CN112225223B - Si-O-C three-dimensional crosslinked structure nano ring, preparation method and application thereof - Google Patents

Si-O-C three-dimensional crosslinked structure nano ring, preparation method and application thereof Download PDF

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CN112225223B
CN112225223B CN202011112161.1A CN202011112161A CN112225223B CN 112225223 B CN112225223 B CN 112225223B CN 202011112161 A CN202011112161 A CN 202011112161A CN 112225223 B CN112225223 B CN 112225223B
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CN112225223A (en
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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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    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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Abstract

The invention relates to a Si-O-C three-dimensional crosslinked nano-ring material, a preparation method and application thereof. The obtained nano ring has a diameter of 100-500 nm, a wall thickness of 20-100 nm, and a specific surface area of 300-800m 2 And/g, the rings are mutually crosslinked to form a three-dimensional network structure. Firstly, the raw materials are subjected to reduction reaction in a molten salt system of anhydrous chloride at a certain temperature to obtain a pre-product. Then, carrying out acid washing treatment on the pre-product, and carbonizing the pre-product in an inert atmosphere at 500-900 ℃ to obtain a Si-O-C three-dimensional crosslinked nano-ring composite material, wherein the Si-O-C three-dimensional crosslinked nano-ring composite material is used as a lithium ion battery anode material, and the stable lithium storage specific capacity of 50 circles is 1003mAh/g under the current density of 0.2A/g, so that the Si-O-C three-dimensional crosslinked nano-ring composite material has higher discharge specific capacity and good cycle stability; meanwhile, the material is used as an adsorption material to show excellent adsorption performance in methylene blue solution, adsorption balance is achieved in 10 hours, and the maximum adsorption capacity is 235mg/g.

Description

Si-O-C three-dimensional crosslinked structure nano ring, 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 crosslinked 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 a silicon material, but also has the advantages of stable physicochemical properties, excellent conductivity and the like of a carbon material, and has 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. Currently, there have been a number of reports focusing on the structural design of silicon-based composites, such as: the Si/C nanowire, nanosphere, nanotube and various three-dimensional assemblies of the nanomaterial are synthesized by a solvothermal method, molten salt assisted electrolysis and other methods. However, three-dimensional crosslinked structures of cyclic nano Si-O-C have been reported so far.
The annular nano structure is between one-dimensional and two-dimensional materials, and the inner surface and the outer surface can be simultaneously utilized due to the unique structure, so that the specific surface area is large, and the material is expected to be endowed with excellent performance. At present, a series of annular materials including ferroferric oxide, zinc oxide, silicon dioxide and the like are prepared by a physical etching technology and a chemical method. Wherein, the physical etching technology for preparing the nano annular material mainly comprises the following steps: template preparation, filling and template removal processes [ Journal of the American Chemical Society,2004,126,35,10830-10831; angewandte Chemie International Edition,2004,114,39,5350-5354]; the chemical method for preparing the nano-ring material mainly utilizes the physical and chemical properties of the material such as two-phase interfaces [ Advanced Functional Materials,2008,18,24,4036-4042], atomic diffusion [ Journal of the American Chemical Society,2008,130,50,16968-16977] and the like to prepare the ring nano-structure. However, the preparation process is complex whether a physical etching technology or the most commonly used solvothermal method for preparing the nano-ring material is adopted. It is difficult to mass-produce, and the resulting nanocycles are often monodisperse structures that cannot form three-dimensional crosslinks.
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 nano ring and a preparation method and application thereof, wherein the Si-O-C nano ring is characterized in that:
the Si-O-C nano ring obtained by the invention has the outer diameter of 100-500 nanometers, the wall thickness of 20-100 nanometers and the specific surface area of 300-800m 2 And/g, the nano rings are mutually crosslinked to form a three-dimensional network structure.
The preparation method of the Si-O-C three-dimensional crosslinked structure nano ring comprises the following steps: (1) The raw materials, the reducing agent and the chloride are put into a high-temperature high-pressure reaction kettle according to a certain proportion under the inert atmosphere condition, fully react at 200-500 ℃, and remove reaction byproducts by utilizing a dilute hydrochloric acid solution to obtain a pre-product; (2) Heating the pre-product obtained in the step (1) to 500-900 ℃ in a tube furnace under inert atmosphere, and preserving heat for 2-6h to obtain the Si-O-C three-dimensional crosslinked structure nano-ring composite material.
The raw materials are one of octaphenyl silsesquioxane, dodecaphenyl silsesquioxane, trapezoidal phenyl silsesquioxane, methyl silicone oil, phenyl trimethoxy silane and phenyl trichlorosilane.
The reducing agent is one of metal aluminum powder and metal magnesium powder.
The chloride salt 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 crosslinked nano ring as a negative electrode material of a lithium ion battery, an adsorption material and the like.
The molten salt low-temperature auxiliary reduction method can effectively control the speed of the metal thermal reduction reaction so as to control the morphology characteristics of the final product. The formation process of the Si-O-C three-dimensional crosslinked nano ring in the fused salt reduction process is as follows: (1) Under the low temperature condition, the reduction reaction activity of magnesium metal or aluminum metal is reduced, and the reduction speed of the magnesium metal or aluminum metal on silicon dioxide and other silicon compounds is reduced, so that a cavity is gradually formed in the initial raw material silsesquioxane; (2) As the reduction reaction proceeds, the internal cavity gradually increases and breaks, and gradually contracts into a ring under the action of surface force so as to minimize the surface energy of the system; (3) With increasing reduction time and increasing carbonization temperature, the diameter and wall thickness of the ring structure increase significantly.
The Si-O-C three-dimensional crosslinked nano-ring composite material prepared by the low-temperature molten salt assisted 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 crushing and pulverization of the material caused by the stress, and improve the circulating stability of the material. The coating structure of amorphous carbon can further relieve the volume expansion of SiOx, and can improve the conductivity of the material so as to improve the cycle stability and the rate performance of the material. The test shows that when the Si-O-C three-dimensional crosslinked nano-ring composite material is used as a lithium ion battery anode material, the mass specific capacity of the Si-O-C three-dimensional crosslinked nano-ring composite material is 1400mA h/g under the current density of 200mA/g, and the Si-O-C three-dimensional crosslinked nano-ring composite material still maintains the specific capacity of 1000mA h/g after 100 circles of circulation, and the Si-O-C three-dimensional crosslinked nano-ring composite material has good circulation stability. And at the same time, the adsorption material shows excellent adsorption effect when used as an adsorption material. Therefore, the invention also provides application of the Si-O-C three-dimensional crosslinked nano-ring composite material prepared by the method as a negative electrode material, an adsorption material and the like of a lithium ion battery.
The invention prepares a composite material with Si-O-C three-dimensional crosslinking nano-rings by using a low-temperature molten salt assisted reduction method. The preparation process has simple technological flow, and the prepared material has stable performance.
Drawings
Fig. 1 is a scanning electron microscope image of S1.
Fig. 2 is a charge-discharge curve of S1.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples, but the present invention is not limited to the following examples.
Example 1
Dodecyl silsesquioxane, aluminum powder and aluminum trichloride were mixed according to a ratio of 1:1:10, loading the mixture into a high-temperature high-pressure reaction kettle in an inert atmosphere, preserving the temperature at 300 ℃ for 30 hours, taking out the mixture, and removing byproducts by using a hydrochloric acid dilute solution to obtain a pre-product. And (3) preserving the pre-product at 800 ℃ for 2 hours in an inert atmosphere to obtain a product S1. The adsorption test result shows that: s1 shows excellent adsorption effect in methylene blue solution, and reaches equilibrium after 10 hours, and the maximum adsorption amount is 235mg/g.
As shown in a scanning electron microscope chart of figure 1, the obtained product S1 is a three-dimensional structure formed by cross-linking of annular SiOx/C composite materials, wherein the diameter of SiOx/C nano-rings is 150 nanometers, and the wall thickness is 50 nanometers.
As shown in an electrochemical test structure of the lithium ion battery in the attached figure 2, the mass specific capacity of the product S1 is 1900.1mA h/g under the current density of 0.2A/g, the specific capacity of 1003.7mA h/g is still maintained after 50 circles of circulation, and the capacity retention rate is more than 52%.
Example 2
Octaphenyl silsesquioxane, aluminum powder and ferric trichloride were mixed according to a ratio of 1:1:10, loading the mixture into a high-temperature high-pressure reaction kettle in an inert atmosphere, preserving the temperature at 450 ℃ for 30 hours, taking out the mixture, and removing byproducts by using a hydrochloric acid dilute solution to obtain a pre-product. And (3) preserving the pre-product at 800 ℃ for 2 hours in an inert atmosphere to obtain a product S2.
The diameter of S2 is measured to be 300 nanometers and the wall thickness is measured to be 90 nanometers. At a current density of 0.2A/g, the mass specific capacity of S2 is 1830.5mA h/g, and the specific capacity of 1050.8mA h/g is still maintained after 50 circles of circulation.
Example 3
Methyl silicone oil, aluminum powder and aluminum trichloride according to a ratio of 1:1:10, loading the mixture into a high-temperature high-pressure reaction kettle in an inert atmosphere, preserving the temperature at 350 ℃ for 15 hours, taking out the mixture, and removing byproducts by using a dilute hydrochloric acid solution to obtain a pre-product. And (3) preserving the pre-product at 800 ℃ for 2 hours in an inert atmosphere to obtain a product S3.
The diameter of S3 is measured to be 100 nanometers and the wall thickness is measured to be 30 nanometers. At a current density of 0.2A/g, the mass specific capacity of S3 is 1833.6mA h/g, and the specific capacity of 996.8mA h/g is still maintained after 50 circles of circulation.
Example 4
Phenyl trimethoxysilane, aluminum powder, aluminum trichloride and sodium chloride were mixed according to a ratio of 1:1:5:5, loading the mixture into a high-temperature high-pressure reaction kettle in an inert atmosphere, preserving the temperature at 400 ℃ for 20 hours, taking out the mixture, and removing byproducts by using a hydrochloric acid dilute solution to obtain a pre-product. And (3) preserving the pre-product at 800 ℃ for 2 hours in an inert atmosphere to obtain a product S4.
The diameter of S4 is measured to be 200 nanometers and the wall thickness is measured to be 50 nanometers. At a current density of 0.2A/g, the mass specific capacity of S4 is 1850.6mA h/g, and the specific capacity of 972.7mA h/g is still maintained after 50 circles of circulation.
Example 5
Octaphenyl silsesquioxane, magnesium powder, aluminum trichloride and sodium chloride were mixed according to a ratio of 1:1:5:5, loading the mixture into a high-temperature high-pressure reaction kettle in an inert atmosphere, preserving the temperature at 200 ℃ for 10 hours, taking out the mixture, and removing byproducts by using a hydrochloric acid dilute solution to obtain a pre-product. And (3) preserving the pre-product at 800 ℃ for 2 hours in an inert atmosphere to obtain a product S5.
The diameter of S5 is measured to be 500 nanometers, and the wall thickness is measured to be 100 nanometers. At a current density of 0.2A/g, the mass specific capacity of S5 is 2001.8mA h/g, and the specific capacity of 1302.5mA h/g is still maintained after 50 circles of circulation.
Example 6
Phenyl trichlorosilane, aluminum powder, aluminum trichloride and zinc chloride are mixed according to the following ratio of 1:1:5:5, loading the mixture into a high-temperature high-pressure reaction kettle in an inert atmosphere, preserving the temperature at 300 ℃ for 20 hours, taking out the mixture, and removing byproducts by using a dilute hydrochloric acid solution to obtain a pre-product. And (3) preserving the pre-product at 800 ℃ for 2 hours in an inert atmosphere to obtain a product S6.
The diameter of S6 is measured to be 500 nanometers, and the wall thickness is measured to be 100 nanometers. At a current density of 0.2A/g, the mass specific capacity of S6 is 1300.2mA h/g, and the specific capacity of 682.9mA h/g is still maintained after 50 circles of circulation.
While the preferred embodiments of the present invention have been illustrated and described, the present invention is not limited to the embodiments, and various equivalent modifications and substitutions can be made by one skilled in the art without departing from the spirit of the present invention, and these equivalent modifications and substitutions are intended to be included in the scope of the present invention as defined in the appended claims.

Claims (3)

1. A nano ring with a Si-O-C three-dimensional cross-linked structure is characterized in that: the diameter of the nano ring is 100-500 nanometers, the wall thickness is 20-100 nanometers, and the specific surface area is 300-800m 2 Between/g, the rings cross-link with each other to form a three-dimensional network structure.
2. The method for preparing the nano-ring with the Si-O-C three-dimensional cross-linked structure according to claim 1, which is characterized by comprising the following steps:
step one: uniformly mixing raw materials, reducing agent magnesium powder or aluminum powder and chloride salt according to a certain proportion, loading the mixture into a high-temperature high-pressure reaction kettle under the inert atmosphere condition, fully reacting at 200-450 ℃, and removing byproducts by utilizing hydrochloric acid solution to obtain a pre-product; the raw materials are one of octaphenyl silsesquioxane, dodecaphenyl silsesquioxane, trapezoidal phenyl silsesquioxane, methyl silicone oil, phenyl trimethoxysilane and phenyl trichlorosilane; the chloride salt is one or more of aluminum trichloride, zinc chloride, ferric trichloride, sodium chloride and calcium chloride;
step two: and (3) placing the pre-product obtained in the step (I) into a high-temperature carbonization furnace, heating to 500-900 ℃ in an inert atmosphere, and preserving heat for 3-6 hours to obtain the Si-O-C three-dimensional crosslinked structure nano ring.
3. An application of the Si-O-C three-dimensional crosslinked structure nano ring disclosed in claim 1 or the Si-O-C three-dimensional crosslinked structure nano ring prepared by the method disclosed in claim 2 in the fields of negative electrode materials and adsorption materials of lithium ion batteries.
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CN112234181B (en) * 2020-10-27 2021-09-14 合肥工业大学 Two-dimensional silicon oxide/carbon composite lithium ion battery cathode material and preparation method thereof
CN113753904B (en) * 2021-10-11 2023-02-28 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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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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