CN102496700A - Graphene-titanium dioxide nanotube composite material and preparation method thereof - Google Patents
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Abstract
The invention discloses a graphene-titanium dioxide nanotube composite material and a preparation method thereof. The graphene-titanium dioxide nanotube composite material is anatase TiO2(PDF 21-1272) and forms a TiO2 nanotube loaded on a graphene layer, wherein the tube diameter is 5-10 nm, and the tube length is 100-300 nm; the graphene-titanium dioxide nanotube composite material is synthesized with a hydrothermal method by taking P25 (20% of rutile type TiO2 and 80% of anatase type TiO2) or anatase TiO2 as a titanium source, adding graphene oxide dispersion and taking NaOH as a solvent; and the Li intercalation/de-intercalation specific capacity performance is improved by use of the large specific surface area and excellent electron conduction performance of graphene through compounding with the TiO2 nanotube. The preparation method of the nano material disclosed by the invention has the advantages of low cost, environmental friendliness, good repeatability and the like, and can be applied to the cathode of a lithium ion cell as well as to the fields of photocatalysts, dye-sensitized solar cells and the like.
Description
Technical field
The present invention relates to a kind of synthesizing graphite alkene-titania nanotube composite material and preparation method thereof.
Background technology
TiO
2Be a kind of important inorganic functional material, various fields such as the storage of its pollutant in the big G&W of photocatalytic degradation, solar energy and utilization, lithium ion battery has broad application prospects.TiO
2Nanotube is expected to improve TiO because the special construction of monodimension nanometer material and hollow tubular structure make it have bigger specific area, stronger adsorption capacity and special physicochemical performance
2Photocatalysis performance and photoelectric conversion efficiency, shown bigger advantage in the utilization of storage aspect the lithium.TiO
2Nano-tube material has shortened Li as the electrode of lithium ion battery
+The evolving path, thereby improve the fast charging and discharging performance of battery.Simultaneously, Li
+Embedding/take off TiO in the process
2Stability Analysis of Structures has been avoided the generation of dendrite lithium, thereby has received concern widely.Li
+In the diffusion rate of material internal is that structure with material itself has close ties, if portion's framework Li within it
+The passage of fast transferring also can improve its fast charging and discharging performance.
Graphene is a kind of by sp
2The cellular two-dimentional carbonaceous new material of periodicity that the carbon atom of hydridization forms with hexagonal array, its particular structural makes it have a lot of special performances.For example the theoretical specific area of Graphene is up to 2630m
2/ g has electron mobility (～15000cm at a high speed under good thermal conductivity (～3000W/ (mK)) and the room temperature
2/ (Vs)), considerably beyond the conduction velocity of electronics in general conductor, thus huge in the potential application space of microelectronic.Graphene-based inorganic nano composite material not only can keep Graphene and inorganic to receive the inherent characteristic of particle simultaneously, and can produce novel cooperative effect.Occurred being applied to the report of lithium ion battery negative material in recent years, made of the application also to some extent development of its excellent electric conductivity in electrochemical field about Graphene and graphene composite material.
Summary of the invention
The object of the invention is, a kind of Graphene-titania nanotube composite material and preparation method is provided, and this Graphene-titania nanotube composite material is anatase TiO
2(PDF21-1272), pattern is the TiO of load on the graphene layer
2Nanotube, wherein caliber is 5-10nm, pipe range is 100-300nm, is with P25 (20% rutile TiO
2With 80% Detitanium-ore-type TiO
2) or anatase TiO
2Be the titanium source, add the graphene oxide dispersion liquid, adopt NaOH, adopt hydro thermal method to synthesize Graphene-titania nanotube composite material, utilize the big specific area and excellent electrical conductivity characteristic of Graphene as solvent, through with TiO
2Nanotube compound improved Li
+Embedding/take off specific capacity performance.Advantages such as that the preparation method of nano material that the present invention relates to has is with low cost, environmental friendliness, favorable repeatability can be used for lithium ion battery negative, also can be used for fields such as photochemical catalyst, DSSC.
A kind of Graphene of the present invention-titania nanotube composite material is characterized in that this Graphene-titania nanotube composite material is anatase TiO
2, pattern is the TiO of load on the graphene layer
2Nanotube, wherein caliber is 5-10nm, pipe range is 100-300nm.
The preparation method of described Graphene-titania nanotube composite material, concrete operations follow these steps to carry out:
A, be raw material, adopt the Hummers method to obtain to have water miscible graphene oxide with the graphite powder; The 5-50mg graphene oxide is dissolved in 10-15ml deionized water or the anhydrous ethanol solvent, ultrasonic Treatment 30-90 minute, obtains the graphene oxide dispersion liquid of 0.3-5g/l concentration;
B, rutile TiO with 20%
2With 80% Detitanium-ore-type TiO
2Or anatase TiO
2Be the titanium source, the molar concentration that joins the 60-70ml volume is that mixing machinery stirred 30 minutes in the NaOH solvent of 10mol/L, adds the graphene oxide dispersion liquid among the step a, continues mechanical agitation 60-90 minute to mixing;
C, the reactant liquor among the step b is moved to hydrothermal reaction kettle, reaction temperature is 140 ℃, and the reaction time is that 24h reacts, the product of gained repeatedly with washed with de-ionized water to neutral, use concentration to be 0.1mol/L HNO again
3Solution soaking 30 minutes, immersion process is followed mechanical agitation, and elimination acid solution is then cleaned to neutral with deionized water and absolute ethyl alcohol respectively again, and product obtains Graphene-titanate nanotube powder at 60 ℃ of following vacuumize 8h of temperature;
D, the powder body material among the step c is placed in the crucible, 450 ℃ of sintering 0.5h-1h of temperature under nitrogen or argon atmospher protection can obtain Graphene-titania nanotube composite material.
The mass ratio in step b graphene oxide and titanium source is 1-10: 200.
The process of the said cleaning of step c is to clean repeatedly with suction method.
The purposes of described Graphene-titania nanotube composite material is for to be used to prepare lithium ion battery negative material.
Graphene of the present invention-titania nanotube composite material is characterized in utilizing hydro-thermal reaction to make Graphene-titania nanotube structural composite material, and raw material is common to be easy to get, and the preparation process is simple and safe.This one step of method hydrothermal reduction graphene oxide has been avoided the use of poisonous reducing agents such as hydrazine hydrate, sodium borohydride, has eco-friendly characteristics.In the products therefrom, TiO
2Nanotube can be dispersed in the Graphene surface, and structural advantage makes it be applied to lithium ion battery negative material has potential value.
Description of drawings:
Fig. 1 is X-ray diffraction of the present invention (XRD) spectrum;
Fig. 2 is transmission electron microscope of the present invention (TEM) photo figure;
Fig. 3 is transmission electron microscope of the present invention (TEM) photo figure;
Fig. 4 is the constant current charge-discharge curve chart under the simulated battery 0.1C multiplying power of the present invention.
Fig. 5 is simulated battery of the present invention cyclicity curve chart under different multiplying.
Embodiment:
Further set forth content of the present invention below in conjunction with embodiment, but these embodiment do not limit protection scope of the present invention.
Embodiment 1
A, be raw material, adopt the Hummers method to obtain to have water miscible graphene oxide with the graphite powder; The 5mg graphene oxide is dissolved in the 10ml absolute ethyl alcohol, and ultrasonic Treatment 30 minutes obtains the graphene oxide dispersion liquid;
B, with P25 (20% rutile TiO
2With 80% Detitanium-ore-type TiO
2) be the titanium source; The molar concentration that joins the 70mL volume is that mixing machinery stirred 30 minutes in the NaOH solvent of 10mol/L; Add the graphene oxide dispersion liquid among the step a, wherein the mass ratio in graphene oxide and titanium source was 1: 200 to the continuation mechanical agitation to mixing in 60 minutes;
C, the reactant liquor among the step b is moved to hydrothermal reaction kettle, reaction temperature is 140 ℃, and the reaction time is that 24h reacts, the product of gained with suction method repeatedly with washed with de-ionized water to neutral, use concentration to be 0.1mol/L HNO again
3Solution soaking 30 minutes, immersion process is followed mechanical agitation, and elimination acid solution is then cleaned to neutral with deionized water and absolute ethyl alcohol respectively again, and product obtains Graphene-titanate radical nanopipe powder at 60 ℃ of following vacuumize 8h of temperature;
D, the powder body material among the step c is placed in the crucible, 450 ℃ of sintering 0.5h of temperature can obtain 1g Graphene-titania nanotube composite material under nitrogen protection.
Embodiment 2
A, be raw material, adopt the Hummers method to obtain to have water miscible graphene oxide with the graphite powder; The 5mg graphene oxide is dissolved in the 10ml anhydrous ethanol solvent, and ultrasonic Treatment 45 minutes obtains the graphene oxide dispersion liquid;
B, with anatase TiO
2Be the titanium source; The molar concentration that joins the 60ml volume is that mixing machinery stirred 30 minutes in the NaOH solvent of 10mol/L; Add the graphene oxide dispersion liquid among the step a, wherein the mass ratio in graphene oxide and titanium source was 1: 200 to the continuation mechanical agitation to mixing in 70 minutes;
C, the reactant liquor among the step b is moved to hydrothermal reaction kettle, reaction temperature is 140 ℃, and the reaction time is that 24h reacts, the product of gained with suction method repeatedly with washed with de-ionized water to neutral, use concentration to be 0.1mol/L HNO again
3Solution soaking 30 minutes, immersion process is followed mechanical agitation, and elimination acid solution is then cleaned to neutral with deionized water and absolute ethyl alcohol respectively again, and product obtains Graphene-titanate radical nanopipe powder at 60 ℃ of following vacuumize 8h of temperature;
D, the powder body material among the step c is placed in the crucible, under the argon atmospher protection, 450 ℃ of sintering 0.8h of temperature can obtain 1.01g Graphene-titania nanotube composite material.
A, be raw material, adopt the Hummers method to obtain to have water miscible graphene oxide with the graphite powder; The 15mg graphene oxide is dissolved in the 15ml absolute ethyl alcohol, and ultrasonic Treatment 50 minutes obtains the graphene oxide dispersion liquid;
B, with P25 (20% rutile TiO
2With 80% Detitanium-ore-type TiO
2) be the titanium source; The molar concentration that joins the 65ml volume is that mixing machinery stirred 30 minutes in the NaOH solvent of 10mol/L; Add the graphene oxide dispersion liquid among the step a, wherein the mass ratio in graphene oxide and titanium source was 3: 200 to the continuation mechanical agitation to mixing in 65 minutes;
C, the reactant liquor among the step b is moved to hydrothermal reaction kettle, reaction temperature is 140 ℃, and the reaction time is that 24h reacts, the product of gained with suction method repeatedly with washed with de-ionized water to neutral, use concentration to be 0.1mol/L HNO again
3Solution soaking 30 minutes, immersion process is followed mechanical agitation, and elimination acid solution is then cleaned to neutral with deionized water and absolute ethyl alcohol respectively again, and product obtains Graphene-titanate radical nanopipe powder at 60 ℃ of following vacuumize 8h of temperature;
D, the powder body material among the step c is placed in the crucible, under nitrogen protection, 450 ℃ of sintering 1h of temperature can obtain 1.01g Graphene-titania nanotube composite material.
Embodiment 4
A, be raw material, adopt the Hummers method to obtain to have water miscible graphene oxide with the graphite powder; The 30mg graphene oxide is dissolved in the 10ml deionized water solvent, and ultrasonic Treatment 70 minutes obtains the graphene oxide dispersion liquid;
B, with anatase TiO
2Be the titanium source; The molar concentration that joins the 70ml volume is that mixing machinery stirred 30 minutes in the NaOH solvent of 10mol/L; Graphene oxide dispersion liquid among the step a is added, and wherein the mass ratio in graphene oxide and titanium source was 6: 200 to the continuation mechanical agitation to mixing in 75 minutes;
C, the reactant liquor among the step b is moved to hydrothermal reaction kettle, reaction temperature is 140 ℃, and the reaction time is that 24h reacts, the product of gained with suction method repeatedly with washed with de-ionized water to neutral, use concentration to be 0.1mol/L HNO again
3Solution soaking 30 minutes, immersion process is followed mechanical agitation, and elimination acid solution is then cleaned to neutral with deionized water and absolute ethyl alcohol respectively again, and product obtains Graphene-titanate radical nanopipe powder at 60 ℃ of following vacuumize 8h of temperature;
D, the powder body material among the step c is placed in the crucible, 450 ℃ of sintering 0.5h of temperature can obtain 1.02g Graphene-titania nanotube composite material under nitrogen protection.
Embodiment 5
A, be raw material, adopt the Hummers method to obtain to have water miscible graphene oxide with the graphite powder; The 40mg graphene oxide is dissolved in the 15ml anhydrous ethanol solvent, and ultrasonic Treatment 80 minutes obtains the graphene oxide dispersion liquid;
B, with P25 (20% rutile TiO
2With 80% Detitanium-ore-type TiO
2) be the titanium source; The molar concentration that joins the 60ml volume is that mixing machinery stirred 30 minutes in the NaOH solvent of 10mol/L; Add the graphene oxide dispersion liquid among the step a, wherein the mass ratio in graphene oxide and titanium source was 8: 200 to the continuation mechanical agitation to mixing in 80 minutes;
C, the reactant liquor among the step b is moved to hydrothermal reaction kettle, reaction temperature is 140 ℃, and the reaction time is that 24h reacts, the product of gained with suction method repeatedly with washed with de-ionized water to neutral, use concentration to be 0.1mol/L HNO again
3Solution soaking 30 minutes, immersion process is followed mechanical agitation, and elimination acid solution is then cleaned to neutral with deionized water and absolute ethyl alcohol respectively again, and product obtains Graphene-titanate radical nanopipe powder at 60 ℃ of following vacuumize 8h of temperature;
D, the powder body material among the step c is placed in the crucible, 450 ℃ of sintering 0.5h of temperature under nitrogen or argon atmospher protection can obtain 1.03g Graphene-titania nanotube composite material.
Embodiment 6
A, be raw material, adopt the Hummers method to obtain to have water miscible graphene oxide with the graphite powder; The 50mg graphene oxide is dissolved in the 15ml deionized water solvent, and ultrasonic Treatment 90 minutes obtains the graphene oxide dispersion liquid;
B, with anatase TiO
2Be the titanium source; The molar concentration that joins the 70ml volume is that mixing machinery stirred 30 minutes in the NaOH solvent of 10mol/L; Add the graphene oxide dispersion liquid among the step a, wherein the mass ratio in graphene oxide and titanium source was 10: 200 to the continuation mechanical agitation to mixing in 90 minutes;
C, the reactant liquor among the step b is moved to hydrothermal reaction kettle, reaction temperature is 140 ℃, and the reaction time is that 24h reacts, the product of gained with suction method repeatedly with washed with de-ionized water to neutral, use concentration to be 0.1mol/L HNO again
3Solution soaking 30 minutes, immersion process is followed mechanical agitation, and elimination acid solution is then cleaned to neutral with deionized water and absolute ethyl alcohol respectively again, and product obtains Graphene-titanate nanotube powder at 60 ℃ of following vacuumize 8h of temperature;
D, the powder body material among the step c is placed in the crucible, 450 ℃ of sintering 1h of temperature under nitrogen or argon atmospher protection can obtain 1.05g Graphene-titania nanotube composite material.
Graphene-titania nanotube composite products the structure that obtains through the method for the invention is anatase TiO
2(seeing accompanying drawing 1); This composite material pattern is the TiO of load on the graphene layer
2Nanotube, wherein caliber is about 5-10nm, and pipe range is about 100～300nm (seeing accompanying drawing 2 and 3).
Graphene of the present invention-titania nanotube composite material lithium ion battery performance test:
Taking by weighing Graphene-titania nanotube composite powder material that 1-5mg obtains is active material, and acetylene black is conductive agent, and polytetrafluoroethylene is a binding agent; Is that 80: 15: 5 mixed is sized mixing with it by mass ratio, this slurry is coated on the aluminum foil current collector, and behind 120 ℃ of following vacuumize 12h of temperature; Be cut into diameter and be about the negative pole of the disk of 1cm, add electrolyte as battery, in being full of the glove box of argon gas with lithium metal for to electrode; Cellgard2400 is a barrier film; Be assembled into button-shaped simulated battery (CR2025), carry out charge-discharge test, discharge and recharge window 3-1V (vs Li/Li with battery test system
+), referring to attaching Figure 4 and 5, as can be seen from the figure this composite material has tangible charge and discharge platform; Plateau potential is about 1.7V; Steadily and longer, 0.1C (1.0C=300mAh/g) when discharging and recharging specific capacity reach 270mAh/g (theoretical embedding lithium specific capacity is 330mAh/g), specific capacity still can reach 125mAh/g when 5C discharges and recharges; And not significantly decay of circulation volume in 50 weeks, cycle performance is excellent.
Claims (5)
1. Graphene-titania nanotube composite material is characterized in that this Graphene-titania nanotube composite material is anatase TiO
2, pattern is the TiO of load on the graphene layer
2Nanotube, wherein caliber is 5-10nm, pipe range is 100-300nm.
2. the preparation method of Graphene according to claim 1-titania nanotube structure is characterized in that concrete operations follow these steps to carry out:
A, be raw material, adopt the Hummers method to obtain to have water miscible graphene oxide with the graphite powder; The 5-50mg graphene oxide is dissolved in 10-15ml deionized water or the anhydrous ethanol solvent, ultrasonic Treatment 30-90 minute, obtains the graphene oxide dispersion liquid of 0.3-5g/l concentration;
B, rutile TiO with 20%
2With 80% Detitanium-ore-type TiO
2Or anatase TiO
2Be the titanium source, the molar concentration that joins the 60-70ml volume is that mixing machinery stirred 30 minutes in the NaOH solvent of 10mol/L, adds the graphene oxide dispersion liquid among the step a, continues mechanical agitation 60-90 minute to mixing;
C, the reactant liquor among the step b is moved to hydrothermal reaction kettle, reaction temperature is 140 ℃, and the reaction time is that 24h reacts, the product of gained repeatedly with washed with de-ionized water to neutral, use concentration to be 0.1mol/L HNO again
3Solution soaking 30 minutes, immersion process is followed mechanical agitation, and elimination acid solution is then cleaned to neutral with deionized water and absolute ethyl alcohol respectively again, and product obtains Graphene-titanate radical nanopipe powder at 60 ℃ of following vacuumize 8h of temperature;
D, the powder body material among the step c is placed in the crucible, 450 ℃ of sintering 0.5h-1h of temperature under nitrogen or argon atmospher protection can obtain Graphene-titania nanotube composite material.
3. preparation method according to claim 2, the mass ratio that it is characterized in that step b graphene oxide and titanium source is 1-10: 200.
4. preparation method according to claim 2 is characterized in that the process of the said cleaning of step c is to clean repeatedly with suction method.
5. the purposes of Graphene according to claim 1-titania nanotube composite material is characterized in that described Graphene-titania nanotube composite material is being used to prepare lithium ion battery negative material.
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