Preparation method of antimony alloy nanosphere negative material for sodium ion battery, pole piece and application thereof

Abstract

The application discloses a preparation method of Sb alloy nanosphere negative material for sodium ion batteries, a negative plate thereof and application, uses antimony trichloride as a precursor, obtains Sb / SbO-based nanometer material by using a hydrothermal synthesis method, and obtains carbon-coated Sb / SbO@C alloy nanosphere material by calcining under a protective gas. The alloy material is better combined together by Sb and carbon, the surface of the Sb material is coated by the carbon material, which is favorable for inhibiting the structural collapse caused by the volume expansion of the Sb material in the charging and discharging process and relieving the capacity attenuation. The carbon-coated Sb / SbO material prepared by the application and the method of the negative plate are simple, easy to operate and simple in technological process, and have high application value in the sodium ion battery negative material.

Description

Technical Field

[0001] This invention relates to the field of sodium-ion battery electrode material preparation, specifically to a method for preparing an antimony alloy negative electrode material, as well as its electrode sheet and applications. Background Technology

[0002] Lithium-ion batteries have been around for over two decades since their introduction. In contrast, sodium-ion batteries have received widespread attention due to their abundant resources and similar electrochemical behavior to lithium-ion batteries. For example, in large-scale energy storage systems, where specific capacity requirements are not as stringent, developing sodium-ion battery electrode materials with high cycle stability while reasonably improving specific capacity holds great promise. The negative electrode material is the carrier of ions and electrons during the charging and discharging process of a sodium-ion battery, determining energy storage and release; carbon-based materials are preferred. Because sodium ions and lithium ions have different radii, sodium ions cannot effectively insert and extract into graphite. To use graphite, the interlayer spacing must be increased, which is difficult to achieve with ordinary graphite materials. Currently, amorphous carbon, metal compounds, and alloy materials are available as negative electrode materials for sodium-ion batteries.

[0003] Alloy-type anode materials such as Sn and Sb have attracted attention due to their high theoretical specific capacity. However, these materials often undergo significant volume changes during charge and discharge, leading to rapid capacity decay and limiting their application in sodium-ion batteries. To improve the cycle stability of these electrode materials, the main strategies include: combining alloy materials with carbon-based materials, using carbon as a substrate to act as a buffer and limit the volume changes of the alloy material. For example, combining elemental Sb with multi-walled carbon nanotubes, combining nanoscale Sb with graphene, and synthesizing Sb-C nanofiber composites using electrospinning can all effectively improve the cycle stability of electrode materials.

[0004] This invention addresses the drawback of large volume changes in alloy anode materials for sodium-ion batteries by disclosing a method for preparing antimony alloy spherical nanomaterials and their applications. The alloy material obtained by this method exhibits good bonding between antimony and carbon, with the surface of the antimony material coated with carbon. This helps suppress structural collapse caused by volume expansion during charge and discharge, mitigating capacity decay. The method uses antimony trichloride as a precursor, employing a hydrothermal method to obtain Sb / SbO-based nanomaterials, followed by calcination under a protective gas atmosphere to obtain carbon-coated Sb / SbO@C alloy nanospheres. The raw materials used in this patent application are widely available, the preparation method is simple, and it has high application value in sodium-ion battery anode materials. Summary of the Invention

[0005] To overcome the above-mentioned defects, the purpose of this invention is to disclose a method for preparing antimony alloy nanosphere anode material for sodium-ion batteries, so as to limit the volume change of sodium-ion battery alloy materials.

[0006] Another object of the present invention is to provide a product prepared by the above method.

[0007] Another object of the present invention is to provide applications of the said product.

[0008] The objective of this invention is achieved through the following solution: A method for preparing antimony alloy nanosphere anode material for sodium-ion batteries involves, in order to limit the volume change of the alloy material in sodium-ion batteries, combining the antimony alloy with carbon materials. Antimony trichloride is used as a precursor, and Sb / SbO-based nanomaterials are obtained via a hydrothermal method. Calcination under a protective gas yields carbon-coated Sb / SbO@C alloy nanospheres. The method includes the following steps: Preparation of carbon-coated antimony alloy nanospheres: Weigh out SbCl3, ascorbic acid, and hexadecyltrimethylammonium bromide (CTAB). Dissolve the three in 50 ml of deionized water at a mass ratio of 1:(1~5):(0.1~0.2), then transfer the solution to a reaction vessel and hydrothermally react at 160 °C for 24 h. After the reaction is complete, centrifuge the solution, wash it several times with ethanol and deionized water, and dry it at 60 °C for 8 h. Place the dried powder into a tube furnace and seal the reaction vessel. Use argon as the carrier gas and heat the tube furnace to 600–700 °C, holding it at this temperature for 6–10 h, controlling the argon flow rate at 100–300 cm⁻¹. 3 / min, carbon-coated Sb / SbO, i.e. Sb / SbO@C alloy nanospheres, were obtained; Preparation of electrode sheet: The active material, conductive agent and binder are mixed into a slurry and uniformly coated onto the current collector copper foil, vacuum dried and pressed to prepare the sodium-ion battery negative electrode sheet.

[0009] This invention provides a new approach for the development and preparation of novel sodium-ion battery anode materials.

[0010] The heating temperature of the tubular furnace is controlled between 600 and 700 ℃, with 650 ℃ being the preferred temperature.

[0011] The heat preservation time of the tubular furnace is controlled between 6 and 10 hours, with 8 hours being the preferred option.

[0012] In the preparation of the electrode sheet, the mass ratio of active material, conductive agent and binder is (4~8): (5~1): 1.

[0013] In the preparation of the electrode sheet, the vacuum drying pressure is 1~6 Pa, the temperature is 60~150 ℃, and the time is 5~12 h.

[0014] The present invention also provides an antimony alloy nanosphere anode material for sodium-ion batteries, which is prepared according to any of the methods described above.

[0015] This invention also provides an application of antimony alloy nanosphere anode material as an electrode in sodium-ion batteries.

[0016] This invention discloses a method for preparing antimony alloy nanosphere anode materials for sodium-ion batteries, as well as the electrode sheet and its application. Using antimony trichloride as a precursor, Sb / SbO-based nanomaterials are obtained via a hydrothermal method, followed by calcination under a protective gas to obtain carbon-coated Sb / SbO@C alloy nanosphere materials. The antimony and carbon in the alloy material are well bonded together, and the surface of the antimony material is coated with carbon, which helps to suppress structural collapse caused by volume expansion during charging and discharging, thus mitigating capacity decay. The method for preparing the carbon-coated Sb / SbO material and anode sheet using this invention is simple, easy to operate, and has a concise process flow, making it highly valuable for application in sodium-ion battery anode materials. Attached Figure Description

[0017] Figure 1 This is a schematic diagram illustrating the preparation of the Sb / SbO@C alloy nanosphere material. Figure 2 The TEM spectrum of the Sb / SbO@C alloy nanospheres prepared in Example 1 is shown below. Figure 3 The image shows the SEM spectrum of the Sb / SbO@C electrode sheet prepared in Example 1.

[0018] This embodiment is implemented based on the technical solution of the present invention, and provides detailed implementation methods and specific operation processes. However, the scope of protection of the present invention is not limited to the following embodiment. Detailed Implementation

[0019] Example 1: An antimony alloy nanosphere anode material for sodium-ion batteries is prepared by combining an antimony alloy with carbon materials, using antimony trichloride as a precursor, obtaining Sb / SbO-based nanomaterials via a hydrothermal method, and then calcining under a protective gas to obtain carbon-coated Sb / SbO@C alloy nanospheres. The preparation steps are as follows: 1) Preparation of carbon-coated antimony alloy nanospheres: Weigh out 1.0 g of SbCl3, 3.0 g of ascorbic acid, and 0.1 g of hexadecyltrimethylammonium bromide (CTAB) according to the specified ratio, dissolve them in 50 ml of deionized water, and transfer them to a reaction vessel for hydrothermal reaction at 160 °C for 24 h. After the reaction is complete, centrifuge the powder, wash it several times with ethanol and deionized water, and dry it at 60 °C for 8 h. Place the dried powder in a tube furnace, seal the reaction vessel, use argon as the carrier gas, heat the tube furnace to 650 °C, and hold it at this temperature for 6–10 h, controlling the argon flow rate at 100 cm⁻¹. 3 / min, carbon-coated Sb / SbO active material material, namely Sb / SbO@C alloy nanosphere material; 2) Preparation of electrode sheets: Sb / SbO@C alloy nanospheres were used as the active material, superconducting carbon black (SP) was used as the conductive agent, and polyvinylidene fluoride (PVDF) was used as the binder. They were mixed evenly at a mass ratio of 6:3:1. N-methylpyrrolidone (NMP) was used as the solvent to form a slurry, which was then uniformly coated onto a copper foil current collector. The mixture was dried under vacuum at 60 °C for 12 h and then pressed into a sheet under a pressure of 3 Pa to prepare the negative electrode sheet for sodium-ion batteries.

[0020] Figure 1 A simplified schematic diagram of the preparation of Sb / SbO@C alloy nanospheres is described. Figure 1 As shown, Sb / SbO@C alloy nanospheres can be obtained through a series of simple processes including mixing, hydrothermal treatment, and calcination. Figure 2 The image shows the TEM spectrum of the prepared Sb / SbO@C alloy nanospheres. As can be seen from the image, the size of the nanospheres is approximately in the range of 100~200 nm, and the surface is covered with a thin carbon layer structure. This helps to suppress the structural collapse caused by the volume expansion of the antimony material during charging and discharging, and alleviate the capacity decay. Figure 3 The SEM image shows the Sb / SbO@C alloy material used to prepare an electrode sheet. As can be seen from the image, the surface of the electrode sheet is relatively uniform and the active material is evenly dispersed, making it a relatively ideal electrode sheet.

[0021] Example 2: An antimony alloy nanosphere anode material for sodium-ion batteries is prepared according to steps similar to those in Example 1, as follows: 1) Preparation of carbon-coated antimony alloy nanospheres: Weigh out 1.0 g of SbCl3, 3.0 g of ascorbic acid, and 0.2 g of hexadecyltrimethylammonium bromide (CTAB) according to the specified ratio, dissolve them in 50 ml of deionized water, and transfer them to a reaction vessel. Perform a hydrothermal reaction at 160 °C for 24 h. After the reaction is complete, centrifuge the powder, wash it repeatedly with ethanol and deionized water, and dry it at 60 °C for 8 h. Place the dried powder into a tube furnace, seal the reaction vessel, and heat the tube furnace to 650 °C using argon as the carrier gas. Hold the temperature for 6–10 h, controlling the argon flow rate at 200 cm⁻¹. 3 / min, carbon-coated Sb / SbO, i.e. Sb / SbO@C alloy nanospheres, were obtained; 2) Preparation of electrode sheet: Sb / SbO@C alloy nanospheres were used as the active material, superconducting carbon black (SP) was selected as the conductive agent, and polyvinylidene fluoride (PVDF) was selected as the binder. Sb / SbO@C alloy nanospheres, superconducting carbon black, and PVDF were mixed uniformly at a mass ratio of 6:3:1. Using N-methylpyrrolidone (NMP) as the solvent, the mixture was slurried and uniformly coated onto a copper current collector foil. The mixture was then placed in a vacuum drying oven and dried at 60 °C for 12 h. Finally, it was pressed into a sheet using a pressure of 4 Pa ​​to obtain the negative electrode sheet for sodium-ion batteries.

[0022] Example 3: An antimony alloy nanosphere anode material for sodium-ion batteries is prepared according to steps similar to those in Example 1, as follows: 1) Preparation of carbon-coated antimony alloy nanospheres: Weigh out 1.0 g of SbCl3, 4.0 g of ascorbic acid, and 0.2 g of hexadecyltrimethylammonium bromide (CTAB) according to the specified ratio, dissolve them in 50 ml of deionized water, and transfer them to a reaction vessel. Perform a hydrothermal reaction at 160 °C for 24 h. After the reaction is complete, centrifuge the powder, wash it repeatedly with ethanol and deionized water, and dry it at 60 °C for 8 h. Place the dried powder into a tube furnace, seal the reaction vessel, and heat the tube furnace to 700 °C using argon as the carrier gas. Hold the temperature for 6–10 h, controlling the argon flow rate at 300 cm⁻¹. 3 / min, carbon-coated Sb / SbO, i.e. Sb / SbO@C alloy nanospheres, are obtained.

[0023] 2) Preparation of electrode sheet: Sb / SbO@C alloy nanospheres are used as active material, superconducting carbon black SP is selected as conductive agent, and polyvinylidene fluoride PVDF is selected as binder. Sb / SbO@C alloy nanospheres, superconducting carbon black and polyvinylidene fluoride are mixed evenly in a mass ratio of 5:4:1. N-methylpyrrolidone (NMP) is used as solvent. After slurry preparation, it is evenly coated on the current collector copper foil and placed in a vacuum drying oven. After drying at 70 ℃ for 12 h, it is pressed into a sheet under a pressure of 5 Pa to obtain the negative electrode sheet for sodium-ion batteries.

[0024] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing Sb / SbO@C nanospheres for sodium-ion batteries, characterized in that, Sb / SbO-based nanomaterials were composited with carbon materials using antimony trichloride as a precursor. The Sb / SbO-based nanomaterials were obtained via a hydrothermal method, followed by calcination under a protective gas atmosphere to yield carbon-coated Sb / SbO@C nanospheres. The process included the following steps: Preparation of carbon-coated Sb / SbO@C nanospheres: Weigh out SbCl3, ascorbic acid, and hexadecyltrimethylammonium bromide (CTAB) according to the specified ratio, and dissolve them in 50 ml of deionized water at a mass ratio of 1:(1~5):(0.1~0.2). Then transfer the solution to a reaction vessel and hydrothermally react at 160 °C for 24 h. After the reaction is complete, centrifuge the solution, wash it several times with ethanol and deionized water, and dry it at 60 °C for 8 h. Place the dried powder into a tube furnace, seal the reaction vessel, and heat the tube furnace to 600–700 °C using argon as the carrier gas. Hold the temperature for 6–10 h, controlling the argon flow rate at 100–300 cm⁻¹. 3 / min, carbon-coated Sb / SbO active material material, namely Sb / SbO@C nanosphere material; Preparation of negative electrode sheet using Sb / SbO@C nanospheres: The active material Sb / SbO@C nanospheres, conductive agent, and binder were mixed into a slurry and uniformly coated onto the current collector copper foil. The mixture was then vacuum dried and pressed into a sheet to prepare the negative electrode sheet for a sodium-ion battery.

2. The method for preparing Sb / SbO@C nanospheres for sodium-ion batteries according to claim 1, characterized in that, The SbCl3, ascorbic acid, and hexadecyltrimethylammonium bromide (CTAB) are present in a mass ratio of 1:3:0.

1.

3. The method for preparing Sb / SbO@C nanospheres for sodium-ion batteries according to claim 1, characterized in that, The tubular furnace is heated to 650 ℃ and held at that temperature for 8 h.

4. The method for preparing Sb / SbO@C nanospheres for sodium-ion batteries according to claim 1, characterized in that, In the preparation of the negative electrode sheet, the mass ratio of active material, conductive agent and binder is (4~8): (5~1):

1.

5. The method for preparing Sb / SbO@C nanospheres for sodium-ion batteries according to claim 1, characterized in that, In the preparation of the electrode, the vacuum drying pressure is 1~6 Pa, the temperature is 60~150 ℃, and the time is 5~12 h.

6. The method for preparing Sb / SbO@C nanospheres for sodium-ion batteries according to any one of claims 1 to 5, characterized in that, Prepare according to the following steps: 1) Preparation of Sb / SbO@C nanospheres: Weigh out 1.0 g of SbCl3, 3.0 g of ascorbic acid, and 0.1 g of hexadecyltrimethylammonium bromide (CTAB) according to the specified ratio, dissolve them in 50 ml of deionized water, and transfer them to a reaction vessel for hydrothermal reaction at 160 °C for 24 h. After the reaction is complete, centrifuge the powder, wash it several times with ethanol and deionized water, and dry it at 60 °C for 8 h. Place the dried powder in a tube furnace, seal the reaction vessel, use argon as the carrier gas, heat the tube furnace to 650 °C, and hold it at this temperature for 6–10 h, controlling the argon flow rate at 100 cm⁻¹. 3 / min, carbon-coated Sb / SbO active material material, namely Sb / SbO@C nanosphere material; 2) Preparation of electrode sheets: Sb / SbO@C nanospheres were used as the active material, superconducting carbon black SP was used as the conductive agent, and polyvinylidene fluoride PVDF was used as the binder. They were mixed evenly at a mass ratio of 6:3:

1. N-methylpyrrolidone (NMP) was used as the solvent to form a slurry, which was then evenly coated onto the current collector copper foil. The mixture was dried under vacuum at 60 °C for 12 h and then pressed into a sheet under a pressure of 3 Pa to prepare the negative electrode sheet for sodium-ion batteries.

7. The method for preparing Sb / SbO@C nanospheres for sodium-ion batteries according to any one of claims 1 to 5, characterized in that, Prepare according to the following steps: 1) Preparation of Sb / SbO@C nanospheres: Weigh out 1.0 g of SbCl3, 3.0 g of ascorbic acid, and 0.2 g of hexadecyltrimethylammonium bromide (CTAB) according to the specified ratio, dissolve them in 50 ml of deionized water, and transfer them to a reaction vessel. Perform a hydrothermal reaction at 160 °C for 24 h. After the reaction is complete, centrifuge the powder, wash it repeatedly with ethanol and deionized water, and dry it at 60 °C for 8 h. Place the dried powder into a tube furnace, seal the reaction vessel, and heat the tube furnace to 650 °C using argon as the carrier gas. Hold the temperature for 6–10 h, controlling the argon flow rate at 200 cm⁻¹. 3 / min, carbon-coated Sb / SbO, i.e. Sb / SbO@C nanospheres, were obtained; 2) Preparation of electrode sheet: Sb / SbO@C nanospheres are used as the active material, superconducting carbon black SP is selected as the conductive agent, and polyvinylidene fluoride PVDF is selected as the binder. Sb / SbO@C nanospheres, superconducting carbon black and polyvinylidene fluoride are mixed evenly in a mass ratio of 6:3:

1. N-methylpyrrolidone (NMP) is used as the solvent. After slurry preparation, the mixture is evenly coated on the current collector copper foil and placed in a vacuum drying oven. After drying at 60 ℃ for 12 h, it is pressed into a sheet under a pressure of 4 Pa ​​to obtain the negative electrode sheet for sodium-ion batteries.

8. The method for preparing Sb / SbO@C nanospheres for sodium-ion batteries according to any one of claims 1 to 5, characterized in that, Prepare according to the following steps: 1) Preparation of Sb / SbO@C nanospheres: Weigh out 1.0 g of SbCl3, 4.0 g of ascorbic acid, and 0.2 g of hexadecyltrimethylammonium bromide (CTAB) according to the specified ratio, dissolve them in 50 ml of deionized water, and transfer them to a reaction vessel. Perform a hydrothermal reaction at 160 °C for 24 h. After the reaction is complete, centrifuge the powder, wash it repeatedly with ethanol and deionized water, and dry it at 60 °C for 8 h. Place the dried powder into a tube furnace, seal the reaction vessel, and heat the tube furnace to 700 °C using argon as the carrier gas. Hold the temperature for 6–10 h, controlling the argon flow rate at 300 cm⁻¹. 3 / min, carbon-coated Sb / SbO, i.e. Sb / SbO@C nanospheres, were obtained; 2) Preparation of electrode sheet: Sb / SbO@C nanospheres are used as active material, superconducting carbon black (SP) is selected as conductive agent, and polyvinylidene fluoride (PVDF) is selected as binder. Sb / SbO@C nanospheres, superconducting carbon black, and PVDF are mixed evenly in a mass ratio of 5:4:

1. N-methylpyrrolidone (NMP) is used as solvent. After slurry preparation, the mixture is evenly coated on copper foil current collector and placed in a vacuum drying oven. After drying at 70 °C for 12 h, it is pressed into a sheet under a pressure of 5 Pa to obtain the negative electrode sheet for sodium-ion batteries.

9. A Sb / SbO@C nanosphere material for sodium-ion batteries, characterized in that... Prepared by the method according to any one of claims 1-8.

10. An application of the Sb / SbO@C nanosphere material for sodium-ion batteries according to claim 9 as a negative electrode in sodium-ion batteries.

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