CN111584844A - Titanium dioxide nano composite electrode material and preparation method thereof - Google Patents

Titanium dioxide nano composite electrode material and preparation method thereof Download PDF

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CN111584844A
CN111584844A CN202010430038.8A CN202010430038A CN111584844A CN 111584844 A CN111584844 A CN 111584844A CN 202010430038 A CN202010430038 A CN 202010430038A CN 111584844 A CN111584844 A CN 111584844A
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titanium dioxide
electrode material
composite electrode
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titanium
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熊帮云
李静静
彭银锭
樊婷
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Foshan University
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Abstract

The invention discloses a titanium dioxide nano-composite electrode material and a preparation method thereof, belonging to the technical field of electrode materials, wherein the method comprises the steps of dispersing graphene and tin dioxide in an alcohol solution, dropwise adding a titanium source, and ultrasonically dispersing for 30-50 min to obtain a ternary precipitate; adding the ternary precipitate into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 180-200 ℃, washing the obtained product with ethanol and deionized water, putting the washed product into a muffle furnace, calcining, and naturally cooling to room temperature; and (5) freeze-drying to obtain the titanium dioxide nano-composite electrode material. The titanium dioxide nanometer clothing composite electrode material prepared by the invention has good circulation stability, higher reversible capacity and more excellent rate capability.

Description

Titanium dioxide nano composite electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of electrode materials, in particular to a titanium dioxide nano composite electrode material and a preparation method thereof.
Background
With social progress and scientific and technological development, the defects of the existing non-renewable energy sources such as coal, petroleum and the like are increasingly highlighted. The development of green new energy and the development of environment-friendly energy storage technology are important development directions in the world at present. The lithium ion battery is one of the most important green energy storage technologies at present, and compared with the traditional energy storage technologies such as lead-acid batteries, nickel-cadmium batteries and nickel-hydrogen batteries, the lithium ion battery has higher energy density, longer service life and better environmental compatibility, and therefore, the lithium ion battery is the most widely applied energy storage technology at present.
The titanium dioxide used as the lithium ion negative electrode material has the advantages of long service life, low cost, no toxicity, no harm and the like. More importantly, the titanium dioxide has small volume change in the lithium ion deintercalation process, and can well solve the problems of capacity retention rate, cyclicity and the like of the negative electrode material during rapid charge and discharge. However, the poor conductivity of titanium dioxide itself limits its application to some extent.
The lithium ion battery mainly comprises anode and cathode materials, a diaphragm, electrolyte and the like. At present, the graphite carbon material is generally adopted as the negative electrode of the commercial lithium ion battery. The graphite has good conductivity and structural stability, rich raw materials and low cost, so the graphite becomes the only commercialized cathode material at present. However, graphite has a low lithium intercalation potential, and may cause lithium dendrite phenomenon during charging and discharging, which may result in a potential short circuit of the battery. On the other hand, graphite is easy to peel off, and the diffusion rate of lithium ions is low, so that the cycle stability and rate performance of the graphite are affected. With the development of electric automobiles nowadays, electrode materials are required to be quickly charged and discharged in a short time, and the electrode materials have good safety performance. Therefore, it is urgently needed to find a new negative electrode material to replace the conventional graphite-based negative electrode.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a titanium dioxide nano composite electrode material with good cycle stability, high reversible capacity and excellent rate performance.
In order to achieve the purpose, the invention provides the following scheme:
the first technical scheme is as follows:
the invention provides a preparation method of a titanium dioxide nano composite electrode material, which comprises the following steps:
(1) dispersing graphene and tin dioxide in an alcohol solution, dropwise adding a titanium source, and ultrasonically dispersing for 30-50 min to obtain a ternary precipitate;
(2) adding the ternary precipitate into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 180-200 ℃, and washing the obtained product with ethanol and deionized water;
(3) freeze-drying the product washed in the step (2);
(4) and (4) putting the product obtained in the step (3) into a muffle furnace, calcining, and naturally cooling to room temperature to obtain the titanium dioxide nano composite electrode material.
As a further improvement of the invention, the titanium source in the step (1) is titanium isopropoxide. The hydrolysis of titanium isopropoxide promotes the formation of ternary precipitates (graphene-tin dioxide-titanium dioxide intermediate products) containing graphene, tin dioxide and amorphous titanium dioxide. And carrying out hydrothermal treatment, freeze drying and calcining to obtain the graphene-tin dioxide-titanium dioxide ternary composite electrode material.
According to the further improvement of the invention, the mass ratio of the graphene, the tin dioxide and the titanium source in the step (1) is 20-30: 15-25: 10-25.
As a further improvement of the invention, the alcoholic solution in the step (1) is absolute ethyl alcohol.
As a further improvement of the invention, the freeze-drying time in the step (3) is 12-24 h.
As a further improvement of the invention, the calcination temperature in the step (4) is 500-700 ℃, and the heating rate is 5-10 ℃/min.
The second technical scheme is as follows:
the invention provides a titanium dioxide nano-composite electrode material prepared by the preparation method of the titanium dioxide nano-composite electrode material.
The invention discloses the following technical effects:
in the ternary composite electrode material, graphene serves as a conductive substrate, and tin dioxide further connects conductive broken circuits existing in the graphene and inhibits the aggregation of the graphene, so that the graphene and the tin dioxide jointly act to form a continuous conductive network. The conductive network composed of the graphene sheets and the tin dioxide is uniformly distributed in the composite electrode material and is in close contact with the nano-rod-shaped titanium dioxide, so that electrons are promoted to enter the inside of the electrode material more quickly. The freeze drying process maintains the titanium dioxide in a fixed shape, and the performance of the electrode is improved. Compared with pure titanium dioxide, graphene-titanium dioxide, tin dioxide-titanium dioxide and other binary composite electrode materials, the ternary composite electrode material synthesized by the method disclosed by the invention has better cycle stability, higher reversible capacity and better rate capability.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
(1) Dispersing 20mg of graphene and 15mg of stannic oxide in 100ml of absolute ethyl alcohol, dropwise adding 10mg of titanium isopropoxide, finishing dropping within 20min, and ultrasonically dispersing for 30min to obtain a ternary precipitate;
(2) adding the ternary precipitate into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 180 ℃, and washing the obtained product to be neutral by using ethanol and deionized water;
(3) freeze-drying the product washed in the step (2) in liquid nitrogen for 12 h;
(4) and (4) putting the product obtained in the step (3) into a muffle furnace, calcining at 500 ℃, and naturally cooling to room temperature to obtain the titanium dioxide nano-composite electrode material, wherein the heating rate is 5 ℃/min.
Example 2
(1) Dispersing 30mg of graphene and 25mg of stannic oxide in 200ml of absolute ethyl alcohol, dropwise adding 25mg of titanium isopropoxide, finishing dropping within 30min, and ultrasonically dispersing for 35min to obtain a ternary precipitate;
(2) adding the ternary precipitate into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 200 ℃, and washing the obtained product to be neutral by using ethanol and deionized water;
(3) freeze-drying the product washed in the step (2) in liquid nitrogen for 18 h;
(4) and (4) putting the product obtained in the step (3) into a muffle furnace, calcining at 600 ℃, and naturally cooling to room temperature to obtain the titanium dioxide nano-composite electrode material, wherein the heating rate is 5 ℃/min.
Example 3
(1) Dispersing 25mg of graphene and 20mg of stannic oxide in 100ml of absolute ethyl alcohol, dropwise adding 15mg of titanium isopropoxide, finishing dropping within 20min, and performing ultrasonic dispersion for 40min to obtain a ternary precipitate;
(2) adding the ternary precipitate into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 190 ℃, and washing the obtained product to be neutral by using ethanol and deionized water;
(3) freeze-drying the product washed in the step (2) in liquid nitrogen for 24 h;
(4) and (4) putting the product obtained in the step (3) into a muffle furnace, calcining at 700 ℃, heating at a rate of 10 ℃/min, and naturally cooling to room temperature to obtain the titanium dioxide nano-composite electrode material.
Example 4
(1) Dispersing 25mg of graphene and 25mg of stannic oxide in 150ml of absolute ethyl alcohol, dropwise adding 15mg of titanium isopropoxide, finishing dropping within 15min, and ultrasonically dispersing for 50min to obtain a ternary precipitate;
(2) adding the ternary precipitate into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 200 ℃, and washing the obtained product to be neutral by using ethanol and deionized water;
(3) freeze-drying the product washed in the step (2) in liquid nitrogen for 12 h;
(4) and (4) putting the product obtained in the step (3) into a muffle furnace, calcining at 650 ℃, heating at a rate of 10 ℃/min, and naturally cooling to room temperature to obtain the titanium dioxide nano-composite electrode material.
Example 5
(1) Dispersing 20mg of graphene and 15mg of stannic oxide in 100ml of absolute ethyl alcohol, dropwise adding 10mg of titanium isopropoxide, finishing dropping within 20min, and ultrasonically dispersing for 30min to obtain a ternary precipitate;
(2) adding the ternary precipitate into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 200 ℃, and washing the obtained product to be neutral by using ethanol and deionized water;
(3) freeze-drying the product washed in the step (2) in liquid nitrogen for 24 h;
(4) and (4) putting the product obtained in the step (3) into a muffle furnace, calcining at 700 ℃, heating at a rate of 10 ℃/min, and naturally cooling to room temperature to obtain the titanium dioxide nano-composite electrode material.
Comparative example 1
The difference from example 1 is that only tin dioxide is not added, and the graphene-titanium dioxide binary composite electrode material is prepared in the comparative example.
Comparative example 2
The difference is that the tin dioxide-titanium dioxide binary composite electrode material is prepared by the comparative example only without adding graphene as in example 1.
Comparative example 3
The only difference from example 1 is that no freeze-drying treatment was performed.
The electrode materials prepared in the examples and the comparative examples and pure titanium dioxide are assembled into a 2032 type button cell to be subjected to electrochemical performance test. The counter electrode is made of a metal lithium sheet, a polypropylene ethylene microporous membrane celgard2400 is adopted as a diaphragm, 1m of lithium hexafluorophosphate/ethylene carbonate + dimethyl carbonate (volume ratio is 1:1) is adopted as electrolyte, a charging and discharging performance test is carried out on the battery by utilizing a Wuhan blue battery test system LAND-CT2001A, the voltage range is set to be 0-3.0V, the multiplying power is set to be 0.1-10C, and 1C is 300 mAh/g. The first cycle discharge, first cycle charge capacity and first cycle efficiency are shown in table 1. From table 1, the first-pass efficiency of the ternary composite material is the highest, which shows that the ternary composite material of the present invention can improve the first-pass efficiency of a single material.
TABLE 1
Figure BDA0002500197030000071
The first-round coulombic efficiency of the ternary composite electrode material prepared by the method is 60.5% -65.2%, the first-round coulombic efficiency of pure titanium dioxide is 50.5, the first-round irreversible capacity mainly comes from the reaction between titanium dioxide and electrolyte, and the irreversible capacity of the ternary composite electrode material is larger and mainly caused by the reaction between functional groups on the surface of graphene and lithium ions. The first-turn constant-current discharge capacity of the pure titanium dioxide reaches 491.3mAh/g, which exceeds the theoretical capacity of the titanium dioxide and is probably caused by the side reaction of the titanium dioxide and the electrolyte. In the second constant current discharge, the specific discharge capacity of the ternary composite electrode material in example 1 is 823mAh/g, the specific discharge capacity of the pure titanium dioxide is 272mAh/g, and the specific capacity of the pure titanium dioxide is smaller than the theoretical capacity of the titanium dioxide, which further illustrates that the first cycle generates side reaction and generates excess capacity. The ternary nano composite electrode material provided by the invention has the advantages that the graphene and the tin dioxide generate a synergistic effect, so that the specific discharge capacity is greatly improved. The capacity retention rate of the battery prepared in the embodiment 1 is 85% after 30000 cycles, the capacity retention rate of pure titanium dioxide is 75% after 300 cycles, the capacity retention rate of the comparative example 1 is 81% after 3000 cycles, the capacity retention rate of the comparative example 2 is 35% after 10000 cycles, the capacity retention rate of the comparative example 2 is 75% after 3000 cycles, and the capacity retention rate of the comparative example 3 is 79% after 3000 cycles.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (7)

1. A preparation method of a titanium dioxide nano-composite electrode material is characterized by comprising the following steps:
(1) dispersing graphene and tin dioxide in an alcohol solution, dropwise adding a titanium source, and ultrasonically dispersing for 30-50 min to obtain a ternary precipitate;
(2) adding the ternary precipitate into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 180-200 ℃, and washing the obtained product with ethanol and deionized water;
(3) freeze-drying the product washed in the step (2);
(4) and (4) putting the product obtained in the step (3) into a muffle furnace, calcining, and naturally cooling to room temperature to obtain the titanium dioxide nano composite electrode material.
2. The method for preparing a titanium dioxide nanocomposite electrode material according to claim 1, wherein the titanium source in the step (1) is titanium isopropoxide.
3. The preparation method of the titanium dioxide nanocomposite electrode material according to claim 1, wherein the mass ratio of the graphene, the tin dioxide and the titanium source in the step (1) is 20-30: 15-25: 10-25.
4. The method for preparing the titanium dioxide nano composite electrode material as claimed in claim 1, wherein the alcohol solution in the step (1) is absolute ethyl alcohol.
5. The preparation method of the titanium dioxide nanocomposite electrode material according to claim 1, wherein the freeze-drying time in the step (3) is 12-24 hours.
6. The preparation method of the titanium dioxide nanocomposite electrode material according to claim 1, wherein the calcination temperature in the step (4) is 500-700 ℃, and the temperature rise rate is 5-10 ℃/min.
7. The titanium dioxide nanocomposite electrode material prepared by the preparation method of the titanium dioxide nanocomposite electrode material according to claims 1-6.
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CN113937272A (en) * 2021-10-15 2022-01-14 佛山科学技术学院 Titanium dioxide nano composite material, preparation method and application
CN113948691A (en) * 2021-10-15 2022-01-18 佛山科学技术学院 Titanium dioxide composite material and application thereof as energy storage material
CN115478277A (en) * 2022-08-30 2022-12-16 中山大学 Solvent-regulated photo-anode material and preparation method and application thereof

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