CN103811721A - Preparation method of negative plate of lithium battery - Google Patents
Preparation method of negative plate of lithium battery Download PDFInfo
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- CN103811721A CN103811721A CN201210475295.9A CN201210475295A CN103811721A CN 103811721 A CN103811721 A CN 103811721A CN 201210475295 A CN201210475295 A CN 201210475295A CN 103811721 A CN103811721 A CN 103811721A
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- 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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- 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 is appropriate for the technical field of lithium battery negative materials, and provides a preparation method of a negative plate of a lithium battery. The preparation method comprises the following steps: preparing graphene nanoplatelets, performing surface modification on the graphene nanoplatelets, mixing the surface modified graphene nanoplatelets and silicon nano particles so as to prepare a graphene-silicon mixed material, preparing a graphene-silicon nano powdery composite material from the graphene-silicon mixed material, and preparing the negative plate of a lithium battery based on the graphene-silicon nano powdery composite material. Compared with other negative materials of a lithium battery, the negative plate prepared by the method has the advantages that the capacity is high and can reach 1200mAh/g, the charging and discharging speed is high and can reach more than 5C, and the cycle life is long.
Description
Technical field
The invention belongs to the negative material technical field of lithium battery, relate in particular to a kind of preparation method of lithium battery cathode plate.
Background technology
Current commercialization lithium cell cathode material is all carbon negative pole material substantially, as electrographite, native graphite, carbonaceous mesophase spherules, petroleum coke, carbon fiber, pyrolysis resin carbon etc.Also not commercial negative material has: 1. tin base cathode material: tin base cathode material can be divided into two kinds of the oxide of tin and tinbase composite oxides.2. lithium-containing transition metal nitride negative pole material.3. alloy type negative material: comprise kamash alloy, silicon-base alloy, germanium-base alloy, acieral, antimony-containing alloy, magnesium base alloy and other alloy.4. nanoscale negative material: CNT (carbon nano-tube), Nanoalloy material.5. nanometer oxide material: current many companies have brought into use nano-titanium oxide and nano silicon oxide to be added on traditional graphite in the past, tin-oxide, CNT (carbon nano-tube) the inside, improves greatly the impulse electricity amount of lithium battery and discharges and recharges number of times.
Graphene is that carbon atom is arranged the Colloidal particles forming according to hexagonal.As monolayer carbon atomic plane material, Graphene can obtain by peeling off graphite material.This graphite crystal film of Graphene just becomes the focus that scientific circles and industrial quarters are paid close attention to after being found by the scientist of University of Manchester from 2004.The thickness of Graphene only has 0.335 nanometer, is not only one the thinnest in known materials, also very firmly hard; As simple substance, it is all faster than known all conductors and semiconductor that it at room temperature transmits the speed of electronics, and in Graphene, the migration velocity of electronics has reached 1/300 of the light velocity.Meanwhile, as monolayer carbon atomic structure, the theoretical specific area of Graphene is up to 2630m2/g.So high specific area makes to become extremely promising energy storage active material with the material based on Graphene.
In addition, the constant current theoretical capacity of silica-base material reaches 4200mAh/g, far away higher than commercial graphite cathode material (372mAh/g), is the lithium cell cathode material of great exploitation potential for its.But in the process of embedding lithium and de-lithium, silicon materials volume expands, and microstructure changes and causes the life-span shorter.
Summary of the invention
The object of the embodiment of the present invention is to overcome problems of the prior art, and the preparation method of a kind of applicable low-cost industrial large-scale production, high-quality, the poisonous lithium battery cathode plate that dumps thing of minimizing is provided.
The embodiment of the present invention is achieved in that a kind of preparation method of lithium battery cathode plate, said method comprising the steps of: prepare Graphene microplate; Graphene microplate is carried out to surface modification; The Graphene microplate mixing nano silicon particles of surface modification is made to Graphene-silica hybrid material; Graphene-silica hybrid material is made to Graphene-silicon nano power powder composite material; And making meets the lithium battery cathode plate of material based on Graphene-silicon nanopowder.
In a preferred embodiment, the described Graphene microplate of preparing comprises the following steps: prepare expanded graphite; The expanded graphite obtaining is mixed with organic solvent; Expanded graphite organic solvent mixed liquor is carried out to ultrasonic dissociating and obtain Graphene microplate suspension; And extract Graphene microplate from Graphene microplate suspension.
In a preferred embodiment, the described expanded graphite of preparing, for expansible graphite is placed in to metal or ceramic crucible, under inert gas shielding, is heated to 300-900 degree, keeps temperature 10-60 to divide, and realizes fully and expanding, and is then cooled to room temperature.
In a preferred embodiment, the described expanded graphite of preparing is for to be placed in ceramic crucible or glassware by expansible graphite, with 600-1200W microwave heating 10-60 second, realizes fully and expanding, and is then cooled to room temperature.
In a preferred embodiment, described the expanded graphite obtaining and organic solvent are mixed into gained expanded graphite is placed in to container, pour 100-1000ml organic solvent into, stir.
In a preferred embodiment, described organic solvent is at least one in NMP, DMP, toluene, chlorobenzene and trichloroethylene.
In a preferred embodiment, describedly expanded graphite organic solvent mixed liquor is carried out to ultrasonic dissociating obtain Graphene microplate suspension for being the 1-24 hour that vibrates under 300-1200W condition at sonic oscillation power, heating-up temperature is 20-150 degree simultaneously, obtains Graphene microplate suspension.
In a preferred embodiment, the described Graphene microplate that extracts from Graphene microplate suspension, for ultrasonic gained Graphene microplate suspension is left standstill to 0.2-5 hour, removes upper strata suspension, removes sediment, after filtration, in 80 degree baking ovens, dries.
In a preferred embodiment, described Graphene microplate is carried out to surface modification for gained Graphene microplate is added in the concentrated sulfuric acid, keep the temperature of solution lower than 4 ℃, slowly add potassium permanganate, in adding procedure, the temperature of solution does not exceed 10 ℃; After potassium permanganate adds, keep the temperature of solution lower than 10 ℃ of magnetic agitation 90min; Then, the in the situation that of magnetic agitation, slowly add deionized water, guarantee that the temperature of solution is lower than 40 ℃ simultaneously; Add hydrogen peroxide, continue to stir 15min; Last filtering drying obtains surface modified graphite alkene microplate.
In a preferred embodiment, it is that the surface modified graphite alkene microplate of gained is added in deionized water that the described Graphene microplate mixing nano silicon particles by surface modification obtains Graphene-silica hybrid material, keep the temperature of solution lower than 35 ℃, ultrasonic dispersion 10-60min; Nano silicon particles is joined in deionized water to ultrasonic dispersion 30-60min; Nano silicon particles is easily mixed with surface modified graphite alkene solution, keep solution temperature lower than 35 ℃, ultrasonic dispersion 30-60min; Finally, filter out solution, obtain surface modified graphite alkene-silica hybrid material.
In a preferred embodiment, described by Graphene-silica hybrid material make Graphene-silicon nano power powder composite material under inert atmosphere protection 300-1000 ℃ annealing 0.1-2h, obtain Graphene-silicon nano power powder composite material.
In a preferred embodiment, described making meets the lithium battery cathode plate of material for adopting coating or rolling pressure method based on Graphene-silicon nanopowder, make lithium battery cathode plate in metal foil substrate.
In an embodiment of the present invention, contrast other lithium cell cathode materials, have the following advantages: 1. capacity is large, can reach 1200mAh/g; 2. 5C discharges and recharges speed fast, more than can be reached; 3. have extended cycle life.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
In an embodiment of the present invention, by Graphene microplate is carried out to surface modification, then adsorb silicon nanopowder and obtain Graphene-silicon nano power powder composite material and make the lithium battery cathode plate based on Graphene-silicon nano power powder composite material.
Details are as follows:
One, prepare Graphene microplate;
1. prepare expanded graphite: expansible graphite is placed in to metal or ceramic crucible, under inert gas shielding, is heated to 300-900 degree, realize fully and expanding, be then cooled to room temperature.
Or expansible graphite is placed in to ceramic crucible or glassware, with 600-1200W microwave heating 10-60 second, realizes fully and expanding, be then cooled to room temperature.
In specific embodiment, raw material is desirable crystalline flake graphite also.
2. the expanded graphite obtaining is mixed with organic solvent: gained expanded graphite is placed in to container, pours 100-1000ml organic solvent into, described organic solvent is NMP, DMP, toluene, chlorobenzene or trichloroethylene, stirs.
3. expanded graphite organic solvent mixed liquor is carried out to ultrasonic dissociating and obtain Graphene microplate suspension: be the 1-24 hour that vibrates under 300-1200W condition at sonic oscillation power, heating simultaneously, temperature is 20-150 degree, obtains Graphene microplate suspension.Ultrasonic jitter time is too short in 60 minutes, to such an extent as to the effect that dispersion is dissociated is bad, and the present invention adopts concussion 1-24 hour, can effectively improve dispersion effect.The heating of taking in addition is also conducive to improve dispersion effect.
4. from Graphene microplate suspension, extract Graphene microplate: ultrasonic gained Graphene microplate suspension is left standstill to 0.2-5 hour, get upper strata suspension, remove sediment, after filtration, in 80 degree baking ovens, dry.The present invention, without centrifugal treating, saves fabrication steps, enhances productivity.
Two. Graphene microplate is carried out to surface modification:
Gained Graphene microplate is added in the concentrated sulfuric acid of 20-100ml, keep the temperature of solution lower than 4 ℃, slowly add the potassium permanganate of 0.5-20g, in adding procedure, the temperature of solution does not exceed 10 ℃.After potassium permanganate adds, keep the temperature of solution lower than 10 ℃ of magnetic agitation 90min.Then, the in the situation that of magnetic agitation, slowly add the deionized water of 150ml, guarantee that the temperature of solution is lower than 40 ℃ simultaneously.Add the hydrogen peroxide of 3ml, continue to stir 15min.Last filtering drying obtains surface modified graphite alkene microplate.
Three. the Graphene microplate mixing nano silicon particles of surface modification is obtained to Graphene-silica hybrid material:
The surface modified graphite alkene microplate of gained is added in 50-500ml deionized water, keep the temperature of solution lower than 35 ℃, ultrasonic dispersion 10-60min.0.5-5g nano silicon particles (30-200nm particle diameter) is joined in 500ml deionized water to ultrasonic dispersion 30-60min.Nano silicon particles is easily mixed with surface modified graphite alkene solution, keep solution temperature lower than 35 ℃, ultrasonic dispersion 30-60min.Finally, filter out solution, obtain surface modified graphite alkene-silica hybrid material.
Four. Graphene-silica hybrid material is made to Graphene-silicon nano power powder composite material: 300-1000 ℃ of annealing 0.1-2h under inert atmosphere protection, obtains Graphene-silicon nano power powder composite material.
Five. adopt coating or roll pressure method, in metal foil substrate, making lithium battery cathode plate.
Below preferred embodiment of the present invention is described in further detail:
Embodiment mono-
The implementing procedure of the cathode of lithium battery piece preparation method based on Graphene-silicon nano power powder composite material in the present embodiment is as follows:
1g50 order expansible graphite is placed in to metal or ceramic crucible, under inert gas shielding, is heated to 900 degree.Gained expanded graphite being placed in to container, pouring 250ml NMP into, stir, is then under 1000W condition, to vibrate 8 hours at sonic oscillation power, heating simultaneously, and heating-up temperature is 80 degree.Filtering drying, obtains Graphene microplate.Gained Graphene microplate is added in the concentrated sulfuric acid of 100ml, keep the temperature of solution lower than 4 ℃, slowly add the potassium permanganate of 0.5g, in adding procedure, the temperature of solution does not exceed 10 ℃.Keep the temperature of solution lower than 10 ℃ of magnetic agitation 90min.Then, the in the situation that of magnetic agitation, slowly add the deionized water of 150ml, guarantee that the temperature of solution is lower than 40 ℃ simultaneously.Add the hydrogen peroxide of 3ml, continue to stir 15min.Filtering drying obtains surface modified graphite alkene microplate.The surface modified graphite alkene microplate of gained is added in 200ml deionized water, keep the temperature of solution lower than 35 ℃, ultrasonic dispersion 10-60min.0.5g nano silicon particles (50nm particle diameter) is joined in 200ml deionized water to ultrasonic dispersion 30min.Nano silicon particles solution is mixed with surface modified graphite alkene solution, keep solution temperature lower than 35 ℃, ultrasonic dispersion 30-60min.Filter out solution, dry and obtain surface modified graphite alkene-silica hybrid material.Under inert atmosphere protection, 800 ℃ of annealing 1h, obtain Graphene-silicon nano power powder composite material.Adopt coating or roll pressure method, in metal foil substrate, making lithium battery cathode plate.
Embodiment bis-
The implementing procedure of the cathode of lithium battery piece preparation method based on Graphene-silicon nano power powder composite material in the present embodiment is as follows:
1g expansible graphite is placed in to ceramic crucible or glassware, with 800W microwave heating 30 seconds.Then be cooled to room temperature.Gained expanded graphite being placed in to container, pouring 250ml NMP into, stir, is then under 1000W condition, to vibrate 8 hours at sonic oscillation power, heating simultaneously, and heating-up temperature is 80 degree.Filtering drying, obtains Graphene microplate.Gained Graphene microplate is added in the concentrated sulfuric acid of 100ml, keep the temperature of solution lower than 4 ℃, slowly add the potassium permanganate of 0.5g, in adding procedure, the temperature of solution does not exceed 10 ℃.Keep the temperature of solution lower than 10 ℃ of magnetic agitation 90min.Then, the in the situation that of magnetic agitation, slowly add the deionized water of 150ml, guarantee that the temperature of solution is lower than 40 ℃ simultaneously.Add the hydrogen peroxide of 3ml, continue to stir 15min.Filtering drying obtains surface modified graphite alkene microplate.The surface modified graphite alkene microplate of gained is added in 200ml deionized water, keep the temperature of solution lower than 35 ℃, ultrasonic dispersion 10-60min.0.5g nano silicon particles (50nm particle diameter) is joined in 200ml deionized water to ultrasonic dispersion 30min.Nano silicon particles solution is mixed with surface modified graphite alkene solution, keep solution temperature lower than 35 ℃, ultrasonic dispersion 30-60min.Filter out solution, dry and obtain surface modified graphite alkene-silica hybrid material.Under inert atmosphere protection, 800 ℃ of annealing 1h, obtain Graphene-silicon nano power powder composite material.Adopt coating or roll pressure method, in metal foil substrate, making lithium battery cathode plate.
Embodiment tri-
The implementing procedure of the cathode of lithium battery piece preparation method based on Graphene-silicon nano power powder composite material in the present embodiment is as follows:
1g crystalline flake graphite being placed in to container, pouring 100ml NMP into, stir, is then under 1000W condition, to vibrate 8 hours at sonic oscillation power, heating simultaneously, and heating-up temperature is 80 degree.Filtering drying, obtains Graphene microplate.Gained Graphene microplate is added in the concentrated sulfuric acid of 50ml, keep the temperature of solution lower than 4 ℃, slowly add the potassium permanganate of 0.5g, in adding procedure, the temperature of solution does not exceed 10 ℃.Keep the temperature of solution lower than 10 ℃ of magnetic agitation 90min.Then, the in the situation that of magnetic agitation, slowly add the deionized water of 100ml, guarantee that the temperature of solution is lower than 40 ℃ simultaneously.Add the hydrogen peroxide of 3ml, continue to stir 15min.Filtering drying obtains surface modified graphite alkene microplate.The surface modified graphite alkene microplate of gained is added in 200ml deionized water, keep the temperature of solution lower than 35 ℃, ultrasonic dispersion 10-60min.0.5g nano silicon particles (50nm particle diameter) is joined in 200ml deionized water to ultrasonic dispersion 30min.Nano silicon particles solution is mixed with surface modified graphite alkene solution, keep solution temperature lower than 35 ℃, ultrasonic dispersion 30-60min.Filter out solution, dry and obtain surface modified graphite alkene-silica hybrid material.Under inert atmosphere protection, 800 ℃ of annealing 1h, obtain Graphene-silicon nano power powder composite material.Adopt coating or roll pressure method, in metal foil substrate, making lithium battery cathode plate.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (12)
1. a preparation method for lithium battery cathode plate, is characterized in that, said method comprising the steps of:
Prepare Graphene microplate;
Graphene microplate is carried out to surface modification;
The Graphene microplate mixing nano silicon particles of surface modification is made to Graphene-silica hybrid material;
Graphene-silica hybrid material is made to Graphene-silicon nano power powder composite material; And
Make the lithium battery cathode plate that meets material based on Graphene-silicon nanopowder.
2. the method for claim 1, is characterized in that, the described Graphene microplate of preparing comprises the following steps:
Prepare expanded graphite;
The expanded graphite obtaining is mixed with organic solvent;
Expanded graphite organic solvent mixed liquor is carried out to ultrasonic dissociating and obtain Graphene microplate suspension; And
From Graphene microplate suspension, extract Graphene microplate.
3. method as claimed in claim 2, is characterized in that, the described expanded graphite of preparing is for to be placed in metal or ceramic crucible by expansible graphite; under inert gas shielding, be heated to 300-900 degree, keep temperature 10-60 to divide; realize fully and expanding, be then cooled to room temperature.
4. method as claimed in claim 2, is characterized in that, the described expanded graphite of preparing is for to be placed in ceramic crucible or glassware by expansible graphite, with 600-1200W microwave heating 10-60 second, realizes fully and expanding, and is then cooled to room temperature.
5. method as claimed in claim 2, is characterized in that, described the expanded graphite obtaining and organic solvent are mixed into gained expanded graphite is placed in to container, pours 100-1000ml organic solvent into, stirs.
6. method as claimed in claim 5, is characterized in that, described organic solvent is at least one in NMP, DMP, toluene, chlorobenzene and trichloroethylene.
7. method as claimed in claim 2, it is characterized in that, describedly expanded graphite organic solvent mixed liquor is carried out to ultrasonic dissociating obtain Graphene microplate suspension for being the 1-24 hour that vibrates under 300-1200W condition at sonic oscillation power, heating-up temperature is 20-150 degree simultaneously, obtains Graphene microplate suspension.
8. method as claimed in claim 2, it is characterized in that, the described Graphene microplate that extracts from Graphene microplate suspension, for ultrasonic gained Graphene microplate suspension is left standstill to 0.2-5 hour, removes upper strata suspension, remove sediment, after filtration, in 80 degree baking ovens, dry.
9. the method for claim 1, it is characterized in that, described Graphene microplate is carried out to surface modification for gained Graphene microplate is added in the concentrated sulfuric acid, keep the temperature of solution lower than 4 ℃, slowly add potassium permanganate, in adding procedure, the temperature of solution does not exceed 10 ℃; After potassium permanganate adds, keep the temperature of solution lower than 10 ℃ of magnetic agitation 90min; Then, the in the situation that of magnetic agitation, slowly add deionized water, guarantee that the temperature of solution is lower than 40 ℃ simultaneously; Add hydrogen peroxide, continue to stir 15min; Last filtering drying obtains surface modified graphite alkene microplate.
10. the method for claim 1, it is characterized in that, it is that the surface modified graphite alkene microplate of gained is added in deionized water that the described Graphene microplate mixing nano silicon particles by surface modification obtains Graphene-silica hybrid material, keep the temperature of solution lower than 35 ℃, ultrasonic dispersion 10-60min; Nano silicon particles is joined in deionized water to ultrasonic dispersion 30-60min; Nano silicon particles is easily mixed with surface modified graphite alkene solution, keep solution temperature lower than 35 ℃, ultrasonic dispersion 30-60min; Finally, filter out solution, obtain surface modified graphite alkene-silica hybrid material.
11. the method for claim 1, is characterized in that, described by Graphene-silica hybrid material make Graphene-silicon nano power powder composite material under inert atmosphere protection 300-1000 ℃ annealing 0.1-2h, obtain Graphene-silicon nano power powder composite material.
12. the method for claim 1, is characterized in that, described making meets the lithium battery cathode plate of material for adopting coating or rolling pressure method based on Graphene-silicon nanopowder, make lithium battery cathode plate in metal foil substrate.
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| CN105742572A (en) * | 2014-12-12 | 2016-07-06 | 国家纳米科学中心 | Three-dimensional conductive network-supported porous silicon nanomaterial and preparation method and application thereof |
| CN106920949A (en) * | 2017-04-24 | 2017-07-04 | 广东烛光新能源科技有限公司 | Silicon-carbon cathode material and preparation method thereof |
| CN106953088A (en) * | 2017-04-24 | 2017-07-14 | 广东烛光新能源科技有限公司 | A kind of silicon-carbon cathode material and preparation method thereof |
| CN107768608A (en) * | 2016-08-15 | 2018-03-06 | 福建新峰二维材料科技有限公司 | The effectively preparation method of the lithium ion battery negative material of buffering silicon bulk effect |
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| CN101746755B (en) * | 2009-12-14 | 2012-07-04 | 重庆大学 | Method for preparing multi-layer graphene |
| CN101924211A (en) * | 2010-08-19 | 2010-12-22 | 北京科技大学 | Graphene/silicon lithium ion battery cathode material and preparation method thereof |
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| CN102431998A (en) * | 2011-09-20 | 2012-05-02 | 深圳市长宜景鑫投资有限公司 | Method for preparing high-quality graphene in large scale by intercalation stripping of graphite by chemical method |
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| CN105742572A (en) * | 2014-12-12 | 2016-07-06 | 国家纳米科学中心 | Three-dimensional conductive network-supported porous silicon nanomaterial and preparation method and application thereof |
| CN107768608A (en) * | 2016-08-15 | 2018-03-06 | 福建新峰二维材料科技有限公司 | The effectively preparation method of the lithium ion battery negative material of buffering silicon bulk effect |
| CN107768608B (en) * | 2016-08-15 | 2020-10-16 | 福建新峰二维材料科技有限公司 | Preparation method of lithium ion battery cathode material capable of effectively buffering silicon volume effect |
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| CN106920949A (en) * | 2017-04-24 | 2017-07-04 | 广东烛光新能源科技有限公司 | Silicon-carbon cathode material and preparation method thereof |
| CN106953088A (en) * | 2017-04-24 | 2017-07-14 | 广东烛光新能源科技有限公司 | A kind of silicon-carbon cathode material and preparation method thereof |
| CN106953088B (en) * | 2017-04-24 | 2020-08-18 | 广东烛光新能源科技有限公司 | Silicon-carbon negative electrode material and preparation method thereof |
| CN108216384A (en) * | 2017-12-18 | 2018-06-29 | 合肥亿恒智能科技股份有限公司 | A kind of automobile rear floor front beam |
| CN111370665A (en) * | 2020-03-19 | 2020-07-03 | 西安越遴新材料研究院有限公司 | Preparation method of high-specific-capacity multi-sheet-layer stacked silicon-carbon composite material |
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