CN108134068A - Titanium dioxide-graphene oxide composite material, preparation method and application - Google Patents
Titanium dioxide-graphene oxide composite material, preparation method and application Download PDFInfo
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- CN108134068A CN108134068A CN201711421262.5A CN201711421262A CN108134068A CN 108134068 A CN108134068 A CN 108134068A CN 201711421262 A CN201711421262 A CN 201711421262A CN 108134068 A CN108134068 A CN 108134068A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation method of titanium dioxide graphene oxide composite material, titanium dioxide graphene oxide composite material and applications.A kind of preparation method of titanium dioxide graphene oxide composite material, includes the following steps：Mixed liquor is provided；Reaction solution is ultrasonically treated and butyl titanate is added dropwise into reaction solution and obtains reaction solution, supersound process is carried out to reaction solution and obtains precursor solution within 1 hour~4 hours；By precursor solution be heated to 100 DEG C~200 DEG C carry out hydro-thermal reaction 12 hours~120 hours after separation of solid and liquid obtain solids, solids is washed and is dried to obtain head product；Processing is ground to head product；And the head product after milled processed at 350 DEG C~450 DEG C is calcined and obtains titanium dioxide graphene oxide composite material.The preparation method preparation process of above-mentioned titanium dioxide graphene oxide composite material is relatively simple and can improve lithium ion battery specific discharge capacity and cyclical stability.
Description
Technical field
The present invention relates to a kind of preparation method of titanium dioxide-graphene oxide composite material, titanium dioxide-oxidation stone
Black alkene composite material and application.
Background technology
In face of global energy shortage and problem of environmental pollution, create new technology and collection of energy, conversion and storage are set
Standby high efficiency is a urgent demand.And be used as energy convert and store with widest lithium ion battery be for
One of most promising energy storage device of various portable electronic devices.For next-generation lithium ion battery, design and synthesis
Cost can be reduced, it is a crucial mesh to improve capacity and improve rate capability and the functional cells material of cycle performance
Mark.In lithium ion battery is studied, studying the cathode of lithium ion battery is particularly important, because the cathode of battery can be very
Big degree influences performance of lithium ion battery.Transition metal oxide is since its superior chemical property is in lithium ion battery
Extensive concern is caused in terms of super capacitor.Titanium dioxide is to study metal oxide negative material earlier, due to knot
The features such as structure is stable, cycle performance is superior, cheap, environment is friendly, safe, becomes research hotspot in recent years.
Titanium dioxide is there are many crystalline structure, including anatase, rutile, rhomboclase, titanium dioxide B etc., wherein rutile titania
Ore deposit and rutile are to manufacture the common negative material of lithium ion battery in current industry.Ostword has found rutile titania in titanium dioxide
Ore deposit is the crystalline structure better than rutile.Titanic oxide material electronic conductivity is low and the diffusion of lithium ion inside it
Coefficient is smaller, thus more research work is intended to the titanic oxide material of synthesis nano-scale, while constructs good structure
Pattern also contributes to improve titanium dioxide chemical property, on the other hand by titanium dioxide and conductive carbon material, metal material,
The progress such as metal oxide materials is compound, improves the electric conductivity of material and then improves specific volume of the titanium dioxide as negative material
Amount.
However, the preparation process of existing anatase structured composite titania material is complex, and prepare sharp
When the composite titania material of perovskite like structure is as lithium ion battery negative material, the specific discharge capacity of lithium ion battery compared with
Low and cyclical stability is bad.
Invention content
Based on this, it is necessary to provide a kind of preparation process it is relatively simple and can improve lithium ion battery specific discharge capacity and
The preparation method of titanium dioxide-graphene oxide composite material of cyclical stability, titanium dioxide-graphene oxide composite wood
Material and application.
A kind of preparation method of titanium dioxide-graphene oxide composite material, includes the following steps：
Mixed liquor is provided, contains lithium hydroxide and graphene in the mixed liquor；
The reaction solution is ultrasonically treated and butyl titanate is added dropwise into the reaction solution and obtains reaction solution, it is right
The reaction solution, which be ultrasonically treated 1 hour~4 hours, obtains precursor solution, wherein, the butyl titanate and the hydrogen
The mass ratio of lithia is 1:3~1:7；
The precursor solution is heated to 100 DEG C~200 DEG C and carries out solid-liquid after hydro-thermal reaction 12 hours~120 hours
The solids is washed and is dried to obtain head product by isolated solids；
Processing is ground to the head product；And
The head product after milled processed at 350 DEG C~450 DEG C is calcined 1 hour~8 hours and obtains titanium dioxide
Titanium-graphene oxide composite material.
The preparation method of above-mentioned titanium dioxide-graphene oxide composite material, using butyl titanate as titanium source, a step
Method generates pure phase anatase titanium dioxide B and mixes type hollow nano structure, compound so as to obtain titanium dioxide-graphene oxide
Material, simple to operation, reaction time is short, and low energy consumption；Dispersant need not be added in reaction process, reduces production cost；It is logical
Overregulate the reaction temperature of hydro-thermal reaction and the pore size of reaction time i.e. controllable titanium dioxide hollow ball；Two prepared
When titanium oxide-graphene oxide composite material is as lithium ion battery negative material, lithium ion battery specific discharge capacity can be improved
And cyclical stability.
The mass ratio of the lithium hydroxide and the graphene is 1000 in one of the embodiments,：1~50： 1.
Also contain water in the mixture in one of the embodiments, the ratio of the lithium hydroxide and the water is
1g:3mL~1g:10mL.
The power of the supersound process is 100W~250W in one of the embodiments,.
The hydro-thermal reaction carries out in autoclave in one of the embodiments,.
In one of the embodiments, in described the step of washing the solids and being dried to obtain head product, use
Ethyl alcohol and inorganic acid alternately wash the solids, reuse deionized water later and wash the solids to neutrality.
The inorganic acid is selected from least one of hydrochloric acid, nitric acid and sulfuric acid in one of the embodiments,.
A concentration of 0.05mol/L~0.5mol/L of the sulfuric acid in one of the embodiments,.
Titanium dioxide-graphene oxide that the preparation method of above-mentioned titanium dioxide-graphene oxide composite material obtains
Composite material.
The application of above-mentioned titanium dioxide-graphene oxide composite material in the battery.
Description of the drawings
Fig. 1 is the X-ray diffraction photo of titanium dioxide-graphene oxide composite material prepared by embodiment 1；
Fig. 2 is the transmission electron microscope figure of titanium dioxide-graphene oxide composite material prepared by embodiment 1；
Fig. 3 is the scanning electron microscope diagram of titanium dioxide-graphene oxide composite material prepared by embodiment 1；
Fig. 4 is the electric current using the lithium ion battery 0.5C of titanium dioxide-graphene oxide composite material of embodiment 1
Charge graph under density；
Fig. 5 is the electric current using the lithium ion battery 0.5C of titanium dioxide-graphene oxide composite material of embodiment 1
Discharge curve under density；
Fig. 6 is the electric current using the lithium ion battery 0.5C of titanium dioxide-graphene oxide composite material of comparative example 1
Charge graph under density；
Fig. 7 is the lithium ion battery 0.5C of titanium dioxide-graphene oxide composite material prepared using comparative example 1
Discharge curve under current density.
Specific embodiment
Below in conjunction with preparation method of the specific embodiment to titanium dioxide-graphene oxide composite material, titanium dioxide
Titanium-graphene oxide composite material and application are further described in detail.
The preparation method of titanium dioxide-graphene oxide composite material of one embodiment, includes the following steps：
Step S110, mixed liquor is provided, contain lithium hydroxide and graphene in mixed liquor.
The mass ratio of lithium hydroxide and graphene is 1000 in one of the embodiments,：1~50：1.
Also contain water in mixture in one of the embodiments, the ratio of lithium hydroxide and water is 1g:3mL~1g:
10mL。
Graphene is graphene prepared by improved Hummers methods in one of the embodiments,.
Mixed liquor is prepared by operations described below in one of the embodiments,：It is 1000 by mass ratio：1~50：1 hydrogen
Lithia adds in deionized water with graphene and is configured to mixed liquor, and the ratio of lithium hydroxide and deionized water is 1g:3mL~
1g:10mL。
Step S120, reaction solution is ultrasonically treated and butyl titanate is added dropwise into reaction solution and obtain reaction solution, it is right
Reaction solution, which be ultrasonically treated 1 hour~4 hours, obtains precursor solution.
The mass ratio of butyl titanate and lithium hydroxide is 1:3~1:7.
The rate of addition of butyl titanate is 1 drop/sec~5 drops/sec in one of the embodiments,.
The power being ultrasonically treated in one of the embodiments, is 100W~250W.
Step S130, by precursor solution be heated to 100 DEG C~200 DEG C carry out hydro-thermal reaction 12 hours~120 hours after
Separation of solid and liquid obtains solids, and solids is washed and is dried to obtain head product.
Hydro-thermal reaction carries out in autoclave in one of the embodiments, is carried out using the pressure that reaction generates
Hydro-thermal reaction.
The time of hydro-thermal reaction is 48 hours in one of the embodiments,.
Solids is alternately washed using ethyl alcohol and inorganic acid in one of the embodiments, reuses deionized water later
Solids is washed to neutrality.Further, inorganic acid is selected from least one of hydrochloric acid, nitric acid and sulfuric acid.Inorganic acid it is dense
It spends for 0.05mol/L~0.5mol/L, further preferably 0.1mol/L.Preferably, using the respectively washing 3 of ethyl alcohol and inorganic acid
It is secondary~6 times.
It is 7 that solids, which is washed to pH value, in one of the embodiments,.
Centrifugation carries out separation of solid and liquid after solids is washed in one of the embodiments,.
Drying is dried processing and obtains at 30 DEG C~90 DEG C after solids is washed in one of the embodiments,
Head product.Preferably, the constant temperature drying at 60 DEG C.
Step S150, processing is ground to head product.
In the step, by grinding can particle it is more tiny, reduce reunite and cause product it is fully calcined, into
And improve chemical property.
The time of milled processed is 0.1 hour~1 hour in one of the embodiments,.
The head product is ground in one of the embodiments, powdered.
Step S160, the head product after milled processed at 350 DEG C~450 DEG C is calcined 1 hour~8 hours and obtains two
Titanium oxide-graphene oxide composite material.
In one of the embodiments, with the heating rate of 1 DEG C/min~5 DEG C/min by the head product after milled processed
It is heated to 350 DEG C~450 DEG C.
The time calcined in one of the embodiments, is 4 hours.
The head product after milled processed is calcined 1 hour~8 at 350 DEG C~450 DEG C in one of the embodiments,
It is ground to obtain titanium dioxide-graphene oxide composite material after hour.Preferably, the mode of grinding is ground for manual mortar
Mill, the time of grinding is 0.1 hour~1 hour.
The preparation method of above-mentioned titanium dioxide-graphene oxide composite material prepares hollow nano knot with one-step method
The titanium dioxide of structure, for butyl titanate directly with the deionized water solution single step reaction containing lithium hydroxide, butyl titanate will
It first tries to be the first with deionized water and reacts generation TiO 2 precursor, ground without washing and drying, later by subsequent water
Thermal response generates the titanium dioxide of hollow nano structure, and using butyl titanate as titanium source, one-step method generates pure phase anatase
Titanium dioxide B mixes type hollow nano structure, simple to operation so as to obtain titanium dioxide-graphene oxide composite material, instead
Should the period it is short, low energy consumption；Dispersant need not be added in reaction process, reduces production cost；By adjusting the anti-of hydro-thermal reaction
Answer the pore size of temperature and reaction time i.e. controllable titanium dioxide hollow ball；Titanium dioxide-graphene oxide of preparation is multiple
When condensation material is as lithium ion battery negative material, lithium ion battery specific discharge capacity and cyclical stability can be improved.
Titanium dioxide-graphene oxide composite material of one embodiment passes through above-mentioned titanium dioxide-graphene oxide
The preparation method of composite material is prepared.
The specific surface area of titanium dioxide-graphene oxide composite material is 100m in one of the embodiments,2/ g~
300m2/g。
The porosity of titanium dioxide-graphene oxide composite material is 10%~60% in one of the embodiments,.
The aperture of titanium dioxide-graphene oxide composite material is 2nm~10nm in one of the embodiments,.
The quality percentage of titanium dioxide contains in titanium dioxide-graphene oxide composite material in one of the embodiments,
It is 70%~99% to measure, and the mass percentage of graphene oxide is 1%~30%.
Negative material of the above-mentioned titanium dioxide-graphene oxide composite material as lithium ion battery, can improve lithium ion
Battery discharge specific capacity and cyclical stability, after lithium ion battery charge and discharge cycles 100 times, specific discharge capacity reaches 353 milliamperes
When every gram.
The application of above-mentioned titanium dioxide-graphene oxide composite material in the battery.
Battery is lithium ion battery in one of the embodiments,.
Cathode material of the titanium dioxide-graphene oxide composite material as lithium ion battery in one of the embodiments,
Material.
Above-mentioned titanium dioxide-graphene oxide composite material is applied to battery, can improve lithium ion battery specific discharge capacity
And cyclical stability, after lithium ion battery charge and discharge cycles 100 times, specific discharge capacity reaches 353 every gram of milliampere hour.
It is illustrated below in conjunction with specific embodiment.
Embodiment 1
The preparation of titanium dioxide-graphene oxide composite material includes the following steps：
It weighs 5g lithium hydroxides solid and 50mg graphenes is dissolved in 30ml deionized waters and is made into mixed liquor, then will be equipped with
The 50ml beakers of mixed liquor are placed under ultrasonic instrument；2ml butyl titanates are drawn with suction pipe, under ultrasonic state, by metatitanic acid four
Butyl ester is added dropwise in mixed liquor；After all instilling, then ultrasound 2h obtains precursor solution under ultrasound environments；
Precursor solution is moved on in autoclave, spontaneous pressure hydro-thermal reaction is carried out at 130 DEG C 48 hours, reaction
After autoclave is cooled down at room temperature, separation of solid and liquid after cooling obtains solids, by solids 50ml ethyl alcohol
With the H of 50ml 0.05M2SO4Alternately washing 3 times, then it is 7 to be washed with deionized to pH value, and head product is obtained after centrifugation, it will
Head product freeze-day with constant temperature at 60 DEG C in an oven, using mortar grinder 0.1 hour；
It is 4 small that head product after milled processed with the heating rate of 1 DEG C/min is heated to 450 DEG C of calcinings in Muffle furnace
When, it can obtain titanium dioxide-graphene oxide composite material later within 0.1 hour using mortar grinder.
Embodiment 2
The preparation of titanium dioxide-graphene oxide composite material includes the following steps：
It weighs 5g lithium hydroxides solid and 75mg graphenes is dissolved in 30ml deionized waters and is made into mixed liquor, then will be equipped with
The 50ml beakers of mixed liquor are placed under ultrasonic instrument；2ml butyl titanates are drawn with suction pipe, under ultrasonic state, by metatitanic acid four
Butyl ester is added dropwise in mixed liquor；After all instilling, then ultrasound 2h obtains precursor solution under ultrasound environments；
Precursor solution is moved on in autoclave, spontaneous pressure hydro-thermal reaction is carried out at 100 DEG C 48 hours, reaction
After autoclave is cooled down at room temperature, separation of solid and liquid after cooling obtains solids, by solids 50ml ethyl alcohol
With 50ml 0.5M H2SO4Alternately washing 6 times, then it is 7 to be washed with deionized to pH values, and head product is obtained after centrifugation, it will just
Product freeze-day with constant temperature at 90 DEG C in an oven, using mortar grinder 1 hour；
It is 2 small that head product after milled processed with the heating rate of 5 DEG C/min is heated to 350 DEG C of calcinings in Muffle furnace
When, it can obtain titanium dioxide-graphene oxide composite material later within 1 hour using mortar grinder.
Embodiment 3
The preparation of titanium dioxide-graphene oxide composite material includes the following steps：
It weighs 5g lithium hydroxides solid and 5mg graphenes is dissolved in 30ml deionized waters and is made into mixed liquor, then will be equipped with mixed
The 50ml beakers for closing liquid are placed under ultrasonic instrument；2ml butyl titanates are drawn with suction pipe, under ultrasonic state, by four fourth of metatitanic acid
Ester is added dropwise in mixed liquor；After all instilling, then ultrasound 2h obtains precursor solution under ultrasound environments；
Precursor solution is moved on in autoclave, spontaneous pressure hydro-thermal reaction is carried out at 160 DEG C 48 hours, reaction
After autoclave is cooled down at room temperature, separation of solid and liquid after cooling obtains solids, by solids 50ml ethyl alcohol
With 50ml 0.1M H2SO4Alternately washing 5 times, then it is 7 to be washed with deionized to pH values, and head product is obtained after centrifugation, it will just
Product freeze-day with constant temperature at 80 DEG C in an oven, grinding；
It is 3 small that head product after milled processed with the heating rate of 3 DEG C/min is heated to 550 DEG C of calcinings in Muffle furnace
When, it can obtain titanium dioxide-graphene oxide composite material later using mortar grinder grinding later in 0.5 hour.
Embodiment 4
The preparation of titanium dioxide-graphene oxide composite material includes the following steps：
It weighs 5g lithium hydroxides solid and 25mg graphenes is dissolved in 30ml deionized waters and is made into mixed liquor, then will be equipped with
The 50ml beakers of mixed liquor are placed under ultrasonic instrument；4ml butyl titanates are drawn with suction pipe, under ultrasonic state, by metatitanic acid four
Butyl ester is added dropwise in mixed liquor；After all instilling, then ultrasound 2h obtains precursor solution under ultrasound environments；
Precursor solution is moved on in autoclave, spontaneous pressure hydro-thermal reaction is carried out at 200 DEG C 48 hours, reaction
After autoclave is cooled down at room temperature, separation of solid and liquid after cooling obtains solids, by solids 50ml ethyl alcohol
With 50ml0.1M H2SO4Alternately washing 4 times, then it is 7 to be washed with deionized to pH value, head product is obtained after centrifugation, by primiparity
Object freeze-day with constant temperature at 30 DEG C in an oven, grinding；
By the head product after milled processed, 450 DEG C of calcinings are ground for 2 hours in Muffle furnace, use mortar grinder 0.8 hour
It can obtain titanium dioxide-graphene oxide composite material later.
Embodiment 5
The preparation of titanium dioxide-graphene oxide composite material includes the following steps：
It weighs 5g lithium hydroxides solid and 100mg graphenes is dissolved in 30ml deionized waters and is made into mixed liquor, then will be equipped with
The 50ml beakers of mixed liquor are placed under ultrasonic instrument；6ml butyl titanates are drawn with suction pipe, under ultrasonic state, by metatitanic acid four
Butyl ester is added dropwise in the mixed liquor for having 30ml deionized waters to prepare；After all instilling, then the ultrasound 2h under ultrasound environments
Obtain precursor solution；
Precursor solution is moved on in autoclave, spontaneous pressure hydro-thermal reaction is carried out at 130 DEG C 48 hours, reaction
After autoclave is cooled down at room temperature, separation of solid and liquid after cooling obtains solids, by solids 50ml ethyl alcohol
With 50ml 0.3M H2SO4Alternately washing 5 times, then it is 7 to be washed with deionized to pH values, and head product is obtained after centrifugation, it will just
Product freeze-day with constant temperature at 40 DEG C in an oven, grinding；
It is 3 small that head product after milled processed with the heating rate of 2 DEG C/min is heated to 450 DEG C of calcinings in Muffle furnace
When grind, using can obtain titanium dioxide-graphene oxide composite material after mortar grinder 0.9 hour.
Comparative example 1
The preparation of titanium dioxide-graphene oxide composite material includes the following steps：
2ml butyl titanates are drawn with suction pipe, under ultrasonic state, it is in have 30ml that butyl titanate, which is added dropwise to,
In deionized water solution, by obtained white emulsion deionized water in beaker soaking and washing several times after in 60 DEG C of constant temperature
Drying box is dried, and is dissolved in 30ml deionized waters with 5g lithium hydroxides solid and 50mg graphenes is made into mixed liquor later, then will
50ml beakers equipped with mixed liquor are placed under ultrasonic instrument；Ultrasound 2h obtains mixed solution under ultrasound environments；
Mixed solution is moved on in autoclave, spontaneous pressure hydro-thermal reaction is carried out at 130 DEG C 48 hours, reaction knot
Autoclave is cooled down at room temperature after beam, separation of solid and liquid after cooling obtains solids, by solids 50ml ethyl alcohol and
50ml0.1M H2SO4Alternately washing 5 times, then it is 7 to be washed with deionized to pH value, head product is obtained after centrifugation, by head product
Freeze-day with constant temperature at 60 DEG C in an oven, grinding；
It is 4 small that head product after milled processed with the heating rate of 1 DEG C/min is heated to 450 DEG C of calcinings in Muffle furnace
When grind, using can obtain titanium dioxide-graphene oxide composite material after mortar grinder 0.1 hour.
Please refer to Fig. 1 to Fig. 3, Fig. 1 is the X of titanium dioxide-graphene oxide composite material prepared by embodiment 1
Ray diffraction images, Fig. 2 are the transmission electron microscope of titanium dioxide-graphene oxide composite material prepared by embodiment 1
Figure, Fig. 3 is the scanning electron microscope diagram of titanium dioxide-graphene oxide composite material prepared by embodiment 1, from Fig. 2~figure
Hollow nano structure titanium dioxide uniform load in 3 in visible composite material is on graphene oxide.
It can be seen that titanium dioxide-graphene oxide composite material of preparation, the titanium dioxide of synthesis from Fig. 1~Fig. 3
For hollow nano structure, and it is evenly distributed on graphene oxide.
Pass through the ratio table of the BET titanium dioxide-graphene oxide composite materials obtained to Examples 1 to 5 and comparative example 1
Area is tested, the titanium dioxide-graphene oxide composite material obtained by BJH to Examples 1 to 5 and comparative example 1
Porosity is tested, the titanium dioxide-graphene oxide composite material obtained by BJH to Examples 1 to 5 and comparative example 1
Aperture tested, the results are shown in Table 1.
Table 1
Titanium dioxide-the graphene oxide obtained using FTIR spectrum analytic approach testing example 1~5 is compound
The composition of material, the composition of titanium dioxide-graphene oxide composite material of test comparison example 1, the results are shown in Table 2.
Table 2
By titanium dioxide-graphene oxide composite material of embodiment 1 and 1 (hereinafter referred to as composite material) of comparative example 1
Charge-discharge test is carried out applied to lithium ion battery.
During charge-discharge test, by composite material and acetylene black, PVDF according to mass ratio 8:8:1 ratio is uniformly mixed
To mixture, it is allowed to form uniformly mixed slurry then to NMP is added dropwise in mixture and stirs 6 hours, slurry is uniformly applied
Copper foil is struck out into 12 millimeters of diameter on copper foil and after 120 DEG C of vacuum drying chamber drying 12 hours, drying using press machine
Sequin.The cathode of lithium ion battery is made with this, in the lithium ion battery applied to model CR2025 types.Wherein,
Lithium piece is used to be used as to electrode, diaphragm PP in the lithium ion battery of model CR2025 types, electrolyte is EC/DMC (volumes
Than 1:1).Charge-discharge test is carried out to lithium ion battery.
It is tested under the current density of 0.5C in blue electricity CT2001A multi-channel battery test systems, final voltage model
It encloses for 1V-2.5V, uses the cycle performance figure of the lithium ion battery of titanium dioxide-graphene oxide composite material of embodiment 1
As shown in Figure 4 and Figure 5, using the cycle performance figure of the lithium ion battery of comparative example 1 as shown in Figure 6 and Figure 7.
Titanium dioxide-graphene oxide composite material of embodiment 1 be can be seen that from Fig. 4 to Fig. 7 as lithium-ion electric
The negative material in pond, under the current density of 0.5C after charge and discharge cycles 100 times, specific discharge capacity reaches 353 every gram of milliampere hour,
Charge specific capacity reaches 344 every gram of milliampere hour, relative to 168 every gram of the milliampere hour of titanium dioxide theoretical specific capacity of pure phase, display
Go out the fine cyclical stability that titanium dioxide-graphene oxide composite material is shown as the negative material of lithium ion battery
With the charging and discharging capacity of raising；Titanium dioxide-graphene oxide composite material of comparative example 1 is as the negative of lithium ion battery
Pole material, under the current density of 0.5C after charge and discharge cycles 100 times, specific discharge capacity is 296 every gram of milliampere hour, and charge specific volume
Amount reaches 297 every gram of milliampere hour.
It can be seen that titanium dioxide-graphene oxide composite material of embodiment 1 relative to comparative example from Fig. 4~Fig. 7
Negative material of the titanium dioxide-graphene oxide composite material as lithium ion battery has higher charging and discharging capacity.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that those of ordinary skill in the art are come
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of titanium dioxide-graphene oxide composite material, which is characterized in that include the following steps：
Mixed liquor is provided, contains lithium hydroxide and graphene in the mixed liquor；
The reaction solution is ultrasonically treated and butyl titanate is added dropwise into the reaction solution and obtains reaction solution, to described anti-
Liquid is answered to carry out supersound process and obtains precursor solution within 1 hour~4 hours, wherein, the butyl titanate and the lithium hydroxide
Mass ratio be 1:3~1:7；
By the precursor solution be heated to 100 DEG C~200 DEG C carry out hydro-thermal reaction 12 hours~120 hours after separation of solid and liquid obtain
To solids, the solids is washed and is dried to obtain head product；
Processing is ground to the head product；And
The head product after milled processed at 350 DEG C~450 DEG C is calcined 1 hour~8 hours and obtains titanium dioxide-oxidation
Graphene composite material.
2. the preparation method of titanium dioxide-graphene oxide composite material according to claim 1, which is characterized in that institute
The mass ratio for stating lithium hydroxide and the graphene is 1000：1~50：1.
3. the preparation method of titanium dioxide-graphene oxide composite material according to claim 1, which is characterized in that institute
It states and also contains water in mixture, the ratio of the lithium hydroxide and the water is 1g:3mL~1g:10mL.
4. the preparation method of titanium dioxide-graphene oxide composite material according to claim 1, which is characterized in that institute
The power for stating supersound process is 100W~250W.
5. the preparation method of titanium dioxide-graphene oxide composite material according to claim 1, which is characterized in that institute
Hydro-thermal reaction is stated to carry out in autoclave.
6. the preparation method of titanium dioxide-graphene oxide composite material according to claim 1, which is characterized in that institute
It states in the step of being washed the solids and being dried to obtain head product, alternately the solid is washed using ethyl alcohol and inorganic acid
Object reuses deionized water and washs the solids to neutrality later.
7. the preparation method of titanium dioxide-graphene oxide composite material according to claim 6, which is characterized in that institute
It states inorganic acid and is selected from least one of hydrochloric acid, nitric acid and sulfuric acid.
8. the preparation method of titanium dioxide-graphene oxide composite material according to claim 7, which is characterized in that institute
State a concentration of 0.05mol/L~0.5mol/L of inorganic acid.
9. obtained by the preparation method of claim 1~8 any one of them titanium dioxide-graphene oxide composite material two
Titanium oxide-graphene oxide composite material.
10. the application of titanium dioxide-graphene oxide composite material in the battery described in claim 9.
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