CN106207186A - Silicon/the carbon composite of a kind of Graphene bridge joint and application - Google Patents
Silicon/the carbon composite of a kind of Graphene bridge joint and application Download PDFInfo
- Publication number
- CN106207186A CN106207186A CN201610663073.8A CN201610663073A CN106207186A CN 106207186 A CN106207186 A CN 106207186A CN 201610663073 A CN201610663073 A CN 201610663073A CN 106207186 A CN106207186 A CN 106207186A
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite
- silicon
- bridge joint
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses silicon/carbon composite and the application of a kind of Graphene bridge joint, nano silica fume and flake graphite are pressed certain weight ratio dispensing by the present invention, through dry ball milling mix homogeneously, obtain Si/FG；Again by Si/FG and saccharide and polymer mixed in deionized water, obtain mixing suspension through wet ball grinding；The spray-dried Si/FG carbohydrate polymer mixture that obtains of mixing suspension, more described Si/FG carbohydrate polymer mixture high-temperature heat treatment is obtained Si/C composite；With hydrazine hydrate, graphite oxide is reduced into Graphene in deionized water；Finally dispersing graphene in deionized water, ultrasonic agitation mix homogeneously, add Si/C composite, ultrasonic agitation mix homogeneously, then sucking filtration, drying obtain Si/C graphene composite material；The features such as the present invention has that preparation technology is simple, low cost, cycle are short, are suitable for industrialized production.
Description
Technical field
The present invention relates to silicon/carbon/graphite in lithium ion batteries thiazolinyl negative pole field, the silicon/carbon being specifically related to a kind of Graphene bridge joint is multiple
Condensation material (Si/C-Graphene) and its preparation method and application.
Background technology
Lithium ion battery is widely used as mobile electronic device now, such as smart mobile phone, notebook computer etc., and at electricity
Net energy storage, electric automobile field have huge market.But, using graphite in traditional lithium ion battery is negative pole, graphite
Capacity (theoretical value 372mAh/g) and energy density relatively low, and owing to its orientation causes high-rate charge-discharge capability relatively
Difference, which has limited its application in extensive energy storage field, such as large-scale use on electric automobile.
Different from the embedding lithium mechanism of graphite, Si material, owing to can react formation lithium alloy with lithium, has high theoretical appearance
Amount (> 4000mAh/g), but alloy machine is comprehended and is caused big change in volume, causes capacity rapid decay.Relatively rational method is
Si material is combined with graphite, in conjunction with both advantage balancing capacity and cycle life, but due in it change in volume
And the stress caused, long-time discharge and recharge eventually results in the stripping of Si, thus causes the decline of capacity, how by Si material and
The material with carbon elements such as graphite carry out effectively being combined still facing significant challenge.Meanwhile, the load of Si also can cause the decline of electrode conductivity
And the decline of high rate performance.
It addition, research finds, graphite material is made the spherical raising being conducive to high rate performance.But make spherical meeting to cause
The decline of active material contact surface each other.A kind of effective way is to insert conductive agent between spherical particle, special for being
There is the conductive agent of electro-chemical activity.Graphene is because it has high electrical conductivity, high mechanical strength, and self has storage
Lithium ability, is the most suitably to fill or bridge material.Therefore, the spherical Si/C composite preparing Graphene bridge joint is preferable
Selection, but there is presently no this respect document report.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that the silicon/carbon composite wood of a kind of Graphene bridge joint
Material and application.Raw material uses business-like material, and preparation technology is simple, and cost is relatively low, is suitable for industrialized production；It is prepared into
To Si/C-graphene composite material there is the Si/C spherical particle of special pattern, i.e. micron-scale by minority layer micron order
Graphene bridged；Gained composite has high electrical conductivity, high capacity, excellent cyclical stability, it is adaptable to high
Energy density, high power, long circulation life lithium ion battery.
It is an object of the invention to be achieved through the following technical solutions: (1) by nano silica fume and flake graphite by weight
Ratio is 1:4～1:10 dispensing, and through dry ball milling mix homogeneously, obtaining Si/FG, described Si/FG is silicon/flake graphite mixture；
The particle size of described nano silica fume is 30-70 nanometer, and the particle size of described flake graphite is 1～10 micron；
The described dry ball milling time is 1～5h, and rotating speed is 100～400rpm；
(2) by step 1 gained Si/FG, saccharide, polymer mixed in deionized water, mixing is obtained through wet ball grinding outstanding
Supernatant liquid；
Described saccharide and Si/FG weight ratio are 1:1～1:10, and described polymer and Si/FG weight ratio are 1:1～1:5；
The described wet ball grinding time is 1～5h, and rotating speed is 100～400rpm；
(3) the spray-dried Si/FG-saccharide-polymeric blends that obtains of mixing suspension step 2 obtained, then will
Described Si/FG-saccharide-polymeric blends high-temperature heat treatment obtains Si/C composite；
The tank inlet temperature of described spray drying is 200～300 DEG C, and outlet temperature is 90～150 DEG C；
The temperature of described heat treatment is 400～800 DEG C, and the time is 2～10h；
Described heat-treating atmosphere is argon；
(4) with hydrazine hydrate, graphite oxide is reduced into Graphene in deionized water；
The proportion relation of described graphite oxide and deionized water is 0.1～0.5g/L；
The weight ratio of described hydrazine hydrate and graphite oxide is 0.5～1.0:1；
Described reduction temperature is 80～95 DEG C, and the recovery time is 1～5h；
(5) step 4 gained graphene dispersion is in deionized water, ultrasonic agitation mix homogeneously, adds step 3 gained
Si/C composite, ultrasonic agitation mix homogeneously, then sucking filtration, drying obtain Si/C-graphene composite material；
The weight ratio of described Si/C and Graphene is 10:1～5:1.
The proportion relation of described Graphene and deionized water is 0.5～5mg/L.
The present invention is with flake graphite, nano Si powder, saccharide and the polymer of business as presoma, by spray drying method,
The saccharide of bound fraction pyrolysis and the cohesive force of polymer, prepare spherical Si/C composite.In Si/C composite, C has two
Being grouped into, flake graphite (FG) provider's capacity, the pyrolytic carbon deriving from saccharide and polymer provides portion capacity and by Si
Nano-particle is fixed on flake graphite, and a small amount of nano Si provides portion capacity.On the one hand Graphene bridges spherical Si/C, rises
Improve its electro-chemical activity to electric action, on the other hand portion capacity is provided.
As preferably, step 3) in, the inlet temperature of spray drying vessel is 240～260 DEG C, outlet temperature be 100～
120℃。
As preferably, step 3) in, heat treatment temperature is 500～700 DEG C, and heat treatment time is 3～5h.
The Si/C-graphene composite material prepared according to above-mentioned method, Si/C a size of micron order, a diameter of 2～20 μ
M, and present spherical.Micron-sized size is conducive to the raising of the electro-chemical activity of material own, and by the moistening of electrolyte；Spherical
Pattern is conducive to the diffusion of lithium ion, improves high rate performance；Carbon in Si/C is made up of two parts, flake graphite therein (FG)
Provider's capacity, and on the one hand pyrolytic carbon provides portion capacity, is on the other hand fixed on flake graphite by Si nano-particle,
Improve the cyclical stability of composite；On the one hand Graphene in composite provides electric action thus improves electrochemistry and live
Property, on the other hand portion capacity is provided.
As preferably, in Si/C composite, the content of Si is 5wt%～10wt%, and too much Si content will cause circulation
The reduction in life-span, Si content, by reducing the capacity of composite, is therefore controlled to compare conjunction in above-mentioned scope by very few Si content
Suitable.
As preferably, in Si/C complex component C, amorphous carbon accounts for 10wt%～15wt%, amorphous carbon too high levels, will drop
The reversible capacity of low composite and bring too high irreversible capacity, amorphous carbon content is too low, is unfavorable for Si nano-particle
It is fixed on flake graphite, reduces the cycle life of composite, therefore amorphous carbon content control is compared conjunction in above-mentioned scope
Suitable.
As preferably, in Si/C-graphene composite material, Graphene is 1:10～1:5 with the weight ratio of Si/C, very few
Graphene is unfavorable for providing enough electrical conductivity, too much Graphene by reduce the density of composite and capacity (Graphene from
Capacity and the density of body are relatively low), it is the most reasonable therefore to be controlled by the content of Graphene.
As preferably, in Si/C-graphene complex, Graphene is minority layer graphene, and the number of plies is less than 10 layers, plane meter
Very little 1～10 μm, the Graphene of this structure is conducive to effective bridge joint of Si/C spherical particle, and provides excellent electrical conductivity.
The purpose of the present invention solves also by techniques below scheme: above-mentioned Si/C-graphene composite material lithium from
Application in sub-battery cathode.
Compared with prior art, there is advantages that
1, the Si/C-Graphene that prepared by the present invention can use business-like raw material to prepare, have that technique is simple, low cost,
Cycle is short, be suitable for the features such as industrialized production；
2, in the Si/C-graphene composite material that prepared by the present invention, it is micron order that Si/C presents spherical and particle size,
Being conducive to high current charge-discharge, spherical Si/C granule is effectively bridged by Graphene, can further improve its electro-chemical activity and big
Current charge-discharge electrical property；
3, in the Si/C-graphene composite material that prepared by the present invention, flaky crystal graphite, amorphous carbon, Graphene, nano-silicon
Powder ratio and structure are optimized simultaneously, make high power capacity and long-life be guaranteed simultaneously, significantly improve combining of composite
Close chemical property.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the Si/C-graphene composite material of embodiment 1 preparation, and in figure, G represents Graphene；
Fig. 2 is the Si/C-graphene composite material cyclical stability schematic diagram of embodiment 1 preparation；
Fig. 3 is the stereoscan photograph of the Si/C composite of comparative example 1 preparation；
Fig. 4 be comparative example 1 preparation Si/C composite cyclical stability schematic diagram.
Detailed description of the invention
Embodiment 1
By business-like nano Si powder (particle size is about 50nm) and flake graphite (FG) 1:9 dispensing, warp by weight
Dry ball milling mix homogeneously (Ball-milling Time is 2 hours, rotating speed 220rpm), obtains silicon/flake graphite mixture (Si/FG)；Will
Above-mentioned Si/FG, glucose and polyvinylpyrrolidone (PVP) (weight ratio 6:2:3) are for being mixed in deionized water, through wet grinding
(Ball-milling Time is 3 hours, rotating speed 220rpm) obtains mixing suspension；Si/ is obtained by spray-dried for above-mentioned mixing suspension
FG-glucose-PVP mixture, wherein spray dryer inlet temperature is 250 DEG C, and outlet temperature is 110 DEG C；Again by above-mentioned spray
Mist desciccate heat treatment under 600 DEG C of argon atmosphers obtains Si/C composite in 4 hours, and in composite, Si content is 8%；Adopt
Prepare graphite oxide by the Hummers method improved, and with hydrazine hydrate, graphite oxide be reduced into Graphene (G) in aqueous,
Wherein the weight ratio of hydrazine hydrate and graphite oxide is 0.7, and reduction temperature is 95 DEG C, and the recovery time is 1h；By Si/C and above-mentioned stone
Ink alkene mixes by weight 10:1, is placed in deionized water, through ultrasonic agitation, then obtains Si/C-Graphene again through sucking filtration, drying
Condensation material.The stereoscan photograph of Fig. 1 shows, in Si/C-graphene composite material, Si/C presents spherical, particle size be 2～
20 μm, spherical Si/C is bridged by the minority layer graphene of 1～10 μm by planar dimension.
The Si/C-Graphene prepared with the present embodiment is as active material, black with conductive acetylene, polyacrylic acid binding agent (weight
Amount than be 8:1:1) mix homogeneously coat Copper Foil composition working electrode, with lithium metal for electrode, the polypropylene film (trade mark
Celgard 2300, Celgard company of the U.S.) it is barrier film, LiPF6Vinyl carbonate/dimethyl carbonate (EC/DMC) molten
Liquid is electrolyte, and assemble in the glove box of full argon carries out charge-discharge test, and its cyclic curve is as shown in Figure 2.Logical
Cross charge-discharge test, detect Si/C-graphene composite material capacity under certain electric current and certain voltage scope and keep energy
Power (i.e. cyclical stability) and coulombic efficiency (the reversible degree of discharge and recharge).Specially record the discharge capacity of each discharge and recharge, charging
Capacity and coulombic efficiency (charging capacity and the ratio of discharge capacity), observe the above-mentioned parameter variation tendency with cycle-index.If holding
Amount is high and holding capacity is good, and coulombic efficiency is close to 100%, and the chemical property of illustrative material is good.
(front 5 primary currents are 200mA/g, and rear 95 circulating currents are 500mA/g, voltage range in constant current charge-discharge test
0.01V～1.5V, wherein capacity and electric current density are based on Si/C-graphene composite material) show, putting first of composite
Capacitance is 732mAh/g, and through 100 circulations, capacity is positively retained at 569mAh/g, and coulombic efficiency is close to 100%, and display is relatively
High capacity degree reversible with excellent cyclical stability and discharge and recharge height.
Comparative example 1
The preparation technology of Si/C composite is same as described above, and difference is to leave out the step for of being combined with Graphene.
Concrete technology is as follows, business-like nano Si powder (particle size is about 50nm) and flake graphite (FG) is joined by weight 1:9
Material, through dry ball milling mix homogeneously (Ball-milling Time is 2 hours, rotating speed 220rpm), obtains silicon/flake graphite mixture (Si/
FG)；By above-mentioned Si/FG, glucose and polyvinylpyrrolidone (PVP) (weight ratio 6:2:3) for being mixed in deionized water, warp
Wet grinding (Ball-milling Time is 3 hours, rotating speed 220rpm) obtains mixing suspension；Obtain spray-dried for above-mentioned mixing suspension
Si/FG-glucose-PVP mixture, wherein spray dryer inlet temperature is 250 DEG C, and outlet temperature is 110 DEG C；Again by above-mentioned
Spray dried products heat treatment under 600 DEG C of argon atmosphers obtains Si/C composite in 4 hours, and in composite, Si content is 8%.
The stereoscan photograph of Fig. 3 shows, Si/C presents spherical, and particle size is 2～20 μm.
The Si/C prepared with the present embodiment is as active material, black with conductive acetylene, polyacrylic acid binding agent (weight ratio is 8:
1:1) mix homogeneously coats Copper Foil composition working electrode, with lithium metal for electrode, polypropylene film (trade mark Celgard
2300, Celgard company of the U.S.) it is barrier film, LiPF6Vinyl carbonate/dimethyl carbonate (EC/DMC) solution for electrolysis
Liquid, assemble in the glove box of full argon, carry out charge-discharge test, its cyclic curve is as shown in Figure 4.Pass through discharge and recharge
Test, detects Si/C composite capacity holding capacity (i.e. cyclical stability) under certain electric current and certain voltage scope
And coulombic efficiency (the reversible degree of discharge and recharge).Specially record the discharge capacity of each discharge and recharge, charging capacity and coulombic efficiency (to fill
Capacitance and the ratio of discharge capacity), observe the above-mentioned parameter variation tendency with cycle-index.If capacity is high and holding capacity is good,
And coulombic efficiency is close to 100%, the chemical property of illustrative material is good.(front 5 primary currents are 200mA/ in constant current charge-discharge test
G, rear 95 circulating currents are 500mA/g, voltage range 0.01V～1.5V, and wherein capacity and electric current density are based on Si/C again
Condensation material) show, the discharge capacity first of composite is 587mAh/g, and through 100 circulations, capacity is maintained at 505mAh/
G, capacity is less than the sample of graphene-containing, it is seen that the bridge joint effect of Graphene can increase the electro-chemical activity of material, thus improves
Capacity.
Embodiment 2
By business-like nano Si powder (particle size is about 50nm) and flake graphite (FG) 1:8 dispensing, warp by weight
Dry ball milling mix homogeneously (Ball-milling Time is 2 hours, rotating speed 220rpm), obtains silicon/flake graphite mixture (Si/FG)；Will
Above-mentioned Si/FG, starch and polyvinyl alcohol (PVA) (weight ratio 10:2:3) are for being mixed in deionized water, through wet grinding (Ball-milling Time
It is 3 hours, rotating speed 220rpm) obtain mixing suspension；By spray-dried for above-mentioned mixing suspension obtain Si/FG-sucrose-
PVA mixture, wherein spray dryer inlet temperature is 240 DEG C, and outlet temperature is 120 DEG C；Again by above-mentioned Spray dried products
At 500 DEG C, under argon atmospher, heat treatment obtains Si/C composite in 5 hours, and in composite, Si content is 9.5%；Use and improve
Hummers method prepare graphite oxide, and with hydrazine hydrate, graphite oxide is reduced into Graphene (G), Qi Zhongshui in aqueous
The weight ratio closing hydrazine and graphite oxide is 0.7, and reduction temperature is 95 DEG C, and the recovery time is 1h；Si/C and above-mentioned Graphene are pressed
Weight ratio 9:1 mixes, and is placed in deionized water, through ultrasonic agitation, then obtains Si/C-graphene composite material through sucking filtration, drying.
Stereoscan photograph shows, in Si/C-graphene composite material, Si/C presents spherical, and particle size is 2～20 μm, spherical Si/C
Bridged by the minority layer graphene of 1～10 μm by planar dimension.
The Si/C-Graphene prepared with the present embodiment is as active material, black with conductive acetylene, polyacrylic acid binding agent (weight
Amount than be 8:1:1) mix homogeneously coat Copper Foil composition working electrode, with lithium metal for electrode, the polypropylene film (trade mark
Celgard 2300, Celgard company of the U.S.) it is barrier film, LiPF6Vinyl carbonate/dimethyl carbonate (EC/DMC) molten
Liquid is electrolyte, and assemble in the glove box of full argon carries out charge-discharge test.
(front 5 primary currents are 200mA/g, rear 95 circulating current 500mA/g, voltage range in constant current charge-discharge test
0.01V～1.5V, wherein capacity and electric current density are based on Si/C-graphene composite material) show, putting first of composite
Capacitance is 760mAh/g, and through 100 circulations, capacity is maintained at 575mAh/g, and coulombic efficiency, close to 100%, shows higher
Capacity and excellent cyclical stability and discharge and recharge reversible degree height.
Embodiment 3
By business-like nano Si powder (particle size is about 50nm) and flake graphite (FG) 1:10 dispensing, warp by weight
Dry ball milling mix homogeneously (Ball-milling Time is 2 hours, rotating speed 220rpm), obtains silicon/flake graphite mixture (Si/FG)；Will
Above-mentioned Si/FG, sucrose and phenolic resin (PF) (weight ratio 20:3:6) are for being mixed in deionized water, through wet grinding (Ball-milling Time
It is 3 hours, rotating speed 220rpm) obtain mixing suspension；Si/FG-sucrose-PF is obtained by spray-dried for above-mentioned mixing suspension
Mixture, spray dryer inlet temperature is 260 DEG C, and outlet temperature is 100 DEG C；Again by above-mentioned Spray dried products at 700 DEG C
Under lower argon atmospher, heat treatment obtains Si/C composite in 3 hours, and in composite, Si content is 6.8%；Use improvement
Hummers method prepares graphite oxide, and with hydrazine hydrate, graphite oxide is reduced into Graphene (G) in aqueous, is wherein hydrated
The weight ratio of hydrazine and graphite oxide is 0.7, and reduction temperature is 95 DEG C, and the recovery time is 1h；Si/C and above-mentioned Graphene are pressed weight
Measure and mix than 8:1, be placed in deionized water, through ultrasonic agitation, then obtain Si/C-graphene composite material through sucking filtration, drying.Sweep
Retouching electromicroscopic photograph to show, in Si/C-graphene composite material, Si/C presents spherical, and particle size is 2～20 μm, spherical Si/C quilt
Planar dimension is bridged by the minority layer graphene of 1～10 μm.
The Si/C-Graphene prepared with the present embodiment is as active material, black with conductive acetylene, polyacrylic acid binding agent (weight
Amount than be 8:1:1) mix homogeneously coat Copper Foil composition working electrode, with lithium metal for electrode, the polypropylene film (trade mark
Celgard 2300, Celgard company of the U.S.) it is barrier film, LiPF6Vinyl carbonate/dimethyl carbonate (EC/DMC) molten
Liquid is electrolyte, and assemble in the glove box of full argon carries out charge-discharge test.
(front 5 primary currents are 200mA/g, rear 95 circulating current 500mA/g, voltage range in constant current charge-discharge test
0.01V～1.5V, wherein capacity and electric current density are based on Si/C-graphene composite material) show, putting first of composite
Capacitance is 680mAh/g, and through 100 circulations, capacity is maintained at 545mAh/g, and coulombic efficiency, close to 100%, shows higher
Capacity and excellent cyclical stability and discharge and recharge reversible degree height.
Above-described embodiment be used for illustrate the present invention rather than limit the invention, the present invention spirit and
In scope of the claims, any modifications and changes that the present invention is made, both fall within protection scope of the present invention.
Claims (9)
1. silicon/the carbon composite of a Graphene bridge joint, it is characterised in that be prepared by the following method and obtain:
(1) by nano silica fume and flake graphite by weight for 1:4～1:10 dispensing, through dry ball milling mix homogeneously, Si/ is obtained
FG, described Si/FG are silicon/flake graphite mixture；
The particle size of described nano silica fume is about 30-70 nanometer, and the particle size of described flake graphite is 1～10 micron；
The described dry ball milling time is about 1～5h, and rotating speed is about 100～400rpm；
(2) by step 1 gained Si/FG, saccharide, polymer mixed in deionized water, mixing suspension is obtained through wet ball grinding；
Described saccharide and Si/FG weight ratio are 1:1～1:10, and described polymer and Si/FG weight ratio are 1:1～1:5；
The described wet ball grinding time is 1～5h, and rotating speed is 100～400rpm；
(3) mixing suspension that step 2 obtained is spray-dried obtains Si/FG-saccharide-polymeric blends, then by described
Si/FG-saccharide-polymeric blends high-temperature heat treatment obtains Si/C composite；
The tank inlet temperature of described spray drying is 200～300 DEG C, and outlet temperature is 90～150 DEG C；
The temperature of described heat treatment is about 400～800 DEG C, and the time is about 2～10h；
Described heat-treating atmosphere is argon；
(4) with hydrazine hydrate, graphite oxide is reduced into Graphene in deionized water；
The proportion relation of described graphite oxide and deionized water is 0.1～0.5g/L；
The weight ratio of described hydrazine hydrate and graphite oxide is 0.5～1.0:1；
Described reduction temperature is 80～95 DEG C, and the recovery time is 1～5h；
(5) step 4 gained graphene dispersion is in deionized water, ultrasonic agitation mix homogeneously, adds the Si/C of step 3 gained
Composite, ultrasonic agitation mix homogeneously, then sucking filtration, drying obtain Si/C-graphene composite material；
The weight ratio of described Si/C and Graphene is 10:1～5:1.
The proportion relation of described Graphene and deionized water is 0.5～5mg/L.
Silicon/the carbon composite of Graphene the most according to claim 1 bridge joint, it is characterised in that in described step 2, institute
The saccharide stated is selected from glucose, sucrose, really sugar and starch, and described polymer is selected from polyvinylpyrrolidone (PVP), polyethylene
Alcohol (PVA), phenolic resin (PF) and polypropylene (PP).
Silicon/the carbon composite of Graphene the most according to claim 1 bridge joint, it is characterised in that in described step 3, spray
In mist dried, carbohydrate fraction thermally decomposes, and and polymer Si/FG is mixed globulate, form spherical Si/FG-saccharide-poly-
Compound presoma.
Silicon/the carbon composite of Graphene the most according to claim 1 bridge joint, it is characterised in that in described step 3, Si/
In C complex, carbon source is in two parts, the flake graphite i.e. crystallized and derive from the pyrolysis amorphous carbon of saccharide and polymer.
Silicon/the carbon composite of Graphene the most according to claim 1 bridge joint, it is characterised in that in described step 3, Si/
In C complex, the ratio of Si is 5wt%～10wt%, and in C, the ratio of amorphous carbon is 10wt%～15wt%.
Silicon/the carbon composite of Graphene the most according to claim 1 bridge joint, it is characterised in that in described step 3, institute
Stating spray drying vessel inlet temperature and be preferably 240～260 DEG C, outlet temperature is preferably 100～120 DEG C, described heat treatment
Temperature is preferably 500～700 DEG C, and the time is preferably 3～5h.
Silicon/the carbon composite of Graphene the most according to claim 1 bridge joint, it is characterised in that in described step 5, Si/
C composite presents spherical, a diameter of 2～20 μm, and is bridged by Graphene.
Silicon/the carbon composite of Graphene the most according to claim 1 bridge joint, it is characterised in that in described step 5, institute
Obtaining Graphene is the minority Rotating fields less than 10 layers, planar dimension 1～10 μm, and the weight ratio of Graphene and Si/C is 1:8～1:
10。
9. silicon/the carbon composite of the Graphene bridge joint described in a claim 18 application in lithium ion battery negative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610663073.8A CN106207186A (en) | 2016-08-12 | 2016-08-12 | Silicon/the carbon composite of a kind of Graphene bridge joint and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610663073.8A CN106207186A (en) | 2016-08-12 | 2016-08-12 | Silicon/the carbon composite of a kind of Graphene bridge joint and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106207186A true CN106207186A (en) | 2016-12-07 |
Family
ID=57514422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610663073.8A Pending CN106207186A (en) | 2016-08-12 | 2016-08-12 | Silicon/the carbon composite of a kind of Graphene bridge joint and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106207186A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301215A (en) * | 2018-09-30 | 2019-02-01 | 陕西煤业化工技术研究院有限责任公司 | A kind of high capacity silicon-carbon cathode active material and preparation method thereof and its application |
| EP3859834A4 (en) * | 2018-09-28 | 2021-10-20 | Posco | Anode active material for lithium secondary battery and lithium secondary battery comprising same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0935306A1 (en) * | 1997-05-30 | 1999-08-11 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery and method for manufacturing negative electrode of the same |
| CN101442124A (en) * | 2007-11-19 | 2009-05-27 | 比亚迪股份有限公司 | Method for preparing composite material of lithium ion battery cathode, and cathode and battery |
| CN102145882A (en) * | 2011-02-24 | 2011-08-10 | 暨南大学 | Method for preparing water soluble graphene |
| CN103346305A (en) * | 2013-07-01 | 2013-10-09 | 华南师范大学 | Preparation and application of lithium battery silicon-carbon composite material taking synthetic graphite as carrier |
| CN104064736A (en) * | 2013-03-21 | 2014-09-24 | 海洋王照明科技股份有限公司 | Carbon nanotube/silicon/graphene composite material, preparation method thereof and lithium ion battery |
| CN104752698A (en) * | 2013-12-25 | 2015-07-01 | 北京有色金属研究总院 | Silicon carbon composite material for lithium ion battery cathode, and preparation method of composite material |
-
2016
- 2016-08-12 CN CN201610663073.8A patent/CN106207186A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0935306A1 (en) * | 1997-05-30 | 1999-08-11 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery and method for manufacturing negative electrode of the same |
| CN101442124A (en) * | 2007-11-19 | 2009-05-27 | 比亚迪股份有限公司 | Method for preparing composite material of lithium ion battery cathode, and cathode and battery |
| CN102145882A (en) * | 2011-02-24 | 2011-08-10 | 暨南大学 | Method for preparing water soluble graphene |
| CN104064736A (en) * | 2013-03-21 | 2014-09-24 | 海洋王照明科技股份有限公司 | Carbon nanotube/silicon/graphene composite material, preparation method thereof and lithium ion battery |
| CN103346305A (en) * | 2013-07-01 | 2013-10-09 | 华南师范大学 | Preparation and application of lithium battery silicon-carbon composite material taking synthetic graphite as carrier |
| CN104752698A (en) * | 2013-12-25 | 2015-07-01 | 北京有色金属研究总院 | Silicon carbon composite material for lithium ion battery cathode, and preparation method of composite material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3859834A4 (en) * | 2018-09-28 | 2021-10-20 | Posco | Anode active material for lithium secondary battery and lithium secondary battery comprising same |
| CN109301215A (en) * | 2018-09-30 | 2019-02-01 | 陕西煤业化工技术研究院有限责任公司 | A kind of high capacity silicon-carbon cathode active material and preparation method thereof and its application |
| CN109301215B (en) * | 2018-09-30 | 2021-04-13 | 陕西煤业化工技术研究院有限责任公司 | High-capacity silicon-carbon negative electrode active material, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Sphere-like SnO2/TiO2 composites as high-performance anodes for lithium ion batteries | |
| CN104157854B (en) | A kind of preparation method of Graphene composite lithium ion cell tertiary cathode material | |
| CN103311522B (en) | A kind of silicon/carbon composite microsphere negative electrode material and its production and use | |
| CN106935860B (en) | A kind of carbon intercalation V2O3Nano material, preparation method and application | |
| CN106025221B (en) | A kind of preparation method of silicon/carbon graphite composite negative pole material | |
| CN102694155B (en) | Silicon-carbon composite material, preparation method thereof and lithium ion battery employing same | |
| CN100565980C (en) | A kind of composite cathode material for lithium ion cell and preparation method thereof | |
| CN104752698B (en) | A kind of Si-C composite material for negative electrode of lithium ion battery and preparation method thereof | |
| CN106711461A (en) | Spherical porous silicon/carbon composite material as well as preparation method and application thereof | |
| CN110767877A (en) | Lithium ion battery silicon monoxide negative electrode material and preparation method and application thereof | |
| CN107799699A (en) | A kind of clay mineral composite lithium battery membrane and preparation method thereof | |
| CN103337631B (en) | Improve lithium titanate high-rate discharge ability and suppress the carbon nitrogen of aerogenesis to be total to method for coating | |
| CN103050704B (en) | Porous conductive additive and preparation method thereof, lithium ion battery | |
| CN105226274B (en) | A kind of preparation method of the scattered LiFePO4/graphene composite material of graphene uniform | |
| CN101728517A (en) | Method for preparing surface self-grown titanium nitride conducting film modified lithium titanate | |
| CN103346302A (en) | Lithium battery silicon-carbon nanotube composite cathode material as well as preparation method and application thereof | |
| CN103904335A (en) | Lithium ion battery negative material structure and preparation method thereof | |
| CN105355908A (en) | Composite negative electrode material for lithium ion battery, preparing method thereof, negative electrode using material and lithium ion battery | |
| CN104466096A (en) | Silicon negative electrode plate of lithium ion battery and preparation method of silicon negative electrode plate | |
| CN105489866B (en) | A kind of lithium ion battery and its anode material and preparation method | |
| CN102324507A (en) | Preparation method for lithium-sulfur battery composite anode material | |
| CN104638253A (en) | Preparation method of Si and C-RG core-shell composite material used as cathode of lithium ion battery | |
| CN106848220B (en) | A kind of preparation method of graphene-iron oxide-graphene composite structure cell negative electrode material | |
| CN104953100A (en) | Preparation method of carbon/graphite/tin composite anode material | |
| CN102610814B (en) | Composite nano-structure carbon-layer-cladded lithium iron phosphate electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161207 |