CN116462178B - Preparation method and application of functional silicon-carbon composite material - Google Patents
Preparation method and application of functional silicon-carbon composite material Download PDFInfo
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- CN116462178B CN116462178B CN202310463030.5A CN202310463030A CN116462178B CN 116462178 B CN116462178 B CN 116462178B CN 202310463030 A CN202310463030 A CN 202310463030A CN 116462178 B CN116462178 B CN 116462178B
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Abstract
The invention discloses a preparation method and application of a functional silicon-carbon composite material, and relates to the technical field of energy storage materials. When the functionalized silicon-carbon composite material is prepared, firstly, tetraallyloxysilane and terminal phthalic anhydride polyacrylonitrile are mixed to obtain a primary mixed material; mixing the primary mixed material and the composite graphene oxide to obtain a secondary mixed material; mixing the re-mixed material with foaming agent urea to obtain a silicon-carbon composite material blank; then sequentially carrying out primary heating, secondary heating and tertiary heating on the silicon-carbon composite material blank to prepare a functional silicon-carbon composite material; the composite graphene oxide is prepared by mixing nickel chloride, 3-aminophthalic anhydride and graphene oxide; the functional silicon-carbon composite material prepared by the method is applied to the field of batteries, and has strong toughness and cyclical stability.
Description
Technical Field
The invention relates to the technical field of energy storage materials, in particular to a preparation method and application of a functional silicon-carbon composite material.
Background
The lithium ion battery has the advantages of large specific energy, high working voltage, good safety, small environmental pollution and the like, and has wide application prospect in the fields of various portable electronic devices, electric automobiles, new energy storage and the like. Generally, the negative electrode material is used as a main body for storing lithium in a lithium ion battery, and is a key for improving the specific capacity, the circularity, the charge and discharge performance and other related performances of the lithium ion battery. The current commercial cathode material is mainly a traditional carbon material mainly comprising graphite, and the specific capacity of the graphite theory is only 372mAh/g, so that the further improvement of the total specific capacity of the lithium ion battery is greatly limited. Therefore, development of a novel anode material having a high specific capacity is very urgent.
Silicon is considered to be the most potential new generation of high capacity lithium ion battery anode materials, and compared with traditional graphite anode materials, silicon has extremely high mass specific capacity which is more than ten times that of natural graphite. The bulk density of silicon in the alloy material is similar to that of lithium, so that the silicon also has high volume specific capacity; unlike graphite material, the high specific capacity of silicon is derived from the alloying process of silicon lithium, so that the silicon anode material and the electrolyte cannot be subjected to solvent co-intercalation, and the application range of the electrolyte is wider; compared with the carbon material, the silicon has higher lithium-removing potential, can effectively avoid precipitation of lithium in the high-rate charge and discharge process, and can improve the safety of the battery. However, due to the volume expansion of silicon, the structure of the silicon can be damaged in the charge and discharge process, so that the active material falls off from the current collector, and an irreversible electrolyte membrane is continuously formed, and finally, the low reversible capacity, poor cycle stability and poor rate capability of the silicon anode material are caused.
Graphene is used as a novel carbon nanomaterial, and a single-layer sp2 carbon atom is closely stacked to form a two-dimensional honeycomb structure. Researches show that graphene has excellent electrical and mechanical properties and high theoretical specific surface area, and the characteristics determine great application potential in the field of lithium ion batteries, and many researchers have developed researches on improving electrochemical properties of lithium ion electrode materials by utilizing graphene compounding. In the prior art, graphene is added and foaming is combined to increase the specific surface area to prepare the silicon-carbon composite material, so that the problems of low reversible capacity, poor circulation stability, poor multiplying power performance and the like of the silicon anode material are solved, however, the graphene and the silicon anode material are extremely easy to adhere and even peel off due to foaming, the mechanical property and the circulation stability of the silicon-carbon composite material are greatly reduced, and the service life of the silicon-carbon composite material is greatly influenced.
Therefore, a preparation method and application of a functionalized silicon-carbon composite material are needed to solve the problem.
Disclosure of Invention
The invention aims to provide a preparation method and application of a functionalized silicon-carbon composite material, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation method of the functional silicon-carbon composite material comprises the following preparation steps:
(1) Mixing tetraallyloxy silane and terminal phthalic anhydride polyacrylonitrile to obtain a primary mixed material;
(2) Mixing the primary mixed material and the composite graphene oxide to obtain a secondary mixed material;
(3) Mixing the re-mixed material with foaming agent urea to obtain a silicon-carbon composite material blank;
(4) And sequentially carrying out primary heating, secondary heating and tertiary heating on the silicon-carbon composite material blank to prepare the functional silicon-carbon composite material.
Further, the preparation method comprises the following preparation steps:
(1) Under the protection of argon, the tetraallyloxy silane, the terminal phthalic anhydride polyacrylonitrile and the dimethylformamide are mixed according to the mass ratio of 1:10: 30-1: 30:50, mixing, stirring for 2-4 hours at the speed of 1200-1400 r/min, then adding an initiator with the mass of 0.01-0.03 times that of the tetraallyloxy silane, heating to 60-80 ℃, and continuously stirring for 3-5 hours to prepare a primary mixed material;
(2) Mixing the primary materials and the composite graphene oxide according to a mass ratio of 1: 0.2-1: 0.4, mixing, and stirring for 30-50 min at 3400-3800 r/min to prepare a remixed material;
(3) Mixing the materials, urea and ammonium molybdate according to the mass ratio of 1:11: 0.5-1: 13:0.7, mixing, and stirring for 30-50 min at 3400-3800 r/min to prepare a silicon-carbon composite material blank;
(4) And sequentially carrying out primary heating, secondary heating and tertiary heating on the silicon-carbon composite material blank to prepare the functional silicon-carbon composite material.
Further, the preparation method of the phthalic anhydride-terminated polyacrylonitrile in the step (1) comprises the following steps: at room temperature, acrylonitrile and dimethylformamide are mixed according to the mass ratio of 1: 10-1: 30, stirring for 20-40 min at 600-800 r/min, and then, according to the mass ratio of 1: 0.01-1: and 0.03 of 4- (1-propynyl) phthalic anhydride and cumene peroxide are added, wherein the mass of the 4- (1-propynyl) phthalic anhydride is 0.036-0.038 times that of acrylonitrile, the temperature is raised to 60-80 ℃, and stirring is continued for 2-4 hours, so that the terminal phthalic anhydride polyacrylonitrile is prepared.
Further, the initiator in the step (1) adopts cumene peroxide.
Further, the preparation method of the composite graphene oxide in the step (2) comprises the following steps: the method comprises the steps of (1) mixing graphene oxide with 60-80% of nickel chloride aqueous solution according to the mass ratio of 1: 10-1: 30, mixing, stirring for 30-50 min at 3400-3800 r/min, standing, baking for 2-3 days at 20-40 ℃ under the protection of nitrogen, and then adding into a 3-aminophthalic anhydride mixed solution with the mass 10-30 times of that of graphene oxide, wherein the mass ratio of 3-aminophthalic anhydride to 10% sodium hydroxide solution in the 3-aminophthalic anhydride mixed solution is 1: 2.8-1: 3.2.
Further, the heating temperature of the primary heating in the step (4) is controlled to be 160-180 ℃, and the heating time is 4-6 min.
Further, the heating temperature of the secondary heating in the step (4) is controlled to be 200-300 ℃, and the heating time is 110-130 min.
Further, the heating temperature of the three times of heating in the step (4) is controlled to be 800-1000 ℃, and the heating time is 10-20 min.
Further, in the step (4), the primary heating, the secondary heating and the tertiary heating are all performed under the argon protection condition and the pressure of 20-50 Pa.
Further, the application of the functionalized silicon-carbon composite material is that the application field of the functionalized silicon-carbon composite material comprises a battery cathode.
Compared with the prior art, the invention has the following beneficial effects:
When the functionalized silicon-carbon composite material is prepared, firstly, tetraallyloxysilane and terminal phthalic anhydride polyacrylonitrile are mixed to obtain a primary mixed material; mixing the primary mixed material and the composite graphene oxide to obtain a secondary mixed material; mixing the re-mixed material with foaming agent urea to obtain a silicon-carbon composite material blank; then sequentially carrying out primary heating, secondary heating and tertiary heating on the silicon-carbon composite material blank to prepare a functional silicon-carbon composite material; the composite graphene oxide is prepared by mixing nickel chloride, 3-aminophthalic anhydride and graphene oxide.
The preparation method comprises the steps of reacting and grafting the tetraallyloxysilane and unsaturated carbon groups on the phthalic anhydride polyacrylonitrile, wrapping a layer of phthalic anhydride polyacrylonitrile on the surface of a silicon atom, adding composite graphene oxide, mixing, quickly immersing the composite graphene oxide into the phthalic anhydride polyacrylonitrile by means of surface phthalic anhydride, moving among molecular chains of the phthalic anhydride polyacrylonitrile, lubricating the molecular chains of the phthalic anhydride polyacrylonitrile, and uniformly dispersing the composite graphene oxide into the phthalic anhydride polyacrylonitrile, so that the toughness of the phthalic anhydride polyacrylonitrile is enhanced.
Then adding urea as a foaming agent for primary heating, decomposing urea to form a large amount of ammonia gas after primary heating, wherein part of ammonia gas escapes from the surface defect of the composite graphene oxide, part of ammonia gas escapes from gaps between the composite graphene oxide and the end phthalic anhydride polyacrylonitrile, a large amount of micropores are formed in the end phthalic anhydride polyacrylonitrile while a large amount of uniform pores are formed in the end phthalic anhydride polyacrylonitrile, so that a large amount of graphene oxide falls off, the cyclic stability of the functionalized silicon-carbon composite material is reduced, then rapidly heating for secondary heating, reacting part of non-decomposed urea with phthalic anhydride, nickel chloride and phthalic anhydride of the end phthalic anhydride polyacrylonitrile in the composite graphene oxide, forming a phthalocyanine nickel conjugated microporous compound between the graphene oxide and the end phthalic anhydride polyacrylonitrile, carbonizing after tertiary heating, and forming a carbon layer containing a large amount of uniformly dispersed pore channels on the surface of each silicon atom, thereby further enhancing the cyclic stability and toughness of the functionalized silicon-carbon composite material.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the method for testing each index of the functionalized silicon-carbon composite material prepared in the following examples is as follows:
Cycle stability test: the functionalized silicon-carbon composite material and the conductive agent acetylene black prepared in the examples and the comparative example are prepared from polyvinylidene fluoride according to the mass ratio of 80:10:10, adding a proper amount of NMP, and stirring for 12 hours by using a magnetic stirrer to obtain battery slurry; uniformly coating the slurry on copper foil, naturally drying in air, transferring to a vacuum drying oven, and vacuum drying at 70 ℃ for 12 hours to obtain a dried pole piece; the half-cell is assembled in a glove box, and the protective atmosphere of the glove box is argon, so that no water and no oxygen are ensured; transferring the dried pole piece into a glove box, taking metal lithium as a counter electrode, putting the pole piece, a 2300 type diaphragm, electrolyte, a metal lithium piece, a steel sheet and a spring piece into a CR2032 type battery shell in sequence, covering the battery shell, sealing by using a battery packaging machine, and manufacturing a button battery, testing the open circuit voltage of the battery to ensure no-path phenomenon, wherein the electrolyte is 1M lithium hexafluorophosphate dissolved in carbo-vinyl ester/dimethyl carbonate/methyl ethyl carbonate; charge and discharge were performed at 0.1C magnification and charge and discharge test at 5C magnification.
Example 1
The preparation method of the functional silicon-carbon composite material comprises the following preparation steps:
(1) Under the protection of argon, the tetraallyloxy silane, the terminal phthalic anhydride polyacrylonitrile and the dimethylformamide are mixed according to the mass ratio of 1:10:30, mixing, stirring for 2 hours at 1200r/min, then adding an initiator cumene peroxide with the mass of 0.01 times that of the tetraallyloxysilane, heating to 60 ℃, and continuously stirring for 3 hours to prepare a primary mixed material;
(2) Mixing the primary materials and the composite graphene oxide according to a mass ratio of 1:0.2, mixing, stirring for 30min at 3400r/min, and preparing to obtain a remixed material;
(3) Mixing the materials, urea and ammonium molybdate according to the mass ratio of 1:11:0.5, mixing, and stirring for 30min at 3400r/min to prepare a silicon-carbon composite material blank;
(4) And sequentially carrying out primary heating, secondary heating and tertiary heating on the silicon-carbon composite material blank to prepare the functional silicon-carbon composite material.
The preparation method of the phthalic anhydride-terminated polyacrylonitrile in the step (1) of the embodiment is as follows: at room temperature, acrylonitrile and dimethylformamide are mixed according to the mass ratio of 1:10, stirring for 20min at 600r/min, and then mixing according to the mass ratio of 1:0.01 of 4- (1-propynyl) phthalic anhydride and cumene peroxide are added, wherein the mass of the 4- (1-propynyl) phthalic anhydride is 0.036 times that of acrylonitrile, the temperature is raised to 60 ℃, and stirring is continued for 2 hours, so that the terminal phthalic anhydride polyacrylonitrile is prepared.
The preparation method of the composite graphene oxide in the step (2) of the embodiment is as follows: the preparation method comprises the following steps of (1) mixing graphene oxide and a 60% nickel chloride aqueous solution in a mass ratio of 1:10, mixing, stirring for 30min at 3400r/min, standing, baking for 2 days at 20 ℃ under the protection of nitrogen, and then adding into a 3-aminophthalic anhydride mixed solution with the mass which is 10 times that of graphene oxide, wherein the mass ratio of 3-aminophthalic anhydride to 10% sodium hydroxide solution in the 3-aminophthalic anhydride mixed solution is 1:2.8.
The heating temperature of the primary heating in the step (4) of this embodiment is controlled at 160 ℃, and the heating time is 4min.
The heating temperature of the secondary heating in the step (4) of this embodiment is controlled at 200 ℃, and the heating time is 110min.
The heating temperature of the third heating in the step (4) of this embodiment is controlled at 800 ℃, and the heating time is 10min.
The primary heating, the secondary heating and the tertiary heating described in the step (4) of this example were all performed under argon protection conditions under a pressure of 20 Pa.
Example 2
The preparation method of the functional silicon-carbon composite material comprises the following preparation steps:
(1) Under the protection of argon, the tetraallyloxy silane, the terminal phthalic anhydride polyacrylonitrile and the dimethylformamide are mixed according to the mass ratio of 1:20:40, stirring for 3 hours at 1300r/min, then adding an initiator cumene peroxide with the mass of 0.02 times of that of the tetraallyloxysilane, heating to 70 ℃, and continuously stirring for 4 hours to prepare a primary mixed material;
(2) Mixing the primary materials and the composite graphene oxide according to a mass ratio of 1:0.3, mixing, stirring for 40min at 3600r/min, and preparing to obtain a remixed material;
(3) Mixing the materials, urea and ammonium molybdate according to the mass ratio of 1:12:0.6, mixing, and stirring for 40min at 3600r/min to prepare a silicon-carbon composite material blank;
(4) And sequentially carrying out primary heating, secondary heating and tertiary heating on the silicon-carbon composite material blank to prepare the functional silicon-carbon composite material.
The preparation method of the phthalic anhydride-terminated polyacrylonitrile in the step (1) of the embodiment is as follows: at room temperature, acrylonitrile and dimethylformamide are mixed according to the mass ratio of 1:20, stirring for 30min at 700r/min, and then mixing according to the mass ratio of 1:0.02 of 4- (1-propynyl) phthalic anhydride and cumene peroxide are added, wherein the mass of the 4- (1-propynyl) phthalic anhydride is 0.037 times that of acrylonitrile, the temperature is raised to 70 ℃, and stirring is continued for 3 hours, so that the terminal phthalic anhydride polyacrylonitrile is prepared.
The preparation method of the composite graphene oxide in the step (2) of the embodiment is as follows: the method comprises the steps of (1) mixing graphene oxide with 70% nickel chloride aqueous solution according to a mass ratio of 1:20, stirring for 40min at 3600r/min, standing, baking for 2.5 days at the temperature of 30 ℃ under the protection of nitrogen, and then adding into a 3-aminophthalic anhydride mixed solution with the mass which is 20 times that of graphene oxide, wherein the mass ratio of 3-aminophthalic anhydride to 10% sodium hydroxide solution in the 3-aminophthalic anhydride mixed solution is 1:3.
The heating temperature of the primary heating in the step (4) of this embodiment is controlled at 170 ℃, and the heating time is 5min.
The heating temperature of the secondary heating in the step (4) of this embodiment is controlled to be 250 ℃, and the heating time is 120min.
The heating temperature of the third heating in the step (4) of this embodiment is controlled at 900 ℃ and the heating time is 15min.
The primary heating, the secondary heating and the tertiary heating described in the step (4) of this example were all performed under argon protection conditions under a pressure of 35 Pa.
Example 3
The preparation method of the functional silicon-carbon composite material comprises the following preparation steps:
(1) Under the protection of argon, the tetraallyloxy silane, the terminal phthalic anhydride polyacrylonitrile and the dimethylformamide are mixed according to the mass ratio of 1:30:50, mixing, stirring for 4 hours at 1400r/min, then adding an initiator cumene peroxide with the mass of 0.03 times of that of the tetraallyloxysilane, heating to 80 ℃, and continuously stirring for 5 hours to prepare a primary mixed material;
(2) Mixing the primary materials and the composite graphene oxide according to a mass ratio of 1:0.4, mixing, and stirring at 3800r/min for 50min to obtain a remixed material;
(3) Mixing the materials, urea and ammonium molybdate according to the mass ratio of 1:13:0.5, mixing, and stirring for 50min at 3800r/min to prepare a silicon-carbon composite material blank;
(4) And sequentially carrying out primary heating, secondary heating and tertiary heating on the silicon-carbon composite material blank to prepare the functional silicon-carbon composite material.
The preparation method of the phthalic anhydride-terminated polyacrylonitrile in the step (1) of the embodiment is as follows: at room temperature, acrylonitrile and dimethylformamide are mixed according to the mass ratio of 1:30, stirring for 40min at 800r/min, and then mixing according to the mass ratio of 1:0.03 of 4- (1-propynyl) phthalic anhydride and cumene peroxide are added, wherein the mass of the 4- (1-propynyl) phthalic anhydride is 0.038 times that of acrylonitrile, the temperature is raised to 80 ℃, and stirring is continued for 4 hours, so that the terminal phthalic anhydride polyacrylonitrile is prepared.
The preparation method of the composite graphene oxide in the step (2) of the embodiment is as follows: the method comprises the steps of (1) mixing graphene oxide with an aqueous solution of nickel chloride with the mass fraction of 80 percent: 30, stirring at 3800r/min for 50min, standing, baking for 3 days at 40 ℃ under the protection of nitrogen, and then adding into a 3-aminophthalic anhydride mixed solution with the mass which is 30 times that of graphene oxide, wherein the mass ratio of 3-aminophthalic anhydride to 10% sodium hydroxide solution in the 3-aminophthalic anhydride mixed solution is 1:3.2.
The heating temperature of the primary heating in the step (4) of this embodiment is controlled at 180 ℃, and the heating time is 6min.
The heating temperature of the secondary heating in the step (4) of this embodiment is controlled at 300 ℃, and the heating time is 130min.
The heating temperature of the third heating in the step (4) of this embodiment is controlled at 1000 ℃, and the heating time is 20min.
The primary heating, the secondary heating and the tertiary heating described in the step (4) of this example were all performed under argon protection conditions under a pressure of 50 Pa.
Comparative example 1
The preparation method of the functional silicon-carbon composite material comprises the following preparation steps:
(1) Under the protection of argon, tetraallyloxy silane and dimethylformamide are mixed according to the mass ratio of 1:20:40, stirring for 3 hours at 1300r/min, then adding an initiator cumene peroxide with the mass of 0.02 times of that of the tetraallyloxysilane, heating to 70 ℃, and continuously stirring for 4 hours to prepare a primary mixed material;
(2) Mixing the primary materials and the composite graphene oxide according to a mass ratio of 1:0.3, mixing, stirring for 40min at 3600r/min, and preparing to obtain a remixed material;
(3) Mixing the materials, urea and ammonium molybdate according to the mass ratio of 1:12:0.6, mixing, and stirring for 40min at 3600r/min to prepare a silicon-carbon composite material blank;
(4) And sequentially carrying out primary heating, secondary heating and tertiary heating on the silicon-carbon composite material blank to prepare the functional silicon-carbon composite material.
The preparation method of the composite graphene oxide in the step (2) of the comparative example comprises the following steps: the method comprises the steps of (1) mixing graphene oxide with 70% nickel chloride aqueous solution according to a mass ratio of 1:20, stirring for 40min at 3600r/min, standing, baking for 2.5 days at the temperature of 30 ℃ under the protection of nitrogen, and then adding into a 3-aminophthalic anhydride mixed solution with the mass which is 20 times that of graphene oxide, wherein the mass ratio of 3-aminophthalic anhydride to 10% sodium hydroxide solution in the 3-aminophthalic anhydride mixed solution is 1:3.
The heating temperature of the primary heating in the step (4) of the comparative example is controlled to 170 ℃ and the heating time is 5min.
The heating temperature of the secondary heating in the step (4) of the comparative example is controlled to be 250 ℃, and the heating time is 120min.
The heating temperature of the three times of heating in the step (4) of the comparative example is controlled to 900 ℃, and the heating time is 15min.
The primary heating, the secondary heating and the tertiary heating described in the step (4) of the comparative example are all performed under the argon protection condition and the pressure of 35 Pa.
Comparative example 2
The preparation method of the functional silicon-carbon composite material comprises the following preparation steps:
(1) Under the protection of argon, the tetraallyloxy silane, the terminal phthalic anhydride polyacrylonitrile and the dimethylformamide are mixed according to the mass ratio of 1:20:40, stirring for 3 hours at 1300r/min, then adding an initiator cumene peroxide with the mass of 0.02 times of that of the tetraallyloxysilane, heating to 70 ℃, and continuously stirring for 4 hours to prepare a primary mixed material;
(2) Mixing the primary materials and graphene oxide according to a mass ratio of 1:0.3, mixing, stirring for 40min at 3600r/min, and preparing to obtain a remixed material;
(3) Mixing the materials, urea and ammonium molybdate according to the mass ratio of 1:12:0.6, mixing, and stirring for 40min at 3600r/min to prepare a silicon-carbon composite material blank;
(4) And sequentially carrying out primary heating, secondary heating and tertiary heating on the silicon-carbon composite material blank to prepare the functional silicon-carbon composite material.
The preparation method of the phthalic anhydride-terminated polyacrylonitrile in the step (1) of the comparative example comprises the following steps: at room temperature, polyacrylonitrile and dimethylformamide are mixed according to the mass ratio of 1:20, stirring for 30min at 700r/min, and then mixing according to the mass ratio of 1:0.02 of 4- (1-propynyl) phthalic anhydride and cumene peroxide are added, wherein the mass of the 4- (1-propynyl) phthalic anhydride is 0.037 times that of polyacrylonitrile, the temperature is raised to 70 ℃, and stirring is continued for 3 hours, so that the terminal phthalic anhydride polyacrylonitrile is prepared.
The heating temperature of the primary heating in the step (4) of the comparative example is controlled to 170 ℃ and the heating time is 5min.
The heating temperature of the secondary heating in the step (4) of the comparative example is controlled to be 250 ℃, and the heating time is 120min.
The heating temperature of the three times of heating in the step (4) of the comparative example is controlled to 900 ℃, and the heating time is 15min.
The primary heating, the secondary heating and the tertiary heating described in the step (4) of the comparative example are all performed under the argon protection condition and the pressure of 35 Pa.
Comparative example 3
The preparation method of the functional silicon-carbon composite material comprises the following preparation steps:
(1) Under the protection of argon, the tetraallyloxy silane, the terminal phthalic anhydride polyacrylonitrile and the dimethylformamide are mixed according to the mass ratio of 1:20:40, stirring for 3 hours at 1300r/min, then adding an initiator cumene peroxide with the mass of 0.02 times of that of the tetraallyloxysilane, heating to 70 ℃, and continuously stirring for 4 hours to prepare a primary mixed material;
(2) Mixing the primary materials and the composite graphene oxide according to a mass ratio of 1:0.3, mixing, stirring for 40min at 3600r/min, and preparing to obtain a remixed material;
(3) Mixing the materials again and ammonium molybdate according to the mass ratio of 1:12:0.6, mixing, and stirring for 40min at 3600r/min to prepare a silicon-carbon composite material blank;
(4) And sequentially carrying out primary heating, secondary heating and tertiary heating on the silicon-carbon composite material blank to prepare the functional silicon-carbon composite material.
The preparation method of the phthalic anhydride-terminated polyacrylonitrile in the step (1) of the comparative example comprises the following steps: at room temperature, acrylonitrile and dimethylformamide are mixed according to the mass ratio of 1:20, stirring for 30min at 700r/min, and then mixing according to the mass ratio of 1:0.02 of 4- (1-propynyl) phthalic anhydride and cumene peroxide are added, wherein the mass of the 4- (1-propynyl) phthalic anhydride is 0.037 times that of acrylonitrile, the temperature is raised to 70 ℃, and stirring is continued for 3 hours, so that the terminal phthalic anhydride polyacrylonitrile is prepared.
The preparation method of the composite graphene oxide in the step (2) of the comparative example comprises the following steps: the method comprises the steps of (1) mixing graphene oxide with 70% nickel chloride aqueous solution according to a mass ratio of 1:20, stirring for 40min at 3600r/min, standing, baking for 2.5 days at the temperature of 30 ℃ under the protection of nitrogen, and then adding into a 3-aminophthalic anhydride mixed solution with the mass which is 20 times that of graphene oxide, wherein the mass ratio of 3-aminophthalic anhydride to 10% sodium hydroxide solution in the 3-aminophthalic anhydride mixed solution is 1:3.
The heating temperature of the primary heating in the step (4) of the comparative example is controlled to 170 ℃ and the heating time is 5min.
The heating temperature of the secondary heating in the step (4) of the comparative example is controlled to be 250 ℃, and the heating time is 120min.
The heating temperature of the three times of heating in the step (4) of the comparative example is controlled to 900 ℃, and the heating time is 15min.
The primary heating, the secondary heating and the tertiary heating described in the step (4) of the comparative example are all performed under the argon protection condition and the pressure of 35 Pa.
Comparative example 4
The preparation method of the functional silicon-carbon composite material comprises the following preparation steps:
(1) Under the protection of argon, the tetraallyloxy silane, the terminal phthalic anhydride polyacrylonitrile and the dimethylformamide are mixed according to the mass ratio of 1:20:40, stirring for 3 hours at 1300r/min, then adding an initiator cumene peroxide with the mass of 0.02 times of that of the tetraallyloxysilane, heating to 70 ℃, and continuously stirring for 4 hours to prepare a primary mixed material;
(2) Mixing the primary materials and the composite graphene oxide according to a mass ratio of 1:0.3, mixing, stirring for 40min at 3600r/min, and preparing to obtain a remixed material;
(3) Mixing the materials, urea and ammonium molybdate according to the mass ratio of 1:12:0.6, mixing, and stirring for 40min at 3600r/min to prepare a silicon-carbon composite material blank;
(4) And sequentially carrying out primary heating and secondary heating on the silicon-carbon composite material blank to prepare the functional silicon-carbon composite material.
The preparation method of the phthalic anhydride-terminated polyacrylonitrile in the step (1) of the comparative example comprises the following steps: at room temperature, acrylonitrile and dimethylformamide are mixed according to the mass ratio of 1:20, stirring for 30min at 700r/min, and then mixing according to the mass ratio of 1:0.02 of 4- (1-propynyl) phthalic anhydride and cumene peroxide are added, wherein the mass of the 4- (1-propynyl) phthalic anhydride is 0.037 times that of acrylonitrile, the temperature is raised to 70 ℃, and stirring is continued for 3 hours, so that the terminal phthalic anhydride polyacrylonitrile is prepared.
The preparation method of the composite graphene oxide in the step (2) of the comparative example comprises the following steps: the method comprises the steps of (1) mixing graphene oxide with 70% nickel chloride aqueous solution according to a mass ratio of 1:20, stirring for 40min at 3600r/min, standing, baking for 2.5 days at the temperature of 30 ℃ under the protection of nitrogen, and then adding into a 3-aminophthalic anhydride mixed solution with the mass which is 20 times that of graphene oxide, wherein the mass ratio of 3-aminophthalic anhydride to 10% sodium hydroxide solution in the 3-aminophthalic anhydride mixed solution is 1:3.
The heating temperature of the primary heating in the step (4) of the comparative example is controlled to be 250 ℃ and the heating time is 120min.
The heating temperature of the secondary heating in the step (4) of the comparative example is controlled to 900 ℃ and the heating time is 15min.
The primary heating and the secondary heating described in the step (4) of the comparative example were performed under argon protection conditions under a pressure of 35 Pa.
Comparative example 5
The preparation method of the functional silicon-carbon composite material comprises the following preparation steps:
(1) Under the protection of argon, the tetraallyloxy silane, the terminal phthalic anhydride polyacrylonitrile and the dimethylformamide are mixed according to the mass ratio of 1:20:40, stirring for 3 hours at 1300r/min, then adding an initiator cumene peroxide with the mass of 0.02 times of that of the tetraallyloxysilane, heating to 70 ℃, and continuously stirring for 4 hours to prepare a primary mixed material;
(2) Mixing the primary materials and the composite graphene oxide according to a mass ratio of 1:0.3, mixing, stirring for 40min at 3600r/min, and preparing to obtain a remixed material;
(3) Mixing the materials, urea and ammonium molybdate according to the mass ratio of 1:12:0.6, mixing, and stirring for 40min at 3600r/min to prepare a silicon-carbon composite material blank;
(4) And sequentially carrying out primary heating and secondary heating on the silicon-carbon composite material blank to prepare the functional silicon-carbon composite material.
The preparation method of the phthalic anhydride-terminated polyacrylonitrile in the step (1) of the comparative example comprises the following steps: at room temperature, acrylonitrile and dimethylformamide are mixed according to the mass ratio of 1:20, stirring for 30min at 700r/min, and then mixing according to the mass ratio of 1:0.02 of 4- (1-propynyl) phthalic anhydride and cumene peroxide are added, wherein the mass of the 4- (1-propynyl) phthalic anhydride is 0.037 times that of acrylonitrile, the temperature is raised to 70 ℃, and stirring is continued for 3 hours, so that the terminal phthalic anhydride polyacrylonitrile is prepared.
The preparation method of the composite graphene oxide in the step (2) of the comparative example comprises the following steps: the method comprises the steps of (1) mixing graphene oxide with 70% nickel chloride aqueous solution according to a mass ratio of 1:20, stirring for 40min at 3600r/min, standing, baking for 2.5 days at the temperature of 30 ℃ under the protection of nitrogen, and then adding into a 3-aminophthalic anhydride mixed solution with the mass which is 20 times that of graphene oxide, wherein the mass ratio of 3-aminophthalic anhydride to 10% sodium hydroxide solution in the 3-aminophthalic anhydride mixed solution is 1:3.
The heating temperature of the primary heating in the step (4) of the comparative example is controlled to 170 ℃ and the heating time is 5min.
The heating temperature of the secondary heating in the step (4) of the comparative example is controlled to 900 ℃ and the heating time is 15min.
The primary heating and the secondary heating described in the step (4) of the comparative example were performed under argon protection conditions under a pressure of 35 Pa.
Effect example
The following table 1 gives the results of analysis of the cyclic stability of the functionalized silicon carbon composites prepared using examples 1 to 3 of the present invention and comparative examples 1 to 4.
TABLE 1
It can be found from table 1 that the functionalized silicon-carbon composite materials prepared in examples 1,2 and 3 have higher cycle stability; from comparison of experimental data of examples 1,2 and 3 and comparative example 1, it can be found that the functionalized silicon-carbon composite material prepared by using the terminal phthalic anhydride polyacrylonitrile has stronger cycle stability; from the experimental data of examples 1,2,3 and comparative example 2, it can be found that the functionalized silicon-carbon composite material prepared by using the composite graphene oxide can form a nickel phthalocyanine conjugated microporous compound, and the prepared functionalized silicon-carbon composite material has stronger cycle stability; from the experimental data of examples 1,2 and 3 and comparative examples 3, 4 and 5, it can be found that the silicon-carbon composite material blank is prepared by using the foaming agent urea, and the functionalized silicon-carbon composite material is prepared by performing primary heating, secondary heating and tertiary heating, so that the nickel phthalocyanine conjugated microporous compound can be formed, and a carbon layer containing a large number of uniformly dispersed pore channels is formed on the surface of each silicon atom, and the prepared silicon-carbon composite material has high cycle stability.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (3)
1. The preparation method of the functional silicon-carbon composite material is characterized by comprising the following preparation steps:
(1) Mixing tetraallyloxy silane and terminal phthalic anhydride polyacrylonitrile to obtain a primary mixed material;
(2) Mixing the primary mixed material and the composite graphene oxide to obtain a secondary mixed material;
(3) Mixing the re-mixed material with foaming agent urea to obtain a silicon-carbon composite material blank;
(4) Sequentially carrying out primary heating, secondary heating and tertiary heating on the silicon-carbon composite material blank to prepare a functional silicon-carbon composite material;
The method comprises the following specific steps:
(1) Under the protection of argon, the tetraallyloxy silane, the terminal phthalic anhydride polyacrylonitrile and the dimethylformamide are mixed according to the mass ratio of 1:10: 30-1: 30:50, mixing, stirring for 2-4 hours at the speed of 1200-1400 r/min, then adding an initiator with the mass of 0.01-0.03 times that of the tetraallyloxy silane, heating to 60-80 ℃, and continuously stirring for 3-5 hours to prepare a primary mixed material;
(2) Mixing the primary materials and the composite graphene oxide according to a mass ratio of 1: 0.2-1: 0.4, mixing, and stirring for 30-50 min at 3400-3800 r/min to prepare a remixed material;
(3) Mixing the materials, urea and ammonium molybdate according to the mass ratio of 1:11: 0.5-1: 13:0.7, mixing, and stirring for 30-50 min at 3400-3800 r/min to prepare a silicon-carbon composite material blank;
(4) Sequentially carrying out primary heating, secondary heating and tertiary heating on the silicon-carbon composite material blank to prepare a functional silicon-carbon composite material;
in the step (1), the preparation method of the phthalic anhydride-terminated polyacrylonitrile comprises the following steps: at room temperature, acrylonitrile and dimethylformamide are mixed according to the mass ratio of 1: 10-1: 30, stirring for 20-40 min at 600-800 r/min, and then, according to the mass ratio of 1: 0.01-1: 0.03 adding 4- (1-propynyl) phthalic anhydride and cumene peroxide, wherein the mass of the 4- (1-propynyl) phthalic anhydride is 0.036-0.038 times that of acrylonitrile, heating to 60-80 ℃, and continuously stirring for 2-4 hours to prepare phthalic anhydride-terminated polyacrylonitrile;
In the step (2), the preparation method of the composite graphene oxide comprises the following steps: the method comprises the steps of (1) mixing graphene oxide with 60-80% of nickel chloride aqueous solution according to the mass ratio of 1: 10-1: 30, mixing, stirring for 30-50 min at 3400-3800 r/min, standing, baking for 2-3 days at 20-40 ℃ under the protection of nitrogen, and then adding into a 3-aminophthalic anhydride mixed solution with the mass 10-30 times of that of graphene oxide, wherein the mass ratio of 3-aminophthalic anhydride to 10% sodium hydroxide solution in the 3-aminophthalic anhydride mixed solution is 1: 2.8-1: 3.2;
The heating temperature of the primary heating in the step (4) is controlled to be 160-180 ℃ and the heating time is 4-6 min; the heating temperature of the secondary heating in the step (4) is controlled to be 200-300 ℃, and the heating time is 110-130 min; the heating temperature of the three times of heating in the step (4) is controlled to be 800-1000 ℃ and the heating time is 10-20 min;
And (4) performing primary heating, secondary heating and tertiary heating under the argon protection condition and the pressure of 20-50 Pa.
2. The method for preparing a functionalized silicon-carbon composite material according to claim 1, wherein the initiator in the step (1) is cumene peroxide.
3. The application of the functionalized silicon-carbon composite material is characterized in that the application field of the functionalized silicon-carbon composite material comprises a battery cathode.
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