CN105977478A - Honeycomb three-dimensional porous silicon/carbon composite material and preparation method thereof - Google Patents
Honeycomb three-dimensional porous silicon/carbon composite material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a honeycomb three-dimensional porous silicon/carbon composite material and a preparation method thereof. The porous silicon/carbon composite material is of a hybrid structure that nano silicon spheres are distributed in a honeycomb continuous three-dimensional porous carbon matrix, wherein the mass content of carbon is 99%-1% and controllable. The honeycomb three-dimensional porous silicon/carbon composite material is prepared from 80-800nm spherical silicon dioxide nanoparticles as a silicon source and thermosetting difunctional acrylate unsaturated resin as a carbon source by employing a method of reduction after compounding; and an acrylate unsaturated resin monomer is vinyl thermosetting resin. The cumbersome problem that traditional thermosetting resin needs to utilize a solvent is solved through in-situ polymerization of vinyl thermosetting resin; post-treatment is not needed; the operation is simple and convenient; and the honeycomb three-dimensional porous silicon/carbon composite material is green and environment-friendly. Meanwhile, the thermosetting resin is difficult to melt in the high-temperature calcination process, so that in-situ carbon formation can be achieved; the distribution condition of silicon dioxide can be effectively regulated and controlled; and the shape and form of the final product are regulated and controlled.
Description
Technical field
The invention belongs to the preparation field of nanoporous composite, be specifically related to a kind of In-situ reaction,
Carbon, magnesiothermic reduction is become to prepare the continuous poriferous Si-C composite material of cellular three-dimensional and method thereof in situ.
Background technology
Along with developing rapidly of the industries such as electric automobile, to high-energy-density and high power density lithium ion
The demand of battery is the most urgent.Commercial Li-ion battery negative material commonly used graphite-like material at present
Material, but the theoretical lithium storage content of graphite only has 372mAh/g, and also intercalation potential platform is close to metal
Lithium, quick charge or low temperature charging easily occur analysis lithium phenomenon to cause potential safety hazard, therefore develop novel height
Performance negative material is extremely the most urgent.The theoretical specific capacity of silicon is up to 4200mAh/g, and removal lithium embedded
Current potential is moderate, aboundresources, is one of most promising high-performance lithium ion negative material.But, silicon exists
Huge change in volume (up to 300%) can be produced during removal lithium embedded, cause that silicon grain is broken, efflorescence,
Lose electroactive, show as the cyclical stability of extreme difference.On the other hand, the electric conductivity of silicon is poor, its times
Rate charge-discharge performance is also performed poor.Therefore, silicium cathode is the most effectively alleviated in battery charging and discharging mistake
Volumetric expansion in journey and how to improve the electric conductivity of silicium cathode material, improving its chemical property is
The problem that this area needs solution badly.
In sum, this area still lacks a kind of lithium ion with height ratio capacity and high cyclical stability
Battery silicon based anode material.
The invention provides the preparation method of a kind of cellular porous Si-C composite material, use existing
Maturation process, process is easy, it is easy to operation；The aperture of the porous silicon carbon composite prepared is divided
Cloth is uniform, and size is adjustable, can use as lithium ion battery negative material, has higher specific capacity
With good cyclical stability.
The most rare about the report of cellular three-dimensional porous Si-C composite material, patent
CN201510054606.8, CN201410276413.2 and CN201510007562.9 report one
The preparation method of porous silicon carbon composite, the cellular continuous structure that gained porous silicon is the most regular.
The present invention uses Nano particles of silicon dioxide as silicon source, uses thermosetting difunctional acrylic acid
Silicon dioxide, as carbon source, is first dispersed in resin monomer and carries out in situ by esters unsaturated-resin
Solidification, obtains the blocks of solid containing silicon dioxide, and then inert atmosphere high-temperature calcination carries out becoming in situ
Carbon, then, carries out magnesiothermic reduction with magnesium powder under inert atmosphere after being mixed by product, suitable post processing is i.e.
The continuous poriferous Si-C composite material of cellular three-dimensional can be prepared, and for lithium ion battery negative material.
Summary of the invention
It is an object of the present invention to provide a kind of simple and easy to do continuous poriferous silicon-carbon of cellular three-dimensional multiple
Condensation material.
This porous silicon carbon composite, is that nano silicon spheres is distributed in three-dimensional porous carbon back cellular, continuous
Hybrid structure in matter；Wherein the mass content of carbon is 99～1 controlled.
Above-mentioned porous silicon carbon composite uses 80～800nm preparing spherical SiO 2 nanoparticles as silicon
Source, uses thermosetting bifunctional acrylate's class unsaturated-resin as carbon source, uses after being first combined
The method of reduction is prepared from；Wherein esters of acrylic acid unsaturated-resin monomer is vinyl thermoset tree
Fat.
It is a further object to provide the preparation method of above-mentioned Si-C composite material, the method
Comprise the concrete steps that:
Step (1), prepare silicon dioxide: use Stober method in alcohol phase medium, use ammonia-catalyzed
Positive silicic acid four butyl ester (TEOS), forms monodispersed preparing spherical SiO 2 particles through hydrolysis-condensation,
Particle diameter is controlled in 80～800 nanometers by regulation pH value；
Step (2), esters of acrylic acid unsaturated-resin monomer and light trigger are stirred at room temperature～80 DEG C
Mix mix homogeneously, obtain mixed liquor；In mixed liquor, the mass content of light trigger is 0.2～2.0；
Described esters of acrylic acid unsaturated-resin monomer is vinyl thermoset resin, specially bis-phenol
A-glycidyl Methacrylate, triethylene glycolbismethyl-acrylate, dimethyl allene
Acid diethylene glycol ester, Ethylene glycol dimethacrylate, TEG dimethylacrylate, 1,6-
One or more in hexanediol dimethacrylate, ethoxylated bisphenol dimethylacrylate；
Described light trigger be 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 (3), step (1) gained silicon dioxide is joined in above-mentioned mixed liquor, stir 1～24
Hour, obtain the mixed solution containing silicon dioxide；Every 10 grams contain containing in silicon dioxide mixed solution
0.001～9 gram of silicon dioxide；
Step (4), the above-mentioned mixed solution containing silicon dioxide is injected in mould, use blue light or
Person's ultraviolet light polymerization, illumination 60～300 seconds under 5～50W power, obtain silicon dioxide/polyacrylic acid
Ester composite solid material；
Step (5), silicon dioxide/polyacrylate composite solid material is pulverized, pulverizes 1～5 minute,
Obtain solid particle.
Step (6), by above-mentioned solid particle at 500～800 DEG C, under inert atmosphere calcine 2～6 hours,
Obtain black powder, for nano silicon/carbon composite.
As preferably, inert atmosphere is nitrogen or argon.
By above-mentioned black powder and magnesium powder according to mass ratio 1:(0.1～1.0 under step (7), room temperature)
Mixing, is placed in tube furnace and is heated to 650～750 DEG C, isothermal reaction 1～24 hours under inert atmosphere,
Then it is down to room temperature, obtains reduction crude product.
Described inert atmosphere can be nitrogen, argon, argon/hydrogen (95/5 volume ratio) gaseous mixture
Body.
Step (8), reduction crude product is placed in the dilute hydrochloric acid that concentration is 0.5～2mol/L and stirs under room temperature
Mix 4～24 hours, be centrifuged and obtain solid product, washed several times with water, obtain pressed powder after drying.
Step (9). above-mentioned pressed powder is placed in room temperature in the diluted hydrofluoric acid that mass fraction is 1～10
Lower immersion 0.5～5 hours, be centrifuged solid product, washed several times with water, obtain cellular three-dimensional after drying
Porous silicon carbon composite.
The present invention uses Nano particles of silicon dioxide as silicon source, uses thermosetting difunctional acrylic acid
Silicon dioxide, as carbon source, is first dispersed in resin monomer and carries out in situ by esters unsaturated-resin
Solidification, obtains the blocks of solid containing silicon dioxide, and then inert atmosphere high-temperature calcination carries out becoming in situ
Carbon, then, carries out magnesiothermic reduction with magnesium powder under inert atmosphere after being mixed by product, suitable post processing is i.e.
The continuous poriferous Si-C composite material of cellular three-dimensional can be prepared.This material structure is stable, hole distribution and
Size all can accuracy controlling.The continuous poriferous Si-C composite material of the cellular three-dimensional of the present invention, and be used for making
For lithium ion battery negative material.
It is an advantage of the current invention that:
1, the present invention passes through vinyl thermoset resin in-situ polymerization, it is to avoid conventional thermosetting resin needs
Solvent to be used loaded down with trivial details, it is not necessary to post processing, easy and simple to handle, environmental protection；Simultaneously because thermosetting
Resin is difficult to occur to melt in high-temperature burning process, it is possible to achieve become carbon in situ, it is possible to Effective Regulation
The distribution situation of silicon dioxide, thus regulate and control the pattern of end product.
2, the present invention uses and is first combined the method reduced afterwards, compared to first reducing for the method being combined afterwards,
The partial hole structure formed after can avoiding reduction is filled in recombination process and loses, the most first
The key point that the cellular structures just of reducing after Fu He is formed.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the cellular three-dimensional porous Si-C composite material of preparation in embodiment 1.
Fig. 2 is the transmission electron microscope picture of the cellular three-dimensional porous Si-C composite material of preparation in embodiment 1.
Fig. 3 is the electrochemistry cyclicity of the cellular three-dimensional porous Si-C composite material of preparation in embodiment 1
Can curve chart.
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is further analyzed.
The preparation method of Si-C composite material of the present invention, comprising the concrete steps that of the method:
Step (1), prepare silicon dioxide: use Stober method in alcohol phase medium, use ammonia-catalyzed
Positive silicic acid four butyl ester (TEOS), forms monodispersed preparing spherical SiO 2 particles through hydrolysis-condensation,
Particle diameter is controlled in 80～800 nanometers by regulation pH value；
Step (2), esters of acrylic acid unsaturated-resin monomer and light trigger are stirred at room temperature～80 DEG C
Mix mix homogeneously, obtain mixed liquor；In mixed liquor, the mass content of light trigger is 0.2～2.0；
Described esters of acrylic acid unsaturated-resin monomer is vinyl thermoset resin, specially bis-phenol
A-glycidyl Methacrylate, triethylene glycolbismethyl-acrylate, dimethyl allene
Acid diethylene glycol ester, Ethylene glycol dimethacrylate, TEG dimethylacrylate, 1,6-
One or more in hexanediol dimethacrylate, ethoxylated bisphenol dimethylacrylate；
Described light trigger be 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 (3), step (1) gained silicon dioxide is joined in above-mentioned mixed liquor, stir 1～24
Hour, obtain the mixed solution containing silicon dioxide；Every 10 grams contain containing in silicon dioxide mixed solution
0.001～9 gram of silicon dioxide；
Step (4), the above-mentioned mixed solution containing silicon dioxide is injected in mould, use blue light or
Person's ultraviolet light polymerization, illumination 60～300 seconds under 5～50W power, obtain silicon dioxide/polyacrylic acid
Ester composite solid material；
Step (5), silicon dioxide/polyacrylate composite solid material is pulverized, pulverizes 1～5 minute,
Obtain solid particle.
Step (6), by above-mentioned solid particle at 500～800 DEG C, under inert atmosphere calcine 2～6 hours,
Obtain black powder, for nano silicon/carbon composite.
As preferably, inert atmosphere is nitrogen or argon.
By above-mentioned black powder and magnesium powder according to mass ratio 1:(0.1～1.0 under step (7), room temperature)
Mixing, is placed in tube furnace and is heated to 650～750 DEG C, isothermal reaction 1～24 hours under inert atmosphere,
Then it is down to room temperature, obtains reduction crude product.
Described inert atmosphere can be nitrogen, argon, argon/hydrogen (95/5 volume ratio) gaseous mixture
Body.
Step (8), reduction crude product is placed in the dilute hydrochloric acid that concentration is 0.5～2mol/L and stirs under room temperature
Mix 4～24 hours, be centrifuged and obtain solid product, washed several times with water, obtain pressed powder after drying.
Step (9). above-mentioned pressed powder is placed in room temperature in the diluted hydrofluoric acid that mass fraction is 1～10
Lower immersion 0.5～5 hours, be centrifuged solid product, washed several times with water, obtain cellular three-dimensional after drying
Porous silicon carbon composite.
The porous silicon carbon composite that said method is prepared from, be nano silicon spheres be distributed in cellular,
Hybrid structure in continuous three-dimensional porous carbon matrix, wherein the mass content of carbon is 99～1 controlled.
Embodiment 1
Step (1), prepare silicon dioxide: use Stober method in alcohol phase medium, use ammonia-catalyzed
Positive silicic acid four butyl ester (TEOS), forms monodispersed preparing spherical SiO 2 particles through hydrolysis-condensation,
Controlling particle diameter by regulation pH value is 400 nanometers；
Step (2), by double to 4g bisphenol-A-glycidyl Methacrylate, 6g triethylene-glycol
Methacrylate, 0.05g gorgeous good solid 819 is uniformly mixed at normal temperatures, obtains 10.05g and mixes
Close liquid；
Step (3), take step (1) gained silica 1 g and join in above-mentioned mixed liquor, stir 2
Hour, obtain the mixed solution containing silicon dioxide；
Step (4), the above-mentioned mixed solution containing silicon dioxide is injected in mould, uses ultraviolet light
Solidification, illumination 300 seconds under 50W power, obtain silicon dioxide/polyacrylate composite solid material；
Step (5), silicon dioxide/polyacrylate composite solid material is pulverized, pulverizes 1 minute,
Obtain solid particle.
Step (6), by above-mentioned solid particle at 800 DEG C, under argon gas atmosphere calcine 4 hours, obtain black
Color powder, for nano silicon/carbon composite.
Under step (7), room temperature, above-mentioned black powder is mixed according to mass ratio 1:0.5 with magnesium powder, put
700 DEG C it are heated in tube furnace, isothermal reaction 4 hours under argon gas atmosphere, then it is down to room temperature,
Obtain reduction crude product.
Step (8), reduction crude product is placed in the dilute hydrochloric acid that concentration is 2mol/L under room temperature and stirs 4
Hour, it is centrifuged and obtains solid product, washed several times with water, obtain pressed powder after drying.
Step (9). above-mentioned pressed powder is placed in the diluted hydrofluoric acid that mass fraction is 1 and soaks under room temperature
Steep 2 hours, be centrifuged solid product, wash four times, obtain cellular three-dimensional porous silicon-carbon after drying
Composite.
Embodiment 1 gained Si-C composite material presents cellular three-dimensional porous structure as depicted in figs. 1 and 2,
Hole size about 350 nanometer, substep is uniformly；As it is shown on figure 3, the many empty silicon-carbons of this cellular three-dimensional are combined
When material is as lithium ion battery negative material, discharge capacity about 1410mAh/g first, circulation 100 circle
Rear discharge capacity still has 700mAh/g, and cyclical stability is good.
Embodiment 2
Step (1), prepare silicon dioxide: use Stober method in alcohol phase medium, use ammonia-catalyzed
Positive silicic acid four butyl ester (TEOS), forms monodispersed preparing spherical SiO 2 particles through hydrolysis-condensation,
Particle diameter is controlled in 80 nanometers by regulation pH value；
Step (2), by gorgeous to 9.98g bisphenol-A-glycidyl Methacrylate and 0.02g good solid
1173 are uniformly mixed at 80 DEG C, obtain mixed liquor；
Step (3), 0.001g step (1) gained silicon dioxide is joined the above-mentioned mixed liquor of 9.999g
In, stir 1 hour, obtain the mixed solution containing silicon dioxide；
Step (4), the above-mentioned mixed solution containing silicon dioxide is injected in mould, uses blue light solid
Change, illumination 300 seconds under 5W power, obtain silicon dioxide/polyacrylate composite solid material；
Step (5), silicon dioxide/polyacrylate composite solid material is pulverized, pulverizes 5 minutes,
Obtain solid particle.
Step (6), by above-mentioned solid particle at 500 DEG C, under nitrogen atmosphere calcine 6 hours, obtain black
Color powder, for nano silicon/carbon composite.
Under step (7), room temperature, above-mentioned black powder is mixed according to mass ratio 1:0.1 with magnesium powder, be placed in
Tube furnace is heated to 650 DEG C, isothermal reaction 24 hours under nitrogen atmosphere, then it is down to room temperature,
To reduction crude product.
Step (8), reduction crude product is placed in the dilute hydrochloric acid that concentration is 0.5mol/L under room temperature and stirs
24 hours, it is centrifuged and obtains solid product, washed several times with water, obtain pressed powder after drying.
Step (9). above-mentioned pressed powder is placed in the diluted hydrofluoric acid that mass fraction is 10 and soaks under room temperature
Steep 0.5 hour, be centrifuged solid product, washed several times with water, obtain cellular three-dimensional porous silicon-carbon after drying
Composite.
Embodiment 3
Step (1), prepare silicon dioxide: use Stober method in alcohol phase medium, use ammonia-catalyzed
Positive silicic acid four butyl ester (TEOS), forms monodispersed preparing spherical SiO 2 particles through hydrolysis-condensation,
Particle diameter is controlled in 800 nanometers by regulation pH value；
Step (2), by gorgeous to 9.8g triethylene glycolbismethyl-acrylate and 0.2g good solid 184
It is uniformly mixed at 80 DEG C, obtains mixed liquor；
Step (3), 5g step (1) gained silicon dioxide is joined in the above-mentioned mixed liquor of 5g, stirring
24 hours, obtain the mixed solution containing silicon dioxide；
Step (4), the above-mentioned mixed solution containing silicon dioxide is injected in mould, adopter's ultraviolet
Photocuring, illumination 60 seconds under 50W power, obtain silicon dioxide/polyacrylate composite solid material；
Step (5), silicon dioxide/polyacrylate composite solid material is pulverized, pulverizes 5 minutes,
Obtain solid particle.
Step (6), by above-mentioned solid particle at 800 DEG C, under argon gas atmosphere calcine 2 hours, obtain black
Color powder, for nano silicon/carbon composite.
Under step (7), room temperature, above-mentioned black powder is mixed according to mass ratio 1:1 with magnesium powder, be placed in
Tube furnace is heated to 750 DEG C, isothermal reaction 1 hour under argon/hydrogen (95/5 volume ratio) atmosphere,
Then it is down to room temperature, obtains reduction crude product.
Step (8), reduction crude product is placed in the dilute hydrochloric acid that concentration is 1mol/L under room temperature and stirs 15
Hour, it is centrifuged and obtains solid product, washed several times with water, obtain pressed powder after drying.
Step (9). above-mentioned pressed powder is placed in the diluted hydrofluoric acid that mass fraction is 2 and soaks under room temperature
Steep 5 hours, be centrifuged solid product, washed several times with water, obtain cellular three-dimensional porous silicon-carbon after drying multiple
Condensation material.
Embodiment 4
Step (1), prepare silicon dioxide: use Stober method in alcohol phase medium, use ammonia-catalyzed
Positive silicic acid four butyl ester (TEOS), forms monodispersed preparing spherical SiO 2 particles through hydrolysis-condensation,
Particle diameter is controlled in 100 nanometers by regulation pH value；
Step (2), by gorgeous to 9.95g dimethacrylate diethylene glycol ester and 0.05g good solid 2959 at 65 DEG C
Under be uniformly mixed, obtain mixed liquor；
Step (3), 0.01g step (1) gained silicon dioxide is joined in the above-mentioned mixed liquor of 9.99g,
Stir 3 hours, obtain the mixed solution containing silicon dioxide；
Step (4), the above-mentioned mixed solution containing silicon dioxide is injected in mould, uses blue light solid
Change, illumination 250 seconds under 10W power, obtain silicon dioxide/polyacrylate composite solid material；
Step (5), silicon dioxide/polyacrylate composite solid material is pulverized, pulverizes 2 minutes,
Obtain solid particle.
Step (6), by above-mentioned solid particle at 600 DEG C, under nitrogen atmosphere calcine 4 hours, obtain black
Color powder, for nano silicon/carbon composite.
Under step (7), room temperature, above-mentioned black powder is mixed according to mass ratio 1:0.5 with magnesium powder, be placed in
Being heated to 700 DEG C in tube furnace, under argon/hydrogen (95/5 volume ratio) atmosphere, isothermal reaction 10 is little
Time, then it is down to room temperature, obtains reduction crude product.
Step (8), reduction crude product is placed in the dilute hydrochloric acid that concentration is 0.8mol/L under room temperature and stirs
18 hours, it is centrifuged and obtains solid product, washed several times with water, obtain pressed powder after drying.
Step (9). above-mentioned pressed powder is placed in the diluted hydrofluoric acid that mass fraction is 3 and soaks under room temperature
Steep 2.5 hours, be centrifuged solid product, washed several times with water, obtain cellular three-dimensional porous silicon-carbon after drying
Composite.
Embodiment 5
Step (1), prepare silicon dioxide: use Stober method in alcohol phase medium, use ammonia-catalyzed
Positive silicic acid four butyl ester (TEOS), forms monodispersed preparing spherical SiO 2 particles through hydrolysis-condensation,
Particle diameter is controlled in 200 nanometers by regulation pH value；
Step (2), by gorgeous to 9.88g Ethylene glycol dimethacrylate and 0.06g good solid 907,0.06g
Gorgeous good solid 369 are uniformly mixed at 70 DEG C, obtain mixed liquor；
Step (3), 0.1g step (1) gained silicon dioxide is joined in the above-mentioned mixed liquor of 9.9g,
Stir 22 hours, obtain the mixed solution containing silicon dioxide；
Step (4), the above-mentioned mixed solution containing silicon dioxide is injected in mould, uses ultraviolet light
Solidification, illumination 200 seconds under 15W power, obtain silicon dioxide/polyacrylate composite solid material；
Step (5), silicon dioxide/polyacrylate composite solid material is pulverized, pulverizes 4 minutes,
Obtain solid particle.
Step (6), by above-mentioned solid particle at 550 DEG C, under argon gas atmosphere calcine 3 hours, obtain black
Color powder, for nano silicon/carbon composite.
Under step (7), room temperature, above-mentioned black powder is mixed according to mass ratio 1:0.2 with magnesium powder, be placed in
Tube furnace is heated to 720 DEG C, isothermal reaction 13 hours under argon gas atmosphere, then it is down to room temperature,
To reduction crude product.
Step (8), reduction crude product is placed in the dilute hydrochloric acid that concentration is 0.6mol/L under room temperature and stirs
17 hours, it is centrifuged and obtains solid product, washed several times with water, obtain pressed powder after drying.
Step (9). above-mentioned pressed powder is placed in the diluted hydrofluoric acid that mass fraction is 7 and soaks under room temperature
Steep 3 hours, be centrifuged solid product, washed several times with water, obtain cellular three-dimensional porous silicon-carbon after drying multiple
Condensation material.
Embodiment 6
Step (1), prepare silicon dioxide: use Stober method in alcohol phase medium, use ammonia-catalyzed
Positive silicic acid four butyl ester (TEOS), forms monodispersed preparing spherical SiO 2 particles through hydrolysis-condensation,
Particle diameter is controlled in 300 nanometers by regulation pH value；
Step (2), by gorgeous to 9.9g TEG dimethylacrylate and 0.1g good solid 907 in room
Temperature～80 DEG C at be uniformly mixed, obtain mixed liquor；
Step (3), 9g step (1) gained silicon dioxide is joined in the above-mentioned mixed liquor of 10g, stirring
13 hours, obtain the mixed solution containing silicon dioxide；
Step (4), the above-mentioned mixed solution containing silicon dioxide is injected in mould, uses ultraviolet light
Solidification, illumination 120 seconds under 40W power, obtain silicon dioxide/polyacrylate composite solid material；
Step (5), silicon dioxide/polyacrylate composite solid material is pulverized, pulverizes 2 minutes,
Obtain solid particle.
Step (6), by above-mentioned solid particle at 600 DEG C, under nitrogen atmosphere calcine 4 hours, obtain black
Color powder, for nano silicon/carbon composite.
Under step (7), room temperature, above-mentioned black powder is mixed according to mass ratio 1:0.9 with magnesium powder, be placed in
Tube furnace is heated to 710 DEG C, isothermal reaction 11 hours under argon gas atmosphere, then it is down to room temperature,
To reduction crude product.
Step (8), reduction crude product is placed in the dilute hydrochloric acid that concentration is 1.2mol/L under room temperature and stirs
5 hours, it is centrifuged and obtains solid product, washed several times with water, obtain pressed powder after drying.
Step (9). above-mentioned pressed powder is placed in the diluted hydrofluoric acid that mass fraction is 5 and soaks under room temperature
Steep 4.5 hours, be centrifuged solid product, washed several times with water, obtain cellular three-dimensional porous silicon-carbon after drying
Composite.
Embodiment 7
Step (1), prepare silicon dioxide: use Stober method in alcohol phase medium, use ammonia-catalyzed
Positive silicic acid four butyl ester (TEOS), forms monodispersed preparing spherical SiO 2 particles through hydrolysis-condensation,
Particle diameter is controlled in 400 nanometers by regulation pH value；
Step (2), by gorgeous to 9.85g1,6-hexanediol dimethacrylate and 0.15g good solid 369
It is uniformly mixed at 70 DEG C, obtains mixed liquor；
Step (3), 2g step (1) gained silicon dioxide is joined in the above-mentioned mixed liquor of 8g, stirring
21 hours, obtain the mixed solution containing silicon dioxide；
Step (4), the above-mentioned mixed solution containing silicon dioxide is injected in mould, uses blue light solid
Change, illumination 100 seconds under 30W power, obtain silicon dioxide/polyacrylate composite solid material；
Step (5), silicon dioxide/polyacrylate composite solid material is pulverized, pulverizes 5 minutes,
Obtain solid particle.
Step (6), by above-mentioned solid particle at 600 DEG C, under argon gas atmosphere calcine 5 hours, obtain black
Color powder, for nano silicon/carbon composite.
Under step (7), room temperature, above-mentioned black powder is mixed according to mass ratio 1:1 with magnesium powder, be placed in pipe
Formula stove is heated to 650 DEG C, isothermal reaction 24 hours under argon/hydrogen (95/5 volume ratio) atmosphere,
Then it is down to room temperature, obtains reduction crude product.
Step (8), reduction crude product is placed in the dilute hydrochloric acid that concentration is 0.8mol/L under room temperature and stirs
22 hours, it is centrifuged and obtains solid product, washed several times with water, obtain pressed powder after drying.
Step (9). above-mentioned pressed powder is placed in the diluted hydrofluoric acid that mass fraction is 6 and soaks under room temperature
Steep 4 hours, be centrifuged solid product, washed several times with water, obtain cellular three-dimensional porous silicon-carbon after drying multiple
Condensation material.
Embodiment 8
Step (1), prepare silicon dioxide: use Stober method in alcohol phase medium, use ammonia-catalyzed
Positive silicic acid four butyl ester (TEOS), forms monodispersed preparing spherical SiO 2 particles through hydrolysis-condensation,
Particle diameter is controlled in 600 nanometers by regulation pH value；
Step (2), by gorgeous to 9.84g ethoxylated bisphenol dimethylacrylate and 0.16g good solid 754
It is uniformly mixed at 80 DEG C, obtains mixed liquor；
Step (3), 2g step (1) gained silicon dioxide is joined in the above-mentioned mixed liquor of 8g, stirring
14 hours, obtain the mixed solution containing silicon dioxide；
Step (4), the above-mentioned mixed solution containing silicon dioxide is injected in mould, uses ultraviolet light
Solidification, illumination 60 seconds under 50W power, obtain silicon dioxide/polyacrylate composite solid material；
Step (5), silicon dioxide/polyacrylate composite solid material is pulverized, pulverizes 5 minutes,
Obtain solid particle.
Step (6), by above-mentioned solid particle at 800 DEG C, under argon gas atmosphere calcine 2 hours, obtain black
Color powder, for nano silicon/carbon composite.
Under step (7), room temperature, above-mentioned black powder is mixed according to mass ratio 1:0.1 with magnesium powder, be placed in
Tube furnace is heated to 750 DEG C, isothermal reaction 1 hour under argon/hydrogen (95/5 volume ratio) atmosphere,
Then it is down to room temperature, obtains reduction crude product.
Step (8), reduction crude product is placed in the dilute hydrochloric acid that concentration is 0.5mol/L under room temperature and stirs
24 hours, it is centrifuged and obtains solid product, washed several times with water, obtain pressed powder after drying.
Step (9). above-mentioned pressed powder is placed in the diluted hydrofluoric acid that mass fraction is 10 and soaks under room temperature
Steep 0.5 hour, be centrifuged solid product, washed several times with water, obtain cellular three-dimensional porous silicon-carbon after drying
Composite.
Embodiment 9
Step (1), prepare silicon dioxide: use Stober method in alcohol phase medium, use ammonia-catalyzed
Positive silicic acid four butyl ester (TEOS), forms monodispersed preparing spherical SiO 2 particles through hydrolysis-condensation,
Particle diameter is controlled in 700 nanometers by regulation pH value；
Step (2), by 4.84g dimethacrylate diethylene glycol ester, 5g ethylene glycol dimethacrylate
Ester and 0.16g camphorquinone are uniformly mixed at 80 DEG C, obtain mixed liquor；
Step (3), 3g step (1) gained silicon dioxide is joined in the above-mentioned mixed liquor of 7g, stirring
24 hours, obtain the mixed solution containing silicon dioxide；
Step (4), the above-mentioned mixed solution containing silicon dioxide is injected in mould, uses blue light solid
Change, illumination 60 seconds under 50W power, obtain silicon dioxide/polyacrylate composite solid material；
Step (5), silicon dioxide/polyacrylate composite solid material is pulverized, pulverizes 5 minutes,
Obtain solid particle.
Step (6), by above-mentioned solid particle at 500 DEG C, under nitrogen atmosphere calcine 6 hours, obtain black
Color powder, for nano silicon/carbon composite.
Under step (7), room temperature, above-mentioned black powder is mixed according to mass ratio 1:0.5 with magnesium powder, be placed in
Tube furnace is heated to 750 DEG C, isothermal reaction 1 hour under nitrogen atmosphere, then it is down to room temperature,
To reduction crude product.
Step (8), reduction crude product is placed in the dilute hydrochloric acid that concentration is 0.5mol/L under room temperature and stirs
24 hours, it is centrifuged and obtains solid product, washed several times with water, obtain pressed powder after drying.
Step (9). above-mentioned pressed powder is placed in the diluted hydrofluoric acid that mass fraction is 1 and soaks under room temperature
Steep 5 hours, be centrifuged solid product, washed several times with water, obtain cellular three-dimensional porous silicon-carbon after drying multiple
Condensation material.
Above-described embodiment is not the restriction for the present invention, and the present invention is not limited only to above-described embodiment,
As long as meeting application claims, belong to protection scope of the present invention.
Claims (8)
1. a Si-C composite material, it is characterised in that it is cellular, three-dimensional continuously to be that nano silicon spheres is distributed in
Hybrid structure in porous carbon substrate；
Above-mentioned porous silicon carbon composite use 80～800nm preparing spherical SiO 2 nanoparticles as silicon source,
Use thermosetting bifunctional acrylate's class unsaturated-resin as carbon source, use first to be combined and reduce afterwards
Method is prepared from；Wherein esters of acrylic acid unsaturated-resin monomer is vinyl thermoset resin.
2. the preparation method of a Si-C composite material, it is characterised in that the method comprises the following steps:
Step (1), prepare silicon dioxide: use Stober method in alcohol phase medium, by ammonia-catalyzed just
Silicic acid four butyl ester (TEOS), forms monodispersed preparing spherical SiO 2 particles through hydrolysis-condensation, passes through
Regulation pH value controls particle diameter in 80～800 nanometers；
Step (2), esters of acrylic acid unsaturated-resin monomer and light trigger are stirred at room temperature～80 DEG C
Mix homogeneously, obtains mixed liquor；In mixed liquor, the mass content of light trigger is 0.2～2.0；
Described esters of acrylic acid unsaturated-resin monomer is vinyl thermoset resin；
Step (3), joining in above-mentioned mixed liquor by step (1) gained silicon dioxide, stirring 1～24 is little
Time, obtain the mixed solution containing silicon dioxide；Every 10 grams contain in silicon dioxide mixed solution containing 0.
001～9 gram of silicon dioxide；
Step (4), the above-mentioned mixed solution containing silicon dioxide is injected in mould, use blue light or
Ultraviolet light polymerization, illumination 60～300 seconds under 5～50W power, obtain silicon dioxide/polyacrylate and be combined
Solid material；
Step (5), silicon dioxide/polyacrylate composite solid material is pulverized, pulverizes 1～5 minute,
Obtain solid particle；
Step (6), by above-mentioned solid particle at 500～800 DEG C, under inert atmosphere calcine 2～6 hours,
Obtain black powder, for nano silicon/carbon composite；
Under step (7), room temperature by above-mentioned black powder with magnesium powder according to mass ratio 1:(0.1～1.0) mix,
It is placed in tube furnace and is heated to 650～750 DEG C, isothermal reaction 1～24 hours under inert atmosphere, then drop
To room temperature, obtain reduction crude product；
Step (8), reduction crude product is placed in the dilute hydrochloric acid that concentration is 0.5～2mol/L under room temperature and stirs
4～24 hours, it is centrifuged and obtains solid product, washed several times with water, obtain pressed powder after drying；
Step (9). above-mentioned pressed powder is placed in the diluted hydrofluoric acid that mass fraction is 1～10 under room temperature
Soak 0.5～5 hour, be centrifuged solid product, washed several times with water, obtain cellular three-dimensional porous after drying
Si-C composite material；
Above-mentioned Si-C composite material is that nano silicon spheres is distributed in three-dimensional porous carbon matrix cellular, continuous
Hybrid structure.
3. a kind of Si-C composite material as claimed in claim 1, it is characterised in that the mass content of carbon is
99～1.
4. a kind of Si-C composite material as claimed in claim 1 or method as claimed in claim 2,
It is characterized in that described esters of acrylic acid unsaturated-resin monomer is specially bisphenol-A-methacrylate contracting
Water glyceride, triethylene glycolbismethyl-acrylate, dimethacrylate diethylene glycol ester, dimethyl
Acrylic acid glycol ester, TEG dimethylacrylate, 1,6-HD dimethylacrylate,
One or more in ethoxylated bisphenol dimethylacrylate.
5. method as claimed in claim 2, it is characterised in that described light trigger be 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 one or several in camphorquinone.
6. method as claimed in claim 2, it is characterised in that step (6) inert atmosphere is nitrogen or argon
Gas.
7. method as claimed in claim 2, it is characterised in that step (7) described inert atmosphere can be
Nitrogen, argon, argon/hydrogen gas mixture.
8. a kind of Si-C composite material as claimed in claim 1, as lithium ion battery negative material
In application.
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| CN114975976A (en) * | 2022-07-15 | 2022-08-30 | 中国人民解放军国防科技大学 | Nano-silicon-inlaid three-dimensional honeycomb carbon composite negative electrode material and preparation method and application thereof |
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