CN110265644A - Preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material with mesh porous structure - Google Patents

Abstract

The invention relates to a preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material with mesh porous structure. Put it into polyacrylic acid aqueous solution for coating treatment, wash and dry; Step 2: Antimony trichloride is added to absolute ethanol to form antimony trichloride solution, and sodium hydroxide aqueous solution is added to the antimony trichloride solution to adjust its pH to obtain Mixed solution; the coated carbon cloth is soaked in the mixed solution; step 3: the carbon cloth obtained in step 2 and the mixed solution are transferred to the reactor for hydrothermal reaction, cooled to room temperature, cleaned and dried to obtain a five Antimony oxide/polyacrylic acid/carbon cloth flexible anode material for sodium-ion batteries. The operation is simple and the repeatability is good. The flexible electrode combines the good mechanical properties of carbon cloth and the high specific capacity of antimony pentoxide, and improves the electrochemical cycle performance as the negative electrode material of the sodium ion battery.

Description

A network-like porous structure of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion Preparation method of battery negative electrode material

technical field

The invention belongs to the technical field of flexible energy storage materials, and in particular relates to a method for preparing a net-like porous structure antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium-ion battery negative electrode material.

Background technique

With the development of flexible and bendable electronic devices, the development of flexible electrode materials with high specific capacity has become an important research direction in the field of energy storage. At present, the main flexible electrode materials usually use carbon materials with good conductivity, such as graphene, carbon nanotubes, carbon cloth, etc. Among them, carbon cloth is widely used as a flexible electrode material substrate because of its good mechanical strength, electrical conductivity and flexibility. In recent years, many researchers have used active materials such as metal oxides on carbon cloth for flexible electrode materials. LongH et al. grew NiO nanosheets directly on carbon cloth substrates by solution method and annealing method, and used them as flexible anodes for lithium-ion batteries (Growth of hierarchical mesoporous NiO nanosheets on carboncloth as binder-free anodes for high-performance flexible lithium-ion batteries [J]. Scientific Reports, 2014, 4: 7413). ZhangY et al prepared a flexible MoSe ₂ /CF composite material by solvothermal method (MoSe ₂ nanosheets grown on carbon cloth with superior electrochemical performance as flexible electrode for sodium ion batteries[J].RSC Advances,2015,6(2): 1440-1444). SangHJ et al. synthesized Na ₂ FeP ₂ O ₇ and porous carbon cloth composites by sol-gel method as flexible anode materials for sodium-ion batteries with good long-term cycle capability (Approach to flexible Na-ion batteries with exceptional rate capability and long lifespan using Na ₂ FeP ₂ O ₇ nanoparticles on porous carbon cloth [J]. Journal of Materials Chemistry A, 2017, 5(11): 5502-5510). RenWN et al. modified three-dimensional flower-like MoS ₂ nanosheet carbon cloth composites by atomic layer deposition TiO ₂ layer (ALD TiO ₂ coated flower-like MoS ₂ nanosheets on carboncloth as sodium ion battery anode with enhanced cycling stability and ratecapability[J].ACS Applied Materials & Interfaces, 2016, 9(1):487-495). However, the above-mentioned method does not involve the problems of bonding between the carbon cloth and the loaded active material and the uniformity of the growth morphology.

The research on negative electrode active materials of sodium ion batteries mainly focuses on carbon materials, alloy materials and compound materials. Each material has advantages and disadvantages, among which metal compound materials have been widely studied due to their large specific capacity. China is a country with large reserves of antimony. Antimony is located in the fifth main group of the periodic table of elements. It has two valence states of trivalent and pentavalent, and the corresponding oxides are Sb ₂ O ₃ and Sb ₂ O ₅ . Among them, Sb ₂ O ₃ has a relatively high theoretical capacity (1102mAhg ^-1 ) and has been extensively studied, while there has been no report on Sb ₂ O ₅ as a battery material.

Contents of the invention

The object of the present invention is to provide a kind of preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material of a kind of simple operation, low cost, green environmental protection and binding force good network porous structure, its pentoxide Diantimony grows into a network-like porous structure and is evenly distributed on the surface of the flexible carbon cloth fiber, which improves the electrochemical cycle performance as a negative electrode material for sodium-ion batteries as a whole.

To achieve the above object, the present invention is achieved through the following technical solutions:

A preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material with mesh porous structure, comprising the following steps:

Step 1: Soak the carbon cloth in acetone to remove surface impurities, wash and dry, then dip the dried carbon cloth into polyacrylic acid aqueous solution for coating treatment, wash and dry;

Step 2: Add 0.3-1.14g of antimony trichloride to 20-60mL of absolute ethanol and stir to form an antimony trichloride solution, add aqueous sodium hydroxide solution to the antimony trichloride solution to adjust its pH to 8-12 to obtain a mixture liquid; soak the coated carbon into the mixed liquid;

Step 3: Transfer the carbon cloth and the mixed solution obtained in step 2 to a reaction kettle for hydrothermal reaction at 120-180°C, cool to room temperature, take out the carbon cloth, wash and dry to obtain antimony pentoxide/polyacrylic acid/ Carbon cloth flexible anode material for sodium-ion batteries.

Further, the carbon arrangement in step 1 is soaked in acetone for 24-72 hours.

Further, the mass concentration of the polyacrylic acid aqueous solution in step 1 is 1-8 mg/mL, and the time for coating the dried carbon cloth into the polyacrylic acid aqueous solution is 1-12 hours.

Further, the average molecular weight of polyacrylic acid is 1,250,000.

Further, the cleaning in step 1 and step 3 is repeated cleaning with deionized water and ethanol respectively.

Further, the coated carbon in step 2 is soaked in the mixed solution and stirred for 20-40 minutes.

Further, the mass concentration of the aqueous sodium hydroxide solution in step 2 is 0.03-0.12 g/mL.

Further, the reaction kettle in step 3 is a polytetrafluoroethylene kettle, and the carbon cloth and the mixed solution are transferred to a polytetrafluoroethylene kettle and placed in a homogeneous reactor for hydrothermal reaction for 4-48 hours.

Further, the carbon cloth is a hydrophilic carbon cloth with a size of 4cm*2cm.

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

The invention provides a preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material with mesh porous structure. The preparation method is coated by immersing the cleaned carbon cloth in polyacrylic acid aqueous solution treatment; then take out the carbon cloth to clean and dry; then put the dried carbon cloth into the ethanol solution of antimony trichloride, use sodium hydroxide aqueous solution as the precipitating agent, and then carry out hydrothermal reaction to obtain the five Antimony oxide/polyacrylic acid/carbon cloth flexible anode material for sodium ion batteries; a layer of polyacrylic acid polymer binder is laid on the carbon cloth substrate, which can not only form a good combination with the carbon cloth substrate, but also Contains a large number of carboxyl groups, which are evenly distributed, and can form a strong chemical bond with Sb ₂ O ₅ , which overcomes the problems of poor uniformity and easy falling off of carbon cloth when loading other electrochemically active substances; In addition, polyacrylic acid has good shape retention and good mechanical properties in the electrolyte; at the same time, the carbon cloth after impregnated with polyacrylic acid is rich in oxygen-containing functional groups without activation treatment, and antimony pentoxide grows into a unique network porous Structure and evenly distributed on the surface of flexible carbon cloth fibers, the flexible electrode combines the flexibility of carbon cloth and the high specific capacity of antimony pentoxide, which improves the electrochemical cycle performance as a negative electrode material for sodium ion batteries as a whole; its preparation method The method is simple and novel, has short preparation cycle and high repeatability, and is suitable for large-scale production preparation.

Description of drawings

Fig. 1 is the X-ray diffraction spectrum of the antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material of the network porous structure prepared in embodiment 3;

Fig. 2 is the scanning electron micrograph of the antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material of the network porous structure prepared in embodiment 3;

FIG. 3 is a diagram of the electrochemical cycle performance of the network porous structure antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material prepared in Example 3.

Detailed ways

The present invention will be further described in detail below in conjunction with specific embodiments, which are explanations of the present invention rather than limitations.

Example 1:

A preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material with mesh porous structure, comprising the following steps:

Step 1: Soak the hydrophilic carbon cloth with a size of 4cm*2cm in 50mL acetone for 24 hours to remove surface impurities, then wash it repeatedly with deionized water and absolute ethanol, and place the carbon cloth in an oven at 60°C to dry Dry; then place the dried carbon cloth into 1mg/mL polyacrylic acid aqueous solution for 1h for coating treatment, wash it repeatedly with deionized water and absolute ethanol respectively, place the carbon cloth in an oven at 60°C and then dry it ; Wherein, polyacrylic acid average molecular weight is 1250000;

Step 2: Add 0.3g antimony trichloride to 20mL of absolute ethanol and stir magnetically to form an antimony trichloride solution, add 0.06g/mL sodium hydroxide aqueous solution to the antimony trichloride solution to adjust its pH to 8 and mix solution; soak the coated carbon into the mixed solution and magnetically stir for 30 minutes;

Step 3: Transfer the carbon cloth and the mixed solution obtained in step 2 to a polytetrafluoroethylene kettle and place it in a homogeneous reactor for hydrothermal reaction at 120°C for 48 hours, cool to room temperature, take out the carbon cloth, wash and dry to obtain a porous mesh Structured antimony pentoxide/polyacrylic acid/carbon cloth flexible anode material for sodium-ion batteries.

Example 2:

A preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material with mesh porous structure, comprising the following steps:

Step 1: Soak the hydrophilic carbon cloth with a size of 4cm*2cm in 50mL acetone for 36 hours to remove surface impurities, then wash it repeatedly with deionized water and absolute ethanol, and place the carbon cloth in an oven at 60°C to dry Dry; then place the dried carbon cloth into 3mg/mL polyacrylic acid aqueous solution for 1h for coating treatment, wash it repeatedly with deionized water and absolute ethanol respectively, place the carbon cloth in an oven at 60°C and then dry it ; Wherein, polyacrylic acid average molecular weight is 1250000;

Step 2: Add 0.57g antimony trichloride to 20mL of absolute ethanol and stir magnetically to form an antimony trichloride solution, add 0.08g/mL sodium hydroxide aqueous solution to the antimony trichloride solution to adjust its pH to 10 and mix solution; soak the coated carbon into the mixed solution and magnetically stir for 30 minutes;

Step 3: Transfer the carbon cloth and the mixed solution obtained in step 2 to a polytetrafluoroethylene kettle and place it in a homogeneous reactor for hydrothermal reaction at 150°C for 48 hours, cool to room temperature, take out the carbon cloth, wash and dry to obtain a porous mesh Structured antimony pentoxide/polyacrylic acid/carbon cloth flexible anode material for sodium-ion batteries.

Example 3:

A preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material with mesh porous structure, comprising the following steps:

Step 1: Soak the hydrophilic carbon cloth with a size of 4cm*2cm in 50mL acetone for 72 hours to remove surface impurities, then wash it repeatedly with deionized water and absolute ethanol, and place the carbon cloth in an oven at 60°C to dry Dry; then place the dried carbon cloth into a 6mg/mL polyacrylic acid aqueous solution for 3 hours for coating treatment, wash it repeatedly with deionized water and absolute ethanol respectively, and place the carbon cloth in an oven at 60°C for further coating. drying; wherein, the average molecular weight of polyacrylic acid is 1,250,000;

Step 2: Add 0.57g antimony trichloride to 20mL of absolute ethanol and stir magnetically to form an antimony trichloride solution, add 0.06g/mL sodium hydroxide aqueous solution to the antimony trichloride solution to adjust its pH to 9 and mix solution; soak the coated carbon into the mixed solution and magnetically stir for 30 minutes;

Step 3: Transfer the carbon cloth and the mixed solution obtained in step 2 to a polytetrafluoroethylene kettle and place it in a homogeneous reactor for hydrothermal reaction at 180°C for 12 hours, cool to room temperature, take out the carbon cloth, wash and dry to obtain a porous mesh Structured antimony pentoxide/polyacrylic acid/carbon cloth flexible anode material for sodium-ion batteries.

As shown in Figure 1, the anode material of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium-ion battery was analyzed by Rigaku D/max2000PCX-ray diffractometer, and it was found that the sample was consistent with the structure of Sb ₂ O ₅ with PDF number 11-0690 . The sample was observed with an S-4800 field emission scanning electron microscope of the American FEI company, as shown in Figure 2, it can be seen that the porous negative electrode material of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery . As shown in Figure 3, the prepared antimony pentoxide/polyacrylic acid/carbon cloth was used as the negative electrode material of the sodium ion battery, and assembled into a CR2032 battery. The cycle performance test was carried out with the blue electric test system, showing a high electrochemical performance. capacity and stability.

Example 4:

A preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material with mesh porous structure, comprising the following steps:

Step 1: Soak the hydrophilic carbon cloth with a size of 4cm*2cm in 50mL acetone for 72 hours to remove surface impurities, then wash it repeatedly with deionized water and absolute ethanol, and place the carbon cloth in an oven at 60°C to dry Dry; then place the dried carbon cloth into 8mg/mL polyacrylic acid aqueous solution for 1h for coating treatment, wash it repeatedly with deionized water and absolute ethanol respectively, place the carbon cloth in an oven at 60°C and dry it ; Wherein, polyacrylic acid average molecular weight is 1250000;

Step 2: Add 1.14g of antimony trichloride to 40mL of absolute ethanol and stir magnetically to form an antimony trichloride solution, add 0.06g/mL of sodium hydroxide aqueous solution to the antimony trichloride solution to adjust its pH to 9 and mix solution; soak the coated carbon into the mixed solution and magnetically stir for 30 minutes;

Step 3: Transfer the carbon cloth and the mixed solution obtained in step 2 to a polytetrafluoroethylene kettle and place it in a homogeneous reactor for hydrothermal reaction at 180°C for 24 hours, cool to room temperature, take out the carbon cloth, wash and dry to obtain a porous mesh Structured antimony pentoxide/polyacrylic acid/carbon cloth flexible anode material for sodium-ion batteries.

Example 5:

A preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material with mesh porous structure, comprising the following steps:

Step 1: Soak the hydrophilic carbon cloth with a size of 4cm*2cm in 50mL acetone for 72 hours to remove surface impurities, then wash it repeatedly with deionized water and absolute ethanol, and place the carbon cloth in an oven at 60°C to dry Dry; then place the dried carbon cloth into 6mg/mL polyacrylic acid aqueous solution for 2h for coating treatment, wash it repeatedly with deionized water and absolute ethanol respectively, place the carbon cloth in an oven at 60°C and then dry it ; Wherein, polyacrylic acid average molecular weight is 1250000;

Step 2: Add 0.57g antimony trichloride to 40mL of absolute ethanol and stir magnetically to form an antimony trichloride solution, add 0.06g/mL sodium hydroxide aqueous solution to the antimony trichloride solution to adjust its pH to 12 and mix solution; soak the coated carbon into the mixed solution and magnetically stir for 30 minutes;

Step 3: Transfer the carbon cloth and the mixed solution obtained in step 2 to a polytetrafluoroethylene kettle and place it in a homogeneous reactor for hydrothermal reaction at 180°C for 48 hours, cool to room temperature, take out the carbon cloth, wash and dry to obtain a porous mesh Structured antimony pentoxide/polyacrylic acid/carbon cloth flexible anode material for sodium-ion batteries.

Embodiment 6:

A preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material with mesh porous structure, comprising the following steps:

Step 1: Soak the hydrophilic carbon cloth with a size of 4cm*2cm in 50mL acetone for 48 hours to remove surface impurities, then wash it repeatedly with deionized water and absolute ethanol, and place the carbon cloth in an oven at 60°C to dry Dry; then place the dried carbon cloth in a 5 mg/mL polyacrylic acid aqueous solution for 12 hours for coating treatment, wash it repeatedly with deionized water and absolute ethanol, and place the carbon cloth in an oven at 60 °C for further coating. drying; wherein, the average molecular weight of polyacrylic acid is 1,250,000;

Step 2: Add 1.14g of antimony trichloride to 60mL of absolute ethanol and stir magnetically to form an antimony trichloride solution, add 0.03g/mL of sodium hydroxide aqueous solution to the antimony trichloride solution to adjust its pH to 10 and mix solution; soak the coated carbon into the mixed solution and magnetically stir for 20 minutes;

Step 3: Transfer the carbon cloth and the mixed solution obtained in step 2 to a polytetrafluoroethylene kettle and place it in a homogeneous reactor for hydrothermal reaction at 180°C for 4 hours, cool to room temperature, take out the carbon cloth, wash and dry to obtain a porous mesh Structured antimony pentoxide/polyacrylic acid/carbon cloth flexible anode material for sodium-ion batteries.

Embodiment 7:

A preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material with mesh porous structure, comprising the following steps:

Step 1: Soak the hydrophilic carbon cloth with a size of 4cm*2cm in 50mL acetone for 48 hours to remove surface impurities, then wash it repeatedly with deionized water and absolute ethanol, and place the carbon cloth in an oven at 60°C to dry Dry; then put the dried carbon cloth into the aqueous solution of 7mg/mL polyacrylic acid for 1h for coating treatment, wash it repeatedly with deionized water and absolute ethanol respectively, and place the carbon cloth in an oven at 60°C for further coating. drying; wherein, the average molecular weight of polyacrylic acid is 1,250,000;

Step 2: Add 0.57g of antimony trichloride to 30mL of absolute ethanol and stir magnetically to form an antimony trichloride solution, add 0.12g/mL of sodium hydroxide aqueous solution to the antimony trichloride solution to adjust its pH to 11 and mix solution; soak the coated carbon into the mixed solution and magnetically stir for 40 minutes;

Step 3: Transfer the carbon cloth and the mixed solution obtained in step 2 to a polytetrafluoroethylene kettle and place it in a homogeneous reactor for hydrothermal reaction at 150°C for 36 hours, cool to room temperature, take out the carbon cloth, wash and dry to obtain a porous mesh Structured antimony pentoxide/polyacrylic acid/carbon cloth flexible anode material for sodium-ion batteries.

In a word, the present invention performs coating treatment by immersing the cleaned carbon cloth in polyacrylic acid aqueous solution; then take out the carbon cloth and wash it repeatedly with deionized water and ethanol, and dry it for later use; then put the dried carbon cloth into trichloro In the antimony ethanol solution, the sodium hydroxide aqueous solution is used as the precipitating agent, and the hydrothermal reaction is carried out to prepare the negative electrode of the antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery with a network porous structure. The invention has simple operation and good repeatability. The carbon cloth after impregnated with polyacrylic acid is rich in oxygen-containing functional groups and does not need activation treatment. Antimony pentoxide grows into a unique mesh-like porous structure and is evenly distributed on the surface of the flexible carbon cloth fiber. The flexible electrode combines the flexibility of carbon cloth and the high specific capacity of antimony pentoxide, which improves the electrochemical cycle performance as a negative electrode material for sodium-ion batteries as a whole.

The above content is a further detailed description of the present application in conjunction with specific implementation modes, and it cannot be considered that the specific implementation of the present application is limited to these descriptions. For those of ordinary skill in the technical field to which this application belongs, without departing from the concept of this application, some simple deduction and replacement can also be made, which should be regarded as belonging to the protection scope of this application.

Claims (9)

1. a preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material of a network porous structure, is characterized in that, comprises the following steps: Step 1: Soak the carbon cloth in acetone to remove surface impurities, wash and dry, then dip the dried carbon cloth into polyacrylic acid aqueous solution for coating treatment, wash and dry; Step 2: Add 0.3-1.14g of antimony trichloride to 20-60mL of absolute ethanol and stir to form an antimony trichloride solution, add aqueous sodium hydroxide solution to the antimony trichloride solution to adjust its pH to 8-12 to obtain a mixture liquid; soak the coated carbon into the mixed liquid; Step 3: Transfer the carbon cloth and the mixed solution obtained in step 2 to a reaction kettle for hydrothermal reaction at 120-180°C, cool to room temperature, take out the carbon cloth, wash and dry to obtain antimony pentoxide/polyacrylic acid/ Carbon cloth flexible anode material for sodium-ion batteries. 2. according to claim 1, the preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium-ion battery negative electrode material of a kind of reticular porous structure, is characterized in that, described step 1 carbon arrangement enters soaking time in acetone For 24 ~ 72h. 3. according to claim 1, the preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material of a kind of network porous structure, is characterized in that, the mass concentration of polyacrylic acid aqueous solution in described step 1 1-8 mg/mL, and the time for coating the dried carbon cloth by immersing it in polyacrylic acid aqueous solution is 1-12 hours. 4. The preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material according to claim 3, characterized in that, the polyacrylic acid average molecular weight is 1,250,000. 5. according to the preparation method of the antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material of a kind of network porous structure according to claim 1, it is characterized in that, in described step 1 and step 3, cleaning is respectively Wash repeatedly with deionized water and ethanol. 6. according to claim 1, the preparation method of the antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material of a kind of reticular porous structure, is characterized in that, in the described step 2, the carbon after coating treatment Arrange it into the mixture, soak and stir for 20-40 minutes. 7. according to claim 1, the preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material of a kind of network porous structure, is characterized in that, the quality of sodium hydroxide aqueous solution in described step 2 The concentration is 0.03～0.12g/mL. 8. according to claim 1, the preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material of a kind of network porous structure, is characterized in that, in described step 3, reaction kettle is polytetrafluoroethylene The ethylene kettle, the carbon cloth and the mixed solution are transferred to a polytetrafluoroethylene kettle and placed in a homogeneous reactor for hydrothermal reaction for 4 to 48 hours. 9. according to claim 1, the preparation method of antimony pentoxide/polyacrylic acid/carbon cloth flexible sodium ion battery negative electrode material of a kind of network porous structure, is characterized in that, described carbon cloth is hydrophilic carbon cloth and The specification is 4cm*2cm.