CN108597904A - A kind of titanium nitride-polypyrrole nanocomposite and its preparation method and application - Google Patents
A kind of titanium nitride-polypyrrole nanocomposite and its preparation method and application Download PDFInfo
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- CN108597904A CN108597904A CN201810556642.8A CN201810556642A CN108597904A CN 108597904 A CN108597904 A CN 108597904A CN 201810556642 A CN201810556642 A CN 201810556642A CN 108597904 A CN108597904 A CN 108597904A
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- carbon paper
- titanium nitride
- polypyrrole
- titanium dioxide
- titanium
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01G11/48—Conductive polymers
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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 titanium nitride polypyrrole nanocomposite, the described method comprises the following steps：Using carbon paper as base material titanium dioxide nanofiber film is grown on its surface；The carbon paper of carried titanium dioxide nano fibrous membrane is subjected to nitrogen treatment and obtains the carbon paper of load titanium nitride nano tunica fibrosa；Polypyrrole is deposited on the carbon paper of load titanium nitride nano tunica fibrosa using general pulse voltammetry, obtains titanium nitride polypyrrole nanocomposite.It is in porous structure to be formed by titanium nitride polypyrrole film layer, and there is great specific surface and high porosity, this structure to help to increase deposition, the specific surface area of polypyrrole, improve the energy storage property of material.Titanium nitride polypyrrole nanocomposite prepared by the present invention can function well as the electrode material of ultracapacitor.
Description
Technical field
The present invention relates to novel energy resource material technology field more particularly to a kind of titanium nitride-polypyrrole nanocomposite and
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 performance of the Nomenclature Composition and Structure of Complexes to capacitor
(such as specific capacitance, internal resistance and cycle life) has conclusive influence.Therefore, how to prepare with high-energy-density and high-specific-power
Electrode material be ultracapacitor research core topic.Currently, the electrode material of ultracapacitor mainly has carbon material (charcoal
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 is a kind of novel electrode material, has excellent electric conductivity and higher specific capacity.Meanwhile nitrogen
Change the conductivity (4000-55500Scm of the superelevation of titanium-1) and mechanical stability make and have very much the super of development potentiality
The electrode material of capacitor, but titanium nitride nano material easily falls off from the surface of electrode, 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 nano combined materials of titanium nitride-polypyrrole
Material and its preparation method and application.
In order to solve the above technical problem, the present invention provides a kind of preparations of titanium nitride-polypyrrole nanocomposite
Method includes the following steps：
S1. using carbon paper as base material, titanium dioxide nanofiber film is grown on its surface, obtains carried titanium dioxide
The carbon paper of nano fibrous membrane；
S2. the carbon paper of the carried titanium dioxide nano fibrous membrane is subjected to nitrogen treatment, obtains load titanium nitride nano
The carbon paper of tunica fibrosa；
S3. general pulse voltammetry is used, polypyrrole is deposited on the carbon paper of the load titanium nitride nano tunica fibrosa, obtains
To titanium nitride-polypyrrole nanocomposite.
Further, the step S1 includes the following steps：
S101., carbon paper is cut into certain size, then acetone and water is used to carry out supersound washing successively, dried later
It is dry, carbon 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, at room temperature
It is stirred continuously to reaction solution and is creamy white, obtain TiO 2 sol；
Wherein step S101 and step S102 interchangeable sequences；
S103. carbon paper after the pretreatment is impregnated in the TiO 2 sol, titanium dioxide is adsorbed in carbon paper surface
Titanium nano particle obtains the carbon paper of carried titanium dioxide nano particle；
S104. the carbon paper of the carried titanium dioxide nano particle is placed in sodium hydroxide solution and carries out hydro-thermal reaction,
Titanium dioxide nanofiber film is grown in carbon paper surface, obtains the carbon paper of carried titanium dioxide nano fibrous membrane.
Preferably, the titanium source and the volume ratio of the absolute ethyl alcohol are 1:4-1:20, the glacial acetic acid and the titanium source
Volume ratio be 1:50-1:250.
Preferably, the titanium source is any one in butyl titanate, tetraethyl titanate, isopropyl titanate, titanium tetrachloride.
Further, the step S103 includes the following steps：
S1031. carbon paper after the pretreatment is impregnated in the TiO 2 sol, is ultrasonically treated 5-10min, then
The drying at 60-80 DEG C is taken out, the carbon paper of single-steeping TiO 2 sol is obtained；
S1032. continue the carbon paper of the single-steeping TiO 2 sol to be impregnated in 1- in the TiO 2 sol
5min takes out dry at 60-80 DEG C later；
S1033. step S1032 is repeated, until the adsorbance of titania nanoparticles is 5-15mgcm on carbon paper-2,
Then 10-30min is kept the temperature at 300-400 DEG C in program-controlled high temperature furnace, later cooled to room temperature, obtains load titanium dioxide
The carbon paper of titanium nano particle；Carbon paper surface titanium dioxide is adjusted above by dipping time of the carbon paper in TiO 2 sol
The adsorbance of nano particle.
Further, the step S104 includes the following steps：
S1041. the carbon paper of carried titanium dioxide nano particle described in step S103 is put into reaction vessel, then to
8-12molL is added in the reaction vessel-1Sodium hydroxide solution, react 12-60h at 170-250 DEG C, taken after cooling
Go out washing, is placed in immersion treatment in hydrochloric acid solution, finally washs and dry, obtain the carbon of carried titanium dioxide nano fibrous membrane
Paper head product；Titanium dioxide nanofiber in the head product is unformed shape；
S1042. the carbon paper head product of the carried titanium dioxide nano fibrous membrane is forged under inert gas protection
Burning processing, calcination temperature are 450-600 DEG C, time 2-5h, and then control cooling, obtains the carried titanium dioxide Nanowire
Tie up the carbon paper of film；After calcining, titanium dioxide nanofiber is converted into more orderly regular anatase crystal from unformed.
Preferably, the step S1042 is specifically included：
The carbon paper head product of the carried titanium dioxide nano fibrous membrane is placed in tube furnace, under inert gas protection
Calcination processing is carried out, the temperature setting of the tube furnace is specially：With 3-10 DEG C of min-1Rate be warming up to 250-300 DEG C,
And the calcining at constant temperature 10-15min at 250-300 DEG C, then with 3-10 DEG C of min-1Rate be warming up to 450-600 DEG C, then exist
Calcining at constant temperature 2-5h, is finally cooled to room temperature at 450-600 DEG C.
Further, the step S2 is specifically included：
Nitrogen treatment is carried out to the carbon paper of the carried titanium dioxide nano fibrous membrane using ammonia, the flow of ammonia is
30-100mL·min-1, reaction temperature is 700-1000 DEG C.
Preferably, the nitrogen treatment is specially：Using high-purity ammonia to the carried titanium dioxide nano fibrous membrane
Carbon paper is restored, and the flow of ammonia is 30-100mLmin-1；Reaction temperature is specially：With 3-10 DEG C of min-1Rate
It 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 heating
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, knot
Shu Chengxu.
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. using the carbon paper of the load titanium nitride nano tunica fibrosa as working electrode, using saturated calomel electrode as reference
Electrode deposits polypyrrole using general pulse voltammetry in the deposition solution, obtains the nitrogen using platinized platinum as auxiliary electrode
Change titanium-polypyrrole nanocomposite；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.
The present invention also provides a kind of titanium nitride-polypyrrole nanocomposite, base material is carbon paper, is born on carbon paper
One layer of titanium nitride nano tunica fibrosa is carried, the every titanium nitride nano fiber is fully wrapped around by one layer of uniform polypyrrole, institute
It is porous structure to state titanium nitride-polypyrrole nanocomposite.
The present invention also provides a kind of applications of titanium nitride-polypyrrole nanocomposite, by titanium nitride-polypyrrole nanometer
Composite material is applied to as electrode material in ultracapacitor.
The present invention has the advantages that：
(1) present invention grows titanium dioxide nanofiber film on its surface and nitridation obtains using carbon paper as base material
Titanium nitride nano tunica fibrosa, compared to existing base material, base material cost of the invention is less expensive, and the nitrogen prepared
Changing titanium nano fibrous membrane has great specific surface and high porosity, while having higher electric conductivity；
(2) present invention further deposited polypyrrole using general pulse voltammetry in titanium nitride nano fiber film surface,
The synergisticing performance for having played titanium nitride and polypyrrole improves capacitance, the cycle life of composite material, optimizes high-power fill
Discharge performance, while titanium nitride nano material falling off from electrode surface also can be effectively prevented, improve the stabilization of composite material
Property；Titanium nitride-polypyrrole nanocomposite prepared by the present invention not only overcomes as the electrode material of ultracapacitor
The problem that polypyrrole material internal resistance is larger, the stability of high power discharge performance and long-term charge and discharge cycles is poor, overcomes simultaneously
Titanium nitride nano material unstable defect；
(3) titanium nitride-polypyrrole nanocomposite prepared by the present invention, each titanium nitride nano fiber is by one layer
Uniform polypyrrole is fully wrapped around, and it is in porous structure to be formed by titanium nitride-polypyrrole film layer, has high porosity, this
Kind structure not only helps increase the deposition and specific surface area, the energy storage property for improving material of polypyrrole, and inside film
The duct of a large amount of intercommunications also contributes to diffusion of the electrolyte to titanium nitride-polypyrrole nanofibers surface, to improve super electricity
The electrical property of container.
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 carbon paper of carried titanium dioxide nano fibrous membrane in the present invention；
Fig. 2 is the SEM figures for the carbon paper that titanium nitride nano tunica fibrosa is loaded in the present invention；
Fig. 3 is the SEM figures of titanium nitride in the present invention-polypyrrole nanocomposite；
Fig. 4 is the carbon paper of the carbon paper of carried titanium dioxide nano fibrous membrane and load titanium nitride nano tunica fibrosa in the present invention
XRD spectra；
Fig. 5 is the Raman spectrogram of titanium nitride in the present invention-polypyrrole nanocomposite；
Fig. 6 is that cyclic voltammetric of the carbon paper of carried titanium dioxide nano fibrous membrane in the present invention under different scanning rates is bent
Line chart；
Fig. 7 is that cyclic voltammetry curve of the carbon paper of titanium nitride nano tunica fibrosa under different scanning rates is loaded in the present invention
Figure；
Fig. 8 is the carbon paper of the carbon paper of carried titanium dioxide nano fibrous membrane and load titanium nitride nano tunica fibrosa in the present invention
It is 20mVs in sweep speed-1When cyclic voltammetry curve figure；
Fig. 9 is the carbon paper of the carbon paper of carried titanium dioxide nano fibrous membrane and load titanium nitride nano tunica fibrosa in the present invention
Area specific capacitance curve graph under different scanning rates；
Figure 10 is the carbon of the carbon paper of carried titanium dioxide nano fibrous membrane and load titanium nitride nano tunica fibrosa in the present invention
Paper is 1mAcm in charging and discharging currents-2When charging and discharging curve figure；
Figure 11 is that charge and discharge of the carbon paper of titanium nitride nano tunica fibrosa under different charging and discharging currents density is loaded in the present invention
Electric curve graph；
Figure 12 is titanium nitride in the present invention-cyclic voltammetry curve of the polypyrrole nanocomposite under different scanning rates
Figure；
Figure 13 is that area specific capacitance of titanium nitride in the present invention-polypyrrole nanocomposite under different scanning rates is bent
Line chart；
It is 1mAcm that Figure 14, which is titanium nitride in the present invention-polypyrrole nanocomposite in current density,-2When charge and discharge
Curve graph；
Figure 15 is charge and discharge of titanium nitride in the present invention-polypyrrole nanocomposite under different charging and discharging currents density
Curve graph；
Figure 16 is the quality specific capacitance of titanium nitride in the present invention-polypyrrole nanocomposite with charging and discharging currents density
Variation relation 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 titanium nitride-polypyrrole nanocomposite, include the following steps：
S1. using carbon paper as base material, titanium dioxide nanofiber film is grown on its surface, obtains carried titanium dioxide
The carbon paper of nano fibrous membrane；
The step S1 includes the following steps：
S101., carbon paper is cut into the small pieces of 50mm × 20mm × 0.20mm, then uses acetone and water to be surpassed successively
Sound washs 10min, is dried at 80 DEG C later, carbon paper after being pre-processed；
S102. it takes 20mL butyl titanates in 200mL beakers, is slowly added to 100mL absolute ethyl alcohols while stirring, then
0.2mL glacial acetic acids are added, is stirred continuously to reaction solution is creamy white at room temperature, obtain TiO 2 sol；
S103. carbon paper after the pretreatment is impregnated in the TiO 2 sol, titanium dioxide is adsorbed in carbon paper surface
Titanium nano particle obtains the carbon paper of carried titanium dioxide nano particle；
The step S103 includes the following steps：
S1031. carbon paper after the pretreatment is impregnated in the TiO 2 sol, is ultrasonically treated 5min, then takes
For drying at 80 DEG C, the carbon paper of single-steeping TiO 2 sol is obtained；
S1032. the carbon paper of the single-steeping TiO 2 sol is continued to be impregnated in the TiO 2 sol
2min takes out dry at 80 DEG C later；
S1033. step S1032 is repeated, until the adsorbance of titania nanoparticles is 10mgcm-2 on carbon paper, so
It keeps the temperature 20min at 350 DEG C in program-controlled high temperature furnace afterwards, later cooled to room temperature, obtains carried titanium dioxide nanometer
The carbon paper of grain；Carbon paper surface titania nanoparticles are adjusted above by dipping time of the carbon paper in TiO 2 sol
Adsorbance；
S104. the carbon paper of the carried titanium dioxide nano particle is placed in sodium hydroxide solution and carries out hydro-thermal reaction,
Titanium dioxide nanofiber film is grown in carbon paper surface, obtains the carbon paper of carried titanium dioxide nano fibrous membrane；
The step S104 includes the following steps：
S1041. the carbon paper of carried titanium dioxide nano particle described in step S103 is put into 50mL stainless steel cauldrons
Polytetrafluoroethyllining lining in, two panels is put in each reaction kettle, it is staggered relatively, then into the reaction kettle be added 40mL concentration
For 10molL-1Sodium hydroxide solution, react 48h at 200 DEG C；Product is taken out after being cooled to room temperature, in the outer of carbon paper
Surface forms one layer of whiteness, shows carbon paper surface supported titanium silicate nanometer tunica fibrosa；Then it is rushed repeatedly with deionized water
The remaining reaction solution of product surface is washed, 0.1molL is placed in-1Hydrochloric acid solution in immersion treatment for 24 hours, make titanate Nanowire
Dimension is changed into titanium dioxide nanofiber, is finally washed with deionized and is dried at 80 DEG C, obtains carried titanium dioxide and receive
The carbon paper head product of rice tunica fibrosa, the titanium dioxide nanofiber in the head product are unformed shape；
S1042. the carbon paper head product of the carried titanium dioxide nano fibrous membrane is placed in tube furnace, in nitrogen protection
Lower carry out calcination processing, the temperature setting of the tube furnace are specially：With 5 DEG C of min-1Rate be warming up to 250 DEG C, and
Calcining at constant temperature 10min at 250 DEG C, then with 5 DEG C of min-1Rate be warming up to 550 DEG C, the then calcining at constant temperature 3h at 550 DEG C,
It is finally cooled to room temperature, obtains the carbon paper of the carried titanium dioxide nano fibrous membrane (referred to as：CP/TiO2- NFs), on carbon paper
The load capacity of titanium dioxide nanofiber film is 6.5mgcm-2；After calcining, titanium dioxide nanofiber is from unformed turn
Turn to more orderly regular anatase crystal.
Nitrogen treatment is carried out to the carbon paper of the carried titanium dioxide nano fibrous membrane using ammonia, the flow of ammonia is
30-100mLmin-1, reaction temperature are 700-1000 DEG C.
S2. the carbon paper of the carried titanium dioxide nano fibrous membrane is subjected to nitrogen treatment, obtains load titanium nitride nano
The carbon paper of tunica fibrosa；
The step S2 is specifically included：
The carbon paper of the carried titanium dioxide nano fibrous membrane is restored using high-purity ammonia, the flow of ammonia is
50mL·min-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
700 DEG C are warming up to, then with 1 DEG C of min-1Rate be warming up to 900 DEG C, and the calcining at constant temperature 1h at 900 DEG C, finally with 5 DEG C
min-1Rate be cooled to 50 DEG C, terminate program, then cooled to room temperature, obtain the carbon of load titanium nitride nano tunica fibrosa
Paper is (referred to as：CP/TiN-NFs), the load capacity of titanium nitride nano fiber is 5.4mgcm on carbon paper-2。
S3. general pulse voltammetry is used, polypyrrole is deposited on the carbon paper of the load titanium nitride nano tunica fibrosa, obtains
To titanium nitride-polypyrrole nanocomposite；
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. using the carbon paper of the load titanium nitride nano tunica fibrosa as working electrode, using saturated calomel electrode as reference
Electrode deposits polypyrrole using general pulse voltammetry in the deposition solution, obtains the nitrogen using platinized platinum as auxiliary electrode
Change titanium-polypyrrole nanocomposite；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 0.001Vs-1, pulse width 0.06s, pulse period 4s, sampling width 0.02s,
Quiescent time is 2s；After deposition process, the working electrode is taken out, is rinsed repeatedly using deionized water, then room temperature
It dries, obtains titanium nitride-polypyrrole nanocomposite (referred to as：CP/TiN-NFs/PPy), the deposition of wherein polypyrrole is
4.2mg·cm-2。
After preparation process, first, using the carbon paper of scanning electron microscopic observation carried titanium dioxide nano fibrous membrane, load
The pattern of carbon paper and titanium nitride-polypyrrole nanocomposite of titanium nitride nano tunica fibrosa.
Fig. 1 is the SEM figures of the carbon paper of carried titanium dioxide nano fibrous membrane in the present invention.As shown, titanium dioxide is received
Rice fiber is in band-like, width 80-200nm, thickness less than 20nm, entire titanium dioxide nanofiber film surface almost without
Fracture and clustering phenomena.Fig. 2 is the SEM figures for the carbon paper that titanium nitride nano tunica fibrosa is loaded in the present invention.As shown, through high temperature
It is in that fiber is band-like, but fiber, with more fracture place, surface is no longer flat that titanium nitride is formed by after nitrogen treatment still
It is whole smooth, but it is covered with hole not of uniform size, although the fracture of fiber band can reduce its electric conductivity, the hole of fiber surface
Then increase the specific surface of titanium nitride nano fiber.Fig. 3 is the SEM figures of titanium nitride in the present invention-polypyrrole nanocomposite.
As shown, after deposition polypyrrole, each nanofiber of the titanium nitride nano fiber film layer on surface is uniform by one layer
Polypyrrole it is fully wrapped around, be formed by titanium nitride-polypyrrole film layer still be in porous structure, have high porosity, this
Kind structure not only helps increase the deposition and specific surface area, the energy storage property for improving material of polypyrrole, and tool inside film
The duct for having a large amount of intercommunications contributes to electrolyte to the diffusion on titanium nitride-polypyrrole nanofibers surface.
Secondly, using XRD spectra and Raman spectrum to the carbon paper of carried titanium dioxide nano fibrous membrane and load titanium nitride
The composition of the carbon paper of nano fibrous membrane is characterized.
Fig. 4 is the carbon paper of the carbon paper of carried titanium dioxide nano fibrous membrane and load titanium nitride nano tunica fibrosa in the present invention
XRD spectra.As shown, it may be clearly seen that rutile titania from the XRD spectra of the carbon paper of carried titanium dioxide nano fibrous membrane
Characteristic peak (the peak position of mine structure titanium dioxide (JCPDS No.21-1272)：25.4°、38.0°、48.0°、54.7°、
63.1 °), illustrate that titanium dioxide nanofiber is mainly made of anatase structured titanium dioxide.In addition, can also from figure
Go out, titanium dioxide nanofiber also has a small amount of monoclinic crystal phase titanic oxide (JCPDS No.46-1237) to exist.Load nitridation
Diffraction maximum in the XRD spectra of the carbon paper of titanium nano fibrous membrane at 37.0 °, 42.9 ° and 62.4 ° corresponds respectively to cubic phase nitridation
Hkl (111), the hkl (200) and hkl (220) crystal face of titanium, and the characteristic peak of titanium dioxide substantially completely disappears in spectrogram.Cause
This, after high-temperature ammonolysis is handled, the titanium dioxide on surface changes the carbon paper of carried titanium dioxide nano fibrous membrane completely substantially
For the titanium nitride of cubic phase.
Fig. 5 is the Raman spectrogram of titanium nitride in the present invention-polypyrrole nanocomposite.As shown, in 1586cm-1、1493cm-1And 1375cm-1The scattering peak at place is drawn by the stretching vibration of C=C, C-C and C-N in polypyrrole molecule respectively
It rises, 1240cm-1Caused by the scattering peak at place is the in-plane bending vibration by c h bond, 1073cm-1And 925cm-1The scattering at place
Peak corresponds to the deformation vibration of c h bond.Therefore, the titanium nitride nano fiber on titanium nitride-polypyrrole nanocomposite surface is complete
It is covered entirely by polypyrrole layer, this is consistent with result shown in the SEM of titanium nitride in Fig. 3-polypyrrole nanocomposite figures.
Embodiment 2
Carbon paper, the load titanium nitride for the carried titanium dioxide nano fibrous membrane that the present embodiment is prepared with embodiment 1 respectively are received
The carbon paper and titanium nitride-polypyrrole nanocomposite of rice tunica fibrosa are working electrode, are to electrode, to be saturated calomel with platinized platinum
Electrode is reference electrode, with 1molL-1Sulfuric acid is tested as test solution using cyclic voltammetry and constant current charge-discharge method
Its chemical property.
Fig. 6 is that cyclic voltammetric of the carbon paper of carried titanium dioxide nano fibrous membrane in the present invention under different scanning rates is bent
Line chart, Fig. 7 are that cyclic voltammetry curve figure of the carbon paper of titanium nitride nano tunica fibrosa under different scanning rates is loaded in the present invention；
The corresponding sweep speed of difference curve is as follows in figure：(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 two kinds of electrode materials is in approximate rectangular
Shape, show electrode material 0-0.6V scanning potential region have good electrochemical reversibility and double-layer electric capacitive
Matter, and with the increase of sweep speed, the response current of electrode significantly increases.
Fig. 8 is the carbon paper of the carbon paper of carried titanium dioxide nano fibrous membrane and load titanium nitride nano tunica fibrosa in the present invention
It is 20mVs in sweep speed-1When cyclic voltammetry curve figure.As shown, under identical sweep speed, titanium nitride is loaded
The response current of the carbon paper of nano fibrous membrane is apparently higher than the carbon paper of carried titanium dioxide nano fibrous membrane, shows to load titanium nitride
The carbon paper of nano fibrous membrane has higher specific capacitance.
Fig. 9 is the carbon paper of the carbon paper of carried titanium dioxide nano fibrous membrane and load titanium nitride nano tunica fibrosa in the present invention
Area specific capacitance curve graph under different scanning rates.As shown, working as sweep speed from 5mVs-1Increase to 200mV
s-1When, the area specific capacitance of the carbon paper of carried titanium dioxide nano fibrous membrane is from 1.49mFcm-2It is down to 0.63mFcm-2, than
The conservation rate of capacitance is 44.3%；The area specific capacitance of the carbon paper of carried titanium dioxide nano fibrous membrane is from 259.6mFcm-2Drop
To 134.8mFcm-2, the conservation rate of specific capacitance is 51.9%.Compared with the carbon paper of carried titanium dioxide nano fibrous membrane, load
The carbon paper of titanium nitride nano tunica fibrosa has higher area specific capacitance and lower capacitance loss, and it is preferable double to show that it has
Electric layer capacitive property, this, which is primarily due to titanium nitride nano array material, has the specific surface area of higher electric conductivity and bigger.
Figure 10 is the carbon of the carbon paper of carried titanium dioxide nano fibrous membrane and load titanium nitride nano tunica fibrosa in the present invention
Paper is 1mAcm in charging and discharging currents-2When charging and discharging curve figure.It can be calculated the carbon paper of carried titanium dioxide nano fibrous membrane
Area specific capacitance with the carbon paper of load titanium nitride nano tunica fibrosa is respectively 1.83mFcm-2And 291.3mFcm-2, load
The IR pressure drops (4.4mV) of the carbon paper of titanium nitride nano tunica fibrosa are less than the carbon paper of carried titanium dioxide nano fibrous membrane
(107.5mV), therefore, the capacitive properties for loading the carbon paper of titanium nitride nano tunica fibrosa are better than carried titanium dioxide nano fibrous membrane
Carbon paper, this is consistent with the analysis result of front.
Figure 11 is that charge and discharge of the carbon paper of titanium nitride nano tunica fibrosa under different charging and discharging currents density is loaded in the present invention
Electric curve graph.As shown, working as charging and discharging currents density from 0.5Ag-1Increase to 5Ag-1When, the quality specific capacitance of electrode
From 45.8Fg-1It is down to 27.8Fg-1, corresponding area specific capacitance is from 247.3mFcm-2It is down to 150.1mFcm-2, capacitance
Conservation rate is 60.7%.
Figure 12 is titanium nitride in the present invention-cyclic voltammetry curve of the polypyrrole nanocomposite under different scanning rates
Scheme, the corresponding sweep speed of difference curve is as follows in figure：(a)5mV·s-1；(b)10mV·s-1；(c)20mV·s-1；(d)
50mV·s-1；(e)100mV·s-1；(f)200mV·s-1.Figure 13 is that titanium nitride in the present invention-polypyrrole nanocomposite exists
Area specific capacitance curve under different scanning rates.As shown, the cyclic voltammetric of titanium nitride-polypyrrole nanocomposite is bent
Line is in approximate rectangular, shows good double layer capacity property, and with the increase of sweep speed, the specific capacitance of electrode is gradually reduced,
When sweep speed is from 5mVs-1Increase to 200mVs-1When, area specific capacitance is from 1212.8mFcm-2It is down to 96.0mF
cm-2, corresponding quality specific capacitance is from 288.8Fg-1It is down to 22.9Fg-1, capacity retention 7.92%.The poly- pyrrole of titanium nitride-
It is mainly since the structure for the polypyrrole nanofibers film that titanium nitride supports is determined to cough up the lower capacity retention of nanocomposite
Fixed.Although there is polypyrrole nanofibers film high porosity, transmission of the electrolyte in its nano pore still to have
Larger resistance needs to adsorb a large amount of ion in the electrode material surface short time with the quick variation of material electrodes current potential,
And the diffusion velocity of nano pore Inner electrolysis matter ion cannot meet the transfer ion populations needed for electrode charge and discharge, make electrode material
The concentration polarization of material and electrolyte interface increases, and causes the capacitance loss that electrode is larger.
It is 1mAcm that Figure 14, which is titanium nitride in the present invention-polypyrrole nanocomposite in current density,-2When charge and discharge
Curve graph.As shown, curve is in symmetrical triangle, show that electrode has good electric double layer capacitance property.The poly- pyrrole of titanium nitride-
The area specific capacitance and quality specific capacitance for coughing up nanocomposite are respectively 1624.7mFcm-2And 386.8Fg-1, show to gather
Pyrroles can increase considerably specific capacitance value in the deposition of titanium nitride nano fiber surface.The nano combined material of titanium nitride-polypyrrole
The IR pressure drops of material are 5.0mV, and (4.4mV) is increased slightly before deposition polypyrrole.
Figure 15 is charge and discharge of titanium nitride in the present invention-polypyrrole nanocomposite under different charging and discharging currents density
Curve graph.Figure 16 is the quality specific capacitance of titanium nitride in the present invention-polypyrrole nanocomposite with charging and discharging currents density
Variation relation figure.As shown, the charging and discharging curve of titanium nitride-polypyrrole nanocomposite is in the triangle of symmetry, say
Bright titanium nitride-polypyrrole nanocomposite has excellent electrochemical capacitor performance.When charging and discharging currents density is from 0.5A
g-1Increase to 5Ag-1When, the quality specific capacitance of electrode is from 328.9Fg-1It is down to 217.5Fg-1, corresponding area specific capacitance
From 1381.3mFcm-2It is down to 913.3mFcm-2, capacity retention 66.1% shows that the good power of the electrode is special
Property.
The present invention has the advantages that：
(1) present invention grows titanium dioxide nanofiber film on its surface and nitridation obtains using carbon paper as base material
Titanium nitride nano tunica fibrosa, compared to existing base material, base material cost of the invention is less expensive, and the nitrogen prepared
Changing titanium nano fibrous membrane has great specific surface and high porosity, while having higher electric conductivity；
(2) present invention further deposited polypyrrole using general pulse voltammetry in titanium nitride nano fiber film surface,
The synergisticing performance for having played titanium nitride and polypyrrole improves capacitance, the cycle life of composite material, optimizes high-power fill
Discharge performance, while titanium nitride nano material falling off from electrode surface also can be effectively prevented, improve the stabilization of composite material
Property；Titanium nitride-polypyrrole nanocomposite prepared by the present invention not only overcomes as the electrode material of ultracapacitor
The problem that polypyrrole material internal resistance is larger, the stability of high power discharge performance and long-term charge and discharge cycles is poor, overcomes simultaneously
Titanium nitride nano material unstable defect；
(3) titanium nitride-polypyrrole nanocomposite prepared by the present invention, each titanium nitride nano fiber is by one layer
Uniform polypyrrole is fully wrapped around, and it is in porous structure to be formed by titanium nitride-polypyrrole film layer, has high porosity, this
Kind structure not only helps increase the deposition and specific surface area, the energy storage property for improving material of polypyrrole, and inside film
The duct of a large amount of intercommunications also contributes to diffusion of the electrolyte to titanium nitride-polypyrrole nanofibers surface, to improve super electricity
The electrical property of container.
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 titanium nitride-polypyrrole nanocomposite, which is characterized in that include the following steps：
S1. using carbon paper as base material, titanium dioxide nanofiber film is grown on its surface, obtains carried titanium dioxide nanometer
The carbon paper of tunica fibrosa；
S2. the carbon paper of the carried titanium dioxide nano fibrous membrane is subjected to nitrogen treatment, obtains load titanium nitride nano fiber
The carbon paper of film；
S3. general pulse voltammetry is used, polypyrrole is deposited on the carbon paper of the load titanium nitride nano tunica fibrosa, obtains nitrogen
Change titanium-polypyrrole nanocomposite.
2. a kind of preparation method of titanium nitride-polypyrrole nanocomposite according to claim 1, which is characterized in that
The step S1 includes the following steps：
S101., carbon paper is cut into certain size, then acetone and water is used to carry out supersound washing successively, dries, obtain later
Carbon paper after to pretreatment；
S102. titanium source is added in reaction vessel, absolute ethyl alcohol is added while stirring, glacial acetic acid is then added, at room temperature constantly
Stirring is creamy white to reaction solution, obtains TiO 2 sol；
S103. carbon paper after the pretreatment is impregnated in the TiO 2 sol, is received in carbon paper surface absorption titanium dioxide
Rice grain obtains the carbon paper of carried titanium dioxide nano particle；
S104. the carbon paper of the carried titanium dioxide nano particle is placed in sodium hydroxide solution and carries out hydro-thermal reaction, in carbon
Paper surface grows titanium dioxide nanofiber film, obtains the carbon paper of carried titanium dioxide nano fibrous membrane.
3. a kind of preparation method of titanium nitride-polypyrrole nanocomposite according to claim 2, which is characterized in that
The titanium source and the volume ratio of the absolute ethyl alcohol are 1:4-1:20, the volume ratio of the glacial acetic acid and the titanium source is 1:50-
1:250。
4. a kind of preparation method of titanium nitride-polypyrrole nanocomposite according to claim 2 or 3, feature exist
In the titanium source is any one in butyl titanate, tetraethyl titanate, isopropyl titanate, titanium tetrachloride.
5. a kind of preparation method of titanium nitride-polypyrrole nanocomposite according to claim 2, which is characterized in that
The step S103 includes the following steps：
S1031. carbon paper after the pretreatment is impregnated in the TiO 2 sol, is ultrasonically treated 5-10min, then takes out
It is dry at 60-80 DEG C, obtain the carbon paper of single-steeping TiO 2 sol；
S1032. continue the carbon paper of the single-steeping TiO 2 sol to be impregnated in 1-5min in the TiO 2 sol,
It takes out later dry at 60-80 DEG C；
S1033. step S1032 is repeated, until the adsorbance of titania nanoparticles is 5-15mgcm on carbon paper-2, then
10-30min is kept the temperature at 300-400 DEG C, later cooled to room temperature, obtain the carbon paper of carried titanium dioxide nano particle.
6. a kind of preparation method of titanium nitride-polypyrrole nanocomposite according to claim 2, which is characterized in that
The step S104 includes the following steps：
S1041. the carbon paper of carried titanium dioxide nano particle described in step S103 is put into reaction vessel, then to described
8-12molL is added in reaction vessel-1Sodium hydroxide solution, react 12-60h at 170-250 DEG C, take out and wash after cooling
It washs, is placed in immersion treatment in hydrochloric acid solution, finally washs and dry, at the beginning of obtaining the carbon paper of carried titanium dioxide nano fibrous membrane
Product；
S1042. the carbon paper head product of the carried titanium dioxide nano fibrous membrane is carried out at calcining under inert gas protection
Reason, calcination temperature are 450-600 DEG C, time 2-5h, and then control cooling, obtains the carried titanium dioxide nano fibrous membrane
Carbon paper.
7. a kind of preparation method of titanium nitride-polypyrrole nanocomposite according to claim 1, which is characterized in that
The step S2 is specifically included：
Nitrogen treatment is carried out to the carbon paper of the carried titanium dioxide nano fibrous membrane using ammonia, the flow of ammonia is 30-
100mL·min-1, reaction temperature is 700-1000 DEG C.
8. a kind of preparation method of titanium nitride-polypyrrole nanocomposite according to claim 1, which is characterized in that
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 carbon paper of the load titanium nitride nano tunica fibrosa as working electrode, using saturated calomel electrode as reference electrode,
Using platinized platinum as auxiliary electrode, polypyrrole is deposited using general pulse voltammetry in the deposition solution, obtains the titanium nitride-
Polypyrrole nanocomposite；The parameter setting of the general pulse voltammetry is as follows：Initial voltage is 0.7V, and final voltage is
1.1V, current potential increment are 0.001-0.004Vs-1, pulse width 0.06s, pulse period 1-10s, sampling width is
0.02s, quiescent time 2s.
9. a kind of titanium nitride-polypyrrole nanocomposite, which is characterized in that base material is carbon paper, and one is loaded on carbon paper
Layer titanium nitride nano tunica fibrosa, the every titanium nitride nano fiber is fully wrapped around by one layer of uniform polypyrrole, the nitrogen
Change titanium-polypyrrole nanocomposite is porous structure.
10. a kind of application of titanium nitride-polypyrrole nanocomposite, which is characterized in that titanium nitride-polypyrrole is nano combined
Material is applied to as electrode material in ultracapacitor.
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