CN109713314B - Preparation method of flexible titanium dioxide/silicon dioxide lithium ion battery electrode - Google Patents
Preparation method of flexible titanium dioxide/silicon dioxide lithium ion battery electrode Download PDFInfo
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- CN109713314B CN109713314B CN201910001594.0A CN201910001594A CN109713314B CN 109713314 B CN109713314 B CN 109713314B CN 201910001594 A CN201910001594 A CN 201910001594A CN 109713314 B CN109713314 B CN 109713314B
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Abstract
The invention discloses a preparation method of a flexible titanium dioxide/silicon dioxide lithium ion battery electrode, which comprises the following steps of taking a carbon cloth as a base layer, growing a layer of titanium dioxide nanowires on the carbon cloth in situ by using the negative electrode material as the base layer, depositing a layer of nano-silicon particles on the surface of the titanium dioxide nanowires in a CVD (chemical vapor deposition) mode, and growing a layer of amorphous SiO on the surface of the carbon cloth2Layer, so that the problem of volume expansion of the silicon can be effectively and slowly released; amorphous SiO as outer layer2The volume expansion of silicon can be slowly released, trace hydrofluoric acid generated by the decomposition of the electrolyte can be prevented, the silicon layer is etched, and the circulation stability of the silicon layer is improved; the preparation method is simple in preparation process and can be used for large-scale production operation.
Description
The technical field is as follows:
the invention relates to the field of new energy of lithium batteries, in particular to a preparation method of a flexible titanium dioxide/silicon dioxide lithium ion battery electrode.
Background art:
the lithium ion battery is the secondary battery with the strongest universality and the widest adaptability so far, has the advantages of high voltage, long cycle life and the like, and is widely applied to various aspects of portable electronic equipment and large and medium-sized electric equipment such as mobile phones, notebook computers, digital cameras, electronic products, electric tools, electric automobiles and the like. With the rapid development of science and technology, flexibility as one of the most promising next generationResearch on foldable optoelectronic devices is of great interest. At present, all electronic products are developed toward being light, thin and flexible. However, to use thin and flexible electronic products, a corresponding high-capacity foldable battery is necessary. Therefore, how to obtain a flexible and high-capacity lithium ion battery becomes a great problem. Development of thin and flexible lithium ion batteries is one of the important research issues in the field of lithium ion batteries. The flexible lithium ion battery is a new research direction in the field of lithium ion batteries, so that the key point is that a flexible and bendable high-capacity electrode material needs to be obtained to realize the flexible lithium ion battery. However, on one hand, considering the existing commercial lithium battery cathode material, the theoretical capacity is 372 mA h g-1The development of a new high-capacity lithium ion battery cathode material has very important theoretical research significance and practical application value. On the other hand, the existing preparation process of the lithium ion battery cathode is to coat an active substance on a copper foil, and the active substance does not have flexibility and bendability.
Therefore, how to develop a flexible and bendable lithium ion battery polar material is a practical problem in the field of current lithium ion batteries, and has a great practical value and a far-reaching economic value.
The invention content is as follows:
the invention aims to provide a preparation method of a flexible titanium dioxide/silicon dioxide lithium ion battery electrode.
Comprises a negative electrode material, a carbon cloth is taken as a base layer, a simple hydrothermal method, CVD deposition Si particles and later-stage coating are adopted to synthesize and prepare a flexible TiO2/Si/SiO2A lithium ion negative electrode material. The carbon cloth is used for replacing the traditional copper foil, and the active material and the current collector are integrally designed, so that the carbon cloth has excellent conductivity and bendability, and has great practical value and economic value.
The invention relates to a preparation method of a flexible titanium dioxide/silicon dioxide lithium ion battery electrode, which comprises the following steps of taking a carbon cloth as a base layer, growing a layer of dioxide on the carbon cloth through a hydrothermal reaction, wherein the carbon cloth is used as the base layer, and the cathode material grows on the carbon cloth in situDepositing nano silicon particles on the surface of the titanium dioxide nanowire in a CVD (chemical vapor deposition) mode, and finally growing a layer of amorphous SiO (silicon dioxide) on the surface of the carbon cloth2And (3) a layer.
The preparation method of the flexible titanium dioxide/silicon dioxide lithium ion battery electrode comprises the following specific steps:
(1) soaking the required carbon cloth in a cleaning solution for cleaning, removing oil stains on the surface of the carbon cloth, taking out and drying;
(2) placing the carbon cloth dried in the step (1) in a titanium tetrachloride ethanol solution, and soaking for 20-28 hours;
(3) preparing tetrabutyl titanate solution, mixing a certain amount of concentrated hydrochloric acid and deionized water with the same amount as the concentrated hydrochloric acid to obtain hydrochloric acid solution, and adding tetrabutyl titanate accounting for 1-2.5% of the hydrochloric acid solution in volume ratio into the hydrochloric acid solution to prepare tetrabutyl titanate solution;
(4) soaking the carbon cloth prepared in the step (2) into the tetrabutyl titanate solution prepared in the step (3), then placing the carbon cloth into a polytetrafluoroethylene reaction kettle for reaction, washing the reaction kettle with ethanol, and drying the reaction kettle to obtain the tetrabutyl titanate-soaked carbon cloth;
(5) depositing a layer of carbon cloth of nano silicon particles on the surface of the titanium dioxide nanowire by the carbon cloth dipped with tetrabutyl titanate in the step (4) by using a CVD (chemical vapor deposition) process;
(6) and (3) placing the carbon cloth prepared in the step (5) into tetrabutyl silicate solution, adding concentrated ammonia water, heating in a water bath at the temperature of 60-80 ℃ for 1-3h, taking out and drying to obtain the flexible titanium dioxide/silicon dioxide lithium ion battery electrode.
Preferably, the titanium tetrachloride ethanol solution in the step (2) is prepared by controlling the ratio of titanium tetrachloride: the mass ratio of ethanol is 1: 3-5.
Preferably, the concentration of the concentrated hydrochloric acid in the step (3) is 11-13 mol/L.
Further, the CVD process in step (5) comprises the following specific steps: and (3) putting the tetrabutyl titanate-impregnated carbon cloth obtained in the step (4) into a CVD furnace, introducing nitrogen to remove the air in the furnace until the oxygen content is lower than 450-550ppm, then heating to 750-850 ℃ at the heating rate of 4-6 ℃/min, roasting for 2-4 hours, introducing silane gas for chemical vapor deposition for 1.5-2.5 hours at the flow rate of 4-6L/min, and then calcining at constant temperature for 1-3 hours to deposit nano silicon on the surface of titanium dioxide, wherein titanate grown hydrothermally is also converted into titanium dioxide at high temperature.
Preferably, the tetrabutyl silicate solution in the step (6) is tetrabutyl silicate: 1 part of water: 4.
preferably, the concentration of the concentrated ammonia water in the step (6) is 25-30 Wt%.
Preferably, the carbon cloth in the step (1) has the specification and the size of 3-4 multiplied by 3-4; the cleaning solution is an acetone solution.
The invention discloses a preparation method of a flexible titanium dioxide/silicon dioxide lithium ion battery electrode, which adopts a simple hydrothermal method, CVD (chemical vapor deposition) Si particles and later-stage coating to prepare and synthesize a flexible TiO2/Si/SiO2A lithium ion negative electrode material. The invention has the following advantages: 1) the carbon cloth is used for replacing the traditional copper foil, the active material and the current collector are integrally designed, and the carbon cloth is processed, so that the carbon cloth not only has excellent conductivity and bendability, but also has good contact force between the active material and the carbon cloth; 2) si is used for replacing the traditional graphite material, the silicon has the highest theoretical specific capacity (4200 mAh/g), and the ultra-Bo high-capacity electrode can be prepared; 3) the silicon is used as an electrode material, the biggest problem is that the volume expansion rate of the silicon is as high as 300 percent along with huge volume change in the charging and discharging processes, the pulverization of the silicon enables an active material to be stripped, and finally the capacity of the electrode is greatly reduced and even completely disabled; 4) amorphous SiO as outer layer2The volume expansion of silicon can be slowly released, trace hydrofluoric acid generated by the decomposition of the electrolyte can be prevented, the silicon layer is etched, and the circulation stability of the silicon layer is improved; the method has simple preparation process and can be scaled upAnd (5) performing die production operation.
Description of the drawings:
fig. 1 is an XRD pattern of titania/silicon dioxide grown on carbon cloth of the method for preparing a flexible titania/silicon dioxide lithium ion battery electrode according to the present invention;
FIG. 2 is a scanning electron micrograph of titania/silicon/silica grown on a carbon cloth according to the present invention;
fig. 3 is a graph of the electrochemical performance of titania/silicon/silica grown on carbon cloth of the present invention.
The specific implementation mode is as follows:
the invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
The invention relates to a preparation method of a flexible titanium dioxide/silicon dioxide lithium ion battery electrode, which is characterized in that a negative electrode material grows on a carbon cloth base in situ, a layer of titanium dioxide nanowires grows on the carbon cloth through hydrothermal reaction, then silicon nanoparticles are deposited on the surfaces of the titanium dioxide nanowires in a CVD (chemical vapor deposition) mode, and finally a layer of amorphous SiO grows on the surfaces of the carbon cloth2A layer;
the method comprises the following specific steps:
(1) soaking a carbon cloth with the thickness of 3 multiplied by 3cm in an acetone solution of a carbon cloth cleaning solution, removing oil stains on the surface of the carbon cloth, taking out and drying;
(2) and (3) placing the carbon cloth cleaned and dried in the step (1) in a titanium tetrachloride ethanol solution, and soaking for 24 hours.
(3) Preparing tetrabutyl titanate solution, namely dissolving 18.76mL of concentrated hydrochloric acid into 18.75mL of deionized water, and finally adding 0.56mL of tetrabutyl titanate to prepare tetrabutyl titanate solution;
(4) immersing the carbon cloth prepared in the step (2) into the tetrabutyl titanate solution prepared in the step (3), then placing the carbon cloth into a 50mL polytetrafluoroethylene reaction kettle device, reacting for 6h at the reaction temperature of 150 ℃, then washing for several times by using the taken ethanol, and drying to obtain the tetrabutyl titanate-immersed carbon cloth;
(5) depositing a layer of carbon cloth of nano silicon particles on the surface of the titanium dioxide nanowire by using a CVD (chemical vapor deposition) process; placing the tetrabutyl titanate-impregnated carbon cloth prepared in the step (4) in a CVD furnace device, introducing nitrogen to remove air in the furnace until the oxygen content is lower than 500ppm, then heating to 800 ℃ at the heating rate of 5 ℃/min, roasting for 3 hours, introducing silane gas for carrying out chemical vapor deposition for 2 hours at the flow rate of 5L/min, then calcining for 2 hours at constant temperature to deposit nano-silicon on the surface of titanium dioxide, and simultaneously converting titanate grown in a water bath into titanium dioxide at high temperature to prepare the carbon cloth with a layer of nano-silicon particles deposited on the surface of titanium dioxide nanowires;
(6) and (3) placing the carbon cloth prepared in the step (5) and deposited with a layer of nano silicon particles on the surface of the titanium dioxide nanowire in tetrabutyl silicate solution, adding 0.5mL of concentrated ammonia water, carrying out water bath at 70 ℃ for 2h, taking out and drying to obtain the flexible titanium dioxide/silicon dioxide lithium ion battery electrode.
The titanium tetrachloride ethanol solution in the step (2) is titanium tetrachloride: the ratio of ethanol is 1: 4.
The concentration of the concentrated hydrochloric acid in the step (3) is 12 mol/L.
The tetrabutyl silicate solution in the step (6) is tetrabutyl silicate: the ratio of water is 1: 4.
The mass concentration of the concentrated ammonia water in the step (6) is 28 percent.
Example 1
The preparation method of the flexible titanium dioxide/silicon dioxide lithium ion battery electrode in the embodiment 1 of the invention comprises the following specific steps:
(1) soaking a 3 x 3cm carbon cloth in an acetone solution, removing oil stains on the surface, taking out and drying;
(2) putting the carbon cloth into a titanium tetrachloride ethanol solution, and soaking for 24 hours;
(3) dissolving concentrated hydrochloric acid in deionized water, and adding tetrabutyl titanate;
(4) soaking carbon cloth in the solution, transferring into a 50mL polytetrafluoroethylene reaction kettle, washing with ethanol for several times at 150 ℃ for 6h, and drying;
(5) depositing a layer of nano silicon particles on the surface of the titanium dioxide nanowire by using a CVD (chemical vapor deposition) process;
(6) putting the carbon cloth into tetrabutyl silicate solution, adding strong ammonia water, carrying out water bath at 70 ℃ for 2h, taking out and drying;
assembling the lithium battery: copper oxide grown in situ on the foamy copper is used as a working electrode, the reference electrode and the counter electrode are both metallic lithium, and the electrolyte is 1M LiPF6EC + DMC + EMC (EC/DMC/EMC =1/1/1 v/v) solution. A CR2032 button cell battery was used as the test vehicle. All assembly was performed in a glove box with inert atmosphere protection.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (3)
1. A preparation method of a flexible titanium dioxide/silicon dioxide lithium ion battery electrode comprises a negative electrode material and takes a carbon cloth as a base layer, and is characterized in that the negative electrode material grows on the carbon cloth base layer in situ, a layer of titanium dioxide nanowires grows on the carbon cloth through hydrothermal reaction, then a layer of nano-silicon particles is deposited on the surface of the titanium dioxide nanowires through a CVD (chemical vapor deposition) mode, and finally a layer of amorphous SiO grows on the surface of the carbon cloth2A layer;
the method comprises the following specific steps:
(1) soaking the required carbon cloth in a cleaning solution for cleaning, removing oil stains on the surface of the carbon cloth, taking out and drying;
(2) placing the carbon cloth dried in the step (1) in a titanium tetrachloride ethanol solution, and soaking for 20-28 hours;
(3) preparing tetrabutyl titanate solution, mixing a certain amount of concentrated hydrochloric acid and deionized water with the volume equal to that of the concentrated hydrochloric acid to obtain hydrochloric acid solution, and adding tetrabutyl titanate accounting for 1-2.5% of the hydrochloric acid solution in volume ratio into the hydrochloric acid solution to prepare tetrabutyl titanate solution;
(4) immersing the carbon cloth prepared in the step (2) into the tetrabutyl titanate solution prepared in the step (3), then placing the solution into a polytetrafluoroethylene reaction kettle for reaction, washing the reaction kettle with ethanol, and drying the reaction kettle to obtain the tetrabutyl titanate-immersed carbon cloth;
(5) depositing a layer of nano silicon particles on the surface of the tetrabutyl titanate dipped carbon cloth obtained in the step (4) by using a CVD (chemical vapor deposition) process;
(6) placing the carbon cloth prepared in the step (5) in tetrabutyl silicate solution, adding concentrated ammonia water, heating in water bath at 60-80 ℃ for 1-3h, taking out and drying to obtain a flexible titanium dioxide/silicon dioxide lithium ion battery electrode;
the titanium tetrachloride ethanol solution in the step (2) is prepared by controlling the following steps: the mass ratio of ethanol is 1: 3-5;
the concentration of the concentrated hydrochloric acid in the step (3) is 11-13 mol/L;
the CVD process in the step (5) comprises the following specific steps: putting the carbon cloth soaked with tetrabutyl titanate in the step (4) into a CVD furnace, introducing nitrogen to remove the air in the furnace until the oxygen content is lower than 450-550ppm, then heating to 750-850 ℃ at the heating rate of 4-6 ℃/min, roasting for 2-4 hours, introducing silane gas for chemical vapor deposition for 1.5-2.5 hours, wherein the flow rate is 4-6L/min, then calcining at constant temperature for 1-3 hours to deposit nano silicon on the surface of titanium dioxide, and simultaneously converting titanate generated by hydrothermal growth into titanium dioxide at high temperature;
the tetrabutyl silicate solution in the step (6) is prepared by controlling tetrabutyl silicate: the water mass ratio is 1: 4.
2. the method for preparing a flexible titanium dioxide/silicon dioxide lithium ion battery electrode as claimed in claim 1, wherein the concentration of the concentrated ammonia water in step (6) is 25-30 wt%.
3. The method for preparing a flexible titanium dioxide/silicon dioxide lithium ion battery electrode according to claim 1, wherein the carbon cloth in the step (1) has a specification size of 3-4 x 3-4; the cleaning solution is an acetone solution.
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| CN111430672B (en) * | 2020-04-03 | 2021-06-04 | 陕西科技大学 | Preparation method and application of silicon dioxide/carbon cloth self-supporting electrode material |
| CN112162439B (en) * | 2020-10-14 | 2021-10-01 | 中国科学技术大学 | Method for enhancing optical regulation and control capability of titanium dioxide electrode |
| CN115101719B (en) * | 2022-05-27 | 2023-06-23 | 长虹三杰新能源有限公司 | Preparation method and application of flexible electrode material |
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