CN102509638B - TiO2 (titanium dioxide)/graphite rod nano-sheet composite electrode material, and preparation method and application thereof - Google Patents
TiO2 (titanium dioxide)/graphite rod nano-sheet composite electrode material, and preparation method and application thereof Download PDFInfo
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- CN102509638B CN102509638B CN 201110380842 CN201110380842A CN102509638B CN 102509638 B CN102509638 B CN 102509638B CN 201110380842 CN201110380842 CN 201110380842 CN 201110380842 A CN201110380842 A CN 201110380842A CN 102509638 B CN102509638 B CN 102509638B
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- graphite rod
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a TiO2 (titanium dioxide)/graphite rod nano-sheet composite electrode material, which belongs to the field of composite materials. The material is prepared from an electrochemically stripped graphite rod nano-sheet as a substrate raw material and TiC13 liquor as electroplating liquid by depositing a layer of dense and uniform TiO2 on the substrate surface of the graphite rod nano-sheet by means of constant-potential electrolytic deposition. The TiO2 (titanium dioxide)/graphite rod nano-sheet composite electrode material prepared by the method has high energy density and power density, has the advantages of double electrode-layer capacitance generated by the graphite rod nano-sheet and pseudocapacitor energy storage generated by TiO2 and is capable of displaying quite high electrochemical capacitance, thereby being directly used for fabricating electrodes of the super capacitor. Besides, the composite electrode material displays excellent magnification performance and fine cycling stability and is quite high in safety. Additionally, the composite electrode material has the advantages of no environmental pollution, long cycle life, simplicity and convenience in preparation process, low cost, wide application and the like.
Description
Technical field
The invention belongs to field of compound material, relate to a kind of TiO
2/ graphite rod nanometer sheet combination electrode material is mainly as electrode of super capacitor.
Background technology
Electrochemical capacitor (Electrochemical capacitors) also claim ultracapacitor (Supercapacitors), is a kind of chemical industry novel energy-storing device that occurs in recent years, also is the important component part of cleaning or green energy resource technology.It can provide the energy density higher than electrostatic condenser, than the higher power density of battery and longer cycle life.In addition, electrochemical capacitor also have environmentally safe, have extended cycle life, characteristics such as security performance height.Make ultracapacitor have broad application prospects based on These characteristics, it has been widely used in fields such as communication industry, consumer electronics, medicine equipments as stand-by power supply or independent current source, and its application is also in continuous expansion.At present, electrochemical capacitor has become one of focus of mechanism of new electrochemical power sources research field because of its excellent performance and wide application prospect.
Difference according to energy storage mechanism can be divided into ultracapacitor two types: a kind of is double electric layer capacitor (Electric Double Layer Capacitors, EDLC), another kind then is called as pseudo capacitance device (Faraday Pseudocapacitors).Because the pseudo capacitance that metal oxide produces at electrode/electrolyte face place is far longer than the electric double layer capacitance that material with carbon element produces, so the research of metal oxide has been caused many research workers' attention.TiO wherein
2Because it has bigger specific area, good electrochemical and chemical stability and be used as a kind of electrochemical energy storage materials.
Combination electrode material not only has than higher electric capacity as a kind of novel electrode material for super capacitor, bigger specific area, but also have good cyclical stability, these advantages all be the unitary electrode material can not have.In addition, combination electrode material is with low cost, prepares easyly, and environmentally safe has good application prospects.
Summary of the invention
The purpose of this invention is to provide a kind of TiO
2/ graphite rod nanometer sheet combination electrode material.
Another object of the present invention provides this TiO
2The preparation method of/graphite rod nanometer sheet combination electrode material.
TiO of the present invention
2/ graphite rod nanometer sheet combination electrode material is that the graphite rod nanometer sheet handled with electrochemical stripping is as the substrate raw material, with TiCl
3Solution is as electroplate liquid, by the constant potential electrodeposition process in the uniform TiO of graphite rod nanometer sheet substrate surface deposition compact
2And get.
TiO of the present invention
2The preparation method of/graphite rod nanometer sheet combination electrode material is will carry out electrochemical stripping earlier through the graphite rod of clean to handle, and obtains the substrate of graphite rod nanometer sheet; Be the TiCl of 0.1 ~ 0.4mol/L again with concentration
3Solution is as electroplate liquid, and as work electrode, platinum guaze is as auxiliary electrode with the substrate of graphite rod nanometer sheet, and saturated calomel electrode is as reference electrode, constant potential electro-deposition 4 ~ 20min under 0.6 ~ 1.0V; After electro-deposition finishes, fully wash with high purity water, in 40 ℃ ~ 60 ℃ following vacuumizes, get TiO
2/ graphite rod nanometer sheet combination electrode material.
Described graphite rod is the natural stone inker, electrographite rod, Pintsch process graphite rod.
The clean technology of graphite rod is: graphite rod is carried out grinding process makes its disc more smooth smooth, with high purity water repeatedly ultrasonic cleaning be placed on etching 20 ~ 60min in the HCl solution of 4 ~ 6 mol/L; Water, acetone soln ultrasonic cleaning successively after etching finishes, vacuumize.
The electrochemical stripping treatment process of described graphite rod is: the aqueous solution that the graphite rod through cleaning is placed 0.01 ~ 0.05mol/L anion surfactant, control voltage is at 2 ~ 9V, handle 10 ~ 15h under 20 ℃ ~ 35 ℃, washing obtains the substrate of graphite rod nanometer sheet.Cationic surfactant can adopt neopelex, lauryl sodium sulfate, sodium cetanesulfonate etc.
TiO below by sem photograph, XRD figure and the present invention's preparation of electrochemical workstation CHI660B
2Structure and the performance of/graphite rod nanosheet composite material elaborate.
Fig. 1 is the SEM figure of graphite rod nanometer sheet.As can be seen from the figure this graphite rod nanometer sheet substrate pattern is very regular, has uniform lamellar structure, and the part nanometer sheet also has slight curling, thereby makes this graphite rod nanometer sheet have very high specific area.Fig. 2 is TiO of the present invention
2The SEM figure of/graphite rod nanometer sheet combination electrode material.Can observe significantly from Fig. 2 and to have deposited one deck TiO on the graphite rod nanometer sheet equably
2Particle.Detect TiO through electronic ruler
2Thickness be 5 ~ 10nm.Fig. 3 is the substrate of graphite rod nanometer sheet and the TiO of unpeeled graphite rod rod, electrochemical stripping
2/ graphite rod nanometer sheet combination electrode material is at the Na of 0.5mol/L
2SO
4Cyclic voltammetry curve figure when sweep speed is 5mv in the solution.Show from the demonstration of Fig. 3, by depositing Ti O
2Particle makes the ratio electric capacity of graphite rod nanometer sheet that significant raising arranged.By Origin7.5 software and formula
C=Q/ (Δ V * S)Handling experimental data can get: the not electric graphite rod rod of peeling off than electric capacity is: 83.9F/m
2, the ratio electric capacity that electricity is peeled off the graphite rod nanometer sheet is: 3670 F/m
2, TiO
2The ratio electric capacity of/graphite rod nanometer sheet combination electrode material is: 8490F/m
2
TiO
2The ratio electric capacity of/graphite rod nanometer sheet combination electrode material, the computing formula of energy density and power density is as follows:
Specific capacity:
C=Q/ (Δ V * S)
Δ V---potential window (volt);
S---the work area of electrode;
Q---Integral area (enclosed pasture) for the cyclic voltammetric discharge curve
Electric weight:
I---instant cathode current (ampere) under certain electromotive force;
T---the sweep time (s) of sample
Energy density:
E=1/2 * C * (Δ V) 2 (Watt hour every square metre
)
Power density:
P=E/T(watt every square metre)
Fig. 4 is TiO
2The XRD spectra of/graphite rod nanometer sheet combination electrode material.Because graphite rod nanometer sheet and TiO
2Synergy cause 2 θ to be 26.5 ° locating characteristic peak intensity and have significantly than other peak intensity and strengthen, explanation truly have TiO
2Particle deposition is in the substrate of graphite rod nanometer sheet, and this is consistent with SEM figure.
In sum, the TiO of the present invention's preparation
2/ graphite rod nanometer sheet combination electrode material has very high energy density and power density, has the graphite rod nanometer sheet concurrently and produces electric double layer capacitance and TiO
2Produce the characteristics of fake capacitance energy storage, demonstrate very high electrochemical capacitor behavior, therefore, can be directly used in the making electrode of super capacitor.This composite material also demonstrates good high rate performance and cyclical stability preferably simultaneously, and has very high security performance.In addition, this composite material also have have extended cycle life, preparation technology is easy, equipment is simple, with low cost, characteristics such as be widely used.
The present invention is relative, and prior art has the following advantages:
(1) because TiO
2Be directly to be deposited in the substrate of graphite rod nanometer sheet, so need not to use any adhesive, therefore reduce the interior resistance of electrode widely, can improve energy density, power density and the efficiency for charge-discharge of ultracapacitor effectively, can directly make electrode of super capacitor.
(2) it has very high specific area, is conducive to fully contacting of active material and electrolyte solution, has strengthened the utilance of electrode material.
(3) TiO that makes by electrochemical deposition method
2/ graphite rod nanometer sheet combination electrode material has bigger potential window, thereby makes TiO
2/ graphite rod nanometer sheet combination electrode material has high energy density and power density.
(4) electrode material that makes by electrochemical deposition method is finer and close, and particle is more even, and the specific area of composite material is greatly improved.
(5) preparation technology of the present invention is easy, and equipment is simple, and is with low cost, is easy to industrialization.
Description of drawings
Fig. 1 is the SEM figure of graphite rod nanometer sheet.
Fig. 2 is TiO
2The SEM figure of/graphite rod nanometer sheet combination electrode material.
Fig. 3 is graphite rod nanometer sheet and the TiO of graphite rod, electrochemical stripping
2/ graphite rod nanometer sheet combination electrode material is at the Na of 0.5mol/L
2SO
4Cyclic voltammetry curve figure when sweep speed is 5mv in the solution.
Fig. 4 is TiO
2The XRD spectra of/graphite rod nanometer sheet combination electrode material.
Embodiment
Below by specific embodiment to TiO of the present invention
2The preparation of/graphite rod nanometer sheet combination electrode material and be described further as the performance of electrode of super capacitor.
Embodiment 1
(1) clean of graphite rod
A. graphite rod being carried out grinding process makes its disc more smooth smooth.
B. graphite rod is placed high purity water to carry out ultrasonic cleaning repeatedly.
C. graphite rod is placed HCl solution etching 20 ~ 60min of 4 ~ 6 mol/L to remove the inorganic matter that graphite rod contains, use the high purity water ultrasonic cleaning, graphite rod surface and inner acid are thoroughly cleaned.
D. graphite rod is placed the ultrasonic several of acetone soln to remove the organic substance that graphite rod contains, after continuing ultrasonic cleaning in the high purity water, place vacuum drying oven to dry to remove residual acetone down at 40 ℃ ~ 60 ℃.
(2) preparation of graphite rod nanometer sheet substrate
A. the graphite rod through cleaning being placed the aqueous solution of 0.01～0.05mol/L anionic surfactant sodium dodecylbenzene sulfonate, is that electricity is peeled off 10 ~ 15h under 2 ~ 9V at voltage.
B. peel off finish after, earlier with the abundant scouring stone inker of high purity water nanometer sheet substrate surface, soak above-mentioned graphite rod nanometer sheet substrate 10 ~ 20h with acetone soln then.
C. from acetone soln, take out the graphite rod nanometer sheet, fully wash with high purity water, both obtained the substrate of graphite rod nanometer sheet.
(3) TiO
2The preparation of/graphite rod nanometer sheet combination electrode material
A. the TiCl of configuration concentration 0.3mol/L under the room temperature condition
3Solution is as electroplate liquid.
B. with TiCl
3Solution is electroplate liquid, and the substrate of graphite rod nanometer sheet is as work electrode, and platinum guaze is as auxiliary electrode, and saturated calomel electrode is carried out the constant potential electro-deposition as reference electrode at CHI-660B type electrochemical workstation.Control constant potential electro-deposition voltage is 1.0V, and depositing temperature is 293K, and sedimentation time is 348s.
C. after the constant potential electro-deposition finishes, fully wash to remove residual electroplate liquid with high purity water, in vacuum drying oven, in 40 ℃ ~ 60 ℃ oven dry down, can make TiO
2/ graphite rod nanometer sheet combination electrode material.Detect TiO through electronic ruler
2Thickness be 6nm.
(4) TiO
2The performance test of/graphite rod nanometer sheet combination electrode material
TiO with preparation
2/ graphite rod nanometer sheet combination electrode material is as work electrode, and platinum guaze is as auxiliary electrode, and saturated calomel electrode is as reference electrode, the Na of 0.5mol/L
2SO
4To be electrolyte solution carry out the cyclic voltammetric test at CHI-660B type electrochemical workstation to solution, the cyclic voltammetry curve figure when obtaining sweep speed and being 5mv.
Can calculate TiO by Origin7.5 software and above-mentioned formula
2Ratio electric capacity, energy density and the power density of/graphite rod nanometer sheet combination electrode material.Test result: TiO
2The ratio electric capacity of/graphite rod nanometer sheet combination electrode material is: 5450F/m
2, energy density is: 3.67Wh/m
2, power density is: 30W/m
2
Embodiment 2
(1) clean of graphite rod: with embodiment 1.
(2) preparation of graphite rod nanometer sheet substrate: with embodiment 1.
(3) TiO
2The preparation of/graphite rod nanometer sheet combination electrode material
A. configuration concentration is the TiCl of 0.3mol/L under the room temperature condition
3Solution is as electroplate liquid.
B. with TiCl
3Solution is electroplate liquid, and the substrate of graphite rod nanometer sheet is as work electrode, and platinum guaze is as auxiliary electrode, and saturated calomel electrode is carried out the constant potential electro-deposition as reference electrode at CHI-660B type electrochemical workstation.Control constant potential electro-deposition voltage is 1.0V, and depositing temperature is 293K, and sedimentation time is 280s.
C. after the constant potential electro-deposition finishes, fully wash to remove residual electroplate liquid with high purity water, in vacuum drying oven, in 40 ℃ ~ 60 ℃ oven dry down, can make TiO
2/ graphite rod nanometer sheet combination electrode material.Detect TiO through electronic ruler
2Thickness be 5nm.
(4) TiO
2The performance test of/graphite rod nanometer sheet combination electrode material
Method of testing is with embodiment 1.
Test result: TiO
2The ratio electric capacity of/graphite rod nanometer sheet combination electrode material is: 8490 F/m
2, energy density is: 5.71 Wh/m
2, power density is: 46.7W/m
2
Embodiment 3
(1) clean of graphite rod: with embodiment 1.
(2) preparation of graphite rod nanometer sheet substrate: with embodiment 1.
(3) TiO
2The preparation of/graphite rod nanometer sheet combination electrode material
A. the TiCl of configuration concentration 0.3mol/L under the room temperature condition
3Solution is as electroplate liquid.
B. with TiCl
3Solution is electroplate liquid, and the substrate of graphite rod nanometer sheet is as work electrode, and platinum guaze is as auxiliary electrode, and saturated calomel electrode is carried out the constant potential electro-deposition as reference electrode at CHI-660B type electrochemical workstation.Control constant potential electro-deposition voltage is 1.0V, and depositing temperature is 293K, and sedimentation time is 1130s.
C. after the constant potential electro-deposition finishes, fully wash to remove residual electroplate liquid with high purity water, in vacuum drying oven, in 40 ℃ ~ 60 ℃ oven dry down, can make TiO
2/ graphite rod nanometer sheet combination electrode material.Detect TiO through electronic ruler
2Thickness be 7nm.
(4) TiO
2The performance test of/graphite rod nanometer sheet combination electrode material
Method of testing is with embodiment 1.
Test result: TiO
2The ratio electric capacity of/graphite rod nanometer sheet combination electrode material is: 5900F/m
2, energy density is: 3.97Wh/m
2, power density is: 32.5W/m
2
Claims (6)
1. TiO
2/ graphite rod nanometer sheet combination electrode material is that the graphite rod nanometer sheet handled with electrochemical stripping is as the substrate raw material, with TiCl
3Solution is as electroplate liquid, and depositing a layer thickness by the constant potential electrodeposition process in graphite rod nanometer sheet substrate surface is 5 ~ 15nm, fine and close TiO uniformly
2And get; The electrochemical stripping treatment process of described graphite rod is: the aqueous solution that the graphite rod through cleaning is placed 0.01 ~ 0.05mol/L anion surfactant, control voltage is at 2 ~ 9V, handle 10 ~ 15h under 20 ℃ ~ 35 ℃, washing obtains the substrate of graphite rod nanometer sheet.
2. TiO according to claim 1
2The preparation method of/graphite rod nanometer sheet combination electrode material is will carry out electrochemical stripping earlier through the graphite rod of clean to handle, and obtains the substrate of graphite rod nanometer sheet; Be the TiCl of 0.1 ~ 0.4mol/L again with concentration
3Solution is as electroplate liquid, and as work electrode, platinum guaze is as auxiliary electrode with the substrate of graphite rod nanometer sheet, and saturated calomel electrode is as reference electrode, constant potential electro-deposition 4 ~ 20min under 0.6 ~ 1.0V; After electro-deposition finished, water fully washed, and in 40 ℃ ~ 60 ℃ following vacuumizes, got TiO
2/ graphite rod nanometer sheet combination electrode material.
3. as TiO as described in the claim 2
2The preparation method of/graphite rod nanometer sheet combination electrode material, it is characterized in that: the clean technology of described graphite rod is: graphite rod is carried out grinding process make its disc more smooth smooth, water ultrasonic cleaning repeatedly is placed on etching 20 ~ 60min in the HCl solution of 4 ~ 6 mol/L; Water, acetone soln ultrasonic cleaning after etching finishes, vacuumize.
4. as TiO as described in the claim 2
2The preparation method of/graphite rod nanometer sheet combination electrode material is characterized in that: described graphite rod is natural stone inker, electrographite rod, Pintsch process graphite rod.
5. TiO according to claim 1
2The preparation method of/graphite rod nanometer sheet combination electrode material is characterized in that: described anion surfactant is: neopelex, lauryl sodium sulfate, sodium cetanesulfonate.
6. TiO according to claim 1
2/ graphite rod nanometer sheet combination electrode material is as electrode of super capacitor.
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