A Sb₂O₃ nanoarray-carbon-based composite material, its preparation method and application
By preparing Sb2O3 nanoarray-carbon-based composite materials, the problems of small capacity of graphite anode materials and easy expansion of Sb2O3 were solved, achieving high electrochemical performance and cycle stability, which is suitable for flexible electrode materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- YANSHAN UNIV
- Filing Date
- 2024-11-15
- Publication Date
- 2026-05-29
AI Technical Summary
Existing graphite anode materials have a relatively small theoretical specific capacity, and their lithium storage performance is insufficient to meet the requirements of high-performance lithium-ion batteries. Furthermore, Sb2O3 anode materials are prone to structural collapse due to volume expansion during charging and discharging.
By preparing Sb2O3 nanoarray-carbon-based composite materials, carbon-based materials are immersed in antimony salt solution, annealed, and then subjected to hydrothermal reaction to form Sb2O3 nanoarrays. Polyvinyl alcohol, hexamethylenetetramine, etc. are used as template agents and precipitants to control their morphology and form a twin flower-like structure.
The electrochemical performance of the material was improved, the specific surface area and active sites were increased, the volume expansion was suppressed, and the conductivity and cycle stability were improved. The first-cycle discharge capacity reached 1900 mAh/g, and it has good activation performance and cycle retention.
Smart Images
Figure CN119503877B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of lithium-ion battery technology, and in particular to an Sb2O3 nanoarray-carbon-based composite material, its preparation method, and its application. Background Technology
[0002] In today's society, where energy demands are constantly increasing, lithium batteries are ubiquitous, frequently used in electronic products and new energy vehicles. To improve the lifespan of these products and vehicles, lithium batteries need to possess excellent fast-charging performance and cycle life. Lithium-ion batteries (LiBs), in particular, are known as green batteries due to their high energy density, high average output voltage, superior cycle performance, rapid charge and discharge capabilities, and long lifespan. The anode material, as a crucial component of LiBs, significantly impacts the energy density, cycle stability, safety, and scale-up performance of lithium-ion batteries. However, currently commercially available graphite anode materials have a relatively low theoretical specific capacity, and their lithium storage performance is insufficient to meet the demands of high-performance lithium-ion batteries. Therefore, the development of high-performance anode materials is urgently needed.
[0003] Among various metal-based anode materials, antimony oxide is considered the most promising energy storage electrode material due to its numerous advantages. It can be used as an electrode material for hybrid supercapacitors and possesses both high energy density and power density. However, Sb₂O₃ anode materials are prone to structural collapse due to volume expansion during charge and discharge, thus limiting their further development and application. Summary of the Invention
[0004] To address the aforementioned technical problems, this invention provides an Sb2O3 nanoarray-carbon-based composite material, its preparation method, and its application.
[0005] The technical solution adopted in this invention is as follows:
[0006] On one hand, the present invention provides a method for preparing Sb2O3 nanoarray-carbon-based composite materials, comprising the following steps:
[0007] (1) Immerse the carbon-based material in an antimony salt solution;
[0008] (2) Anneal the soaked carbon-based material;
[0009] (3) An annealed carbon-based material is subjected to a hydrothermal reaction in an epitaxial growth solution to obtain an Sb2O3 nanoarray on the carbon-based material; the epitaxial growth solution contains an antimony source, a template agent and a precipitant.
[0010] In a preferred embodiment, in step (1), the carbon-based material is selected from at least one of carbon fiber cloth, carbon paper, carbon cloth, carbon felt and reticulated glassy carbon;
[0011] Preferably, the antimony salt solution is selected from at least one of antimony acetate solution and antimony glycol ethanol solution;
[0012] Preferably, the concentration of the antimony salt solution is 0.005–0.02 mol / L;
[0013] Preferably, the soaking time is 24 to 48 hours.
[0014] In a preferred embodiment, in step (1), the carbon-based material undergoes an acidification pretreatment; the acidification involves heating the carbon-based material in an acid solution; the acid solution is selected from any one of concentrated nitric acid, concentrated sulfuric acid, and a mixed solution of concentrated nitric acid; the heating temperature is 60–80°C; and the heating time is 2–4 hours.
[0015] Preferably, the carbon-based material undergoes a pretreatment of washing and drying before acidification;
[0016] Preferably, the carbon-based material further includes post-treatment of washing and drying after acidification; the drying is performed at 60-80°C for 10-12 hours.
[0017] In a preferred embodiment, in step (2), the annealing temperature is 350–400°C; and the annealing time is 20–30 min.
[0018] Preferably, the annealing heating rate is 3-5°C / min;
[0019] In the technical solution of this invention, annealing can cause the antimony-containing compound on the carbon-based material to lose water and transform into antimony oxide seed crystals, thereby completing the seed crystal operation.
[0020] In a preferred embodiment, in step (3), the antimony source is selected from at least one of SbCl3 and potassium antimony tartrate;
[0021] Preferably, the template agent is polyvinyl alcohol; the molecular weight of the polyvinyl alcohol is 10,000 to 70,000.
[0022] Preferably, the precipitant is selected from at least one of hexamethylenetetramine, ammonia, and sodium hydroxide;
[0023] Preferably, the ratio of the antimony source, template agent, and precipitant is 0.8-1:0.4-0.5:1.
[0024] In a preferred embodiment, in step (3), the temperature of the hydrothermal reaction is 140-160°C, and the time of the hydrothermal reaction is 14-16 hours.
[0025] In some specific embodiments, step (3) further includes post-treatment of washing and drying the carbon-based material after the hydrothermal reaction; the washing is water and ethanol washing; the drying is drying at 60-80°C for 10-12 hours.
[0026] In another aspect, the present invention provides Sb2O3 nanoarray-carbon-based composite material obtained by the above preparation method.
[0027] In another aspect, the present invention provides the application of the above-mentioned Sb2O3 nanoarray-carbon-based composite material in the preparation of batteries;
[0028] Preferably, its application in the preparation of lithium-ion battery anode materials.
[0029] Compared with the prior art, the present invention has the following advantages:
[0030] This invention obtains a Sb2O3 nanowire array-carbon-based composite material with twin flower-like structure through in-situ preparation of seed crystals and hydrothermal reaction. This composite material can be further applied to flexible electrode materials.
[0031] (1) The preparation method provided by this invention enables the controllable synthesis of antimony oxides, significantly improving the electrochemical performance of the material by controlling its morphology. The Sb2O3 nanowire array prepared by this invention has a twin-flower-like morphology, which can fully participate in the charging and discharging process of the battery. Due to its high specific surface area and large contact surface, it can provide more active sites for subsequent electrochemical reactions, thereby exposing more active materials in the electrolyte and reducing the length of the lithium diffusion path, which helps to improve its utilization rate and rate performance. The composite material provided by this invention not only has good activation performance and excellent discharge capacity, with an initial discharge capacity of 1900 mAh / g, but also has high cycle stability and high cycle retention rate.
[0032] (2) The Sb2O3 nanowire array-carbon-based composite material provided by the present invention combines Sb2O3 nanowire array with carbon-based material, which not only greatly improves the conductivity of the material, but also suppresses the volume expansion of the electrode material and improves its electrochemical performance.
[0033] (3) The Sb2O3 nanowire array-carbon-based composite material provided by this invention can be used as a self-supporting flexible electrode material. It can be used directly as an electrode material without secondary treatment such as binder coating. The self-supporting substrate itself has good conductivity, which can effectively improve the electron transport of electrode materials with poor conductivity and promote the efficient transport of charge carriers during catalysis. Strong interaction can be formed between the active material and the substrate, which can efficiently transport electrons and reduce the reaction barrier.
[0034] (4) The raw materials used in this invention are readily available, inexpensive, and the preparation process is simple and easy to control, making it highly practical. Attached Figure Description
[0035] Figure 1 This is a SEM image of the Sb2O3 nanowire array-carbon-based composite material prepared in Example 1 of this invention.
[0036] Figure 2 This is a cycle stability diagram of the Sb2O3 nanowire array-carbon-based composite material prepared in Example 1 of this invention.
[0037] Figure 3 This is a rate performance diagram of the Sb2O3 nanowire array-carbon-based composite material prepared in Example 1 of this invention.
[0038] Figure 4 This is a SEM image of the Sb2O3 nanowire array-carbon-based composite material prepared in Example 2 of this invention. Detailed Implementation
[0039] The following embodiments are merely some, not all, of the embodiments of the present invention. Therefore, the detailed descriptions of the embodiments provided below are not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.
[0040] In this invention, unless otherwise specified, all equipment and raw materials are commercially available or commonly used in the industry. The methods described in the following embodiments are conventional methods in the art, unless otherwise specified.
[0041] In the following examples, the M of polyvinyl alcohol W The range is 13,000 to 23,000.
[0042] Example 1
[0043] This embodiment provides a Sb₂O₃ nanowire array-carbon-based composite material, and the preparation process is as follows:
[0044] (1) Cleaning carbon cloth
[0045] Cut the carbon cloth into 3cm*4cm squares, and ultrasonically clean it with acetone, water and ethanol for 15 minutes each. After cleaning, place it in a vacuum drying oven and dry it at 60℃ for 12 hours.
[0046] (2) Carbon cloth seed crystal
[0047] After cleaning and drying, place the carbon cloth in a beaker containing 65% concentrated nitric acid and bathe it in a water bath at 60°C for 2 hours; then clean it with deionized water and dry it in a vacuum drying oven at 60°C for 12 hours.
[0048] The dried carbon cloth was soaked in a 0.005 mol / L antimony acetate solution for 24 h, and then placed in a muffle furnace and heated to 350 °C at a rate of 5 °C / min for annealing for 30 min.
[0049] (3) Synthesis of Sb2O3 nanowire array-carbon-based composite material
[0050] Add 0.6g of polyvinyl alcohol (PVA) to 50mL of deionized water, heat at 60℃ until dissolved, and cool naturally to room temperature; add 1.2g of hexamethylenetetramine and the seeded carbon cloth from step (2), and stir for 15min; add 1.14g of SbCl3 and continue stirring for 15min;
[0051] The stirred solution and carbon cloth were transferred to a 100mL reaction vessel and placed in a vacuum drying oven at 140℃ for 14h.
[0052] The carbon cloth after hydrothermal reaction was washed three times with deionized water and anhydrous ethanol, and then dried in a vacuum drying oven at 60°C for 12 hours to obtain Sb2O3 nanowire array-carbon-based composite material.
[0053] Figure 1 The image shows a SEM image of the Sb2O3 nanowire array-carbon-based composite material prepared in this embodiment. As can be seen from the image, the composite material has a nanowire array composed of nanowires growing outward from the seed crystal nucleus point. The overall structure grows symmetrically and is named a twin flower-like nanowire array structure.
[0054] In this embodiment, the above-mentioned Sb₂O₃ nanowire array-carbon-based composite material was used to prepare a battery, and its electrochemical performance was tested. The process is as follows: The Sb₂O₃ nanowire array-carbon-based composite material was cut into sheets, and an active mass of 1.0 mg / cm² was selected as the electrode sheet. A CR2032 type lithium-ion battery was assembled. The assembly sequence was: negative electrode shell, lithium sheet, separator, electrolyte, electrode sheet, gasket, and spring sheet. The separator was a polypropylene membrane; the electrolyte was a 1 mol / L LiPF₆ solution, and the solvent was a mixed solution of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) in a volume ratio of 1:1:1. The assembly process was carried out in an argon-filled glove box with an oxygen content ≤0.01 ppm. In this embodiment, the Land-2001B battery was used to test its telephone performance. For the rate performance test, the current densities were set sequentially to 0.1 A / g, 0.2 A / g, 0.5 A / g, 1 A / g, 2 A / g, 4 A / g, and 5 A / g, and the battery was run for 5 cycles at each current density. For the long-cycle performance test, the current density was set to 1 A / g, and the test voltage range was 0.01–3 V. The test results are shown below. Figure 2-3 ,from Figure 2 As can be seen from this, the electrode material prepared in this embodiment has stable cycling performance, maintaining a specific capacity of 1800 mAh / g after 100 cycles, with a coulombic efficiency as high as 92% in the first cycle and stabilizing at around 100% in subsequent cycles. Figure 3 As can be seen from this, the electrode material prepared in this embodiment has good rate performance. During the process of changing from a small current of 0.1A to a large current of 5A and then back to 0.1A, the capacity still remains at around 2000mAh / g, which shows good rate performance.
[0055] Example 2
[0056] This embodiment provides a Sb₂O₃ nanowire array-carbon-based composite material, and the preparation process is as follows:
[0057] (1) Cleaning carbon cloth
[0058] Cut the carbon cloth into 3cm*4cm squares, and ultrasonically clean it with acetone, water and ethanol for 15 minutes each. After cleaning, place it in a vacuum drying oven and dry it at 60℃ for 12 hours.
[0059] (2) Carbon cloth seed crystal
[0060] After cleaning and drying, place the carbon cloth in a beaker containing 65% concentrated nitric acid and bathe it in a water bath at 60°C for 2 hours; then clean it with deionized water and dry it in a vacuum drying oven at 60°C for 12 hours.
[0061] The dried carbon cloth was soaked in a 0.005 mol / L antimony acetate solution for 24 h, and then placed in a muffle furnace and heated to 400 °C at a rate of 5 °C / min for annealing for 25 min.
[0062] (3) Synthesis of Sb2O3 nanowire array-carbon-based composite material
[0063] Add 0.6g of polyvinyl alcohol (PVA) to 50mL of deionized water, heat at 60℃ until dissolved, and cool naturally to room temperature; add 1.4g of hexamethylenetetramine and the seeded carbon cloth from step (2), and stir for 15min; add 1.14g of SbCl3 and continue stirring for 15min;
[0064] The stirred solution and carbon cloth were transferred to a 100 mL reaction vessel and placed in a vacuum drying oven at 140 °C for 10 h.
[0065] The carbon cloth after hydrothermal reaction was washed three times with deionized water and anhydrous ethanol, and then dried in a vacuum drying oven at 60°C for 12 hours to obtain Sb2O3 nanowire array-carbon-based composite material.
[0066] The SEM image of the composite material prepared in this embodiment is shown below. Figure 4 As can be seen from the image, its growth is not perfect, exhibiting a symmetrical butterfly-shaped structure.
[0067] Example 3
[0068] This embodiment provides a Sb₂O₃ nanowire array-carbon-based composite material, and the preparation process is as follows:
[0069] (1) Cleaning carbon cloth
[0070] Cut the carbon cloth into 3cm*4cm squares, and ultrasonically clean it with acetone, water and ethanol for 15 minutes each. After cleaning, place it in a vacuum drying oven and dry it at 60℃ for 12 hours.
[0071] (2) Carbon cloth seed crystal
[0072] After cleaning and drying, place the carbon cloth in a beaker containing 65% concentrated nitric acid and bathe it in a water bath at 60°C for 2 hours; then clean it with deionized water and dry it in a vacuum drying oven at 60°C for 12 hours.
[0073] The dried carbon cloth was soaked in a 0.005 mol / L antimony acetate solution for 24 h, and then placed in a muffle furnace and heated to 350 °C at a rate of 5 °C / min for annealing for 25 min.
[0074] (3) Synthesis of Sb2O3 nanowire array-carbon-based composite material
[0075] Add 0.6g of polyvinyl alcohol (PVA) to 50mL of deionized water, heat at 60℃ until dissolved, and cool naturally to room temperature; add 1.3g of hexamethylenetetramine and the seeded carbon cloth from step (2), and stir for 15min; add 1.14g of SbCl3 and continue stirring for 15min;
[0076] The stirred solution and carbon cloth were transferred to a 100mL reaction vessel and placed in a vacuum drying oven at 140℃ for 16 hours.
[0077] The carbon cloth after hydrothermal reaction was washed three times with deionized water and anhydrous ethanol, and then dried in a vacuum drying oven at 80°C for 12 hours to obtain Sb2O3 nanowire array-carbon-based composite material.
[0078] The microstructure of the composite material prepared in this embodiment is not significantly different from that in Example 1.
[0079] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for preparing Sb₂O₃ nanoarray-carbon-based composite material, characterized in that, Includes the following steps: (1) Immerse the carbon-based material in an antimony salt solution; (2) Anneal the soaked carbon-based material; (3) An annealed carbon-based material is subjected to a hydrothermal reaction in an epitaxial growth solution to obtain an Sb2O3 nanoarray on the carbon-based material; the epitaxial growth solution contains an antimony source, a template agent and a precipitant; In step (1), the carbon-based material undergoes an acidification pretreatment; the acidification involves heating the carbon-based material in an acid solution; the antimony salt solution is an antimony acetate solution. In step (2), the annealing temperature is 350~400℃; the annealing time is 20~30 min; In step (3), the antimony source is SbCl3; the template agent is polyvinyl alcohol; the molecular weight of the polyvinyl alcohol is 13000-23000; the precipitant is hexamethylenetetramine; and the ratio of the amounts of the antimony source, template agent, and precipitant is 1.14:0.6:1.2~1.
3. In step (3), the temperature of the hydrothermal reaction is 140°C; the time of the hydrothermal reaction is 14~16 h.
2. The preparation method according to claim 1, characterized in that, In step (1), the carbon-based material is selected from at least one of carbon fiber cloth, carbon paper, carbon cloth, carbon felt and reticulated glassy carbon.
3. The preparation method according to claim 1, characterized in that, In step (1), the concentration of the antimony salt solution is 0.005~0.02 mol / L.
4. The preparation method according to claim 1, characterized in that, In step (1), the soaking time is 24~48h.
5. The preparation method according to claim 1, characterized in that, In step (1), the acid solution is selected from any one of concentrated nitric acid, concentrated sulfuric acid and concentrated nitric acid mixture; the heating temperature is 60~80℃; the heating time is 2~4 h.
6. The preparation method according to claim 1, characterized in that, The carbon-based material undergoes a pretreatment process of washing and drying before acidification.
7. The preparation method according to claim 1, characterized in that, The carbon-based material also undergoes post-treatment after acidification, including washing and drying; the drying process is carried out at 60-80°C for 10-12 hours.
8. The preparation method according to claim 1, characterized in that, In step (2), the heating rate of the annealing is 3~5℃ / min.
9. The preparation method according to claim 1, characterized in that, Step (3) also includes post-treatment of washing and drying the carbon-based material after hydrothermal reaction; the washing is water and ethanol washing; the drying is drying at 60~80℃ for 10~12 h.
10. The Sb2O3 nanoarray-carbon-based composite material obtained by any of the preparation methods described in claims 1-9.
11. The application of the Sb2O3 nanoarray-carbon-based composite material according to claim 10 in the preparation of batteries.
12. The application according to claim 11, characterized in that, Applications in the preparation of lithium-ion battery anode materials.