CN103035890A - Silicon and graphene composite electrode material and preparation method thereof - Google Patents
Silicon and graphene composite electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN103035890A CN103035890A CN2011103028113A CN201110302811A CN103035890A CN 103035890 A CN103035890 A CN 103035890A CN 2011103028113 A CN2011103028113 A CN 2011103028113A CN 201110302811 A CN201110302811 A CN 201110302811A CN 103035890 A CN103035890 A CN 103035890A
- Authority
- CN
- China
- Prior art keywords
- silicon
- graphene
- electrode material
- nano
- combination electrode
- 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.)
- Granted
Links
Images
Classifications
-
- 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 relates to a silicon and graphene composite electrode material and a preparation method thereof. The preparation method comprises the steps of mixing a graphene oxide solution with a nanometer silicon solution and then reducing the graphene oxide through a hydrothermal method. Nanometer silicon can be well scattered among graphene sheet layers, the graphene is prevented from being agglomerated and the specific surface area of the composite electrode material can be enabled to be larger; and at the same time, the preparation process flow is simple, the reaction time is short, the raw material loss during reaction is less and the yield is relatively higher. According to the prepared silicon and graphene composite electrode material, since the high conductivity of the graphene can enable electrons to be well transferred onto elementary silicon, the conductivity is improved, the high capacity characteristic of the silicon can be fully exerted, the stability of the silicon can also be improved and the silicon and graphene composite electrode material can be used as an anode material for lithium ion batteries.
Description
[technical field]
The present invention relates to the battery electrode material field, relate in particular to a kind of silicon and graphene combination electrode material and preparation method thereof.
[background technology]
The lithium ion battery of traditional commodities adopts lithium graphite system mostly, although the chemical property of this class system is excellent, but because itself storage lithium ability is lower, be 372mAh/g such as the theoretical lithium storage content of graphite, so novel transition metal oxide/graphite system attracts widespread attention.
In the intercalation materials of li ions at present, pure silicon is because having the highest theoretical lithium storage content (4200mAh/g), relatively low embedding lithium current potential, charge and discharge process is difficult for reuniting, have higher physical stability and chemical stability than other metal_based materials, become the study hotspot in lithium ion battery negative material field.But silica-base material because the effect of stress that bulk effect produces easily causes avalanche and the material efflorescence of silicon lattice structure, causes active material to break away from the electrode material system and loses activity in degree of depth removal lithium embedded process, therefore has very poor cyclical stability.Compound to mainly improved one's methods metals such as adopting Ni, Fe and Cu and silicon of silica-base material, formation is take silicon as the activated centre, activity take inert metal as dispersible carrier/inertia compound system when improving the electric conductivity of material, has improved the cycle performance of material.But this material easily forms the metallic silicon phase of inertia, and the molal weight of these metals itself is larger, belongs to non-intercalation materials of li ions, has therefore weakened to a certain extent the specific capacity of silica-base material; Metal itself has electron conduction in addition, does not possess ionic conductivity, so that electrolyte is difficult to immersion, thereby loses activity.Another method is exactly the method that material with carbon element coats, and is lower than the molal weight of metal, and electrolyte is easy to immerse, and effect will be got well than metal relatively, and material property has certain improvement, but relatively poor.
Graphene has good conductivity, the space distributes and higher mechanical performance, utilizes grapheme material to substitute traditional material with carbon element, and silicon and the graphene combination electrode material for preparing of being combined with silicon has good electrochemical stability.Traditional silicon and graphene combination electrode material generally adopt the preparation of silicon-containing compound reducing process, and process is loaded down with trivial details, length consuming time, and productive rate is influenced.
[summary of the invention]
Based on this, be necessary to provide the relatively simple silicon of a kind of preparation process and graphene combination electrode material and preparation method thereof.
A kind of silicon and graphene combination electrode material is characterized in that, described combination electrode material comprises nano-silicon and Graphene, wherein, Graphene is layer structure, and nano-silicon is dispersed among the layer structure of Graphene, and the mass percent of nano-silicon in described combination electrode material is 10～50%.
The preparation method of a kind of silicon and graphene combination electrode material comprises the steps:
Step 1: prepare respectively homodisperse graphene oxide solution and nano-silicon solution;
Step 2: be to mix at 1～9: 1 described graphene oxide solution and nano-silicon solution according to the mass ratio of graphene oxide and nano-silicon, obtain the mixed solution of homodisperse graphene oxide and nano-silicon;
Step 3: described mixed solution is carried out the hydrothermal reduction reaction, obtain described silicon and graphene combination electrode material.
In preferred embodiment, in the step 1, prepare described graphene oxide solution and comprise the steps: graphite oxide was joined in the solvent ultrasonic dispersion 0.5～1 hour, to form the homodisperse graphene oxide solution of monolithic layer.
In preferred embodiment, described graphite oxide prepares according to following step:
Graphite raw material is provided;
Graphite raw material, potassium peroxydisulfate and phosphorus pentoxide be added in 80 ℃ the concentrated sulfuric acid, stir, cooling is more than 6 hours, suction filtration, and washing is to neutral, and drying obtains biased sample;
Described biased sample is added in 0 ℃ the concentrated sulfuric acid, add potassium permanganate, the temperature of system remains on below 20 ℃ again, then keeps after 30 minutes in 35 ℃ oil bath, slowly add deionized water, after 15 minutes, add again the deionized water that contains hydrogen peroxide, until the color of the solution becomes glassy yellow, suction filtration while hot, be that 10% hydrochloric acid washs with concentration again, suction filtration, 60 ℃ of vacuumizes namely obtain graphite oxide.
In preferred embodiment, described graphite raw material is that purity is not less than 99.5% natural flake graphite.
In preferred embodiment, described solvent is DMF, DMA, 1-METHYLPYRROLIDONE.
In preferred embodiment, in the step 1, prepare homodisperse nano-silicon solution and comprise the steps: the powder of nano-silicon is joined in the solvent, ultrasonic dispersion 10～30 minutes obtains homodisperse nano-silicon solution.
In preferred embodiment, described solvent is DMF, DMA, 1-METHYLPYRROLIDONE.
In preferred embodiment, the particle diameter of described nano-silicon is 20-60nm.
In preferred embodiment, hydro-thermal reaction is reduced described mixed solution and is comprised the steps: described mixed solution is placed hydrothermal reaction kettle in the step 3,100～150 ℃ of lower reactions 5～10 hours, when the question response system is cooled to room temperature, filter, obtain crude product, wash crude product repeatedly with methyl alcohol and deionized water, namely obtain described silicon and graphene combination electrode material under the room temperature after the drying.
Graphene oxide solution is mixed with nano-silicon solution, and then by the hydro thermal method redox graphene, nano-silicon can be good at being dispersed between the lamella of Graphene, prevents the Graphene reunion, can make combination electrode material reach higher specific area; Simultaneously, this preparation technology's flow process is simple, and the reaction time is short, thereby the loss of course of reaction Raw is less, and productive rate is relatively high.In the silicon and graphene combination electrode material that makes, since the high conductivity of Graphene can be well with electrical conductivity to elemental silicon, improved conductivity, can give full play to the high capacity characteristics of silicon, can improve its stability again, be suitable as the negative material of lithium ion battery.
[description of drawings]
Fig. 1 is the silicon of an execution mode and the preparation flow figure of graphene combination electrode material;
Fig. 2 is the silicon that makes of embodiment 1 and the SEM picture of graphene combination electrode material.
[embodiment]
The below mainly is described in further detail silicon and graphene combination electrode material and preparation method thereof in conjunction with the drawings and the specific embodiments.
Present embodiment provides a kind of silicon and graphene combination electrode material and preparation method thereof, and this combination electrode material comprises nano-silicon and Graphene.Wherein, Graphene is layer structure, and nano-silicon is dispersed among the layer structure of Graphene, and the mass percent of nano-silicon is 10～50% in the composite material.Nano-silicon and Graphene can reach other mixing of molecular level, and good consistency and uniformity are arranged; Adsorb nano-silicon on large stretch of graphene film, can offer the nano-silicon ionic conductivity, can significantly improve the electronic conductivity of nano-silicon simultaneously.
The silicon of present embodiment and the preparation method of graphene combination electrode material, preparation technology's flow process is as follows:
Mixed solution → the silicon of graphite → graphite oxide → graphene oxide and nano-silicon and graphene combination electrode material
As shown in Figure 1, this preparation process comprises the steps:
Step S1: prepare respectively homodisperse graphene oxide solution and nano-silicon solution.Specifically comprise the steps:
Step S11: graphite raw material is provided.
The preferred purity of graphite raw material is not less than 99.5% natural flake graphite.
Step S12: graphite raw material, potassium peroxydisulfate and phosphorus pentoxide be added in 80 ℃ the concentrated sulfuric acid, stir, cooling is more than 6 hours, suction filtration, and washing is to neutral, and drying obtains biased sample;
Described biased sample is added in 0 ℃ the concentrated sulfuric acid, add potassium permanganate, the temperature of system remains on below 20 ℃ again, then keeps after 30 minutes in 35 ℃ oil bath, slowly add deionized water, after 15 minutes, add again the deionized water that contains hydrogen peroxide, until the color of the solution becomes glassy yellow, suction filtration while hot, be that 10% hydrochloric acid washs with concentration again, suction filtration, 60 ℃ of vacuumizes namely obtain graphite oxide.
Step S13: the graphite oxide that makes was joined in the solvent ultrasonic dispersion 0.5～1 hour, to form the homodisperse graphene oxide solution of monolithic layer.
Wherein, solvent can be the organic solvents such as DMF, DMA, 1-METHYLPYRROLIDONE.
Step S14: the powder of nano-silicon is joined in the solvent, and ultrasonic dispersion 10～30 minutes obtains homodisperse nano-silicon solution.
The particle diameter of nano-silicon is preferably 20-60nm.
Preferably, fully mix for ease of nano-silicon solution and graphene oxide solution, the solvent that is used for the dissolving nano-silicon is selected with the solvent phase that is used for dissolved oxygen graphite same.
Step S2: be to mix at 2～3: 1 described graphene oxide solution and nano-silicon solution according to the mass ratio of graphene oxide and nano-silicon, obtain the mixed solution of homodisperse graphene oxide and nano-silicon.
Step S3: described mixed solution is carried out the hydrothermal reduction reaction, obtain described silicon and graphene combination electrode material.
Specific as follows: that the mixed solution of graphene oxide and nano-silicon is placed hydrothermal reaction kettle, 100～150 ℃ of lower reactions 5～10 hours, when the question response system is cooled to room temperature, filter, obtain crude product, wash crude product repeatedly with methyl alcohol and deionized water, namely obtain described silicon and graphene combination electrode material under the room temperature after the drying.
By graphene oxide solution is mixed with nano-silicon solution, hydro thermal method redox graphene then, nano-silicon can be good at being dispersed between the lamella of Graphene, prevents that Graphene from reuniting, and can make combination electrode material reach higher specific area; Simultaneously, this preparation technology's flow process is simple, and the reaction time is short, thereby the loss of course of reaction Raw is less, and productive rate is relatively high.In the silicon and graphene combination electrode material that makes, since the high conductivity of Graphene can be well with electrical conductivity to elemental silicon, improved conductivity, can give full play to the high capacity characteristics of silicon, can improve its stability again, be suitable as the negative material of lithium ion battery.
Below be the specific embodiment part:
Embodiment 1
The silicon of the present embodiment and graphene combination electrode material technological process are as follows:
Mixed solution → the silicon of natural flake graphite → graphite oxide → graphene oxide and nano-silicon and graphene combination electrode material
(1) natural flake graphite: purity 99.5%.
(2) graphite oxide:
20g graphite raw material, 10g potassium peroxydisulfate and 10g phosphorus pentoxide added in 80 ℃ the concentrated sulfuric acid, stir, cooling is more than 6 hours, suction filtration, and washing is to neutral, and drying gets biased sample;
Dried biased sample is added in 0 ℃, the concentrated sulfuric acid of 230mL, adds 60g potassium permanganate again, the temperature of system remains on below 20 ℃, then keeps slowly adding the 920mL deionized water after 30 minutes in 35 ℃ oil bath;
After 15 minutes, in system, add the 2.8L deionized water again, until the mixture color becomes glassy yellow, suction filtration while hot, be that 10% hydrochloric acid washs with 5L concentration again, suction filtration namely obtained graphite oxide in 48 hours 60 ℃ of vacuumizes, wherein, containing 50mL concentration in the above-mentioned 2.8L deionized water is 30% hydrogen peroxide.
(3) mixed solution of graphite oxide and nano-silicon: the graphite oxide for preparing was joined in DMF (DMF) solvent ultrasonic dispersion 0.5 hour, form with the homodisperse graphene oxide solution of monolithic layer;
The nano-silicon powder that takes by weighing 20g is dissolved in DMF (DMF) solvent, and ultrasonic dispersion 10 minutes is to form finely dispersed nano-silicon solution;
Nano-silicon solution is slowly joined in the graphene oxide solution, and room temperature vigorous stirring 0.5 hour obtains the mixed solution of homodisperse graphene oxide and nano-silicon;
(4) silicon and graphene combination electrode material: the graphene oxide of step (3) gained and the mixed solution of nano-silicon are put into hydrothermal reaction kettle, 100 ℃ of lower reduction reactions 10 hours, when treating that solution is cooled to room temperature, with sample filtering, with methyl alcohol and water washing three times, namely obtain silicon and graphene combination electrode material under the room temperature after the drying.As shown in Figure 2, can find out from the SEM picture of silicon and graphene combination electrode material, nano-silicon can be good at being dispersed between the lamella of Graphene.
Embodiment 2
The silicon of the present embodiment and graphene combination electrode material technological process are as follows:
Mixed solution → the silicon of natural flake graphite → graphite oxide → graphene oxide and nano-silicon and graphene combination electrode material
(1) preparation process of graphite oxide is with embodiment 1.
(2) mixed solution of graphite oxide and nano-silicon: the graphite oxide for preparing was joined in DMA (DMAc) solvent ultrasonic dispersion 1 hour, form with the homodisperse graphene oxide solution of monolithic layer;
The nano-silicon powder that takes by weighing 10g is dissolved in DMF (DMF) solvent, and ultrasonic dispersion 30 minutes is to form finely dispersed nano-silicon solution;
Nano-silicon solution is slowly joined in the graphene oxide solution, and room temperature vigorous stirring 1 hour obtains the mixed solution of homodisperse graphene oxide and nano-silicon;
(3) silicon and graphene combination electrode material: the graphene oxide of step (2) gained and the mixed solution of nano-silicon are put into hydrothermal reaction kettle, 120 ℃ of lower reduction reactions 5 hours, when treating that solution is cooled to room temperature, with sample filtering, with methyl alcohol and water washing three times, namely obtain silicon and graphene combination electrode material under the room temperature after the drying.
Embodiment 3
The silicon of the present embodiment and graphene combination electrode material technological process are as follows:
Mixed solution → the silicon of natural flake graphite → graphite oxide → graphene oxide and nano-silicon and graphene combination electrode material
(1) preparation process of graphite oxide is with embodiment 1.
(2) mixed solution of graphite oxide and nano-silicon: the graphite oxide for preparing was joined in DMF (DMF) solvent ultrasonic dispersion 0.5 hour, form with the homodisperse graphene oxide solution of monolithic layer;
The nano-silicon powder that takes by weighing 5g is dissolved in 1-METHYLPYRROLIDONE (NMP) solvent, and ultrasonic dispersion 10 minutes is to form finely dispersed nano-silicon solution;
Nano-silicon solution is slowly joined in the graphene oxide solution, and room temperature vigorous stirring 0.5 hour obtains the mixed solution of homodisperse graphene oxide and nano-silicon;
(3) silicon and graphene combination electrode material: the graphene oxide of step (2) gained and the mixed solution of nano-silicon are put into hydrothermal reaction kettle, 150 ℃ of lower reduction reactions 10 hours, when treating that solution is cooled to room temperature, with sample filtering, with methyl alcohol and water washing three times, namely obtain silicon and graphene combination electrode material under the room temperature after the drying.
Embodiment 4
The silicon of the present embodiment and graphene combination electrode material technological process are as follows:
Mixed solution → the silicon of natural flake graphite → graphite oxide → graphene oxide and nano-silicon and graphene combination electrode material
(1) preparation process of graphite oxide is with embodiment 1.
(2) mixed solution of graphite oxide and nano-silicon: the graphite oxide for preparing was joined in DMF (DMF) solvent ultrasonic dispersion 1 hour, form with the homodisperse graphene oxide solution of monolithic layer;
The nano-silicon powder that takes by weighing 2.3g is dissolved in DMF (DMF) solvent, and ultrasonic dispersion 30 minutes is to form finely dispersed nano-silicon solution;
Nano-silicon solution is slowly joined in the graphene oxide solution, and room temperature vigorous stirring 1 hour obtains the mixed solution of homodisperse graphene oxide and nano-silicon;
(3) silicon and graphene combination electrode material: the graphene oxide of step (2) gained and the mixed solution of nano-silicon are put into hydrothermal reaction kettle, 150 ℃ of lower reduction reactions 5 hours, when treating that solution is cooled to room temperature, with sample filtering, with methyl alcohol and water washing three times, namely obtain silicon and graphene combination electrode material under the room temperature after the drying.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a silicon and graphene combination electrode material, it is characterized in that, described combination electrode material comprises nano-silicon and Graphene, wherein, Graphene is layer structure, nano-silicon is dispersed among the layer structure of Graphene, and the mass percent of nano-silicon in described combination electrode material is 10～50%.
2. the preparation method of a silicon and graphene combination electrode material is characterized in that, comprises the steps:
Step 1: prepare respectively homodisperse graphene oxide solution and nano-silicon solution;
Step 2: be to mix at 1～9: 1 described graphene oxide solution and nano-silicon solution according to the mass ratio of graphene oxide and nano-silicon, obtain the mixed solution of homodisperse graphene oxide and nano-silicon;
Step 3: described mixed solution is carried out the hydrothermal reduction reaction, obtain described silicon and graphene combination electrode material.
3. the preparation method of silicon as claimed in claim 2 and graphene combination electrode material, it is characterized in that, in the step 1, prepare described graphene oxide solution and comprise the steps: graphite oxide was joined in the solvent ultrasonic dispersion 0.5～1 hour, to form the homodisperse graphene oxide solution of monolithic layer.
4. the preparation method of silicon as claimed in claim 3 and graphene combination electrode material is characterized in that, described graphite oxide prepares according to following step:
Graphite raw material is provided;
Described graphite raw material, potassium peroxydisulfate and phosphorus pentoxide be added in 80 ℃ the concentrated sulfuric acid, stir, cooling is more than 6 hours, suction filtration, and washing is to neutral, and drying obtains biased sample;
Described biased sample is added in 0 ℃ the concentrated sulfuric acid, add potassium permanganate, the temperature of system remains on below 20 ℃ again, then keeps after 30 minutes in 35 ℃ oil bath, slowly add deionized water, after 15 minutes, add again the deionized water that contains hydrogen peroxide, until the color of the solution becomes glassy yellow, suction filtration while hot, be that 10% hydrochloric acid washs with concentration again, suction filtration, 60 ℃ of vacuumizes namely obtain graphite oxide.
5. the preparation method of silicon as claimed in claim 4 and graphene combination electrode material is characterized in that, described graphite raw material is that purity is not less than 99.5% natural flake graphite.
6. such as the preparation method of claim 3 or 4 described silicon and graphene combination electrode material, it is characterized in that, described solvent is DMF, DMA, 1-METHYLPYRROLIDONE.
7. the preparation method of silicon as claimed in claim 2 and graphene combination electrode material, it is characterized in that, in the step 1, preparing homodisperse nano-silicon solution comprises the steps: the powder of nano-silicon is joined in the solvent, ultrasonic dispersion 10～30 minutes obtains homodisperse nano-silicon solution.
8. the preparation method of silicon as claimed in claim 7 and graphene combination electrode material is characterized in that, described solvent is DMF, DMA, 1-METHYLPYRROLIDONE.
9. such as the preparation method of claim 2 or 7 described silicon and graphene combination electrode material, it is characterized in that, the particle diameter of described nano-silicon is 20-60nm.
10. the preparation method of silicon as claimed in claim 2 and graphene combination electrode material, it is characterized in that, hydro-thermal reaction is reduced described mixed solution and is comprised the steps: described mixed solution is placed hydrothermal reaction kettle in the step 3,100～150 ℃ of lower reactions 5～10 hours, when the question response system is cooled to room temperature, filter, obtain crude product, wash described crude product at least three times with methyl alcohol and deionized water, namely obtain described silicon and graphene combination electrode material under the room temperature after the drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110302811.3A CN103035890B (en) | 2011-10-09 | 2011-10-09 | Silicon and graphene composite electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110302811.3A CN103035890B (en) | 2011-10-09 | 2011-10-09 | Silicon and graphene composite electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103035890A true CN103035890A (en) | 2013-04-10 |
| CN103035890B CN103035890B (en) | 2015-07-08 |
Family
ID=48022554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110302811.3A Active CN103035890B (en) | 2011-10-09 | 2011-10-09 | Silicon and graphene composite electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103035890B (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346325A (en) * | 2013-06-28 | 2013-10-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery |
| CN103400970A (en) * | 2013-07-20 | 2013-11-20 | 深圳粤网节能技术服务有限公司 | Nanometer silicon/graphene lithium ion battery cathode material and preparation method thereof |
| CN104466104A (en) * | 2014-11-19 | 2015-03-25 | 东莞市翔丰华电池材料有限公司 | Germanium-graphene composite cathode material for lithium ion battery and preparation method thereof |
| CN104701035A (en) * | 2015-03-20 | 2015-06-10 | 中国科学院青海盐湖研究所 | Preparation method of metal oxide/graphene or multi-metal oxide/graphene composite electrode material |
| CN104993110A (en) * | 2015-06-11 | 2015-10-21 | 江苏大学 | Preparation method of composite negative electrode material for lithium ion battery |
| CN105702959A (en) * | 2016-04-14 | 2016-06-22 | 华东理工大学 | Preparation method of silicon-based lithium ion battery anode material |
| CN105762360A (en) * | 2016-04-01 | 2016-07-13 | 上海交通大学 | Graphene-silicon-coated composite negative electrode material and preparing method and application thereof |
| CN106099061A (en) * | 2016-07-14 | 2016-11-09 | 中国科学院宁波材料技术与工程研究所 | A kind of porous graphene/silicon composite, its preparation method and lithium ion battery |
| CN106450319A (en) * | 2016-11-30 | 2017-02-22 | 电子科技大学 | Graphene-silicon composite material, preparation method and application thereof |
| CN106784765A (en) * | 2016-12-15 | 2017-05-31 | 电子科技大学 | Graphene enhancing Si-C composite material and its production and use |
| CN107293708A (en) * | 2017-05-18 | 2017-10-24 | 山东玉皇新能源科技有限公司 | The improved method that solvent-thermal method prepares graphene silicon composite |
| CN107293725A (en) * | 2017-07-18 | 2017-10-24 | 深圳市泽纬科技有限公司 | A kind of preparation method of nanometer of red phosphorus and graphene composite negative pole |
| CN107346822A (en) * | 2017-04-25 | 2017-11-14 | 山东玉皇新能源科技有限公司 | A kind of method that solvent-thermal method prepares graphene silicon composite cathode material |
| CN107845782A (en) * | 2016-09-19 | 2018-03-27 | 中国科学院宁波材料技术与工程研究所 | A kind of silicon/graphene composite negative pole and its preparation method and application |
| CN108183204A (en) * | 2017-12-06 | 2018-06-19 | 华南农业大学 | A kind of silicon nanometer sheet-graphene nanometer sheet composite material and preparation and application |
| CN108232146A (en) * | 2017-12-28 | 2018-06-29 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of lithium ion battery negative material |
| CN108428884A (en) * | 2018-04-24 | 2018-08-21 | 盐城师范学院 | A kind of preparation method of sheet layer graphene and silicon electrode material |
| CN108428883A (en) * | 2018-04-24 | 2018-08-21 | 盐城师范学院 | A kind of small size edge is grapheme modified with silicon combination electrode material preparation method |
| CN108598434A (en) * | 2018-04-24 | 2018-09-28 | 盐城师范学院 | A kind of electrostatic self-assembled preparation method of graphene/silicon electrode material |
| CN109873150A (en) * | 2019-03-14 | 2019-06-11 | 西北师范大学 | The method for preparing nanometer silicon composite material as raw material using palygorskite |
| CN109887767A (en) * | 2019-04-03 | 2019-06-14 | 山东星火科学技术研究院 | A kind of micro super capacitor and preparation method thereof based on graphene |
| CN110429331A (en) * | 2019-08-13 | 2019-11-08 | 福建翔丰华新能源材料有限公司 | Graphene compound coating material fills solid electrolyte and preparation method thereof |
| CN111253170A (en) * | 2020-03-13 | 2020-06-09 | 江苏嘉明碳素新材料有限公司 | Method for preparing silicified graphite structure material |
| CN111403711A (en) * | 2020-03-26 | 2020-07-10 | 内蒙古杉杉科技有限公司 | Sulfur-nitrogen co-doped graphene loaded nano-silicon three-dimensional electrode material and preparation method thereof |
| CN114497483A (en) * | 2021-12-31 | 2022-05-13 | 惠州锂威新能源科技有限公司 | Negative plate, preparation method thereof and lithium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101593827A (en) * | 2009-07-10 | 2009-12-02 | 浙江大学 | Silicon/negative pole made of silicon/graphite nanosheet composite material of lithium ion battery and preparation method thereof |
| 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 |
| CN102142540A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Lithium ion battery electrode made of graphene/SnS2 composite nanometer material and preparation method thereof |
-
2011
- 2011-10-09 CN CN201110302811.3A patent/CN103035890B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101593827A (en) * | 2009-07-10 | 2009-12-02 | 浙江大学 | Silicon/negative pole made of silicon/graphite nanosheet composite material of lithium ion battery and preparation method thereof |
| 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 |
| CN102142540A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Lithium ion battery electrode made of graphene/SnS2 composite nanometer material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JEONG K. LEE ET AL.: "Silicon nanoparticles-graphene paper composites for Li ion battery anodes", 《CHEM. COMMUN.》, vol. 46, 10 February 2010 (2010-02-10), pages 2025 - 2027 * |
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346325B (en) * | 2013-06-28 | 2015-12-23 | 中国科学院宁波材料技术与工程研究所 | A kind of lithium ion battery negative material, its preparation method and lithium ion battery |
| CN103346325A (en) * | 2013-06-28 | 2013-10-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery |
| CN103400970A (en) * | 2013-07-20 | 2013-11-20 | 深圳粤网节能技术服务有限公司 | Nanometer silicon/graphene lithium ion battery cathode material and preparation method thereof |
| WO2015010437A1 (en) * | 2013-07-20 | 2015-01-29 | 深圳粤网节能技术服务有限公司 | A nano silicon/graphene lithium ion battery cathode material and preparation method thereof |
| CN103400970B (en) * | 2013-07-20 | 2015-07-08 | 深圳粤网节能技术服务有限公司 | Nanometer silicon/graphene lithium ion battery cathode material and preparation method thereof |
| CN104466104A (en) * | 2014-11-19 | 2015-03-25 | 东莞市翔丰华电池材料有限公司 | Germanium-graphene composite cathode material for lithium ion battery and preparation method thereof |
| CN104701035A (en) * | 2015-03-20 | 2015-06-10 | 中国科学院青海盐湖研究所 | Preparation method of metal oxide/graphene or multi-metal oxide/graphene composite electrode material |
| CN104993110A (en) * | 2015-06-11 | 2015-10-21 | 江苏大学 | Preparation method of composite negative electrode material for lithium ion battery |
| CN105762360A (en) * | 2016-04-01 | 2016-07-13 | 上海交通大学 | Graphene-silicon-coated composite negative electrode material and preparing method and application thereof |
| CN105762360B (en) * | 2016-04-01 | 2019-07-16 | 上海交通大学 | Graphene coated silicon composite cathode material and its preparation method and application |
| CN105702959A (en) * | 2016-04-14 | 2016-06-22 | 华东理工大学 | Preparation method of silicon-based lithium ion battery anode material |
| CN106099061A (en) * | 2016-07-14 | 2016-11-09 | 中国科学院宁波材料技术与工程研究所 | A kind of porous graphene/silicon composite, its preparation method and lithium ion battery |
| CN106099061B (en) * | 2016-07-14 | 2018-10-09 | 中国科学院宁波材料技术与工程研究所 | A kind of porous graphene/silicon composite, preparation method and lithium ion battery |
| CN107845782A (en) * | 2016-09-19 | 2018-03-27 | 中国科学院宁波材料技术与工程研究所 | A kind of silicon/graphene composite negative pole and its preparation method and application |
| CN107845782B (en) * | 2016-09-19 | 2021-04-09 | 中国科学院宁波材料技术与工程研究所 | Silicon/graphene composite negative electrode material and preparation method and application thereof |
| CN106450319A (en) * | 2016-11-30 | 2017-02-22 | 电子科技大学 | Graphene-silicon composite material, preparation method and application thereof |
| CN106784765A (en) * | 2016-12-15 | 2017-05-31 | 电子科技大学 | Graphene enhancing Si-C composite material and its production and use |
| CN107346822A (en) * | 2017-04-25 | 2017-11-14 | 山东玉皇新能源科技有限公司 | A kind of method that solvent-thermal method prepares graphene silicon composite cathode material |
| CN107293708A (en) * | 2017-05-18 | 2017-10-24 | 山东玉皇新能源科技有限公司 | The improved method that solvent-thermal method prepares graphene silicon composite |
| CN107293725A (en) * | 2017-07-18 | 2017-10-24 | 深圳市泽纬科技有限公司 | A kind of preparation method of nanometer of red phosphorus and graphene composite negative pole |
| CN107293725B (en) * | 2017-07-18 | 2020-07-28 | 深圳市泽纬科技有限公司 | Preparation method of nano red phosphorus and graphene composite negative electrode material |
| CN108183204A (en) * | 2017-12-06 | 2018-06-19 | 华南农业大学 | A kind of silicon nanometer sheet-graphene nanometer sheet composite material and preparation and application |
| CN108232146A (en) * | 2017-12-28 | 2018-06-29 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of lithium ion battery negative material |
| CN108428884A (en) * | 2018-04-24 | 2018-08-21 | 盐城师范学院 | A kind of preparation method of sheet layer graphene and silicon electrode material |
| CN108598434A (en) * | 2018-04-24 | 2018-09-28 | 盐城师范学院 | A kind of electrostatic self-assembled preparation method of graphene/silicon electrode material |
| CN108428883A (en) * | 2018-04-24 | 2018-08-21 | 盐城师范学院 | A kind of small size edge is grapheme modified with silicon combination electrode material preparation method |
| CN109873150A (en) * | 2019-03-14 | 2019-06-11 | 西北师范大学 | The method for preparing nanometer silicon composite material as raw material using palygorskite |
| CN109887767A (en) * | 2019-04-03 | 2019-06-14 | 山东星火科学技术研究院 | A kind of micro super capacitor and preparation method thereof based on graphene |
| CN110429331A (en) * | 2019-08-13 | 2019-11-08 | 福建翔丰华新能源材料有限公司 | Graphene compound coating material fills solid electrolyte and preparation method thereof |
| CN110429331B (en) * | 2019-08-13 | 2022-06-07 | 四川翔丰华新能源材料有限公司 | Graphene composite coating material filled solid electrolyte and preparation method thereof |
| CN111253170A (en) * | 2020-03-13 | 2020-06-09 | 江苏嘉明碳素新材料有限公司 | Method for preparing silicified graphite structure material |
| CN111403711A (en) * | 2020-03-26 | 2020-07-10 | 内蒙古杉杉科技有限公司 | Sulfur-nitrogen co-doped graphene loaded nano-silicon three-dimensional electrode material and preparation method thereof |
| CN111403711B (en) * | 2020-03-26 | 2023-03-14 | 内蒙古杉杉科技有限公司 | Sulfur-nitrogen co-doped graphene loaded nano-silicon three-dimensional electrode material and preparation method thereof |
| CN114497483A (en) * | 2021-12-31 | 2022-05-13 | 惠州锂威新能源科技有限公司 | Negative plate, preparation method thereof and lithium ion battery |
| CN114497483B (en) * | 2021-12-31 | 2023-07-04 | 惠州锂威新能源科技有限公司 | Negative plate, preparation method thereof and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103035890B (en) | 2015-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103035890B (en) | Silicon and graphene composite electrode material and preparation method thereof | |
| EP3128585B1 (en) | Composite cathode material and preparation method thereof, cathode pole piece of lithium ion secondary battery, and lithium ion secondary battery | |
| EP3726628A1 (en) | Lithium ion battery negative electrode material and preparation method therefor | |
| CN102130334B (en) | Graphene-based nano iron oxide composite material and preparation method thereof | |
| CN103165862B (en) | A kind of high performance lithium ionic cell cathode material and preparation method thereof | |
| CN103022436B (en) | Electrode composite material preparation method | |
| US20120315550A1 (en) | Graphene-modified lithium iron phosphate positive electrode active material, preparation of the same and lithium-ion secondary cell | |
| CN110289408B (en) | Nano silicon and silicon/carbon composite material based on cutting silicon waste material, preparation method and application | |
| CN102522534B (en) | Silicon-carbon composite material with high specific capacity, preparation method of silicon-carbon composite material, lithium ion battery anode material and lithium ion battery | |
| CN103165894B (en) | Graphene-hydroxyl lithium composite and its preparation method and application | |
| CN102694155A (en) | Silicon-carbon composite material, preparation method thereof and lithium ion battery employing same | |
| CN103035881B (en) | Preparation method of graphene-silicon composite material | |
| CN104300129A (en) | Battery, battery cathode, battery cathode material and preparation method thereof | |
| CN102983317A (en) | Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery | |
| CN105355877A (en) | Graphene-metal oxide composite negative electrode material and preparation method therefor | |
| CN106450265A (en) | In-situ nitrogen-doped carbon coated lithium titanate composite electrode material and preparation method thereof | |
| CN103151504A (en) | Preparation method of silver doped carbon-silicon composite negative electrode material | |
| CN102351163B (en) | Nano carbon microsphere cathode material of lithium ion cell and preparation method thereof | |
| Gan et al. | Polymeric carbon encapsulated Si nanoparticles from waste Si as a battery anode with enhanced electrochemical properties | |
| CN110112408A (en) | A kind of graphene-silicon composite and preparation method thereof, electrode material and battery | |
| CN104979540A (en) | Preparation method and application of bicontinuous-structural nanocomposite material | |
| CN103066255A (en) | A nano-metal coated sulfur composite material and applications thereof | |
| CN103579627A (en) | Graphene-tin composite material, preparation method of graphene-tin composite material, lithium ion battery and preparation method of lithium ion battery | |
| CN111646459A (en) | Preparation method and application of boron-doped graphene material | |
| CN103579626A (en) | Graphene/tin composite material, preparation method of grapheme/tin composite material, lithium ion battery and preparation method of lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |