CN102496700B - 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, the various fields such as the storage of its pollutant in the large G&W of photocatalytic degradation, solar energy and utilization, lithium ion battery has broad application prospects.TiO
2nanotube, because the special construction of monodimension nanometer material and the tubular structure of hollow make it have larger specific area, stronger adsorption capacity and special physical and chemical performance, is expected to improve TiO
2photocatalysis performance and photoelectric conversion efficiency, the utilization in storage aspect lithium has shown larger advantage.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.Meanwhile, Li
+tiO in embedding/de-process
2stability Analysis of Structures, has avoided the generation of dendrite lithium, thereby has been subject to paying close attention to widely.Li
+diffusion rate at material internal is to have close ties with the structure of material itself, 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 special structure 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 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 the inorganic inherent characteristic of receiving particle simultaneously, and can produce novel cooperative effect.There is being in recent years applied to about Graphene and graphene composite material the report of lithium ion battery negative material, made its excellent electric conductivity in the also development to some extent of application of electrochemical field.
Summary of the invention
The object of the invention is, a kind of graphene-titanium dioxide nanotube composite material and preparation method are provided, and this graphene-titanium dioxide nanotube composite material is anatase TiO
2(PDF21-1272), pattern is the TiO of load on 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
2for titanium source, add graphene oxide dispersion liquid, adopt NaOH as solvent, adopt hydro thermal method to synthesize graphene-titanium dioxide nanotube composite material, utilize the large specific area of Graphene and excellent Electronic Transport of Two Benzene, by with TiO
2nanotube compound, improves Li
+embedding/de-specific capacity performance.The advantages such as that the preparation method of nano material 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 the fields such as photochemical catalyst, DSSC.
A kind of graphene-titanium dioxide nanotube composite material of the present invention, is characterized in that this graphene-titanium dioxide nanotube composite material is anatase TiO
2, pattern is the TiO of load on graphene layer
2nanotube, wherein caliber is 5-10nm, pipe range is 100-300nm.
The preparation method of described graphene-titanium dioxide nanotube composite material, concrete operations follow these steps to carry out:
A, take graphite powder as raw material, adopt Hummers method to obtain and there is water miscible graphene oxide; 5-50mg graphene oxide is dissolved in 10-15ml deionized water or anhydrous ethanol solvent, and ultrasonic wave is processed 30-90 minute, obtains the graphene oxide dispersion liquid of 0.3-5g/l concentration;
B, the rutile TiO with 20%
2with 80% Detitanium-ore-type TiO
2or anatase TiO
2for titanium source, in the NaOH solvent that the molar concentration that joins 60-70ml volume is 10mol/L, mixing machinery stirs 30 minutes, adds the graphene oxide dispersion liquid in step a, continues mechanical agitation 60-90 minute to mixing;
C, the reactant liquor in 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 by washed with de-ionized water to neutral, then be 0.1mol/L HNO by concentration
3solution soaks 30 minutes, and immersion process is followed mechanical agitation, then elimination acid solution, then with deionized water and absolute ethyl alcohol, clean to neutral respectively, product is vacuumize 8h under temperature 60 C, obtains Graphene-titanate nanotube powder;
D, the powder body material in step c is placed in crucible, 450 ℃ of sintering 0.5h-1h of temperature under nitrogen or argon atmospher protection, can obtain graphene-titanium dioxide nanotube composite material.
The mass ratio in step b graphene oxide and titanium source is 1-10: 200.
The process of cleaning described in step c is repeatedly to clean with suction method.
The purposes of described graphene-titanium dioxide nanotube composite material is for the preparation of lithium ion battery negative material.
Graphene-titanium dioxide nanotube composite material of the present invention, is characterized in utilizing hydro-thermal reaction to make graphene-titanium dioxide nanotube structural composite material, and raw material is common to be easy to get, and preparation process is simple and safe.The method one step hydrothermal reduction graphene oxide, has avoided the use of the poisonous reducing agents such as hydrazine hydrate, sodium borohydride, has eco-friendly feature.In products therefrom, TiO
2nanotube can be uniformly dispersed in Graphene surface, and structural advantage makes it be applied to lithium ion battery negative material potential value.
Accompanying drawing explanation:
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 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:
Below in conjunction with embodiment, further set forth content of the present invention, but these embodiment do not limit the scope of the invention.
Embodiment 1
A, take graphite powder as raw material, adopt Hummers method to obtain and there is water miscible graphene oxide; 5mg graphene oxide is dissolved in 10ml absolute ethyl alcohol, and ultrasonic wave is processed 30 minutes, obtains graphene oxide dispersion liquid;
B, with P25 (20% rutile TiO
2with 80% Detitanium-ore-type TiO
2) be titanium source, in the NaOH solvent that the molar concentration that joins 70mL volume is 10mol/L, mixing machinery stirs 30 minutes, add the graphene oxide dispersion liquid in step a, within 60 minutes, to mixing, wherein the mass ratio in graphene oxide and titanium source is 1: 200 to continuation mechanical agitation;
C, the reactant liquor in 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 by washed with de-ionized water to neutral, then be 0.1mol/L HNO by concentration
3solution soaks 30 minutes, and immersion process is followed mechanical agitation, then elimination acid solution, then with deionized water and absolute ethyl alcohol, clean to neutral respectively, product is vacuumize 8h under temperature 60 C, obtains Graphene-titanate radical nanopipe powder;
D, the powder body material in step c is placed in crucible, under nitrogen protection, 450 ℃ of sintering 0.5h of temperature, can obtain 1g graphene-titanium dioxide nanotube composite material.
Embodiment 2
A, take graphite powder as raw material, adopt Hummers method to obtain and there is water miscible graphene oxide; 5mg graphene oxide is dissolved in 10ml anhydrous ethanol solvent, and ultrasonic wave is processed 45 minutes, obtains graphene oxide dispersion liquid;
B, with anatase TiO
2for titanium source, in the NaOH solvent that the molar concentration that joins 60ml volume is 10mol/L, mixing machinery stirs 30 minutes, add the graphene oxide dispersion liquid in step a, within 70 minutes, to mixing, wherein the mass ratio in graphene oxide and titanium source is 1: 200 to continuation mechanical agitation;
C, the reactant liquor in 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 by washed with de-ionized water to neutral, then be 0.1mol/L HNO by concentration
3solution soaks 30 minutes, and immersion process is followed mechanical agitation, then elimination acid solution, then with deionized water and absolute ethyl alcohol, clean to neutral respectively, product is vacuumize 8h under temperature 60 C, obtains Graphene-titanate radical nanopipe powder;
D, the powder body material in step c is placed in crucible, under argon atmospher protection, 450 ℃ of sintering 0.8h of temperature, can obtain 1.01g graphene-titanium dioxide nanotube composite material.
A, take graphite powder as raw material, adopt Hummers method to obtain and there is water miscible graphene oxide; 15mg graphene oxide is dissolved in 15ml absolute ethyl alcohol, and ultrasonic wave is processed 50 minutes, obtains graphene oxide dispersion liquid;
B, with P25 (20% rutile TiO
2with 80% Detitanium-ore-type TiO
2) be titanium source, in the NaOH solvent that the molar concentration that joins 65ml volume is 10mol/L, mixing machinery stirs 30 minutes, add the graphene oxide dispersion liquid in step a, within 65 minutes, to mixing, wherein the mass ratio in graphene oxide and titanium source is 3: 200 to continuation mechanical agitation;
C, the reactant liquor in 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 by washed with de-ionized water to neutral, then be 0.1mol/L HNO by concentration
3solution soaks 30 minutes, and immersion process is followed mechanical agitation, then elimination acid solution, then with deionized water and absolute ethyl alcohol, clean to neutral respectively, product is vacuumize 8h under temperature 60 C, obtains Graphene-titanate radical nanopipe powder;
D, the powder body material in step c is placed in crucible, under nitrogen protection, 450 ℃ of sintering 1h of temperature, can obtain 1.01g graphene-titanium dioxide nanotube composite material.
Embodiment 4
A, take graphite powder as raw material, adopt Hummers method to obtain and there is water miscible graphene oxide; 30mg graphene oxide is dissolved in 10ml deionized water solvent, and ultrasonic wave is processed 70 minutes, obtains graphene oxide dispersion liquid;
B, with anatase TiO
2for titanium source, in the NaOH solvent that the molar concentration that joins 70ml volume is 10mol/L, mixing machinery stirs 30 minutes, graphene oxide dispersion liquid in step a is added, and within 75 minutes, to mixing, wherein the mass ratio in graphene oxide and titanium source is 6: 200 to continuation mechanical agitation;
C, the reactant liquor in 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 by washed with de-ionized water to neutral, then be 0.1mol/L HNO by concentration
3solution soaks 30 minutes, and immersion process is followed mechanical agitation, then elimination acid solution, then with deionized water and absolute ethyl alcohol, clean to neutral respectively, product is vacuumize 8h under temperature 60 C, obtains Graphene-titanate radical nanopipe powder;
D, the powder body material in step c is placed in crucible, under nitrogen protection, 450 ℃ of sintering 0.5h of temperature, can obtain 1.02g graphene-titanium dioxide nanotube composite material.
Embodiment 5
A, take graphite powder as raw material, adopt Hummers method to obtain and there is water miscible graphene oxide; 40mg graphene oxide is dissolved in 15ml anhydrous ethanol solvent, and ultrasonic wave is processed 80 minutes, obtains graphene oxide dispersion liquid;
B, with P25 (20% rutile TiO
2with 80% Detitanium-ore-type TiO
2) be titanium source, in the NaOH solvent that the molar concentration that joins 60ml volume is 10mol/L, mixing machinery stirs 30 minutes, add the graphene oxide dispersion liquid in step a, within 80 minutes, to mixing, wherein the mass ratio in graphene oxide and titanium source is 8: 200 to continuation mechanical agitation;
C, the reactant liquor in 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 by washed with de-ionized water to neutral, then be 0.1mol/L HNO by concentration
3solution soaks 30 minutes, and immersion process is followed mechanical agitation, then elimination acid solution, then with deionized water and absolute ethyl alcohol, clean to neutral respectively, product is vacuumize 8h under temperature 60 C, obtains Graphene-titanate radical nanopipe powder;
D, the powder body material in step c is placed in crucible, 450 ℃ of sintering 0.5h of temperature under nitrogen or argon atmospher protection, can obtain 1.03g graphene-titanium dioxide nanotube composite material.
Embodiment 6
A, take graphite powder as raw material, adopt Hummers method to obtain and there is water miscible graphene oxide; 50mg graphene oxide is dissolved in 15ml deionized water solvent, and ultrasonic wave is processed 90 minutes, obtains graphene oxide dispersion liquid;
B, with anatase TiO
2for titanium source, in the NaOH solvent that the molar concentration that joins 70ml volume is 10mol/L, mixing machinery stirs 30 minutes, add the graphene oxide dispersion liquid in step a, within 90 minutes, to mixing, wherein the mass ratio in graphene oxide and titanium source is 10: 200 to continuation mechanical agitation;
C, the reactant liquor in 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 by washed with de-ionized water to neutral, then be 0.1mol/L HNO by concentration
3solution soaks 30 minutes, and immersion process is followed mechanical agitation, then elimination acid solution, then with deionized water and absolute ethyl alcohol, clean to neutral respectively, product is vacuumize 8h under temperature 60 C, obtains Graphene-titanate nanotube powder;
D, the powder body material in step c is placed in crucible, 450 ℃ of sintering 1h of temperature under nitrogen or argon atmospher protection, can obtain 1.05g graphene-titanium dioxide nanotube composite material.
The graphene-titanium dioxide nanotube composite material product structure obtaining by the method for the invention is anatase TiO
2(seeing accompanying drawing 1); This composite material pattern is the TiO of load on graphene layer
2nanotube, wherein caliber is about 5-10nm, and pipe range is about 100～300nm (seeing accompanying drawing 2 and 3).
Graphene-titanium dioxide nanotube composite material performance of lithium ion battery test of the present invention:
Taking the graphene-titanium dioxide nanotube composite powder material that 1-5mg obtains is active material, acetylene black is conductive agent, polytetrafluoroethylene is binding agent, the ratio mixing that is 80: 15: 5 in mass ratio by it is sized mixing, this slurry is coated in aluminum foil current collector, and at 120 ℃ of temperature after vacuumize 12h, be cut into diameter and be about the disk of 1cm as the negative pole of battery, add electrolyte, in being full of the glove box of argon gas, take lithium metal as to electrode, Cellgard2400 is barrier film, be assembled into button-shaped simulated battery (CR2025), with battery test system, carry out charge-discharge test, discharge and recharge window 3-1V (vs Li/Li
+), referring to attached Figure 4 and 5, as can be seen from the figure this composite material has obvious charge and discharge platform, plateau potential is in 1.7V left and right, steadily and longer, when 0.1C (1.0C=300mAh/g) discharges and recharges, specific capacity reaches 270mAh/g (theoretical embedding lithium specific capacity is 330mAh/g), and when 5C discharges and recharges, specific capacity still can reach 125mAh/g, and not significantly decay of circulation volume in 50 weeks, cycle performance is excellent.
Claims (3)
1. a preparation method for graphene-titanium dioxide nanotube composite material, is characterized in that this graphene-titanium dioxide nanotube composite material is anatase TiO
2, pattern is the TiO of load on graphene layer
2nanotube, wherein caliber is 5-10nm, and pipe range is 100-300nm, and concrete operations follow these steps to carry out:
A, take graphite powder as raw material, adopt Hummers method to obtain and there is water miscible graphene oxide; 5-50mg graphene oxide is dissolved in 10-15ml deionized water or anhydrous ethanol solvent, and ultrasonic wave is processed 30-90 minute, obtains the graphene oxide dispersion liquid of 0.3-5g/l concentration;
B, the rutile TiO with 20%
2with 80% Detitanium-ore-type TiO
2or anatase TiO
2for titanium source, in the NaOH solvent that the molar concentration that joins 60-70ml volume is 10mol/L, mixing machinery stirs 30 minutes, adds the graphene oxide dispersion liquid in step a, continues mechanical agitation 60-90 minute to mixing;
C, the reactant liquor that step b is obtained move to hydrothermal reaction kettle, and reaction temperature is 140 ℃, and the reaction time is that 24h reacts, and the product of gained is repeatedly extremely neutral by washed with de-ionized water, then is 0.1mol/L HNO by concentration
3solution soaks 30 minutes, and immersion process is followed mechanical agitation, then elimination acid solution, then with deionized water and absolute ethyl alcohol, clean to neutral respectively, product is vacuumize 8h under temperature 60 C, obtains Graphene-titanate radical nanopipe powder;
D, the powder body material that step c is obtained are placed in crucible, and 450 ℃ of sintering 0.5h-1h of temperature under nitrogen or argon atmospher protection, can obtain graphene-titanium dioxide nanotube composite material.
2. preparation method according to claim 1, the mass ratio that it is characterized in that step b graphene oxide and titanium source is 1-10: 200.
3. preparation method according to claim 1, is characterized in that the process of cleaning described in step c is repeatedly to clean with suction method.
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