CN114551816A - Method for preparing silicon-carbon composite material by utilizing organosilane - Google Patents
Method for preparing silicon-carbon composite material by utilizing organosilane Download PDFInfo
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 18
- 150000001282 organosilanes Chemical class 0.000 title claims abstract description 12
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011247 coating layer Substances 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 230000001360 synchronised effect Effects 0.000 claims abstract description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- FTEPVGGPJFNOIK-UHFFFAOYSA-N [C].[C].[Si] Chemical compound [C].[C].[Si] FTEPVGGPJFNOIK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- 239000012467 final product Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing a silicon-carbon composite material by utilizing organosilane, silicon oxide and a carbon composite coating layer formed by adopting a synchronous polymerization in-situ coating method of silane and chemical acid resistance are deposited on the surface of a nano silicon particle to form a layer of silicon oxide/carbon film coated on the surface of the nano silicon particle, and the content of silicon is 10-60%. And carrying out centrifugal drying treatment on the reacted material, and then pyrolyzing the composite coating layer of the material into silicon dioxide/amorphous carbon under inert protective gas. Compared with the prior method for preparing the silicon/carbon composite material, the method adopts the synchronous polymerization sourceThe bit coating method has mild conditions, simple steps, no need of complex and expensive equipment, and is beneficial to large-scale popularization, and the prepared silicon/carbon composite material has a specific discharge capacity of more than 1000 mAh.g after 200 charge-discharge cycles‑1Compared with the silicon/carbon composite material prepared by simple mixing, the electrochemical performance is obviously improved.
Description
Technical Field
The invention relates to the field of preparation of lithium ion battery cathode materials, in particular to a method for preparing a silicon/carbon composite material of a lithium ion battery by utilizing organosilane.
Background
Lithium Ion Batteries (LIBs) have the advantages of high energy density, long service life, environmental protection, and the like, are one of the most attractive energy storage devices at present, and play an increasingly important role in modern society. They have already taken the market for portable electronic products such as mobile phones, notebook computers and digital cameras, and have also been identified as the preferred power source for electric vehicles and stationary energy storage. However, the lithium ion negative electrode material commercialized at present is a graphite material, but the theoretical specific capacity of the lithium ion negative electrode material is only 372mAh g-1And the huge market demand of the high-specific-capacity lithium ion battery cannot be met, so that the development of a novel lithium ion battery cathode material with high specific capacity, long service life and high safety is urgently required.
Among the lithium ion battery negative electrode materials proposed at the present stage, silicon is considered as the most promising material to replace graphite. It is the second most abundant element in the crust, environmentally friendly, and has ultra high theoretical capacity (4200 mAhg)-1) More than 10 times of the theoretical specific capacity of the commercial graphite electrode material. Although silicon-based materials have a high theoretical capacity, there are two major problems that limit the practical application of silicon: (1) volume expansion during the cycle (>400%), resulting in poor cycle performance; (2) low conductivity, limiting its rate capability. Research has shown that the preparation of silicon/carbon composites is an effective way to solve the above problems. However, the traditional single carbon coating layer has low capacity and low strength, and the development of high specific capacity negative electrode materials is limited.
Disclosure of Invention
The invention aims to overcome the defects of the existing preparation method, and provides a new preparation method, which is characterized in that organosilane is used for preparing a silicon/carbon composite material of a lithium ion battery to be used as a negative electrode material of the lithium ion battery for modification, so that the silicon/carbon composite material with good electrochemical performance is prepared, and the industrial production of the silicon/carbon composite material is promoted.
The technical purpose of the invention is realized by the following technical scheme.
A method for preparing a silicon-carbon composite material by utilizing organosilane is carried out according to the following steps:
step 1, silane and ascorbic acid are mixed in a molar ratio of 3: (1-10), adding the mixture into a solution in which nano silicon particles are uniformly dispersed, reacting at 60-80 ℃ for 5-15 hours, depositing a silicon oxide and carbon composite coating layer formed by a synchronous polymerization in-situ coating method of silane and chemical acid resistance on the surface of the nano silicon particles, and finally forming a layer of silicon oxide/carbon film to coat the surface of the nano silicon particles, wherein the content of silicon is 10-60 wt%;
step 2, after centrifugal drying treatment is carried out on the material reacted in the step 1, the material is placed under inert protective gas for pyrolysis, so as to obtain a silicon dioxide/amorphous carbon silicon-carbon composite material; the pyrolysis temperature is 800-900 ℃, and the pyrolysis time is 3-8 hours.
Furthermore, in step 1, the silane is 3-aminopropyltriethoxysilane.
Furthermore, in step 1, the molar ratio of silane to ascorbic acid was 3: (4-8).
Further, in step 1, the reaction is carried out at 60 to 80 ℃ for 6 to 10 hours.
Furthermore, in step 2, the inert shielding gas is nitrogen, argon or helium.
In step 2, the pyrolysis temperature is 800-850 ℃ and the pyrolysis time is 3-6 hours.
The silicon-carbon composite material prepared by the method is applied to preparing the lithium ion battery cathode material.
Compared with the existing method for preparing the silicon/carbon composite material, the synchronous polymerization in-situ coating method adopted by the invention has the advantages of mild conditions, simple steps, no need of complex and expensive equipment and contribution to large-scale popularization. And the prepared silicon/carbon composite material has a specific discharge capacity of more than 500 mAh.g after 200 times of charge-discharge circulation-1Even more than 1000mAh g-1Compared with the silicon/carbon composite material prepared by simple mixing (after charging and discharging for 200 times)The specific capacity is 500mAh g-1) The electrochemical performance of the catalyst is obviously improved.
Drawings
FIG. 1 is a scanning electron micrograph of a silicon-carbon composite material according to example 1 of the present invention.
FIG. 2 is a SEM photograph of the Si-C composite material in example 2 of the present invention.
FIG. 3 is a scanning electron micrograph of a silicon-carbon composite in example 3 of the present invention.
FIG. 4 is a transmission electron micrograph of a silicon-carbon composite in example 1 of the present invention.
FIG. 5 is a transmission electron micrograph of a silicon-carbon composite in example 2 of the present invention.
FIG. 6 is a TEM image of the Si-C composite material obtained in example 3 of the present invention.
FIG. 7 is an X-ray diffraction pattern of a silicon-carbon composite material in example 3 of the present invention.
FIG. 8 is an XPS line plot of a silicon-carbon composite of example 3 of the present invention.
Fig. 9 is a thermogravimetric plot of a silicon-carbon composite in example 3 of the present invention.
Fig. 10 is a graph of the cycle life and coulombic efficiency curves for the silicon-carbon composite of example 3 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples. The grain diameter of the used nano silicon powder is 50-80 nm.
Example 1
(1) 0.02g of nano silicon powder is dispersed in 120mL of absolute ethyl alcohol by ultrasonic waves, and the absolute ethyl alcohol solution of uniformly dispersed silicon nano particles is obtained after 2 hours of ultrasonic waves.
(2) Preparing 6mL of 0.1M aqueous solution of the chemical-resistant acid, stirring until the chemical-resistant acid is completely dissolved, adding the solution obtained in the step (1), and stirring and mixing uniformly in a water bath at 60 ℃.
(3) Adding 400 mu L of 3-aminopropyltriethoxysilane into a mixed solution of 120mL of absolute ethyl alcohol and 6mL of water, namely the mixed solution of the step (1) and the step (2), stirring in a water bath at 60 ℃, reacting for 8 hours, centrifuging, washing with water, and drying the sample after the reaction is finished.
(4) And putting the dried sample into a tubular furnace protected by argon atmosphere to calcine for 3 hours at 800 ℃ to obtain a final product.
Example 2
(1) 0.1g of nano silicon powder is dispersed in 120mL of absolute ethyl alcohol by ultrasonic waves, and the absolute ethyl alcohol solution of uniformly dispersed silicon nano particles is obtained after 2 hours of ultrasonic waves.
(2) Preparing 6mL of 0.1M aqueous solution of the chemical-resistant acid, stirring until the chemical-resistant acid is completely dissolved, adding the solution obtained in the step (1), and stirring and mixing uniformly in a water bath at 60 ℃.
(3) Adding 400 mu L of 3-aminopropyltriethoxysilane into a mixed solution of 120mL of absolute ethyl alcohol and 6mL of water, namely the mixed solution of the step (1) and the step (2), stirring in a water bath at 70 ℃, reacting for 8 hours, centrifuging, washing with water, and drying the sample after the reaction is finished.
(4) And putting the dried sample into a tubular furnace protected by argon atmosphere to calcine for 4 hours at 800 ℃ to obtain a final product.
Example 3
(1) 0.15g of nano silicon powder is dispersed in 120mL of absolute ethyl alcohol by ultrasonic waves, and the absolute ethyl alcohol solution of uniformly dispersed silicon nano particles is obtained after 2 hours of ultrasonic waves.
(2) Preparing 6mL of 0.1M aqueous solution of the chemical-resistant acid, stirring until the chemical-resistant acid is completely dissolved, adding the solution obtained in the step (1), and stirring and mixing uniformly in a water bath at 60 ℃.
(3) Adding 400 mu L of 3-aminopropyltriethoxysilane into a mixed solution of 120mL of absolute ethyl alcohol and 6mL of water, namely the mixed solution of the step (1) and the step (2), stirring in a water bath at 60 ℃, reacting for 8 hours, centrifuging, washing with water, and drying the sample after the reaction is finished.
(4) And putting the dried sample into a tubular furnace protected by argon atmosphere, and calcining for 3 hours at 800 ℃ to obtain a final product.
Example 4
(1) 0.1g of nano silicon powder is dispersed in 120mL of absolute ethyl alcohol by ultrasonic waves, and the absolute ethyl alcohol solution of uniformly dispersed silicon nano particles is obtained after 2 hours of ultrasonic waves.
(2) Preparing 6mL of 0.1M aqueous solution of the chemical-resistant acid, stirring until the chemical-resistant acid is completely dissolved, adding the solution obtained in the step (1), and stirring and mixing uniformly in a water bath at 60 ℃.
(3) Adding 400 mu L of 3-aminopropyltriethoxysilane into a mixed solution of 120mL of absolute ethyl alcohol and 6mL of water, namely the mixed solution of the step (1) and the step (2), stirring in a water bath at 70 ℃, reacting for 6 hours, centrifuging, washing with water, and drying the sample after the reaction is finished.
(4) And putting the dried sample into a tubular furnace protected by argon atmosphere to calcine for 4 hours at 800 ℃ to obtain a final product.
Example 5
(1) 0.1g of nano silicon powder is dispersed in 120mL of absolute ethyl alcohol by ultrasonic waves, and the absolute ethyl alcohol solution of uniformly dispersed silicon nano particles is obtained after 2 hours of ultrasonic waves.
(2) Preparing 6mL of 0.1M aqueous solution of the chemical-resistant acid, stirring until the chemical-resistant acid is completely dissolved, adding the solution obtained in the step (1), and stirring and mixing uniformly in a water bath at 60 ℃.
(3) Adding 400 mu L of 3-aminopropyltriethoxysilane into a mixed solution of 120mL of absolute ethyl alcohol and 6mL of water, namely the mixed solution of the step (1) and the step (2), stirring in a water bath at 60 ℃, reacting for 10 hours, centrifuging, washing with water and drying the sample after the reaction is finished.
(4) And putting the dried sample into a tubular furnace protected by argon atmosphere to calcine for 3 hours at 800 ℃ to obtain a final product.
Example 6
(1) 0.1g of nano silicon powder is dispersed in 120mL of absolute ethyl alcohol by ultrasonic waves, and the absolute ethyl alcohol solution of uniformly dispersed silicon nano particles is obtained after 2 hours of ultrasonic waves.
(2) Preparing 6mL of 0.1M aqueous solution of the chemical-resistant acid, stirring until the chemical-resistant acid is completely dissolved, adding the solution obtained in the step (1), and stirring and mixing uniformly in a water bath at 60 ℃.
(3) Adding 400 mu L of 3-aminopropyltriethoxysilane into a mixed solution of 120mL of absolute ethyl alcohol and 6mL of water, namely the mixed solution of the step (1) and the step (2), stirring in a water bath at 80 ℃, reacting for 8 hours, centrifuging, washing with water, and drying the sample after the reaction is finished.
(4) And putting the dried sample into a tubular furnace protected by argon atmosphere, and calcining for 3h at 900 ℃ to obtain a final product.
Example 7
(1) 0.1g of nano silicon powder is dispersed in 120mL of absolute ethyl alcohol by ultrasonic waves, and the absolute ethyl alcohol solution of uniformly dispersed silicon nano particles is obtained after 2 hours of ultrasonic waves.
(2) Preparing 6mL of 0.1M aqueous solution of the chemical-resistant acid, stirring until the chemical-resistant acid is completely dissolved, adding the solution obtained in the step (1), and stirring and mixing uniformly in a water bath at 60 ℃.
(3) Adding 400 mu L of 3-aminopropyltriethoxysilane into a mixed solution of 120mL of absolute ethyl alcohol and 6mL of water, namely the mixed solution of the step (1) and the step (2), stirring in a water bath at 65 ℃, reacting for 8 hours, centrifuging, washing with water, and drying the sample after the reaction is finished.
(4) And putting the dried sample into a tubular furnace protected by argon atmosphere to calcine for 3 hours at 850 ℃ to obtain a final product.
Example 8
(1) 0.1g of nano silicon powder is dispersed in 120mL of absolute ethyl alcohol by ultrasonic waves, and the absolute ethyl alcohol solution of uniformly dispersed silicon nano particles is obtained after 2 hours of ultrasonic waves.
(2) Preparing 6mL of 0.1M aqueous solution of the anti-chemical acid, stirring until the anti-chemical acid is completely dissolved, adding the solution obtained in the step (1), and stirring and mixing uniformly in a water bath at 60 ℃.
(3) Adding 400 mu L of 3-aminopropyltriethoxysilane into a mixed solution of 120mL of absolute ethyl alcohol and 6mL of water, namely the mixed solution of the step (1) and the step (2), stirring in a water bath at 60 ℃, reacting for 10 hours, centrifuging, washing with water and drying the sample after the reaction is finished.
(4) And putting the dried sample into a tubular furnace protected by argon atmosphere to calcine for 6 hours at 800 ℃ to obtain a final product.
Taking examples 1 to 3 as examples for characterization, fig. 1, 2 and 3 are scanning electron micrographs of the silicon-carbon composite materials prepared in examples 1, 2 and 3, respectively, and nano silicon is uniformly coated and forms a structure in which coating layers are cross-linked with each other, which is beneficial to improving the conductivity of the composite material and promoting the transmission of lithium ions. As can be seen from the picture 1, the coated nano silicon coexists with the microspheres generated by copolymerization and condensation of APTES and l-AA. As shown in FIGS. 2 and 3, with the increase of nano-silicon in the system, microspheres generated by copolymerization and condensation of APTES and l-AA disappear, and all the microspheres form a coating layer to coat the surface of the nano-silicon particles. Fig. 4, 5 and 6 are transmission electron micrographs of the silicon-carbon composite materials prepared in example 1, example 2 and example 3, respectively, and it can be clearly seen from the pictures that the surface of the nano silicon has a coating layer with uniform thickness, and the coating layer can inhibit the volume expansion of the nano silicon particles in the lithium intercalation/de-intercalation process, so as to achieve the purpose of improving the cycle stability.
Referring to the XRD, XPS and thermogravimetric characterization of example 3, fig. 7 is an X-ray diffraction picture of the silicon-carbon composite material in example 3, which can determine that silicon exists in the composite material and the broad peak at 24 ° is a characteristic peak of amorphous carbon and silicon dioxide. Fig. 8 is an xps pattern of the silicon-carbon composite material of example 3, which contains O, C, Si elements on the surface, in accordance with XRD measurements. FIG. 9 is a thermogravimetric plot of the silicon-carbon composite of example 3, determining a carbon content of approximately 15% in the composite. The remaining embodiments, as tested, exhibited substantially consistent performance. Fig. 10 is a graph of cycle life and coulombic efficiency for a silicon/carbon composite. The first charge capacity of the material is 1480.7mAh g-1After 200 cycles, the reversible capacity of the material is 1095.5mAh g-1. In addition, after the composite material is circulated for 10 times, the coulombic efficiency can reach more than 99%.
The electrical properties of the materials prepared by the examples of the present invention were tested and are shown in the following table:
the preparation of the silicon-carbon composite material can be realized by adjusting the process parameters according to the content of the invention, and the test shows that the performance is basically consistent with that of the invention. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (7)
1. A method for preparing a silicon-carbon composite material by utilizing organosilane is characterized by comprising the following steps:
step 1, silane and ascorbic acid are mixed in a molar ratio of 3: (1-10), adding the mixture into a solution in which nano silicon particles are uniformly dispersed, reacting at 60-80 ℃ for 5-15 hours, depositing a silicon oxide and carbon composite coating layer formed by a synchronous polymerization in-situ coating method of silane and chemical acid resistance on the surface of the nano silicon particles, and finally forming a layer of silicon oxide/carbon film to coat the surface of the nano silicon particles, wherein the content of silicon is 10-60 wt%;
step 2, after centrifugal drying treatment is carried out on the material reacted in the step 1, the material is placed under inert protective gas for pyrolysis, so as to obtain a silicon dioxide/amorphous carbon silicon-carbon composite material; the pyrolysis temperature is 800-900 ℃, and the pyrolysis time is 3-8 hours.
2. The method for preparing a silicon-carbon composite material using an organosilane as set forth in claim 1, wherein the silane is 3-aminopropyltriethoxysilane in the step 1.
3. The method for preparing a silicon-carbon composite material using organosilane as claimed in claim 1, wherein the molar ratio of silane to ascorbic acid in step 1 is 3: (4-8).
4. The method for preparing a silicon-carbon composite material using an organosilane as set forth in claim 1, wherein the reaction is carried out at 60 to 80 ℃ for 6 to 10 hours in step 1.
5. The method for preparing a silicon-carbon composite material using organosilane as claimed in claim 1, wherein the inert shielding gas is nitrogen, argon or helium in the step 2.
6. The method for preparing a silicon-carbon composite material using an organosilane as set forth in claim 1, wherein the pyrolysis temperature is 800 to 850 ℃ and the pyrolysis time is 3 to 6 hours in step 2.
7. Use of a silicon-carbon composite material prepared by the method according to any one of claims 1 to 6 for the preparation of a negative electrode material for a lithium ion battery.
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