CN108630919A - A kind of carbon coating silicon/graphene complex and its preparation method and application - Google Patents
A kind of carbon coating silicon/graphene complex and its preparation method and application Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of carbon coating silicon/graphene complexes and its preparation method and application, its prepare include presoma silica/graphene complex silicon/graphene complex for coating of preparation, magnesiothermic reduction, more poly phosphazenes, final high temperature is carbonized to obtain carbon coating silicon/graphene complex.Present invention employs surface aggregate methods to load ultrathin carbon films in nanometer two dimension silicon/graphene surface, utilize Triphosphazene and 4, more poly phosphazene low surface tensions, highly viscous characteristic obtained by 4 dihydroxydiphenylsulisomers, the constantly cladding crosslinking on the silicon face with high surface energy, control ultrasound and material proportion during the reaction can realize uniformly cladding and ultra-thin load；Then it is heat-treated under the protection of non-oxidizing atmosphere, removes more poly phosphazene hetero atoms, form the porous C film of uniform load.
Description
Technical field
The present invention relates to a kind of lithium ion battery negative material fields, multiple more particularly to a kind of carbon coating silicon/graphene
Close object and its preparation method and application.
Background technology
Electrode material of the silicon as theoretical capacity highest (4200mAh/g) is that lithium cell cathode material is the most so far
One of ideal candidate.In general, pure silicon has the following problems as battery cathode active substance：Occur in process of intercalation
Huge volume expansion, commercialization battery structure tend to allow electrode material volume change within 6%~8%.Silicon electrode
In charge and discharge process there are huge bulk effect (>300%).In the process, dusting, rupture occur for electrode material, living
Property substance is gradually removed with collector, and material conductivity is greatly reduced, and cycle performance of battery is bad；Its structure breaking becomes with volume
Change, new section exposure continuously emerges in the electrolytic solution, silicon face is difficult to form stable SEI films, and the SEI films constantly formed disappear
A large amount of lithium ions are consumed, form a large amount of irreversible capacities, therefore silicon active material is always along under first charge discharge efficiency and capacity declines
Subtract rapid.In addition, silicon, as semiconductor nonmetallic materials, conductivity only has 2.52 × 10-6S cm-1, need that abundance is added
Conductive agent, the requirement with society for the growing energy density of lithium ion battery contradict.
For the above problem, in the patent application of many silicium cathodes, be absorbed in by silicon particle nanosizing and carbon it is compound with
Its volume cushion space is provided, reduces the internal stress during the embedding de- lithium of active material, while improving the electricity of active material
Electron conductivity.But traditional silicon-carbon is compound in addition to that must solve the problems, such as that silicon particle is fully dispersed, it is necessary to avoid excessively introducing
Carbon component reduces the problem of silicon activity substance content.Si-SiOx is coated on by CN 1041103821A using chemical deposition
Carbon base body surface, then coated to obtain well dispersed Si-C composite material, porous Si-SiOx structures drop by pyrolytic carbon
The low bulk effect of Si active substances.But surface packet is carried out as carbon source using glucose in water solution system
It covers, easily forms carbon ball, product purity is made to be difficult to ensure, and the presence of particle inside and outside carbon-coating reduces the reality of silicon active material
Border content.
Invention content：
To overcome technical problem to be solved, the present invention to provide a kind of system of the two-dimentional Si-C composite material uniformly coated
Preparation Method.
Technical solution of the invention is as follows：
A kind of preparation method of carbon coating silicon/graphene complex comprising following steps：
(1) preparation of presoma：First graphene oxide, cetyl trimethylammonium bromide, sodium hydroxide and water are mixed
It is slowly added in mixed solution at mixed solution, then by ethyl orthosilicate, hydro-thermal reaction after stirring；Then to reaction solution carry out from
After the heart, washing, filtering, drying, calcining obtains silica/graphene complex；
(2) magnesiothermic reduction：Silica/graphene complex is mixed with magnesium powder, fused salt, and is put into closed stainless steel
In reactor, the pyroreaction under the protection of inert gas atmosphere；Reaction product uses hf etching, then to it through taking out
Filter, washing, vacuum drying obtain silicon/graphene mixture；
(3) by silicon/graphene mixture, Triphosphazene and 4,4- dihydroxydiphenylsulisomers are added in absolute ethyl alcohol, add
Triethylamine, 8~12h of thermostatic ultrasonic, mixture is centrifuged, ethyl alcohol washs, is dried in vacuo, and obtains more poly phosphazene claddings
Silicon/graphene complex；
(4) high temperature cabonization：Silicon/graphene complex that more poly phosphazenes are coated high temperature cabonization under inert gas atmosphere,
Two-dimensional carbon coating silicon/graphene complex of coated with carbon is obtained after then cooling to room temperature.
Further scheme, graphene oxide, cetyl trimethylammonium bromide, sodium hydroxide described in step (1)
Mass ratio is 3000~5000：200~300：4~5.
Further scheme, the stirring described in step (1) be at 40~60 DEG C stirring 12~for 24 hours；Hydro-thermal reaction be
12~48h is reacted at 120~180 DEG C；The centrifugal rotational speed is 2000~6000rpm；80~120 DEG C of the temperature of the drying,
Calcining, which is that protection under inert gas atmosphere is lower, to be carried out, and temperature is 600~800 DEG C.
Further scheme, silica/graphene complex and the mass ratio of magnesium powder, fused salt described in step (2) are
1：1~1.5：10~15；The fused salt is one or two kinds of mixing in sodium chloride, potassium chloride.
Further scheme, the temperature of pyroreaction is 600~800 DEG C described in step (2), the reaction time is 1~3h；Institute
The time for stating hf etching is 1~3h.
Further scheme, the matter of silicon/graphene mixture, Triphosphazene, 4,4- dihydroxydiphenylsulisomers described in step (3)
Amount is than being 2~4：1：4.3；The dripping quantity of the triethylamine is 8~20ml.
Further scheme, ultrasonic time described in step (3) be 8~12h, mixture centrifuge rotating speed be 4000~
6000rpm。
Further scheme, high temperature cabonization described in step (4) be two-part heating, wherein first segment be first from room temperature with
Heating rate is that 1 DEG C/min is warming up to 600 DEG C, keeps the temperature 2h；Second segment is warming up to from 600 DEG C for 1 DEG C/min with heating rate
It is heat-treated 3h at 900 DEG C.
Another goal of the invention of the present invention provides the carbon coating silicon/graphene complex prepared through above-mentioned preparation method.
Another goal of the invention of the present invention provides the purposes of above-mentioned carbon coating silicon/graphene complex, the carbon packet
Cover the negative material that silicon/graphene complex is used as lithium ion battery.
The present invention by ethyl orthosilicate be added containing trimethylammonium bromide, sodium hydroxide, graphene oxide aqueous solution in
Water-bath is carried out, ethyl orthosilicate is made to be deposited in the surface hydrolysis of graphene oxide；Further hydro-thermal reaction, centrifugation, washing, mistake
Silica/graphene complex is obtained after filter, dry, calcining；It is then mixed into magnesium powder, fused salt, under inert gas protection magnesium heat
Reaction is restored to elemental silicon, obtains silicon/graphene mixture；Finally it polymerize to form more poly phosphazenes, surface using Triphosphazene
The characteristics of tension low easy cladding silicon face, under conditions of keeping ultrasonic disperse, it polymerize to form one layer of thin layer in silicon surface
Polymer finally puts it into inert atmosphere stove and carries out calcining removing P, S hetero atom, to obtain thin layer carbon coating silicon/stone
Black alkene compound.
The beneficial effects of the present invention are：
Present invention employs surface aggregate methods to load ultrathin carbon films in nanometer two dimension silicon/graphene surface, utilizes trimerization phosphine
Nitrile and 4, the more poly phosphazene low surface tensions of 4- dihydroxydiphenylsulisomer gained, highly viscous characteristic, in the silicon face with high surface energy
Upper constantly cladding crosslinking, control ultrasound and material proportion, can realize uniformly cladding and ultra-thin load during the reaction；Then
It is heat-treated under the protection of non-oxidizing atmosphere, removes more poly phosphazene hetero atoms, form the porous C film of uniform load.
Carbon coating silicon prepared by the present invention/negative material of the graphene complex as lithium ion battery, both avoided
Activated silica and electrolyte are in direct contact, while also making graphene and surface carbon film content extremely low, have given full play to silicon active matter
The advantage of matter high power capacity.
Description of the drawings
Fig. 1 is the SEM electron microscopes of carbon-coated silicon/graphene complex in the embodiment of the present invention 1
The cycle comparison diagram of materials A in Fig. 2 present invention, B, C
Specific implementation mode：
Embodiment 1
This example provides a kind of preparation method of carbon coating silicon/graphene negative material, and preparation method is as follows：
The preparation of step 1, presoma：Take graphene oxide water solution (1g/ml) 40ml, sodium hydroxide 40mg, hexadecane
Base trimethylammonium bromide 2g adds water until 100ml is mixed into mixed solution.2ml ethyl orthosilicates are taken to be slowly added into above-mentioned mixed
It closes constant temperature at 40 DEG C of liquid and stirs 12h.Mixed liquor pours into water heating kettle, reacts 48h at 180 DEG C, take out liquid 4000rpm rotating speeds from
Lower 600 DEG C of calcinings are protected to obtain silica/graphene complex under the heart, washing, filtering, 80 DEG C of dryings, inert gas atmospheres.
Step 2, magnesiothermic reduction：Silica/graphene complex 0.4g and magnesium powder 0.48g, sodium chloride 4g is taken uniformly to mix
Conjunction is put into closed stainless steel reactor, in Ar2Under the protection of atmosphere, 600 DEG C of reaction 3h of high temperature；Product uses hydrofluoric acid
(1mol/L) etching 1h, suction filtration washing, 80 DEG C of vacuum drying obtain silicon/graphene complex.
Step 3 takes silicon/graphene complex 0.2g, Triphosphazene 0.05g and 4, the 0.215g additions of 4- dihydroxydiphenylsulisomers
To 10ml triethylamines (TEA) are added in 300ml anhydrous ethanol solvents after mixing, thermostatic ultrasonic 12h at a temperature of 40 DEG C.It is mixed
It closes object 5000rpm to centrifuge, be dried in vacuo after washing, at 80 DEG C, before obtaining silicon/graphene complex of more poly phosphazene claddings
Body；
Step 4, high temperature cabonization：Step 3 is obtained into precursor powder high temperature cabonization under inert gas atmosphere, is cooled to room
Carbon coating silicon/graphene complex of material with carbon-coated surface is obtained after temperature.
Wherein high temperature cabonization heats up for two-part：
First segment：Room temperature is warming up to 600 DEG C of heat preservation 2h, and heating rate is controlled in 1 DEG C/min；
Second segment：600 DEG C are warming up to 900 DEG C of heat treatment 3h, and heating rate is controlled in 1 DEG C/min.
Carbon coating silicon prepared by the present embodiment 1/graphene complex carries out electron-microscope scanning, as shown in Figure 1, carbon coating
Silicon/graphene complex meets two-dimensional appearance feature, does not reunite between lamella, carbon layer on surface is evenly coated.
Comparative example 1
With embodiment 1, difference from Example 1 is：The second segment of high temperature cabonization is to be warming up to 700 DEG C from 600 DEG C
Lower heat treatment 3h, heating rate are controlled in 1 DEG C/min.
Comparative example 2
With embodiment 1, difference from Example 1 is：The second segment of high temperature cabonization is to be warming up to 1000 DEG C from 600 DEG C
Lower heat treatment 3h, heating rate are controlled in 1 DEG C/min.
The chemical property for the material that embodiment 1 is prepared with comparative example 1,2 is studied using button half-cell.
Above-described embodiment 1 is respectively adopted with the material of the preparation of comparative example 1,2 as negative material, distinguishes in the following manner
Button half-cell A, B, C are prepared, it is as shown in Figure 2 then to test its cycle performance.
Experiment is used as using metal lithium sheet to electrode, and electrolyte is dimethyl carbonate/ethylene carbonate (volume ratio 1:1),
Diaphragm uses Celgard2300 microporous polypropylene membranes, uses Kynoar for binder, and Super C are conductive agent, N- methyl
Pyrrolidones is solvent；It is 8 by active material carbon coating silicon/graphene complex, PVDF and Super C mass ratioes：1：1 uniformly
It is mixed and made into viscous paste, is coated onto on copper foil of affluxion body, coating thickness is 90 μm, the dry 1h in 80 DEG C of baking ovens,
In being assembled into battery in glove box after even slice, tabletting, drying, stand for 24 hours.
Cycle performance test is carried out to above-mentioned button cell：Charge and discharge voltage range is 0.005~2.5V, and current density is
100mA/g。
Button half-cell A, B, C that the material that Fig. 2 is prepared by embodiment 1 and comparative example 1,2 is assembled as negative material
Cycle performance figure.As shown in Figure 2, the carburizing temperature of 1 material of comparative example is low, causes material carbonization incomplete, impurity is not complete
It removes, material conductivity reduces, and charging capacity reduces.But the carbonization of material is higher than 900 DEG C in comparative example 2, and charging capacity also compares
Embodiment 1 is low.
So high temperature carbonization of the present invention is critically important, the cycle performance of battery made of negative material is made to be optimal.
Embodiment 2
This example provides a kind of preparation method of carbon coating silicon/graphene negative material, and preparation method is as follows：
The preparation of step 1, presoma：Take graphene oxide water solution (1g/ml) 50ml, sodium hydroxide, cetyl three
Methyl bromide ammonium is respectively 40mg, 2g, adds water until 100ml.2ml ethyl orthosilicates are taken to be slowly added into above-mentioned mixed liquor 40
Constant temperature stirs 12h at DEG C.Mixed liquor pours into water heating kettle, reacts 48h at 180 DEG C, take out the centrifugation of liquid 4000rpm rotating speeds, washing,
Lower 700 DEG C of calcinings are protected to obtain silica/graphene complex under filtering, 80 DEG C of dryings, inert gas atmospheres.
Step 2, magnesiothermic reduction：Take product 0.4g in step 2, magnesium powder 0.48g and potassium chloride 6g mixing be put into it is closed not
In rust steel reactor, in Ar2Under the protection of atmosphere, 800 DEG C of high temperature, react 1h, product using hydrofluoric acid (1mol/L) etching 1h,
Filter washing, 80 DEG C of vacuum drying obtain silicon/graphene complex.
Step 3 takes above-mentioned 0.1g products, 0.05g Triphosphazenes and 4,4-dihydroxydiphenylsulisomers of 0.215g to be added to
It is added 20ml triethylamines (TEA) in 300ml anhydrous ethanol solvents after mixing, at a temperature of 40 DEG C, thermostatic ultrasonic 12h.Mixing
Object 5000rpm is centrifuged, is dried in vacuo after washing, at 80 DEG C, obtains body before silicon/graphene complex of more poly phosphazene claddings
Body；
Step 4, high temperature cabonization：Step 3 is obtained into precursor powder, high temperature cabonization, is cooled under inert gas atmosphere
Two-dimentional silicon/graphene complex of material with carbon-coated surface is obtained after room temperature.
Wherein high temperature cabonization heats up for two-part：
First segment：Room temperature heats up 600 DEG C, keeps the temperature 2h, and heating rate is controlled in 1 DEG C/min；
Second segment：600 DEG C are warming up at 900 DEG C and are heat-treated 3h, and heating rate is controlled in 1 DEG C/min.
Embodiment 3
The preparation of step 1, presoma：Take graphene oxide water solution (1g/ml) 30ml, sodium hydroxide, cetyl three
Methyl bromide ammonium is respectively 50mg, 3g, adds water until 100ml.3ml ethyl orthosilicates are taken to be slowly added into above-mentioned mixed liquor 60
Constant temperature stirs 12h at DEG C.Mixed liquor pours into water heating kettle, reacts 12h at 120 DEG C, take out the centrifugation of liquid 4000rpm rotating speeds, washing,
Lower 800 DEG C of calcinings are protected to obtain silica/graphene complex under filtering, 120 DEG C of dryings, inert gas atmospheres.
Step 2, magnesiothermic reduction：Take in step 2 product 0.4g uniformly mixed with magnesium powder 0.52g, sodium chloride 4g be put into it is closed
Stainless steel reactor in, in Ar2Under the protection of atmosphere, 600 DEG C of high temperature reacts 3h, and product is carved using hydrofluoric acid (1mol/L)
Erosion 3h, suction filtration washing, 80 DEG C of vacuum drying obtain silicon/graphene complex.
Step 3 takes above-mentioned 0.2g products, 0.05g Triphosphazenes and 4,4-dihydroxydiphenylsulisomers of 0.215g to be added to
It is added 10ml triethylamines in 300ml anhydrous ethanol solvents after mixing, at a temperature of 40 DEG C, thermostatic ultrasonic 12h.Mixture
5000rpm is centrifuged, is dried in vacuo after washing, at 80 DEG C, obtains body before silicon/graphene complex of more poly phosphazene claddings
Body；
Step 4, high temperature cabonization：Step 3 is obtained into precursor powder, high temperature cabonization, is cooled under inert gas atmosphere
Two-dimentional silicon/graphene complex of material with carbon-coated surface is obtained after room temperature.
Wherein high temperature cabonization heats up for two-part：
First segment：Room temperature heats up 600 DEG C, keeps the temperature 2h, and heating rate is controlled in 1 DEG C/min；
Second segment：600 DEG C are warming up at 900 DEG C and are heat-treated 3h, and heating rate is controlled in 1 DEG C/min；
Embodiment 4
The preparation of step 1, presoma：Take graphene oxide water solution (1g/ml) 40ml, sodium hydroxide 40mg, hexadecane
Base trimethylammonium bromide 2g adds water until 100ml is mixed into mixed solution.2ml ethyl orthosilicates are taken to be slowly added into above-mentioned mixed
It closes constant temperature at 40 DEG C of liquid and stirs 12h.Mixed liquor pours into water heating kettle, reacts 48h at 180 DEG C, take out liquid 4000rpm rotating speeds from
Lower 600 DEG C of calcinings are protected to obtain silica/graphene complex under the heart, washing, filtering, 80 DEG C of dryings, inert gas atmospheres.
Step 2, magnesiothermic reduction：Silica/graphene complex 0.4g and magnesium powder 0.48g, sodium chloride 4g is taken uniformly to mix
Conjunction is put into closed stainless steel reactor, in Ar2Under the protection of atmosphere, 600 DEG C of reaction 3h of high temperature；Product uses hydrofluoric acid
(1mol/L) etching 1h, suction filtration washing, 80 DEG C of vacuum drying obtain silicon/graphene complex.
Step 3 takes silicon/graphene complex 0.2g, 0.1g Triphosphazene and 4,4-dihydroxydiphenylsulisomers of 0.43g to add
To 20ml triethylamines are added after mixing in 600ml anhydrous ethanol solvents.At a temperature of 40 DEG C, thermostatic ultrasonic 12h.Mixture
5000rpm is centrifuged, is dried in vacuo after washing, at 80 DEG C, obtains body before silicon/graphene complex of more poly phosphazene claddings
Body.
Step 4, high temperature cabonization：Step 3 is obtained into precursor powder high temperature cabonization under inert gas atmosphere, is cooled to room
Carbon coating silicon/graphene complex of material with carbon-coated surface is obtained after temperature.
Wherein high temperature cabonization heats up for two-part：
First segment：Room temperature is warming up to 600 DEG C of heat preservation 2h, and heating rate is controlled in 1 DEG C/min；
Second segment：600 DEG C are warming up to 900 DEG C of heat treatment 3h, and heating rate is controlled in 1 DEG C/min.
The present invention does not limit to above-mentioned specific implementation mode, and every technical staff is made any on the basis of the invention
Conspicuously improved, replacement or modification all belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of carbon coating silicon/graphene complex, it is characterised in that：Include the following steps：
（1）The preparation of presoma：First graphene oxide, cetyl trimethylammonium bromide, sodium hydroxide and water are mixed into mixed
Solution is closed, then ethyl orthosilicate is slowly added in mixed solution, hydro-thermal reaction after stirring；Then reaction solution is centrifuged,
After washing, filtering, drying, calcining obtains silica/graphene complex；
（2）Magnesiothermic reduction：Silica/graphene complex is mixed with magnesium powder, fused salt, and is put into closed stainless steel reaction
In device, the pyroreaction under the protection of inert gas atmosphere；Reaction product uses hf etching, then to it through suction filtration, water
It washes, be dried in vacuo and obtain silicon/graphene mixture；
（3）By silicon/graphene mixture, Triphosphazene and 4,4- dihydroxydiphenylsulisomers are added in absolute ethyl alcohol, add three second
Amine, 8 ~ 12 h of thermostatic ultrasonic, mixture is centrifuged, ethyl alcohol washs, is dried in vacuo, and obtains silicon/stone of more poly phosphazene claddings
Black alkene compound；
（4）High temperature cabonization：Silicon/graphene complex that more poly phosphazenes are coated high temperature cabonization under inert gas atmosphere, then
Two-dimensional carbon coating silicon/graphene complex of coated with carbon is obtained after being cooled to room temperature.
2. preparation method according to claim 1, it is characterised in that：Step（1）Described in graphene oxide, hexadecane
Base trimethylammonium bromide, sodium hydroxide mass ratio be 3000 ~ 5000：200~300：4~5.
3. preparation method according to claim 1, it is characterised in that：Step（1）Described in stirring be at 40 ~ 60 DEG C
Stirring 12 ~ for 24 hours；Hydro-thermal reaction is 12 ~ 48h of reaction at 120 ~ 180 DEG C；The centrifugal rotational speed is 2000 ~ 6000rpm；It is described
80 ~ 120 DEG C of dry temperature, calcining, which is that protection under inert gas atmosphere is lower, to be carried out, and temperature is 600 ~ 800 DEG C.
4. preparation method according to claim 1, it is characterised in that：Step（2）Described in silica/graphene it is multiple
The mass ratio for closing object and magnesium powder, fused salt is 1：1~1.5：10~15；The fused salt is sodium chloride, one kind in potassium chloride or two
Kind mixing.
5. preparation method according to claim 1, it is characterised in that：Step（2）Described in pyroreaction temperature be 600
~ 800 DEG C, the reaction time be 1 ~ 3 h；The time of the hf etching is 1 ~ 3 h.
6. preparation method according to claim 1, it is characterised in that：Step（3）Described in silicon/graphene mixture, three
Poly phosphazene, 4,4- dihydroxydiphenylsulisomers mass ratio be 2 ~ 4：1：4.3；The dripping quantity of the triethylamine is 8 ~ 20 ml.
7. preparation method according to claim 1, it is characterised in that：Step（3）Described in ultrasonic time be 8 ~ 12 h, mix
It is 4000 ~ 6000 rpm to close the rotating speed that object centrifuges.
8. preparation method according to claim 1, it is characterised in that：Step（4）Described in high temperature cabonization be two-part
Heating, wherein first segment are first to be warming up to 600 DEG C from room temperature with heating rate for 1 DEG C/min, keep the temperature 2h；Second segment is to heat up
Rate is 1 DEG C/min, is warming up to from 600 DEG C at 900 DEG C and is heat-treated 3h.
9. a kind of carbon coating silicon/graphene complex prepared by preparation method as described in claim 1.
10. the purposes of carbon coating silicon/graphene complex as claimed in claim 9, it is characterised in that：The carbon coating silicon/
Graphene complex is used as the negative material of lithium ion battery.
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| CN110729471A (en) * | 2019-10-24 | 2020-01-24 | 长沙晟天新材料有限公司 | Silicon @ graphene/CVD carbon composite anode material for lithium ion battery and preparation method and application thereof |
| CN110729135A (en) * | 2019-09-11 | 2020-01-24 | 江苏大学 | Preparation method of molybdenum disulfide/polyphosphazene/ferroferric oxide electrode material |
| CN110818926A (en) * | 2019-10-21 | 2020-02-21 | 深圳市超导新材料有限公司 | Graphene/polymer composite conductive film and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101632913A (en) * | 2009-07-09 | 2010-01-27 | 上海交通大学 | Preparation method of silicon/porous carbon nano-composite particle |
| US20140183415A1 (en) * | 2012-12-31 | 2014-07-03 | Cheil Industries Inc. | Graphene-Based Composite and Method of Preparing the Same |
| CN105702959A (en) * | 2016-04-14 | 2016-06-22 | 华东理工大学 | Preparation method of silicon-based lithium ion battery anode material |
| CN106848273A (en) * | 2017-01-19 | 2017-06-13 | 深圳市沃特玛电池有限公司 | A kind of preparation method of Si-C composite material |
-
2018
- 2018-04-04 CN CN201810305760.1A patent/CN108630919A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101632913A (en) * | 2009-07-09 | 2010-01-27 | 上海交通大学 | Preparation method of silicon/porous carbon nano-composite particle |
| US20140183415A1 (en) * | 2012-12-31 | 2014-07-03 | Cheil Industries Inc. | Graphene-Based Composite and Method of Preparing the Same |
| CN105702959A (en) * | 2016-04-14 | 2016-06-22 | 华东理工大学 | Preparation method of silicon-based lithium ion battery anode material |
| CN106848273A (en) * | 2017-01-19 | 2017-06-13 | 深圳市沃特玛电池有限公司 | A kind of preparation method of Si-C composite material |
Cited By (15)
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| EP3653576A3 (en) * | 2018-11-16 | 2020-09-30 | National Chung-Shan Institute of Science and Technology | Anode material of nano-silicon having multilayer-graphene as carrier and coated with silicon suboxide and with amorphous carbon layer and method for fabricating the same |
| US10879530B2 (en) | 2018-12-13 | 2020-12-29 | National Chung-Shan Institute Of Science And Technology | Anode material of nano-silicon having multilayer-graphene as carrier and coated with silicon suboxide and with amorphous carbon layer and method for fabricating the same |
| CN109713271A (en) * | 2018-12-27 | 2019-05-03 | 山东精工电子科技有限公司 | The synthetic method of the carbon composite of high-energy density three-dimensional texture |
| CN110729135B (en) * | 2019-09-11 | 2021-08-03 | 江苏大学 | Preparation method of molybdenum disulfide/polyphosphazene/ferroferric oxide electrode material |
| CN110729135A (en) * | 2019-09-11 | 2020-01-24 | 江苏大学 | Preparation method of molybdenum disulfide/polyphosphazene/ferroferric oxide electrode material |
| CN110818926A (en) * | 2019-10-21 | 2020-02-21 | 深圳市超导新材料有限公司 | Graphene/polymer composite conductive film and preparation method thereof |
| CN110729471A (en) * | 2019-10-24 | 2020-01-24 | 长沙晟天新材料有限公司 | Silicon @ graphene/CVD carbon composite anode material for lithium ion battery and preparation method and application thereof |
| CN111082035A (en) * | 2019-12-20 | 2020-04-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of sheet-graphene @ silicon @ amorphous carbon-sandwich structure composite material, and product and application thereof |
| CN111082035B (en) * | 2019-12-20 | 2022-09-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of sheet-graphene @ silicon @ amorphous carbon-sandwich structure composite material, and product and application thereof |
| CN111446432A (en) * | 2020-04-20 | 2020-07-24 | 上海交通大学 | Preparation method of nano silicon/carbon composite negative electrode material for lithium ion battery |
| CN111653779A (en) * | 2020-05-29 | 2020-09-11 | 山东海科创新研究院有限公司 | High-stability silicon-carbon graphene composite negative electrode material, preparation method thereof and obtained product |
| CN111900365A (en) * | 2020-09-04 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
| CN113363458A (en) * | 2021-06-03 | 2021-09-07 | 开封平煤新型炭材料科技有限公司 | Preparation method of silicon-carbon negative electrode material |
| CN116002660A (en) * | 2022-12-28 | 2023-04-25 | 太原科技大学 | Preparation method of carbon-silicon composite material, carbon-silicon composite material and lithium battery |
| CN116002660B (en) * | 2022-12-28 | 2023-07-18 | 太原科技大学 | Preparation method of carbon-silicon composite material, carbon-silicon composite material and lithium battery |
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