CN112225223A - Si-O-C three-dimensional cross-linked structure nanoring, preparation method and application thereof - Google Patents

Si-O-C three-dimensional cross-linked structure nanoring, preparation method and application thereof Download PDF

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CN112225223A
CN112225223A CN202011112161.1A CN202011112161A CN112225223A CN 112225223 A CN112225223 A CN 112225223A CN 202011112161 A CN202011112161 A CN 202011112161A CN 112225223 A CN112225223 A CN 112225223A
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宋怀河
林谢吉
李昂
陈晓红
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Beijing University of Chemical Technology
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Abstract

The invention relates to a Si-O-C three-dimensional crosslinking nano-ring material, a preparation method and application thereof. The diameter of the obtained nano ring is 100-500 nm, the wall thickness is 20-100 nm, and the specific surface area is 300-800m2And/g, the rings are mutually crosslinked to form a three-dimensional network structure. Firstly, the raw materials are reduced at a certain temperature in a molten salt system of anhydrous chloride saltThe pre-product is obtained by the original reaction. Then carrying out acid cleaning treatment on the pre-product, carrying out carbonization treatment in inert atmosphere at 500-900 ℃ to obtain a Si-O-C three-dimensional cross-linked nano-ring composite material, and taking the material as a lithium ion battery negative electrode material, wherein the lithium storage specific capacity of 50 cycles of circulation is stable and reaches 1003mAh/g under the current density of 0.2A/g, and the material has higher specific discharge capacity and good circulation stability; meanwhile, the adsorbent material has excellent adsorption performance in methylene blue solution, the adsorption balance is achieved within 10 hours, and the maximum adsorption capacity is 235 mg/g.

Description

Si-O-C three-dimensional cross-linked structure nanoring, preparation method and application thereof
Technical Field
The invention relates to the field of nano materials and preparation, in particular to a Si-O-C three-dimensional cross-linked structure nano ring, a preparation method and application thereof.
Background
The silicon-based (Si-C, Si-O-C) composite material not only has the characteristics of environment friendliness, abundant reserves and the like of the silicon material, but also has the advantages of stable physical and chemical properties, excellent conductivity and the like of the carbon material, and shows great application potential in the fields of separation, adsorption, catalysis, electrochemical energy storage, conversion and the like. The properties of materials often depend on the structure and composition of the material, with structural factors being particularly important for nanomaterials. At present, there are a number of reports focusing on the structural design of silicon-based composites, such as: the Si/C nano-wire, the nano-sphere, the nano-tube and various three-dimensional assemblies thereof and other nano-materials are synthesized by a solvothermal method, a molten salt auxiliary electrolysis method and other methods. However, the three-dimensional cross-linked structure of the cyclic nano Si-O-C has been reported so far.
The annular nano structure is between one-dimensional and two-dimensional materials, and due to the unique structure, the inner surface and the outer surface can be simultaneously utilized, so that the specific surface area is large, and the material is expected to have excellent performance. At present, a series of annular materials are prepared by a physical etching technology and a chemical method, and comprise ferroferric oxide, zinc oxide, silicon dioxide and the like. The preparation of the nano annular material by the physical etching technology mainly comprises the following steps: template preparation, filling and removing of template [ Journal of the American Chemical Society,2004,126,35, 10830-; angewandte Chemie International Edition,2004,114,39, 5350-; the Chemical method for preparing the nano ring-shaped material mainly utilizes the physicochemical properties of the material such as two-phase interfaces [ Advanced Functional Materials,2008,18,24, 4036-. However, the physical etching technology or the most commonly adopted solvothermal method for preparing the nano-ring material has a complex preparation process. It is difficult to mass-produce, and the resulting nanorings are often monodisperse structures that cannot be three-dimensionally crosslinked.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a Si-O-C three-dimensional cross-linked structure nanoring and a preparation method and application thereof, wherein the Si-O-C nanoring is characterized by comprising the following steps:
the Si-O-C nano ring obtained by the invention has the outer diameter of 100-500 nm, the wall thickness of 20-100 nm and the specific surface area of 300-800m2And/g, the nanorings are mutually crosslinked to form a three-dimensional network structure.
The preparation method of the Si-O-C three-dimensional crosslinking structure nano-ring comprises the following steps: (1) the raw materials, a reducing agent and chloride are loaded into a high-temperature high-pressure reaction kettle according to a certain proportion under the condition of inert atmosphere, the reaction is fully carried out at the temperature of 200 ℃ and 500 ℃, and a reaction by-product is removed by using a dilute hydrochloric acid solution to obtain a pre-product; (2) and (2) heating the pre-product obtained in the step (1) to 900 ℃ in a tubular furnace under inert atmosphere, and preserving heat for 2-6h to obtain the Si-O-C three-dimensional cross-linked structure nano-ring composite material.
The raw material is one of octaphenyl silsesquioxane, dodecaphenyl silsesquioxane, trapezoidal phenyl silsesquioxane, methyl silicone oil, phenyl trimethoxysilane and phenyl trichlorosilane.
The reducing agent is one of metal aluminum powder and metal magnesium powder.
The chloride is one or more of aluminum trichloride, zinc chloride, ferric trichloride, sodium chloride, calcium chloride and the like.
In addition, the invention also provides application of the Si-O-C three-dimensional cross-linked nanoring as a lithium ion battery cathode material, an adsorption material and other fields.
By using the method of molten salt low-temperature auxiliary reduction, the speed of the metallothermic reduction reaction can be effectively controlled to control the morphological characteristics of the final product. The formation process of the Si-O-C three-dimensional crosslinking nanoring in the molten salt reduction process is as follows: (1) under the condition of low temperature, the reduction reaction activity of metal magnesium or aluminum is reduced, and the reduction speed of the metal magnesium or aluminum on silicon oxide compounds such as silicon dioxide is reduced, so that a cavity is gradually formed inside the initial raw material silsesquioxane; (2) along with the reduction reaction, the internal cavity is gradually enlarged and cracked, and gradually shrinks into a ring under the action of surface force so as to ensure that the surface energy of the system is minimum; (3) the diameter and wall thickness of the ring structure increase significantly with increasing reduction time and increasing carbonization temperature.
The Si-O-C three-dimensional cross-linked nano-ring composite material prepared by the low-temperature molten salt auxiliary reduction method can be used as a negative electrode material, a functional ceramic material, an adsorption material and the like of a lithium ion battery. The volume effect of the Si-O-C with the annular structure in the circulating process mainly occurs in the radial direction, and the unique annular structure can effectively relieve the problems of stress and the like caused by the volume effect so as to inhibit the problem of material crushing and pulverization caused by the stress and improve the circulating stability of the material. The amorphous carbon coating structure can further relieve the volume expansion of SiOx, and can improve the conductivity of the material so as to improve the cycle stability and rate capability of the material. Tests show that when the Si-O-C three-dimensional cross-linked nanoring composite material is used as a lithium ion battery cathode material, the specific mass capacity of the Si-O-C three-dimensional cross-linked nanoring composite material is 1400mA h/g under the current density of 200mA/g, and the Si-O-C three-dimensional cross-linked nanoring composite material still maintains the specific capacity of 1000mA h/g after being circulated for 100 circles, so that good circulation stability is shown. Meanwhile, the adsorbent is used as an adsorbing material and shows excellent adsorbing effect. Therefore, the invention also provides the application of the Si-O-C three-dimensional crosslinking nano-ring composite material prepared by the method as a lithium ion battery cathode material, an adsorption material and the like.
The invention utilizes a method of low-temperature molten salt auxiliary reduction to prepare a composite material with Si-O-C three-dimensional crosslinking nanorings. The preparation process is simple in process flow, and the prepared material is stable in performance.
Drawings
Fig. 1 is a scanning electron micrograph of S1.
Fig. 2 is a charge and discharge curve of S1.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, but the present invention is not limited to the following examples.
Example 1
Mixing dodecaphenyl silsesquioxane, aluminum powder and aluminum trichloride according to the weight ratio of 1: 1: 10 in inert atmosphere, placing the mixture into a high-temperature high-pressure reaction kettle, preserving the heat at 300 ℃ for 30 hours, taking the mixture out, and removing by-products by using a dilute hydrochloric acid solution to obtain a pre-product. And (3) preserving the temperature of the pre-product at 800 ℃ for 2h in an inert atmosphere to obtain a product S1. The adsorption test results show that: s1 shows excellent adsorption effect in methylene blue solution, the adsorption reaches balance after 10 hours, and the maximum adsorption amount is 235 mg/g.
As shown in the scanning electron microscope image of the attached figure 1, the obtained product S1 is a three-dimensional structure formed by mutual crosslinking of annular SiOx/C composite materials, wherein the diameter of the SiOx/C nanoring is 150 nm, and the wall thickness is 50 nm.
As shown in an electrochemical test structure of the lithium ion battery shown in the attached figure 2, the product S1 has a specific mass capacity of 1900.1mA h/g under a current density of 0.2A/g, and after circulating for 50 circles, the product S1 still maintains a specific capacity of 1003.7mA h/g, and the capacity retention rate is more than 52%.
Example 2
Mixing octaphenyl silsesquioxane, aluminum powder and ferric trichloride according to the proportion of 1: 1: 10 in inert atmosphere, placing the mixture into a high-temperature high-pressure reaction kettle, preserving the heat at 450 ℃ for 30 hours, taking the mixture out, and removing by-products by using a dilute hydrochloric acid solution to obtain a pre-product. And (3) preserving the temperature of the pre-product at 800 ℃ for 2h in an inert atmosphere to obtain a product S2.
The diameter of S2 was found to be 300 nm, and the wall thickness was found to be 90 nm. Under the current density of 0.2A/g, the specific capacity of S2 is 1830.5mA h/g, and the specific capacity of 1050.8mA h/g can be maintained after 50 cycles of circulation.
Example 3
And (2) mixing methyl silicone oil, aluminum powder and aluminum trichloride according to the proportion of 1: 1: 10 in inert atmosphere, placing the mixture into a high-temperature high-pressure reaction kettle, preserving the heat at 350 ℃ for 15 hours, taking the mixture out, and removing by-products by using a dilute hydrochloric acid solution to obtain a pre-product. And (3) preserving the temperature of the pre-product at 800 ℃ for 2h in an inert atmosphere to obtain a product S3.
The diameter of S3 was measured to be 100 nm and the wall thickness to 30 nm. Under the current density of 0.2A/g, the specific capacity of S3 is 1833.6mA h/g, and the specific capacity of 996.8mA h/g can be maintained after 50 cycles of circulation.
Example 4
Mixing phenyl trimethoxy silane, aluminum powder, aluminum trichloride and sodium chloride according to the weight ratio of 1: 1: 5: 5 in inert atmosphere, placing the mixture into a high-temperature high-pressure reaction kettle, preserving the heat at 400 ℃ for 20 hours, taking the mixture out, and removing by-products by using a dilute hydrochloric acid solution to obtain a pre-product. And (3) preserving the temperature of the pre-product at 800 ℃ for 2h in an inert atmosphere to obtain a product S4.
The diameter of S4 was measured to be 200 nm and the wall thickness 50 nm. Under the current density of 0.2A/g, the specific capacity of S4 is 1850.6mA h/g, and the specific capacity of 972.7mA h/g can be maintained after 50 cycles of circulation.
Example 5
Octaphenyl silsesquioxane, magnesium powder, aluminum trichloride and sodium chloride were mixed in a ratio of 1: 1: 5: 5 in inert atmosphere, putting the mixture into a high-temperature high-pressure reaction kettle, preserving the heat at 200 ℃ for 10 hours, taking the mixture out, and removing by-products by using a dilute hydrochloric acid solution to obtain a pre-product. And (3) preserving the temperature of the pre-product at 800 ℃ for 2h in an inert atmosphere to obtain a product S5.
The diameter of S5 was measured to be 500 nm and the wall thickness to 100 nm. Under the current density of 0.2A/g, the specific capacity of S5 is 2001.8mA h/g, and the specific capacity of 1302.5mA h/g can be maintained after 50 cycles of circulation.
Example 6
Phenyl trichlorosilane, aluminum powder, aluminum trichloride and zinc chloride are mixed according to the proportion of 1: 1: 5: 5 in inert atmosphere, placing the mixture into a high-temperature high-pressure reaction kettle, preserving the heat at 300 ℃ for 20 hours, taking the mixture out, and removing by-products by using a dilute hydrochloric acid solution to obtain a pre-product. And (3) preserving the temperature of the pre-product at 800 ℃ for 2h in an inert atmosphere to obtain a product S6.
The diameter of S6 was measured to be 500 nm and the wall thickness to 100 nm. Under the current density of 0.2A/g, the specific capacity of S6 is 1300.2mA h/g, and the specific capacity of 682.9mA h/g can be maintained after 50 cycles of circulation.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (6)

1. An SiOx/C nanoring, characterized in that: the diameter is 100-500 nm, the wall thickness is 20-100 nm, and the specific surface area is 300-800m2Between/g, the rings are cross-linked to form a three-dimensional network structure.
2. The Si-O-C three-dimensional cross-linked structure nanoring, the preparation method and the application thereof as claimed in claim 1 are characterized in that the method comprises the following steps:
the method comprises the following steps: uniformly mixing the raw materials, a reducing agent and chloride according to a certain proportion, loading the mixture into a high-temperature high-pressure reaction kettle under the condition of inert atmosphere, fully reacting at the temperature of 200-450 ℃, and removing by-products by using a hydrochloric acid solution to obtain a pre-product;
step two: and (3) putting the pre-product obtained in the step one into a high-temperature carbonization furnace, heating to 500-900 ℃ under an inert atmosphere, and preserving heat for 3-6 hours to obtain the Si-O-C three-dimensional cross-linked structure nanoring.
3. A Si-O-C three-dimensional cross-linked structure nanoring and a method for preparing the same according to claims 1 and 2, wherein: the raw material is one of octaphenyl silsesquioxane, dodecaphenyl silsesquioxane, trapezoidal phenyl silsesquioxane, methyl silicone oil, phenyl trimethoxysilane and phenyl trichlorosilane.
4. A Si-O-C three-dimensional cross-linked structure nanoring and a method for preparing the same according to claims 1 and 2, wherein: the reducing agent is one of magnesium powder and aluminum powder.
5. A Si-O-C three-dimensional cross-linked structure nanoring and a method for preparing the same according to claims 1 and 2, wherein: the chloride is one or more of aluminum trichloride, zinc chloride, ferric trichloride, sodium chloride, calcium chloride and the like.
6. Use of the Si-O-C three-dimensional cross-linked structure nanoring material prepared by the method of claims 1 to 5.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN112234181A (en) * 2020-10-27 2021-01-15 合肥工业大学 Two-dimensional silicon oxide/carbon composite lithium ion battery cathode material and preparation method thereof
CN113753904A (en) * 2021-10-11 2021-12-07 安徽大学 Porous silicon dioxide nanoring and preparation method thereof
CN116081627A (en) * 2023-02-15 2023-05-09 盐城工学院 In-situ liquid phase preparation method of porous SiOx@C composite material

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CN111470486A (en) * 2020-04-14 2020-07-31 陕西煤业化工技术研究院有限责任公司 Three-dimensional silicon-carbon composite negative electrode material, preparation method thereof and application thereof in lithium ion battery

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US3535092A (en) * 1968-06-14 1970-10-20 Gen Electric Reduction of halogen-containing silicon compounds
JP2004203683A (en) * 2002-12-25 2004-07-22 Catalysts & Chem Ind Co Ltd Method of manufacturing silica-based fine particle and base material with coating film containing the silica-based fine particle
CN101200283A (en) * 2007-12-14 2008-06-18 天津理工大学 Simple method for preparing large-area metal or metal-oxide nano ring
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112234181A (en) * 2020-10-27 2021-01-15 合肥工业大学 Two-dimensional silicon oxide/carbon composite lithium ion battery cathode material and preparation method thereof
CN113753904A (en) * 2021-10-11 2021-12-07 安徽大学 Porous silicon dioxide nanoring and preparation method thereof
CN116081627A (en) * 2023-02-15 2023-05-09 盐城工学院 In-situ liquid phase preparation method of porous SiOx@C composite material
CN116081627B (en) * 2023-02-15 2024-06-25 盐城工学院 In-situ liquid phase preparation method of porous SiOx@C composite material

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