阅读说明：本技术 一种五氧化二锑/二氧化硅/碳布柔性材料的制备及其作钠离子电池负极的应用 (Preparation of antimony pentoxide/silicon dioxide/carbon cloth flexible material and application of antimony pentoxide/silicon dioxide/carbon cloth flexible material as sodium-ion battery cathode ) 是由 费杰 王娜 黄剑锋 曹丽云 许占位 李嘉胤 郑欣慧 李盟 于 2019-09-24 设计创作，主要内容包括：本发明公开了一种五氧化二锑/二氧化硅/碳布柔性材料的制备及其作钠离子电池负极的应用,将二氧化硅研磨后加入到去离子水中并溶解,得溶液A；将三氯化锑加入到乙醇溶液中并溶解,得三氯化锑溶液,向三氯化锑溶液中加入氢氧化钠水溶液调节其pH,得溶液B；将溶液A加入到溶液B并搅拌,得溶液C；将活化后的碳布置于溶液C中浸渍,将溶液C和碳布转至反应釜中水热反应,冷却至室温取出碳布,清洗烘干得五氧化二锑/二氧化硅/碳布柔性钠离子电池负极材料。其操作简单、成本低及能够将硅材应用到钠离子电池负极材料中。(The invention discloses a preparation method of an antimony pentoxide/silicon dioxide/carbon cloth flexible material and application thereof as a sodium ion battery cathode, wherein silicon dioxide is ground and then added into deionized water to be dissolved, so as to obtain a solution A; adding antimony trichloride into an ethanol solution and dissolving to obtain an antimony trichloride solution, and adding a sodium hydroxide aqueous solution into the antimony trichloride solution to adjust the pH value of the antimony trichloride solution to obtain a solution B; adding the solution A into the solution B and stirring to obtain a solution C; and (3) dipping the activated carbon cloth in the solution C, transferring the solution C and the carbon cloth to a reaction kettle for hydrothermal reaction, cooling to room temperature, taking out the carbon cloth, cleaning and drying to obtain the antimony pentoxide/silicon dioxide/carbon cloth flexible sodium-ion battery cathode material. The method is simple to operate, low in cost and capable of applying the silicon material to the negative electrode material of the sodium-ion battery.)

1. The preparation method of the antimony pentoxide/silicon dioxide/carbon cloth flexible material is characterized by comprising the following steps of:

step 1: adding 0.038-0.15 g of silicon dioxide into 15-25 ml of deionized water and dissolving to obtain a solution A;

step 2: adding 0.3-1.1 g of antimony trichloride into 20-40 mL of ethanol solution and dissolving to obtain an antimony trichloride solution, and adding a strong base solution into the antimony trichloride solution to adjust the pH value to 8-14 to obtain a solution B;

and step 3: adding the solution A into the solution B and stirring to obtain a solution C;

and 4, step 4: and (3) dipping the activated carbon cloth in the solution C, transferring the solution C and the carbon cloth into a reaction kettle for hydrothermal reaction at the temperature of 150-180 ℃, cooling to room temperature, taking out the carbon cloth, cleaning and drying to obtain the antimony pentoxide/silicon dioxide/carbon cloth flexible sodium-ion battery cathode material.

2. The preparation method of the antimony pentoxide/silicon dioxide/carbon cloth flexible material as claimed in claim 1, wherein the dissolving in the step 1 is carried out by ultrasonic treatment for 1-2 h.

3. The preparation method of the antimony pentoxide/silicon dioxide/carbon cloth flexible material as claimed in claim 1, wherein the strong alkali solution in the step 2 is 0.06g/mL of sodium hydroxide aqueous solution.

4. The preparation method of the antimony pentoxide/silicon dioxide/carbon cloth flexible material as claimed in claim 1, wherein the stirring in the step 3 is magnetic stirring for 20-120 min.

5. The preparation method of the antimony pentoxide/silicon dioxide/carbon cloth flexible material as claimed in claim 1, wherein the activation in the step 4 is anodic oxidation in 20g/L sodium dihydrogen phosphate aqueous solution under the electrolysis voltage of 3-8V for 2-15 min.

6. The preparation method of the antimony pentoxide/silicon dioxide/carbon cloth flexible material as claimed in claim 1, wherein the dipping time in the step 4 is 20-60 min.

7. The preparation method of the antimony pentoxide/silica/carbon cloth flexible material as claimed in claim 1, wherein the reaction kettle in the step 4 is a polytetrafluoroethylene kettle, the solution C and the carbon cloth are transferred to the polytetrafluoroethylene kettle and placed in a homogeneous phase reactor for hydrothermal reaction for 12-48 h.

8. The preparation method of the antimony pentoxide/silicon dioxide/carbon cloth flexible material as claimed in claim 1, wherein the cleaning in the step 4 is performed by using deionized water and ethanol.

9. The use of the antimony pentoxide/silica/carbon cloth flexible material prepared according to claim 1 as a negative electrode of a sodium ion battery.

Technical Field

The invention belongs to the technical field of new energy materials, and relates to preparation of an antimony pentoxide/silicon dioxide/carbon cloth flexible material and application of the antimony pentoxide/silicon dioxide/carbon cloth flexible material as a sodium-ion battery cathode.

Background

Metal oxides are widely studied as relatively common and inexpensive materials due to their high theoretical capacity. The metal oxide undergoes conversion reaction and alloying reaction during the charging and discharging process of the battery. However, severe volume expansion occurs during repeated sodium intercalation, resulting in severe capacity fade, which affects the cycle stability of the battery. This is also a big problem to overcome the oxide as electrode material, and researchers have designed various solutions, such as compounding with carbon material, designing into cladding structure and core-shell structure, etc., in an attempt to solve this problem.

In recent years, it has been found that the cycle stability of a lithium ion battery can be improved by doping silica into a negative electrode material of the battery. Li J and the like take PVC as carbon sources to synthesize SiO₂the/C is used as the cathode material of the lithium ion battery and is 100mAg^-1At a current density of 695mAh g, the reversible capacity remained after 200 cycles^-1。(Facile synthesis of SiO₂/C anode using PVC as carbon source for lithium-ion batteries[J]Journal of Materials Science: Materials in Electronics, 2018). Prasath A and the like prepare SiO by a sol-gel method₂/Co₃O₄Lithium ion battery negative electrode material (Sol-gel-assisted preparation of SiO)₂@Co₃O₄heterostructure from laboratory glass waste as a potential anode for lithium-ion battery[J].Journal of Sol-Gel Science and Technology,2019)。SiO₂@Co₃O₄When the lithium ion battery cathode is used as a lithium ion battery cathode, the reversible capacity is maintained at 507mAh g after 50 cycles of circulation under the current density of 0.5C^-1。

Silica is an amorphous, non-toxic, tasteless, and pollution-free white powdery non-metallic material, and as an excellent structural and functional material, it has wide applications in many fields such as ceramics, plastics, rubbers, and catalysts. However, silicon materials are generally considered to be unsuitable as negative electrode materials of sodium ion batteries, so that application of silicon dioxide to the negative electrode of the sodium ion battery is rarely reported.

Disclosure of Invention

The invention aims to provide the preparation of the antimony pentoxide/silicon dioxide/carbon cloth flexible material which is simple to operate and low in cost and can apply the silicon material to the cathode of the sodium-ion battery and the application of the antimony pentoxide/silicon dioxide/carbon cloth flexible material as the cathode of the sodium-ion battery.

The invention is realized by the following technical scheme:

the preparation method of the antimony pentoxide/silicon dioxide/carbon cloth flexible material comprises the following steps:

step 1: adding 0.038-0.15 g of silicon dioxide into 15-25 ml of deionized water and dissolving to obtain a solution A;

step 2: adding 0.3-1.1 g of antimony trichloride into 20-40 mL of ethanol solution and dissolving to obtain an antimony trichloride solution, and adding a sodium hydroxide aqueous solution into the antimony trichloride solution to adjust the pH value to 8-14 to obtain a solution B;

and step 3: adding the solution A into the solution B and stirring to obtain a solution C;

and 4, step 4: and (3) dipping the activated carbon cloth in the solution C, transferring the solution C and the carbon cloth into a reaction kettle for hydrothermal reaction at the temperature of 150-180 ℃, cooling to room temperature, taking out the carbon cloth, cleaning and drying to obtain the antimony pentoxide/silicon dioxide/carbon cloth flexible sodium-ion battery cathode material.

Further, in the step 1, ultrasonic treatment is adopted for 1-2 hours for dissolution.

Further, the strong alkali solution in step 2 is 0.06g/mL of aqueous sodium hydroxide solution.

Further, the stirring in the step 3 is magnetic stirring for 30-120 min.

Further, in the step 4, the activation is performed by anodizing for 2-15 min in 20g/L sodium dihydrogen phosphate aqueous solution under the electrolysis voltage of 3-8V.

Further, the dipping time in the step 4 is 20-60 min.

Further, in the step 4, the reaction kettle is a polytetrafluoroethylene kettle, the solution C and the carbon cloth are transferred to the polytetrafluoroethylene kettle and placed in a homogeneous phase reactor for hydrothermal reaction for 12-48 h.

Further, the cleaning in the step 4 is performed by using deionized water and ethanol.

Furthermore, the prepared antimony pentoxide/silicon dioxide/carbon cloth flexible material is used as a negative electrode of the sodium-ion battery.

Compared with the prior art, the invention has the following beneficial technical effects:

the invention provides a preparation method of antimony pentoxide/silicon dioxide/carbon cloth flexible material and application thereof as a sodium ion battery cathode₂The material is applied to the field of sodium ion battery cathode materials, and the method is simple to operate, low in cost and environment-friendly; due to Sb as antimony₂O₅Bisb₂O₃The valence is higher, and the material can provide more electrons to participate in reaction when being used as a negative electrode material of a sodium-ion battery, so that the material has higher specific capacity property; activating the carbon cloth to enable the carbon cloth to activate more activated carbon atoms, wherein the activated carbon atoms can generate C-Sb bonds with antimony pentoxide in the later hydrothermal reaction, and the bonds are firmer; SiO 2₂And Sb₂O₅Blending, in the process of charging and discharging, SiO₂Can buffer Sb₂O₅Volume effect of (1), absorption factor Sb₂O₅The stress generated by the huge change of the volume improves the circulation of the materialProperty such that Sb₂O₅The sodium ion battery is more stable. The prepared electrode material is applied to the field of batteries, has high electrochemical cycle stability and has wide application prospect in the field of negative electrode materials of sodium-ion batteries.

Drawings

FIG. 1 is an X-ray diffraction pattern of the antimony pentoxide/silica/carbon cloth flexible sodium-ion battery negative electrode material prepared in example 1;

FIG. 2 is a scanning electron micrograph of the antimony pentoxide/silica/carbon cloth flexible sodium ion battery negative electrode material prepared in example 1;

FIG. 3 is a scanning electron micrograph of the antimony pentoxide/silica/carbon cloth flexible sodium ion battery negative electrode material prepared in example 1 after 200 cycles;

FIG. 4 is a graph comparing the electrochemical cycling performance of the flexible sodium ion battery negative electrode materials of the silica-doped antimony pentoxide/carbon cloth and the silica-undoped antimony pentoxide/carbon cloth prepared in example 1;

fig. 5 is a graph of electrochemical cycle performance for 400 cycles of the antimony pentoxide/silica/carbon cloth flexible sodium-ion battery negative electrode material prepared in example 1.

Detailed Description

Specific examples are given below.