Antimony trioxide composite particle and application thereof
By preparing antimony trioxide composite particles with a raspberry-like microstructure, and using imidazole β-cyclodextrin to react with antimony salt to generate MOF structures, and then combining them with phenolic resin coating, the structural problem caused by the volume change of antimony trioxide in lithium-ion batteries was solved, thereby improving electrochemical performance and lithium storage capacity.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HUNAN LOUDI HUAXING ANTIMONY IND
- Filing Date
- 2025-12-02
- Publication Date
- 2026-04-24
Smart Images
Figure CN121922590A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of inorganic materials, specifically to a type of antimony trioxide composite particle and its applications. Background Technology
[0002] Antimony trioxide (antimony trioxide) possesses the highest theoretical capacity among antimony-based electrode materials because its conversion and alloying reactions during charging and discharging contribute to its high capacity. However, antimony trioxide undergoes significant volume changes during cycling, leading to structural expansion and even collapse. Carbon materials are conductors with excellent mechanical properties and structural stability. Coating antimony trioxide particles with carbon materials can prevent agglomeration during lithium / sodium intercalation / deintercalation. The excellent mechanical properties of carbon can buffer volume expansion, thereby stabilizing the structure and improving its electrochemical performance. However, improving the composite method to further enhance the electrochemical performance of the composite material remains a research hotspot. Summary of the Invention
[0003] Purpose of the invention: To address the above-mentioned technical problems, this invention proposes an antimony trioxide composite particle and its application.
[0004] The technical solution adopted is as follows: A type of antimony trioxide composite particle: The antimony trioxide composite particles are composed of antimony trioxide and carbon, and have a raspberry-like microstructure.
[0005] Furthermore, the method for preparing the antimony trioxide composite particles is as follows: Acrylated β-cyclodextrin was reacted with diallylamine via a Michael addition reaction to obtain an intermediate. The intermediate was then reacted with mercaptoimidazole via a mercapto-olefin click chemistry to obtain imidazole β-cyclodextrin. The product obtained by reacting imidazole β-cyclodextrin with antimony salt was added to a mixed solvent of anhydrous ethanol and water, followed by the addition of CTAB, ammonia, resorcinol, and formaldehyde. After the reaction, the precursor was obtained by filtration, drying, and sintering.
[0006] Furthermore, the preparation method of the acryloylated β-cyclodextrin is as follows: Ethylenediamine β-cyclodextrin and DCC (dicyclohexylcarbodiimide) were dissolved in DMF (N,N-dimethylformamide), and then acrylic acid was added to carry out the reaction. After the reaction was completed, the precipitated solid was removed by filtration, and acetone was added to the filtrate to precipitate the product. The product was then filtered again, collected, and dried.
[0007] Furthermore, the specific reaction method of the acrylated β-cyclodextrin with diallylamine is as follows: Acrylate-β-cyclodextrin and diallylamine were dissolved in DMF to obtain solutions A and B, respectively. Solution B was mixed with an alkaline catalyst to activate it to obtain solution C. Solution C was added to solution A, the reaction was stirred and then quenched, dialyzed, and the dialyzed solution was freeze-dried.
[0008] Furthermore, the specific reaction method between the intermediate and the mercaptoimidazole is as follows: The intermediate, mercaptoimidazole, and photoinitiator are added to DMF, reacted under ultraviolet light, and then the small molecules are removed by vacuum distillation.
[0009] Further, the mercaptoimidazole is any one of 2-mercaptoimidazole, 2-mercaptomethylimidazole, 2-mercaptoethylimidazole, 2-mercaptopropylimidazole, and 2-mercaptobutylimidazole.
[0010] Furthermore, the mass ratio of imidazolyl β-cyclodextrin to antimony salt is 1-5:1.
[0011] Furthermore, the antimony salt is antimony trichloride or antimony glycolate.
[0012] Furthermore, the sintering temperature is 500-600℃.
[0013] The present invention also provides the application of the above-mentioned antimony trioxide composite particles in secondary batteries.
[0014] The secondary battery described in this invention, also known as a rechargeable battery or storage battery, refers to a type of battery that can be reused after being discharged by recharging to activate the active materials. Its working principle is based on the reversibility of chemical reactions. The main types include lead-acid batteries, lithium-ion batteries, sodium-ion batteries, and nickel-metal hydride batteries.
[0015] The beneficial effects of this invention are: This invention provides a method for preparing antimony trioxide composite particles. β-Cyclodextrin is a cyclic oligosaccharide composed of seven glucose units, possessing a rigid conical cavity with an inner hydrophobic and an outer hydrophilic structure. Upon pyrolysis, it forms a hierarchical porous carbon structure, significantly improving ion transport efficiency. The imidazole group serves as a strong coordinating site and can interact with Sb. 3+Stable coordination bonds are formed to construct an ordered β-cyclodextrin / antimony composite MOF structure. After pyrolysis, nano-antimony particles are uniformly confined on the surface of the MOF-derived carbon framework, which avoids antimony agglomeration and lays the foundation for subsequent oxidation. The covalent radius of sulfur atoms is much larger than that of carbon atoms. After doping, they insert into the carbon lattice, increasing the interlayer spacing of the carbon layers. The larger interlayer spacing lowers the energy barrier for lithium-ion insertion / extraction, significantly improving the ion diffusion rate and thus improving rate performance. Moreover, sulfur doping introduces additional defect sites and active sites, which can serve as additional lithium-ion storage centers, increasing lithium storage capacity. Phenolic resin coating can achieve performance breakthroughs through the dual carbon source synergistic mechanism and also coat the antimony trioxide generated by oxidation, preventing the antimony trioxide from falling off. Furthermore, after the composite pyrolysis of β-cyclodextrin and phenolic resin, a layered and hierarchical porous structure is formed, in which antimony trioxide generated by oxidation is embedded to form a special raspberry-like micromorphology. This structure is conducive to the rapid diffusion of electrolyte and ion transport, effectively alleviating the volume expansion of the negative electrode material caused by lithium ion insertion / extraction during charging and discharging, and improving the electrochemical performance of the prepared antimony trioxide composite particles. Attached Figure Description
[0016] Figure 1 This is a SEM image of the antimony trioxide composite particles prepared in Example 1 of the present invention. Detailed Implementation
[0017] Unless otherwise specified in the examples, the conditions were performed under standard conditions or as recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products. Techniques not mentioned in this invention refer to existing technologies. Unless otherwise specified, the following examples and comparative examples are parallel experiments, using the same processing steps and parameters.
[0018] Example 1: A method for preparing antimony trioxide composite particles: 20 mmol of ethylenediamine β-cyclodextrin (CAS: 60984-63-6) and 20.5 mmol of DCC were dissolved in 200 ml of DMF. 20.5 mmol of acrylic acid was added dropwise at 15 °C. After stirring for 30 min, the mixture was reacted at room temperature for 8 h. After the reaction was completed, the precipitated solid was removed by filtration. 1000 ml of acetone was added to the filtrate to precipitate the product. The product was collected by filtration again and dried to obtain acrylated β-cyclodextrin.
[0019] 15 mmol of acrylated β-cyclodextrin and 16 mmol of diallylamine (CAS: 124-02-7) were dissolved in 150 ml of DMF to obtain solutions A and B, respectively. 16 mmol of sodium hydride was added to solution B under ice bath conditions, and the mixture was stirred and activated for 60 min to obtain solution C. Solution C was added to solution A under ice bath conditions. After stirring for 12 h under ice bath conditions, 50 ml of methanol was added to quench the reaction. The resulting reaction solution was transferred to a dialysis bag (molecular weight cutoff 3500 Da) and dialyzed with deionized water for 48 h, with the water changed every 12 h to remove small molecules. Finally, the dialyzed solution was freeze-dried (-50 °C, 24 h) to obtain the intermediate.
[0020] Add 10 mmol of intermediate, 10 mmol of 2-mercaptoethylimidazole (CAS: 111543-56-7), 0.5 g of photoinitiator 651 and 200 ml of DMF, stir and irradiate with ultraviolet light for 30 min. After the reaction is complete, remove small molecules by vacuum distillation to obtain imidazole β-cyclodextrin.
[0021] 9 g of imidazole β-cyclodextrin was dissolved in 100 ml of methanol to obtain a cyclodextrin solution. 3 g of SbCl3 was dissolved in 30 ml of methanol to obtain an antimony salt solution. The antimony salt solution was added to the cyclodextrin solution, and the mixture was stirred and reacted for 60 min, then allowed to stand for 24 h. The resulting product was then washed with methanol, centrifuged, and dried. 0.2 g of the product was added to a mixed solvent of 6 ml anhydrous ethanol and 14 ml deionized water, and stirred for 30 min. Then, 0.46 g of CTAB, 0.2 ml of ammonia, and 0.07 g of resorcinol were added, and the mixture was stirred for another 30 min. 0.12 ml of formaldehyde was then added, and the reaction was continued for 8 h. The product was collected, washed with anhydrous ethanol, and dried to obtain the precursor. The precursor was sintered in a tube furnace at a heating rate of 5 °C / min, a sintering temperature of 550 °C, a sintering atmosphere of dry air, and a sintering time of 2 h. The sample was then naturally cooled to room temperature. The SEM image is shown below. Figure 1 It can be seen that it has a raspberry-like microstructure.
[0022] Example 2: A method for preparing antimony trioxide composite particles: The preparation method of imidazole β-cyclodextrin is the same as in Example 1. 3g of imidazole β-cyclodextrin was dissolved in 100ml of methanol to obtain a cyclodextrin solution. 3g of SbCl3 was dissolved in 30ml of methanol to obtain an antimony salt solution. The antimony salt solution was added to the cyclodextrin solution, and the mixture was stirred and reacted for 60min. After standing and aging for 24h, the obtained product was washed with methanol, centrifuged, and dried. 0.2g of the above product was added to a mixed solvent consisting of 6ml of anhydrous ethanol and 14ml of deionized water. After stirring for 30min, 0.46g of CTAB, 0.2ml of ammonia and 0.07g of resorcinol were added, and the mixture was stirred for another 30min. Then, 0.12ml of formaldehyde was added, and the mixture was stirred and reacted for another 8h. The product was collected, washed with anhydrous ethanol and dried to obtain the precursor. The precursor was placed in a tube furnace for sintering at a heating rate of 5℃ / min, a sintering temperature of 500℃, a sintering atmosphere of dry air, and a sintering time of 2h. The sample was then naturally cooled to room temperature.
[0023] Example 3: A method for preparing antimony trioxide composite particles: The preparation method of imidazole β-cyclodextrin is the same as in Example 1. 15g of imidazole β-cyclodextrin was dissolved in 100ml of methanol to obtain a cyclodextrin solution. 3g of SbCl3 was dissolved in 30ml of methanol to obtain an antimony salt solution. The antimony salt solution was added to the cyclodextrin solution, and the mixture was stirred and reacted for 60min. After standing and aging for 24h, the obtained product was washed with methanol, centrifuged, and dried. 0.2g of the above product was added to a mixed solvent consisting of 6ml of anhydrous ethanol and 14ml of deionized water. After stirring for 30min, 0.46g of CTAB, 0.2ml of ammonia and 0.07g of resorcinol were added, and the mixture was stirred for another 30min. Then, 0.12ml of formaldehyde was added, and the mixture was stirred and reacted for another 8h. The product was collected, washed with anhydrous ethanol and dried to obtain the precursor. The precursor was placed in a tube furnace for sintering at a heating rate of 5℃ / min, a sintering temperature of 600℃, a sintering atmosphere of dry air, and a sintering time of 2h. The sample was then naturally cooled to room temperature.
[0024] Comparative Example 1: The process is basically the same as in Example 1, except that the reaction product of imidazole β-cyclodextrin and SbCl3 is directly sintered.
[0025] 20 mmol of ethylenediamine β-cyclodextrin (CAS: 60984-63-6) and 20.5 mmol of DCC were dissolved in 200 ml of DMF. 20.5 mmol of acrylic acid was added dropwise at 15 °C. After stirring for 30 min, the mixture was reacted at room temperature for 8 h. After the reaction was completed, the precipitated solid was removed by filtration. 1000 ml of acetone was added to the filtrate to precipitate the product. The product was collected by filtration again and dried to obtain acrylated β-cyclodextrin.
[0026] 15 mmol of acrylated β-cyclodextrin and 16 mmol of diallylamine (CAS: 124-02-7) were dissolved in 150 ml of DMF to obtain solutions A and B, respectively. 16 mmol of sodium hydride was added to solution B under ice bath conditions, and the mixture was stirred and activated for 60 min to obtain solution C. Solution C was added to solution A under ice bath conditions. After stirring for 12 h under ice bath conditions, 50 ml of methanol was added to quench the reaction. The resulting reaction solution was transferred to a dialysis bag (molecular weight cutoff 3500 Da) and dialyzed with deionized water for 48 h, with the water changed every 12 h to remove small molecules. Finally, the dialyzed solution was freeze-dried (-50 °C, 24 h) to obtain the intermediate.
[0027] Add 10 mmol of intermediate, 10 mmol of 2-mercaptoethylimidazole (CAS: 111543-56-7), 0.5 g of photoinitiator 651 and 200 ml of DMF, stir and irradiate with ultraviolet light for 30 min. After the reaction is complete, remove small molecules by vacuum distillation to obtain imidazole β-cyclodextrin.
[0028] 9g of imidazole β-cyclodextrin was dissolved in 100ml of methanol to obtain a cyclodextrin solution. 3g of SbCl3 was dissolved in 30ml of methanol to obtain an antimony salt solution. The antimony salt solution was added to the cyclodextrin solution, and the mixture was stirred and reacted for 60min. The mixture was then allowed to stand and age for 24h. The resulting product was then washed with methanol, centrifuged, dried, and sintered in a tube furnace at a heating rate of 5℃ / min, a sintering temperature of 550℃, a sintering atmosphere of dry air, and a sintering time of 2h. The product was then allowed to cool naturally to room temperature to obtain the sample. Scanning electron microscopy revealed that the microstructure was irregular granular and did not exhibit a raspberry-like microstructure.
[0029] Comparative Example 2: It is basically the same as Example 1, except that 2-methylimidazole (CAS: 693-98-1) is used instead of imidazole β-cyclodextrin.
[0030] 9g of 2-methylimidazole was dissolved in 100ml of methanol to obtain an imidazole solution, and 3g of SbCl3 was dissolved in 30ml of methanol to obtain an antimony salt solution. The antimony salt solution was added to the imidazole solution, and the mixture was stirred and reacted for 60min. The mixture was then allowed to stand for 24h. The resulting product was then washed with methanol, centrifuged, and dried. 0.2g of the product was added to a mixed solvent consisting of 6ml of anhydrous ethanol and 14ml of deionized water. After stirring for 30min, 0.46g of CTAB, 0.2ml of ammonia, and 0.07g of resorcinol were added. After stirring for another 30min, 0.12ml of formaldehyde was added. The mixture was stirred and reacted for another 8h. The product was collected, washed with anhydrous ethanol, and dried to obtain the precursor. The precursor was then placed in a tube furnace for sintering at a heating rate of 5℃ / min, a sintering temperature of 550℃, a sintering atmosphere of dry air, and a sintering time of 2h. The sample was then naturally cooled to room temperature.
[0031] Comparative Example 3: It is basically the same as Example 1, except that antimony trioxide is added directly.
[0032] 0.2 g of antimony trioxide was added to a mixed solvent consisting of 6 ml of anhydrous ethanol and 14 ml of deionized water. After stirring for 30 min, 0.46 g of CTAB, 0.2 ml of ammonia, and 0.07 g of resorcinol were added and stirred for another 30 min. Then, 0.12 ml of formaldehyde was added and the reaction was continued for 8 h. The product was collected, washed with anhydrous ethanol, and dried to obtain the precursor. The precursor was placed in a tube furnace for sintering at a heating rate of 5 °C / min, a sintering temperature of 550 °C, a sintering atmosphere of dry air, and a sintering time of 2 h. The sample was then naturally cooled to room temperature.
[0033] Comparative Example 4: This is essentially the same as Example 1, except that β-cyclodextrin-coated antimony trioxide is used as a precursor.
[0034] 0.2 g of antimony trioxide was added to a mixed solvent consisting of 6 ml of anhydrous ethanol and 14 ml of deionized water. After stirring for 30 min, 1 g of β-cyclodextrin was added and stirred evenly. The reaction solution was then transferred to a rotary evaporator to remove small molecules under reduced pressure to obtain the precursor. The precursor was then placed in a tube furnace for sintering at a heating rate of 5 °C / min, a sintering temperature of 550 °C, a sintering atmosphere of dry air, and a sintering time of 2 h. The sample was then naturally cooled to room temperature.
[0035] Comparative Example 5: Take 0.2g of antimony trioxide and 1g of carbon powder, mix and grind them together to make a sample.
[0036] Performance testing The samples prepared in Examples 1-3 and Comparative Examples 1-5 were mixed and ground uniformly with polyvinylidene fluoride (PVDF), polyimide, carbon black and carbon nanotubes in a mass ratio of 6:1:1:1.9:0.1. N-methylpyrrolidone was used as a solvent to form a uniform slurry. The slurry was uniformly coated onto copper foil with a scraper and dried in a vacuum oven at 80°C after vacuuming. Electrode sheets were cut using a cutting machine and dried in a vacuum oven at 120°C for 24 hours to serve as the negative electrode. A lithium metal sheet was used as the positive electrode. The electrolyte was 1 mol / L LiPF6 / (DEC+EC+DMC, volume ratio 1:1:1). A CR2025 coin-type lithium-ion battery was assembled in an argon glove box with a water and oxygen content of less than 5%. The positive and negative electrodes were separated by a Celgard 2400 separator. The battery was left to stand at room temperature for 24 hours and then charged and discharged using a Blue Electric testing system (Wuhan Jinno Electronics Co., Ltd., CT2001A). The voltage range was 0.05-3.00V, and the current density was 500 mA / g. The test results are shown in Table 1 below. Table 1: As shown in Table 1 above, the antimony trioxide composite particles prepared in this invention have excellent electrochemical properties.
[0037] A comparison between Example 1 and Comparative Example 1 shows that in-situ generated phenolic resin coating can further enhance the electrochemical performance of antimony trioxide composite particles and promote the formation of raspberry-like micromorphology.
[0038] The comparison between Example 1 and Comparative Example 2 shows that, compared with 2-methylimidazole, imidazole-based β-cyclodextrin, as a precursor, provides a greater improvement in the electrochemical performance of antimony trioxide composite particles.
[0039] A comparison of Example 1 with Comparative Examples 3-5 shows that the electrochemical performance of the antimony trioxide composite particles prepared by in-situ phenolic resin, β-cyclodextrin-coated antimony trioxide, or direct mixing of antimony trioxide with carbon powder is inferior to that of the present invention.
[0040] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A composite particle of antimony trioxide, characterized in that, The antimony trioxide composite particles are composed of antimony trioxide and carbon, and have a raspberry-like microstructure.
2. The antimony trioxide composite particles as described in claim 1, characterized in that, Its preparation method is as follows: Acrylated β-cyclodextrin was reacted with diallylamine via a Michael addition reaction to obtain an intermediate. The intermediate was then reacted with mercaptoimidazole via a mercapto-olefin click chemistry to obtain imidazole β-cyclodextrin. The product obtained by reacting imidazole β-cyclodextrin with antimony salt was added to a mixed solvent of anhydrous ethanol and water, followed by the addition of CTAB, ammonia, resorcinol, and formaldehyde. After the reaction, the precursor was obtained by filtration, drying, and sintering.
3. The antimony trioxide composite particles as described in claim 2, characterized in that, The preparation method of the acryloylated β-cyclodextrin is as follows: Ethylenediamine β-cyclodextrin and DCC were dissolved in DMF, and then acrylic acid was added to react. After the reaction was completed, the precipitated solid was removed by filtration. Acetone was added to the filtrate to precipitate the product. The product was then filtered again, collected, and dried.
4. The antimony trioxide composite particles as described in claim 2, characterized in that, The specific reaction method of acrylamide β-cyclodextrin with diallylamine is as follows: Acrylated β-cyclodextrin and diallylamine were dissolved in DMF to obtain solutions A and B, respectively. Solution B was mixed with an alkaline catalyst to activate it to obtain solution C. Solution C was added to solution A, the reaction was stirred and then quenched, dialyzed, and the dialyzed solution was freeze-dried.
5. The antimony trioxide composite particles as described in claim 2, characterized in that, The specific reaction method between the intermediate and thioimidazole is as follows: The intermediate, mercaptoimidazole, and photoinitiator are added to DMF, reacted under ultraviolet light, and then the small molecules are removed by vacuum distillation.
6. The antimony trioxide composite particles as described in claim 2, characterized in that, The mercaptoimidazole is any one of 2-mercaptoimidazole, 2-mercaptomethylimidazole, 2-mercaptoethylimidazole, 2-mercaptopropylimidazole, and 2-mercaptobutylimidazole.
7. The antimony trioxide composite particles as described in claim 2, characterized in that, The mass ratio of imidazole β-cyclodextrin to antimony salt is 1-5:
1.
8. The antimony trioxide composite particles as described in claim 2, characterized in that, The antimony salt is antimony trichloride or antimony glycol.
9. The antimony trioxide composite particles as described in claim 2, characterized in that, The sintering temperature is 500-600℃.
10. The application of antimony trioxide composite particles as described in any one of claims 1-9 in secondary batteries.