CN107331530A - A kind of low-temperature-doped graphene and preparation method thereof and ultracapacitor - Google Patents
A kind of low-temperature-doped graphene and preparation method thereof and ultracapacitor Download PDFInfo
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- CN107331530A CN107331530A CN201710493810.9A CN201710493810A CN107331530A CN 107331530 A CN107331530 A CN 107331530A CN 201710493810 A CN201710493810 A CN 201710493810A CN 107331530 A CN107331530 A CN 107331530A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a kind of preparation method of low-temperature-doped graphene, comprise the following steps：The dispersion liquid of graphene oxide and reducing agent are mixed, in 40~120 DEG C of reactions, doped graphene is obtained；The reducing agent is aminoguanidine, 1,3 diaminoguanidine, triaminoguanidine, thiosemicarbazide, any one or more in guanyl thiourea and thio methylhydrazine.The preparation method that the present invention is provided, using specific reductant, plays a part of reducing and adulterates, reaction condition is not only gentle but also simple simultaneously to graphene oxide at low temperature, and a step can prepare doped graphene, and nitrating and to mix sulfur content all very high.
Description
Technical field
The present invention relates to material chemistry technical field, more particularly to a kind of low-temperature-doped graphene and preparation method thereof and super
Level capacitor.
Background technology
With the development of the social economy, more and more severeer the problem of energy crisis, development green energy resource is particularly important.
Ultracapacitor as a kind of new type of energy storage device, have the advantages that to have extended cycle life, power density it is high so as to causing everybody
Extensive concern.Capacitor can be divided into double layer capacitor and fake capacitance capacitor according to energy storage mechnism.Double layer capacitor is
Electric charge is stored by charge effect；By electrode active material redox reaction to occur for fake capacitance capacitor store electricity
Lotus.But compared to battery, relatively low (the ＜ 10W h kg of energy density of most commercial ultracapacitor-1), it is difficult to meet
Growing energy demand, so electrode material of the development with bigger serface, high conductivity and structural stability is to close
Key.
Graphene has unique two-dimensional structure, outstanding theoretical specific surface area (2600m2/ g), it is high conductivity, good
The advantages of mechanical performance, chemical stability, so as to have great potentiality in terms of ultracapacitor.However, current graphene
The capacitance of ultracapacitor is still much lower than its theoretical value (550F g-1), limit the large-scale application of grapheme material.
Because π-π interactions very strong between graphene film and Van der Waals force promote stacking between piece, so that specific surface area
Reduction, causes the reduction of capacitance.
At this stage, the developing direction of graphene ultracapacitor is intended to increase its energy density, cost is reduced, while again not
The advantages of sacrificing its excellent power density and cyclical stability.Compromise method has several at present, and one is doping fake capacitance material
Expect (metal oxide, conducting polymer) formation composite, such as polyaniline/graphene, graphene/manganese dioxide, graphite
The hybrid supercapacitors such as alkene/ruthenic oxide, but the capacitor for preparing of this method due to irreversible redox reaction and
The expansion reaction of electrode causes cyclical stability poor (＜ 10000 is enclosed)；By contrast, the method for Heteroatom doping has one
Fixed advantage, such as nitrogen, element sulphur etc..Heteroatomic pair of electrons can significantly regulate and control the characteristic electron of carbon material and in carbon table
Extra functional group is produced on face, not only can increase capacitance by improving fake capacitance, the wetting of graphene can also be increased
Property, electrode material is fully contacted with electrolyte.
But the hetero atom Graphene electrodes material of preparation uniform doping, high content is extremely difficult.Preparation method master at this stage
To be chemical vapor deposition or plasma etching, this method needs the very harsh condition such as HTHP, causes cost ratio
It is higher, also higher is required to experimental facilities, it is difficult to volume production.
Such as Lin, T., et al., Nitrogen-doped mesoporous carbon of
extraordinarycapacitance for electrochemical energy storage.Science,2015.350
(6267):P.1508-1513. it is disclosed, using mesoporous silicon oxide as template, carved using chemical vapor deposition and by template
The method of erosion is prepared for orderly meso-porous carbon material, and chemical vapor deposition needs the condition of a HTHP, and temperature is 1000
DEG C, atmosphere is Ar:CH4:H2:NH3=300:10:20:100.Itrogen content of getter with nitrogen doped is 8~11at%, and capacitance reaches 855F/g.
In addition, also some other methods such as solvent-thermal method, hydro-thermal process etc., the preparation condition of these methods still compares
More harsh, preparation temperature is higher, while the functional group of doping is typically unstable, homogeneity is poor.Preparation process compares simultaneously
Cumbersome, the doped graphene material capacitive property of preparation is low.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of low-temperature-doped graphene and preparation method thereof
And ultracapacitor, doped graphene is prepared by simple, gentle method.
The invention provides a kind of preparation method of low-temperature-doped graphene, comprise the following steps：
The dispersion liquid of graphene oxide and reducing agent are mixed, in 40~120 DEG C of reactions, doped graphene is obtained；
The reducing agent is aminoguanidine, 1,3- diaminoguanidine, triaminoguanidine, thiosemicarbazide, guanyl thiourea and thio first
Any one or more in hydrazine.
Above-mentioned graphene oxide is the graphene oxide prepared by modified Hummers methods, preferably according to lower section
It is prepared by method：
A) graphite flakes are added in the mixed solution of the concentrated sulfuric acid and concentrated phosphoric acid, potassium permanganate is then added, is reacted；
B after) reaction terminates, the concentrated sulfuric acid and concentrated phosphoric acid on upper strata is centrifuged off, sediment is obtained；
C) above-mentioned sediment is reacted in ice-water bath with hydroxylamine hydrochloride, gold is switched to by aubergine to solution colour
Yellow, obtains graphene oxide.
It is preferred that, the volume of the concentrated sulfuric acid, the volume of concentrated phosphoric acid, the quality of graphite flakes, the quality of potassium permanganate
Ratio is (50-100):(4-15):1:(5-10), more preferably (60-70):(7-8):1:(6-8).
Then the graphene oxide being scattered in solvent, obtains dispersion liquid, the concentration of the dispersion liquid is preferably 2~
7mg·mL-1.The solvent is preferably water.
The dispersion liquid of above-mentioned graphene oxide and reducing agent are mixed, reacted under the conditions of 40~120 DEG C, you can mixed
Miscellaneous graphene.
The reducing agent can be nitrating class reducing agent, such as aminoguanidine, 1,3- diaminoguanidine, and triaminoguanidine etc. is preferably
1,3- diaminoguanidine；Or it is co-doped with miscellany reducing agent, such as thiosemicarbazide for nitrogen sulphur, guanyl thiourea or thio methylhydrazine etc., preferably
For thio methylhydrazine.Reducing agent of the present invention can be the combination of any one or more in above-claimed cpd.
The reducing agent and graphene oxide mass ratio are preferably (1-6):1, more preferably 3:1
The pH of above-mentioned reaction is preferably 9~14, and more preferably 12~14.
The temperature of the reaction is preferably 40~120 DEG C, more preferably 60~120 DEG C, in some specific realities of the present invention
Apply in example, the reaction temperature is 60 DEG C.Reaction time is preferably 6~12h, more preferably 12h.
After completion of the reaction, centrifuge washing is carried out to system, to neutrality, you can.The present invention has no special limit to the centrifugation
Fixed, the rotating speed of the centrifugation is preferably 8000rpm.
Present invention also offers a kind of low-temperature-doped graphene, prepared according to above-mentioned preparation method.
Present invention also offers application of the above-mentioned doped graphene in ultracapacitor field is prepared.
Present invention also offers a kind of ultracapacitor, the doped graphene prepared by above-mentioned preparation method or above-mentioned doping
Graphene is prepared.
The ultracapacitor of the above-mentioned doped graphene assembling provided using the present invention, chemical property is very excellent, than
Capacitance is high, has extended cycle life, and energy density is high.
Compared with prior art, the invention provides a kind of preparation method of low-temperature-doped graphene, comprise the following steps：
The dispersion liquid of graphene oxide and reducing agent are mixed, in 40~120 DEG C of reactions, doped graphene is obtained；The reducing agent is
Any one or more in aminoguanidine, 1,3- diaminoguanidine, triaminoguanidine, thiosemicarbazide, guanyl thiourea and thio methylhydrazine.
The preparation method that the present invention is provided, using specific reductant, plays a part of reducing and adulterates simultaneously to graphene oxide, reaction
Condition is not only gentle but also simple, reduction and progress simultaneously of adulterating, and a step can prepare doped graphene, and nitrating and to mix sulfur content all non-
Chang Gao.
Brief description of the drawings
Fig. 1 is the high resolution transmission electron microscopy of the nitrogen-doped graphene material of embodiment 1；
Fig. 2 is the x-ray photoelectron power spectrum spectrogram of the nitrogen-doped graphene material of embodiment 1；
Fig. 3 finely composes comparison diagram for the C 1s XPS of the nitrogen-doped graphene material of embodiment 1 and graphene oxide；
Fig. 4 is the fine spectrograms of nitrogen-doped graphene material N 1s XPS of embodiment 1；
Fig. 5 is under the electrode conditions of embodiment 2 three, the cyclic voltammetry curve of nitrogen-doped graphene ultracapacitor, scanning is fast
Spend for 10~100mV/s；
Fig. 6 is under the electrode conditions of embodiment 2 three, the constant current charge-discharge curve of nitrogen-doped graphene ultracapacitor is electric
Current density is 2~50A/g；
Fig. 7 is under 3 liang of electrode conditions of embodiment, the cyclic voltammetry curve of nitrogen-doped graphene ultracapacitor, scanning is fast
Spend for 5~100mV/s；
Fig. 8 is under 3 liang of electrode conditions of embodiment, the constant current charge-discharge curve of nitrogen-doped graphene ultracapacitor is electric
Current density is 1~10A/g；
Fig. 9 is the cycle life test chart of the nitrogen-doped graphene ultracapacitor of embodiment 3；
Figure 10 is the high-resolution transmission electricity for the nitrogen-doped graphene that embodiment 4 is prepared using 1,3- diaminoguanidine as reducing agent
Sub- microscope figure；
Figure 11 is that the C 1sXPS for the nitrogen-doped graphene that embodiment 4 is prepared using 1,3- diaminoguanidine as reducing agent are fine
Spectrogram；
Figure 12 is that the N 1sXPS for the nitrogen-doped graphene that embodiment 4 is prepared using 1,3- diaminoguanidine as reducing agent are fine
Spectrogram；
Figure 13 be the electrode conditions of embodiment 5 three under, nitrogen, the cyclic voltammetry curve of sulphur codope graphene ultracapacitor,
Sweep speed is 10~100mV/s；
Under Figure 14 is the electrode conditions of embodiment 5 three, nitrogen, sulphur codope graphene ultracapacitor constant current charge-discharge it is bent
Line, current density is 1~50A/g.
Embodiment
The doped graphene provided to further illustrate the present invention with reference to embodiment the present invention and its preparation side
Method and ultracapacitor are described in detail.
Embodiment 1
1st, graphene oxide is prepared by modified Hummers methods
(1) under conditions of ice-water bath, the concentrated phosphoric acid of the 135mL concentrated sulfuric acid and 15mL is added to 250mL reaction bulb
In, 2g graphite flakes, then slow addition 12g potassium permanganate several times are added under conditions of stirring, then turns reaction bulb
In the water-bath for moving on to 50 DEG C, stirring reaction 24h；
(2) after having reacted, product is transferred in centrifuge tube, 10min is centrifuged under 3500rpm rotating speeds, upper strata is removed
Concentrated acid, this is conducive to controlling temperature and protection graphene oxide sheet structure in terminating reaction；
(3) and then by centrifuge tube sediment it is diluted in ice-water bath, hydroxylamine hydrochloride solution is slowly added dropwise, until solution colour
It is changed into golden yellow from aubergine；Using 2mol/L watery hydrochloric acid centrifuge washing repeatedly until removing the metal ion in solution, most
Deionized water centrifuge washing is used afterwards, removes unnecessary acid.
2nd, the preparation of doped graphene material
(1) graphene oxide is scattered in 100mL water, concentration is 2mgmL-1, 0.6g aminoguanidines are added, using hydrogen-oxygen
Changing sodium adjusts pH to be 12 or so, and high-speed stirred reacts 12h under the conditions of 60 DEG C.
(2) after completion of the reaction, multiple centrifuge washing is neutrality to pH under the conditions of 8000rpm, and nitrogen-doped graphene is made
Material.
Take appropriate doped graphene solution or be freeze-dried to carry out material characterization, as a result see Fig. 1~Fig. 4.
Wherein, Fig. 1 is the high resolution transmission electron microscopy of nitrogen-doped graphene material, it will be seen from figure 1 that graphite
Alkene piece shows the thin layer state of similar transparent, shows that graphene film is not stacked.In the curling of marginal existence, belong to stone
The inherent characteristic of black alkene piece.The SEAD figure innermost layer in the upper left corner is 6 diffraction spots of hexagon, and secondary internal layer is many
Brilliant ring, shows that graphene film has the number of plies of certain crystallinity and graphene film fewer, illustrates that aminoguanidine has good
Reproducibility.
Fig. 2 is x-ray photoelectron power spectrum (XPS) spectrogram of nitrogen-doped graphene material, figure it is seen that N doping
There is the signal of an obviously nitrogen in x-ray photoelectron power spectrum (XPS) spectrogram of grapheme material, illustrate nitrogen content very
Height, is 8.23at%.Corresponding elementary analysis test shows that the mass ratio of nitrogen content is 9.62wt%.
Fig. 3 is that the C 1s XPS of nitrogen-doped graphene material and graphene oxide finely compose comparison diagram, in figure 3, oxidation
The C 1s spectrograms of graphene correspond to C-C, C-OH, C=O, O=respectively in 284.7,286.5,287.3 and 288.2eV, tetra- positions
Tetra- kinds of group peaks of C-O.And the C1s spectrograms of corresponding nitrogen-doped graphene piece, the disappearance of C=O functional groups and other oxygen-containing functions
The content of group is reduced.In addition, there is the new peak of a C-N key in 285.92eV place, the doping of nitrogen is represented.
Fig. 4 is the fine spectrograms of nitrogen-doped graphene material N 1s XPS, from the N 1s spectrograms of Fig. 4 nitrogen-doped graphene pieces
Find out, the type of N doping is mainly three kinds of pyridine, pyrroles and graphite nitrogen.The content of pyrroles's nitrogen is occupied an leading position.XPS spectrum chart
Bright aminoguanidine not only as nitrogen source, can make as reducing agent but also at low temperature reduction and the step of N doping one of graphene oxide
Complete.
Under the electrode conditions of embodiment 2 three, the test of doped graphene ultracapacitor chemical property
The concentration of graphene solution is demarcated by the method for freeze-drying, then takes the graphene solution of respective quality to load
In, as working electrode, load capacity is 0.5mg/cm on carbon cloth2, using stainless steel substrates as to electrode, made with Ag/AgCl electrodes
For reference electrode, three electrode tests, test loop volt-ampere curve and constant current charge and discharge are carried out in 1mol/L sulfuric acid electrolyte
Electric curve is as shown in Figures 5 and 6.Fig. 5 cyclic voltammetry curve has obviously redox peaks, demonstrates again that nitrogen-atoms
Doping, under conditions of height sweeps fast 100mV/s, redox peaks still clearly, illustrate electrolyte ion spread
Speed is very fast, and Fig. 6 constant current charge-discharge curve also has corresponding redox platform, while can be calculated according to formula
Go out specific capacitance value and reach 925.55F/g (2A/g).
The assembling of the high specific capacitance doped graphene ultracapacitor of embodiment 3
Graphene solution is taken to be carried on an equal amount of carbon cloth of two panels, load capacity is 0.5mg/cm2, then be soaked in
In sulfuric acid solution so that the abundant impregnation electrolyte solution of electrode material；Then carbon cloth is dipped into a small amount of PVA-H2SO4Solid state electrolysis
Matter, treat its drying after, with PVA-H3PO4Film is that barrier film assembles them into ultracapacitor device, carries out two electrode tests.
As shown in Figures 7 and 8, cyclic voltammetry curve is presented rectangular-shaped, shows this capacitor for cyclic voltammetric and constant current charge-discharge curve
For preferable capacitor.Specific capacitance value reaches 905.52F/g (1A/g, compared with three electrodes), and energy density is up to 31.44W h/
Kg, this is substantially better than the graphene ultracapacitor under same electrolyte.Specific capacitance value does not drop after circulating 10000 times
It is low, illustrate that cycle life is very excellent, the functional group for the nitrogen that adulterates is more stable, as shown in Figure 9.
The preparation of nitrogen-doped graphene material of the embodiment 4 using 1,3- diaminoguanidine as reducing agent
It is that reducing agent is changed to 1,3- diaminoguanidine by aminoguanidine with the difference of the preparation method of embodiment 1.
(1) graphene oxide is scattered in 100mL water, concentration is 2mgmL-1, addition 0.6g 1,3- diaminoguanidine,
Sodium hydroxide is used to adjust pH for 12 or so, high-speed stirred reacts 12h under the conditions of 60 DEG C.
(2) after completion of the reaction, multiple centrifuge washing is neutrality to pH under the conditions of 8000rpm, and nitrogen-doped graphene is made
Electrode material.
Take appropriate doped graphene solution or be freeze-dried to carry out material characterization, as a result see Figure 10~
Figure 12.
Wherein, Figure 10 is the high resolution transmission electron microscopy of nitrogen-doped graphene material, it can be seen that with embodiment
Fig. 1 is similar in 2, and graphene film shows the lamelliform of similar transparent, shows that graphene film thickness is several layers of for minority.Compared to it
Under, Fig. 6 diffraction spot of SEAD in the lower left corner becomes apparent, and shows the graphene film crystallinity of diaminoguanidine reduction
More preferably, structure is more regular.Figure 11 is the fine spectrograms of C 1s XPS of nitrogen-doped graphene material, equally with graphene oxide phase
Than C=O functional groups are disappeared and the content of other oxygen-containing functional groups is reduced.Show that diaminoguanidine can be realized at low temperature
The reduction of graphene.In addition, there is the new peak of a C-N key in 285.92eV place, the doping of nitrogen is represented.Figure 12 N 1s
The fine spectrograms of XPS show that nitrogen content is 7.82at%, and the type of N doping is mainly three kinds of pyridine, pyrroles and graphite nitrogen, wherein
Based on pyrroles's nitrogen.Above spectrogram it is provable at low temperature, 1.3- diaminoguanidine not only can be as reducing agent but also can conduct
Nitrogen source, while completing the reduction of graphene oxide and the doping of high content nitrogen atom.
Nitrogen, the preparation of sulphur codope graphene and its performance of the supercapacitor of the embodiment 5 using thio methylhydrazine as reducing agent
Test
1st, the preparation of nitrogen sulphur codope graphene
(1) graphene oxide is scattered in 100mL water, concentration is 2mgmL-1, the thio methylhydrazines of 0.6g are added, using hydrogen
Sodium oxide molybdena adjusts pH to be 12 or so, and high-speed stirred reacts 12h under the conditions of 60 DEG C.
(2) after completion of the reaction, multiple centrifuge washing is neutrality to pH under the conditions of 8000rpm, and nitrogen, sulphur codope stone is made
Black alkene electrode material.
Take appropriate nitrogen sulphur codope graphene film to carry out freeze-drying and carry out elementary analysis test, as a result show the content of nitrogen
For 3.45wt%, the content of sulphur is 2.26wt%, it was demonstrated that realize nitrogen sulphur codope at low temperature.
2nd, the test of performance of the supercapacitor
It is same as Example 2, the concentration of graphene solution is demarcated by the method for freeze-drying, respective quality is then taken
Graphene solution is carried on carbon cloth as working electrode, and load capacity is 0.5mg/cm2, using stainless steel substrates as to electrode,
Using Ag/AgCl electrodes as reference electrode, three electrode tests are carried out in 1mol/L sulfuric acid electrolyte, test loop volt-ampere is bent
Line and constant current charge-discharge curve are as shown in FIG. 13 and 14.The specific capacitance value of nitrogen sulphur codope ultracapacitor can be calculated
For 835.6F/g (1A/g).
From above-described embodiment, the present invention prepares doped graphene material using a kind of method of simplicity as mild as a dove,
Temperature is only 60 DEG C, at a lower temperature, has been successfully prepared the carbon material of Heteroatom doping, and reduce and one step of doping
Complete, enormously simplify experimental procedure, cost is low, suitable volume production.The doped graphene material nitrogen atom doping and/or sulphur of preparation
Atom doped content is very high.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (9)
1. a kind of preparation method of low-temperature-doped graphene, it is characterised in that comprise the following steps：
The dispersion liquid of graphene oxide and reducing agent are mixed, in 40~120 DEG C of reactions, doped graphene is obtained；
The reducing agent is aminoguanidine, 1,3- diaminoguanidine, triaminoguanidine, thiosemicarbazide, in guanyl thiourea and thio methylhydrazine
Any one or more.
2. preparation method according to claim 1, it is characterised in that the graphene oxide dispersion be concentration 2~
7mg·mL-1Graphene oxide dispersion.
3. preparation method according to claim 1, it is characterised in that the graphene oxide is prepared in accordance with the following methods：
A) graphite flakes are added in the mixed solution of the concentrated sulfuric acid and concentrated phosphoric acid, potassium permanganate is then added, is reacted；
B after) reaction terminates, the concentrated sulfuric acid and concentrated phosphoric acid on upper strata is centrifuged off, sediment is obtained；
C) above-mentioned sediment is reacted in ice-water bath with hydroxylamine hydrochloride, golden yellow is switched to by aubergine to solution colour,
Obtain graphene oxide.
4. preparation method according to claim 3, it is characterised in that the volume of the concentrated sulfuric acid, the volume of concentrated phosphoric acid, stone
The quality of black scale, the ratio of the quality of potassium permanganate are (50-100):(4-15):1:(5-10).
5. preparation method according to claim 1, it is characterised in that the reducing agent is with graphene oxide mass ratio
(1-6):1。
6. preparation method according to claim 1, it is characterised in that the pH of the reaction is 9~14.
7. preparation method according to claim 1, it is characterised in that the time of the reaction is 6~12h.
8. a kind of low-temperature-doped graphene, it is characterised in that prepared according to the preparation method described in any one of claim 1~7
Obtain.
9. a kind of ultracapacitor, it is characterised in that the doping prepared as the preparation method described in any one of claim 1~7
Doped graphene described in graphene or claim 8 is prepared.
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