CN105702473A

CN105702473A - Carbon-based electrode material having super high specific capacitance and combined electrode material thereof

Info

Publication number: CN105702473A
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: 2016-06-22
Anticipated expiration: 2034-11-26
Also published as: CN105702473B

Abstract

The invention relates to a carbon-based electrode material having super high specific capacitance and a combined electrode material thereof. Capacitance of the carbon-based electrode material comprises two parts, including double-electric-layer capacitance and Faradaic pseudo capacitance, the double-electric-layer capacitance is 20-60% of the capacitance of the carbon-based electrode material, the specific capacitance of the carbon-based electrode material under the 1A/g current density is more than 400, the volume specific capacitance is more than 300 F/ml, the energy density of a symmetric device of a water-based electrolyte is more than 20 Wh/kg, and the volume energy density is more than 15Wh/kg.

Description

There is carbon-based electrode material and the combination electrode material thereof of super high specific capacitance

Technical field

The present invention relates to the carbon-based electrode material of a kind of super high specific capacitance and combination electrode material thereof, belong to material, electrochemical technical field。

Background technology

Ultracapacitor has power density height, have extended cycle life and the feature such as safe and reliable, can be widely applied to hybrid-electric car, high-power outut device etc.。In current global range, ultracapacitor has formed a considerable market scale, and 2010 annual value of production reach 4.7 hundred million dollars, keeps the rate of increase of nearly 20% in recent years。Although ultracapacitor industrial prospect highlights, but being constrained to energy density, too low (regular activated charcoal super capacitor quality is than electric capacity<200F/g, volumetric capacitance<200F/mL, energy density<10Wh/kg), far below lithium battery (>100Wh/kg), and cause cannot large-scale application。The reason that activated carbon electrodes energy density is low is in that, a large amount of microcellular structures are unfavorable for the effective mobility of electric charge, causes that a large amount of avtive spot energy storage was lost efficacy, and high fault of construction causes it stability is not good under high voltages simultaneously, limits the lifting of energy density。Another major reason is, the carbon atom of porous carbon materials is many with sp³It is hybridized to master, sp²Hybridized atom ratio is low, poorly conductive (typical < 100S/cm)。Obtain the Carbon Materials with high conductivity, it is necessary to improve the sp of carbon atom²Hybridization ratios。Although having bibliographical information at present there is high sp²The material with carbon element of hydridization, and the sp2 hydridization of this kind of material has locality, its local conductivity is good, but the electric conductivity of entirety still cannot meet the requirement of electrode for capacitors。High sp²The Graphene of hydridization can have high-specific surface area (2,620m concurrently²/ g), high conductivity and high structural stability, it is possible to overcome the performance bottleneck of active carbon electrode material。But, the specific capacity of current carbon electrode still far below theoretical value (550F/g), key factor in actual specific surface area lower than 1000m²/ g；In addition the bulk density of Graphene is low, also can reduce the volume energy density of device。

In order to obtain higher ratio electric capacity, existing bibliographical information is by doped chemical, such as nitrogen, oxygen, sulfur, boron etc., is incorporated in porous carbon or Graphene, by occurring redox reaction to produce faraday's electric capacity。But, this kind of material of bibliographical information has two fatal problems: a doped chemical being introduced into can substantially reduce the electric conductivity of material；Two is faraday's capacitance ratio produced by doped chemical very low (being typically less than 10%), and this main reasons is that substantial amounts of doping active center cannot effectively utilize。

Additionally, high sp²The material with carbon element of hydridization can also carry out load as the carrier with high-specific surface area and high conductivity, and other has the active material of height ratio capacity, thus improving the specific energy density of electrode material further。Faradic electricity container (such as polymer, transition metal oxide etc.) is although the redox reaction that can pass through in charge and discharge process obtains higher ratio electric capacity, but because of its poor stability (after 5,000 circulations, capacity retention is less than 50%), power density relatively low (less than 1 kilowatt of per kilogram), limits the practical application of Faradic electricity container。And, there is the electrode material of faraday's electric capacity after being fabricated to super capacitor device, because the voltage of positive and negative polarities is different, it is impossible to reach oxidation-reduction potential, it is impossible to show the energy storage characteristic of super electrode material completely simultaneously。At present, based on the capacitor element of 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, the advantage combining high-specific surface area material with carbon element, High-conductivity carbon material and faraday electric capacity three are provided, abandon respective shortcoming, thus obtaining, there is the super capacitor material of super high specific capacitance and energy density, being one of the study hotspot of this area。

Summary of the invention

It is contemplated that overcome the defect of existing C-base composte material, the invention provides the carbon-based electrode material of a kind of super high specific capacitance and combination electrode material thereof and preparation method。

The invention provides a kind of carbon-based electrode material with super high specific capacitance, it is characterized in that, the electric capacity of described carbon-based electrode material is made up of electric double layer capacitance and Faraday pseudo-capacitance two parts, described electric double layer capacitance accounts for the 20～60% of the electric capacity of described carbon-based electrode material, described carbon-based electrode material specific capacity under the electric current density of 1A/g 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 15-watt-hour more than every liter。

The basic ideas of the present invention are: introduce avtive spot by element doping in the material with carbon element of high connductivity and high-specific surface area, produce Faraday pseudo-capacitance, doped chemical is one or both combinations in nitrogen, boron, phosphorus, sulfur, and the atomic concentration of doped chemical is 0.5%-20%。After doping, the electric conductivity of carbon-based material is not decreased obviously, and the dispersibility in water significantly improves, and zeta current potential is less than-15mV；

Material with carbon element provided by the invention, except having ratio electric capacity and the energy density characteristics of superelevation, is also had another important advantage, can be regulated the oxidation-reduction potential of electrode material by the content of controlled doping element and doped structure, it is achieved different faraday's electric capacity。For the mesoporous Graphene of the N doping of gained of the present invention, combination between nitrogen and carbon comprises pyridine type, pyrroles's type and graphite mould three kinds, wherein can there is reversible redox reaction with hydrion in pyridine type and pyrroles's type nitrogen-atoms, it it is the avtive spot that effectively adulterates, redox reaction current potential, by the impact of pyridine type and the ratio of pyrroles's type nitrogen-atoms, can regulate and control the oxidation-reduction potential of the mesoporous Graphene of N doping by regulating the ratio of pyridine type and pyrroles's type nitrogen-atoms。And the series connection principle according to two electrode capacitances, the total capacitance C=C of device₁C₂/(C₁+C₂), after there is the doping carbon base electrode Material cladding of different oxidation-reduction potential, positive and negative polarities can be made simultaneously to reach oxidation-reduction potential under multiple voltages, obtain maximum faraday's electric capacity, i.e. C1=C2 simultaneously, now can obtain maximum ratio electric capacity。The ratio electric capacity of the ratio electric capacity of thus obtained device and material itself is compared, within 5%。After device made by the single material with faraday's electric capacity, its capacitance loss more than 15%。

It is preferred that the sp of the carbon atom in described carbon-based electrode material²The ratio of hydridization is more than 60%, and the conductivity of described carbon-based electrode material is more than 200 Siemens per centimeter。

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

It is preferred that described carbon-based electrode material in water zeta current potential less than-15mV。

Described carbon-based electrode material, says from structure, structure that is that mainly formed high-specific surface area by the carbon atom of sp2 hydridization and that comprise defect, and specific surface area is 1200 square metres more than every gram；Chemically composition, comprises the foreign atom of non-carbon；From zeta current potential water, described carbon-based electrode material is less than-15mV。

Producing it is preferred that described carbon-based electrode material Faraday pseudo-capacitance introduces avtive spot by doped chemical of adulterating, described doped chemical is at least one in nitrogen, boron, phosphorus, sulfur, and the doping of doped chemical is 0.5%-20%。

It is preferred that be combined with charged ion by described doped chemical, redox reaction is occurred to introduce described avtive spot。

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

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

It is preferred that described carbon-based electrode material is the mesoporous Graphene of described doped chemical high-ratio surface of adulterating, the sp of carbon atom in the mesoporous Graphene of described high-ratio surface²The ratio of hydridization is more than 80%, and specific surface area is 1500 square metres more than every gram, and conductivity is more than 400 Siemens per centimeter, and the number of plies of Graphene is 3-5 layer。

It is preferred that doping high specific surface area three-dimensional Graphene, having the conductive network of three-dimensional communication, its conductivity is more than 300 Siemens per centimeter, and specific surface area is more than 2000 square metres every gram, and its density is less than 0.1 gram every cubic centimetre。

It is preferred that described carbon-based electrode material is one of preferred, comprising mesoporous and two kinds of pore passage structures of micropore, the pore diameter range of described micropore is 0.5 2 nanometers, and mesoporous pore diameter range is 2 20 nanometers。

In addition, present invention also offers a kind of combination electrode material including above-mentioned carbon-based electrode material, described composite is composited by the described carbon-based electrode material with different oxidation-reduction potential, or is composited by described carbon-based electrode material metallizing thing and/or conducting polymer。

Preferably, described metallic compound includes at least one in manganese oxide, nickel oxide, cobalt oxide, niobium oxide, tantalum oxide, ruthenium-oxide, titanium sulfide, molybdenum sulfide, vanadic sulfide, sulfuration tantalum, selenizing vanadium, selenizing tantalum, and described conducting polymer includes polyaniline, polypyrrole and/or polythiophene。

Following Summary, for described carbon-based electrode material for doped with Graphene at least one in nitrogen, boron, phosphorus, sulfur, describing preparation method。

In the preparation of carbon-based electrode material, in doped source, nitrogenous source include tripolycyanamide, aminoguanidine, ammonia, aminoacid, at least one in ethylenediamine, boron source includes at least one in Boron tribromide, boron trifluoride, boric acid, pure boron, phosphorus source includes at least one in trioctylphosphine phosphorus, triphenyl phosphorus, phosphorus pentoxide, and sulfur source includes at least one in thiourea, thiophene, benzyl disulfide；

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

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

In source metal, Ni source includes at least one in nickel nitrate, nickel acetate, Nickel dichloride., nickel sulfate；Cu source includes at least one in copper nitrate, Schweinfurt green, copper chloride, copper sulfate；Co source includes at least one in cobalt nitrate, cobaltous acetate, cobaltous chloride, cobaltous sulfate；Fe source includes at least one in ferric nitrate, iron acetate, iron chloride, iron sulfate。

The first preparation method preparing a kind of example carbon-based electrode material that the present invention also provides for, described preparation method includes:

First, by having the metal form of three-dimensional continuous aperture structure, organic carbon source, doped source are scattered in solvent, ultrasonic disperse, prepare organic carbon source and metal form/organic carbon source/doped source xerogel that doped source is filled in metal form, then, by metal form/organic carbon source/doped source xerogel successively through chemical vapour deposition (CVD), removal impurity, prepare described carbon-based electrode material；

Or,

First, having porous oxide or the porous ceramics of three-dimensional continuous aperture structure, after mixing with source metal solution, stirring, ultrasonic disperse, evacuation also treat solution evaporation or dried, obtain being filled with the porous oxide of source metal or porous ceramics colloidal sol；Will be filled with again the porous oxide of source metal or porous ceramics colloidal sol protective atmosphere, at 300 500 DEG C insulation obtain being filled with porous oxide or the porous ceramics of metallic catalyst; described porous oxide or porous ceramics include but not limited to that porous oxide includes silicon dioxide, magnesium oxide, titanium dioxide, strontium titanates, Barium metatitanate., sodium silicate, calcium silicates, magnesium silicate etc.

Secondly, will be filled with the porous oxide of metallic catalyst or porous ceramics, organic carbon source, doped source are scattered in solvent, ultrasonic disperse, dry, obtain organic carbon source, doped source is filled in porous oxide or porous oxide in porous ceramics 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 chemical vapour deposition (CVD), remove impurity, prepare described carbon-based electrode material；

Wherein, the temperature of chemical vapour deposition technique is 600-1100 DEG C, and chemical vapour deposition (CVD) is gases used includes hydrogen, gaseous carbon source。

The present invention prepares the basic ideas of mesoporous Graphene: with mesoporous silicon oxide for template, with the one or more combination in poly furfuryl alcohol, sucrose, glucose, phenolic resin, polymethyl methacrylate, polystyrene for carbon source, in duct under the catalysis of metal, utilizing chemical vapour deposition technique, the wall along mesoporous silicon oxide grows into mesoporous Graphene。Metallic catalyst used is the combination of one or more in Ni, Cu, Co, Fe。Ni source is the one or more combination in nickel nitrate, nickel acetate, Nickel dichloride., nickel sulfate；Cu source is the one or more combination in copper nitrate, Schweinfurt green, copper chloride, copper sulfate；Co source is the one or more combination in cobalt nitrate, cobaltous acetate, cobaltous chloride, cobaltous sulfate；Fe source is the one or more combination in ferric nitrate, iron acetate, iron chloride, iron sulfate。The mass ratio of source metal and silicon dioxide is 0.25-2.5。Carrier gas used by chemical vapour deposition technique is nitrogen or argon, and reducibility gas is hydrogen, and gaseous carbon sources is the one or more combination in methane, ethylene, acetylene, methanol, ethanol etc.；Graphene growth temperature is 800-1100 DEG C。

It is preferred that organic carbon source includes at least one in poly furfuryl alcohol, sucrose, glucose, phenolic resin, polymethyl methacrylate, polystyrene。

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

Preferably, it is 0.1-2.0mol/L that source metal GOLD FROM PLATING SOLUTION belongs to the concentration in source, the mass ratio of source metal and porous oxide or porous ceramics is 0.25-2.5, the mass ratio of doped source and carbon source is (0.1-2): 1, being preferably (0.5-1): 1, the mass ratio of porous oxide or porous ceramics and carbon source is (0.2 2): 1。

It is preferred that preparation is filled with the porous oxide of metallic catalyst or porous ceramics temperature retention time is 2-5 hour, protective atmosphere is the noble gas doped with 1 20% hydrogen。

It is preferred that the mode filled includes priming by vacuum method, injection pressure is 1 100Pa。

Preferably, chemical vapour deposition (CVD) temperature 800-1100 DEG C, sedimentation time is 5-60 minute, it is preferable that 10-30 minute, chemical vapour deposition (CVD) is gases used also includes nitrogen or argon, ammonia, steam and/or carbon dioxide, gas flow 50 500sccm, including: the flow of nitrogen or argon is 50 400sccm, flow 5 100sccm of hydrogen, flow 1 20sccm of gaseous carbon source, flow 0.5 20sccm of ammonia, flow 0.5 10sccm of steam, flow 0.5 10sccm of carbon dioxide。

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

1) in graphite, activator, doped source and source metal are added, after ball milling, at 600-1000 DEG C, comprise in the gas of gaseous carbon source, hydrogen, heat 0.5-10 hour, then remove impurity after cooling, obtain described carbon-based electrode material, wherein, activator is at least one in potassium hydroxide, sodium hydroxide, zinc chloride, and the mass ratio between graphite, activator, doped source and source metal is 1:(0.5 2): (0.01 1): (0.5 2)；Or,

A) in Graphene, activator is first added, then under 500-1000 DEG C, argon or nitrogen atmosphere, reacting by heating 0.5-10 hour, prepare defective Graphene, wherein, the mass ratio of activator and Graphene is (0.5-4): 1, and activator is at least one in potassium hydroxide, sodium hydroxide, zinc chloride；

B) after defective Graphene, doped source and the mixing of source metal ball milling prepared by step a), it is placed in chemical vapor deposition stove, argon or nitrogen are warming up to 800 1100 DEG C, pass into the gas including hydrogen, gaseous carbon source, it is incubated 10-30 minute, then removes impurity after cooling, obtain described carbon-based electrode material, wherein, the mass ratio between defective Graphene, doped source and source metal is 1:(0.01 1): (0.5 2)。

Preferably, step 1) or step a) in, heating 2-10 hour at 600-900 DEG C, reaction atmosphere also includes ammonia, nitrogen, steam and/or carbon dioxide, and gas flow is 50 300sccm, including: flow 2 20sccm of gaseous carbon source, flow 5 20sccm of hydrogen, flow 10 20sccm of ammonia, flow 200 300sccm of nitrogen, flow 5 20sccm of steam, flow 5 20sccm of carbon dioxide。

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

Except above-mentioned preparation method, the preparation method that present invention also offers also a kind of example carbon-based electrode material, described method includes:

First, by graphene oxide, doped source, source metal is dispersed in the alcohol solvent with nano-high molecule ball, pass through lyophilization, obtain three-dimensional porous presoma, wherein, graphene oxide, doped source, mass ratio between source metal is 1:(0.01 1): (0.5 2), or, by graphene oxide, doped source, nano silicon, source metal dispersion is contained in the aqueous solution containing polymer binder, heating prepares gel, gel is deviate from, 250 350 DEG C of heating, the char-forming material that moisture obtains for 5 10 hours, wherein, graphene oxide, doped source, nano silicon, mass ratio between source metal is 1:(0.01 1): (0.5 2): (0.5 2)；

Then, the char-forming material after the three-dimensional porous presoma of aforementioned preparation or ball milling is placed in chemical vapor deposition stove, in argon or nitrogen, is warming up to 800-1100 DEG C, pass into the gas including hydrogen, gaseous carbon sources, it is incubated 10-30 minute, removes impurity after cooling, obtain described carbon-based electrode material。

It is preferred that nano-high molecule ball is 0.1 5g/mL in alcohol solvent concentration, nano-high molecule bag draws together nano pipe/polyhenylethylene ball, polymethyl methacrylate, polyethylene。

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

Preferably, in the aqueous solution of polymer binder, the concentration of polymer binder is 0.05 0.5g/mL, and polymer binder includes starch, polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternium, Polyethylene Glycol。

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

It is preferred that by hydrochloric acid, Fluohydric acid. leaching, and by water, washing with alcohol, remove the impurity including template and/or source metal and/or metallic catalyst。

Beneficial effects of the present invention:

Carbon-based electrode material provided by the invention and combination electrode material thereof, the advantage combining high-specific surface area material with carbon element, High-conductivity carbon material and faraday electric capacity three, abandon respective shortcoming, thus obtaining the super capacitor material with super high specific capacitance and energy density；

Compared with the porous carbon materials of business, the doped meso-porous Graphene of gained of the present invention has better electric conductivity, and the transmission for electric charge provides express passway；Compared with traditional Graphene, the Graphene of gained of the present invention has the order mesoporous and microcellular structure of prosperity, provides more by all kinds of means with electrolytical interaction for Graphene。Doped chemical makes the electrode material of gained of the present invention that redox reaction can occur in charge and discharge process, produces faraday's electric capacity, thus obtaining higher ratio electric capacity and energy density。Compared with faraday's capacitance electrode material traditional with transition metal oxide (such as nickel oxide, manganese oxide etc.), polymer (such as polyaniline, polypyrrole etc.) etc., the mesoporous nitrogen-doped graphene of gained of the present invention has ratio electric capacity close with it and energy density, but has the speed of response, higher power density and better charge and discharge cycles stability faster。

Accompanying drawing explanation

Fig. 1 illustrate in the present invention foreign atom of the doping carbon-based electrode material of preparation and carbon atom in conjunction with schematic diagram, for N doping；

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

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

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

Fig. 5 illustrates the narrow spectrum scanning figure (for N doping) of XPSN1s of the carbon-based electrode material of preparation in an embodiment of the invention；

Fig. 6 illustrates result (sweep speed is 2mV/s) (a) and its charging and discharging curve (b) that in an embodiment of the invention, the carbon-based electrode material of the N doping of preparation obtains in three-electrode system by cyclic voltammetry；

Fig. 7 illustrates result (sweep speed is 2mV/s) (a) and the charging and discharging curve (b) thereof that in an embodiment of the invention, the carbon-based electrode material of the N doping of preparation obtains in symmetry electrode system by cyclic voltammetry；

The result (sweep speed is 2mV/s) (b) that the new combination electrode material that Fig. 8 obtains after illustrating in the present invention result (sweep speed is 2mV/s) (a) and this three kinds of carbon-based electrode compounds that the nitrogen-doped carbon base electrode of three kinds of different oxidation-reduction potentials of preparation obtains by cyclic voltammetry in three-electrode system obtains by cyclic voltammetry in three-electrode system。

Detailed description of the invention

The present invention is further illustrated, it should be appreciated that accompanying drawing and following embodiment are merely to illustrate the present invention below in conjunction with accompanying drawing and following embodiment, and the unrestricted present invention。

It is an object of the invention to provide a kind of carbon-based electrode material for high-performance super capacitor and combination electrode material thereof, its electrochemical properties is: electric capacity is made up of electric double layer capacitance and Faraday pseudo-capacitance two parts, specific capacity is more than 400 farads every gram, or volume and capacity ratio is more than 300 farads every milliliter；Electric double layer capacitance proportion 20%-60%；Or the energy density of the symmetrical device of water based electrolyte is more than 20 watt-hour per kilograms, or volume energy density is more than 15 watt-hour every liter。The architectural feature with the carbon-based electrode material of such excellent electrochemical performance is in that carbon atom passes through sp²Hydridization, its ratio is more than 60%；Having significantly high electric conductivity, conductivity is more than 200 Siemens per centimeter；Having significantly high specific surface area, specific surface area is more than 1200 square metres every gram。

The basic ideas of the present invention are: introduce avtive spot by element doping in the material with carbon element of high connductivity and high-specific surface area, produce Faraday pseudo-capacitance, doped chemical is one or both combinations in nitrogen, boron, phosphorus, sulfur, and the atomic concentration of doped chemical is 0.5%-20%。After doping, the electric conductivity of carbon-based material is not decreased obviously, and the dispersibility in water significantly improves, and zeta current potential is less than-15mV。As preferably, the feature of the mesoporous Graphene of N doping is sp²The atom ratio of hydridization is more than 80%, and conductivity is more than 400 Siemens per centimeter, and specific surface area is more than 1500 square metres every gram。Good dispersion in water, zeta current potential is less than-15mV, and the combination between nitrogen and carbon in N doping carbon-based electrode material comprises pyridine type, pyrroles's type and graphite mould three kinds, and wherein the ratio shared by pyridine type and pyrroles's type is more than 70%。

Material with carbon element provided by the invention, except having ratio electric capacity and the energy density characteristics of superelevation, is also had another important advantage, can be regulated the oxidation-reduction potential of electrode material by the content of controlled doping element and doped structure, it is achieved different faraday's electric capacity。Combination between doped chemical and carbon includes the one in doping in ring, border doping, height defective bit doping or combination。Activated doped chemical in carbon-based electrode material is combined with charged ion, and redox reaction occurs。For the mesoporous Graphene of the N doping of gained of the present invention, combination between nitrogen and carbon comprises pyridine type, pyrroles's type and graphite mould three kinds, wherein the ratio shared by pyridine type and pyrroles's type is more than 70%, as shown in Figure 1, wherein can there is reversible redox reaction with hydrion in pyridine type and pyrroles's type nitrogen-atoms, it it is the avtive spot that effectively adulterates, redox reaction current potential, by the impact of pyridine type and the ratio of pyrroles's type nitrogen-atoms, can regulate and control the oxidation-reduction potential of the mesoporous Graphene of N doping by regulating the ratio of pyridine type and pyrroles's type nitrogen-atoms。And the series connection principle according to two electrode capacitances, the total capacitance C=C of device₁C₂/(C₁+C₂), after there is the doping carbon base electrode Material cladding of different oxidation-reduction potential, positive and negative polarities can be made simultaneously to reach oxidation-reduction potential under multiple voltages, obtain maximum faraday's electric capacity, i.e. C simultaneously₁=C₂, now can obtain maximum ratio electric capacity。The ratio electric capacity of the ratio electric capacity of thus obtained device and material itself is compared, within 5%。After device made by the single material with faraday's electric capacity, 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 conductivity is more than 400 Siemens per centimeter, and specific surface area is more than 1500 square metres every gram。

Described doping graphene with high specific surface, as preferably, adulterate high specific surface area and mesoporous Graphene, has mesoporous and two kinds of pore passage structures of micropore, and 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 conventional super capacitor material compound, improves the performance of capacitor。These materials include the Carbon Materials that mesoporous carbon, activated carbon, Graphene, CNT etc. are conventional；One or more metallic compound in manganese oxide, nickel oxide, cobalt oxide, niobium oxide, tantalum oxide, ruthenium-oxide, titanium sulfide, molybdenum sulfide, vanadic sulfide, sulfuration tantalum, selenizing vanadium, selenizing tantalum etc.；Or one or more the conducting polymer compound in polyaniline, polypyrrole, polythiophene etc.。Wherein, more than 15% is improved with after conventional Carbon Materials and metallic compound compound than electric capacity；More than 40% is improve with the conducting polymer compound Posterior circle life-span。

As preferably, the present invention prepares the basic ideas of mesoporous Graphene and is: with mesoporous silicon oxide for template, is filled in the duct of silicon dioxide by metallic catalyst, carbon source and doped source, prepares doped meso-porous Graphene through chemical vapour deposition technique。

With mesoporous silicon oxide for template, with the one or more combination in poly furfuryl alcohol, sucrose, glucose, phenolic resin, polymethyl methacrylate, polystyrene for carbon source, in duct under the catalysis of metal, utilizing chemical vapour deposition technique, the wall along mesoporous silicon oxide grows into mesoporous Graphene。Metallic catalyst used is the combination of one or more in Ni, Cu, Co, Fe。Ni source is the one or more combination in nickel nitrate, nickel acetate, Nickel dichloride., nickel sulfate；Cu source is the one or more combination in copper nitrate, Schweinfurt green, copper chloride, copper sulfate；Co source is the one or more combination in cobalt nitrate, cobaltous acetate, cobaltous chloride, cobaltous sulfate；Fe source is the one or more combination in ferric nitrate, iron acetate, iron chloride, iron sulfate。The mass ratio of source metal and silicon dioxide is 0.25-2.5。Carrier gas used by chemical vapour deposition technique is nitrogen or argon, and reducibility gas is hydrogen, and gaseous carbon sources is the one or more combination in methane, ethylene, acetylene, methanol, ethanol etc.；Graphene growth temperature is 800-1100 DEG C。

It is priming by vacuum method that described metallic catalyst is filled into method used in mesoporous silicon oxide or porous ceramics duct, and injection pressure is 1-100Pa。

The mesoporous Graphene of doping can be obtained when adding nitrogen, boron, p and s source in duct。The concentration of doped chemical can be regulated by the addition of doped source, and when the mass ratio of doped source Yu carbon source is 0.01-0.5, gained atomic concentration is 0.5%-15%。Nitrogenous source include tripolycyanamide, aminoguanidine, ammonia, aminoacid, the combination of one or more in ethylenediamine；Boron source includes the one or more combination in Boron tribromide, boron trifluoride, boric acid, pure boron；Phosphorus source is the one or more combination in trioctylphosphine phosphorus, triphenyl phosphorus, phosphorus pentoxide；Sulfur source includes the one or more combination in thiourea, thiophene, benzyl disulfide。The doped source of two kinds of element codopes can choose the one stated in nitrogenous source, boron source, phosphorus source and sulfur source respectively。

As preferably, high-specific surface area doped graphene may also pass through doping and the activation two step gained of Graphene, and activator is one or more the combination in potassium hydroxide, sodium hydroxide, ammonia, zinc chloride, steam, carbon dioxide etc.；The ratio of activator and Graphene is 0.5-4；Activation temperature is 500-1000 DEG C；Soak time is 0.5-8 hour。

As preferably, high-specific surface area doped graphene can be the doping high specific surface area three-dimensional Graphene with three-dimensional communication pore passage structure, there are good conduction and passage of heat, its conductivity is more than 300 Siemens per centimeter, specific surface area is more than 2000 square metres every gram, and its density is less than 0.1 gram every cubic centimetre。Its preparation method is with the metal form with three-dimensional continuous aperture structure for catalyst, after filling carbon source and doped source, prepares doping high specific surface area three-dimensional Graphene through chemical vapour deposition technique；Or with the one in the porous ceramics with three-dimensional continuous aperture structure or porous silica for template, metallic catalyst, carbon source and doped source are filled in duct, prepare doping high specific surface area three-dimensional Graphene through chemical vapour deposition technique。The temperature of chemical vapour deposition technique is 600-1000 DEG C, and the response time is 5-60 minute, and gas is noble gas, carbon source, hydrogen and activated gas, and gas flow is 1-500sccm。Activated gas is one or more the combination in steam, ammonia, carbon dioxide。

The method of another kind of preparation doping high specific surface area three-dimensional Graphene is Graphene, doped source, source metal are dispersed in the alcohol solvent with nano-high molecule ball, passes through lyophilization, it is thus achieved that three-dimensional porous presoma。It is placed in chemical vapor deposition stove, in argon or nitrogen, is warming up to 800-1100 DEG C, pass into hydrogen, ammonia and gaseous carbon sources, be incubated 10-30 minute, be cooled to room temperature, take out sample。Product removes the impurity such as nickel by nitric acid, prepares specific surface area more than 1200-2000m²The doped graphene of/g。

Two or more the described doping carbon base electrode Material cladding with different oxidation-reduction potential forms；Within the specific capacity little 5% of the device specific capacity of the symmetric form ultracapacitor of described electrode composite material and material。

It is described below in detail the carbon-based electrode material of three kinds of (being not limited to this) super high specific capacitances and prepared by combination electrode material and the process of sign。

1. its preparation method is with the metal form with three-dimensional continuous aperture structure for catalyst, after filling carbon source and doped source, prepares doping high specific surface area three-dimensional Graphene through chemical vapour deposition technique；Or with the one in the porous ceramics with three-dimensional continuous aperture structure or porous silica for template, metallic catalyst, carbon source and doped source are filled in duct, prepare doping high specific surface area three-dimensional Graphene through chemical vapour deposition technique。The temperature of chemical vapour deposition technique is 600-1000 DEG C, and the response time is 5-60 minute, and gas is noble gas, carbon source, hydrogen and activated gas, and gas flow is 1-500sccm。Activated gas is one or more the combination in steam, ammonia, carbon dioxide。

Particularly as follows:

Doped meso-porous doped graphene

1) metallic catalyst is filled in mesoporous silicon oxide duct

Configuration concentration is the aqueous solution of 0.1-2.0mol/L source metal, is that 0.25-2.5 mixes with commercial mesoporous silicon oxide by metal and the mass ratio of silicon dioxide。Stirring, ultrasonic disperse, being evacuated to pressure is 1-100Pa, becomes colloidal sol after solution evaporation。In the argon gas atmosphere containing 5% hydrogen, it is warming up to 450 DEG C, is incubated 2-5 hour, obtain being filled with the mesoporous silicon oxide (silicon dioxide/metal) of metallic catalyst；

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

Take carbon source and one or both doped source and be dissolved in the dissolving that water, ethanol etc. are suitable, add step 1) in the silicon dioxide/metal of gained, ultrasonic disperse, dry, obtain silicon dioxide/metal/carbon source/doped source。The ratio of doped source and carbon source regulates according to doping content, and that general is 0.01-0.5；

3) chemical vapour deposition technique growth Graphene

By step 2) in the silicon dioxide/metal/carbon source/doped source of gained be placed in atmosphere furnace, in argon or nitrogen, be warming up to 800-1100 DEG C, pass into hydrogen, ammonia and gaseous carbon sources, be incubated 10-30 minute。It is cooled to room temperature, takes out sample。Reaction temperature and time determine according to the kind of carbon source and metallic catalyst；

4) etching of template and sample cleanup

By step 3) sample of gained is soaked in the mixed solution of hydrochloric acid and Fluohydric acid., after 24 hours, filters, by substantial amounts of deionized water and washing with alcohol。Remember mesoporous doped graphene after drying；

5) pattern of mesoporous doped graphene and structural characterization

Gained Graphene sample of the present invention is observed by transmission electron microscope (JEM2010) pattern of sample。The structure of Graphene is characterized with Raman spectrum (RenishawinviaRamanMicroscope, excitation wavelength is 514.5nm)。Each element relative amount ratio and the chemical combination state thereof of sample surfaces is analyzed with x-ray photoelectron spectroscopy (XPS, PHI5000CESCASystem)。The electric conductivity of Graphene is measured with four probes VanDerPauw method (AccentHL5500)。The meso-hole structure of Graphene is characterized with nitrogen adsorption/detachment assays。Mesoporous doped graphene dispersibility in water is characterized with zeta current potential；

6) the ultracapacitor performance characterization of mesoporous doped graphene

Take 50 milligrams of mesoporous doped graphene sample, be scattered in the N-methyl ketopyrrolidine (NMP) of 5 milliliters, stir。It is slowly injected in three-dimensional graphene foam, dry, it is pressed into electrode slice。The density of electrode slice is 0.7-0.85 gram every cubic centimetre。With 0.5mol/L lithium sulfate for electrolyte, make symmetrical electrochemical capacitor, be used for testing。

2. the Graphene of the element doping of superelevation specific surface, can have two kinds of methods to obtain:

1) in commercial graphite, add the one in potassium hydroxide, sodium hydroxide, zinc chloride or the ratio as activator, activator and Graphene that combines is 0.5-4。Add doped source and source metal, ball milling 2-8 hour。Compound is placed in the stove containing methane, hydrogen, argon or nitrogen (during N doping, can lead to ammonia) of 600-1000 DEG C, reacting by heating 0.5-10 hour。Product removes the impurity such as catalyst by acid, prepares specific surface area more than 1500-2500m²The doped graphene of/g。This method doped chemical content is controlled, and material preparation cost is low, simple；

2) doped chemical can also be completed by two step method: (a) adds the one in potassium hydroxide, sodium hydroxide, zinc chloride in commercial graphite or the ratio as activator, activator and Graphene that combines is 0.5-4。It is subsequently placed in the argon of 600-900 DEG C or the stove of nitrogen protection, reacting by heating 2-10 hour, prepares specific surface area 1500-2500m²The defective Graphene of/g。B () is by the defective Graphene of high-specific surface area and doped source and the mixing of source metal ball milling, Ball-milling Time is 0.5-4 hour, it is subsequently placed in chemical vapor deposition stove, argon or nitrogen are warming up to 800-1100 DEG C, pass into hydrogen, ammonia (or borine) and gaseous carbon sources, be incubated 10-30 minute。It is cooled to room temperature, takes out sample。Reaction temperature and time determine according to the kind of carbon source and metallic catalyst。Product removes the impurity such as catalyst by acid, prepares specific surface area more than 1500-2500m²The doped graphene of/g。This method relatively one-step method, it is possible to obtain the product of more dominance energy。

3, superelevation specific surface doping three-dimensional grapheme, can have two kinds of methods to obtain:

1) graphene oxide, doped source, source metal are dispersed in the alcohol solvent with nano-high molecule ball, pass through lyophilization, it is thus achieved that three-dimensional porous presoma。It is placed in chemical vapor deposition stove, in argon or nitrogen, is warming up to 800-1100 DEG C, pass into hydrogen, ammonia and gaseous carbon sources, be incubated 10-30 minute, be cooled to room temperature, take out sample。Product removes the impurity such as nickel by nitric acid, prepares specific surface area more than 1200-2000m²The doped graphene of/g；

2) graphene oxide, doped source, nano silicon, source metal dispersion being contained in the aqueous solution containing polymer binder, colloid mixing high viscous uniformly is prepared in heating；After continuing heating acquisition gel, heat 5-10 hour in 250-350 DEG C of Muffle furnace, slowly deviate from moisture。The char-forming material obtained, by, after simple ball milling, being placed in chemical vapor deposition stove, be warming up to 800-1100 DEG C in argon or nitrogen, pass into hydrogen, ammonia and gaseous carbon sources, be incubated 10-30 minute, is cooled to room temperature, takes out sample。Product removes the impurity such as catalyst, silicon dioxide by acid, prepares specific surface area more than 1200-2000m²The doped graphene of/g。

Foreign atom and the carbon atom of the doping carbon-based electrode material that Fig. 1 present invention obtains in conjunction with schematic diagram, for N doping；

The Raman spectrogram of the carbon-based electrode material that Fig. 2 present invention obtains, this figure shows that gained carbon-based electrode material of the present invention has significantly high quality。Position～the 2685cm at 2D peak as can be seen from Figure^-1And there is the strength ratio I at good symmetry, 2D peak and G peak_2D/I_G=0.5, the half-peak breadth at 2D peak is 55cm^-1, the Graphene of this explanation gained of the present invention is 3-5 layer；G peak is significantly stronger than D peak, intensity ratio I_G/I_D～2.5, illustrate that gained Graphene defect of the present invention is few；

Fig. 3 small angle X-ray diffraction figure, it was shown that gained Graphene of the present invention has six side's ordered mesopore structure, and corresponding space group is p6mm；

Fig. 4 graph of pore diameter distribution。Pore-size distribution is obtained, it was shown that the Graphene of gained of the present invention contains mesoporous (4-6 nanometer) and two kinds of pore passage structures of micropore (0.5-2.0 nanometer) by the absorption/detachment assays of nitrogen；

The narrow spectrum scanning figure of Fig. 5 XPSN1s。Show that the sample of the mesoporous Graphene of gained contains nitrogen (for N doping)；

Fig. 6 a is for the mesoporous Graphene of N doping, and in three-electrode system, the result obtained by cyclic voltammetry, sweep speed is 2mV/s。Symmetrical well oxidoreduction peak and peak position difference 59mV it is clearly visible from figure。Show the electrochemical reaction speed of doped graphene of gained of the present invention quickly。Fig. 6 b is charging and discharging curve；

Fig. 7 a is for the mesoporous Graphene of N doping, and in the device detection of symmetric form ultracapacitor, the result obtained by cyclic voltammetry, sweep speed is 2mV/s；Fig. 7 b is charging and discharging curve；

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

Enumerate embodiment further below to describe the present invention in detail。It is also understood that; following example are served only for the present invention is further described; it is not intended that limiting the scope of the invention, some nonessential improvement and adjustment that those skilled in the art makes according to the foregoing of the present invention belong to protection scope of the present invention。The technological parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in hereafter example。

The mesoporous nitrogen-doped carbon sill of embodiment 1

Configuration concentration is the aqueous solution of 0.1mol/L nickel nitrate, is that 1:2 mixes with commercial mesoporous silicon oxide SBA-15 by nickel and the mass ratio of silicon dioxide。Stirring, ultrasonic disperse, being evacuated to pressure is 20Pa, becomes colloidal sol after solution evaporation。In the argon gas atmosphere containing 5% hydrogen, it is warming up to 450 DEG C, is incubated 2 hours, obtain being filled with the mesoporous silicon oxide (SBA-15/Ni) of metallic nickel；

Take carbon source poly furfuryl alcohol and aminoguanidine and be dissolved in ethanol by the ratio of 5:1, add SBA-15/Ni, ultrasonic disperse 30 minutes, 100 DEG C dry 10 hours, obtain SBA-15/Ni/ poly furfuryl alcohol/aminoguanidine xerogel；

Being placed in atmosphere furnace by 50 grams of above-mentioned sample, be warming up to 900 DEG C in argon or nitrogen, pass into hydrogen, ammonia and methane, its ratio is 20:15:10sccm, is incubated 10-30 minute。It is cooled to room temperature, takes out sample；

Above-mentioned gained sample is soaked in the mixed solution of hydrochloric acid and Fluohydric acid., after 24 hours, filters, by substantial amounts of deionized water and washing with alcohol。The mesoporous doped graphene of dried gained N doping；

The pattern of sample is observed by transmission electron microscope (JEM2010)。The structure of Graphene is characterized with Raman spectrum (RenishawinviaRamanMicroscope, excitation wavelength is 514.5nm)。Each element relative amount ratio and the chemical combination state thereof of sample surfaces is analyzed with x-ray photoelectron spectroscopy (XPS, PHI5000CESCASystem)。The electric conductivity of Graphene is measured with four probes VanDerPauw method (AccentHL5500)。The meso-hole structure of Graphene is characterized with nitrogen adsorption/detachment assays。Mesoporous doped graphene dispersibility in water is characterized with zeta current potential；

Take 50 milligrams of mesoporous nitrogen-doped graphene sample, be scattered in the N-methyl ketopyrrolidine (NMP) of 5 milliliters, stir。It is slowly injected in three-dimensional graphene foam, dry, it is pressed into electrode slice。The density of electrode slice is 0.75 gram every cubic centimetre。With 0.5mol/L lithium sulfate for electrolyte, make symmetrical electrochemical capacitor, be used for testing；

Gained sample specific capacity under the electric current density of 1A/g is 650F/g, and volume and capacity ratio is 480F/cm³, the conservation rate of 10,000 abundant electricity after currents is 92.5%, and energy density is 58Wh/kg, and power density is 45kW/kg。

In carbon-based electrode material prepared by the present embodiment, the atomic concentration of doped chemical is 7.8%, the sp of carbon atom²The ratio 98% of hydridization, between nitrogen and carbon, pyridine type and pyrroles's type combination account for the ratio of whole nitrogen element is 82%, and in nitrogen element, 82% is avtive spot, produces Faraday pseudo-capacitance, and 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 of the nitrogen-doped graphene that the present embodiment obtains。N-5 in figure represents pyrroles's type nitrogen, and N-6 represents pyridine type nitrogen, and N-Q represents the nitrogen of graphite mould。Wherein N-5 and N-6 can produce Faraday pseudo-capacitance。

Fig. 2 is the Raman spectrogram of the carbon-based electrode material that the present embodiment obtains, and this figure shows that gained carbon-based electrode material of the present invention has significantly high quality。Position～the 2685cm at 2D peak as can be seen from Figure^-1And there is the strength ratio I at good symmetry, 2D peak and G peak_2D/I_G=0.5, the half-peak breadth at 2D peak is 55cm^-1, the Graphene of this explanation gained of the present invention is 3-5 layer；G peak is significantly stronger than D peak, intensity ratio I_G/I_D～2.5, illustrate that gained Graphene defect of the present invention is few。

Fig. 3 is the small angle X-ray diffraction figure of carbon-based electrode material prepared by this example, it was shown that gained Graphene of the present invention has six side's ordered mesopore structure, and corresponding space group is p6mm。

Fig. 4 is the graph of pore diameter distribution of the carbon-based electrode material of this enforcement preparation。Pore-size distribution is obtained, it was shown that the Graphene of gained of the present invention contains mesoporous (4-6 nanometer) and two kinds of pore passage structures of micropore (0.5-2.0 nanometer) by the absorption/detachment assays of nitrogen。

Fig. 5 is the narrow spectrum scanning figure of XPSN1s of the carbon-based electrode material of this enforcement preparation。Show that the sample of the mesoporous Graphene of gained contains nitrogen (for N doping)。

The mesoporous Graphene of the N doping that Fig. 6 a is prepared for the present embodiment, in three-electrode system, the result obtained by cyclic voltammetry, sweep speed is 2mV/s。Symmetrical well oxidoreduction peak and peak position difference 59mV it is clearly visible from figure。Show the electrochemical reaction speed of doped graphene of gained of the present invention quickly。Fig. 6 b is be the charging and discharging curve under 0.5A/g in electric current density, there it can be seen that the charging interval is 1350 seconds, discharge time is 1420 seconds, and specific capacitance is 675 farads every gram, and its coulombic efficiency is more than 95% simultaneously。

Fig. 7 a is for the mesoporous Graphene of N doping, and in the device detection of symmetric form ultracapacitor, the result obtained by cyclic voltammetry, sweep speed is 2mV/s；Fig. 7 b is the charging and discharging curve under the electric current density of 0.5A/g。There it can be seen that the discharge and recharge time is close, and present straight line, it was shown that have good charge-discharge velocity and coulombic efficiency。

The mesoporous N doping amorphous carbon of comparative example 1

Take carbon source poly furfuryl alcohol and aminoguanidine and be dissolved in ethanol by the ratio of 5:1, add mesoporous silicon oxide SBA-15, ultrasonic disperse 30 minutes, 100 DEG C dry 10 hours, obtain SBA-15/ poly furfuryl alcohol/aminoguanidine xerogel；

50 grams of above-mentioned sample is placed in atmosphere furnace, argon or nitrogen are warming up to 900 DEG C, be incubated 1030 minutes。It is cooled to room temperature, takes out sample；

Above-mentioned gained sample is soaked in the mixed solution of Fluohydric acid., after 24 hours, filters, by substantial amounts of deionized water and washing with alcohol。The amorphous carbon of dried gained N doping；

The preparation of electrode of super capacitor and characterizing method are identical with embodiment 1；

Gained sample specific capacity under the electric current density of 1A/g is 185F/g, and volume and capacity ratio is 75F/cm³, the conservation rate of 10,000 abundant electricity after currents is 83%, and energy density is 8Wh/kg, and power density is 0.92kW/kg。

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

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

Take carbon source poly furfuryl alcohol and be dissolved separately in ethanol with aminoguanidine by the ratio of 5:1 (i.e. embodiment 1), 2:1 and 1:1, add SBA-15/Ni, ultrasonic disperse 30 minutes, dry 10 hours at 100 DEG C, obtain three groups of SBA-15/Ni/ poly furfuryl alcohol/aminoguanidines xerogel；

Taking each 50 grams of above-mentioned sample and be respectively placed in atmosphere furnace, be warming up to 900 DEG C, pass into hydrogen, ammonia and methane in argon or nitrogen, its ratio is 20:15:10sccm, is incubated 10-30 minute。It is cooled to room temperature, takes out sample；

Above-mentioned gained sample is soaked in the mixed solution of hydrochloric acid and Fluohydric acid., after 24 hours, filters, by substantial amounts of deionized water and washing with alcohol。Obtain the mesoporous doped graphene of three kinds of N doping after drying；

Take the sample of above-mentioned three kinds of different nitrogen contents, respectively take 50 milligrams, be scattered in the N-methyl ketopyrrolidine (NMP) of 15 milliliters, stir。It is slowly injected in three-dimensional graphene foam, dry, it is pressed into electrode slice。The density of electrode slice is 0.75 gram every cubic centimetre。With 0.5mol/L lithium sulfate for electrolyte, running voltage is 0-1.6 volt, makes symmetrical electrochemical capacitor, is used for testing；

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

After the doping carbon sill compound of the present embodiment difference oxidation-reduction potential in the carbon-based composite electrode material of preparation, the atomic concentration of doped chemical is 8.2%, the sp of carbon atom²The ratio 97.5% of hydridization, between nitrogen and carbon, pyridine type and pyrroles's type combination account for the ratio of whole nitrogen element is 88%, and in nitrogen element, 88% is avtive spot, produces Faraday pseudo-capacitance, and the specific surface area of carbon-based composite electrode material is 2100 square metres every gram。

As shown in Figure 8, compared with the single dopant material described in embodiment 1, after the doping carbon sill compound of the different oxidation-reduction potentials described in embodiment 2, it is promoted to 820F/g than electric capacity from 650F/g, improves 26%；Energy density is promoted to 71Wh/kg from 58, improves 22%。

The mesoporous boron doping carbon sill of embodiment 3

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

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

Being placed in atmosphere furnace by 50 grams of above-mentioned sample, be warming up to 800 DEG C in argon or nitrogen, pass into hydrogen and methane, its ratio is 20:10sccm, is incubated 10-30 minute。It is cooled to room temperature, takes out sample；

Above-mentioned gained sample is soaked in the mixed solution of hydrochloric acid and Fluohydric acid., after 24 hours, filters, by substantial amounts of deionized water and washing with alcohol。The boron doped mesoporous doped graphene of dried gained；

The sign of mesoporous boron doped graphene and electro-chemical test are identical with embodiment 1；

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

In carbon-based electrode material prepared by the present embodiment, the atomic concentration of doped chemical is 6.1%, the sp of carbon atom²The ratio 98.2% of hydridization, boron element and in Graphene combination between carbon atom include doping in ring, border doping and height defective bit doping, 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 and be dissolved in ethanol with triphenyl phosphorus in the ratio of 6:1, add SBA-15/Ni, ultrasonic disperse 40 minutes, dry 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 Fluohydric acid., after 24 hours, filters, by substantial amounts of deionized water and washing with alcohol。The mesoporous doped graphene of dried gained phosphorus doping；

The sign of mesoporous phosphorus doping Graphene and electro-chemical test are identical with embodiment 1；

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

In carbon-based electrode material prepared by the present embodiment, the atomic concentration of doped chemical is 3.9%, the sp of carbon atom²The ratio 92% of hydridization, P elements and in Graphene combination between carbon atom include doping in ring, border doping and height defective bit doping, 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

It is filled with the preparation of mesoporous silicon oxide (SBA-15/Co) of metallic cobalt with embodiment 1, is different in that and cobalt nitrate is replaced nickel nitrate；

Take carbon source glucose and be dissolved in ethanol with thiourea in the ratio of 4:1, add SBA-15/Co, ultrasonic disperse 60 minutes, dry 10 hours at 100 DEG C, obtain the xerogel of SBA-15/Co/ glucose/thiourea phenolic resin；

Above-mentioned gained sample is soaked in the mixed solution of hydrochloric acid and Fluohydric acid., after 24 hours, filters, by substantial amounts of deionized water and washing with alcohol。The mesoporous doped graphene of dried gained sulfur doping；

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

In carbon-based electrode material prepared by the present embodiment, the atomic concentration of doped chemical is 5.7%, the sp of carbon atom²The ratio 90.8% of hydridization, in element sulphur and Graphene, the combination between carbon atom includes border doping and height defective bit doping, the ratio of all types of combinations is: the sulfur of border doping accounts for 82%, in element sulphur, 65% is avtive spot, producing Faraday pseudo-capacitance, the specific surface area of carbon-based electrode material is 2150 square metres every gram。

The mesoporous doping carbon sill of embodiment 6 and conducting polymer compound

It is complex as example with polyaniline and mesoporous nitrogen-doped carbon sill and the feasibility of the present invention is described；

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

In ice-water bath, the mesoporous nitrogen-doped carbon sill 0.05 gram of preparation in embodiment (1) is joined in the aniline hydrochloride aqueous solution that 100 ml concns are 1 mole every liter。After mix homogeneously to be mixed, it is slowly dropped into the ammonium persulfate solution that 50 ml concns are 0.2 mole every liter, stirs 6 hours。Filter, with deionized water wash, the composite of mesoporous nitrogen-doped carbon sill/polyaniline can be obtained after drying；

Take 50 milligrams of above-mentioned composite, be scattered in the N-methyl ketopyrrolidine (NMP) of 5 milliliters, stir。It is slowly injected in three-dimensional graphene foam, dry, it is pressed into electrode slice。With 0.5mol/L sulphuric acid for electrolyte, make symmetrical electrochemical capacitor, be used for testing；

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

The conventional conducting polymer of comparative example 2

Similar with embodiment 6, it is different in that in aniline polymerization process and is added without doping carbon sill；

In ice-water bath, 100 ml concns are in the aniline hydrochloride aqueous solution of 1 mole every liter。After mix homogeneously to be mixed, it is slowly dropped into the ammonium persulfate solution that 50 ml concns are 0.2 mole every liter, stirs 6 hours。Filter, with deionized water wash, the composite of polyaniline can be obtained after drying；

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

The composite of doping carbon/polyaniline provided by the invention is compared with pure polyaniline, and cycle life improves 58%, and power density improves more than 50 times。

The Graphene of the N doping of embodiment 7 superelevation specific surface, is implemented by method 2.1

Adding 5 grams of potassium hydroxide in 10 grams of commercial graphite as activator, add the aminoguanidine of 5 grams as nitrogenous source, 5 grams of nickel acetates are catalyst, ball milling 2 hours。Compound is placed in tube furnace, is warming up to 1000 DEG C, passes into methane, hydrogen, argon and nitrogen, and its ratio is 20:50:300:20sccm, reacting by heating 0.5 hour。Product removes the impurity such as metalNicatalyst by hydrochloric acid, prepares specific surface area more than 2500m²The doped graphene of/g；

The sign of the doped graphene of superhigh specific surface area and electro-chemical test are identical with embodiment 1；

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

In carbon-based electrode material prepared by the present embodiment, the atomic concentration of doped chemical is 5%, the sp of carbon atom²The ratio 89% of hydridization, between nitrogen and carbon, the ratio of pyridine type and pyrroles's type combination is 72%, and in nitrogen element, 72% is avtive spot, produces Faraday pseudo-capacitance, and the specific surface area of carbon-based electrode material is 2750 square metres every gram。

The boron doped specific area Graphene of embodiment 8 superelevation specific surface, is implemented by method 2.2

10 grams of commercial Graphenes add 5 grams of potassium hydroxide as activator, ball milling 10 hours。Compound is placed in tube furnace, passes into nitrogen for protection gas, is warming up to 900 DEG C, reacts 2 hours, prepare specific surface area 2000m²The defective Graphene of/g；

The boric acid of the defective Graphene of above-mentioned high-specific surface area and doped source 20 grams and catalyst cobalt nitrate ball milling are mixed, Ball-milling Time is 4 hours, is subsequently placed in chemical vapor deposition stove, is warming up to 800 DEG C in argon or nitrogen, pass into argon, hydrogen and methane, be incubated 30 minutes。It is cooled to room temperature, takes out sample。Product removes the impurity such as catalyst by acid, prepares specific surface area more than 2200m²The doped graphene of/g；

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

In carbon-based electrode material prepared by the present embodiment, the sp of carbon atom²The ratio 85% of hydridization, boron element and in Graphene combination between carbon atom include doping in ring, border doping and height defective bit doping, the specific surface area of carbon-based electrode material is 1890 square metres every gram。

Embodiment 9 superelevation specific surface N doping three-dimensional grapheme

With the one in the porous silica with three-dimensional continuous aperture structure for template, metallic catalyst, carbon source and doped source are filled in duct, prepare N doping high specific surface area three-dimensional Graphene through chemical vapour deposition technique。Concrete step is:

Configuration concentration is the aqueous solution of 0.1mol/L nickel nitrate, is that 1:1 mixes with three-dimensional porous silicon dioxide by nickel and the mass ratio of silicon dioxide。Stirring, ultrasonic disperse, being evacuated to pressure is 10Pa, treats that solution is waved。In the argon gas atmosphere containing 5% hydrogen, it is warming up to 400 DEG C, is incubated 2 hours, obtain being filled with the three-dimensional porous silicon dioxide (SiO of metallic nickel₂/ Ni)；

Take carbon source poly furfuryl alcohol and be dissolved in ethanol with aminoguanidine by the ratio of 4:1, add SiO₂/ Ni, ultrasonic disperse 30 minutes, dry 10 hours at 100 DEG C, obtain SiO₂/ Ni/ poly furfuryl alcohol/aminoguanidine presoma；

Above-mentioned sample being warming up to 900 DEG C in argon or nitrogen, passes into hydrogen, ammonia, methane and steam, its ratio is 20:15:10:5sccm, is incubated 30 minutes。It is cooled to room temperature, takes out sample；

Above-mentioned gained sample is soaked in the mixed solution of hydrochloric acid and Fluohydric acid., after 24 hours, filters, by substantial amounts of deionized water and washing with alcohol。The high specific surface area three-dimensional Graphene of dried gained N doping；

The sign of the N doping three-dimensional grapheme of superhigh specific surface area and electro-chemical test are identical with embodiment 1；

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

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

Embodiment 11 superelevation specific surface N doping three-dimensional grapheme

2 grams of graphene oxides, 1 gram of glycine, the ferric nitrate of 1.5 grams are dispersed in the alcohol solvent (100 milliliters) with nano pipe/polyhenylethylene ball, pass through lyophilization, it is thus achieved that three-dimensional porous presoma。Being placed in chemical vapor deposition stove, be warming up to 800 DEG C in argon, pass into hydrogen, ammonia and gaseous carbon sources, its ratio is 20:15:10sccm, is incubated 30 minutes, is cooled to room temperature, takes out sample。Product removes the impurity such as ferrum by nitric acid, prepares specific surface area more than 2000m²The doped graphene of/g；

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

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

Embodiment 12 superelevation specific surface N doping three-dimensional grapheme

2 grams of graphene oxides, 1 gram of glycine, the cobalt nitrate of 3 grams are dispersed in the aqueous solution being contained in containing polymer binder PEG, are heated to 60 DEG C, stir 2 hours, prepare colloid mixing high viscous uniformly。Colloid heats 5 hours in 350 DEG C of Muffle furnaces, slowly deviates from moisture。The char-forming material obtained, by, after simple ball milling, being placed in chemical vapor deposition stove, be warming up to 1100 DEG C in argon or nitrogen, pass into hydrogen, ammonia, methane and ammonia, 20:15:10:10sccm, be incubated 30 minutes, is cooled to room temperature, takes out sample。Product removes the impurity such as catalyst, silicon dioxide by acid, prepares specific surface area 2000m²The doped graphene of/g；

In carbon-based electrode material prepared by the present embodiment, the atomic concentration of doped chemical is 10.8%, the sp of carbon atom²The ratio 76% of hydridization, between nitrogen and carbon, the ratio of pyridine type and pyrroles's type combination is 66%, and in nitrogen element, 66% is avtive spot, produces Faraday pseudo-capacitance, and the specific surface area of carbon-based electrode material is 2840 square metres every gram。

Claims

1. a carbon-based electrode material with super high specific capacitance, it is characterized in that, the electric capacity of described carbon-based electrode material is made up of electric double layer capacitance and Faraday pseudo-capacitance two parts, described electric double layer capacitance accounts for the 20～60% of the electric capacity of described carbon-based electrode material, described carbon-based electrode material specific capacity under the electric current density of 1A/g 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 15 watt-hour more than every liter。

2. the carbon-based electrode material with super high specific capacitance according to claim 1, it is characterised in that the carbon atom in described carbon-based electrode materialsp ²The ratio of hydridization is more than 60%, and the conductivity of described carbon-based electrode material is more than 200 Siemens per centimeter。

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

4. the carbon-based electrode material with super high specific capacitance according to claim 1 and 2, it is characterised in that described carbon-based electrode material in water zeta current potential less than-15mV。

5. the carbon-based electrode material with super high specific capacitance according to any one of claim 1-4, it is characterized in that, described carbon-based electrode material Faraday pseudo-capacitance introduces avtive spot by doped chemical of adulterating and produces, described doped chemical is at least one in nitrogen, boron, phosphorus, sulfur, and the doping of doped chemical is 0.5%-20%。

6. the carbon-based electrode material with super high specific capacitance according to claim 5, it is characterised in that be combined with charged ion by described doped chemical, occurs redox reaction to introduce described avtive spot。

7. the carbon-based electrode material with super high specific capacitance according to claim 5 or 6, it is characterised in that the combination between described doped chemical and carbon atom includes doping in ring, border doping and height defective bit doping。

8. according to described carbon-based electrode material arbitrary in claim 5-7, it is characterized in that, described doped chemical is nitrogen, and in described carbon-based electrode material, the combination of nitrogen and carbon comprises pyridine type, pyrroles's type and graphite mould three kinds, and wherein the ratio shared by pyridine type and pyrroles's type is more than 70%。

9. according to described carbon-based electrode material arbitrary in claim 5-8, it is characterised in that described carbon-based electrode material is the mesoporous Graphene of described doped chemical high-ratio surface of adulterating, carbon atom in the mesoporous Graphene of described high-ratio surfacesp ²The ratio of hydridization is more than 80%, and specific surface area is 1500 square metres more than every gram, and conductivity is more than 400 Siemens per centimeter, and the number of plies of Graphene is 3-5 layer。

10. carbon-based electrode material according to claim 9, it is characterised in that doping high specific surface area three-dimensional Graphene, there is the conductive network of three-dimensional communication, its conductivity is more than 300 Siemens per centimeter, and specific surface area is more than 2000 square metres every gram, and its density is less than 0.1 gram every cubic centimetre。

11. the carbon-based electrode material according to any one of claim 1-10, it is characterised in that described carbon-based electrode material comprises mesoporous and two kinds of pore passage structures of micropore, and the pore diameter range of described micropore is 0.5 2 nanometers, and mesoporous pore diameter range is 2 20 nanometers。

12. one kind includes the combination electrode material of arbitrary described carbon-based electrode material in claim 1-11, it is characterized in that, described composite is composited by the described carbon-based electrode material with different oxidation-reduction potential, or is composited by described carbon-based electrode material metallizing thing and/or conducting polymer。

13. combination electrode material according to claim 12, it is characterized in that, described metallic compound includes at least one in manganese oxide, nickel oxide, cobalt oxide, niobium oxide, tantalum oxide, ruthenium-oxide, titanium sulfide, molybdenum sulfide, vanadic sulfide, sulfuration tantalum, selenizing vanadium, selenizing tantalum, and described conducting polymer includes polyaniline, polypyrrole and/or polythiophene。