CN108134068B - Titanium dioxide-graphene oxide composite material, and preparation method and application thereof - Google Patents

Titanium dioxide-graphene oxide composite material, and preparation method and application thereof Download PDF

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CN108134068B
CN108134068B CN201711421262.5A CN201711421262A CN108134068B CN 108134068 B CN108134068 B CN 108134068B CN 201711421262 A CN201711421262 A CN 201711421262A CN 108134068 B CN108134068 B CN 108134068B
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titanium dioxide
graphene oxide
composite material
oxide composite
solid
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CN108134068A (en
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于开锋
王宇
张勋龙
曹兴刚
王中书
邹康迪
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Shenzhen Nalon Battery Co ltd
Jilin University
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Jilin University
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a preparation method of a titanium dioxide-graphene oxide composite material, the titanium dioxide-graphene oxide composite material and application. A preparation method of a titanium dioxide-graphene oxide composite material comprises the following steps: providing a mixed solution; carrying out ultrasonic treatment on the reaction liquid, dropwise adding tetrabutyl titanate into the reaction liquid to obtain the reaction liquid, carrying out ultrasonic treatment on the reaction liquid for 1-4 hours to obtain a precursor solution, heating the precursor solution to 100-200 ℃, carrying out hydrothermal reaction for 12-120 hours, carrying out solid-liquid separation to obtain a solid, washing the solid and drying to obtain an initial product; grinding the primary product; and calcining the ground primary product at 350-450 ℃ to obtain the titanium dioxide-graphene oxide composite material. The preparation method of the titanium dioxide-graphene oxide composite material is simple in preparation process and can improve the discharge specific capacity and the cycling stability of the lithium ion battery.

Description

Titanium dioxide-graphene oxide composite material, and preparation method and application thereof
Technical Field
The invention relates to a preparation method of a titanium dioxide-graphene oxide composite material, the titanium dioxide-graphene oxide composite material and application.
Background
Facing global energy shortages and environmental pollution issues, creating new technologies that make efficient energy collection, conversion and storage devices an urgent need. And the most widely used lithium ion battery as an energy conversion and storage device is one of the most promising energy storage devices for various portable electronic devices. For the next generation of lithium ion batteries, designing and synthesizing functional battery materials that can reduce cost, increase capacity, and improve rate performance and cycle performance is a key goal. In the study of lithium ion batteries, it is very important to study the negative electrode of the lithium ion battery, because the negative electrode of the battery can greatly affect the performance of the lithium ion battery. Transition metal oxides have attracted considerable attention in lithium ion batteries and supercapacitors due to their superior electrochemical properties. Titanium dioxide is an earlier-researched metal oxide negative electrode material, and has become a hot point of research in recent years due to the characteristics of stable structure, excellent cycle performance, low price, environmental friendliness, high safety and the like.
Titanium dioxide has various crystal structures, including anatase, rutile, brookite, titanium dioxide B and the like, wherein anatase and rutile are common negative electrode materials for manufacturing lithium ion batteries in the industry at present. Ostword finds that anatase in titanium dioxide is a better crystal structure than rutile. The titanium dioxide material has low electronic conductivity and small diffusion coefficient of lithium ions in the titanium dioxide material, so that more research works aim at synthesizing the titanium dioxide material with a nano size, and meanwhile, the titanium dioxide material with a good structure morphology is also beneficial to improving the electrochemical performance of the titanium dioxide, and on the other hand, the titanium dioxide is compounded with a conductive carbon material, a metal oxide material and the like, so that the conductivity of the material is improved, and further, the specific capacity of the titanium dioxide as a negative electrode material is improved.
However, the existing preparation process of the titanium dioxide composite material with the anatase structure is complex, and when the prepared titanium dioxide composite material with the anatase structure is used as a negative electrode material of a lithium ion battery, the discharge specific capacity of the lithium ion battery is low and the cycle stability is not good.
Disclosure of Invention
Therefore, a preparation method of the titanium dioxide-graphene oxide composite material, the titanium dioxide-graphene oxide composite material and the application are needed, wherein the preparation process is simple, and the specific discharge capacity and the cycle stability of the lithium ion battery can be improved.
A preparation method of a titanium dioxide-graphene oxide composite material comprises the following steps:
providing a mixed solution, wherein the mixed solution contains lithium hydroxide and graphene;
carrying out ultrasonic treatment on the reaction liquid, dropwise adding tetrabutyl titanate into the reaction liquid to obtain the reaction liquid, and carrying out ultrasonic treatment on the reaction liquid for 1-4 hours to obtain a precursor solution, wherein the mass ratio of tetrabutyl titanate to lithium hydroxide is 1: 3-1: 7;
heating the precursor solution to 100-200 ℃ for hydrothermal reaction for 12-120 hours, then carrying out solid-liquid separation to obtain a solid, washing and drying the solid to obtain a primary product;
grinding the primary product; and
calcining the ground primary product at 350-450 ℃ for 1-8 hours to obtain the titanium dioxide-graphene oxide composite material.
According to the preparation method of the titanium dioxide-graphene oxide composite material, tetrabutyl titanate is used as a titanium source, and a pure-phase anatase titanium dioxide B mixed type nano hollow structure is generated by a one-step method, so that the titanium dioxide-graphene oxide composite material is obtained, and the preparation method is simple and easy to operate, short in reaction period and low in energy consumption; a dispersant is not required to be added in the reaction process, so that the production cost is reduced; the pore size of the titanium dioxide hollow sphere can be controlled by adjusting the reaction temperature and the reaction time of the hydrothermal reaction; when the prepared titanium dioxide-graphene oxide composite material is used as a lithium ion battery negative electrode material, the discharge specific capacity and the cycling stability of the lithium ion battery can be improved.
In one embodiment, the mass ratio of the lithium hydroxide to the graphene is 1000: 1-50: 1.
In one embodiment, the mixture further comprises water, and the ratio of the lithium hydroxide to the water is 1g:3 mL-1 g:10 mL.
In one embodiment, the power of the ultrasonic treatment is 100W to 250W.
In one embodiment, the hydrothermal reaction is carried out in an autoclave.
In one embodiment, in the step of washing and drying the solid to obtain the initial product, the solid is washed by using ethanol and inorganic acid alternately, and then the solid is washed to be neutral by using deionized water.
In one embodiment, the inorganic acid is selected from at least one of hydrochloric acid, nitric acid, and sulfuric acid.
In one embodiment, the concentration of the sulfuric acid is 0.05mol/L to 0.5 mol/L.
The titanium dioxide-graphene oxide composite material is prepared by the preparation method of the titanium dioxide-graphene oxide composite material.
The titanium dioxide-graphene oxide composite material is applied to a battery.
Drawings
Fig. 1 is an X-ray diffraction photograph of the titanium dioxide-graphene oxide composite prepared in example 1;
fig. 2 is a transmission electron microscope image of the titanium dioxide-graphene oxide composite prepared in example 1;
fig. 3 is a scanning electron microscope image of the titanium dioxide-graphene oxide composite prepared in example 1;
fig. 4 is a charge profile at 0.5C current density for a lithium ion battery using the titanium dioxide-graphene oxide composite of example 1;
fig. 5 is a discharge curve plot at 0.5C current density for a lithium ion battery using the titanium dioxide-graphene oxide composite of example 1;
fig. 6 is a charge profile at a current density of 0.5C for a lithium ion battery using the titanium dioxide-graphene oxide composite of comparative example 1;
fig. 7 is a discharge curve diagram at a current density of 0.5C of a lithium ion battery using the titanium dioxide-graphene oxide composite prepared in comparative example 1.
Detailed Description
The preparation method of the titanium dioxide-graphene oxide composite material, the titanium dioxide-graphene oxide composite material and the application thereof will be further described in detail with reference to the specific embodiments.
A method of preparing a titanium dioxide-graphene oxide composite material according to an embodiment includes the steps of:
step S110, providing a mixed solution, wherein the mixed solution contains lithium hydroxide and graphene.
In one embodiment, the mass ratio of lithium hydroxide to graphene is 1000: 1-50: 1.
in one embodiment, the mixture further comprises water, and the ratio of lithium hydroxide to water is 1g:3mL to 1g:10 mL.
In one embodiment, the graphene is prepared by a modified Hummers method.
In one embodiment, the mixed liquor is prepared by: mixing the components in a mass ratio of 1000: 1-50: 1, adding lithium hydroxide and graphene into deionized water to prepare a mixed solution, wherein the ratio of the lithium hydroxide to the deionized water is 1g:3 mL-1 g:10 mL.
And step S120, carrying out ultrasonic treatment on the reaction liquid, dropwise adding tetrabutyl titanate into the reaction liquid to obtain the reaction liquid, and carrying out ultrasonic treatment on the reaction liquid for 1-4 hours to obtain a precursor solution.
The mass ratio of tetrabutyl titanate to lithium hydroxide is 1: 3-1: 7.
In one embodiment, the dropping rate of tetrabutyl titanate is 1 drop/second to 5 drops/second.
In one embodiment, the power of the ultrasonic treatment is 100W to 250W.
And S130, heating the precursor solution to 100-200 ℃, carrying out hydrothermal reaction for 12-120 hours, carrying out solid-liquid separation to obtain a solid, washing the solid, and drying to obtain an initial product.
In one embodiment, the hydrothermal reaction is carried out in an autoclave, and the pressure generated by the reaction is used for carrying out the hydrothermal reaction.
In one embodiment, the hydrothermal reaction time is 48 hours.
In one embodiment, the solids are washed alternately with ethanol and mineral acid, followed by washing the solids to neutrality with deionized water. Further, the inorganic acid is at least one selected from hydrochloric acid, nitric acid and sulfuric acid. The concentration of the inorganic acid is 0.05mol/L to 0.5mol/L, and more preferably 0.1 mol/L. Preferably, the washing is performed 3 to 6 times using ethanol and a mineral acid, respectively.
In one of the examples, the solids were washed to a pH of 7.
In one embodiment, the solids are washed and centrifuged to effect solid-liquid separation.
In one embodiment, the solid is washed, dried at 30-90 ℃ and dried to obtain a primary product. Preferably, the drying is carried out at a constant temperature of 60 ℃.
And step S150, grinding the primary product.
In the step, the particles can be made finer through grinding, the agglomeration is reduced, and the product is fully calcined, so that the electrochemical performance is improved.
In one embodiment, the time for the milling treatment is 0.1 to 1 hour.
In one embodiment, the primary product is ground to a powder.
And step S160, calcining the ground primary product at 350-450 ℃ for 1-8 hours to obtain the titanium dioxide-graphene oxide composite material.
In one embodiment, the initial product after grinding treatment is heated to 350-450 ℃ at a heating rate of 1-5 ℃/min.
In one embodiment, the calcination time is 4 hours.
In one embodiment, the primary product after grinding treatment is calcined at 350-450 ℃ for 1-8 hours and then ground to obtain the titanium dioxide-graphene oxide composite material. Preferably, the grinding is performed by hand mortar grinding, and the grinding time is 0.1 to 1 hour.
According to the preparation method of the titanium dioxide-graphene oxide composite material, the titanium dioxide with the nano hollow structure is prepared by a one-step method, tetrabutyl titanate directly reacts with a deionized water solution containing lithium hydroxide in one step, the tetrabutyl titanate is firstly reacted with the deionized water in advance to generate a titanium dioxide precursor without being washed, dried and ground, then the titanium dioxide with the nano hollow structure is generated by the subsequent hydrothermal reaction, and the pure-phase anatase titanium dioxide B mixed nano hollow structure is generated by the one-step method by taking the tetrabutyl titanate as a titanium source, so that the titanium dioxide-graphene oxide composite material is obtained, and the preparation method is simple and easy to operate, short in reaction period and low in energy consumption; a dispersant is not required to be added in the reaction process, so that the production cost is reduced; the pore size of the titanium dioxide hollow sphere can be controlled by adjusting the reaction temperature and the reaction time of the hydrothermal reaction; when the prepared titanium dioxide-graphene oxide composite material is used as a lithium ion battery negative electrode material, the discharge specific capacity and the cycling stability of the lithium ion battery can be improved.
The titanium dioxide-graphene oxide composite material according to an embodiment is prepared by the above preparation method of a titanium dioxide-graphene oxide composite material.
In one embodiment, the titanium dioxide-graphene oxide composite material has a specific surface area of 100m2/g ～300m2/g。
In one embodiment, the titanium dioxide-graphene oxide composite has a porosity of 10% to 60%.
In one embodiment, the pore size of the titanium dioxide-graphene oxide composite material is 2nm to 10 nm.
In one embodiment, the titanium dioxide-graphene oxide composite material contains 70-99% of titanium dioxide by mass and 1-30% of graphene oxide by mass.
The titanium dioxide-graphene oxide composite material is used as a negative electrode material of the lithium ion battery, the discharge specific capacity and the cycling stability of the lithium ion battery can be improved, and after the lithium ion battery is charged and discharged for 100 times in a cycling mode, the discharge specific capacity reaches 353 milliampere per gram.
The titanium dioxide-graphene oxide composite material is applied to a battery.
In one embodiment, the battery is a lithium ion battery.
In one embodiment, the titanium dioxide-graphene oxide composite material is used as a negative electrode material of a lithium ion battery.
The titanium dioxide-graphene oxide composite material is applied to a battery, the discharge specific capacity and the cycle stability of the lithium ion battery can be improved, and after the lithium ion battery is charged and discharged for 100 times in a cycle, the discharge specific capacity reaches 353 milliampere per gram.
The following description will be given with reference to specific examples.
Example 1
The preparation method of the titanium dioxide-graphene oxide composite material comprises the following steps:
weighing 5g of lithium hydroxide solid and 50mg of graphene, dissolving in 30ml of deionized water to prepare a mixed solution, and placing a 50ml beaker filled with the mixed solution under an ultrasonic instrument; sucking 2ml of tetrabutyl titanate by a suction pipe, and dropwise adding tetrabutyl titanate into the mixed solution under an ultrasonic state; after all the solution is dripped, performing ultrasonic treatment for 2 hours in an ultrasonic environment to obtain a precursor solution;
transferring the precursor solution into a high-pressure reaction kettle, carrying out self-generated hydrothermal reaction at 130 ℃ for 48 hours, cooling the high-pressure reaction kettle at room temperature after the reaction is finished, carrying out solid-liquid separation after cooling to obtain a solid, and carrying out solid-liquid separation on the solid by using 50ml of ethanol and 50ml of 0.05M H2SO4Alternately washing for 3 times, washing with deionized water until the pH value is 7, centrifuging to obtain a primary product, drying the primary product in an oven at a constant temperature of 60 ℃, and grinding for 0.1 hour by using a mortar;
and heating the ground primary product in a muffle furnace at the heating rate of 1 ℃/min to 450 ℃ for calcining for 4 hours, and grinding for 0.1 hour by using a mortar to obtain the titanium dioxide-graphene oxide composite material.
Example 2
The preparation method of the titanium dioxide-graphene oxide composite material comprises the following steps:
weighing 5g of lithium hydroxide solid and 75mg of graphene, dissolving the lithium hydroxide solid and the graphene in 30ml of deionized water to prepare a mixed solution, and placing a 50ml beaker filled with the mixed solution under an ultrasonic instrument; sucking 2ml of tetrabutyl titanate by a suction pipe, and dropwise adding tetrabutyl titanate into the mixed solution under an ultrasonic state; after all the components are dripped, performing ultrasonic treatment for 2 hours in an ultrasonic environment to obtain a precursor solution;
transferring the precursor solution into a high-pressure reaction kettle, carrying out self-generated hydrothermal reaction at 100 ℃ for 48 hours, cooling the high-pressure reaction kettle at room temperature after the reaction is finished, carrying out solid-liquid separation after cooling to obtain a solid, and carrying out solid-liquid separation on the solid by using 50ml of ethanol and 50ml of 0.5M H2SO4Alternately washing for 6 times, washing with deionized water until the pH value is 7, centrifuging to obtain a primary product, drying the primary product in an oven at a constant temperature of 90 ℃, and grinding for 1 hour by using a mortar;
and heating the ground primary product in a muffle furnace at the heating rate of 5 ℃/min to 350 ℃ for calcining for 2 hours, and grinding for 1 hour by using a mortar to obtain the titanium dioxide-graphene oxide composite material.
Example 3
The preparation method of the titanium dioxide-graphene oxide composite material comprises the following steps:
weighing 5g of lithium hydroxide solid and 5mg of graphene, dissolving in 30ml of deionized water to prepare a mixed solution, and placing a 50ml beaker filled with the mixed solution under an ultrasonic instrument; sucking 2ml of tetrabutyl titanate by a suction pipe, and dropwise adding tetrabutyl titanate into the mixed solution under an ultrasonic state; after all the components are dripped, performing ultrasonic treatment for 2 hours in an ultrasonic environment to obtain a precursor solution;
transferring the precursor solution into a high-pressure reaction kettle, carrying out self-generated pressure hydrothermal reaction at 160 ℃ for 48 hours, cooling the high-pressure reaction kettle at room temperature after the reaction is finished, and carrying out solid-liquid separation after cooling to obtain the productAdding 50ml ethanol and 50ml0.1M H into the solid2SO4Alternately washing for 5 times, washing with deionized water until pH is 7, centrifuging to obtain primary product, drying the primary product in oven at constant temperature of 80 deg.C, and grinding;
and heating the ground primary product in a muffle furnace at the heating rate of 3 ℃/min to 550 ℃ for calcining for 3 hours, grinding for 0.5 hour by using a mortar, and grinding to obtain the titanium dioxide-graphene oxide composite material.
Example 4
The preparation method of the titanium dioxide-graphene oxide composite material comprises the following steps:
weighing 5g of lithium hydroxide solid and 25mg of graphene, dissolving in 30ml of deionized water to prepare a mixed solution, and placing a 50ml beaker filled with the mixed solution under an ultrasonic instrument; sucking 4ml of tetrabutyl titanate by a suction pipe, and dropwise adding tetrabutyl titanate into the mixed solution under an ultrasonic state; after all the components are dripped, performing ultrasonic treatment for 2 hours in an ultrasonic environment to obtain a precursor solution;
transferring the precursor solution into a high-pressure reaction kettle, carrying out self-generated hydrothermal reaction at 200 ℃ for 48 hours, cooling the high-pressure reaction kettle at room temperature after the reaction is finished, carrying out solid-liquid separation after cooling to obtain a solid, and carrying out solid-liquid separation on the solid by using 50ml of ethanol and 50ml of 0.1M H2SO4Alternately washing for 4 times, washing with deionized water until pH is 7, centrifuging to obtain primary product, drying the primary product in oven at constant temperature of 30 deg.C, and grinding;
and calcining the ground primary product in a muffle furnace at 450 ℃ for 2 hours, grinding the calcined product by using a mortar for 0.8 hour, and obtaining the titanium dioxide-graphene oxide composite material.
Example 5
The preparation method of the titanium dioxide-graphene oxide composite material comprises the following steps:
weighing 5g of lithium hydroxide solid and 100mg of graphene, dissolving in 30ml of deionized water to prepare a mixed solution, and placing a 50ml beaker filled with the mixed solution under an ultrasonic instrument; absorbing 6ml of tetrabutyl titanate by a suction pipe, and dropwise adding tetrabutyl titanate into a mixed solution prepared by 30ml of deionized water under an ultrasonic state; after the whole part is dripped, performing ultrasonic treatment for 2 hours in an ultrasonic environment to obtain a precursor solution;
transferring the precursor solution into a high-pressure reaction kettle, carrying out self-generated hydrothermal reaction at 130 ℃ for 48 hours, cooling the high-pressure reaction kettle at room temperature after the reaction is finished, carrying out solid-liquid separation after cooling to obtain a solid, and carrying out solid-liquid separation on the solid by using 50ml of ethanol and 50ml of 0.3M H2SO4Alternately washing for 5 times, washing with deionized water until pH is 7, centrifuging to obtain a primary product, drying the primary product in an oven at constant temperature of 40 deg.C, and grinding;
and heating the ground primary product in a muffle furnace at the heating rate of 2 ℃/min to 450 ℃, calcining for 3 hours, grinding for 0.9 hour by using a mortar, and thus obtaining the titanium dioxide-graphene oxide composite material.
Comparative example 1
The preparation method of the titanium dioxide-graphene oxide composite material comprises the following steps:
absorbing 2ml of tetrabutyl titanate by using a suction pipe, dropwise adding tetrabutyl titanate into a 30ml deionized water solution under an ultrasonic state, soaking and cleaning the obtained white emulsion deionized water in a beaker for a plurality of times, drying the white emulsion deionized water in a constant-temperature drying oven at 60 ℃, dissolving 5g of lithium hydroxide solid and 50mg of graphene in 30ml of deionized water to prepare a mixed solution, and then placing the 50ml beaker filled with the mixed solution under an ultrasonic instrument; carrying out ultrasonic treatment for 2 hours in an ultrasonic environment to obtain a mixed solution;
transferring the mixed solution into a high-pressure reaction kettle, carrying out self-generated hydrothermal reaction at 130 ℃ for 48 hours, cooling the high-pressure reaction kettle at room temperature after the reaction is finished, carrying out solid-liquid separation after cooling to obtain a solid, and carrying out solid-liquid separation on the solid by using 50ml of ethanol and 50ml of 0.1M H2SO4Alternately washing for 5 times, washing with deionized water until pH is 7, centrifuging to obtain primary product, drying the primary product in oven at 60 deg.C, and grinding;
heating the ground primary product in a muffle furnace at the heating rate of 1 ℃/min to 450 ℃, calcining for 4 hours, grinding, and grinding for 0.1 hour by using a mortar to obtain the titanium dioxide-graphene oxide composite material.
Referring to fig. 1 to 3, fig. 1 is an X-ray diffraction photograph of the titanium dioxide-graphene oxide composite material prepared in example 1, fig. 2 is a transmission electron microscope photograph of the titanium dioxide-graphene oxide composite material prepared in example 1, fig. 3 is a scanning electron microscope photograph of the titanium dioxide-graphene oxide composite material prepared in example 1, and it can be seen from fig. 2 to 3 that the nano hollow structure titanium dioxide in the composite material is uniformly loaded on the graphene oxide.
As can be seen from fig. 1 to 3, in the prepared titanium dioxide-graphene oxide composite material, the synthesized titanium dioxide is in a nano hollow structure and is uniformly distributed on the graphene oxide.
The specific surface areas of the titanium dioxide-graphene oxide composite materials obtained in examples 1 to 5 and comparative example 1 were measured by BET, the porosities of the titanium dioxide-graphene oxide composite materials obtained in examples 1 to 5 and comparative example 1 were measured by BJH, and the pore diameters of the titanium dioxide-graphene oxide composite materials obtained in examples 1 to 5 and comparative example 1 were measured by BJH, and the results are shown in table 1.
TABLE 1
Figure BDA0001523092910000101
The compositions of the titanium dioxide-graphene oxide composite materials obtained in examples 1 to 5 were tested by fourier infrared spectroscopy, and the compositions of the titanium dioxide-graphene oxide composite material of comparative example 1 were tested, and the results are shown in table 2.
TABLE 2
Figure BDA0001523092910000102
The titanium dioxide-graphene oxide composite material of example 1 and comparative example 1 (hereinafter, collectively referred to as composite material) were applied to a lithium ion battery to perform charge and discharge tests.
During charging and discharging tests, the composite material, acetylene black and PVDF are uniformly mixed according to the mass ratio of 8:8:1 to obtain a mixture, then NMP is dropwise added into the mixture and stirred for 6 hours to form uniformly mixed slurry, the slurry is uniformly coated on copper foil and dried for 12 hours in a vacuum drying oven at 120 ℃, and the copper foil is punched into small wafers with the diameter of 12 mm by using a punching machine after drying. The negative electrode of the lithium ion battery prepared by the method is applied to a lithium ion battery with the model number of CR 2025. Among them, the CR2025 type lithium ion battery uses a lithium sheet as a counter electrode, a separator is PP, and an electrolyte is EC/DMC (volume ratio 1: 1). And carrying out charge and discharge tests on the lithium ion battery.
The test was performed at a current density of 0.5C on a blue CT2001A multi-channel cell test system, the termination voltage range was 1V to 2.5V, the cycle performance of the lithium ion battery using the titanium dioxide-graphene oxide composite of example 1 is shown in fig. 4 and 5, and the cycle performance of the lithium ion battery using the comparative example 1 is shown in fig. 6 and 7.
As can be seen from fig. 4 to 7, when the titanium dioxide-graphene oxide composite material of example 1 is used as the negative electrode material of the lithium ion battery, after 100 times of charge and discharge cycles at a current density of 0.5C, the specific discharge capacity reaches 353 milliampere per gram, the specific charge capacity reaches 344 milliampere per gram, and the titanium dioxide-graphene oxide composite material shows good cycle stability and improved specific charge and discharge capacity as the negative electrode material of the lithium ion battery, relative to the theoretical specific capacity of 168 milliampere per gram of pure-phase titanium dioxide; the titanium dioxide-graphene oxide composite material of the comparative example 1 is used as a negative electrode material of a lithium ion battery, and after 100 times of charge and discharge cycles at a current density of 0.5C, the specific discharge capacity is 296 milliampere per gram, and the specific charge capacity is 297 milliampere per gram.
As can be seen from fig. 4 to 7, the titanium dioxide-graphene oxide composite material of example 1 has a higher specific charge/discharge capacity than the titanium dioxide-graphene oxide composite material of the comparative example, which is used as the negative electrode material of the lithium ion battery.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A preparation method of a titanium dioxide-graphene oxide composite material is characterized by comprising the following steps:
providing a mixed solution, wherein the mixed solution contains lithium hydroxide, water and graphene oxide;
carrying out ultrasonic treatment on the mixed solution, dropwise adding tetrabutyl titanate into the mixed solution to obtain a reaction solution, and carrying out ultrasonic treatment on the reaction solution for 1-4 hours to obtain a precursor solution, wherein the mass ratio of tetrabutyl titanate to lithium hydroxide is 1: 3-1: 7;
heating the precursor solution to 100-160 ℃, carrying out hydrothermal reaction for 12-48 hours, carrying out solid-liquid separation to obtain a solid, washing and drying the solid to obtain a primary product;
grinding the primary product; and
calcining the ground primary product at 350-450 ℃ for 1-8 hours to obtain the titanium dioxide-graphene oxide composite material.
2. The method for preparing the titanium dioxide-graphene oxide composite material according to claim 1, wherein the mass ratio of the lithium hydroxide to the graphene oxide is 1000: 1-50: 1.
3. the method for preparing the titanium dioxide-graphene oxide composite material according to claim 1, wherein the ratio of the lithium hydroxide to the water is 1g:3mL to 1g:10 mL.
4. The method for preparing the titanium dioxide-graphene oxide composite material according to claim 1, wherein the power of the ultrasonic treatment is 100W to 250W.
5. The method for preparing the titanium dioxide-graphene oxide composite material according to claim 1, wherein the hydrothermal reaction is performed in a high-pressure reaction kettle.
6. The method for preparing a titanium dioxide-graphene oxide composite material according to claim 1, wherein in the step of washing and drying the solid to obtain the primary product, the solid is alternately washed with ethanol and a mineral acid, and then washed to be neutral with deionized water.
7. The method for producing the titanium dioxide-graphene oxide composite material according to claim 6, wherein the inorganic acid is at least one selected from hydrochloric acid, nitric acid, and sulfuric acid.
8. The method for producing the titanium dioxide-graphene oxide composite material according to claim 7, wherein the concentration of the inorganic acid is 0.05 to 0.5 mol/L.
9. The titanium dioxide-graphene oxide composite material obtained by the method for producing a titanium dioxide-graphene oxide composite material according to any one of claims 1 to 8.
10. Use of the titanium dioxide-graphene oxide composite material according to claim 9 in a battery.
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