CN105977478B - Cellular three-dimensional porous Si-C composite material of one kind and preparation method thereof - Google Patents
Cellular three-dimensional porous Si-C composite material of one kind and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses cellular three-dimensional porous Si-C composite material of one kind and preparation method thereof.The porous Si-C composite material is the hybrid structure that nano silicon spheres are distributed in cellular, continuous three-dimensional porous carbon matrix；Wherein the mass content of carbon is that 99~1 ﹪ are controllable.It is prepared using the first compound rear method restored using thermosetting property bifunctional acrylate's class unsaturated-resin as carbon source as silicon source using 80~800nm preparing spherical SiO 2s nano-particle；Wherein esters of acrylic acid unsaturated-resin monomer is vinyl thermoset resin.The present invention is avoided conventional thermosetting resin and is needed using the cumbersome of solvent by vinyl thermoset resin in-situ polymerization, easy to operate without post-processing, environmentally protective；Simultaneously because thermosetting resin is difficult to happen melting in high-temperature burning process, original position may be implemented into carbon, be capable of the distribution situation of Effective Regulation silica, to regulate and control the pattern of final product.
Description
Technical field
The invention belongs to the preparation fields of nanoporous composite material, and in particular to a kind of In-situ reaction, in situ at carbon, magnesium
Thermal reduction prepares the continuous poriferous Si-C composite material of cellular three-dimensional and its method.
Background technology
With the rapid development of the industries such as electric vehicle, the demand to high-energy density and high power density lithium ion battery
It is increasingly urgent to.Commercial Li-ion battery negative material generally uses graphite type material at present, but the theoretical storage lithium of graphite holds
Amount only has 372mAh/g, and intercalation potential platform easily occurs analysis lithium phenomenon and draw close to lithium metal, quick charge or low temperature charging
Security risk is sent out, therefore it is extremely urgent to develop novel high-performance negative material.The theoretical specific capacity of silicon is up to 4200mAh/g,
And removal lithium embedded current potential is moderate, resourceful, is one of most promising high-performance lithium ion negative material.However silicon is de-
It will produce huge volume change (up to 300%) in process of intercalation, cause silicon particle to be crushed, dusting, lose electroactive, performance
For very poor cyclical stability.On the other hand, the electric conductivity of silicon is poor, and rate charge-discharge performance is also performed poor.Therefore, such as
What effective volume expansion for alleviating silicium cathode in battery charge and discharge process and the electric conductivity for how improving silicium cathode material,
Improve the problem of its chemical property is this field urgent need to resolve.
In conclusion still to lack a kind of lithium ion battery silicon substrate with height ratio capacity and high circulation stability negative for this field
Pole material.
The present invention provides a kind of preparation method of cellular porous Si-C composite material, using existing maturation process,
Process is easy, easily operated；The even aperture distribution for the porous Si-C composite material being prepared, size is adjustable, can be used as lithium
Ion battery cathode material uses, and has higher specific capacity and good cyclical stability.
The current report in relation to cellular three-dimensional porous Si-C composite material is more rare, patent
CN201510054606.8, CN201410276413.2 and CN201510007562.9 report a kind of porous Si-C composite material
Preparation method, gained porous silicon is not regular cellular continuous structure.
The present invention uses Nano particles of silicon dioxide as silicon source, unsaturated using thermosetting property bifunctional acrylate class
Silica is dispersed in resin monomer first and carries out in-situ solidifying, obtained containing silica by resin as carbon source
Blocks of solid, then inert atmosphere high-temperature calcination carry out in situ at carbon, then, after product is mixed with magnesium powder under inert atmosphere into
Row magnesiothermic reduction, appropriate post-processing can prepare the cellular continuous poriferous Si-C composite material of three-dimensional, and be used for lithium ion battery
Negative material.
Invention content
It is an object of the present invention to provide a kind of easy-to-use cellular continuous poriferous Si-C composite materials of three-dimensional.
The porous Si-C composite material is the hydridization that nano silicon spheres are distributed in cellular, continuous three-dimensional porous carbon matrix
Structure；Wherein the mass content of carbon is that 99~1 ﹪ are controllable.
Above-mentioned porous Si-C composite material uses 80~800nm preparing spherical SiO 2s nano-particle as silicon source, using heat
Solidity bifunctional acrylate's class unsaturated-resin is prepared as carbon source using the first compound rear method restored；Wherein
Esters of acrylic acid unsaturated-resin monomer is vinyl thermoset resin.
It is a further object to provide the preparation method of above-mentioned Si-C composite material, the specific steps of this method
It is：
Step (1) prepares silica：Using Stober methods in alcohol phase medium, with the positive tetrabutyl silicate of ammonia-catalyzed
(TEOS), monodispersed preparing spherical SiO 2 particles are formed by hydrolysis-condensation, by adjust pH value control grain size 80~
800 nanometers；
Esters of acrylic acid unsaturated-resin monomer and photoinitiator are stirred by step (2) at room temperature~80 DEG C
It is even, obtain mixed liquor；The mass content of photoinitiator is 0.2~2.0 ﹪ in mixed liquor；
The esters of acrylic acid unsaturated-resin monomer is vinyl thermoset resin, specially the bis- methyl-props of bisphenol-A-
Olefin(e) acid ethylene oxidic ester, triethylene glycolbismethyl-acrylate, dimethacrylate diethylene glycol (DEG) ester, dimethacrylate second
Diol ester, tetraethylene glycol dimethylacrylate, 1,6-HD dimethylacrylate, ethoxylated bisphenol dimethacrylate
One or more of ester；
The photoinitiator is gorgeous good solid 1173, it is gorgeous good solid 184, gorgeous good solid 2959, gorgeous good solid 907, gorgeous good solid 369,
One or several kinds in gorgeous good solid 819, gorgeous good solid 754 or camphorquinone；
Silica obtained by step (1) is added in above-mentioned mixed liquor by step (3), is stirred 1~24 hour, is contained
There is the mixed solution of silica；Every 10 grams contain in silica mixed solution containing 0.001~9 gram of silica；
The above-mentioned mixed solution containing silica is injected into mold by step (4), using blue light or UV light
Change, illumination 60~300 seconds, obtains silica/polyacrylate composite solid material under 5~50W power；
Step (5) crushes silica/polyacrylate composite solid material, crushes 1~5 minute, obtains solid
Grain.
Step (6), by above-mentioned solid particle at 500~800 DEG C, calcined 2~6 hours under inert atmosphere, obtain black powder
End is nano silicon dioxide/carbon composite.
Preferably, inert atmosphere is nitrogen or argon gas.
By above-mentioned black powder and magnesium powder according to mass ratio 1 under step (7), room temperature:(0.1~1.0) it mixes, is placed in tubular type
650~750 DEG C are heated in stove, isothermal reaction 1~24 hour, is then down to room temperature under inert atmosphere, obtains reduction crude product.
The inert atmosphere can be nitrogen, argon gas, argon gas/hydrogen (95/5 volume ratio) mixed gas.
Step (8), will reduction crude product to be placed in the dilute hydrochloric acid of a concentration of 0.5~2mol/L under room temperature stirring 4~24 small
When, centrifugation obtains solid product, and washed several times with water obtains solid powder after dry.
Above-mentioned solid powder is placed in the diluted hydrofluoric acid that mass fraction is 1~10 ﹪ by step (9) impregnates 0.5 under room temperature
~5 hours, solid product was arrived in centrifugation, and washed several times with water obtains cellular three-dimensional porous Si-C composite material after dry.
The present invention uses Nano particles of silicon dioxide as silicon source, unsaturated using thermosetting property bifunctional acrylate class
Silica is dispersed in resin monomer first and carries out in-situ solidifying, obtained containing silica by resin as carbon source
Blocks of solid, then inert atmosphere high-temperature calcination carry out in situ at carbon, then, after product is mixed with magnesium powder under inert atmosphere into
Row magnesiothermic reduction, appropriate post-processing can prepare the cellular continuous poriferous Si-C composite material of three-dimensional.The material structure is stablized, hole
Hole is distributed and size can accuracy controlling.The cellular continuous poriferous Si-C composite material of three-dimensional of the present invention, and for be used as lithium from
Sub- cell negative electrode material.
The advantage of the invention is that：
1, the present invention avoids conventional thermosetting resin and needs to use solvent by vinyl thermoset resin in-situ polymerization
It is cumbersome, without post-processing, it is easy to operate, it is environmentally protective；Simultaneously because thermosetting resin is difficult to send out in high-temperature burning process
Raw melting may be implemented original position into carbon, be capable of the distribution situation of Effective Regulation silica, to regulate and control the shape of final product
Looks.
2, the present invention is using the method restored after first compound, can be to avoid after first restore for compound method
It restores the part pore structure formed later to be filled and lose in recombination process, while first compound rear reduction is exactly cellular more
The key point that pore structure is formed.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the cellular three-dimensional porous Si-C composite material prepared in embodiment 1.
Fig. 2 is the transmission electron microscope picture of the cellular three-dimensional porous Si-C composite material prepared in embodiment 1.
Fig. 3 is the electrochemistry cycle performance curve graph of the cellular three-dimensional porous Si-C composite material prepared in embodiment 1.
Specific implementation mode
The present invention is further analyzed below in conjunction with the accompanying drawings.
The preparation method of Si-C composite material of the present invention, this method comprise the concrete steps that：
Step (1) prepares silica：Using Stober methods in alcohol phase medium, with the positive tetrabutyl silicate of ammonia-catalyzed
(TEOS), monodispersed preparing spherical SiO 2 particles are formed by hydrolysis-condensation, by adjust pH value control grain size 80~
800 nanometers；
Esters of acrylic acid unsaturated-resin monomer and photoinitiator are stirred by step (2) at room temperature~80 DEG C
It is even, obtain mixed liquor；The mass content of photoinitiator is 0.2~2.0 ﹪ in mixed liquor；
The esters of acrylic acid unsaturated-resin monomer is vinyl thermoset resin, specially the bis- methyl-props of bisphenol-A-
Olefin(e) acid ethylene oxidic ester, triethylene glycolbismethyl-acrylate, dimethacrylate diethylene glycol (DEG) ester, dimethacrylate second
Diol ester, tetraethylene glycol dimethylacrylate, 1,6-HD dimethylacrylate, ethoxylated bisphenol dimethacrylate
One or more of ester；
The photoinitiator is gorgeous good solid 1173, it is gorgeous good solid 184, gorgeous good solid 2959, gorgeous good solid 907, gorgeous good solid 369,
One or several kinds in gorgeous good solid 819, gorgeous good solid 754 or camphorquinone；
Silica obtained by step (1) is added in above-mentioned mixed liquor by step (3), is stirred 1~24 hour, is contained
There is the mixed solution of silica；Every 10 grams contain in silica mixed solution containing 0.001~9 gram of silica；
The above-mentioned mixed solution containing silica is injected into mold by step (4), using blue light or UV light
Change, illumination 60~300 seconds, obtains silica/polyacrylate composite solid material under 5~50W power；
Step (5) crushes silica/polyacrylate composite solid material, crushes 1~5 minute, obtains solid
Grain.
Step (6), by above-mentioned solid particle at 500~800 DEG C, calcined 2~6 hours under inert atmosphere, obtain black powder
End is nano silicon dioxide/carbon composite.
Preferably, inert atmosphere is nitrogen or argon gas.
By above-mentioned black powder and magnesium powder according to mass ratio 1 under step (7), room temperature:(0.1~1.0) it mixes, is placed in tubular type
650~750 DEG C are heated in stove, isothermal reaction 1~24 hour, is then down to room temperature under inert atmosphere, obtains reduction crude product.
The inert atmosphere can be nitrogen, argon gas, argon gas/hydrogen (95/5 volume ratio) mixed gas.
Step (8), will reduction crude product to be placed in the dilute hydrochloric acid of a concentration of 0.5~2mol/L under room temperature stirring 4~24 small
When, centrifugation obtains solid product, and washed several times with water obtains solid powder after dry.
Above-mentioned solid powder is placed in the diluted hydrofluoric acid that mass fraction is 1~10 ﹪ by step (9) impregnates 0.5 under room temperature
~5 hours, solid product was arrived in centrifugation, and washed several times with water obtains cellular three-dimensional porous Si-C composite material after dry.
The porous Si-C composite material that the above method is prepared, it is more to be that nano silicon spheres are distributed in cellular, continuous three-dimensional
Hybrid structure in the carbon matrix of hole, the wherein mass content of carbon are that 99~1 ﹪ are controllable.
Embodiment 1
Step (1) prepares silica：Using Stober methods in alcohol phase medium, with the positive tetrabutyl silicate of ammonia-catalyzed
(TEOS), monodispersed preparing spherical SiO 2 particles are formed by hydrolysis-condensation, is received for 400 by adjusting pH value control grain size
Rice；
Step (2), by 4g bisphenol-As-glycidyl Methacrylate, 6g triethylene-glycol methacrylates
Ester, 0.05g gorgeous good solid 819 is uniformly mixed at normal temperatures, obtains 10.05g mixed liquors；
Step (3) takes silica 1 g obtained by step (1) to be added in above-mentioned mixed liquor, stirs 2 hours, is contained
The mixed solution of silica；
The above-mentioned mixed solution containing silica is injected into mold by step (4), is cured using ultraviolet light, 50W work(
Illumination 300 seconds under rate obtain silica/polyacrylate composite solid material；
Step (5) crushes silica/polyacrylate composite solid material, crushes 1 minute, obtains solid particle.
Step (6), by above-mentioned solid particle at 800 DEG C, calcined 4 hours under argon gas atmosphere, obtain black powder, be nanometer
Silicon/carbon dioxide composite material.
By above-mentioned black powder and magnesium powder according to mass ratio 1 under step (7), room temperature:0.5 mixing, is placed in tube furnace and adds
Heat is to 700 DEG C, and isothermal reaction 4 hours, are then down to room temperature under argon gas atmosphere, obtains reduction crude product.
Reduction crude product is placed in the dilute hydrochloric acid of a concentration of 2mol/L under room temperature and stirs 4 hours by step (8), centrifuges
To solid product, washed several times with water obtains solid powder after dry.
Above-mentioned solid powder is placed in the diluted hydrofluoric acid that mass fraction is 1 ﹪ by step (9) to be impregnated 2 hours under room temperature, from
The heart is washed four times to solid product, and cellular three-dimensional porous Si-C composite material is obtained after dry.
Cellular three-dimensional porous structure, hole size is presented in 1 gained Si-C composite material of embodiment as depicted in figs. 1 and 2
About 350 nanometers, substep is uniformly；As shown in figure 3, cellular three-dimensional more empty Si-C composite materials are as negative electrode of lithium ion battery material
When material, discharge capacity about 1410mAh/g for the first time, discharge capacity still has 700mAh/g, cyclical stability good after 100 circle of cycle.
Embodiment 2
Step (1) prepares silica：Using Stober methods in alcohol phase medium, with the positive tetrabutyl silicate of ammonia-catalyzed
(TEOS), monodispersed preparing spherical SiO 2 particles are formed by hydrolysis-condensation, is received 80 by adjusting pH value control grain size
Rice；
Step (2), by 9.98g bisphenol-As-glycidyl Methacrylate and 0.02g gorgeous good solid 1173 at 80 DEG C
It is uniformly mixed, obtains mixed liquor；
Silica obtained by 0.001g steps (1) is added in the above-mentioned mixed liquors of 9.999g by step (3), and stirring 1 is small
When, obtain the mixed solution containing silica；
The above-mentioned mixed solution containing silica is injected into mold by step (4), is cured using blue light, 5W power
Lower illumination 300 seconds obtains silica/polyacrylate composite solid material；
Step (5) crushes silica/polyacrylate composite solid material, crushes 5 minutes, obtains solid particle.
Step (6), by above-mentioned solid particle at 500 DEG C, calcined 6 hours under nitrogen atmosphere, obtain black powder, be nanometer
Silicon/carbon dioxide composite material.
By above-mentioned black powder and magnesium powder according to mass ratio 1 under step (7), room temperature:0.1 mixing, is placed in tube furnace and adds
Heat is to 650 DEG C, and isothermal reaction 24 hours, are then down to room temperature under nitrogen atmosphere, obtains reduction crude product.
Reduction crude product is placed in the dilute hydrochloric acid of a concentration of 0.5mol/L under room temperature and stirs 24 hours by step (8), centrifuges
Solid product is obtained, washed several times with water obtains solid powder after dry.
Above-mentioned solid powder is placed in the diluted hydrofluoric acid that mass fraction is 10 ﹪ that 0.5 is impregnated under room temperature is small by step (9)
When, solid product is arrived in centrifugation, and washed several times with water obtains cellular three-dimensional porous Si-C composite material after dry.
Embodiment 3
Step (1) prepares silica：Using Stober methods in alcohol phase medium, with the positive tetrabutyl silicate of ammonia-catalyzed
(TEOS), monodispersed preparing spherical SiO 2 particles are formed by hydrolysis-condensation, is received 800 by adjusting pH value control grain size
Rice；
9.8g triethylene glycolbismethyl-acrylates and 0.2g gorgeous good solid 184 is stirred at 80 DEG C and is mixed by step (2)
It closes uniformly, obtains mixed liquor；
Silica obtained by 5g steps (1) is added in the above-mentioned mixed liquors of 5g by step (3), is stirred 24 hours, is contained
There is the mixed solution of silica；
The above-mentioned mixed solution containing silica is injected into mold by step (4), the solidification of adopter's ultraviolet light, 50W
Illumination 60 seconds under power obtain silica/polyacrylate composite solid material；
Step (5) crushes silica/polyacrylate composite solid material, crushes 5 minutes, obtains solid particle.
Step (6), by above-mentioned solid particle at 800 DEG C, calcined 2 hours under argon gas atmosphere, obtain black powder, be nanometer
Silicon/carbon dioxide composite material.
By above-mentioned black powder and magnesium powder according to mass ratio 1 under step (7), room temperature:1 mixing, is placed in tube furnace and heats
To 750 DEG C, isothermal reaction 1 hour, is then down to room temperature under argon gas/hydrogen (95/5 volume ratio) atmosphere, obtains reduction crude product.
Reduction crude product is placed in the dilute hydrochloric acid of a concentration of 1mol/L under room temperature and stirs 15 hours by step (8), centrifuges
To solid product, washed several times with water obtains solid powder after dry.
Above-mentioned solid powder is placed in the diluted hydrofluoric acid that mass fraction is 2 ﹪ by step (9) to be impregnated 5 hours under room temperature, from
The heart is to solid product, washed several times with water, and cellular three-dimensional porous Si-C composite material is obtained after dry.
Embodiment 4
Step (1) prepares silica：Using Stober methods in alcohol phase medium, with the positive tetrabutyl silicate of ammonia-catalyzed
(TEOS), monodispersed preparing spherical SiO 2 particles are formed by hydrolysis-condensation, is received 100 by adjusting pH value control grain size
Rice；
9.95g dimethacrylate diethylene glycol (DEG) esters and 0.05g gorgeous good solid 2959 is stirred by step (2) at 65 DEG C
Uniformly, mixed liquor is obtained；
Silica obtained by 0.01g steps (1) is added in the above-mentioned mixed liquors of 9.99g by step (3), is stirred 3 hours,
Obtain the mixed solution containing silica；
The above-mentioned mixed solution containing silica is injected into mold by step (4), is cured using blue light, 10W power
Lower illumination 250 seconds obtains silica/polyacrylate composite solid material；
Step (5) crushes silica/polyacrylate composite solid material, crushes 2 minutes, obtains solid particle.
Step (6), by above-mentioned solid particle at 600 DEG C, calcined 4 hours under nitrogen atmosphere, obtain black powder, be nanometer
Silicon/carbon dioxide composite material.
By above-mentioned black powder and magnesium powder according to mass ratio 1 under step (7), room temperature:0.5 mixing, is placed in tube furnace and adds
Heat is to 700 DEG C, and isothermal reaction 10 hours, is then down to room temperature, obtains restoring thick production under argon gas/hydrogen (95/5 volume ratio) atmosphere
Object.
Reduction crude product is placed in the dilute hydrochloric acid of a concentration of 0.8mol/L under room temperature and stirs 18 hours by step (8), centrifuges
Solid product is obtained, washed several times with water obtains solid powder after dry.
Above-mentioned solid powder is placed in the diluted hydrofluoric acid that mass fraction is 3 ﹪ by step (9) to be impregnated 2.5 hours under room temperature,
Solid product is centrifuged, washed several times with water obtains cellular three-dimensional porous Si-C composite material after dry.
Embodiment 5
Step (1) prepares silica：Using Stober methods in alcohol phase medium, with the positive tetrabutyl silicate of ammonia-catalyzed
(TEOS), monodispersed preparing spherical SiO 2 particles are formed by hydrolysis-condensation, is received 200 by adjusting pH value control grain size
Rice；
Step (2) exists the gorgeous good 907,0.06g gorgeous good solid 369 that consolidates of 9.88g ethylene glycol dimethacrylate and 0.06g
It is uniformly mixed at 70 DEG C, obtains mixed liquor；
Silica obtained by 0.1g steps (1) is added in the above-mentioned mixed liquors of 9.9g by step (3), is stirred 22 hours, is obtained
To the mixed solution containing silica；
The above-mentioned mixed solution containing silica is injected into mold by step (4), is cured using ultraviolet light, 15W work(
Illumination 200 seconds under rate obtain silica/polyacrylate composite solid material；
Step (5) crushes silica/polyacrylate composite solid material, crushes 4 minutes, obtains solid particle.
Step (6), by above-mentioned solid particle at 550 DEG C, calcined 3 hours under argon gas atmosphere, obtain black powder, be nanometer
Silicon/carbon dioxide composite material.
By above-mentioned black powder and magnesium powder according to mass ratio 1 under step (7), room temperature:0.2 mixing, is placed in tube furnace and adds
Heat is to 720 DEG C, and isothermal reaction 13 hours, are then down to room temperature under argon gas atmosphere, obtains reduction crude product.
Reduction crude product is placed in the dilute hydrochloric acid of a concentration of 0.6mol/L under room temperature and stirs 17 hours by step (8), centrifuges
Solid product is obtained, washed several times with water obtains solid powder after dry.
Above-mentioned solid powder is placed in the diluted hydrofluoric acid that mass fraction is 7 ﹪ by step (9) to be impregnated 3 hours under room temperature, from
The heart is to solid product, washed several times with water, and cellular three-dimensional porous Si-C composite material is obtained after dry.
Embodiment 6
Step (1) prepares silica：Using Stober methods in alcohol phase medium, with the positive tetrabutyl silicate of ammonia-catalyzed
(TEOS), monodispersed preparing spherical SiO 2 particles are formed by hydrolysis-condensation, is received 300 by adjusting pH value control grain size
Rice；
Step (2) stirs 9.9g tetraethylene glycols dimethylacrylate and 0.1g gorgeous good solid 907 at room temperature~80 DEG C
It is uniformly mixed, obtains mixed liquor；
Silica obtained by 9g steps (1) is added in the above-mentioned mixed liquors of 10g by step (3), is stirred 13 hours, is obtained
Mixed solution containing silica；
The above-mentioned mixed solution containing silica is injected into mold by step (4), is cured using ultraviolet light, 40W work(
Illumination 120 seconds under rate obtain silica/polyacrylate composite solid material；
Step (5) crushes silica/polyacrylate composite solid material, crushes 2 minutes, obtains solid particle.
Step (6), by above-mentioned solid particle at 600 DEG C, calcined 4 hours under nitrogen atmosphere, obtain black powder, be nanometer
Silicon/carbon dioxide composite material.
By above-mentioned black powder and magnesium powder according to mass ratio 1 under step (7), room temperature:0.9 mixing, is placed in tube furnace and adds
Heat is to 710 DEG C, and isothermal reaction 11 hours, are then down to room temperature under argon gas atmosphere, obtains reduction crude product.
Reduction crude product is placed in the dilute hydrochloric acid of a concentration of 1.2mol/L under room temperature and stirs 5 hours by step (8), centrifuges
Solid product is obtained, washed several times with water obtains solid powder after dry.
Above-mentioned solid powder is placed in the diluted hydrofluoric acid that mass fraction is 5 ﹪ by step (9) to be impregnated 4.5 hours under room temperature,
Solid product is centrifuged, washed several times with water obtains cellular three-dimensional porous Si-C composite material after dry.
Embodiment 7
Step (1) prepares silica：Using Stober methods in alcohol phase medium, with the positive tetrabutyl silicate of ammonia-catalyzed
(TEOS), monodispersed preparing spherical SiO 2 particles are formed by hydrolysis-condensation, is received 400 by adjusting pH value control grain size
Rice；
9.85g1,6- hexanediol dimethacrylates and 0.15g gorgeous good solid 369 is stirred at 70 DEG C and is mixed by step (2)
It closes uniformly, obtains mixed liquor；
Silica obtained by 2g steps (1) is added in the above-mentioned mixed liquors of 8g by step (3), is stirred 21 hours, is contained
There is the mixed solution of silica；
The above-mentioned mixed solution containing silica is injected into mold by step (4), is cured using blue light, 30W power
Lower illumination 100 seconds obtains silica/polyacrylate composite solid material；
Step (5) crushes silica/polyacrylate composite solid material, crushes 5 minutes, obtains solid particle.
Step (6), by above-mentioned solid particle at 600 DEG C, calcined 5 hours under argon gas atmosphere, obtain black powder, be nanometer
Silicon/carbon dioxide composite material.
By above-mentioned black powder and magnesium powder according to mass ratio 1 under step (7), room temperature:1 mixing, is placed in tube furnace and heats
To 650 DEG C, isothermal reaction 24 hours, is then down to room temperature, obtains restoring thick production under argon gas/hydrogen (95/5 volume ratio) atmosphere
Object.
Reduction crude product is placed in the dilute hydrochloric acid of a concentration of 0.8mol/L under room temperature and stirs 22 hours by step (8), centrifuges
Solid product is obtained, washed several times with water obtains solid powder after dry.
Above-mentioned solid powder is placed in the diluted hydrofluoric acid that mass fraction is 6 ﹪ by step (9) to be impregnated 4 hours under room temperature, from
The heart is to solid product, washed several times with water, and cellular three-dimensional porous Si-C composite material is obtained after dry.
Embodiment 8
Step (1) prepares silica：Using Stober methods in alcohol phase medium, with the positive tetrabutyl silicate of ammonia-catalyzed
(TEOS), monodispersed preparing spherical SiO 2 particles are formed by hydrolysis-condensation, is received 600 by adjusting pH value control grain size
Rice；
9.84g ethoxylated bisphenols dimethylacrylate and 0.16g gorgeous good solid 754 is stirred at 80 DEG C and is mixed by step (2)
It closes uniformly, obtains mixed liquor；
Silica obtained by 2g steps (1) is added in the above-mentioned mixed liquors of 8g by step (3), is stirred 14 hours, is contained
There is the mixed solution of silica；
The above-mentioned mixed solution containing silica is injected into mold by step (4), is cured using ultraviolet light, 50W work(
Illumination 60 seconds under rate obtain silica/polyacrylate composite solid material；
Step (5) crushes silica/polyacrylate composite solid material, crushes 5 minutes, obtains solid particle.
Step (6), by above-mentioned solid particle at 800 DEG C, calcined 2 hours under argon gas atmosphere, obtain black powder, be nanometer
Silicon/carbon dioxide composite material.
By above-mentioned black powder and magnesium powder according to mass ratio 1 under step (7), room temperature:0.1 mixing, is placed in tube furnace and adds
Heat is to 750 DEG C, and isothermal reaction 1 hour, is then down to room temperature, obtains restoring thick production under argon gas/hydrogen (95/5 volume ratio) atmosphere
Object.
Reduction crude product is placed in the dilute hydrochloric acid of a concentration of 0.5mol/L under room temperature and stirs 24 hours by step (8), centrifuges
Solid product is obtained, washed several times with water obtains solid powder after dry.
Above-mentioned solid powder is placed in the diluted hydrofluoric acid that mass fraction is 10 ﹪ that 0.5 is impregnated under room temperature is small by step (9)
When, solid product is arrived in centrifugation, and washed several times with water obtains cellular three-dimensional porous Si-C composite material after dry.
Embodiment 9
Step (1) prepares silica：Using Stober methods in alcohol phase medium, with the positive tetrabutyl silicate of ammonia-catalyzed
(TEOS), monodispersed preparing spherical SiO 2 particles are formed by hydrolysis-condensation, is received 700 by adjusting pH value control grain size
Rice；
Step (2), by 4.84g dimethacrylate diethylene glycol (DEG)s ester, 5g ethylene glycol dimethacrylate and 0.16g camphors
Quinone is uniformly mixed at 80 DEG C, obtains mixed liquor；
Silica obtained by 3g steps (1) is added in the above-mentioned mixed liquors of 7g by step (3), is stirred 24 hours, is contained
There is the mixed solution of silica；
The above-mentioned mixed solution containing silica is injected into mold by step (4), is cured using blue light, 50W power
Lower illumination 60 seconds obtains silica/polyacrylate composite solid material；
Step (5) crushes silica/polyacrylate composite solid material, crushes 5 minutes, obtains solid particle.
Step (6), by above-mentioned solid particle at 500 DEG C, calcined 6 hours under nitrogen atmosphere, obtain black powder, be nanometer
Silicon/carbon dioxide composite material.
By above-mentioned black powder and magnesium powder according to mass ratio 1 under step (7), room temperature:0.5 mixing, is placed in tube furnace and adds
Heat is to 750 DEG C, and isothermal reaction 1 hour, is then down to room temperature under nitrogen atmosphere, obtains reduction crude product.
Reduction crude product is placed in the dilute hydrochloric acid of a concentration of 0.5mol/L under room temperature and stirs 24 hours by step (8), centrifuges
Solid product is obtained, washed several times with water obtains solid powder after dry.
Above-mentioned solid powder is placed in the diluted hydrofluoric acid that mass fraction is 1 ﹪ by step (9) to be impregnated 5 hours under room temperature, from
The heart is to solid product, washed several times with water, and cellular three-dimensional porous Si-C composite material is obtained after dry.
Above-described embodiment is not for the limitation of the present invention, and the present invention is not limited only to above-described embodiment, as long as meeting
The present invention claims all belong to the scope of protection of the present invention.
Claims (9)
1. a kind of Si-C composite material, it is characterised in that be that nano silicon spheres are distributed in cellular, continuous three-dimensional porous carbon matrix
Hybrid structure；
Above-mentioned Si-C composite material uses 80~800nm preparing spherical SiO 2s nano-particle as silicon source, using the double officials of thermosetting property
Esters of acrylic acid unsaturated-resin can be rolled into a ball as carbon source, be prepared using the first compound rear method restored；Wherein acrylate
Class unsaturated-resin monomer is the monomer of vinyl thermoset resin；
The method restored after the elder generation is compound is first compound silicon source and carbon source, then by reducing silica at silicon.
2. a kind of Si-C composite material as described in claim 1, it is characterised in that the mass content of carbon matrix is 1~99 ﹪.
3. a kind of Si-C composite material as described in claim 1, it is characterised in that the esters of acrylic acid unsaturated-resin
Monomer is bisphenol-A-glycidyl Methacrylate, triethylene glycolbismethyl-acrylate, dimethacrylate two
Glycol ester, ethylene glycol dimethacrylate, tetraethylene glycol dimethylacrylate, 1,6-hexanediol dimethacrylates,
One or more of ethoxylated bisphenol dimethylacrylate.
4. a kind of preparation method of Si-C composite material, it is characterised in that this approach includes the following steps：
Step (1) prepares silica：Using Stober methods in alcohol phase medium, with the positive tetrabutyl silicate of ammonia-catalyzed, pass through
Hydrolysis-condensation forms monodispersed preparing spherical SiO 2 particles, and grain size is controlled at 80~800 nanometers by adjusting pH value；
Esters of acrylic acid unsaturated-resin monomer and photoinitiator are uniformly mixed by step (2) at room temperature~80 DEG C, are obtained
To mixed liquor；The mass content of photoinitiator is 0.2~2.0 ﹪ in mixed liquor；
The esters of acrylic acid unsaturated-resin monomer is the monomer of vinyl thermoset resin；
Silica obtained by step (1) is added in above-mentioned mixed liquor by step (3), is stirred 1~24 hour, is obtained containing two
The mixed solution of silica；Every 10 grams contain in silica mixed solution containing 0. 001~9 grams of silica；
The above-mentioned mixed solution containing silica is injected into mold by step (4), is cured using blue light or ultraviolet light, 5
Illumination 60~300 seconds under~50W power, obtains silica/polyacrylate composite solid material；
Step (5) crushes silica/polyacrylate composite solid material, crushes 1~5 minute, obtains solid particle；
Step (6), by above-mentioned solid particle at 500~800 DEG C, calcined 2~6 hours under inert atmosphere, obtain black powder, be
Nano silicon dioxide/carbon composite；
By above-mentioned black powder and magnesium powder according to mass ratio 1 under step (7), room temperature:（0.1~1.0）Mixing, is placed in tube furnace
650~750 DEG C are heated to, isothermal reaction 1~24 hour, is then down to room temperature under inert atmosphere, obtains reduction crude product；
Reduction crude product is placed in the dilute hydrochloric acid of a concentration of 0.5~2mol/L under room temperature and stirs 4~24 hours by step (8), from
Gains in depth of comprehension are to solid product, washed several times with water, and solid powder is obtained after dry；
Above-mentioned solid powder is placed in the diluted hydrofluoric acid that mass fraction is 1~10 ﹪ that 0.5~5 is impregnated under room temperature is small by step (9)
When, solid product is arrived in centrifugation, and washed several times with water obtains cellular three-dimensional porous Si-C composite material after dry；
Above-mentioned Si-C composite material is the hybrid structure that nano silicon spheres are distributed in cellular, continuous three-dimensional porous carbon matrix.
5. method as claimed in claim 4, it is characterised in that the esters of acrylic acid unsaturated-resin monomer is specially double
Phenol A- glycidyl Methacrylates, triethylene glycolbismethyl-acrylate, dimethacrylate diethylene glycol (DEG) ester, two
Methacrylic acid glycol ester, tetraethylene glycol dimethylacrylate, 1,6-hexanediol dimethacrylates, ethyoxyl are double
One or more of phenol dimethylacrylate.
6. method as claimed in claim 4, it is characterised in that the photoinitiator is 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 kinds.
7. method as claimed in claim 4, it is characterised in that step (6) inert atmosphere is nitrogen or argon gas.
8. method as claimed in claim 4, it is characterised in that step (7) described inert atmosphere is nitrogen, argon gas, argon gas/hydrogen
One kind in oxygen mixture.
9. a kind of application of the Si-C composite material as described in claim 1 in lithium ion battery negative material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102259858A (en) * | 2011-06-07 | 2011-11-30 | 同济大学 | Method for preparing porous silicon by magnesiothermic reduction |
| CN103022435A (en) * | 2011-09-20 | 2013-04-03 | 宁波杉杉新材料科技有限公司 | Lithium ion battery silicon-carbon composite negative electrode material and preparation method thereof |
| CN104577049A (en) * | 2014-12-26 | 2015-04-29 | 中天科技精密材料有限公司 | Hierarchical pore structure silicon-based negative electrode material for lithium battery and preparation method of hierarchical pore structure silicon-based negative electrode material |
| CN104979536A (en) * | 2014-04-10 | 2015-10-14 | 宁德新能源科技有限公司 | Anode active material of lithium ion battery and preparation method thereof |
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| KR101578262B1 (en) * | 2012-07-24 | 2015-12-28 | 주식회사 엘지화학 | Porous silicon based electrode active material and secondary battery comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102259858A (en) * | 2011-06-07 | 2011-11-30 | 同济大学 | Method for preparing porous silicon by magnesiothermic reduction |
| CN103022435A (en) * | 2011-09-20 | 2013-04-03 | 宁波杉杉新材料科技有限公司 | Lithium ion battery silicon-carbon composite negative electrode material and preparation method thereof |
| CN104979536A (en) * | 2014-04-10 | 2015-10-14 | 宁德新能源科技有限公司 | Anode active material of lithium ion battery and preparation method thereof |
| CN104577049A (en) * | 2014-12-26 | 2015-04-29 | 中天科技精密材料有限公司 | Hierarchical pore structure silicon-based negative electrode material for lithium battery and preparation method of hierarchical pore structure silicon-based negative electrode material |
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