Preparation method of feather-shaped antimony nano-anode material, antimony nano-anode material and application thereof

Abstract

The present invention provides a preparation method for a feather-like antimony nano-anode material, an antimony nano-anode material, and its application, belonging to the technical field of antimony nano-materials. The method of the present invention comprises the following steps: 1) fully dissolving an antimony source in a reaction medium, adding a reducing agent, and ultrasonically treating the solution to obtain a solution containing black particles; 2) heating the solution containing black particles obtained in step 1) to obtain a black precipitate; 3) filtering the black precipitate obtained in step 2) to obtain a first product; and 4) washing, soaking, filtering, and drying the first product obtained in step 3) to obtain the feather-like antimony nano-anode material. The method provided by the present invention is simple to operate and has low production costs. The product prepared mainly through ultrasonic treatment and heating has high purity and good reproducibility. The feather-like antimony nano-material is used as the negative electrode of a sodium-ion battery, which not only improves the problem of volume expansion of antimony during charging and discharging, but also expands the application of nano-antimony materials in the field of sodium-ion batteries.

Description

Technical Field

[0001] The present invention belongs to the technical field of antimony nanomaterials, and in particular relates to a preparation method of a feather-shaped antimony nano-anode material, the antimony nano-anode material and applications thereof. Background Art

[0002] With the global emphasis on renewable energy and the rapid expansion of the electric vehicle market, demand for energy storage devices has skyrocketed. Lithium-ion batteries are the preferred choice due to their high energy density, long cycle life, and widespread commercial application. However, the limited availability and cost of lithium resources have prompted researchers to explore alternatives, such as sodium-ion batteries, which offer the potential for lower costs due to the far greater abundance of sodium in the Earth's crust.

[0003] The development of suitable electrode materials is crucial for the development and application of sodium-ion batteries. Antimony (Sb), as a potential high-capacity anode material, has attracted widespread attention in both lithium-ion and sodium-ion batteries. However, during charge and discharge, Sb undergoes significant volume changes, leading to structural destruction and electrode pulverization, which in turn affects the battery's cycle stability and lifespan.

[0004] Therefore, alleviating volume expansion is an effective way to improve the electrochemical performance of antimony anodes, such as by reducing the particle size of antimony and designing nanoscale antimony materials. However, most methods for preparing antimony nanomaterials have the disadvantages of complex processes or the use of hazardous chemicals. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a method for preparing a feather-shaped antimony nano-anode material, an antimony nano-anode material and its application. The preparation method provided by the present invention is simple to operate, has low production cost, and the prepared product has high purity and good reproducibility.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a method for preparing a feather-like antimony nano-anode material, comprising the following steps:

[0008] 1) fully dissolving the antimony source in a reaction medium, adding a reducing agent, and ultrasonically treating to obtain a solution with black particles;

[0009] 2) heating the black solution obtained in step 1) to obtain a black precipitate;

[0010] 3) filtering the black precipitate obtained in step 2) to obtain the first product;

[0011] 4) washing, soaking, filtering and drying the first product obtained in step 3) to obtain a feather-like antimony nano-anode material.

[0012] Preferably, the antimony source includes antimony chloride, and the reducing agent includes aluminum powder.

[0013] Preferably, the reaction medium comprises ethylene glycol.

[0014] Preferably, the molar ratio of the antimony source to the aluminum powder is 1 to 3:1.

[0015] Preferably, the heating temperature is 25-100° C., and the heating time is 0.5-10 h.

[0016] Preferably, the washing and soaking method in step 4) comprises: washing the first product with ethanol and deionized water in sequence, and then soaking it in a sodium hydroxide solution.

[0017] Preferably, the concentration of the sodium hydroxide solution is 0.4-0.6 mol / L.

[0018] Preferably, the drying temperature is 50-80° C., and the drying time is 8-12 hours.

[0019] The present invention also provides a feather-shaped antimony nanometer negative electrode material prepared by the above preparation method.

[0020] The present invention also provides the use of the feather-shaped antimony nano-anode material in the preparation of sodium ion batteries.

[0021] The method provided by the present invention is simple to operate and has low production costs. It primarily uses antimony chloride as the antimony source, aluminum powder as the reducing agent, and ethylene glycol as the reaction medium. Through ultrasonic treatment and heating, the resulting product exhibits high purity and excellent reproducibility. The feather-like antimony nanomaterial prepared by the present invention can be used as the negative electrode of sodium-ion batteries, not only alleviating the volume expansion problem of antimony during charge and discharge, but also paving the way for the expanded application of nanoantimony materials in sodium-ion batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is the XRD pattern of the feather-like nanoantimony prepared in Example 1;

[0023] Figure 2 This is the SEM image of the feather-like nanoantimony prepared in Example 1;

[0024] Figure 3 This is a graph showing the cycling performance of the feather-like nano-antimony prepared in Example 1 as a negative electrode for sodium-ion batteries;

[0025] Figure 4 This is the rate performance diagram of the feather-shaped nano-antimony prepared in Example 1 as the negative electrode of sodium ion battery. DETAILED DESCRIPTION

[0026] The present invention provides a method for preparing a feather-like antimony nano-anode material, comprising the following steps:

[0027] 1) fully dissolving the antimony source in a reaction medium, adding a reducing agent, and ultrasonically treating to obtain a solution with black particles;

[0028] 2) heating the black solution obtained in step 1) to obtain a black precipitate;

[0029] 3) filtering the black precipitate obtained in step 2) to obtain the first product;

[0030] 4) washing, soaking, filtering and drying the first product obtained in step 3) to obtain a feather-like antimony nano-anode material.

[0031] In the present invention, the antimony source is preferably antimony chloride. The present invention has no particular limitation on the source of the antimony chloride, and conventional commercial products in the art can be used.

[0032] In the present invention, the reaction medium is preferably ethylene glycol. The present invention has no particular limitation on the source of the ethylene glycol, and any commercially available product in the art can be used.

[0033] In the present invention, the reducing agent is preferably aluminum powder. The present invention has no particular limitation on the source of the aluminum powder, and any commercially available product in the art can be used.

[0034] In the present invention, the particle size of the aluminum powder is preferably below 300 mesh.

[0035] In the present invention, the molar ratio of the antimony source to the aluminum powder is preferably 1 to 3:1, more preferably 2:1.

[0036] The present invention has no particular limitation on the ultrasonic method, and conventional ultrasonic methods in the art may be used.

[0037] In the present invention, the ultrasonic time is preferably 5 to 60 minutes, more preferably 30 minutes.

[0038] In the present invention, the heating temperature is preferably 25 to 100° C., more preferably 30° C.; the heating time is preferably 0.5 to 10 hours, more preferably 1 to 6 hours. In the present invention, the purpose of heating the solution in which black particles appear is to increase the yield.

[0039] The present invention has no particular limitation on the washing method. Preferably, the first product is washed with ethanol and deionized water in sequence, and then immersed in a sodium hydroxide solution.

[0040] In the present invention, the concentration of the sodium hydroxide solution is preferably 0.4 to 0.6 mol / L, more preferably 0.5 mol / L.

[0041] The present invention has no particular limitation on the drying method, and conventional drying methods in the art may be used.

[0042] In the present invention, the drying temperature is preferably 50 to 80° C., more preferably 60° C.; the drying time is preferably 8 to 12 hours, more preferably 10 hours.

[0043] The present invention also provides a feather-shaped antimony nanometer negative electrode material prepared by the above preparation method.

[0044] The present invention also provides the use of the feather-shaped antimony nano-anode material in the preparation of sodium ion batteries.

[0045] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0046] Example 1

[0047] Dissolve 0.004 mol of SbCl3 in 40 ml of ethylene glycol, add 0.002 mol of aluminum powder, and ultrasonicate for 30 minutes to uniformly disperse it in the solution to obtain a black solution. Heat it at 30°C for 1 hour, filter the obtained black powder, wash it with ethanol and deionized water in turn, soak the obtained powder in 0.5 mol / L sodium hydroxide solution for 0.5 hour to remove the residual aluminum powder, filter it and wash it again, and finally dry it in an oven at 60°C for 10 hours.

[0048] Example 2

[0049] Dissolve 0.004 mol of SbCl3 in 40 ml of ethylene glycol, add 0.002 mol of aluminum powder, and ultrasonicate for 30 minutes to uniformly disperse it in the solution to obtain a black solution. Heat it at 100°C for 6 hours, filter the obtained black powder, wash it with ethanol and deionized water in turn, soak the obtained powder in 0.5 mol / L sodium hydroxide solution for 0.5 hour to remove the residual aluminum powder, filter it and wash it again, and finally dry it in an oven at 60°C for 10 hours.

[0050] Example 3

[0051] Dissolve 0.002 mol of SbCl3 in 40 ml of ethylene glycol, add 0.002 mol of aluminum powder, and ultrasonicate for 30 minutes to uniformly disperse it in the solution to obtain a black solution. Heat it at 30°C for 1 hour, filter the obtained black powder, wash it with ethanol and deionized water in turn, soak the obtained powder in 0.5 mol / L sodium hydroxide solution for 0.5 hour to remove the residual aluminum powder, then filter and wash it, and finally dry it in an oven at 60°C for 10 hours.

[0052] Example 4

[0053] The powder obtained in Example 1 was characterized using an X-ray diffractometer, and the results are shown in the attached figure. Figure 1 As shown, the curve is in good agreement with the standard PDF card of antimony (PDF#35-0732), and no impurity peaks are present, indicating that the obtained product is antimony.

[0054] Example 5

[0055] The final product obtained in Example 1 was characterized using a scanning electron microscope. The results are shown in the attached figure. Figure 2 As shown, it can be seen that the morphology of the product obtained in Example 1 is feather-like, indicating that the feather-like antimony nanomaterial is successfully synthesized.

[0056] Example 6

[0057] The feather-like antimony nanomaterial obtained in Example 1 was mixed with SuperP and CMC in a ratio of 7:2:1 to form a slurry, which was then coated on copper foil as the negative electrode. Glass fiber was used as the separator, the electrolyte was 1M NaClO4 in EC:PC=1:1 Vol% with 5% FEC, and a sodium metal sheet was used as the positive electrode. A button half-cell was assembled in an argon-filled glove box to test the electrochemical cycling performance and rate performance. The results are shown in the attached figure. Figure 3 、 4 As shown in the attached Figure 3 As shown in the figure, the constant current charge and discharge at a current density of 100 mA / g can still maintain 548.06 mAh g after 50 cycles. -1 Capacity; as attached Figure 4 As shown in the figure, after the battery was charged and discharged for five cycles at rates of 0.1C, 0.2C, 0.5C, 1C, and 2C, and then returned to the rate of 0.1C for charge and discharge, the capacity was close to that of the initial charge and discharge at the rate of 0.1C. These results show that the prepared antimony negative electrode has good cycle stability and rate performance.

[0058] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a feather-like antimony nano-anode material, characterized in that: The following steps are involved: 1) fully dissolving an antimony source in a reaction medium, adding a reducing agent, and ultrasonically treating to obtain a solution with black particles, wherein the antimony source is antimony chloride, the reducing agent is aluminum powder, the reaction medium is ethylene glycol, and the molar ratio of the antimony source to the aluminum powder is 1 to 3:1; 2) heating the black particle solution obtained in step 1) to obtain a black precipitate, wherein the heating temperature is 25 to 100° C. and the heating time is 0.5 to 10 hours; 3) filtering the black precipitate obtained in step 2) to obtain the first product; 4) washing, soaking, filtering and drying the first product obtained in step 3) to obtain a feather-like antimony nano-anode material.

2. The method for preparing a feather-like antimony nano-anode material according to claim 1, characterized in that: The washing and soaking method in step 4) comprises: washing the first product with ethanol and deionized water in sequence, and then soaking it in a sodium hydroxide solution.

3. The method for preparing a feather-like antimony nano-anode material according to claim 2, characterized in that: The concentration of the sodium hydroxide solution is 0.4-0.6 mol / L.

4. The method for preparing a feather-like antimony nano-anode material according to claim 1, characterized in that: The drying temperature in step 4) is 50-80° C., and the drying time is 8-12 hours.

5. The feather-like antimony nano-anode material prepared by the preparation method according to any one of claims 1 to 4.

6. Use of the feather-like antimony nano-anode material according to claim 5 in the preparation of sodium ion batteries.

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