CN108538628A - A kind of flexibility titanium nitride-polypyrrole nano column array material and its preparation method and application - Google Patents
A kind of flexibility titanium nitride-polypyrrole nano column array material and its preparation method and application Download PDFInfo
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- CN108538628A CN108538628A CN201810555706.2A CN201810555706A CN108538628A CN 108538628 A CN108538628 A CN 108538628A CN 201810555706 A CN201810555706 A CN 201810555706A CN 108538628 A CN108538628 A CN 108538628A
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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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 present invention relates to a kind of preparation method and application of flexible titanium nitride polypyrrole nano column array material, the described method comprises the following steps：S1. using graphite paper as base material, nano titania column array material is grown on its surface, obtains the graphite paper of carried titanium dioxide nano column array；S2. the graphite paper of carried titanium dioxide nano column array is subjected to nitrogen treatment, obtains the graphite paper of load titanium nitride nano column array；S3. general pulse voltammetry is used, polypyrrole is deposited on the graphite paper of load titanium nitride nano column array, obtains flexible titanium nitride polypyrrole nano column array material.The titanium nitride polypyrrole nano column array material that the present invention is prepared using graphite paper as base material, since the good conductivity of titanium nitride nano column, specific surface are big, and each titanium nitride nano column surface is fully wrapped around by one layer of uniform polypyrrole, improves the capacitive properties of material.
Description
Technical field
The present invention relates to novel energy resource material technology field more particularly to a kind of flexible titanium nitride-polypyrrole nano column arrays
Material and its preparation method and application.
Background technology
With the increasingly depleted of the non-renewable resources such as coal, oil, natural gas, the exploitation of new energy materials and energy storage device
It is current global important topic.Wherein, the research of ultracapacitor increasingly obtains extensive concern, and becomes novel energy-storing device
One research hotspot of part.Ultracapacitor, i.e. electrochemical capacitor, with charge/discharge rates are fast, efficiency for charge-discharge is high, power
Density is high, have extended cycle life, the safe and many merits such as at low cost, electric vehicle, mobile communication, information technology,
The fields such as mobile electronic device and aerospace have broad application prospects.
Electrode material is the key factor for determining performance of the supercapacitor, main property of the Nomenclature Composition and Structure of Complexes to capacitor
Can, as specific capacitance, internal resistance and cycle life suffer from conclusive influence.Therefore, the electricity with high-energy-density and high-specific-power
The preparation of pole material is the core topic of ultracapacitor research.Currently, the electrode material of ultracapacitor mainly has carbon material
(carbon black, activated carbon, graphene, carbon nanotube, carbon nano-fiber etc.), metal oxide (RuO2、IrO2、NiO、MnO2、CoOx、
V2O5、MoO3Deng) and conducting polymer (polypyrrole, polythiophene, polyaniline etc. and its derivative).Wherein, polypyrrole
(polypyrrole, PPy) is used as a kind of typical conducting polymer, has conductivity height, electrochemical reversibility strong, chemical steady
The advantages that qualitative good, easy film forming, nontoxic, easily prepared and doping, be a kind of electrode of super capacitor having very much development potentiality
Material.However, merely using polypyrrole as capacitor electrode material, internal resistance is larger, high power discharge performance and long-term charge and discharge
The stability of cycle is poor.
Metal nitride has excellent electron conduction and high specific capacity, is a kind of novel electrode material.Nitridation
Conductivity (the 4000-55500Scm of the superelevation of titanium-1) and mechanical stability make the super electricity for having very much development potentiality
The electrode material of container, but titanium nitride nano material easily falling off from electrode surface, it is unstable.
In conclusion there is also many defects for the electrode material of existing ultracapacitor, reality cannot be met well
The demand of application, therefore, it is necessary to be improved to electrode material for super capacitor.
Invention content
For the above problem of the prior art, the object of the present invention is to provide a kind of flexible titanium nitride-polypyrrole nano-pillars
Array material and its preparation method and application.
In order to solve the above technical problem, the present invention provides a kind of flexible titanium nitride-polypyrrole nano column array materials
Preparation method, include the following steps：
S1. using graphite paper as base material, nano titania column array material is grown on its surface, obtains load two
The graphite paper of TiOx nano column array；
S2. the graphite paper of the carried titanium dioxide nano column array is subjected to nitrogen treatment, obtains load titanium nitride and receives
The graphite paper of rice column array；
S3. general pulse voltammetry is used, polypyrrole is deposited on the graphite paper of the load titanium nitride nano column array,
Obtain flexible titanium nitride-polypyrrole nano column array material.
Preferably, the step S1 includes the following steps：
S101., graphite paper is cut into certain size, then acetone and water is used to carry out supersound washing successively, dried later
It is dry, graphite paper after being pre-processed；
S102. titanium source is added in reaction vessel, absolute ethyl alcohol is added while stirring, glacial acetic acid is then added, constantly stirs
It mixes to reaction solution and is creamy white, obtain TiO 2 sol；
Wherein step S101 and step S102 interchangeable sequences；
S103. graphite paper after the pretreatment is impregnated in the TiO 2 sol, in graphite paper adsorption two
Titanium dioxide nanoparticle obtains the graphite paper of carried titanium dioxide nano particle；
S104. the graphite paper of the carried titanium dioxide nano particle is placed in hydrochloric acid and the mixed solution of titanium source and is carried out
Hydro-thermal reaction grows the nano titania column array on graphite paper surface, obtains the carried titanium dioxide nano-pillar battle array
The graphite paper of row.
Preferably, titanium source described in step S102 and the volume ratio of the absolute ethyl alcohol are 1:4-1:20, the glacial acetic acid
Volume ratio with the titanium source is 1:50-1:250.
Preferably, the titanium source is any one in butyl titanate, tetraethyl titanate, isopropyl titanate, titanium tetrachloride.
Further, the step S103 is specially：
Graphite paper after the pretreatment is impregnated into 5-10min in the TiO 2 sol, is then taken out in 60-80 DEG C
Lower drying, and at 300-400 DEG C keep the temperature 10-30min after cooled to room temperature, obtain carried titanium dioxide nano particle
Graphite paper.
Further, the step S104 includes the following steps：
S1041. it is 1 according to volume ratio with deionized water by concentrated hydrochloric acid that mass concentration is 36-38%:1 mixing, then adds
Enter titanium source, the volume ratio of the titanium source and the concentrated hydrochloric acid is 1:25-1:60, it stirs and evenly mixs up to the hydrochloric acid and the titanium source
Mixed solution；
S1042. the graphite paper of carried titanium dioxide nano particle described in step S103 is put into reaction vessel, then
The mixed solution of the hydrochloric acid and the titanium source is added into the reaction vessel, 4-20h is reacted at 150-200 DEG C, washs
And dry, obtain the graphite paper head product of carried titanium dioxide nano column array；
S1043. the graphite paper head product of the carried titanium dioxide nano column array is subjected to calcination processing, calcination temperature
It it is 400-600 DEG C, time 1-3h obtains the graphite paper of carried titanium dioxide nano column array.
Preferably, the step S1043 is specially：
The graphite paper head product of the carried titanium dioxide nano column array is placed in program-controlled high temperature furnace and is carried out at calcining
Reason, the temperature setting of the program-controlled high temperature furnace are specially：With 3-10 DEG C of min-1Rate be warming up to 250-300 DEG C, and
Calcining at constant temperature 10-15min at 250-300 DEG C, then with 3-10 DEG C of min-1Rate be warming up to 400-600 DEG C, then in 400-
Calcining at constant temperature 1-3h, is finally cooled to room temperature at 600 DEG C.
Further, the step S2 is specially：
Nitrogen treatment, the stream of the ammonia are carried out to the graphite paper of the carried titanium dioxide nano column array using ammonia
Amount is 30-100mLmin-1, reaction temperature is 700-1000 DEG C.
Preferably, the nitrogen treatment is specially：Using high-purity ammonia to the carried titanium dioxide nano column array
Graphite paper is restored, and the flow of ammonia is 30-100mLmin-1；Reaction temperature is specially：With 3-10 DEG C of min-1Speed
Rate is warming up to 250-300 DEG C, then with 2-5 DEG C of min-1Rate be warming up to 700 DEG C, then with 1-2 DEG C of min-1Rate liter
Temperature is to 800-1000 DEG C, and the calcining at constant temperature 1h at 800-1000 DEG C, finally with 5-10 DEG C of min-1Rate be cooled to 50 DEG C,
Terminate program.
Further, the step S3 includes the following steps：
S301. acetonitrile, lithium perchlorate and pyrroles is added into reaction vessel successively, is uniformly mixed, obtains depositing molten
The mass ratio of liquid, the lithium perchlorate and the acetonitrile is 1:50-1:100, the mass ratio of the pyrroles and the acetonitrile is 1:
50-1:150；
S302. it is ginseng with saturated calomel electrode using the graphite paper of the load titanium nitride nano column array as working electrode
Than electrode, using platinized platinum as auxiliary electrode, polypyrrole is deposited using general pulse voltammetry in the deposition solution, obtains flexibility
Titanium nitride-polypyrrole nano column array material；The parameter setting of the general pulse voltammetry is as follows：Initial voltage is 0.7V,
Final voltage is 1.1V, and current potential increment is 0.001-0.004Vs-1, pulse width 0.06s, pulse period 1-10s are adopted
Sample width is 0.02s, quiescent time 2s.
The present invention also provides a kind of flexible titanium nitride-polypyrrole nano column array materials, and base material is graphite paper,
Growth has the more titanium nitride nano column arrays being in the form of a column, the every titanium nitride nano column array equal by one layer on graphite paper
Even polypyrrole is fully wrapped around.
The present invention also provides a kind of applications of flexible titanium nitride-polypyrrole nano column array material, by the poly- pyrrole of titanium nitride-
Nano column array material is coughed up as electrode material to be applied in ultracapacitor.
The present invention has the advantages that：
(1) present invention is using graphite paper as base material, it is conductive it is good, property is stable, cheap and flexible etc.
Advantage, grows nano titania column and is nitrogenized on graphite paper and obtain titanium nitride nano column, the size of titanium nitride nano column with
It is little compared to variation before nitridation, but its surface is more coarse, and this coarse surface can dramatically increase the surface area of material, favorably
In the raising of its specific capacitance.
(2) the titanium nitride nano column array that the present invention is grown on graphite paper is in the form of a column, and is separated from each other, is conducive to polypyrrole
Ion transmission in electrolyte transport and charge and discharge process in deposition process.
(3) present invention further deposited polypyrrole using general pulse voltammetry on titanium nitride nano column surface, play
The synergisticing performance of titanium nitride and polypyrrole, improves capacitance, the cycle life of composite material, optimizes high-power charge and discharge
Performance, while titanium nitride nano material falling off from electrode surface also can be effectively prevented, improve the stability of composite material.It will
Titanium nitride prepared by the present invention-electrode material of the polypyrrole nanocomposite as ultracapacitor, not only overcomes poly- pyrrole
The poor problem of the stability of larger material resistance, high power discharge performance and long-term charge and discharge cycles is coughed up, while overcoming nitrogen
Change the unstable defect of titanium nano material.
(4) flexible titanium nitride-polypyrrole nano column array material prepared by the present invention, due to the conduction of titanium nitride nano column
Property is good, specific surface is big, and each titanium nitride nano column is fully wrapped around by one layer of uniform polypyrrole, improves the capacitance of material
Property.
Description of the drawings
It, below will be to required in embodiment or description of the prior art in order to illustrate more clearly of technical scheme of the present invention
The attached drawing used is briefly described.It should be evident that drawings in the following description are only some embodiments of the invention, it is right
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings
Its attached drawing.
Fig. 1 is the SEM figures of the graphite paper of carried titanium dioxide nano column array in the present invention；
Fig. 2 is the SEM figures of titanium dioxide in the present invention-polypyrrole nano column array material；
Fig. 3 is the SEM figures for the graphite paper that titanium nitride nano column array is loaded in the present invention；
Fig. 4 is the SEM figures of titanium nitride in the present invention-polypyrrole nano column array material；
Fig. 5 is the SEM figures of graphite paper-polypyrrole material in the present invention；
Fig. 6 is the graphite paper of carried titanium dioxide nano column array and load titanium nitride nano column array material in the present invention
Graphite paper XRD spectra；
Fig. 7 is graphite paper-polypyrrole material in the present invention, titanium dioxide-polypyrrole nano column array material and flexible nitrogen
Change the Raman spectrogram of titanium-polypyrrole nano column array material；
Fig. 8 is cyclic voltammetry curve figure of the graphite paper under different scanning rates in the present invention；
Fig. 9 is cyclic voltammetric of the graphite paper of carried titanium dioxide nano column array in the present invention under different scanning rates
Curve graph；
Figure 10 is that cyclic voltammetric of the graphite paper of titanium nitride nano column array under different scanning rates is loaded in the present invention
Curve graph；
Figure 11 is graphite paper in the present invention, the graphite paper of carried titanium dioxide nano column array and load titanium nitride nano column
The graphite paper of array is in 20mVs-1Cyclic voltammetry curve figure under sweep speed；
Figure 12 is graphite paper in the present invention, the graphite paper of carried titanium dioxide nano column array and load titanium nitride nano column
Area specific capacitance curve graph of the graphite paper of array under different scanning rates；
Figure 13 is graphite paper in the present invention, the graphite paper of carried titanium dioxide nano column array and load titanium nitride nano column
The graphite paper of array is 1mAcm in current density-2When charging and discharging curve figure；
Figure 14 is graphite paper the filling under different charging and discharging currents density that titanium nitride nano column array is loaded in the present invention
Discharge curve；
Figure 15 is that the quality specific capacitance for the graphite paper that titanium nitride nano column array is loaded in the present invention is close with charging and discharging currents
The variation relation figure of degree；
Figure 16 is cyclic voltammetry curve figure of the graphite paper-polypyrrole material under different scanning rates in the present invention；
Figure 17 is titanium dioxide in the present invention-cyclic voltammetric of the polypyrrole nano column array material under different scanning rates
Curve graph；
Figure 18 is cycle volt of the flexible titanium nitride-polypyrrole nano column array material under different scanning rates in the present invention
Pacify curve graph；
Figure 19 is graphite paper-polypyrrole material in the present invention, titanium dioxide-polypyrrole nano column array material and flexible nitrogen
It is 20mVs to change titanium-polypyrrole nano column array material in sweep speed-1When cyclic voltammetry curve figure；
Figure 20 is graphite paper-polypyrrole material in the present invention, titanium dioxide-polypyrrole nano column array material and flexible nitrogen
Change area specific capacitance curve graph of the titanium-polypyrrole nano column array material under different scanning rates；
Figure 21 is graphite paper-polypyrrole material in the present invention, titanium dioxide-polypyrrole nano column array material and flexible nitrogen
It is 1mAcm to change titanium-polypyrrole nano column array material in current density-2When charging and discharging curve figure；
Figure 22 is charging and discharging curve figure of the graphite paper-polypyrrole material under different current densities in the present invention；
Figure 23 is that charge and discharge of titanium dioxide in the present invention-polypyrrole nano column array material under different current densities are bent
Line chart；
Figure 24 is flexible titanium nitride-charge and discharge of the polypyrrole nano column array material under different current densities in the present invention
Curve graph；
Figure 25 is graphite paper-polypyrrole material in the present invention, titanium dioxide-polypyrrole nano column array material and flexible nitrogen
Change titanium-quality of the polypyrrole nano column array material under different current densities than capacitance curve figure.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art obtained without making creative work it is all its
His embodiment, shall fall within the protection scope of the present invention.
Embodiment 1
The present embodiment provides a kind of preparation methods of flexible titanium nitride-polypyrrole nano column array material, including following step
Suddenly：
S1. using graphite paper as base material, nano titania column array material is grown on its surface, obtains load two
The graphite paper of TiOx nano column array；
The step S1 includes the following steps：
S101., graphite paper is cut into the small pieces of 50mm × 20mm × 0.10mm, then acetone and water is used to carry out successively
Supersound washing 10min is dried at 80 DEG C later, graphite paper after being pre-processed；
S102. it takes 10mL butyl titanates in 100mL beakers, is slowly added to 50mL absolute ethyl alcohols while stirring, then
0.1mL glacial acetic acids are added, is stirred continuously to reaction solution is creamy white at room temperature, obtain TiO 2 sol；
S103. graphite paper after the pretreatment is impregnated into 5min in the TiO 2 sol, then taken out in 80 DEG C
Lower drying, and place it in program-controlled high temperature furnace 20min is kept the temperature at 350 DEG C after cooled to room temperature, obtain load dioxy
Change the graphite paper of titanium nano particle；
S104. the graphite paper of the carried titanium dioxide nano particle is placed in hydrochloric acid and the mixed solution of titanium source and is carried out
Hydro-thermal reaction grows the nano titania column array on graphite paper surface, obtains the carried titanium dioxide nano-pillar battle array
The graphite paper of row；
The step S104 includes the following steps：
S1041. it takes 18mL deionized waters in 50mL beakers, the concentrated hydrochloric acid that 18mL mass concentrations are 36-38% is added, stirs
5min is mixed, 0.54mL butyl titanates are then added, quickly stir 10min, obtains the hydrochloric acid and the butyl titanate
Mixed solution；
S1042. the graphite paper of the carried titanium dioxide nano particle is put into the reaction kettle polytetrafluoroethylene (PTFE) of 50mL
In lining, the mixed solution of the hydrochloric acid and the butyl titanate is then added, reacts 10h at 180 DEG C；After reaction,
Cooled to room temperature is respectively formed one layer of whiteness in the tow sides of graphite paper, and gained sample is rushed repeatedly with deionized water
The reaction solution for removing material remained on surface is removed, dries, obtains the graphite paper head product of carried titanium dioxide nano column array, it is described
Nano titania column in head product is unformed shape；
S1043. the graphite paper head product of the carried titanium dioxide nano column array is placed in program-controlled high temperature furnace and is carried out
The temperature setting of calcination processing, the program-controlled high temperature furnace is specially：With 5 DEG C of min-1Rate be warming up to 250 DEG C, and 250
Calcining at constant temperature 10min at DEG C, then with 5 DEG C of min-1Rate be warming up to 500 DEG C, the then calcining at constant temperature 1.5h at 500 DEG C, most
Postcooling obtains the graphite paper of carried titanium dioxide nano column array (referred to as to room temperature：GP/TiO2-NRAs)；At calcining
After reason, nano titania column array is converted into more orderly regular rutile crystal type from unformed.
S2. the graphite paper of the carried titanium dioxide nano column array is placed in tube furnace, using high-purity ammonia to it
It is restored, the flow of ammonia is 50mLmin-1；Reaction temperature is specially：With 5 DEG C of min-1Rate be warming up to 300 DEG C,
Then with 2 DEG C of min-1Rate be warming up to 700 DEG C, then with 1 DEG C of min-1Rate be warming up to 900 DEG C, and at 900 DEG C
Calcining at constant temperature 1h, finally with 5 DEG C of min-1Rate be cooled to 50 DEG C, terminate program, then cooled to room temperature, is born
Carry the graphite paper of titanium nitride nano column array (referred to as：GP/TiN-NRAs)；
S3. general pulse voltammetry is used, polypyrrole is deposited on the graphite paper of the load titanium nitride nano column array,
Obtain flexible titanium nitride-polypyrrole nano column array material；
The step S3 includes the following steps：
S301. it takes 50mL acetonitriles in beaker, tri- perchloric acid hydrate lithiums of 0.81g is added, stirring makes it completely dissolved, then
0.52mL pyrroles is added, is uniformly mixed, obtains deposition solution；
S302. it is ginseng with saturated calomel electrode using the graphite paper of the load titanium nitride nano column array as working electrode
Than electrode, using platinized platinum as auxiliary electrode, polypyrrole is deposited using general pulse voltammetry in the deposition solution, obtains flexibility
Titanium nitride-polypyrrole nano column array material；The parameter setting of the general pulse voltammetry is as follows：Initial voltage is 0.7V,
Final voltage is 1.1V, and current potential increment is 0.001Vs-1, pulse width 0.06s, pulse period 4s, sampling width is
0.02s, quiescent time 2s；After deposition process, the working electrode is taken out, is rinsed repeatedly using deionized water, so
Room temperature is dried to get flexible titanium nitride-polypyrrole nano column array material (referred to as afterwards：GP/TiN-NRA/PPy).
Comparative example 1
Using the method for embodiment 1, polypyrrole is deposited on graphite paper surface, obtains graphite paper-polypyrrole material (referred to as：
GP/PPy)。
Comparative example 2
Using the method for embodiment 1, polypyrrole is deposited on the graphite paper surface of carried titanium dioxide nano column array, is obtained
Titanium dioxide-polypyrrole nano column array material is (referred to as：GP/TiO2-NRA/PPy)。
Embodiment 2
Graphite paper, load titanium nitride nano column of the present embodiment using scanning electron microscope to carried titanium dioxide nano column array
Graphite paper, graphite paper-polypyrrole material, titanium dioxide-polypyrrole nano column array material and the poly- pyrrole of flexible titanium nitride-of array
The appearance structure for coughing up nano column array material is studied.
Fig. 1 is the SEM figures of the graphite paper of carried titanium dioxide nano column array in the present invention.As shown, titanium dioxide
Nano-pillar is in four prism type, and width 200-350nm, cylinder is smooth, and each nano-pillar is about 15nm's by multiple width
Nano titania column high-sequential close-packed arrays form；It is separated from each other between nano titania column, this structure is conducive to
Ion of the titanium dioxide into the conversion of titanium nitride and charge and discharge process in electrolyte is transmitted to electrode surface in nitridation process.Figure
3 be the SEM figures for the graphite paper that titanium nitride nano column array is loaded in the present invention.As shown, institute's shape after high-temperature ammonolysis is handled
At titanium nitride nano column array be still in the form of a column, be separated from each other, this be conducive to deposit polypyrrole during electrolyte transport and
Ion transmission in charge and discharge process；The size of titanium nitride nano column changes less compared with before nitridation, but its surface is more thick
Rough, this coarse surface can dramatically increase the surface area of material, be conducive to the raising of its specific capacitance.Fig. 2 is two in the present invention
The SEM of titanium oxide-polypyrrole nano column array material schemes, and Fig. 4 is titanium nitride in the present invention-polypyrrole nano column array material
SEM schemes.As shown, a strata pyrroles is equably wrapped in the surface of nano column array, titanium dioxide-polypyrrole nano-pillar battle array
The nano-pillar of row material and flexible titanium nitride-polypyrrole nano column array material surface is apparent compared with depositing before polypyrrole to be become
Thick, showing can be in the graphite paper and load titanium nitride nano column of carried titanium dioxide nano column array with general pulse voltammetry
The graphite paper surface of array deposits one layer of uniform polypyrrole；In addition, flexible titanium nitride-polypyrrole nano column array material surface
Polypyrrole layer be obviously thicker than the polypyrrole layer of titanium dioxide-polypyrrole nano column array material surface, this be by titanium nitride compared with
Caused by high electric conductivity.Fig. 5 is the SEM figures of graphite paper-polypyrrole material in the present invention.As shown, in the table of graphite paper
Face is covered with a strata pyrroles, although being formed by the rough-shape state in polypyrrole surface, compared with polypyrrole nano column array,
Its specific surface greatly reduces, and this structure of graphite paper surface polypyrrole layer will cause its specific capacitance to be significantly less than polypyrrole to receive
Rice column array material.
Embodiment 3
The present embodiment characterizes the composition of material using XRD spectra and Raman spectrum.Fig. 6 is loaded in the present invention
The XRD spectra of the graphite paper of nano titania column array and the graphite paper of load titanium nitride nano column array material.Load two
Diffraction maximum in the spectrogram of the graphite paper of TiOx nano column array at 27.6 °, 36.2 °, 41.4 ° and 54.5 ° corresponds respectively to
Hkl (110), hkl (101), hkl (111) and hkl (211) crystal face of red schorl phase titanium dioxide；The spectrogram of GP/TiN-NRAs
In diffraction maximum at 37.0 °, 42.9 ° and 62.4 ° correspond respectively to the hkl (111), hkl (200) and hkl of cubic phase titanium nitride
(220) crystal face, and the characteristic peak of red schorl phase titanium dioxide substantially completely disappears in spectrogram.Therefore, this is in acid medium
The nano titania column of the graphite paper sample surfaces of the middle carried titanium dioxide nano column array prepared using hydrothermal synthesis method
For Rutile Type, and after high-temperature ammonolysis is handled, the titanium dioxide of Rutile Type is completely transformed into the nitridation of cubic phase substantially
Titanium.
Fig. 7 is graphite paper-polypyrrole material in the present invention, titanium dioxide-polypyrrole nano column array material and flexible nitrogen
Change the Raman spectrogram of titanium-polypyrrole nano column array material.As shown, the characteristic peak positions of this three sample Raman spectrums
It is essentially the same, it is the characteristic peak of polypyrrole, wherein 1586cm-1、1493cm-1And 1375cm-1The scattering peak at place is by gathering respectively
Caused by the stretching vibration of C=C, C-C and C-N in pyrroles's molecule, 1240cm-1The scattering peak at place is curved in the face by c h bond
Caused by Qu Zhendong, 1073cm-1And 925cm-1The scattering peak at place corresponds to the deformation vibration of c h bond.Therefore, this three kinds of materials
Surface be completely covered by one layer of polypyrrole layer, result is consistent shown in this SEM figure with sample.
Embodiment 4
The present embodiment is respectively with graphite paper, the graphite paper of carried titanium dioxide nano column array, load titanium nitride nano column
Graphite paper, graphite paper-polypyrrole material, titanium dioxide-polypyrrole nano column array material and the poly- pyrrole of flexible titanium nitride-of array
Nano column array material is coughed up as working electrode, is to electrode, using saturated calomel electrode as reference electrode, with 1mol with platinized platinum
L-1Sulfuric acid is test solution, its chemical property is tested using cyclic voltammetry and constant current charge-discharge method.Wherein, cyclic voltammetric
The scanning potential region of curve test is 0-0.6V (relative to saturated calomel electrode), and electrode area is 1cm2。
Fig. 8 is cyclic voltammetry curve figure of the graphite paper under different scanning rates in the present invention, and Fig. 9 is loaded in the present invention
Cyclic voltammetry curve figure of the graphite paper of nano titania column array under different scanning rates, Figure 10 are loaded in the present invention
Cyclic voltammetry curve figure of the graphite paper of titanium nitride nano column array under different scanning rates, different in figure curve is corresponding sweeps
It is as follows to retouch rate：(a)5mV·s-1；(b)10mV·s-1；(c)20mV·s-1；(d)50mV·s-1；(e)100mV·s-1；(f)
200mV·s-1.As shown, the cyclic voltammetry curve of this three kinds of electrode materials is in approximate rectangular shape, show electrode material
Expecting the scanning potential region in 0-0.6V has good electrochemical reversibility and double layer capacity property, and with the increasing of sweep speed
Add, response current significantly increases.
Figure 11 is graphite paper in the present invention, the graphite paper of carried titanium dioxide nano column array and load titanium nitride nano column
The graphite paper of array is in 20mVs-1Cyclic voltammetry curve figure under sweep speed.As shown, graphite paper, carried titanium dioxide
The area that the cyclic voltammetry curve of the graphite paper of the graphite paper of nano column array and load titanium nitride nano column array is surrounded according to
Secondary increase, therefore its area specific capacitance also successively increases.
Figure 12 is graphite paper in the present invention, the graphite paper of carried titanium dioxide nano column array and load titanium nitride nano column
Area specific capacitance curve graph of the graphite paper of array under different scanning rates.As shown, under identical sweep speed, three
The area specific capacitance of person increases successively.When sweep speed is from 5mVs-1Increase to 200mVs-1When, the area of graphite paper is than electricity
Hold from 28.5mFcm-2It is down to 16.6mFcm-2, the conservation rate of area specific capacitance is 58.2%；Carried titanium dioxide nano-pillar
The area specific capacitance of the graphite paper of array is from 53.9mFcm-2It is down to 17.3mFcm-2, the conservation rate of area specific capacitance is
32.1%；The area specific capacitance of the graphite paper of titanium nitride nano column array is loaded from 93.7mFcm-2It is down to 53.6mFcm-2,
The conservation rate of area specific capacitance is 57.2%.Compared with the graphite paper of carried titanium dioxide nano column array, load titanium nitride is received
The graphite paper electrode of rice column array has higher area specific capacitance and lower capacitance loss, shows that it has preferable double electricity
Layer capacitance performance, this, which is primarily due to titanium nitride nano array material, has the specific surface of higher electric conductivity and bigger.
Figure 13 is graphite paper in the present invention, the graphite paper of carried titanium dioxide nano column array and load titanium nitride nano column
The graphite paper of array is 1mAcm in current density-2When charging and discharging curve figure.Graphite paper, load dioxy are calculated by figure
The graphite paper of change titanium nano column array and the area specific capacitance of the graphite paper of load titanium nitride nano column array are respectively
26.8mF·cm-2、43.8mF·cm-2And 94.7mFcm-2.Compared with graphite paper, although carried titanium dioxide nano column array
The nano-pillar array structure of graphite paper surface titanium dioxide greatly improve the specific surface of electrode, but due to titanium dioxide
Electric conductivity it is poor, specific capacitance merely adds 17mFcm-2, and load the ratio electricity of the graphite paper of titanium nitride nano column array
Rong Ze increases 67.9mFcm than graphite paper-2, this promotion by a relatively large margin is mainly due to the titanium nitride nano on its surface
Column array has higher electric conductivity and specific surface.IR pressure drops (drop of potential of electric discharge initial time) during electrode discharge
It can reflect the size of electrode material internal resistance, the IR pressure drops of this three kinds of electrode materials are respectively 15.5mV, 48.9mV and 4.9mV, are said
The graphite paper of bright load titanium nitride nano column array has more than the graphite paper of graphite paper and carried titanium dioxide nano column array
Small internal resistance.Therefore, the capacitive properties of the graphite paper of load titanium nitride nano column array are better than graphite paper and carried titanium dioxide
The graphite paper electrode of nano column array, this is consistent with the result of cyclic voltammetry.
Figure 14 is graphite paper the filling under different charging and discharging currents density that titanium nitride nano column array is loaded in the present invention
Discharge curve.As shown, used charging and discharging currents density section is 1-10mAcm when test-2, corresponding matter
Amount current density section is 0.595-5.95Ag-1(quality of electrode surface titanium nitride is 1.68mgcm-2).Figure 15 is this
The quality specific capacitance of the graphite paper of titanium nitride nano column array is loaded in invention with the variation relation figure of charging and discharging currents density.Such as
Shown in figure, when charging and discharging currents density is from 0.595Ag-1Increase to 5.95Ag-1When, the quality specific capacitance of electrode from
56.35F·g-1Drop to 45.65Fg-1, corresponding area specific capacitance is from 94.7mFcm-2Drop to 76.7mFcm-2, electricity
It is 81.0% to hold conservation rate.The high capacitance conservation rate for loading the graphite paper of titanium nitride nano column array shows it with good work(
Rate characteristic.
In conclusion the high-ratio surface and high conductivity of the graphite paper of the load titanium nitride nano column array of the present invention are allowed to
With higher specific capacitance and good power characteristic, therefore as the backing material of electric polypyrrole, play titanium nitride
The advantage of nano column array and electric polypyrrole obtains the electrode material with good capacitive properties.
Figure 16 is cyclic voltammetry curve figure of the graphite paper-polypyrrole material under different scanning rates, Figure 17 in the present invention
It is cyclic voltammetry curve figure of titanium dioxide in the present invention-polypyrrole nano column array material under different scanning rates, Figure 18
It is cyclic voltammetry curve figure of the flexible titanium nitride-polypyrrole nano column array material under different scanning rates, figure in the present invention
The corresponding sweep speed of middle difference curve is as follows：(a)5mV·s-1；(b)10mV·s-1；(c)20mV·s-1；(d)50mV·s-1；
(e)100mV·s-1；(f)200mV·s-1.As shown, the cyclic voltammetry curve of this three kinds of electrode materials is in approximate rectangular
Shape, show electrode material have good electrochemical reversibility and double layer capacity property；With the increase of sweep speed, electrode
Response current significantly increase.
Figure 19 is graphite paper-polypyrrole material in the present invention, titanium dioxide-polypyrrole nano column array material and flexible nitrogen
It is 20mVs to change titanium-polypyrrole nano column array material in sweep speed-1When cyclic voltammetry curve figure.As shown, graphite
Paper-polypyrrole material, titanium dioxide-polypyrrole nano column array material and flexible titanium nitride-polypyrrole nano column array material
The area that is surrounded of cyclic voltammetry curve be sequentially increased, therefore, area specific capacitance also successively increases.
Figure 20 is graphite paper-polypyrrole material in the present invention, titanium dioxide-polypyrrole nano column array material and flexible nitrogen
Change area specific capacitance curve graph of the titanium-polypyrrole nano column array material under different scanning rates.As shown, when scanning speed
Rate is from 5mVs-1Increase to 200mVs-1When, the area specific capacitance of graphite paper-polypyrrole material is from 106.9mFcm-2It is down to
29.5mF·cm-2, the conservation rate of area specific capacitance is 27.6%；The area ratio of titanium dioxide-polypyrrole nano column array material
Capacitance is from 291.8mFcm-2It is down to 59.1mFcm-2, the conservation rate of area specific capacitance is 20.3%；The flexible poly- pyrrole of titanium nitride-
The area specific capacitance of nano column array material is coughed up from 521.3mFcm-2It is down to 207.7mFcm-2, the holding of area specific capacitance
Rate is 39.8%.As it can be seen that under identical sweep speed, graphite paper-polypyrrole material, titanium dioxide-polypyrrole nano-pillar battle array
The area specific capacitance of row material and flexible titanium nitride-polypyrrole nano column array material increases successively.With the two of graphite paper surface
Titanium oxide and titanium nitride nano column array are remarkably improved the specific surface of polypyrrole as support, to significantly improve electrode material
Specific capacitance.Compared with graphite paper-polypyrrole material and titanium dioxide-polypyrrole nano column array material, flexible titanium nitride-is poly-
Pyrroles's nano column array material has higher area specific capacitance and capacity retention, shows it with preferable electric double layer capacitance
Performance, the electric conductivity that this is primarily due to titanium dioxide is poor, the knot of graphite paper and polypyrrole in graphite paper-polypyrrole material
It closes defective tightness and causes its resistance also bigger, and the titanium nitride nano column with high conductance is used as support, it can be preferable
Ground improves transmission rate of the ion in material matrix, while also promoting the speed of the ion exchange between electrolyte and polypyrrole
Rate.
Figure 21 is graphite paper-polypyrrole material in the present invention, titanium dioxide-polypyrrole nano column array material and flexible nitrogen
It is 1mAcm to change titanium-polypyrrole nano column array material in current density-2When charging and discharging curve figure.As shown, graphite
Paper-polypyrrole material, titanium dioxide-polypyrrole nano column array material and flexible titanium nitride-polypyrrole nano column array material
Discharge time successively increase, illustrate that its area specific capacitance also successively increases, with cyclic voltammetry curve analysis acquired results it is consistent.
The IR pressure drops of three are respectively 14.3mV, 9.6mV and 3.6mV, this illustrates flexible titanium nitride-polypyrrole nano column array material ratio
Graphite paper-polypyrrole material and titanium dioxide-polypyrrole nano column array material have higher conductivity, thus can get compared with
High specific capacitance and preferable power-performance.It is 1mAcm that table 1, which gives three in charging and discharging currents density,-2When area ratio
Capacitance and quality specific capacitance.As it can be seen that polypyrrole can dramatically increase the specific capacitance of electrode, and titanium nitride in the deposition of electrode surface
The polypyrrole array material of nano-pillar support has better relative to the polypyrrole array material that nano titania column supports
Electrochemical energy storage property.In 1mAcm-2Discharge current density under, the face of flexible titanium nitride-polypyrrole nano column array material
Product specific capacitance is 959.0mFcm-2, than graphite paper-polypyrrole material (128.8mFcm-2) and load titanium nitride nano column battle array
Graphite paper (the 94.7mFcm of row-2) sum of the two is much larger, this is because polypyrrole is in titanium nitride nano column array surface
Deposition not only greatly improves the specific surface of electrode, but also helps to play the synergistic effect that titanium nitride is received with polypyrrole, will
The functionality of the two is integrated in one.
1 graphite paper of table-polypyrrole material, titanium dioxide-polypyrrole nano column array material and flexible titanium nitride-polypyrrole
Nano column array material exists
1mA·cm-2Specific capacitance when lower electric discharge
Figure 22 is charging and discharging curve figure of the graphite paper-polypyrrole material under different current densities, Tu23Shi in the present invention
Titanium dioxide-charging and discharging curve figure of the polypyrrole nano column array material under different current densities in the present invention, Figure 24 are these
Flexible titanium nitride-charging and discharging curve figure of the polypyrrole nano column array material under different current densities in invention.As shown,
Under different current densities, the symmetry of charging and discharging curve is relatively good, illustrates that these three electrode materials all have excellent electrochemistry
Capacitive properties.
Figure 25 is graphite paper-polypyrrole material in the present invention, titanium dioxide-polypyrrole nano column array material and flexible nitrogen
Change titanium-quality of the polypyrrole nano column array material under different current densities than capacitance curve figure.As shown, flexible nitridation
Titanium-polypyrrole nano column array material is in 0.5Ag-1Specific capacitance value under current density is 464.9Fg-1, titanium dioxide-
Polypyrrole nano column array material is in 0.55Ag-1Specific capacitance value under current density is 302.2Fg-1, the poly- pyrrole of graphite paper-
Material is coughed up in 1Ag-1Specific capacitance value is 170.5Fg under current density-1, it is seen then that flexible titanium nitride-polypyrrole nano-pillar battle array
The capacitive properties of row material are substantially better than graphite paper-polypyrrole material and titanium dioxide-polypyrrole nano column array material.Generally
For, with the increase of current density, due to being influenced and insufficient utilization of electroactive material by ohm voltage drop, electrode material
Specific capacity value can continuously decrease, however even if in 5.0Ag-1Discharge current density under, flexible titanium nitride-polypyrrole nanometer
The specific capacity value of column array material is still 276.5Fg-1, about it is in 0.5Ag-1Current density under specific capacity value
59.5%, show the good power characteristic of the electrode.
The present invention has the advantages that：
(1) present invention is using graphite paper as base material, it is conductive it is good, property is stable, cheap and flexible etc.
Advantage, grows nano titania column and is nitrogenized on graphite paper and obtain titanium nitride nano column, the size of titanium nitride nano column with
It is little compared to variation before nitridation, but its surface is more coarse, and this coarse surface can dramatically increase the surface area of material, favorably
In the raising of its specific capacitance.
(2) the titanium nitride nano column array that the present invention is grown on graphite paper is in the form of a column, and is separated from each other, is conducive to polypyrrole
Ion transmission in electrolyte transport and charge and discharge process in deposition process.
(3) present invention further deposited polypyrrole using general pulse voltammetry on titanium nitride nano column surface, play
The synergisticing performance of titanium nitride and polypyrrole, improves capacitance, the cycle life of composite material, optimizes high-power charge and discharge
Performance, while titanium nitride nano material falling off from electrode surface also can be effectively prevented, improve the stability of composite material.It will
Titanium nitride prepared by the present invention-electrode material of the polypyrrole nanocomposite as ultracapacitor, not only overcomes poly- pyrrole
The poor problem of the stability of larger material resistance, high power discharge performance and long-term charge and discharge cycles is coughed up, while overcoming nitrogen
Change the unstable defect of titanium nano material.
(4) flexible titanium nitride-polypyrrole nano column array material prepared by the present invention, due to the conduction of titanium nitride nano column
Property is good, bigger than table, and each titanium nitride nano column is fully wrapped around by one layer of uniform polypyrrole, improves the capacitive character of material
Matter.
Above description has fully disclosed the specific implementation mode of the present invention.It should be pointed out that being familiar with the field
Technical staff is to any change for being done of specific implementation mode of the present invention all without departing from the range of claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (10)
1. a kind of preparation method of flexibility titanium nitride-polypyrrole nano column array material, which is characterized in that include the following steps：
S1. using graphite paper as base material, nano titania column array material is grown on its surface, obtains load titanium dioxide
The graphite paper of titanium nano column array；
S2. the graphite paper of the carried titanium dioxide nano column array is subjected to nitrogen treatment, obtains load titanium nitride nano column
The graphite paper of array；
S3. general pulse voltammetry is used, polypyrrole is deposited on the graphite paper of the load titanium nitride nano column array, obtains
Flexible titanium nitride-polypyrrole nano column array material.
2. a kind of preparation method of flexible titanium nitride-polypyrrole nano column array material according to claim 1, feature
It is, the step S1 includes the following steps：
S101., graphite paper is cut into certain size, then acetone and water is used to carry out supersound washing successively, dried later,
Graphite paper after being pre-processed；
S102. by titanium source be added reaction vessel in, absolute ethyl alcohol is added while stirring, glacial acetic acid is then added, be stirred continuously to
Reaction solution is creamy white, and obtains TiO 2 sol；
S103. graphite paper after the pretreatment is impregnated in the TiO 2 sol, in graphite paper adsorption titanium dioxide
Titanium nano particle obtains the graphite paper of carried titanium dioxide nano particle；
S104. the graphite paper of the carried titanium dioxide nano particle is placed in hydrochloric acid and the mixed solution of titanium source and carries out hydro-thermal
Reaction grows the nano titania column array on graphite paper surface, obtains the carried titanium dioxide nano column array
Graphite paper.
3. a kind of preparation method of flexible titanium nitride-polypyrrole nano column array material according to claim 2, feature
It is, the volume ratio of titanium source described in step S102 and the absolute ethyl alcohol is 1:4-1:20, the glacial acetic acid and the titanium source
Volume ratio be 1:50-1:250.
4. a kind of preparation method of flexible titanium nitride-polypyrrole nano column array material according to claim 2 or 3,
It is characterized in that, the titanium source is any one in butyl titanate, tetraethyl titanate, isopropyl titanate, titanium tetrachloride.
5. a kind of preparation method of flexible titanium nitride-polypyrrole nano column array material according to claim 2, feature
It is, the step S103 is specially：
Graphite paper after the pretreatment is impregnated into 5-10min in the TiO 2 sol, then takes out and is dried at 60-80 DEG C
It is dry, and cooled to room temperature after 10-30min is kept the temperature at 300-400 DEG C, obtain the graphite of carried titanium dioxide nano particle
Paper.
6. a kind of preparation method of flexible titanium nitride-polypyrrole nano column array material according to claim 2, feature
It is, the step S104 includes the following steps：
S1041. it is 1 according to volume ratio with deionized water by concentrated hydrochloric acid that mass concentration is 36-38%:1 mixing, is then added titanium
The volume ratio of source, the titanium source and the concentrated hydrochloric acid is 1:25-1:60, it stirs and evenly mixs up to the mixed of the hydrochloric acid and the titanium source
Close solution；
S1042. the graphite paper of carried titanium dioxide nano particle described in step S103 is put into reaction vessel, then to institute
The mixed solution that the hydrochloric acid and the titanium source are added in reaction vessel is stated, reacts 4-20h at 150-200 DEG C, washs and dries in the air
It is dry, obtain the graphite paper head product of carried titanium dioxide nano column array；
S1043. the graphite paper head product of the carried titanium dioxide nano column array is subjected to calcination processing, calcination temperature is
400-600 DEG C, time 1-3h obtains the graphite paper of carried titanium dioxide nano column array.
7. a kind of preparation method of flexible titanium nitride-polypyrrole nano column array material according to claim 1, feature
It is, the step S2 is specially：
Nitrogen treatment is carried out to the graphite paper of the carried titanium dioxide nano column array using ammonia, the flow of the ammonia is
30-100mL·min-1, reaction temperature is 700-1000 DEG C.
8. a kind of preparation method of flexible titanium nitride-polypyrrole nano column array material according to claim 1, feature
It is, the step S3 includes the following steps：
S301. acetonitrile, lithium perchlorate and pyrroles is added into reaction vessel successively, is uniformly mixed, obtains deposition solution, institute
The mass ratio for stating lithium perchlorate and the acetonitrile is 1:50-1:100, the mass ratio of the pyrroles and the acetonitrile is 1:50-1:
150；
S302. using the graphite paper of the load titanium nitride nano column array as working electrode, using saturated calomel electrode as reference electricity
Pole deposits polypyrrole using general pulse voltammetry in the deposition solution, obtains flexible nitridation using platinized platinum as auxiliary electrode
Titanium-polypyrrole nano column array material；The parameter setting of the general pulse voltammetry is as follows：Initial voltage is 0.7V, is terminated
Voltage is 1.1V, and current potential increment is 0.001-0.004Vs-1, pulse width 0.06s, pulse period 1-10s, sampling width
Degree is 0.02s, quiescent time 2s.
9. a kind of flexibility titanium nitride-polypyrrole nano column array material, which is characterized in that base material is graphite paper, in graphite
Growth has the more titanium nitride nano column arrays being in the form of a column, the every titanium nitride nano column array uniform by one layer on paper
Polypyrrole is fully wrapped around.
10. a kind of application of flexibility titanium nitride-polypyrrole nano column array material, which is characterized in that by the poly- pyrrole of flexible titanium nitride-
Nano column array material is coughed up as electrode material to be applied in ultracapacitor.
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