CN105098136B - Preparation method and application of silicon oxycarbide/carbon composite micronano material - Google Patents

Preparation method and application of silicon oxycarbide/carbon composite micronano material Download PDF

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CN105098136B
CN105098136B CN201510535697.7A CN201510535697A CN105098136B CN 105098136 B CN105098136 B CN 105098136B CN 201510535697 A CN201510535697 A CN 201510535697A CN 105098136 B CN105098136 B CN 105098136B
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carbon composite
silicon oxide
silane
carbon
preparation
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CN105098136A (en
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程亚军
王梅梅
朱锦
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

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Abstract

The invention discloses preparation method and application of a silicon oxycarbide/carbon composite micronano material. The preparation method comprises the following steps of mixing a thermosetting resin monomer and a photoinitiator according to a certain proportion to serve as a reaction medium and a carbon source; adding a siliane coupling agent; mixing the siliane coupling agent with the thermosetting resin monomer and the photoinitiator in a molecular level; calcining and reducing in an inert atmosphere by combining a photocuring polymerization method to obtain ultra small silicon oxide nano particles uniformly dispersed in a carbon substrate and having controlled morphology; and preparing to obtain the silicon oxycarbide/carbon composite micronano material. The preparation method is simple and feasible, operation time is short, post-treatment of the traditional organic solvent is avoided, and the silicon oxycarbide/carbon composite micronano material is green and environment friendly and has favorable performance when serving as an anode material of a lithium ion battery.

Description

A kind of preparation method and applications of silicon oxide carbide/carbon composite micro-nano rice material
Technical field
The invention belongs to polymeric material field, is related to the preparation method of silicon oxide carbide/carbon composite micro-nano rice material, and Application of the material of preparation in lithium ion battery negative material.
Background technology
Silicon oxide carbide is a kind of ceramic material of carbon elements, can be by silicones or methane-siliconic acid in an inert atmosphere 600 DEG C～1000 DEG C at thermal cracking and obtain, with excellent electrical insulation capability and heat endurance.
In recent years, silicon oxide carbide obtained in polysiloxanes is due to good charge/discharge capacity and cycle performance, in lithium ion Field of batteries causes the interest of many researchers.Silica carbon network structure therein is very stable, has very during discharge and recharge Little Volume Changes, can as far as possible ensure the integrality of electrode material, bring good cyclical stability.At present document report is more Silicon oxycarbide compound is obtained by carrying out cracking to linear or lightly crosslinked polysiloxanes.These methods are for regulation and control silica Carbon/carbon compound material micro-structural and carbon content are limited in one's ability, are unfavorable for further optimizing its structural behaviour, hinder It is used as lithium ion battery negative material practical application.
The content of the invention
It is an object of the invention to be directed to the deficiencies in the prior art, there is provided a kind of silicon oxide carbide/carbon composite micro-nano rice material The preparation method of material.The method adopts thermosetting acrylate resin monomer as reaction dissolvent and carbon source, can be with acrylate The silane coupler of polymerization reacts as silicon oxycarbide compound presoma with reference to visible light polymerization, using silane coupler and heat Solidity acrylate resin monomer copolyreaction, in molecular level silane coupler/thermosetting resin nano-hybrid material is constructed. Further combined with inert atmosphere calcining, by the way that original position is coupled with original position into carbon into silicon oxycarbide compound, Effective Regulation silica carbon And carbon matrix micro-structural and content.It is feasible that the method has widened silica carbon/carbon nano-hybrid material structure-performance regulation and control significantly Property.Additionally, this method is simple, the operating time is short, it also avoid conventional organic solvents post processing, environmental protection.
The inventive method is comprised the concrete steps that：
Step (1). light trigger is added in thermosetting acrylate resin solution, is set after stirring under normal temperature Lipoprotein solution；Wherein the mass content of light trigger is 0.2%～2.0%；
Described thermosetting acrylate resin is bisphenol-A glycerine double methyl methacrylate, bisphenol-A methacrylic acid Ethylene oxidic ester, urethanes dimethylacrylate, TEGDMA, bisphenol-A epoxy acrylic acid In ester, IPDI urethane methacrylates, ethoxylated bisphenol A dimethylacrylates, aliphatic urethane acrylate One or several；
Described light trigger be double (2,4,6- trimethylbenzoyls) phosphine oxide of phenyl, gorgeous good solid 1173, it is gorgeous good solid 184th, gorgeous good solid 2959, gorgeous good solid 907, gorgeous good solid 369, gorgeous good solid 819, gorgeous good solid 754 or camphorquinone in it is a kind of or several Kind；
Step (2). silane coupler, acrylic monomers are added in the resin solution that step (1) is obtained, are stirred To mixed solution；Contain 0.125g～2g acrylic monomers, 0.125g～24g silane couplers in per 2g resin solutions；
Described silane coupler is hexadecyl trimethoxy silane, the γ-ethoxy of (methacryloxy) propyl group three Base silane, n- octyl group trimethoxy silanes, n- octyltri-ethoxysilanes, trimethoxysilane, the ethoxy of isobutyl group three Base silane, vinyl trimethoxy Ethoxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, dodecyl three Ethoxysilane, dodecyltrimethoxysilane, VTES, vinyltrimethoxy silane, vinyl Triacetoxysilane, γ-(methacryloxy) propyl trimethoxy silicane, γ-(methacryloxypropyl) hydroxypropyl methyl Dimethoxysilane, 17 fluorine decyl triethoxysilanes or γ-glycydoxy trimethoxy silane；
Described acrylic monomers is acrylic or methacrylic acid；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2～3 minutes, and 6～24h is then incubated at 30 DEG C～80 DEG C to have solidified Entirely；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, is calcined under inert atmosphere, obtained To silicon oxide carbide/carbon composite powder.
Described calcination temperature range is 600 DEG C～1200 DEG C, is calcined 1～8 hour.
Another object of the present invention is silicon oxide carbide/carbon composite powder for preparing of said method in lithium ion battery Application in terms of negative material.
The inventive method cooks reactant from the ripe thermosetting resin of polymerization, silane coupler cheap and easy to get, both The mixing of molecular level is reached by the effect of covalent bond, the less silicon oxide carbide of size/carbon composite micro-nano rice material, carbon is obtained Silicon oxide particle can be evenly dispersed in carbon matrix in molecular level.Using light initiation polymerization, time short operation is easy, instead System is answered not have poor solvent, environmental protection.Material as lithium ion battery negative material, with preferable lithium electrical property.
Description of the drawings
Fig. 1 is the silicon oxide carbide/carbon composite powder transmission electron microscope picture prepared in embodiment 1；
Fig. 2 is the silicon oxide carbide/carbon composite powder XRD prepared in embodiment 3；
Fig. 3 is the silicon oxide carbide/carbon composite powder performance of lithium ion battery data prepared in embodiment 5.
Specific embodiment
The present invention is further analyzed below in conjunction with the accompanying drawings.
Embodiment 1.
Step (1). double (2,4,6- trimethylbenzoyls) phosphine oxides of 2g light triggers phenyl are added into 998g bisphenol-As third In triol double methyl methacrylate solution, after stirring 5 minutes under normal temperature 1kg resin solutions are obtained；
Step (2). 200g steps (1) resin solution is taken, 12.5g silane coupler hexadecyl trimethoxy silicon is added In alkane, 12.5g acrylic acid, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 24h is then incubated at 30 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 600 DEG C of inert atmosphere is forged Burn 8 hours, obtain silicon oxide carbide/carbon composite powder.
Silicon oxide carbide particle can be uniform in carbon matrix in silicon oxide carbide/carbon composite powder that the embodiment is prepared Dispersion, as shown in Figure 1.
Embodiment 2.
Step (1). 20g light triggers gorgeous good solid 1173 are added into 980g bisphenol-A GMA solution In, obtain 1kg resin solutions after stirring 5 minutes under normal temperature；
Step (2). 200g steps (1) resin solution is taken, 200g silane coupler γ-(methacryloxy) third is added In ethyl triethoxy silicane alkane, 50g methacrylic acids, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 3 minutes, and 6h is then incubated at 80 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 1200 DEG C of inert atmosphere is forged Burn 1 hour, obtain silicon oxide carbide/carbon composite powder.
Embodiment 3.
Step (1). 5g light triggers gorgeous good solid 184 are added into 995g urethanes dimethylacrylate solution In, obtain 1kg resin solutions after stirring 5 minutes under normal temperature；
Step (2). take 200g steps (1) resin solution, add 15g silane coupler n- octyl group trimethoxy silanes, In 2400g acrylic acid, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2.5 minutes, and 22h is then incubated at 40 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 700 DEG C of inert atmosphere is forged Burn 7.5 hours, obtain silicon oxide carbide/carbon composite powder.XRD data prove that silicon oxide carbide particle is amorphous state, are present in micro- In the carbon matrix of crystal structure (Fig. 2).
Embodiment 4.
Step (1). 10g light triggers gorgeous good solid 2959 are added in 990g TEGDMA solution, 1kg resin solutions are obtained after stirring 5 minutes under normal temperature；
Step (2). take 200g steps (1) resin solution, add 20g silane coupler n- octyltri-ethoxysilanes, In 2000g methacrylic acids, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 20h is then incubated at 50 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 800 DEG C of inert atmosphere is forged Burn 7 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 5.
Step (1). 15g light triggers gorgeous good solid 907 are added in 985g bisphenol A epoxy acrylate solution, under normal temperature Stirring obtains 1kg resin solutions after 5 minutes；
Step (2). take 200g steps (1) resin solution, add 50g silane coupler trimethoxysilanes, In 1500g acrylic acid, stirring obtains mixed solution in 5 minutes；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 3 minutes, and 15h is then incubated at 60 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 900 DEG C of inert atmosphere is forged Burn 6 hours, obtain silicon oxide carbide/carbon composite powder.Fig. 3 illustrates that it has preferable lithium electricity as lithium ion battery negative material Performance.
Embodiment 6.
Step (1). 12g light triggers gorgeous good solid 369 are added in 988g IPDI urethane methacrylate solution, 1kg resin solutions are obtained after stirring 5 minutes under normal temperature；
Step (2). take 200g steps (1) resin solution, add 120g silane coupler isobutyl triethoxy silanes, In 1000g acrylic acid, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 8h is then incubated at 70 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 1000 DEG C of inert atmosphere is forged Burn 2 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 7.
Step (1). 8g light triggers gorgeous good solid 819 are added in 992g vinyl trimethoxy Ethoxysilane solution, 1kg resin solutions are obtained after stirring 5 minutes under normal temperature；
Step (2). 200g steps (1) resin solution is taken, 150g silane coupling agent vinyl trimethoxy ethyoxyls are added In silane, 50g methacrylic acids, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 7h is then incubated at 80 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 1100 DEG C of inert atmosphere is forged Burn 2 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 8.
Step (1). 2g light triggers gorgeous good solid 754 are added in 998g aliphatic urethane acrylate solution, normal temperature Lower stirring obtains 1kg resin solutions after 5 minutes；
Step (2). 200g steps (1) resin solution is taken, 12.5g silane coupler 2- (3,4- epoxycyclohexyl) second is added In base trimethoxy silane, 100g acrylic acid, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 24h is then incubated at 30 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 800 DEG C of inert atmosphere is forged Burn 5 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 9.
Step (1). 2g light triggers camphorquinone is added in 998g bisphenol-A glycerine double methyl methacrylate solution, often The lower stirring of temperature obtains 1kg resin solutions after 5 minutes；
Step (2). 200g steps (1) resin solution is taken, 12.5g silane coupler dodecyl triethoxysilicanes are added In alkane, 12.5g acrylic acid, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 24h is then incubated at 30 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 600 DEG C of inert atmosphere is forged Burn 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 10.
Step (1). double (2,4,6- trimethylbenzoyls) phosphine oxides of 2g light triggers phenyl are added into 998g bisphenol-As third In triol double methyl methacrylate solution, after stirring 5 minutes under normal temperature 1kg resin solutions are obtained；
Step (2). 200g steps (1) resin solution is taken, 12.5g silane coupler dodecyl trimethoxy silicon is added In alkane, 12.5g acrylic acid, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 24h is then incubated at 30 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 600 DEG C of inert atmosphere is forged Burn 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 11.
Step (1). double (2,4,6- trimethylbenzoyls) phosphine oxides of 2g light triggers phenyl are added into 998g bisphenol-As third In triol double methyl methacrylate solution, after stirring 5 minutes under normal temperature 1kg resin solutions are obtained；
Step (2). take 200g steps (1) resin solution, add 12.5g silane coupling agent vinyl triethoxysilanes, In 12.5g acrylic acid, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 24h is then incubated at 30 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 600 DEG C of inert atmosphere is forged Burn 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 12.
Step (1). double (2,4,6- trimethylbenzoyls) phosphine oxides of 2g light triggers phenyl are added into 998g bisphenol-As third In triol double methyl methacrylate solution, after stirring 5 minutes under normal temperature 1kg resin solutions are obtained；
Step (2). take 200g steps (1) resin solution, add 12.5g silane coupling agent vinyl trimethoxy silanes, In 12.5g acrylic acid, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 24h is then incubated at 30 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 600 DEG C of inert atmosphere is forged Burn 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 13.
Step (1). double (2,4,6- trimethylbenzoyls) phosphine oxides of 2g light triggers phenyl are added into 998g bisphenol-As third In triol double methyl methacrylate solution, after stirring 5 minutes under normal temperature 1kg resin solutions are obtained；
Step (2). 200g steps (1) resin solution is taken, 12.5g silane coupling agent vinyl triacetoxyl group silicon is added In alkane, 12.5g acrylic acid, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 24h is then incubated at 30 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 600 DEG C of inert atmosphere is forged Burn 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 14.
Step (1). double (2,4,6- trimethylbenzoyls) phosphine oxides of 2g light triggers phenyl are added into 998g bisphenol-As third In triol double methyl methacrylate solution, after stirring 5 minutes under normal temperature 1kg resin solutions are obtained；
Step (2). 200g steps (1) resin solution is taken, 12.5g silane coupler γ-(methacryloxy) is added Propyl trimethoxy silicane, 12.5g acrylic acid, are uniformly mixing to obtain mixed solution；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 24h is then incubated at 30 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 600 DEG C of inert atmosphere is forged Burn 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 15.
Step (1). double (2,4,6- trimethylbenzoyls) phosphine oxides of 2g light triggers phenyl are added into 998g bisphenol-As third In triol double methyl methacrylate solution, after stirring 5 minutes under normal temperature 1kg resin solutions are obtained；
Step (2). 200g steps (1) resin solution is taken, 12.5g silane coupler γ-(methacryloxypropyl) third is added In ylmethyl dimethoxysilane, 12.5g acrylic acid, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 24h is then incubated at 30 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 600 DEG C of inert atmosphere is forged Burn 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 16.
Step (1). double (2,4,6- trimethylbenzoyls) phosphine oxides of 2g light triggers phenyl are added into 998g bisphenol-As third In triol double methyl methacrylate solution, after stirring 5 minutes under normal temperature 1kg resin solutions are obtained；
Step (2). 200g steps (1) resin solution is taken, the fluorine decyl triethoxysilicane of 12.5g silane couplers 17 is added During alkane, 12.5g acrylic acid are added to, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 24h is then incubated at 30 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 600 DEG C of inert atmosphere is forged Burn 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 17.
Step (1). double (2,4,6- trimethylbenzoyls) phosphine oxides of 2g light triggers phenyl are added into 998g bisphenol-As In glycerine double methyl methacrylate solution, after stirring 5 minutes under normal temperature 1kg resin solutions are obtained；
Step (2). 200g steps (1) resin solution is taken, 12.5g silane coupler γ-glycidol ether epoxide third is added In base trimethoxy silane, 12.5g methacrylic acids, mixed solution is uniformly mixing to obtain；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then upper Side covers a slide, and upper and lower surface respectively solidifies 2 minutes, and 24h is then incubated at 30 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, lower 600 DEG C of inert atmosphere is forged Burn 8 hours, obtain silicon oxide carbide/carbon composite powder.
Silicon oxide carbide particle can be in carbon matrix in silicon oxide carbide/carbon composite powder obtained by above-described embodiment preparation Even dispersion, and silicon oxide carbide particle is amorphous state, in being present in the carbon matrix of microstructure.Simultaneously above-mentioned material can conduct Lithium ion battery negative material, with preferable lithium electrical property.

Claims (8)

1. the preparation method of a kind of silicon oxide carbide/carbon composite micro-nano rice material, it is characterised in that using thermosetting acrylate tree Alicyclic monomer is closed as reaction dissolvent and carbon source, the silane coupler that polymerisation can occur with acrylate as silicon oxycarbide Thing presoma, with reference to visible light polymerization reaction, using silane coupler and thermosetting acrylate resin monomer copolyreaction, Molecular level constructs silane coupler/thermosetting resin nano-hybrid material；Further combined with inert atmosphere calcining, by by original Position couples with situ into carbon into silicon oxycarbide compound, Effective Regulation silica carbon and carbon matrix micro-structural and content.
2. a kind of preparation method of silicon oxide carbide/carbon composite micro-nano rice material as claimed in claim 1, it is characterised in that the party Method is comprised the following steps：
Step (1). light trigger is added in thermosetting acrylate resin solution, resin is obtained after stirring under normal temperature molten Liquid；Wherein the mass content of light trigger is 0.2%～2.0%；
Step (2). silane coupler, acrylic monomers are added in the resin solution that step (1) is obtained, are uniformly mixing to obtain mixed Close solution；Contain 0.125g～2g acrylic monomers, 0.125g～24g silane couplers in per 2g resin solutions；
Step (3). the mixed solution for obtaining step (2) is imported in the silica gel pattern mould being placed on slide, then is up covered A upper slide, upper and lower surface respectively solidifies 2～3 minutes, and 6～24h is then incubated at 30 DEG C～80 DEG C with completion of cure；
Step (4). step (3) gained solid is placed in corundum crucible, tube furnace is placed in, is calcined under inert atmosphere, obtain carbon Silica/carbon composite powder.
3. the preparation method of a kind of silicon oxide carbide/carbon composite micro-nano rice material as claimed in claim 1 or 2, it is characterised in that Described thermosetting acrylate resin is bisphenol-A glycerine double methyl methacrylate, bisphenol-A methyl propenoic acid glycidyl Ester, urethanes dimethylacrylate, TEGDMA, bisphenol A epoxy acrylate, IPDI gather It is a kind of or several in urethane methacrylate, ethoxylated bisphenol A dimethylacrylates, aliphatic urethane acrylate Kind.
4. the preparation method of a kind of silicon oxide carbide/carbon composite micro-nano rice material as claimed in claim 2, it is characterised in that described Light trigger be double (2,4,6- trimethylbenzoyls) phosphine oxide of phenyl, gorgeous good solid 1173, gorgeous good solid 184, it is gorgeous good solid 2959th, gorgeous good solid 907, gorgeous good solid 369, gorgeous good solid 819, gorgeous good solid 754 or camphorquinone in one or several.
5. the preparation method of a kind of silicon oxide carbide/carbon composite micro-nano rice material as claimed in claim 1 or 2, it is characterised in that Described silane coupler is hexadecyl trimethoxy silane, γ-(methacryloxy) propyl-triethoxysilicane, n- Octyl group trimethoxy silane, n- octyltri-ethoxysilanes, trimethoxysilane, isobutyl triethoxy silane, second Thiazolinyl trimethoxy Ethoxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, dodecyl triethoxysilicane Alkane, dodecyltrimethoxysilane, VTES, vinyltrimethoxy silane, vinyl triacetyl oxygen Base silane, γ-(methacryloxy) propyl trimethoxy silicane, γ-(methacryloxypropyl) hydroxypropyl methyl dimethoxy Silane, 17 fluorine decyl triethoxysilanes or γ-glycydoxy trimethoxy silane.
6. the preparation method of a kind of silicon oxide carbide/carbon composite micro-nano rice material as claimed in claim 2, it is characterised in that described Acrylic monomers be acrylic or methacrylic acid.
7. the preparation method of a kind of silicon oxide carbide/carbon composite micro-nano rice material as claimed in claim 1 or 2, it is characterised in that Described calcination temperature range is 600 DEG C～1200 DEG C, is calcined 1～8 hour.
8. method as claimed in claim 1 or 2 prepares gained silicon oxide carbide/carbon composite powder in lithium ion battery negative material The application of aspect.
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