CN112164781A - Porous SiO2Coated multi-shell hollow SnO2Lithium ion battery cathode material - Google Patents
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Abstract
The invention relates to the technical field of lithium ion batteries and discloses a porous SiO2Coated multi-shell hollow SnO2The lithium ion battery cathode material takes hydroxyl carbon nanospheres as templates, Sn4+Uniformly modifying the surface of the hydroxyl carbon nanospheres, and removing the carbon nanosphere template through regulating the proportion of tin tetrachloride to the hydroxyl carbon nanospheres and high-temperature thermal cracking to prepare the multi-shell hollow SnO2The nanosphere has a unique hierarchical multi-shell hollow structure, has an ultra-high specific surface area, can increase the active sites of electrochemical reaction, thereby improving the actual specific capacity of the cathode material, and simultaneously has hollow SnO in the multi-shell hollow SnO through interfacial polymerization2A layer of porous nano SiO is generated on the surface of the nanosphere2Through porous nano SiO2The function of the coating layer effectively relieves SnO in the process of lithium ion deintercalation2The volume change of the alloy buffers the cyclic stress and reduces SnO2The active substance is pulverized and dropped off, and the electrochemical cycle stability of the negative electrode material is enhanced.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to porous SiO2Coated multi-shell hollow SnO2The lithium ion battery cathode material.
Background
The lithium ion battery has the characteristics of high energy density, good rate performance, long cycle life and the like, and is widely applied to the fields of mobile electronic equipment, electric automobile energy devices and the like.
The current lithium ion battery cathode materials mainly comprise carbon cathode materials such as graphene and carbon nano tubes, manganese dioxide and SnO2Equal transition metal oxide electrode materials, and conductive polymer electrode materials, wherein SnO2Has high theoretical specific capacity and is a lithium ion battery cathode material with great potential, but SnO2The volume expansion is easy to occur in the process of lithium insertion/removal, and larger cyclic stress is generated in the electrode material, so that electrode active material is pulverized and falls into electrolyte, and SnO is seriously influenced2Electrochemical cycling stability of the negative electrode material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides high-efficiency porous SiO2The lithium ion battery cathode material coated with the multi-shell hollow SnO2 solves the problem of SnO2The volume expansion of the negative electrode material is easy to occur, and the electrochemical cycling stability of the negative electrode material is seriously influenced.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: porous SiO2Coated multi-shell hollow SnO2The lithium ion battery negative electrode material: the porous SiO2Coated multi-shell hollow SnO2The preparation method of the lithium ion battery negative electrode material comprises the following steps:
(1) adding distilled water solvent and glucose into a reaction bottle, stirring uniformly, pouring into a hydrothermal reaction kettle, placing into a reaction kettle device, heating to 180 ℃ and 200 ℃, stirring at a constant speed for reaction for 2-4h, filtering the solvent, washing the product with distilled water and ethanol, and drying to prepare the carbon nanosphere.
(2) Adding distilled water solvent, carbon nanospheres and sodium hydroxide into a reaction bottle, uniformly dispersing by ultrasonic wave, heating to 40-80 ℃, uniformly stirring and activating for 3-6h, filtering the solvent, washing the product by using distilled water, and drying to prepare the hydroxyl carbon nanospheres.
(3) Adding distilled water solvent and stannic chloride into a reaction bottle, uniformly stirring, adding hydroxyl carbon nanospheres, uniformly stirring at 20-40 ℃ for 4-10h after ultrasonic dispersion, removing the solvent by vacuum drying, placing the solid mixed product in a resistance furnace, heating to 480-540 ℃ at the heating rate of 1-3 ℃/min, and carrying out heat preservation and calcination for 2-3h to prepare the multi-shell hollow SnO2Nanospheres.
(4) Adding a mixed solvent of ethanol solvent and distilled water into a reaction bottle, wherein the volume ratio of the ethanol solvent to the distilled water is 8-15:1, adding ammonia water to adjust the pH of the solution to 10-11, and then adding multi-shell hollow SnO2Uniformly dispersing nanospheres and hexadecyl trimethyl ammonium bromide by ultrasonic, uniformly stirring for 6-12h, slowly dropwise adding ethyl orthosilicate, uniformly stirring for reacting for 2-6h, filtering the solvent, washing the product by using distilled water and ethanol, drying, placing the solid mixed product in a resistance furnace, calcining to obtain porous SiO2Coated multi-shell hollow SnO2The lithium ion battery cathode material.
Preferably, the reaction kettle device in the step (1) comprises a motor, the motor is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a large gear tray, a large reaction kettle is arranged above the large gear tray, the large gear tray is movably connected with a small guide wheel tray through teeth, and a small reaction kettle is arranged above the small guide wheel tray.
Preferably, the mass ratio of the tin tetrachloride to the hydroxyl carbon nanospheres in the step (3) is 15-25: 1.
Preferably, in the step (4), the multi-shell hollow SnO2The mass ratio of the nanospheres, the hexadecyl trimethyl ammonium bromide and the ethyl orthosilicate is 100:2-8: 5-20.
Preferably, the temperature rise rate of the calcination process in the step (4) is 2-10 ℃/min, the calcination temperature is 450-.
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:
the porous SiO2Coating ofMulti-shell hollow SnO2The lithium ion battery cathode material takes hydroxyl carbon nanospheres as templates, Sn4+Uniformly modifying the surface of the hydroxyl carbon nanospheres, and removing the carbon nanosphere template through regulating the proportion of tin tetrachloride to the hydroxyl carbon nanospheres and high-temperature thermal cracking to prepare the multi-shell hollow SnO2The nanosphere has a unique hierarchical multi-shell hollow structure, has an ultra-high specific surface area, can increase the active sites of electrochemical reaction, thereby improving the actual specific capacity of the cathode material, and simultaneously has hollow SnO in the multi-shell hollow SnO through interfacial polymerization2A layer of porous nano SiO is generated on the surface of the nanosphere2Through porous nano SiO2The function of the coating layer effectively relieves SnO in the process of lithium ion deintercalation2The volume change of the alloy buffers the cyclic stress and reduces SnO2The active substance is pulverized and dropped off, the electrochemical cycle stability of the cathode material is enhanced, and the porous nano SiO2The abundant pore structure is beneficial to the diffusion and the migration of lithium ions, and the transmission path of the lithium ions is shortened.
Drawings
FIG. 1 is a schematic front view of a reactor apparatus;
fig. 2 is a schematic top view of a bull gear tray.
1-a reaction kettle device; 2, a motor; 3-a rotating shaft; 4-bull gear tray; 5-large reaction kettle; 6-tooth; 7-a small guide wheel tray; 8-small reaction kettle.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples:
porous SiO2Coated multi-shell hollow SnO2The lithium ion battery negative electrode material: the porous SiO2Coated multi-shell hollow SnO2The preparation method of the lithium ion battery negative electrode material comprises the following steps:
(1) adding distilled water solvent and glucose into a reaction bottle, stirring uniformly, pouring into a hydrothermal reaction kettle, and placing into a reaction kettle device, wherein the reaction kettle device comprises a motor, the motor is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a large gear tray, a large reaction kettle is arranged above the large gear tray, the large gear tray is movably connected with a small guide wheel tray through teeth, a small reaction kettle is arranged above the small guide wheel tray, heating is carried out to 180 degrees and 200 degrees centigrade, stirring and reacting for 2-4 hours at a constant speed, filtering the solvent, washing the product with distilled water and ethanol, and drying to prepare the carbon nanosphere.
(2) Adding distilled water solvent, carbon nanospheres and sodium hydroxide into a reaction bottle, uniformly dispersing by ultrasonic wave, heating to 40-80 ℃, uniformly stirring and activating for 3-6h, filtering the solvent, washing the product by using distilled water, and drying to prepare the hydroxyl carbon nanospheres.
(3) Adding distilled water solvent and stannic chloride into a reaction bottle, uniformly stirring, adding hydroxyl carbon nanospheres with the mass ratio of 15-25:1, uniformly dispersing by ultrasonic, uniformly stirring for 4-10h at 20-40 ℃, vacuum drying to remove the solvent, placing the solid mixed product into a resistance furnace with the temperature rise rate of 1-3 ℃/min, raising the temperature to 480-540 ℃, and carrying out heat preservation and calcination for 2-3h to prepare the multi-shell hollow SnO2Nanospheres.
(4) Adding a mixed solvent of ethanol solvent and distilled water into a reaction bottle, wherein the volume ratio of the ethanol solvent to the distilled water is 8-15:1, adding ammonia water to adjust the pH of the solution to 10-11, and then adding multi-shell hollow SnO2Uniformly stirring nanospheres and hexadecyl trimethyl ammonium bromide for 6-12h at uniform speed after ultrasonic dispersion, and slowly dropwise adding tetraethoxysilane, wherein the hollow SnO with multiple shell layers2The mass ratio of the nanospheres, the hexadecyl trimethyl ammonium bromide and the tetraethoxysilane is 100:2-8:5-20, the mixture is stirred at a constant speed for reaction for 2-6h, the solvent is filtered, the product is washed by distilled water and ethanol and dried, the solid mixed product is placed in a resistance furnace, the heating rate is 2-10 ℃/min, the calcining temperature is 450-doped 500 ℃, the calcining time is 3-5h, and the porous SiO is prepared by calcining2Coated multi-shell hollow SnO2The lithium ion battery cathode material.
Example 1
(1) Adding distilled water solvent and glucose into a reaction bottle, pouring the distilled water solvent and the glucose into a hydrothermal reaction kettle after uniformly stirring, and placing the hydrothermal reaction kettle into a reaction kettle device, wherein the reaction kettle device comprises a motor, the motor is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a large gear tray, a large reaction kettle is arranged above the large gear tray, the large gear tray is movably connected with a small guide wheel tray through teeth, a small reaction kettle is arranged above the small guide wheel tray, the small reaction kettle is heated to 180 ℃, the uniform stirring reaction is carried out for 2 hours, a solvent is filtered, products are washed by using distilled water and ethanol and dried, and the carbon nanospheres.
(2) Adding distilled water solvent, carbon nanospheres and sodium hydroxide into a reaction bottle, uniformly dispersing by ultrasonic wave, heating to 40 ℃, uniformly stirring and activating for 3 hours, filtering the solvent, washing the product by using distilled water, and drying to prepare the hydroxyl carbon nanospheres.
(3) Adding distilled water solvent and stannic chloride into a reaction bottle, uniformly stirring, adding hydroxyl carbon nanospheres with the mass ratio of 15:1, uniformly stirring at 20 ℃ for 4 hours after ultrasonic dispersion, removing the solvent by vacuum drying, placing a solid mixed product into a resistance furnace, heating to 480 ℃ at the heating rate of 1 ℃/min, and carrying out heat preservation and calcination for 2 hours to prepare multi-shell hollow SnO2Nanospheres.
(4) Adding a mixed solvent of ethanol solvent and distilled water into a reaction bottle, wherein the volume ratio of the ethanol solvent to the distilled water is 8:1, adding ammonia water to adjust the pH of the solution to 10, and then adding multi-shell hollow SnO2Uniformly ultrasonically dispersing nanospheres and hexadecyl trimethyl ammonium bromide, uniformly stirring for 6 hours, and slowly dropwise adding tetraethoxysilane, wherein the hollow SnO of multiple shells2The mass ratio of the nanospheres to the hexadecyl trimethyl ammonium bromide to the ethyl orthosilicate is 100:2:5, the mixture is stirred at a constant speed for reaction for 2 hours, a solvent is filtered, a product is washed by distilled water and ethanol and dried, a solid mixed product is placed in a resistance furnace, the heating rate is 2 ℃/min, the calcining temperature is 450 ℃, the calcining time is 3 hours, the calcining process is carried out, and the porous SiO is prepared2Coated multi-shell hollow SnO2The negative electrode material 1 for a lithium ion battery.
Example 2
(1) Adding distilled water solvent and glucose into a reaction bottle, pouring the distilled water solvent and the glucose into a hydrothermal reaction kettle after uniformly stirring, and placing the hydrothermal reaction kettle into a reaction kettle device, wherein the reaction kettle device comprises a motor, the motor is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a large gear tray, a large reaction kettle is arranged above the large gear tray, the large gear tray is movably connected with a small guide wheel tray through teeth, a small reaction kettle is arranged above the small guide wheel tray, heating is carried out to 200 ℃, stirring and reacting for 2 hours at a constant speed, filtering a solvent, washing a product with distilled water and ethanol and drying, and preparing to obtain the carbon nanospheres.
(2) Adding distilled water solvent, carbon nanospheres and sodium hydroxide into a reaction bottle, uniformly dispersing by ultrasonic wave, heating to 40 ℃, uniformly stirring and activating for 6 hours, filtering the solvent, washing the product by using distilled water, and drying to prepare the hydroxyl carbon nanospheres.
(3) Adding distilled water solvent and stannic chloride into a reaction bottle, uniformly stirring, adding hydroxyl carbon nanospheres with the mass ratio of 18:1, uniformly stirring at 30 ℃ for 10h, vacuum drying to remove the solvent, placing a solid mixed product in a resistance furnace with the heating rate of 1 ℃/min, heating to 540 ℃, preserving heat and calcining for 2h to prepare the multi-shell hollow SnO2Nanospheres.
(4) Adding a mixed solvent of ethanol solvent and distilled water into a reaction bottle, wherein the volume ratio of the ethanol solvent to the distilled water is 10:1, adding ammonia water to adjust the pH of the solution to 10, and then adding multi-shell hollow SnO2Uniformly stirring nanospheres and hexadecyl trimethyl ammonium bromide for 12 hours at constant speed after ultrasonic dispersion, and slowly dropwise adding tetraethoxysilane, wherein the hollow SnO of multiple shells2The mass ratio of the nanospheres to the hexadecyl trimethyl ammonium bromide to the ethyl orthosilicate is 100:4:10, the mixture is stirred at a constant speed for reaction for 4 hours, a solvent is filtered, a product is washed by distilled water and ethanol and dried, a solid mixed product is placed in a resistance furnace, the heating rate is 5 ℃/min, the calcining temperature is 500 ℃, the calcining time is 5 hours, the calcining process is carried out, and the porous SiO is prepared2Coated multi-shell hollow SnO2The negative electrode material 2 for a lithium ion battery.
Example 3
(1) Adding distilled water solvent and glucose into a reaction bottle, stirring uniformly, pouring into a hydrothermal reaction kettle, placing into a reaction kettle device, wherein the reaction kettle device comprises a motor, the motor is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a large gear tray, a large reaction kettle is arranged above the large gear tray, the large gear tray is movably connected with a small guide wheel tray through teeth, a small reaction kettle is arranged above the small guide wheel tray, heating is carried out to 190 ℃, stirring and reacting for 3 hours at a constant speed, filtering a solvent, washing a product by using distilled water and ethanol, and drying to prepare the carbon nanosphere.
(2) Adding distilled water solvent, carbon nanospheres and sodium hydroxide into a reaction bottle, uniformly dispersing by ultrasonic wave, heating to 60 ℃, uniformly stirring and activating for 5 hours, filtering the solvent, washing the product by using distilled water, and drying to prepare the hydroxyl carbon nanospheres.
(3) Adding distilled water solvent and stannic chloride into a reaction bottle, uniformly stirring, adding hydroxyl carbon nanospheres with the mass ratio of 18:1, uniformly stirring at 30 ℃ for 6h after ultrasonic dispersion, removing the solvent by vacuum drying, placing a solid mixed product in a resistance furnace with the heating rate of 2 ℃/min, heating to 500 ℃, and carrying out heat preservation and calcination for 2.5h to prepare the multi-shell hollow SnO2Nanospheres.
(4) Adding a mixed solvent of ethanol solvent and distilled water into a reaction bottle, wherein the volume ratio of the ethanol solvent to the distilled water is 10:1, adding ammonia water to adjust the pH of the solution to 10, and then adding multi-shell hollow SnO2Uniformly stirring nanospheres and hexadecyl trimethyl ammonium bromide for 10 hours at constant speed after ultrasonic dispersion, and slowly dropwise adding tetraethoxysilane, wherein the hollow SnO of multiple shells2The mass ratio of the nanospheres to the hexadecyl trimethyl ammonium bromide to the ethyl orthosilicate is 100:6:15, the mixture is stirred at a constant speed for reaction for 4 hours, a solvent is filtered, a product is washed by distilled water and ethanol and dried, a solid mixed product is placed in a resistance furnace, the heating rate is 8 ℃/min, the calcining temperature is 480 ℃, the calcining time is 4 hours, the calcining process is carried out, and the porous SiO is prepared2Coated multi-shell hollow SnO2The negative electrode material 3 for a lithium ion battery.
Example 4
(1) Adding distilled water solvent and glucose into a reaction bottle, pouring the distilled water solvent and the glucose into a hydrothermal reaction kettle after uniformly stirring, and placing the hydrothermal reaction kettle into a reaction kettle device, wherein the reaction kettle device comprises a motor, the motor is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a large gear tray, a large reaction kettle is arranged above the large gear tray, the large gear tray is movably connected with a small guide wheel tray through teeth, a small reaction kettle is arranged above the small guide wheel tray, heating is carried out to 200 ℃, stirring and reacting for 4 hours at a constant speed, filtering a solvent, washing a product by using distilled water and ethanol, and drying the product to prepare the carbon nanosphere.
(2) Adding distilled water solvent, carbon nanospheres and sodium hydroxide into a reaction bottle, uniformly dispersing by ultrasonic wave, heating to 80 ℃, uniformly stirring and activating for 6 hours, filtering the solvent, washing the product by using distilled water, and drying to prepare the hydroxyl carbon nanospheres.
(3) Adding distilled water solvent and stannic chloride into a reaction bottle, uniformly stirring, adding hydroxyl carbon nanospheres with the mass ratio of 25:1, uniformly stirring at 40 ℃ for 10h, vacuum drying to remove the solvent, placing a solid mixed product in a resistance furnace with the heating rate of 3 ℃/min, heating to 540 ℃, preserving heat and calcining for 3h to prepare the multi-shell hollow SnO2Nanospheres.
(4) Adding a mixed solvent of ethanol solvent and distilled water into a reaction bottle, wherein the volume ratio of the ethanol solvent to the distilled water is 15:1, adding ammonia water to adjust the pH of the solution to 11, and then adding multi-shell hollow SnO2Uniformly stirring nanospheres and hexadecyl trimethyl ammonium bromide for 12 hours at constant speed after ultrasonic dispersion, and slowly dropwise adding tetraethoxysilane, wherein the hollow SnO of multiple shells2The mass ratio of the nanospheres to the hexadecyl trimethyl ammonium bromide to the ethyl orthosilicate is 100:8:20, the mixture is stirred at a constant speed for reaction for 6 hours, a solvent is filtered, a product is washed by distilled water and ethanol and dried, a solid mixed product is placed in a resistance furnace, the heating rate is 10 ℃/min, the calcining temperature is 500 ℃, the calcining time is 5 hours, the calcining process is carried out, and the porous SiO is prepared2Coated multi-shell hollow SnO2The negative electrode material 4 for a lithium ion battery.
Comparative example 1
(1) Adding distilled water solvent and glucose into a reaction bottle, pouring the distilled water solvent and the glucose into a hydrothermal reaction kettle after uniformly stirring, and placing the hydrothermal reaction kettle into a reaction kettle device, wherein the reaction kettle device comprises a motor, the motor is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a large gear tray, a large reaction kettle is arranged above the large gear tray, the large gear tray is movably connected with a small guide wheel tray through teeth, a small reaction kettle is arranged above the small guide wheel tray, the small reaction kettle is heated to 180 ℃, the uniform stirring reaction is carried out for 4 hours, filtering a solvent, washing a product by using distilled water and ethanol and drying the product, and preparing the carbon.
(2) Adding distilled water solvent, carbon nanospheres and sodium hydroxide into a reaction bottle, uniformly dispersing by ultrasonic wave, heating to 80 ℃, uniformly stirring and activating for 6 hours, filtering the solvent, washing the product by using distilled water, and drying to prepare the hydroxyl carbon nanospheres.
(3) Adding distilled water solvent and stannic chloride into a reaction bottle, uniformly stirring, adding hydroxyl carbon nanospheres with the mass ratio of 10:1, uniformly stirring at 30 ℃ for 10h after ultrasonic dispersion, removing the solvent by vacuum drying, placing a solid mixed product in a resistance furnace with the heating rate of 3 ℃/min, heating to 500 ℃, and carrying out heat preservation and calcination for 3h to prepare multi-shell hollow SnO2Nanospheres.
(4) Adding a mixed solvent of ethanol solvent and distilled water into a reaction bottle, wherein the volume ratio of the ethanol solvent to the distilled water is 5:1, adding ammonia water to adjust the pH of the solution to 11, and then adding multi-shell hollow SnO2Uniformly stirring nanospheres and hexadecyl trimethyl ammonium bromide for 8 hours at constant speed after ultrasonic dispersion, and slowly dropwise adding ethyl orthosilicate, wherein the hollow SnO with multiple shell layers2The mass ratio of the nanospheres to the hexadecyl trimethyl ammonium bromide to the ethyl orthosilicate is 100:1:2.5, the mixture is stirred at a constant speed for reaction for 2 hours, a solvent is filtered, a product is washed by distilled water and ethanol and dried, a solid mixed product is placed in a resistance furnace, the heating rate is 15 ℃/min, the calcining temperature is 400 ℃, the calcining time is 6 hours, and the porous SiO is prepared by calcining2Coated multi-shell hollow SnO2The lithium ion battery negative electrode material of (1).
Porous SiO in the examples and comparative examples2Coated multi-shell hollow SnO2The lithium ion battery negative electrode material is placed in an N-pyrrolidone solvent, polyvinylidene fluoride and conductive carbon black are added, slurry is respectively coated on the surface of a copper foil current collector and dried to be used as a working negative electrode of the lithium ion battery, a lithium sheet is used as a working positive electrode, and 1mol/L LiPF6The method comprises the steps of using a solution of diethyl carbonate, dimethyl carbonate and ethylene carbonate as an electrolyte, using a Celgard2400 membrane as a diaphragm, assembling the solution into a CR2025 type button cell in an argon atmosphere, and testing the electrochemical cycling stability performance in a Chenghua CHI760D electrochemical workstation, wherein the test standard is GB/T36276-2018。
Claims (5)
1. Porous SiO2Coated multi-shell hollow SnO2The lithium ion battery cathode material is characterized in that: the porous SiO2Coated multi-shell hollow SnO2The preparation method of the lithium ion battery negative electrode material comprises the following steps:
(1) adding distilled water solvent and glucose into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a reaction kettle device, heating to 180 ℃ and 200 ℃, reacting for 2-4h, filtering, washing and drying to prepare the carbon nanospheres;
(2) adding carbon nanospheres and sodium hydroxide into a distilled water solvent, uniformly dispersing by ultrasonic, heating to 40-80 ℃, stirring and activating for 3-6h, filtering, washing and drying to prepare hydroxyl carbon nanospheres;
(3) adding stannic chloride into distilled water solvent, stirring uniformly, adding hydroxyl carbon nanospheres, stirring for 4-10h at 20-40 ℃ after ultrasonic dispersion is uniform, removing solvent, placing solid mixed product into a resistance furnace, heating up to 480-540 ℃ at the heating rate of 1-3 ℃/min, carrying out heat preservation and calcination for 2-3h, and preparing to obtain multi-shell hollow SnO2Nanospheres;
(4) adding ammonia water into a mixed solvent of ethanol and distilled water with a volume ratio of 8-15:1 to adjust the pH of the solution to 10-11, and then adding multi-shell hollow SnO2Uniformly dispersing nanospheres and hexadecyl trimethyl ammonium bromide by ultrasonic, stirring for 6-12h, dropwise adding ethyl orthosilicate, reacting for 2-6h, filtering, washing and drying, placing a solid mixed product in a resistance furnace, and calcining to obtain porous SiO2Coated multi-shell hollow SnO2The lithium ion battery cathode material.
2. A porous SiO as claimed in claim 12Coated multi-shell hollow SnO2The lithium ion battery cathode material is characterized in that: the reaction kettle device in the step (1) comprises electricityThe machine, motor swing joint have the rotation axis, rotation axis fixedly connected with gear wheel tray, gear wheel tray top is provided with big reation kettle, gear wheel tray pass through tooth and little guide pulley tray swing joint, and little guide pulley tray top is provided with little reation kettle.
3. A porous SiO as claimed in claim 12Coated multi-shell hollow SnO2The lithium ion battery cathode material is characterized in that: the mass ratio of the stannic chloride to the hydroxyl carbon nanospheres in the step (3) is 15-25: 1.
4. A porous SiO as claimed in claim 12Coated multi-shell hollow SnO2The lithium ion battery cathode material is characterized in that: in the step (4), the hollow SnO with multiple shell layers2The mass ratio of the nanospheres, the hexadecyl trimethyl ammonium bromide and the ethyl orthosilicate is 100:2-8: 5-20.
5. A porous SiO as claimed in claim 12Coated multi-shell hollow SnO2The lithium ion battery cathode material is characterized in that: the temperature rise rate of the calcination process in the step (4) is 2-10 ℃/min, the calcination temperature is 450-.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135588A (en) * | 2021-04-19 | 2021-07-20 | 合肥工业大学 | Carbon-coated SnO2Preparation method of hollow nanosphere |
| CN114249348A (en) * | 2021-12-15 | 2022-03-29 | 浙江中金格派锂电产业股份有限公司 | Preparation method of superfine nano lithium lanthanum zirconium oxygen-based solid electrolyte powder |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182032A (en) * | 2007-11-15 | 2008-05-21 | 电子科技大学 | Method for preparing stannic oxide/silica nano composite material |
| CN101510601A (en) * | 2009-03-27 | 2009-08-19 | 广州鸿森材料有限公司 | Method for preparing silicon stannum alloy cathode material of lithium ion battery |
| KR20110112215A (en) * | 2010-04-05 | 2011-10-12 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Negative electrode material for nonaqueous electrolytic secondary battery, process for producing negative electrode material for nonaqueous electrolytic secondary battery, and lithium ion secondary battery |
| CN105932253A (en) * | 2016-06-03 | 2016-09-07 | 广东工业大学 | Lithium ion anode material SiO2@SnO2 with coated structure and preparation method and application thereof |
| CN108321376A (en) * | 2018-02-08 | 2018-07-24 | 合肥工业大学 | A kind of N doping porous carbon nanofiber@tin dioxide lithium ion battery negative pole materials and preparation method thereof |
| CN108767207A (en) * | 2018-04-24 | 2018-11-06 | 合肥国轩高科动力能源有限公司 | High-performance oxide coated nano SnO2Preparation method of negative electrode material |
| CN108807935A (en) * | 2016-11-23 | 2018-11-13 | 清华大学 | Lithium ion battery silicon substrate tinbase composite particles, preparation method, cathode and lithium ion battery comprising it |
| CN109817932A (en) * | 2019-01-29 | 2019-05-28 | 西安航空学院 | One-step method prepares N- and adulterates porous carbon coating SnO2-Co3O4The method and its application of composite material |
| CN111600019A (en) * | 2020-05-20 | 2020-08-28 | 严竹旺 | Nitrogen-doped porous carbon-multi-shell hollow SnS2Lithium ion battery cathode material and preparation method thereof |
-
2020
- 2020-09-25 CN CN202011025985.5A patent/CN112164781A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182032A (en) * | 2007-11-15 | 2008-05-21 | 电子科技大学 | Method for preparing stannic oxide/silica nano composite material |
| CN101510601A (en) * | 2009-03-27 | 2009-08-19 | 广州鸿森材料有限公司 | Method for preparing silicon stannum alloy cathode material of lithium ion battery |
| KR20110112215A (en) * | 2010-04-05 | 2011-10-12 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Negative electrode material for nonaqueous electrolytic secondary battery, process for producing negative electrode material for nonaqueous electrolytic secondary battery, and lithium ion secondary battery |
| CN105932253A (en) * | 2016-06-03 | 2016-09-07 | 广东工业大学 | Lithium ion anode material SiO2@SnO2 with coated structure and preparation method and application thereof |
| CN108807935A (en) * | 2016-11-23 | 2018-11-13 | 清华大学 | Lithium ion battery silicon substrate tinbase composite particles, preparation method, cathode and lithium ion battery comprising it |
| CN108321376A (en) * | 2018-02-08 | 2018-07-24 | 合肥工业大学 | A kind of N doping porous carbon nanofiber@tin dioxide lithium ion battery negative pole materials and preparation method thereof |
| CN108767207A (en) * | 2018-04-24 | 2018-11-06 | 合肥国轩高科动力能源有限公司 | High-performance oxide coated nano SnO2Preparation method of negative electrode material |
| CN109817932A (en) * | 2019-01-29 | 2019-05-28 | 西安航空学院 | One-step method prepares N- and adulterates porous carbon coating SnO2-Co3O4The method and its application of composite material |
| CN111600019A (en) * | 2020-05-20 | 2020-08-28 | 严竹旺 | Nitrogen-doped porous carbon-multi-shell hollow SnS2Lithium ion battery cathode material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| CUI, ZHI-MIN等: "Having it both ways: delicate hierarchical structure and robust mechanical stability on micro/nanomaterials with mesoporous silica coating", 《JOURNAL OF POROUS MATERIALS》 * |
| 王子匀等: "3DOM SnO2-SiO2锂离子电池负极材料的制备及电化学性能", 《功能材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135588A (en) * | 2021-04-19 | 2021-07-20 | 合肥工业大学 | Carbon-coated SnO2Preparation method of hollow nanosphere |
| CN114249348A (en) * | 2021-12-15 | 2022-03-29 | 浙江中金格派锂电产业股份有限公司 | Preparation method of superfine nano lithium lanthanum zirconium oxygen-based solid electrolyte powder |
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