CN105098136A - 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 PDFInfo
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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
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- 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
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- 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
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/139—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
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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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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 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
Technical field
The invention belongs to polymeric material field, relate to the preparation method of silicon oxide carbide/carbon composite micro-nano rice material, and the application of material in lithium ion battery negative material of preparation.
Background technology
Silicon oxide carbide is a kind of ceramic material of carbon elements, can be obtained by thermal cracking at silicones or methane-siliconic acid 600 DEG C in an inert atmosphere ~ 1000 DEG C, has excellent electrical insulation capability and thermal stability.
In recent years, the silicon oxide carbide that polysiloxanes obtains, due to good charge/discharge capacity and cycle performance, causes the interest of many researchers in field of lithium ion battery.Silica carbon network configuration is wherein very stable, has very little change in volume in the process of discharge and recharge, can ensure the integrality of electrode material as far as possible, bring good cyclical stability.Current bibliographical information is many obtains silicon oxycarbide compound by carrying out cracking to linear or lightly crosslinked polysiloxanes.These methods for regulation and control silica carbon/carbon compound material micro-structural and carbon content limited in one's ability, be unfavorable for further optimizing its structural behaviour, hinder it as lithium ion battery negative material practical application.
Summary of the invention
An object of the present invention is for the deficiencies in the prior art, the preparation method of a kind of silicon oxide carbide/carbon composite micro-nano rice material is provided.The method adopts thermosetting acrylate resin monomer as reaction dissolvent and carbon source, can with the silane coupler of acrylic ester polymerization as silicon oxycarbide compound presoma, react in conjunction with visible light polymerization, utilize silane coupler and the copolyreaction of thermosetting acrylate resin monomer, construct silane coupler/thermosetting resin nano-hybrid material at molecular level.Further combined with inert atmosphere calcining, by original position being become carbon and original position to become silicon oxycarbide compound to be coupled, Effective Regulation silica carbon and carbon matrix micro-structural and content.The method has widened silica carbon/carbon nano-hybrid material structure-performance regulation and control feasibility greatly.In addition, this method is simple, and the operating time is short, it also avoid conventional organic solvents reprocessing, environmental protection.
The concrete steps of the inventive method are:
Step (1). light trigger is added in thermosetting acrylate resin solution, after stirring under normal temperature, obtain resin solution; Wherein the mass content of light trigger is 0.2% ~ 2.0%;
Described thermosetting acrylate resin is one or several in bisphenol-A glycerol double methyl methacrylate, bisphenol-A glycidyl methacrylate, urethanes dimethylacrylate, TEGDMA, bisphenol A epoxy acrylate, IPDI urethane methacrylate, ethoxylated bisphenol A dimethylacrylate, aliphatic urethane acrylate;
Described light trigger is phenyl two (2,4,6-trimethylbenzoyl) phosphine oxide, gorgeous good solid 1173, gorgeous good solid 184, gorgeous good solid 2959, gorgeous good solid 907, gorgeous good solid 369, gorgeous good solid 819, gorgeous good solid 754 or camphorquinone in one or several;
Step (2). silane coupler, acrylic monomers are added in the resin solution that step (1) obtains, stir and obtain mixed solution; Containing 0.125g ~ 2g acrylic monomers, 0.125g ~ 24g silane coupler in every 2g resin solution;
Described silane coupler is hexadecyl trimethoxy silane, γ-(methacryloxy) propyl-triethoxysilicane, n-octyl group trimethoxy silane, n-octyltri-ethoxysilane, trimethoxysilane, isobutyl triethoxy silane, vinyl trimethoxy Ethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, dodecyl triethoxysilane, dodecyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyltriacetoxy silane, 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). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, cover a slide more up, upper and lower surface respectively solidifies 2 ~ 3 minutes, at 30 DEG C ~ 80 DEG C, is then incubated 6 ~ 24h with completion of cure;
Step (4). step (3) gained solid is placed in corundum crucible, is placed in tube furnace, calcine under inert atmosphere, obtain silicon oxide carbide/carbon composite powder.
Described calcination temperature range is 600 DEG C ~ 1200 DEG C, calcines 1 ~ 8 hour.
Another object of the present invention is the application of silicon oxide carbide/carbon composite powder in lithium ion battery negative material that said method prepares.
The thermosetting resin that the inventive method selects polymerization ripe, silane coupler cheap and easy to get cooks reactant, both reach the mixing of molecular level by the effect of covalent bond, obtain the less silicon oxide carbide of size/carbon composite micro-nano rice material, silicon oxide carbide particle can be evenly dispersed in carbon matrix at molecular level.Adopt light initiation polymerization, time short operation is easy, and reaction system does not have poor solvent, environmental protection.Material, as lithium ion battery negative material, has good lithium electrical property.
Accompanying drawing explanation
Fig. 1 is the silicon oxide carbide/carbon composite powder transmission electron microscope picture of preparation in embodiment 1;
Fig. 2 is that the silicon oxide carbide/carbon composite powder XRD of preparation in embodiment 3 schemes;
Fig. 3 is the silicon oxide carbide/carbon composite powder performance of lithium ion battery data of preparation in embodiment 5.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further analyzed.
Embodiment 1.
Step (1). two for 2g light trigger phenyl (2,4,6-trimethylbenzoyl) phosphine oxide is added in 998g bisphenol-A glycerol double methyl methacrylate solution, stirs under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 12.5g silane coupler hexadecyl trimethoxy silane, 12.5g acrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 30 DEG C, is incubated 24h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 600 DEG C of calcinings of inert atmosphere 8 hours, obtain silicon oxide carbide/carbon composite powder.
In silicon oxide carbide/carbon composite powder that this embodiment prepares, silicon oxide carbide particle can be dispersed in carbon matrix, as shown in Figure 1.
Embodiment 2.
Step (1). add in 980g bisphenol-A glycidyl methacrylate solution by gorgeous for 20g light trigger good solid 1173, stir under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 200g silane coupler γ-(methacryloxy) propyl-triethoxysilicane, 50g methacrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 3 minutes, then at 80 DEG C, is incubated 6h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 1200 DEG C of calcinings of inert atmosphere 1 hour, obtain silicon oxide carbide/carbon composite powder.
Embodiment 3.
Step (1). add in 995g urethanes dimethylacrylate solution by gorgeous for 5g light trigger good solid 184, stir under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 15g silane coupler n-octyl group trimethoxy silane, 2400g acrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2.5 minutes, then at 40 DEG C, is incubated 22h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 700 DEG C of calcinings of inert atmosphere 7.5 hours, obtain silicon oxide carbide/carbon composite powder.XRD digital proof silicon oxide carbide particle is amorphous state, is present in (Fig. 2) in the carbon matrix of microstructure.
Embodiment 4.
Step (1). add in 990g TEGDMA solution by gorgeous for 10g light trigger good solid 2959, stir under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 20g silane coupler n-octyltri-ethoxysilane, 2000g methacrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 50 DEG C, is incubated 20h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 800 DEG C of calcinings of inert atmosphere 7 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 5.
Step (1). add in 985g bisphenol A epoxy acrylate solution by gorgeous for 15g light trigger good solid 907, stir under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 50g silane coupler trimethoxysilane, 1500g acrylic acid, stir and obtain mixed solution in 5 minutes;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 3 minutes, then at 60 DEG C, is incubated 15h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 900 DEG C of calcinings of inert atmosphere 6 hours, obtain silicon oxide carbide/carbon composite powder.Fig. 3 illustrates that it has good lithium electrical property as lithium ion battery negative material.
Embodiment 6.
Step (1). add in 988gIPDI urethane methacrylate solution by gorgeous for 12g light trigger good solid 369, stir under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 120g silane coupler isobutyl triethoxy silane, 1000g acrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 70 DEG C, is incubated 8h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 1000 DEG C of calcinings of inert atmosphere 2 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 7.
Step (1). add in 992g vinyl trimethoxy Ethoxysilane solution by gorgeous for 8g light trigger good solid 819, stir under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 150g silane coupling agent vinyl trimethoxy Ethoxysilane, 50g methacrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 80 DEG C, is incubated 7h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 1100 DEG C of calcinings of inert atmosphere 2 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 8.
Step (1). add in 998g aliphatic urethane acrylate solution by gorgeous for 2g light trigger good solid 754, stir under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 12.5g silane coupler 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 100g acrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 30 DEG C, is incubated 24h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 800 DEG C of calcinings of inert atmosphere 5 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 9.
Step (1). 2g light trigger camphorquinone is added in 998g bisphenol-A glycerol double methyl methacrylate solution, stir under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 12.5g silane coupler dodecyl triethoxysilane, 12.5g acrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 30 DEG C, is incubated 24h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 600 DEG C of calcinings of inert atmosphere 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 10.
Step (1). two for 2g light trigger phenyl (2,4,6-trimethylbenzoyl) phosphine oxide is added in 998g bisphenol-A glycerol double methyl methacrylate solution, stirs under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 12.5g silane coupler dodecyltrimethoxysilane, 12.5g acrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 30 DEG C, is incubated 24h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 600 DEG C of calcinings of inert atmosphere 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 11.
Step (1). two for 2g light trigger phenyl (2,4,6-trimethylbenzoyl) phosphine oxide is added in 998g bisphenol-A glycerol double methyl methacrylate solution, stirs under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 12.5g silane coupling agent vinyl triethoxysilane, 12.5g acrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 30 DEG C, is incubated 24h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 600 DEG C of calcinings of inert atmosphere 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 12.
Step (1). two for 2g light trigger phenyl (2,4,6-trimethylbenzoyl) phosphine oxide is added in 998g bisphenol-A glycerol double methyl methacrylate solution, stirs under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 12.5g silane coupling agent vinyl trimethoxy silane, 12.5g acrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 30 DEG C, is incubated 24h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 600 DEG C of calcinings of inert atmosphere 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 13.
Step (1). two for 2g light trigger phenyl (2,4,6-trimethylbenzoyl) phosphine oxide is added in 998g bisphenol-A glycerol double methyl methacrylate solution, stirs under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 12.5g silane coupling agent vinyl triacetoxysilane, 12.5g acrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 30 DEG C, is incubated 24h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 600 DEG C of calcinings of inert atmosphere 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 14.
Step (1). two for 2g light trigger phenyl (2,4,6-trimethylbenzoyl) phosphine oxide is added in 998g bisphenol-A glycerol double methyl methacrylate solution, stirs under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add 12.5g silane coupler γ-(methacryloxy) propyl trimethoxy silicane, 12.5g acrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 30 DEG C, is incubated 24h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 600 DEG C of calcinings of inert atmosphere 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 15.
Step (1). two for 2g light trigger phenyl (2,4,6-trimethylbenzoyl) phosphine oxide is added in 998g bisphenol-A glycerol double methyl methacrylate solution, stirs under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 12.5g silane coupler γ-(methacryloxypropyl) hydroxypropyl methyl dimethoxysilane, 12.5g acrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 30 DEG C, is incubated 24h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 600 DEG C of calcinings of inert atmosphere 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 16.
Step (1). two for 2g light trigger phenyl (2,4,6-trimethylbenzoyl) phosphine oxide is added in 998g bisphenol-A glycerol double methyl methacrylate solution, stirs under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add 12.5g silane coupler 17 fluorine decyl triethoxysilane, during 12.5g acrylic acid is added to, stirs and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 30 DEG C, is incubated 24h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 600 DEG C of calcinings of inert atmosphere 8 hours, obtain silicon oxide carbide/carbon composite powder.
Embodiment 17.
Step (1). two for 2g light trigger phenyl (2,4,6-trimethylbenzoyl) phosphine oxide is added in 998g bisphenol-A glycerol double methyl methacrylate solution, stirs under normal temperature after 5 minutes and obtain 1kg resin solution;
Step (2). get 200g step (1) resin solution, add in 12.5g silane coupler γ-glycydoxy trimethoxy silane, 12.5g methacrylic acid, stir and obtain mixed solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, then covers a slide up, and upper and lower surface respectively solidifies 2 minutes, then at 30 DEG C, is incubated 24h with completion of cure;
Step (4). be placed in corundum crucible by step (3) gained solid, be placed in tube furnace, the lower 600 DEG C of calcinings of inert atmosphere 8 hours, obtain silicon oxide carbide/carbon composite powder.
Above-described embodiment prepares silicon oxide carbide particle in the silicon oxide carbide/carbon composite powder of gained can be dispersed in carbon matrix, and silicon oxide carbide particle is amorphous state, is present in the carbon matrix of microstructure.Above-mentioned material all can be used as lithium ion battery negative material simultaneously, has good lithium electrical property.
Claims (8)
1. the preparation method of silicon oxide carbide/carbon composite micro-nano rice material, it is characterized in that adopting thermosetting acrylate resin monomer as reaction dissolvent and carbon source, with the silane coupler of acrylic ester polymerization as silicon oxycarbide compound presoma, react in conjunction with visible light polymerization, utilize silane coupler and the copolyreaction of thermosetting acrylate resin monomer, construct silane coupler/thermosetting resin nano-hybrid material at molecular level; Further combined with inert atmosphere calcining, by original position being become carbon and original position to become silicon oxycarbide compound to be coupled, Effective Regulation silica carbon and carbon matrix micro-structural and content.
2. the preparation method of a kind of silicon oxide carbide as claimed in claim 1/carbon composite micro-nano rice material, is characterized in that the method specifically comprises the following steps:
Step (1). light trigger is added in thermosetting acrylate resin solution, after stirring under normal temperature, obtain resin solution; 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) obtains, stir and obtain mixed solution; Containing 0.125g ~ 2g acrylic monomers, 0.125g ~ 24g silane coupler in every 2g resin solution;
Step (3). mixed solution step (2) obtained imports in the silica gel pattern mould be placed on slide, cover a slide more up, upper and lower surface respectively solidifies 2 ~ 3 minutes, at 30 DEG C ~ 80 DEG C, is then incubated 6 ~ 24h with completion of cure;
Step (4). step (3) gained solid is placed in corundum crucible, is placed in tube furnace, calcine under inert atmosphere, obtain silicon oxide carbide/carbon composite powder.
3. the preparation method of a kind of silicon oxide carbide as claimed in claim 1 or 2/carbon composite micro-nano rice material, is characterized in that described thermosetting acrylate resin is one or several in bisphenol-A glycerol double methyl methacrylate, bisphenol-A glycidyl methacrylate, urethanes dimethylacrylate, TEGDMA, bisphenol A epoxy acrylate, IPDI urethane methacrylate, ethoxylated bisphenol A dimethylacrylate, aliphatic urethane acrylate.
4. the preparation method of a kind of silicon oxide carbide as claimed in claim 1 or 2/carbon composite micro-nano rice material; it is characterized in that described light trigger is phenyl two (2; 4,6-trimethylbenzoyl) phosphine oxide, gorgeous good solid 1173, gorgeous good solid 184, gorgeous good solid 2959, 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 as claimed in claim 1 or 2/carbon composite micro-nano rice material, it is characterized in that described silane coupler is hexadecyl trimethoxy silane, γ-(methacryloxy) propyl-triethoxysilicane, n-octyl group trimethoxy silane, n-octyltri-ethoxysilane, trimethoxysilane, isobutyl triethoxy silane, vinyl trimethoxy Ethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, dodecyl triethoxysilane, dodecyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyltriacetoxy silane, γ-(methacryloxy) propyl trimethoxy silicane, γ-(methacryloxypropyl) hydroxypropyl methyl dimethoxysilane, 17 fluorine decyl triethoxysilanes or γ-glycydoxy trimethoxy silane.
6. the preparation method of a kind of silicon oxide carbide as claimed in claim 1 or 2/carbon composite micro-nano rice material, is characterized in that described acrylic monomers is acrylic or methacrylic acid.
7. the preparation method of a kind of silicon oxide carbide as claimed in claim 1 or 2/carbon composite micro-nano rice material, is characterized in that described calcination temperature range is 600 DEG C ~ 1200 DEG C, calcines 1 ~ 8 hour.
8. method as claimed in claim 1 or 2 prepares the application of gained silicon oxide carbide/carbon composite powder in lithium ion battery negative material.
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