CN109390570A - A kind of graphene coated silicon and preparation method thereof, application - Google Patents
A kind of graphene coated silicon and preparation method thereof, application Download PDFInfo
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Abstract
The present invention discloses a kind of graphene coated silicon and preparation method thereof, application, method is comprising steps of the silicon particle that the surface is coated with oxide passivated film generates the silicon particle with positive charge under the modification of coating material, the silicon particle with positive charge is obtaining the silicon particle of graphene oxide cladding by self assembly mode with graphene oxide, and the last graphene oxide coated Si obtains graphene coated silicon particle by being heated at high temperature reduction treatment in nitrogen atmosphere.The present invention avoids acid pickling step during preparing graphene coated silicon using silicon powder as silicon source, and without by-product, production process environmental protection, silicon utilization rate is high.In addition graphene oxide technology maturation is heat-treated, therefore production process is with more controllability, suitable large-scale production.
Description
Technical field
The present invention relates to lithium battery silicium cathode fields more particularly to a kind of graphene coated silicon and preparation method thereof, application.
Background technique
With new-energy automobile in practical applications to course continuation mileage require continuous improvement, high-energy density become lithium from
The energy density of the future directions of sub- battery, conventional graphite cathode is no longer satisfied demand.Silica-base material is because having
High density, abundant raw material, the at low cost, advantages of environment protection of 4200mAh/g, and be expected to become next-generation high-energy density lithium
Battery cathode.During removal lithium embedded, the volume change of silicon is huge, reaches 300%, and this greatly limits silicium cathode materials
Practical application.
Graphene is as a kind of novel carbon material, because it is with high-ratio surface, excellent electric conductivity and mechanical property etc.
Advantage can be widely used in positive and negative pole material field in terms of lithium ion battery charge conduction.Graphene coated can mention for silicon
For volume cushioning frame, while also promoting negative conductive performance.The chemical property of silicon more inertia, graphene are not easy directly to coat
Its surface.Therefore, ACS Appl.Mater.Interfaces, 2014,6(5), the articles such as pp 3546-3552 use silica
For silicon source, the silica of graphene oxide cladding is prepared by self-assembling method, silicon is then obtained by magnesiothermic reduction, is finally led to
It crosses HCl and removes MgO and Mg2Si by-product.However, the magnesiothermic reduction condition that the method uses easily generates SiC, and further relate to
By-product and pickling by-product bring problem of environmental pollution.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of graphene coated silicon and its preparation sides
Method, application, it is intended to which the preparation method feature of environmental protection for solving existing graphene coated silicon is poor, by-product is more and unsuitable scale metaplasia
The problem of production.
Technical scheme is as follows:
A kind of preparation method of graphene coated silicon, wherein comprising steps of
The silicon particle solution that surface is coated with oxide passivated film is provided；
By the silicon particle solution and positive charged surface activating agent and negative charged surface activating agent alternate treatment, and pass through Zeta electricity
Bit test obtains positively charged silicon particle.
Silicon particle and graphene oxide by the surface with positive charge are scattered in distilled water according to predetermined mass ratio,
Silicon particle and graphene oxide of the surface with positive charge generate graphene oxide cladding by way of electrostatic self-assembled
Silicon；
In a nitrogen atmosphere, the heat treatment that 700-1200 DEG C is carried out to the graphene oxide coated Si, obtains graphene packet
Cover silicon.
The preparation method of the graphene coated silicon, wherein the positively charged surfactant is cetyl
Trimethylammonium bromide, dimethyl benzyl dodecyl ammonium bromide, benzyltriethylammoinium chloride, octadecyltrimethylammonium chloride,
Benzalkonium bromide, N, N- dimethyl dodecylamine, 3- aminopropyl trimethoxy siloxane, 3- aminopropyl-triethoxy siloxanes,
Organosilicon quaternary ammonium salt, bi-imidazoline quaternary ammonium salt, dodecanamide propyl sulfuric ester ammonium, cationic-type polyacrylamide, PVP-Q sun from
Sub- co-polymer, polyethyleneimine quaternary ammonium salt, aliphatic triethanolamine acetate, lauryl amine acetate, quaternized panthenol,
Diallyl dimethyl ammoniumchloride, acrylic acid diethylaminoethyl ammonium chloride, dimethyl diallyl ammonium chloride, trialkyl chlorine
Change one of ammonium or a variety of.
The preparation method of the graphene coated silicon, wherein the negatively charged surfactant is to methylbenzene
Vinyl sulfonate, poly styrene sulfonate, dodecylated diphenyl ether disulfonate, 3- chlorine-2-hydroxyl propanesulfonate, polyether carboxylic acid
Surfactant, carboxymethyl cellulose salt, fat carboxylate, alkyl phosphate hydroxyethyl ether, alkoxy phosphate, allyl alcohol ether
Phosphate, dialkyl phosphate, alkyl sulfosuccinic acid monoester disodium salt, hexyl succinamide sodium sulfonate, acrylic acid-the third
Alkene sulfonic acid-isopropyl alkenyl phosphoric acid copolymer, polyacrylamide it is one or more.
The preparation method of the graphene coated silicon, wherein by the silicon particle solution and positive charged surface activating agent
With negative charged surface activating agent alternate treatment, and the step of obtaining positively charged silicon particle by Zeta potential test method packet
It includes:
The silicon particle solution is mixed with the positively charged aqueous surfactant solution, after vibrating 1-30min, using deionization
After water is cleaned and dried, the positively charged silicon particle of single layer is obtained；
The positively charged silicon particle of the single layer is mixed with the negatively charged aqueous surfactant solution, after vibrating 1-30min,
After being cleaned and dried using deionized water, the silicon particle that surface has negative electrical charge is obtained；
It repeats above step and obtains different layers of positively charged silicon particles, by the silicon particle disperse water that surface is positively charged
In, charge is tested using Zeta potential, when Zeta potential test result is greater than 0.05 and when less than 0.5, then stops above-mentioned step
Suddenly.
The preparation method of the graphene coated silicon, wherein the oxide passivated film with a thickness of 1-1000nm.
The preparation method of the graphene coated silicon, wherein silicon particle and oxidation stone of the surface with positive charge
The predetermined mass ratio 0.5-3:1 of black alkene.
The preparation method of the graphene coated silicon, wherein described 700-1200 DEG C of heating treatment time is
10min-5h。
The preparation method of the graphene coated silicon, wherein the graphene oxide is scattered in the concentration after distilled water
For 0.5-10mg/ml.
A kind of graphene coated silicon, wherein a kind of above-mentioned preparation method is used to be prepared.
A kind of application of graphene coated silicon, wherein be applied to the graphene coated silicon to prepare cathode of lithium battery.
The utility model has the advantages that the present invention, using silicon powder as silicon source, the silicon powder surface can not be kept away in production, storage and transportational process
Oxide thin layer silicon passivating film is generated with exempting from, i.e., the silicon particle that surface is coated with oxide passivated film (is expressed as Si@SiO2), institute
State Si@SiO2The Si@SiO for having positive charge is generated under the modification by coating material2, the Si@with positive charge
SiO2It is being scattered in distilled water with graphene oxide (GO) according to predetermined mass ratio, graphite oxide is obtained by self assembly mode
The silicon particle (being expressed as Si@SiO2@GO) of alkene cladding, the last Si@SiO2@GO is in nitrogen atmosphere by high-temperature heating
Reason obtains graphene coated silicon particle.The present invention avoids pickling during preparing graphene coated silicon using silicon powder as silicon source
Step, without by-product, production process environmental protection, silicon utilization rate is high.In addition graphene oxide technology maturation is heat-treated, therefore is produced
Process is with more controllability, suitable large-scale production.
Detailed description of the invention
Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of graphene coated silicon of the present invention.
Fig. 2 is the Electronic Speculum schematic diagram that graphene oxide prepared by the embodiment of the present invention 1 coats silicon particle.
Fig. 3 is the Electronic Speculum schematic diagram of graphene coated silicon particle prepared by the embodiment of the present invention 1.
Specific embodiment
The present invention provides a kind of graphene coated silicon and preparation method thereof, application, to make the purpose of the present invention, technical solution
And effect is clearer, clear, the present invention is described in more detail below.It should be appreciated that specific implementation described herein
Example is only used to explain the present invention, is not intended to limit the present invention.
Referring to Fig. 1, Fig. 1 is a kind of process of the preparation method preferred embodiment of graphene coated silicon provided by the invention
Figure, wherein as shown, comprising steps of
S10, the silicon particle solution that surface is coated with oxide passivated film is provided；
S20, by the silicon particle solution and positive charged surface activating agent and negative charged surface activating agent alternate treatment, and pass through
Zeta potential test obtains positively charged silicon particle；
S30, the silicon particle by the surface with positive charge and graphene oxide are scattered in distilled water according to predetermined mass ratio,
Silicon particle and graphene oxide of the surface with positive charge generate graphene oxide cladding by way of electrostatic self-assembled
Silicon；
S40, in a nitrogen atmosphere carries out 700-1200 DEG C of heat treatment to the graphene oxide coated Si, obtains graphite
Alkene coated Si.
Specifically, for the present invention using silicon powder as silicon source, the silicon powder surface can not in production, storage and transportational process
It has generated oxide thin layer silicon passivating film with avoiding, that is, has formed surface and be coated with the silicon particle of oxide passivated film and (be expressed as Si@
SiO2), the silicon particle assigns its positive surface charge by the modification of coating material, after formed by electrostatic self-assembled mode
The silicon particle of graphene oxide cladding, obtains the silicon particle of graphene coated finally by thermal reduction.The present invention is preparing stone
Acid pickling step is avoided during black alkene coated Si, without by-product, production process environmental protection, silicon utilization rate is high.In addition it heat-treats
Graphene oxide technology maturation, therefore production process is with more controllability, suitable large-scale production.
In the present invention, by the way that surface to be coated with to silicon particle (the Si@SiO of oxide passivated film2) it is scattered in distilled water
In, after being ultrasonically treated 30-180min, obtain finely dispersed Si@SiO2Aqueous solution.Preferably, the Si@SiO2Aqueous solution
Concentration be 0.5-3mg/ml.
Further, by replacing the silicon particle solution with positive charged surface activating agent and negative charged surface activating agent
Processing obtains positively charged silicon particle eventually by Zeta test.Specifically, present embodiment passes through silicon particle surface
Oxide passivated film and positively charged and negative electrical charge surfactant alternate grafting, to obtain the silicon that surface has positive charge
Particle.It is preferred that the concentration of the positively charged surfactant and negatively charged surfactant is 0.005-0.5g/ml.
Further, the oxide passivated film on the silicon particle surface with a thickness of 1-1000nm.Preferably 400-800nm,
Such as 500nm, 600nm, 700nm.Silica in the thickness range is easier to be grafted with surfactant, to generate table
Face has the silicon particle of positive charge.
In a preferred embodiment, by the silicon particle solution and positive charged surface activating agent and negative charged surface
Activating agent alternate treatment, and the step of obtaining positively charged silicon particle by Zeta potential test method includes:
The silicon particle solution is mixed with the positively charged aqueous surfactant solution, after vibrating 1-30min, using deionization
After water is cleaned and dried, the positively charged silicon particle of single layer is obtained；By the positively charged silicon particle of the single layer with it is described negatively charged
Aqueous surfactant solution mixing after vibrating 1-30min, after being cleaned and dried using deionized water, obtains surface with negative electrical charge
Silicon particle；It repeats above step and obtains different layers of positively charged silicon particles, by the positively charged silicon particle in surface point
In aproll, charge is tested using Zeta potential, on Zeta potential test result is greater than 0.05 and when less than 0.5, then stops
State step.
As a wherein specific embodiment, by the silicon particle solution and diallyl dimethyl ammoniumchloride (PDDA)
The positively charged silicon particle that zeta current potential is 0.05, i.e. PDDA+ Si@SiO2 particle can be obtained in aqueous solution mixing.The list
The positively charged PDDA+ Si@SiO2 particle of layer can directly and graphene oxide by electrostatic self-assembled mode generates graphite oxide
Alkene coated Si.
As wherein another specific embodiment, first by the silicon particle solution and diallyl dimethyl ammoniumchloride
(PDDA) aqueous solution mixes, and after shaken at room temperature 1-30min, after being cleaned and dried using deionized water, it is positively charged to obtain single layer
Silicon particle, i.e. PDDA+ Si@SiO2 particle；Later by the positively charged silicon particle of the single layer and the kayexalate
Aqueous solution mixing, after being cleaned and dried using deionized water, obtains negatively charged silicon particle, i.e. PSS/PDDA-Si@SiO2
Grain；It is finally that the PSS/PDDA-Si@SiO2 silicon particle is water-soluble with the diallyl dimethyl ammoniumchloride (PDDA) again
Liquid mixing, after being cleaned and dried using deionized water, finally obtains two layers of positively charged silicon particle, i.e. PDDA/PSS/PDDA+
Si@SiO2 particle, Zeta potential test its aqueous solution, are 0.12.Compared to the silicon particle positively charged with single layer, by described two layers
Positively charged silicon particle and graphene oxide generates the packaging efficiency of graphene oxide coated Si by electrostatic self-assembled mode
Higher, silicon powder utilization rate is high.
In the present invention, silicon particle and graphene oxide of the surface with positive charge are according to predetermined mass ratio 0.5-3:
1 is scattered in distilled water, and silicon particle and graphene oxide of the surface with positive charge are raw by way of electrostatic self-assembled
At graphene oxide coated Si.As a wherein specific embodiment, surface is had to the silicon particle and graphite oxide of positive charge
Alkene is scattered in distilled water according to the amount that mass ratio is 2:1, and shaken at room temperature 30min-5h obtains graphene oxide coated Si (Si@
SiO2@GO).Preferably, it is equal to be scattered in the concentration after distilled water for silicon particle and graphene oxide of the surface with positive charge
For 0.5-10mg/ml.
Further, the graphene oxide coated Si is put into atmosphere furnace, in a nitrogen atmosphere, in temperature be 700-
Heating reduction treatment is carried out within the scope of 1200 DEG C, the processing time is 10min-5h, finally obtains graphene coated silicon.Also due to heat
Former graphene oxide technology is more mature, therefore the preparation process of graphene coated silicon provided by the invention has more controllability, fits
Close large-scale production.As a wherein specific embodiment, the graphene oxide coated Si is put into atmosphere furnace, in nitrogen
Under atmosphere, it is to carry out heating reduction treatment 30min within the scope of 1000 DEG C in temperature, graphene coated silicon can be efficiently made.
Further, it the present invention also provides a kind of graphene coated silicon, is prepared into using any one of the above preparation method
It arrives.
Further, the present invention also provides a kind of applications of graphene coated silicon, by above-mentioned graphene coated silicon application
In preparing cathode of lithium battery.
A kind of preparation method of graphene coated silicon of the present invention is further explained below by specific embodiment
It is bright:
Embodiment 1
The Si powder 2.5g of buying is distributed in 200ml distilled water, ultrasonic disperse 1 hour, obtains component A.Prepare 1mg/ml
PDDA aqueous solution, be named as component B.Component A and component B are mixed to concussion 60min, centrifugation at room temperature, distilled water cleans 2 times
Positively charged Si particle is obtained, is centrifuged, it is dry.2.5g silicon particle after taking drying is distributed in distilled water (2mg/ml), with
The graphene oxide solution of 500ml (0.5mg/ml) mixes,
Room temperature electrostatic self-assembled obtains the silicon particle solution of graphene oxide cladding, and last centrifugal drying obtains graphene oxide packet
The silicon particle covered.The silicon particle that the graphene oxide coats is put into atmosphere furnace, restores 1h under 1000 degrees celsius
Obtain the silicon particle of graphene coated.
Embodiment 2
The Si powder 2.5g of buying is placed in 150 degree of baking oven heating after ten minutes, is distributed in 200ml distilled water, ultrasonic disperse 1
Hour, obtain component A.The PDDA aqueous solution for preparing 1mg/ml, is named as component B.Prepare the kayexalate of 1mg/ml
PSS aqueous solution, is named as component C.200ml component A and 100ml component B is mixed to concussion 60min, centrifugation, distilled water at room temperature
Mix after cleaning 2 times with 100ml component C, after cleaning 2 times, then with component B is mixed to get positively charged Si particle, is centrifuged, it is dry
It is dry.2.5g silicon particle after taking drying is distributed in distilled water (2mg/ml), the graphene oxide with 500ml (0.5mg/ml)
Solution mixing, room temperature electrostatic self-assembled obtain the silicon particle solution of graphene oxide cladding, and last centrifugal drying obtains oxidation stone
Black alkene coats silicon particle, and the electron microscope of the graphene oxide cladding silicon particle is as shown in Figure 2.The graphene oxide is coated
Silicon particle is put into atmosphere furnace, and 1h is restored under 1000 degrees celsius and obtains graphene coated silicon particle, the graphene packet
The electron microscope for covering silicon particle is as shown in Figure 3.
In conclusion the present invention, using silicon powder as silicon source, the silicon powder surface can not be kept away in production, storage and transportational process
Oxide thin layer silicon passivating film is generated with exempting from, i.e., the silicon particle that surface is coated with oxide passivated film (is expressed as Si@SiO2), institute
State Si@SiO2The Si@SiO for having positive charge is generated under the modification by coating material2, the Si@with positive charge
SiO2It is being scattered in distilled water with graphene oxide (GO) according to predetermined mass ratio, graphite oxide is obtained by self assembly mode
The silicon particle (being expressed as Si@SiO2@GO) of alkene cladding, the last Si@SiO2@GO is in nitrogen atmosphere by high-temperature heating
Reason obtains graphene coated silicon particle.The present invention avoids pickling during preparing graphene coated silicon using silicon powder as silicon source
Step, without by-product, production process environmental protection, silicon utilization rate is high.In addition graphene oxide technology maturation is heat-treated, therefore is produced
Process is with more controllability, suitable large-scale production.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of preparation method of graphene coated silicon, which is characterized in that comprising steps of
The silicon particle solution that surface is coated with oxide passivated film is provided；
By the silicon particle solution and positive charged surface activating agent and negative charged surface activating agent alternate treatment, and pass through Zeta electricity
Bit test obtains positively charged silicon particle；
Silicon particle and graphene oxide by the surface with positive charge are scattered in distilled water according to predetermined mass ratio, described
Silicon particle and graphene oxide of the surface with positive charge generate graphene oxide coated Si by way of electrostatic self-assembled；
In a nitrogen atmosphere, the heat treatment that 700-1200 DEG C is carried out to the graphene oxide coated Si, obtains graphene packet
Cover silicon.
2. the preparation method of graphene coated silicon according to claim 1, which is characterized in that the positively charged surface
Activating agent is cetyl trimethylammonium bromide, dimethyl benzyl dodecyl ammonium bromide, benzyltriethylammoinium chloride, octadecane
Base trimethyl ammonium chloride, benzalkonium bromide, N, N- dimethyl dodecylamine, 3- aminopropyl trimethoxy siloxane, 3- aminopropyl
Triethoxy siloxanes, organosilicon quaternary ammonium salt, bi-imidazoline quaternary ammonium salt, dodecanamide propyl sulfuric ester ammonium, cationic poly third
Acrylamide, PVP-Q cationic copolymerss, polyethyleneimine quaternary ammonium salt, aliphatic triethanolamine acetate, lauryl amine vinegar
Hydrochlorate, quaternized panthenol, diallyl dimethyl ammoniumchloride, acrylic acid diethylaminoethyl ammonium chloride, two allyl of dimethyl
One of ammonium chloride, tri alkyl ammomium chloride are a variety of.
3. the preparation method of graphene coated silicon according to claim 1, which is characterized in that the negatively charged surface
Activating agent is p-methylstyrene sulfonate, poly styrene sulfonate, dodecylated diphenyl ether disulfonate, 3- chlorine-2-hydroxyl
Propanesulfonate, polyether carboxylic acid's surfactant, carboxymethyl cellulose salt, fat carboxylate, alkyl phosphate hydroxyethyl ether, alcoxyl
Based phosphates, allyl alcohol ether phosphate, dialkyl phosphate, alkyl sulfosuccinic acid monoester disodium salt, hexyl succinic acid acyl
Amine sodium sulfonate, acrylic acid-acrylic sulfonic acid-isopropyl alkenyl phosphoric acid copolymer, polyacrylamide it is one or more.
4. the preparation method of graphene coated silicon according to claim 1, which is characterized in that by the silicon particle solution with
Positive charged surface activating agent and negative charged surface activating agent alternate treatment, and positively charged silicon is obtained by Zeta potential test
The step of particle includes:
The silicon particle solution is mixed with the positively charged aqueous surfactant solution, after vibrating 1-30min, using deionization
After water is cleaned and dried, the positively charged silicon particle of single layer is obtained；
The positively charged silicon particle of the single layer is mixed with the negatively charged aqueous surfactant solution, after vibrating 1-30min,
After being cleaned and dried using deionized water, the silicon particle that surface has negative electrical charge is obtained；
It repeats above step and obtains different layers of positively charged silicon particles, by the silicon particle disperse water that surface is positively charged
In, charge is tested using Zeta potential, when Zeta potential test result is greater than 0.02 and when less than 2, then stops above-mentioned steps.
5. the preparation method of graphene coated silicon according to claim 1, which is characterized in that the oxide passivated film
With a thickness of 1-1000nm.
6. the preparation method of graphene coated silicon according to claim 1, which is characterized in that the surface has positive charge
Silicon particle and graphene oxide predetermined mass ratio 0.5-3:1.
7. the preparation method of graphene coated silicon according to claim 1, which is characterized in that described 700-1200 DEG C plus
Heat treatment time is 10min-5h.
8. the preparation method of graphene coated silicon according to claim 1, which is characterized in that the graphene oxide dispersion
Concentration after distilled water is 0.5-10mg/ml.
9. a kind of graphene coated silicon, which is characterized in that using claim 1-8, any one preparation method is prepared.
10. a kind of application of graphene coated silicon, which is characterized in that graphene coated silicon as claimed in claim 9 to be applied to
Prepare cathode of lithium battery.
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| CN112002885A (en) * | 2020-09-10 | 2020-11-27 | 中国空间技术研究院 | Silicon-carbon composite material, preparation method thereof and lithium ion battery |
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| CN114613971A (en) * | 2022-03-31 | 2022-06-10 | 南京工业大学 | Preparation method and application of compact and stable pomegranate-shaped silicon-graphene composite electrode material |
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| CN110993930B (en) * | 2019-11-22 | 2021-09-24 | 芜湖天弋能源科技有限公司 | Preparation method of graphene-coated nano-silicon composite material and application of graphene-coated nano-silicon composite material as negative electrode material of lithium ion battery |
| CN111106352A (en) * | 2019-12-30 | 2020-05-05 | 国联汽车动力电池研究院有限责任公司 | Cross-linking type water-based binder for lithium ion battery and electrode prepared from cross-linking type water-based binder |
| CN112002885A (en) * | 2020-09-10 | 2020-11-27 | 中国空间技术研究院 | Silicon-carbon composite material, preparation method thereof and lithium ion battery |
| WO2022062394A1 (en) * | 2020-09-23 | 2022-03-31 | 江西艾特新材料有限公司 | Method for coating magnetic powder core with sodium silicate |
| CN112978803A (en) * | 2021-02-23 | 2021-06-18 | 四川大学 | Preparation method of water-soluble superparamagnetic ferroferric oxide microspheres with positively charged surfaces |
| CN114613971A (en) * | 2022-03-31 | 2022-06-10 | 南京工业大学 | Preparation method and application of compact and stable pomegranate-shaped silicon-graphene composite electrode material |
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