CN111943259A - Carbon-coated mesoporous dual-phase titanium dioxide and preparation method and energy storage application thereof - Google Patents
Carbon-coated mesoporous dual-phase titanium dioxide and preparation method and energy storage application thereof Download PDFInfo
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Abstract
The invention discloses carbon-coated mesoporous two-phase titanium dioxide and a preparation method and energy storage application thereof. The material synthesized by the invention has rich mesoporous structure, B-phase and anatase-phase double-crystal structure and large specific surface area, and the advantages of the three are combined, so that the transmission distance of lithium ions and electrons is greatly shortened, the ion diffusion rate and the conductivity of the material are improved, and the material shows excellent specific capacity and rate capability when being applied to a lithium ion battery cathode material, and is an ideal electrode material.
Description
Technical Field
The invention belongs to the field of functional material preparation, and particularly relates to carbon-coated mesoporous dual-phase titanium dioxide, and a preparation method and an energy storage application thereof.
Background
Among transition metal oxides, titanium dioxide of a nano structure has attracted extensive attention of researchers as a key material for basic research and technical application in the fields of semiconductors, optical devices, catalysts, gas sensing and electrochemical storage due to its excellent physicochemical properties, abundant crystal structure and non-toxicity. In the field of lithium ion batteries, the problem of lithium dendrite generation at the negative electrode can be solved by the higher de-intercalation lithium potential of titanium dioxide, and meanwhile, the material has lower solubility in organic electrolyte and smaller volume change in the de-intercalation lithium process, and is favorable for improving the cycle performance and the service life of the material. However, the intrinsic ionic mobility and the electrical conductivity of the titanium dioxide are low, so that the rate performance of the titanium dioxide is seriously influenced, and the wide application of the titanium dioxide in the field of energy storage is limited.
In order to solve the above problems, researchers have made a lot of work, and one effective measure is to construct a porous structure nano material, to increase the specific surface area of the material, to increase the contact between an electrode and an electrolyte, and to shorten the transmission path of lithium ions and electrons; another method is to compound titanium dioxide with a highly conductive material, such as a metal, a metal oxide, a carbon-based material, etc., which can significantly improve the conductivity of the material.
In recent years, the application of titanium dioxide with a mixed crystal structure in the field of electrochemical energy storage attracts the attention of many researchers. Common crystal structures of titanium dioxide are brookite, B-phase titanium dioxide, anatase and rutile. Among the titanium dioxide with various crystal structures, the B-phase titanium dioxide has the following characteristics, so that the excellent electrochemical lithium storage performance is shown: first, the B-phase titanium dioxide is made of TiO6OctahedraThe body is arranged at the same side and the same angle, so that more open channels are provided, and the migration rate of lithium ions in a crystal structure is favorably accelerated; second, phase B titanium dioxide has a higher theoretical capacity (335mAh g) than the anatase phase-1) (ii) a Meanwhile, the volume of the B-phase titanium dioxide hardly changes in the charging and discharging processes; finally, pseudo-capacitance behavior exists in the diffusion dynamics process of the B-phase titanium dioxide, which is beneficial to improving the rate capability of the titanium dioxide. Studies have shown that in Li+In the storage process, the B phase/anatase phase titanium dioxide has more advantages. On the one hand, anatase phase titanium dioxide is beneficial for electron conduction, while B phase titanium dioxide accelerates Li+A transmission process; on the other hand, the phase boundary generated between the two can provide rich Li through charge separation and interface defect+The active site, so the mixed crystal structure can play the synergistic effect of the two, and the rate capability of the titanium dioxide is obviously improved; although some progress has been made in the related art, the phase B titanium dioxide is an intermediate phase between titanic acid and anatase phase, and the phase B will undergo a phase transition to anatase phase with an increase in temperature. Therefore, the phase change of the phase B at high temperature is inhibited, the controllable proportion of the phase B and the anatase phase in the titanium dioxide is realized by utilizing the capacity contribution of the phase B in the titanium dioxide material, and the key for improving the electrochemical performance of the titanium dioxide material is to fully play the synergistic effect of the phase B and the anatase phase.
According to the invention, a titanium dioxide precursor is prepared by a hydrothermal method, and then high-temperature calcination is carried out to obtain the carbon-coated mesoporous two-phase titanium dioxide. In the high-temperature calcination process, the titanium dioxide precursor is decomposed at high temperature to generate gas, a rich mesoporous structure is generated, meanwhile, ethylene glycol is pyrolyzed at high temperature to generate a carbon source, the carbon source is carbonized in situ on the surface of the titanium dioxide to form a carbon coating layer, and the proportion of the B phase and the anatase phase in the titanium dioxide is regulated and controlled by adjusting the calcination temperature. The method for preparing the carbon-coated mesoporous dual-phase titanium dioxide has not been reported.
Disclosure of Invention
Based on the problems in the prior art, the invention aims to provide carbon-coated mesoporous dual-phase titanium dioxide and a preparation method and energy storage application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of carbon-coated mesoporous two-phase titanium dioxide is characterized by comprising the following steps: firstly, preparing a titanic acid nanobelt as a titanium dioxide precursor; and then soaking the titanium dioxide precursor in ethylene glycol, and calcining at high temperature to obtain the carbon-coated mesoporous two-phase titanium dioxide. The method specifically comprises the following steps:
0.3-1.0 g of titanium dioxide is weighed and dissolved in 6-12 mol L-1Carrying out hydrothermal reaction in a sodium hydroxide solution, wherein the hydrothermal temperature is 100-200 ℃, the heat preservation time is 12-60 h, then centrifuging, washing with water, drying, and collecting a powder product;
putting the collected powder product in 0.1-1.0 mol L-1Carrying out ion exchange in a hydrochloric acid solution for 8-12 h, and then centrifuging, washing and drying to obtain a titanic acid nanobelt, namely a titanium dioxide precursor;
Soaking 100-200 mg of the titanium dioxide precursor in 1-10 mL of ethylene glycol, and standing for 2-24 h to obtain a carbon-coated mesoporous dual-phase titanium dioxide precursor solution;
step 3, preparing carbon-coated mesoporous dual-phase titanium dioxide by high-temperature calcination
Placing the carbon-coated mesoporous dual-phase titanium dioxide precursor liquid in a tube furnace, and calcining at a high temperature under the protection of argon, wherein the calcining temperature is 300-800 ℃, the heat preservation time is 60-240 min, and the heating rate is 0.5-10 ℃ for min-1And naturally cooling to room temperature after calcination is finished to obtain the carbon-coated mesoporous two-phase titanium dioxide.
Further, in the high-temperature calcination process, ethylene glycol is pyrolyzed at high temperature to serve as a carbon source, and a carbon coating layer is formed on the surface of titanium dioxide in situ. The controllable carbon coating amount can be realized by regulating and controlling the use amounts of the titanium dioxide precursor and the ethylene glycol.
Further, in the high-temperature calcination process, the titanium dioxide precursor is decomposed at high temperature to generate a large amount of gas, and a rich mesoporous structure is promoted to be generated in the titanium dioxide matrix. The formed mesoporous structure increases the contact area between the electrode and the electrolyte, shortens the transmission distance of lithium ions and electrons, and further improves the electrochemical performance of the material.
Furthermore, the proportion of the B phase and the anatase phase in the titanium dioxide can be adjusted by regulating and controlling the high-temperature calcination temperature, so that the electrochemical performance is optimized.
The carbon-coated mesoporous two-phase titanium dioxide prepared by the method can be used as an electrochemical energy storage material, such as a battery electrode material, and shows higher specific capacity. In addition, the carbon-coated mesoporous dual-phase titanium dioxide prepared by the method has great potential in the fields of catalysis, sensing and the like.
Compared with the prior art, the invention has the beneficial effects that:
1. the carbon-coated mesoporous two-phase titanium dioxide material synthesized by the method has the advantages of rich mesoporous structure, B-phase and anatase-phase double-crystal structure and large specific surface area, and the advantages of the three are combined, so that the transmission distance of lithium ions and electrons is greatly shortened, and the ion diffusion rate and the electrical conductivity of the material are improved. When the material is applied to a lithium ion battery cathode material, the material shows excellent specific capacity and rate capability, and is an ideal electrode material.
2. The preparation method of the carbon-coated mesoporous two-phase titanium dioxide does not need to additionally add a carbon source, has simple process and is beneficial to industrial production.
3. According to the preparation method, ethylene glycol is used for high-temperature pyrolysis, a carbon coating layer is formed on the surface of carbon dioxide in situ, and the thickness of the carbon coating layer is controlled by adjusting the proportion of ethylene glycol and titanium dioxide and the calcination temperature; the method comprises the steps of utilizing gas generated in the process of high-temperature decomposition of a titanium dioxide precursor to promote generation of a rich mesoporous structure; the ratio of the B phase to the anatase phase in the titanium dioxide can be controlled by adjusting the calcining temperature. For example, when the carbon coating layer thickness of the obtained product is about 3nm, the mesoporous diameter is 2-30 nm, and the mass fractions of B phase and anatase phase in titanium dioxide are 70% and 30% respectively when ethylene glycol (2mL), titanic acid (200mg), the calcining temperature is 600 ℃ and the holding time is 2 hoursHigher specific discharge capacity (503mA h g)-1Current density 100mA g-1)。
Drawings
FIG. 1 is a FESEM photograph of a titanium dioxide precursor prepared in example 1;
FIG. 2 is a TEM photograph of a titania precursor prepared in example 1;
FIG. 3 is a FESEM photograph of the carbon-coated mesoporous dual-phase titanium dioxide precursor solution prepared in example 1;
FIG. 4 is a FESEM photograph of the dual phase titanium dioxide prepared in example 5;
FIG. 5 is an XRD spectrum of the biphasic titanium dioxide prepared in examples 2-5;
fig. 6 is a FESEM photograph of the carbon-coated mesoporous dual-phase titania prepared in example 6;
fig. 7 is a FESEM photograph of the carbon-coated mesoporous dual-phase titania prepared in example 7;
fig. 8 is a FESEM photograph of the carbon-coated mesoporous dual-phase titania prepared in example 8;
fig. 9 is a FESEM photograph of the carbon-coated mesoporous dual-phase titania prepared in example 9;
FIG. 10 is an XRD spectrum of the carbon-coated mesoporous dual-phase titania prepared in examples 6 to 9;
FIG. 11 is a bar graph of the mass percentage of the B-phase titania in the two-phase titania and carbon-coated mesoporous two-phase titania materials prepared in examples 2 to 9;
fig. 12 is a TEM photograph of the carbon-coated mesoporous dual-phase titania prepared in example 8;
FIG. 13 shows the two-phase titania and carbon-coated mesoporous two-phase titania prepared in examples 5 and 8 at different current densities (100-10000 mA g/g)-1) The magnification curve of (2).
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention can be embodied in many different forms other than those herein described and many modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.
Example 1
This example prepares a titanium dioxide precursor by a hydrothermal method:
And 2, weighing 200mg of the prepared titanic acid nanobelt, soaking the nanobelt in 2mL of ethylene glycol, and standing for 12 hours to obtain a carbon-coated mesoporous dual-phase titanium dioxide precursor solution, wherein an FESEM photograph of the carbon-coated mesoporous dual-phase titanium dioxide precursor solution is shown in figure 3.
Example 2
This example prepares biphasic titanium dioxide as follows:
Example 3
This example prepares biphasic titanium dioxide as follows:
Example 4
This example prepares biphasic titanium dioxide as follows:
Example 5
This example prepares biphasic titanium dioxide as follows:
Example 6
In this example, carbon-coated mesoporous dual-phase titania was prepared as follows:
And 2, soaking 200mg of titanium dioxide precursor in 2mL of ethylene glycol, and standing for 12h to obtain the carbon-coated mesoporous two-phase titanium dioxide precursor solution.
And 3, placing the carbon-coated mesoporous two-phase titanium dioxide precursor liquid in a tubular furnace, and calcining at a high temperature under the protection of argon, wherein the calcining temperature is 400 ℃, the heat preservation time is 120min, and the heating rate is 2 ℃ for min-1And naturally cooling to room temperature after calcination is finished to obtain the carbon-coated mesoporous dual-phase titanium dioxide, wherein FESEM pictures and XRD patterns of the carbon-coated mesoporous dual-phase titanium dioxide are respectively shown in figures 6 and 10.
Example 7
In this example, carbon-coated mesoporous dual-phase titania was prepared as follows:
And 2, soaking 200mg of titanium dioxide precursor in 2mL of ethylene glycol, and standing for 12h to obtain the carbon-coated mesoporous two-phase titanium dioxide precursor solution.
And 3, placing the carbon-coated mesoporous two-phase titanium dioxide precursor liquid in a tubular furnace, and calcining at a high temperature under the protection of argon, wherein the calcining temperature is 500 ℃, the heat preservation time is 120min, and the heating rate is 5 ℃ for min-1And naturally cooling to room temperature after calcination is finished to obtain the carbon-coated mesoporous dual-phase titanium dioxide, wherein FESEM pictures and XRD patterns of the carbon-coated mesoporous dual-phase titanium dioxide are respectively shown in figures 7 and 10.
Example 8
In this example, carbon-coated mesoporous dual-phase titania was prepared as follows:
And 2, soaking 200mg of titanium dioxide precursor in 2mL of ethylene glycol, and standing for 12h to obtain the carbon-coated mesoporous two-phase titanium dioxide precursor solution.
And 3, placing the carbon-coated mesoporous two-phase titanium dioxide precursor liquid in a tubular furnace, and calcining at high temperature under the protection of argon, wherein the calcining temperature is 600 ℃, the heat preservation time is 120min, and the heating rate is 2 ℃ for min-1And naturally cooling to room temperature after calcination is finished to obtain the carbon-coated mesoporous two-phase titanium dioxide, wherein FESEM pictures, TEM pictures and XRD patterns of the carbon-coated mesoporous two-phase titanium dioxide are respectively shown in figures 8, 12 and 10.
Example 9
In this example, carbon-coated mesoporous dual-phase titania was prepared as follows:
step (ii) of1. 0.3g of titanium dioxide was weighed out and dissolved in 10mol L-1Carrying out hydrothermal reaction in a sodium hydroxide solution, wherein the hydrothermal temperature is 160 ℃, the heat preservation time is 48h, then centrifuging, washing, drying at 80 ℃, and collecting a powder product. The collected powder product was placed in a 0.1mol L-1Ion exchange is carried out for 10h in hydrochloric acid solution, and then the titanic acid nanobelt, namely the titanium dioxide precursor, is obtained after centrifugation, water washing and drying at 80 ℃.
And 2, soaking 200mg of titanium dioxide precursor in 2mL of ethylene glycol, and standing for 12h to obtain the carbon-coated mesoporous two-phase titanium dioxide precursor solution.
And 3, placing the carbon-coated mesoporous two-phase titanium dioxide precursor liquid in a tubular furnace, and calcining at a high temperature under the protection of argon, wherein the calcining temperature is 700 ℃, the heat preservation time is 120min, and the heating rate is 2 ℃ for min-1And naturally cooling to room temperature after calcination is finished to obtain the carbon-coated mesoporous dual-phase titanium dioxide, wherein the FESEM pictures and XRD patterns of the carbon-coated mesoporous dual-phase titanium dioxide are respectively shown in figures 9 and 10.
Referring to the above examples, the present invention researches the influence of different calcination temperatures on the microstructure, phase composition and electrochemical properties of carbon-coated mesoporous dual-phase titanium dioxide. As can be seen from fig. 6 to 9, the diameter of the carbon-coated titanium dioxide nanobelt is slightly wider than that of the precursor, but the morphology thereof is basically unchanged. As can be seen from fig. 2 and 12, rich mesoporous structures in the carbon-coated mesoporous dual-phase titanium dioxide are formed in the pyrolysis stage of the titanium dioxide precursor, the diameter of the mesoporous structure ranges from 2 nm to 30nm, and the thickness of the carbon-coated layer is about 3nm, wherein the generation of the mesoporous structure is beneficial to increasing the contact area between the electrode and the electrolyte and accelerating the transmission of lithium ions. The XRD pattern in figure 10 shows that the phase composition is B phase and anatase phase titanium dioxide.
Fig. 11 is a histogram of mass percentages of the B-phase titanium dioxide in the dual-phase titanium dioxide and the carbon-coated mesoporous dual-phase titanium dioxide materials prepared in examples 2 to 9 in the titanium dioxide, and the results show that the proportion of the B-phase to the anatase phase in the titanium dioxide can be adjusted by adjusting the carbonization temperature.
To test the performance of the materials obtained in examples 5 and 8 as electrochemical energy storage materials, the following were carried outIt was assembled into cells and electrochemically tested as follows: preparing the materials synthesized in the embodiments 5 and 8, carbon black and polyvinylidene fluoride (PVDF) into slurry according to the mass ratio of 8:1:1, respectively, and coating the slurry on a copper foil to prepare an electrode plate; 1.0mol L of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (volume ratio of 1:1) dissolved in-1LiPF6Is an electrolyte; a2320 type polypropylene microporous membrane is taken as a diaphragm, and the diaphragm is assembled into a 2032 type button battery in an argon glove box. Adopting a LAND CT-2001A test system to test the voltage of 100-10000 mA g in a voltage range of 0.01-3.0V at room temperature-1Constant current charge and discharge tests were performed at the current density of (1).
FIG. 13 shows the two-phase titania prepared in example 5 and the carbon-coated mesoporous two-phase titania prepared in example 8 at different current densities (100 to 10000 mAg)-1) Performance of (c) is compared with the graph. The result shows that the carbon-coated mesoporous dual-phase titanium dioxide electrode material prepared in example 8 has more excellent electrochemical performance, and the electrochemical performance is 100mA g-1When the current density is lower, the specific discharge capacity is 503.0mAh g-1At 10000mA g-1The specific discharge capacity of the lithium ion battery can still maintain 95.3mAh g under the current density-1Can be used as an ideal lithium ion battery cathode material.
Claims (8)
1. A preparation method of carbon-coated mesoporous two-phase titanium dioxide is characterized by comprising the following steps: firstly, preparing a titanic acid nanobelt as a titanium dioxide precursor; and then soaking the titanium dioxide precursor in ethylene glycol, and calcining at high temperature to obtain the carbon-coated mesoporous two-phase titanium dioxide.
2. The method for preparing carbon-coated mesoporous biphasic titanium dioxide according to claim 1, which is characterized by comprising the following steps:
step 1, preparing titanium dioxide precursor by hydrothermal method
0.3-1.0 g of titanium dioxide is weighed and dissolved in 6-12 mol L-1Carrying out hydrothermal reaction in a sodium hydroxide solution, wherein the hydrothermal temperature is 100-200 ℃, the heat preservation time is 12-60 h, then centrifuging, washing with water, drying, and collecting a powder product;
putting the collected powder product in 0.1-1.0 mol L-1Carrying out ion exchange in a hydrochloric acid solution for 8-12 h, and then centrifuging, washing and drying to obtain a titanic acid nanobelt, namely a titanium dioxide precursor;
step 2, obtaining carbon-coated mesoporous dual-phase titanium dioxide precursor solution by soaking method
Soaking 100-200 mg of the titanium dioxide precursor in 1-10 mL of ethylene glycol, and standing for 2-24 h to obtain a carbon-coated mesoporous dual-phase titanium dioxide precursor solution;
step 3, preparing carbon-coated mesoporous dual-phase titanium dioxide by high-temperature calcination
Placing the carbon-coated mesoporous dual-phase titanium dioxide precursor liquid in a tube furnace, and calcining at a high temperature under the protection of argon, wherein the calcining temperature is 300-800 ℃, the heat preservation time is 60-240 min, and the heating rate is 0.5-10 ℃ for min-1And naturally cooling to room temperature after calcination is finished to obtain the carbon-coated mesoporous two-phase titanium dioxide.
3. The method for preparing carbon-coated mesoporous biphasic titanium dioxide according to claim 1 or 2, wherein the carbon-coated mesoporous biphasic titanium dioxide comprises the following steps: in the high-temperature calcination process, ethylene glycol is pyrolyzed at high temperature to be used as a carbon source, and a carbon coating layer is formed on the surface of titanium dioxide in situ.
4. The method for preparing carbon-coated mesoporous dual-phase titanium dioxide according to claim 3, wherein the method comprises the following steps: the controllable carbon coating amount can be realized by regulating and controlling the use amounts of the titanium dioxide precursor and the ethylene glycol.
5. The method for preparing carbon-coated mesoporous biphasic titanium dioxide according to claim 1 or 2, wherein the carbon-coated mesoporous biphasic titanium dioxide comprises the following steps: in the high-temperature calcination process, the titanium dioxide precursor is decomposed at high temperature to generate gas, and a rich mesoporous structure is promoted to be generated in the titanium dioxide matrix.
6. The method for preparing carbon-coated mesoporous biphasic titanium dioxide according to claim 1 or 2, wherein the carbon-coated mesoporous biphasic titanium dioxide comprises the following steps: the proportion of the B phase and the anatase phase in the titanium dioxide can be adjusted by regulating and controlling the high-temperature calcination temperature.
7. A carbon-coated mesoporous two-phase titanium dioxide obtained by the preparation method of any one of claims 1 to 6.
8. An energy storage application of the carbon-coated mesoporous two-phase titanium dioxide of claim 7, wherein: the material is used as a negative electrode material of a lithium ion battery.
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| CN113526559A (en) * | 2021-07-12 | 2021-10-22 | 郑州轻工业大学 | Preparation method and application of dual-phase manganese dioxide heterojunction |
| CN114551850A (en) * | 2022-01-25 | 2022-05-27 | 合肥国轩电池材料有限公司 | Silicon-carbon cathode composite material with porous structure and preparation method and application thereof |
| CN115094478A (en) * | 2022-07-12 | 2022-09-23 | 国家纳米科学中心 | Titanium dioxide/graphite oxide composite material and preparation method and application thereof |
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| CN113526559A (en) * | 2021-07-12 | 2021-10-22 | 郑州轻工业大学 | Preparation method and application of dual-phase manganese dioxide heterojunction |
| CN113526559B (en) * | 2021-07-12 | 2023-07-28 | 郑州轻工业大学 | Preparation method and application of double-phase manganese dioxide heterojunction |
| CN114551850A (en) * | 2022-01-25 | 2022-05-27 | 合肥国轩电池材料有限公司 | Silicon-carbon cathode composite material with porous structure and preparation method and application thereof |
| CN115094478A (en) * | 2022-07-12 | 2022-09-23 | 国家纳米科学中心 | Titanium dioxide/graphite oxide composite material and preparation method and application thereof |
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