ratio between graphene oxide, doped source, source metal is 1： (0.01—1)：(0.5-2), or, graphene oxide, doped source, nano silicon, source metal are disperseed to be contained in containing height In the aqueous solution of molecular adhesion agent, gel is prepared in heating, by gel in 250-350 DEG C of heating, 5-10 hours abjection moisture The char-forming material of acquisition, wherein, the mass ratio between graphene oxide, doped source, nano silicon, source metal is 1： (0.01—1)：(0.5—2)：(0.5—2)；

Then, the char-forming material after the three-dimensional porous presoma or ball milling of foregoing preparation is placed in chemical vapor deposition stove It is interior, 800-1100 DEG C is warming up in argon gas or nitrogen, is passed through the gas including hydrogen, gaseous carbon sources, is incubated 10-30 minutes, The removal of impurity is gone after cooling, obtains the carbon-based electrode material.

It is preferred that nano-high molecule ball is 0.1-5g/mL in alcohol solvent concentration, nano-high molecule ball gathers including nanometer Styrene ball, polymethyl methacrylate, polyethylene.

It is preferred that freeze drying process includes：Temperature-50-- 80,5-20 hours time.

It is preferred that the concentration of polymer binder is 0.05-0.5g/mL in the aqueous solution of polymer binder, macromolecule Adhesive includes starch, polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, HPMA, poly- quaternary amine Salt, polyethylene glycol.

It is preferred that 300-500sccm of gas flow, including：250-450sccm of flow of nitrogen, the flow of hydrogen 20-50sccm, 5-10sccm of flow of gaseous carbon source, 5-10sccm of flow of ammonia, 2-5sccm of flow of vapor, 2-5sccm of flow of carbon dioxide.

It is preferred that soak by hydrochloric acid, hydrofluoric acid, and wash with water, ethanol, remove include template, and/or source metal, And/or the impurity of metallic catalyst.

Beneficial effects of the present invention：

Carbon-based electrode material and its combination electrode material provided by the invention, combine high-specific surface area carbon material, height is led Electrical carbon material and the advantages of faraday electric capacity three, abandons the shortcomings that respective, close with superelevation specific capacitance and energy so as to obtain The super capacitor material of degree；

Compared with the porous carbon materials of business, the doped meso-porous graphene of present invention gained has more preferable electric conductivity, is The transmission of electric charge provides express passway；Compared with traditional graphene, the graphene of present invention gained has flourishing orderly Jie Hole and microcellular structure, the interaction for graphene and electrolyte provide more by all kinds of means.Doped chemical causes obtained by the present invention Redox reaction can occur in charge and discharge process for electrode material, faraday's electric capacity be produced, so as to obtain higher specific capacitance And energy density.Passed with transition metal oxide (such as nickel oxide, manganese oxide), polymer (such as polyaniline, polypyrrole) etc. Faraday's capacitance electrode material of system is compared, the present invention gained mesoporous nitrogen-doped graphene have therewith similar specific capacitance and Energy density, but have the faster speed of response, higher power density and more preferable charge and discharge cycles stability.

Brief description of the drawings

Fig. 1 shows that the combination of the foreign atom and carbon atom of the doping carbon-based electrode material prepared in the present invention is illustrated Figure, by taking N doping as an example；

Fig. 2 shows the Raman spectrogram of the carbon-based electrode material prepared in an embodiment of the invention；

Fig. 3 shows the small angle X-ray diffraction figure of the carbon-based electrode material prepared in an embodiment of the invention；

Fig. 4 shows the graph of pore diameter distribution of the carbon-based electrode material prepared in an embodiment of the invention；

Fig. 5 shows the narrow spectrum scanning figures of the XPS N1s of the carbon-based electrode material prepared in an embodiment of the invention (by taking N doping as an example)；

Fig. 6 shows the carbon-based electrode material of the N doping prepared in an embodiment of the invention in three-electrode system The middle result (sweep speed 2mV/s) (a) obtained with cyclic voltammetry and its charging and discharging curve (b)；

Fig. 7 shows the carbon-based electrode material of the N doping prepared in an embodiment of the invention in symmetry electrode body The result (sweep speed 2mV/s) (a) and its charging and discharging curve (b) obtained in system with cyclic voltammetry；

Fig. 8 shows the nitrogen-doped carbon base electrode of the three kinds of different oxidation-reduction potentials prepared in the present invention in three electrode bodies Obtained after the result (sweep speed 2mV/s) (a) and three kinds of carbon-based electrodes that are obtained in system with cyclic voltammetry are compound The result (sweep speed 2mV/s) (b) that new combination electrode material is obtained in three-electrode system with cyclic voltammetry.

Embodiment

The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that accompanying drawing and following embodiments The present invention is merely to illustrate, is not intended to limit the present invention.

It is an object of the invention to provide a kind of carbon-based electrode material and its compound electric for high-performance super capacitor Pole material, its electrochemical properties are：Electric capacity is made up of electric double layer capacitance and Faraday pseudo-capacitance two parts, and specific capacity is more than 400 Every gram of farad, or volume and capacity ratio are more than 300 farads every milliliter；Electric double layer capacitance proportion 20%-60%；Or water base electrolysis The energy density of the symmetrical device of liquid is more than 20 watt-hour per kilograms, or volume energy density is more than 15 every liter of watt-hours.With such as The architectural feature of the carbon-based electrode material of this excellent electrochemical performance is that carbon atom passes through sp²Hydridization, its ratio are more than 60%； With very high electric conductivity, conductance is more than 200 Siemens per centimeters；With very high specific surface area, specific surface area is more than 1200 square metres every gram.

The present invention basic ideas be：Activity is introduced by element doping in the highly conductive and carbon material of high-specific surface area Site, Faraday pseudo-capacitance is produced, doped chemical is that one or both of nitrogen, boron, phosphorus, sulphur combine, the atom of doped chemical Concentration is 0.5%-20%.After doping, the electric conductivity of carbon-based material is not decreased obviously, and the dispersiveness in water substantially carries Height, zeta current potentials are less than -15mV.Preferably, the feature of the mesoporous graphene of N doping is sp²The atom ratio of hydridization is big In 80%, conductance is more than 400 Siemens per centimeters, and specific surface area is more than 1500 square metres every gram.The good dispersion in water, Zeta current potentials are less than -15mV, and the combination between nitrogen and carbon in N doping carbon-based electrode material includes pyridine type, Bi Kaxing With three kinds of graphite mould, the wherein ratio shared by pyridine type and pyrroles's type is more than 70%.

Carbon material provided by the invention also has another important except specific capacitance and energy density characteristics with superelevation Advantage, the oxidation-reduction potential of electrode material can be adjusted by controlling content and the doped structure of doped chemical, realized different Faraday's electric capacity.Combination between doped chemical and carbon is included in doping in ring, border doping, the doping of height defective bit One kind or combination.Active doped chemical in carbon-based electrode material is combined with charged ion, and redox reaction occurs. By taking the mesoporous graphene of the N doping obtained by the present invention as an example, the combination between nitrogen and carbon includes pyridine type, pyrroles's type and stone Black three kinds of type, the wherein ratio shared by pyridine type and pyrroles's type are more than 70%, as shown in figure 1, wherein pyridine type and pyrroles's type nitrogen With hydrogen ion reversible redox reaction can occur for atom, be effective doping avtive spot, redox reaction current potential by The influence of the ratio of pyridine type and pyrroles's type nitrogen-atoms, you can regulated and controled by adjusting the ratio of pyridine type and pyrroles's type nitrogen-atoms The oxidation-reduction potential of the mesoporous graphene of N doping.And according to the tandem principle of two electrode capacitances, the total capacitance C=C of device₁C₂/ (C₁+C₂), have different oxidation-reduction potentials doping carbon-based electrode Material cladding after, may be such that positive and negative polarities in multiple electricity Pressure reaches oxidation-reduction potential simultaneously, while obtains faraday's electric capacity of maximum, i.e. C₁=C₂, can now obtain maximum ratio Electric capacity.The specific capacitance of thus obtained device is compared with material specific capacitance in itself, within 5%.Single has farad After the material of electric capacity makes device, its capacitance loss more than 15%.

The feature of the graphene with high specific surface of doping is sp²The atom ratio of hydridization is more than 80%, and conductance is more than 400 Siemens per centimeters, specific surface area are more than 1500 square metres every gram.

Described doping graphene with high specific surface, preferably, adulterating high specific surface area and mesoporous graphene, have mesoporous With two kinds of pore passage structures of micropore, the pore diameter range of micropore is 0.52 nanometer, and mesoporous pore diameter range is 220 nanometers.

High-performance carbon-based electrode material provided by the invention, is alternatively arranged as additive and the super capacitor material of routine is answered Close, improve the performance of capacitor.These materials include the conventional Carbon Materials such as mesoporous carbon, activated carbon, graphene, CNT； Manganese oxide, nickel oxide, cobalt oxide, niobium oxide, tantalum oxide, ruthenium-oxide, titanium sulfide, molybdenum sulfide, vanadic sulfide, vulcanization tantalum, selenizing vanadium, One or more kinds of metallic compounds in selenizing tantalum etc.；Or one kind or one kind in polyaniline, polypyrrole, polythiophene etc. Conducting polymer above is compound.Wherein, more than 15% is improved with the compound rear specific capacitance of conventional Carbon Materials and metallic compound；With The conducting polymer compound Posterior circle life-span improves more than 40%.

Preferably, the basic ideas that the present invention prepares mesoporous graphene are：Using mesoporous silicon oxide as template, by metal Catalyst, carbon source and doped source are filled in the duct of silica, are prepared by chemical vapour deposition technique doped meso-porous Graphene.

Using mesoporous silicon oxide as template, with poly furfuryl alcohol, sucrose, glucose, phenolic resin, polymethyl methacrylate, One or more combination in polystyrene is carbon source, in duct under the catalysis of metal, using chemical vapour deposition technique, along The wall of mesoporous silicon oxide grows into mesoporous graphene.Metallic catalyst used is Ni, Cu, Co, the one or more in Fe Combination.Ni sources are the one or more combination in nickel nitrate, nickel acetate, nickel chloride, nickel sulfate；Cu sources are copper nitrate, acetic acid One or more combination in copper, copper chloride, copper sulphate；Co sources are one kind in cobalt nitrate, cobalt acetate, cobalt chloride, cobaltous sulfate Or several combinations；Fe sources are the one or more combination in ferric nitrate, ferric acetate, iron chloride, ferric sulfate.Source metal and titanium dioxide The mass ratio of silicon is 0.25-2.5.Carrier gas used in chemical vapour deposition technique is nitrogen or argon gas, and reducibility gas is hydrogen, Gaseous carbon sources are the one or more combination in methane, ethene, acetylene, methanol, ethanol etc.；Graphene growth temperature is 800- 1100℃。

Described metallic catalyst is filled into method used in mesoporous silicon oxide or porous ceramics duct and filled for vacuum Note method, injection pressure 1-100Pa.

The mesoporous graphene of doping can be obtained when adding nitrogen, boron, p and ses source in duct.The concentration of doped chemical It can be adjusted by the addition of doped source, when the mass ratio of doped source and carbon source is 0.01-0.5, gained atomic concentration is 0.5%-15%.Nitrogen source includes one or more of combinations in melamine, aminoguanidine, ammonia, amino acid, ethylenediamine；Boron Source includes the one or more combination in Boron tribromide, boron trifluoride, boric acid, pure boron；Phosphorus source is trioctylphosphine phosphorus, triphenyl One or more combination in phosphorus, phosphorus pentoxide；Sulphur source includes one or more of groups in thiocarbamide, thiophene, benzyl disulfide Close.The doped source of two kinds of element codopes can choose the one kind stated in nitrogen source, boron source, phosphorus source and sulphur source respectively.

Preferably, high-specific surface area doped graphene may also pass through obtained by two steps of doping and activation of graphene, it is living Agent is one or more kinds of groups in potassium hydroxide, sodium hydroxide, ammonia, zinc chloride, vapor, carbon dioxide etc. Close；The ratio of activator and graphene is 0.5-4；Activation temperature is 500-1000 DEG C；Soak time is 0.5-8 hours.

Preferably, high-specific surface area doped graphene can be the doping high-ratio surface for having three-dimensional communication pore passage structure Product three-dimensional grapheme, has good conduction and passage of heat, its conductance is more than 300 Siemens per centimeters, and specific surface area is more than 2000 square metres every gram, its density is per cubic centimeter less than 0.1 gram.Its preparation method is with the gold with three-dimensional continuous pore structure Category template is catalyst, and after filling carbon source and doped source, doping high-specific surface area three is prepared by chemical vapour deposition technique Tie up graphene；Or with one kind in porous ceramics or porous silica with three-dimensional continuous pore structure for template, by gold Metal catalyst, carbon source and doped source are filled in duct, and doping high-specific surface area three is prepared by chemical vapour deposition technique Tie up graphene.The temperature of chemical vapour deposition technique is 600-1000 DEG C, and the reaction time be 5-60 minutes, gas be inert gas, Carbon source, hydrogen and activated gas, gas flow 1-500sccm.Activated gas is one in vapor, ammonia, carbon dioxide Kind or more than one combination.

The method that another kind prepares doping high specific surface area three-dimensional graphene is to disperse graphene, doped source, source metal In the alcohol solvent with nano-high molecule ball, by freeze-drying, three-dimensional porous presoma is obtained.It is placed in chemical gaseous phase In cvd furnace, 800-1100 DEG C is warming up in argon gas or nitrogen, is passed through hydrogen, ammonia and gaseous carbon sources, 10-30 points of insulation Clock, room temperature is cooled to, takes out sample.Product removes the impurity such as nickel by nitric acid, prepares specific surface area more than 1200- 2000m²/ g doped graphene.

Two or more the described doping carbon-based electrode Material cladding with different oxidation-reduction potentials forms； Within the device specific capacity of the symmetric form ultracapacitor of the electrode composite material and the specific capacity small 5% of material.

The carbon-based electrode material and its combination electrode material system of three kinds of (not limited to this) superelevation specific capacitances are described below in detail Standby and sign process.

1. its preparation method is using the metal form with three-dimensional continuous pore structure as catalyst, carbon source and doped source are filled Afterwards, doping high specific surface area three-dimensional graphene is prepared by chemical vapour deposition technique；Or with three-dimensional continuous aperture knot One kind in the porous ceramics or porous silica of structure is template, and metallic catalyst, carbon source and doped source are filled in into duct It is interior, doping high specific surface area three-dimensional graphene is prepared by chemical vapour deposition technique.The temperature of chemical vapour deposition technique is 600-1000 DEG C, the reaction time is 5-60 minutes, and gas is inert gas, carbon source, hydrogen and activated gas, gas flow 1- 500sccm.Activated gas is one or more kinds of combinations in vapor, ammonia, carbon dioxide.

Specially：

Doped meso-porous doped graphene

1) metallic catalyst is filled into mesoporous silicon oxide duct

Configuration concentration is the aqueous solution of 0.1-2.0mol/L source metals, and metal and titanium dioxide are pressed with commercial mesoporous silicon oxide The mass ratio of silicon mixes for 0.25-2.5.Stirring, ultrasonic disperse, it is 1-100Pa, the Cheng Rong after solution evaporation to be evacuated to pressure Glue.In the argon gas atmosphere containing 5% hydrogen, 450 DEG C are warming up to, is incubated 2-5 hours, is obtained mesoporous filled with metallic catalyst Silica (silica/metal)；

2) carbon source, doped source are filled into mesoporous silicon oxide duct

Take carbon source to be dissolved in one or two kinds of doped sources in the suitably dissolving such as water, ethanol, add gained in step 1) Silica/metal, ultrasonic disperse, drying, obtain silica/metal/carbon source/doped source.The ratio of doped source and carbon source Example is adjusted according to doping concentration, in general 0.01-0.5；

3) chemical vapour deposition technique growth graphene

Silica/metal/carbon source/doped source of gained in step 2) is placed in atmosphere furnace, in argon gas or nitrogen 800-1100 DEG C is warming up to, is passed through hydrogen, ammonia and gaseous carbon sources, is incubated 10-30 minutes.Room temperature is cooled to, takes out sample.Instead Temperature and time is answered depending on carbon source and the species of metallic catalyst；

4) etching and sample cleanup of template

Sample obtained by step 3) is soaked in the mixed solution of hydrochloric acid and hydrofluoric acid, after 24 hours, filtering, with a large amount of Deionized water and ethanol washing.Mesoporous doped graphene is remembered after drying；

5) pattern and structural characterization of mesoporous doped graphene

The pattern of sample is observed graphene sample obtained by the present invention by transmission electron microscope (JEM2010).With drawing Graceful spectrum (Renishaw invia Raman Microscope, excitation wavelength 514.5nm) characterizes the structure of graphene.With X-ray photoelectron spectroscopy (XPS, PHI 5000C ESCA System) analysis sample surfaces each element relative amount ratio and Its compound state.With the electric conductivity of four probe Van Der Pauw methods (Accent HL5500) measure graphene.With nitrogen adsorption/ Detachment assays characterize the meso-hole structure of graphene.Dispersiveness of the mesoporous doped graphene in water is characterized with zeta current potentials；

6) performance of the supercapacitor of mesoporous doped graphene characterizes

Mesoporous 50 milligrams of doped graphene sample is taken, is scattered in 5 milliliters of N-methyl pyrrolidones (NMP), stirring is equal It is even.It is slowly injected into three-dimensional graphene foam, dries, be pressed into electrode slice.The density of electrode slice is 0.7-0.85 grams every cube li Rice.Using 0.5mol/L lithium sulfates as electrolyte, symmetrical electrochemical capacitor is made, for testing.

2. surpass the graphene of the element doping of high-ratio surface, there can be two methods acquisition：

1) potassium hydroxide, sodium hydroxide, one kind in zinc chloride or combination are added in graphite purchased in market and is used as activator, The ratio of activator and graphene is 0.5-4.Add doped source and source metal, ball milling 2-8 hours.Compound is placed in 600-1000 DEG C containing methane, hydrogen, argon gas or nitrogen (during N doping, ammonia can be led to) stove in, heating response 0.5-10 hours.Production Thing removes the impurity such as catalyst by acid, prepares specific surface area more than 1500-2500m²/ g doped graphene.The method is adulterated Constituent content is controllable, and material preparation cost is low, simple and easy；

2) doped chemical can also be completed by two step method：(a) potassium hydroxide, hydroxide are added in graphite purchased in market One kind in sodium, zinc chloride or combination are used as activator, and the ratio of activator and graphene is 0.5-4.It is subsequently placed in 600-900 DEG C argon gas or nitrogen protection stove in, heating response 2-10 hours, prepare specific surface area 1500-2500m²Having for/g is scarce Sunken graphene.(b) by the defective graphene and doped source and source metal ball milling mixing of high-specific surface area, Ball-milling Time For 0.5-4 hours, be subsequently placed in chemical vapor deposition stove, 800-1100 DEG C be warming up in argon gas or nitrogen, be passed through hydrogen, Ammonia (or borine) and gaseous carbon sources, it is incubated 10-30 minutes.Room temperature is cooled to, takes out sample.Reaction temperature and time are according to carbon Depending on the species of source and metallic catalyst.Product removes the impurity such as catalyst by acid, prepares specific surface area more than 1500- 2500m²/ g doped graphene.The method compared with one-step method, can obtain more dominance can product.

3rd, superelevation can have two methods acquisition than surface doping three-dimensional grapheme：

1) graphene oxide, doped source, source metal are dispersed in the alcohol solvent with nano-high molecule ball, by cold It is lyophilized dry, obtain three-dimensional porous presoma.It is placed in chemical vapor deposition stove, 800-1100 is warming up in argon gas or nitrogen DEG C, hydrogen, ammonia and gaseous carbon sources are passed through, are incubated 10-30 minutes, are cooled to room temperature, take out sample.Product is removed by nitric acid The impurity such as nickel, specific surface area is prepared more than 1200-2000m²/ g doped graphene；

2) graphene oxide, doped source, nano silicon, source metal are disperseed to be contained in the water containing polymer binder In solution, uniform mixing high viscous colloid is prepared in heating；After continuing heating acquisition gel, in 250-350 DEG C of Muffle furnace Middle heating 5-10 hours, slowly deviate from moisture.After the char-forming material of acquisition is by simple ball milling, chemical vapor deposition stove is placed in It is interior, 800-1100 DEG C is warming up in argon gas or nitrogen, is passed through hydrogen, ammonia and gaseous carbon sources, is incubated 10-30 minutes, cooling To room temperature, sample is taken out.Product removes the impurity such as catalyst, silica by acid, prepares specific surface area more than 1200- 2000m²/ g doped graphene.

The foreign atom of doping carbon-based electrode material and the combination schematic diagram of carbon atom that Fig. 1 present invention obtains, are mixed with nitrogen Exemplified by miscellaneous；

The Raman spectrogram for the carbon-based electrode material that Fig. 2 present invention obtains, the bright present invention gained carbon-based electrode material of the chart Material has very high quality.Position~the 2685cm at 2D peaks as can be seen from Figure^-1And there is good symmetry, 2D peaks and G peaks Intensity compare I_2D/I_GThe a width of 55cm of half-peak at=0.5,2D peak^-1, the graphene of this explanation present invention gained is 3-5 layers；G peaks are bright It is aobvious to be better than D peaks, intensity ratio I_G/I_D~2.5, illustrate that gained graphene defect of the invention is few；

Fig. 3 small angle X-ray diffraction figures, show that graphene obtained by the present invention has six side's ordered mesopore structures, corresponding sky Between group be p6mm；

Fig. 4 graph of pore diameter distribution.Pore-size distribution is obtained by absorption/detachment assays of nitrogen, shows the stone obtained by the present invention Black alkene contains mesoporous (4-6 nanometers) and two kinds of pore passage structures of micropore (0.5-2.0 nanometers)；

The narrow spectrum scanning figures of Fig. 5 XPS N1s.Show that the sample of the mesoporous graphene of gained contains nitrogen (by taking N doping as an example)；

Fig. 6 a are by taking the mesoporous graphene of N doping as an example, in three-electrode system, the result that is obtained with cyclic voltammetry, and scanning Speed is 2mV/s.Symmetrical good redox peaks, and peak position difference 59mV are clearly visible from figure.Show institute of the present invention The electrochemical reaction speed of the doped graphene obtained is quickly.Fig. 6 b are charging and discharging curve；

Fig. 7 a in the device detection of symmetric form ultracapacitor, use cyclic voltammetric by taking the mesoporous graphene of N doping as an example The result that method obtains, sweep speed 2mV/s；Fig. 7 b are charging and discharging curve；

After the nitrogen-doped graphenes of tri- kinds of different oxidation-reduction potentials of Fig. 8 is compound, hence it is evident that improve specific capacity.

Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this Invention is further described, it is impossible to is interpreted as limiting the scope of the invention, those skilled in the art is according to this hair Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.

The mesoporous nitrogen-doped carbon sill of embodiment 1

Configuration concentration is the aqueous solution of 0.1mol/L nickel nitrates, and nickel and titanium dioxide are pressed with commercial mesoporous silicon oxide SBA-15 The mass ratio of silicon is 1:2 mixing.Stirring, ultrasonic disperse, it is 20Pa to be evacuated to pressure, into colloidal sol after solution evaporation.Containing In the argon gas atmosphere of 5% hydrogen, 450 DEG C are warming up to, is incubated 2 hours, obtains the mesoporous silicon oxide (SBA- filled with metallic nickel 15/Ni)；

Take carbon source poly furfuryl alcohol with aminoguanidine by 5:1 ratio is dissolved in ethanol, adds SBA-15/Ni, ultrasonic disperse 30 Minute, dried 10 hours at 100 DEG C, obtain the xerogel of SBA-15/Ni/ poly furfuryl alcohols/aminoguanidine；

Above-mentioned 50 grams of sample is placed in atmosphere furnace, 900 DEG C are warming up in argon gas or nitrogen, be passed through hydrogen, ammonia and Methane, its ratio are 20:15:10sccm, it is incubated 10-30 minutes.Room temperature is cooled to, takes out sample；

Above-mentioned gained sample is soaked in the mixed solution of hydrochloric acid and hydrofluoric acid, after 24 hours, filtering, with largely going Ionized water and ethanol washing.The mesoporous doped graphene of gained N doping after drying；

The pattern of sample is observed by transmission electron microscope (JEM2010).With Raman spectrum (Renishaw invia Raman Microscope, excitation wavelength 514.5nm) characterize graphene structure.With x-ray photoelectron spectroscopy (XPS, PHI5000C ESCA System) analysis sample surfaces each element relative amount ratio and its compound state.With four probe Van Der Pauw methods (Accent HL5500) determine the electric conductivity of graphene.Jie of graphene is characterized with nitrogen adsorption/detachment assays Pore structure.Dispersiveness of the mesoporous doped graphene in water is characterized with zeta current potentials；

Mesoporous 50 milligrams of nitrogen-doped graphene sample is taken, is scattered in 5 milliliters of N-methyl pyrrolidones (NMP), is stirred Uniformly.It is slowly injected into three-dimensional graphene foam, dries, be pressed into electrode slice.The density of electrode slice is 0.75 gram per cubic centimeter. Using 0.5mol/L lithium sulfates as electrolyte, symmetrical electrochemical capacitor is made, for testing；

Specific capacity of the gained sample under 1A/g current density is 650F/g, volume and capacity ratio 480F/cm³, 10,000 times Fully the conservation rate of electric current is 92.5% after electricity, energy density 58Wh/kg, power density 45kW/kg.

In carbon-based electrode material manufactured in the present embodiment, the atomic concentration of doped chemical is 7.8%, the sp of carbon atom²It is miscellaneous The ratio 98% of change, the ratio that pyridine type and pyrroles's type combination account for whole nitrogens between nitrogen and carbon are 82%, nitrogen In 82% be avtive spot, produce Faraday pseudo-capacitance, the specific surface area of carbon-based composite electrode material is 1852 square metres every gram；

Fig. 1 is the combination between the nitrogen carbon for the nitrogen-doped graphene that the present embodiment obtains.N-5 in figure represents pyrroles Type nitrogen, N-6 represent pyridine type nitrogen, and N-Q represents the nitrogen of graphite mould.Wherein N-5 and N-6 can produce Faraday pseudo-capacitance.

The Raman spectrogram for the carbon-based electrode material that Fig. 2 obtains for the present embodiment, the carbon-based electricity of the bright present invention gained of the chart Pole material has very high quality.Position~the 2685cm at 2D peaks as can be seen from Figure^-1And there is good symmetry, 2D peaks with The intensity at G peaks compares I_2D/I_GThe a width of 55cm of half-peak at=0.5,2D peak^-1, the graphene of this explanation present invention gained is 3-5 layers；G peaks It is significantly stronger than D peaks, intensity ratio I_G/I_D~2.5, illustrate that gained graphene defect of the invention is few.

Fig. 3 is the small angle X-ray diffraction figure of carbon-based electrode material prepared by this example, shows graphene tool obtained by the present invention There are six side's ordered mesopore structures, corresponding space group is p6mm.

Fig. 4 is the graph of pore diameter distribution of carbon-based electrode material prepared by this implementation.Obtained by absorption/detachment assays of nitrogen Pore-size distribution, show that the graphene obtained by the present invention contains mesoporous (4-6 nanometers) and two kinds of duct knots of micropore (0.5-2.0 nanometers) Structure.

Fig. 5 is the narrow spectrum scanning figures of XPS N1s of carbon-based electrode material prepared by this implementation.Show the mesoporous graphene of gained Sample contains nitrogen (by taking N doping as an example).

Fig. 6 a are by taking the mesoporous graphene of N doping manufactured in the present embodiment as an example, in three-electrode system, use cyclic voltammetry Obtained result, sweep speed 2mV/s.Symmetrical good redox peaks are clearly visible from figure, and peak position differs 59mV.Show the electrochemical reaction speed of the doped graphene obtained by the present invention quickly.It in current density is 0.5A/g that Fig. 6 b, which are, Under charging and discharging curve, there it can be seen that the charging interval be 1350 seconds, discharge time be 1420 seconds, specific capacitance is 675 methods Every gram is drawn, while its coulombic efficiency is more than 95%.

Fig. 7 a in the device detection of symmetric form ultracapacitor, use cyclic voltammetric by taking the mesoporous graphene of N doping as an example The result that method obtains, sweep speed 2mV/s；Fig. 7 b are the charging and discharging curve under 0.5A/g current density.Therefrom can be with Find out, the discharge and recharge time is close, and straight line is presented, and shows there is good charge-discharge velocity and coulombic efficiency.

The mesoporous N doping amorphous carbon of comparative example 1

Take carbon source poly furfuryl alcohol with aminoguanidine by 5:1 ratio is dissolved in ethanol, adds mesoporous silicon oxide SBA-15, is surpassed Sound is scattered 30 minutes, is dried 10 hours at 100 DEG C, obtains the xerogel of SBA-15/ poly furfuryl alcohols/aminoguanidine；

Above-mentioned 50 grams of sample is placed in atmosphere furnace, 900 DEG C are warming up in argon gas or nitrogen, is incubated 1030 minutes.It is cold But to room temperature, sample is taken out；

Above-mentioned gained sample is soaked in the mixed solution of hydrofluoric acid, after 24 hours, filtering, with substantial amounts of deionized water Washed with ethanol.The amorphous carbon of gained N doping after drying；

The preparation of electrode of super capacitor and characterizing method are same as Example 1；

Specific capacity of the gained sample under 1A/g current density is 185F/g, volume and capacity ratio 75F/cm³, 10,000 times Fully the conservation rate of electric current is 83% after electricity, energy density 8Wh/kg, power density 0.92kW/kg.

The mesoporous nitrogen-doped graphene of 2 different oxidation-reduction potentials of embodiment

The preparation method for obtaining the mesoporous silicon oxide (SBA-15/Ni) filled with metallic nickel is identical with embodiment 1；

Take carbon source poly furfuryl alcohol with aminoguanidine by 5:1 (i.e. embodiment 1), 2:1 and 1:1 ratio is dissolved separately in ethanol, SBA-15/Ni is added, ultrasonic disperse 30 minutes, is dried 10 hours at 100 DEG C, obtains three groups of SBA-15/Ni/ poly furfuryl alcohols/amino The xerogel of guanidine；

Take each 50 grams of above-mentioned sample to be respectively placed in atmosphere furnace, 900 DEG C be warming up in argon gas or nitrogen, be passed through hydrogen, Ammonia and methane, its ratio are 20:15:10sccm, it is incubated 10-30 minutes.Room temperature is cooled to, takes out sample；

Above-mentioned gained sample is soaked in the mixed solution of hydrochloric acid and hydrofluoric acid, after 24 hours, filtering, with largely going Ionized water and ethanol washing.The mesoporous doped graphene of three kinds of N dopings is obtained after drying；

The sample of above-mentioned three kinds of different nitrogen contents is taken, respectively takes 50 milligrams, is scattered in 15 milliliters of N-methyl pyrrolidones (NMP) in, stir.It is slowly injected into three-dimensional graphene foam, dries, be pressed into electrode slice.The density of electrode slice is 0.75 It is gram per cubic centimeter.Using 0.5mol/L lithium sulfates as electrolyte, operating voltage lies prostrate for 0-1.6, makes symmetric form electrochemical capacitor Device, for testing；

Specific capacity of the electrode obtained under 1A/g current density is 820F/g, volume and capacity ratio 630F/cm³, 10,000 times Fully the conservation rate of electric current is 93% after electricity, energy density 71Wh/kg, power density 85kW/kg；

In the compound rear carbon-based composite electrode material prepared of doping carbon-based material of the present embodiment difference oxidation-reduction potential, The atomic concentration of doped chemical is 8.2%, the sp of carbon atom²The ratio 97.5% of hydridization, pyridine type and pyrroles between nitrogen and carbon The ratio that type combination accounts for whole nitrogens is 88%, and 88% is avtive spot in nitrogen, produces Faraday pseudo-capacitance, carbon The specific surface area of based combined electrode material is 2100 square metres every gram.

As shown in figure 8, compared with the single dopant material described in embodiment 1, the different redox electricity described in embodiment 2 After the doping carbon-based material of position is compound, specific capacitance is promoted to 820F/g from 650F/g, improves 26%；Energy density is promoted to from 58 71Wh/kg, improve 22%.

3 mesoporous boron of embodiment adulterates carbon-based material

The preparation of mesoporous silicon oxide (SBA-15/Ni) filled with metallic nickel is the same as embodiment 1；

Take carbon source poly furfuryl alcohol (PFA) and Boron tribromide (BBr₃) press 5:2 ratio is dissolved in ethanol, adds SBA-15/ Ni, ultrasonic disperse 30 minutes, dried 10 hours at 100 DEG C, obtain SBA-15/Ni/PFA/BBr₃Xerogel；

Above-mentioned 50 grams of sample is placed in atmosphere furnace, 800 DEG C are warming up in argon gas or nitrogen, is passed through hydrogen and methane, Its ratio is 20:10sccm, it is incubated 10-30 minutes.Room temperature is cooled to, takes out sample；

Above-mentioned gained sample is soaked in the mixed solution of hydrochloric acid and hydrofluoric acid, after 24 hours, filtering, with largely going Ionized water and ethanol washing.The boron doped mesoporous doped graphene of gained after drying；

The sign and electro-chemical test of mesoporous boron doped graphene are same as Example 1；

Specific capacity of the sample of the mesoporous boron doped graphene of gained under 1A/g current density is 520F/g, volume specific volume Measure as 370F/cm³, the conservation rate of 10,000 electric currents fully after electricity is 90.5%, energy density 46Wh/kg, and power density is 32kW/kg；

In carbon-based electrode material manufactured in the present embodiment, the atomic concentration of doped chemical is 6.1%, the sp of carbon atom²It is miscellaneous The ratio 98.2% of change, the combination in boron element and graphene between carbon atom include doping in ring, border doping and Height defective bit is adulterated, and the specific surface area of carbon-based electrode material is 2450 square metres every gram.

The mesoporous phosphorus doping carbon-based material of embodiment 4

Take carbon source phenolic resin with triphenyl phosphorus by 6:1 ratio is dissolved in ethanol, adds SBA-15/Ni, ultrasound point Dissipate 40 minutes, dried 10 hours at 100 DEG C, obtain the xerogel of SBA-15/Ni/ phenolic resin/triphenyl phosphorus；

Above-mentioned gained sample is soaked in the mixed solution of hydrochloric acid and hydrofluoric acid, after 24 hours, filtering, with largely going Ionized water and ethanol washing.The mesoporous doped graphene of gained phosphorus doping after drying；

The sign and electro-chemical test of mesoporous phosphorus doping graphene are same as Example 1；

Specific capacity of the sample of the mesoporous boron doped graphene of gained under 1A/g current density is 420F/g, volume specific volume Measure as 330F/cm³, the conservation rate of 10,000 electric currents fully after electricity is 90.0%, energy density 37Wh/kg, and power density is 28kW/kg；

In carbon-based electrode material manufactured in the present embodiment, the atomic concentration of doped chemical is 3.9%, the sp of carbon atom²It is miscellaneous The ratio 92% of change, the combination in P elements and graphene between carbon atom include doping in ring, border doping and high Defective bit doping is spent, the specific surface area of carbon-based electrode material is 1720 square metres every gram.

The mesoporous sulfur doping carbon-based material of embodiment 5

With embodiment 1, difference is nitre for the preparation of mesoporous silicon oxide (SBA-15/Co) filled with metallic cobalt Sour cobalt substitutes nickel nitrate；

Take carbon source glucose with thiocarbamide by 4:1 ratio is dissolved in ethanol, adds SBA-15/Co, and ultrasonic disperse 60 divides Clock, dried 10 hours at 100 DEG C, obtain the xerogel of SBA-15/Co/ glucose/thiocarbamide phenolic resin；

Above-mentioned gained sample is soaked in the mixed solution of hydrochloric acid and hydrofluoric acid, after 24 hours, filtering, with largely going Ionized water and ethanol washing.The mesoporous doped graphene of gained sulfur doping after drying；

Specific capacity of the sample of the mesoporous phosphorus doping graphene of gained under 1A/g current density is 580F/g, volume specific volume Measure as 440F/cm³, the conservation rate of 10,000 electric currents fully after electricity is 93.0%, energy density 52Wh/kg, and power density is 46kW/kg；

In carbon-based electrode material manufactured in the present embodiment, the atomic concentration of doped chemical is 5.7%, the sp of carbon atom²It is miscellaneous The ratio 90.8% of change, the combination in element sulphur and graphene between carbon atom include border and adulterated and height defective bit Doping, the ratio of all types of combinations are：The sulphur of border doping accounts for 82%, and 65% is avtive spot in element sulphur, produces method Fake capacitance is drawn, the specific surface area of carbon-based electrode material is 2150 square metres every gram.

The mesoporous doping carbon-based material of embodiment 6 and conducting polymer are compound

Illustrate the feasibility of the present invention so that polyaniline and mesoporous nitrogen-doped carbon sill are compound as an example；

The preparation of mesoporous nitrogen-doped carbon sill is identical with embodiment 1；

In ice-water bath, by 0.05 gram of the mesoporous nitrogen-doped carbon sill prepared in embodiment (1) be added to 100 milliliters it is dense Spend in the aniline hydrochloride aqueous solution for 1 mole every liter.It is to be mixed it is well mixed after, be slowly dropped into 50 milliliters of concentration as 0.2 mole Every liter of ammonium persulfate solution, stir 6 hours.Filtering, is washed with deionized, and it is carbon-based to can obtain mesoporous N doping after drying The composite of material/polyaniline；

Above-mentioned 50 milligrams of composite is taken, is scattered in 5 milliliters of N-methyl pyrrolidones (NMP), stirs.Slowly Inject in three-dimensional graphene foam, dry, be pressed into electrode slice.Using 0.5mol/L sulfuric acid as electrolyte, symmetric form electrochemistry is made Capacitor, for testing；

The mesoporous doping carbon-based material of gained and specific capacity of the compound sample of conducting polymer under 1A/g current density For 1080F/g, the conservation rate of 10,000 electric currents fully after electricity is 76.0%, energy density 92Wh/kg, power density 26kW/ kg。

2 conventional conducting polymer of comparative example

Similar with embodiment 6, difference is to be added without doping carbon-based material during aniline polymerization；

In ice-water bath, 100 milliliters of concentration are in 1 mole every liter of the aniline hydrochloride aqueous solution.It is to be mixed it is well mixed after, The ammonium persulfate solution that 50 milliliters of concentration are 0.2 mole every liter is slowly dropped into, is stirred 6 hours.Filtering, is washed with deionized, The composite of polyaniline is can obtain after drying；

Specific capacity of the compound sample of gained conducting polymer under 1A/g current density is 920F/g, and 10,000 times fully The conservation rate of electric current is 48.0% after electricity, energy density 83Wh/kg, power density 0.45kW/kg.

Compared with pure polyaniline, cycle life improves the composite of doped carbon/polyaniline provided by the invention 58%, power density improves more than 50 times.

Embodiment 7 surpasses the graphene of the N doping of high-ratio surface, is implemented by method 2.1

5 grams of potassium hydroxide are added in 10 grams of graphite purchased in market and are used as activator, the aminoguanidine of 5 grams of addition is as nitrogen source, and 5 Gram nickel acetate is catalyst, ball milling 2 hours.Compound is placed in tube furnace, is warming up to 1000 DEG C, is passed through methane, hydrogen, argon gas And nitrogen, its ratio are 20:50:300:20sccm, heating response 0.5 hour.Product removes metalNicatalyst by hydrochloric acid Deng impurity, specific surface area is prepared more than 2500m²/ g doped graphene；

The sign of the doped graphene of superhigh specific surface area and electro-chemical test are same as Example 1；

The nitrogen content of the sample of gained is 5%, and the specific capacity under 1A/g current density is 620F/g, volume and capacity ratio For 460F/cm³, the conservation rate of 10,000 electric currents fully after electricity is 92.5%, energy density 42Wh/kg, and power density is 31kW/kg；

In carbon-based electrode material manufactured in the present embodiment, the atomic concentration of doped chemical is 5%, the sp of carbon atom²Hydridization Ratio 89%, the ratio of pyridine type and pyrroles's type combination is 72% between nitrogen and carbon, and 72% is active sites in nitrogen Point, Faraday pseudo-capacitance is produced, the specific surface area of carbon-based electrode material is 2750 square metres every gram.

Embodiment 8 surpasses the boron doped specific area graphene of high-ratio surface, is implemented by method 2.2

5 grams of potassium hydroxide are added in 10 grams of graphenes purchased in market as activator, ball milling 10 hours.Compound is placed in pipe In formula stove, nitrogen is passed through as protection gas, 900 DEG C is warming up to, reacts 2 hours, prepare specific surface area 2000m²/ g's is defective Graphene；

By the defective graphene of above-mentioned high-specific surface area and the boric acid and catalyst cobalt nitrate ball of 20 grams of doped source Mill mixing, Ball-milling Time are 4 hours, are subsequently placed in chemical vapor deposition stove, 800 DEG C are warming up in argon gas or nitrogen, are led to Enter argon gas, hydrogen and methane, be incubated 30 minutes.Room temperature is cooled to, takes out sample.Product removes the impurity such as catalyst by acid, system It is standby go out specific surface area more than 2200m²/ g doped graphene；

The Boron contents of the sample of gained are 8%, and the specific capacity under 1A/g current density is 680F/g, volume and capacity ratio For 490F/cm³, the conservation rate of 10,000 electric currents fully after electricity is 91.2%, energy density 46Wh/kg, and power density is 37kW/kg；

In carbon-based electrode material manufactured in the present embodiment, the sp of carbon atom²The ratio 85% of hydridization, boron element and graphene Combination between middle carbon atom includes doping in ring, border doping and the doping of height defective bit, carbon-based electrode material Specific surface area is 1890 square metres every gram.

The superelevation of embodiment 9 is than surface N doping three-dimensional grapheme

With one kind in the porous silica with three-dimensional continuous pore structure for template, by metallic catalyst, carbon source and Doped source is filled in duct, and N doping high specific surface area three-dimensional graphene is prepared by chemical vapour deposition technique.Specifically The step of be：

Configuration concentration is the aqueous solution of 0.1mol/L nickel nitrates, the matter with three-dimensional porous silica by nickel and silica Amount is than being 1:1 mixing.Stirring, ultrasonic disperse, it is 10Pa to be evacuated to pressure, treats that solution is waved.In the argon gas atmosphere containing 5% hydrogen In, 400 DEG C are warming up to, is incubated 2 hours, obtains the three-dimensional porous silica (SiO filled with metallic nickel₂/Ni)；

Take carbon source poly furfuryl alcohol with aminoguanidine by 4:1 ratio is dissolved in ethanol, adds SiO₂/ Ni, ultrasonic disperse 30 divide Clock, dried 10 hours at 100 DEG C, obtain SiO₂The presoma of/Ni/ poly furfuryl alcohols/aminoguanidine；

Above-mentioned sample is warming up to 900 DEG C in argon gas or nitrogen, is passed through hydrogen, ammonia, methane and vapor, its ratio For 20:15:10:5sccm, it is incubated 30 minutes.Room temperature is cooled to, takes out sample；

Above-mentioned gained sample is soaked in the mixed solution of hydrochloric acid and hydrofluoric acid, after 24 hours, filtering, with largely going Ionized water and ethanol washing.The high specific surface area three-dimensional graphene of gained N doping after drying；

The sign and electro-chemical test of the N doping three-dimensional grapheme of superhigh specific surface area are same as Example 1；

The nitrogen content of the sample of gained is 14%, specific surface area 2400m²/ g, the specific volume under 1A/g current density Measure as 460F/g, volume and capacity ratio 320F/cm³, the conservation rate of 10,000 electric currents fully after electricity is 90.6%, and energy density is 32Wh/kg, power density 21kW/kg；

In carbon-based electrode material manufactured in the present embodiment, the sp of carbon atom²The ratio 78% of hydridization, pyridine between nitrogen and carbon The ratio of type and pyrroles's type combination is 67%, and 67% is avtive spot in nitrogen, produces Faraday pseudo-capacitance, carbon-based electricity The specific surface area of pole material is 2220 square metres every gram.

The superelevation of embodiment 11 is than surface N doping three-dimensional grapheme

2 grams of graphene oxides, 1 gram of glycine, 1.5 grams of ferric nitrate are dispersed in the ethanol with nano pipe/polyhenylethylene ball In solvent (100 milliliters), by freeze-drying, three-dimensional porous presoma is obtained.It is placed in chemical vapor deposition stove, in argon gas In be warming up to 800 DEG C, be passed through hydrogen, ammonia and gaseous carbon sources, its ratio be 20:15:10sccm, 30 minutes are incubated, is cooled to Room temperature, take out sample.Product removes the impurity such as iron removaling by nitric acid, prepares specific surface area more than 2000m²/ g doped graphite Alkene；

The nitrogen content of the sample of gained is 3.6%, and the specific capacity under 1A/g current density is 410F/g, volume specific volume Measure as 270F/cm³, the conservation rate of 10,000 electric currents fully after electricity is 92.8%, energy density 21Wh/kg, and power density is 14kW/kg；

In carbon-based electrode material manufactured in the present embodiment, the sp of carbon atom²The ratio 89% of hydridization, pyridine between nitrogen and carbon The ratio of type and pyrroles's type combination is 76%, and 76% is avtive spot in nitrogen, produces Faraday pseudo-capacitance, carbon-based electricity The specific surface area of pole material is 2450 square metres every gram.

The superelevation of embodiment 12 is than surface N doping three-dimensional grapheme

2 grams of graphene oxides, 1 gram of glycine, 3 grams of cobalt nitrate are dispersed in and be contained in containing polymer binder PEG's In the aqueous solution, 60 DEG C are heated to, is stirred 2 hours, prepares uniform mixing high viscous colloid.Colloid is in 350 DEG C of Muffle furnaces Middle heating 5 hours, slowly deviates from moisture.After the char-forming material of acquisition is by simple ball milling, it is placed in chemical vapor deposition stove, 1100 DEG C are warming up in argon gas or nitrogen, is passed through hydrogen, ammonia, methane and ammonia, 20:15:10:10sccm, 30 minutes are incubated, Room temperature is cooled to, takes out sample.Product removes the impurity such as catalyst, silica by acid, prepares specific surface area 2000m²/ G doped graphene；

In carbon-based electrode material manufactured in the present embodiment, the atomic concentration of doped chemical is 10.8%, the sp of carbon atom²It is miscellaneous The ratio 76% of change, the ratio of pyridine type and pyrroles's type combination is 66% between nitrogen and carbon, and 66% is activity in nitrogen Site, Faraday pseudo-capacitance is produced, the specific surface area of carbon-based electrode material is 2840 square metres every gram.

Claims

1. a kind of carbon-based electrode material with superelevation specific capacitance, it is characterised in that the electric capacity of the carbon-based electrode material is by double Electric layer electric capacity and Faraday pseudo-capacitance two parts composition, the electric double layer capacitance account for the electric capacity of the carbon-based electrode material 20~ 60%, carbon-based electrode material specific capacity under 1A/g current density is 400 farads more than every gram, and volume and capacity ratio is 300 More than every milliliter of farad.

2. the carbon-based electrode material according to claim 1 with superelevation specific capacitance, it is characterised in that the carbon-based electrode Carbon atom in materialsp ²For the ratio of hydridization more than 60%, the conductance of the carbon-based electrode material is every in 200 Siemens More than centimetre.

3. the carbon-based electrode material according to claim 1 or 2 with superelevation specific capacitance, it is characterised in that described carbon-based The specific surface area of electrode material is 1200 square metres more than every gram.

4. the carbon-based electrode material according to claim 1 or 2 with superelevation specific capacitance, it is characterised in that described carbon-based Electrode material zeta current potentials in water are less than -15 mV.

5. the carbon-based electrode material according to claim 1 with superelevation specific capacitance, it is characterised in that the carbon-based electrode Material Faraday pseudo-capacitance introduces avtive spot generation by adulterating doped chemical, and the doped chemical is in nitrogen, boron, phosphorus, sulphur At least one, the atomic concentration of doped chemical is 0.5%-20%.

6. the carbon-based electrode material according to claim 5 with superelevation specific capacitance, it is characterised in that pass through the doping Element is combined with charged ion, and redox reaction occurs and introduces the avtive spot.

7. the carbon-based electrode material with superelevation specific capacitance according to claim 5 or 6, it is characterised in that the doping Combination between element and carbon atom includes doping in ring, border doping and the doping of height defective bit.

8. carbon-based electrode material according to claim 5, it is characterised in that the doped chemical is nitrogen, the carbon-based electricity The combination of nitrogen and carbon includes three kinds of pyridine type, pyrroles's type and graphite mould in the material of pole, wherein shared by pyridine type and pyrroles's type Ratio be more than 70%.

9. carbon-based electrode material according to claim 5, it is characterised in that the carbon-based electrode material is to be mixed described in doping The mesoporous graphene of miscellaneous element high-specific surface area, carbon atom in the mesoporous graphene of the high-specific surface areasp ²The ratio of hydridization Example more than 80%, specific surface area be 1500 square metres more than every gram, conductance more than 400 Siemens per centimeters, graphene The number of plies is 3-5 layers.

10. carbon-based electrode material according to claim 5, it is characterised in that the carbon-based electrode material is described in doping The three-dimensional grapheme of doped chemical high-specific surface area, it has the conductive network of three-dimensional communication, and its conductance is more than 300 Siemens Per cm, specific surface area is more than 2000 square metres every gram, and its density is per cubic centimeter less than 0.1 gram.

11. carbon-based electrode material according to claim 1, it is characterised in that the carbon-based electrode material include it is mesoporous and Two kinds of pore passage structures of micropore, the pore diameter range of the micropore is 0.5-2 nanometers, and mesoporous pore diameter range is 2-20 nanometers.

A kind of 12. combination electrode material of any described carbon-based electrode material in 1-11 including claim, it is characterised in that The composite is combined by the carbon-based electrode material with different oxidation-reduction potentials, or by the carbon-based electricity Pole material is combined with metallic compound and/or conducting polymer.

13. combination electrode material according to claim 12, it is characterised in that the metallic compound include manganese oxide, Nickel oxide, cobalt oxide, niobium oxide, tantalum oxide, ruthenium-oxide, titanium sulfide, molybdenum sulfide, vanadic sulfide, vulcanization tantalum, selenizing vanadium, selenizing tantalum At least one of, the conducting polymer includes polyaniline, polypyrrole and/or polythiophene.