CN103035890B - 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
- CN103035890B CN103035890B CN201110302811.3A CN201110302811A CN103035890B CN 103035890 B CN103035890 B CN 103035890B CN 201110302811 A CN201110302811 A CN 201110302811A CN 103035890 B CN103035890 B CN 103035890B
- Authority
- CN
- China
- Prior art keywords
- silicon
- graphene
- electrode material
- nano
- solution
- 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.)
- Active
Links
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 battery electrode material field, particularly relate 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 electrochemical performance of this kind of system, but because itself storage lithium ability is lower, the theoretical lithium storage content as graphite is 372mAh/g, so novel transition metal oxide/graphite system attracts widespread attention.
In intercalation materials of li ions known at present, pure silicon is because having the highest theoretical lithium storage content (4200mAh/g), relatively low intercalation potential, charge and discharge process is not easily reunited, compared with other metal_based materials, there is higher physical stability and chemical stability, become the study hotspot in lithium ion battery negative material field.But the effect of stress that silica-base material produces due to bulk effect in degree of depth removal lithium embedded process easily causes avalanche and the material efflorescence of silicon lattice structure, cause active material depart from electrode material system and lose activity, therefore there is very poor cyclical stability.Silica-base material is mainly improved one's methods and has adopted metal and the silicon compound such as Ni, Fe and Cu, being formed with silicon is activated centre, take inert metal as the activity/inertia compound system of dispersible carrier, while improving the electric conductivity of material, improve 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, therefore weakens the specific capacity of silica-base material to a certain extent; Metal itself has electron conduction in addition, does not possess ionic conductivity, makes electrolyte be difficult to immerse, thus loses activity.Another method is exactly the coated method of material with carbon element, lower than the molal weight of metal, and electrolyte is easy to immerse, and relative efficacy comparatively metal will be got well, and material property has certain improvement, but poor.
Graphene has good conductivity, space distribution and higher mechanical performance, utilizes grapheme material to substitute traditional material with carbon element, is combined the silicon prepared and graphene combination electrode material has good electrochemical stability with silicon.Traditional silicon and graphene combination electrode material generally adopt silicon-containing compound reducing process to prepare, 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 the silicon and graphene combination electrode material and preparation method thereof that provide a kind of preparation process relatively simple.
A kind of 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, 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%.
A preparation method for silicon and graphene combination electrode material, comprises the steps:
Step one: prepare homodisperse graphene oxide solution and nano-silicon solution respectively;
Step 2: be to mix at 1 ~ 9: 1 according to graphene oxide and the mass ratio of nano-silicon by described graphene oxide solution and nano-silicon solution, obtains the mixed solution of homodisperse graphene oxide and nano-silicon;
Step 3: described mixed solution is carried out hydrothermal reduction reaction, obtains described silicon and graphene combination electrode material.
In a preferred embodiment, in step one, prepare described graphene oxide solution and to comprise the steps: graphite oxide to join in solvent ultrasonic disperse 0.5 ~ 1 hour, to form the homodisperse graphene oxide solution of monolithic layer.
In a preferred embodiment, described graphite oxide is prepared according to following step:
Graphite raw material is provided;
Graphite raw material, potassium peroxydisulfate and phosphorus pentoxide are added in the concentrated sulfuric acid of 80 DEG C, stir, cool more than 6 hours, suction filtration, washing is to neutral, dry, obtains biased sample;
Described biased sample is added in the concentrated sulfuric acid of 0 DEG C, add potassium permanganate again, the temperature of system remains on less than 20 DEG C, then keeps after 30 minutes in the oil bath of 35 DEG C, slowly add deionized water, after 15 minutes, then add the deionized water containing hydrogen peroxide, until the color of solution becomes glassy yellow, suction filtration while hot, wash with the hydrochloric acid that concentration is 10%, suction filtration, namely 60 DEG C of vacuumizes obtain graphite oxide again.
In a preferred embodiment, described graphite raw material is the natural flake graphite that purity is not less than 99.5%.
In a preferred embodiment, described solvent is DMF, DMA, 1-METHYLPYRROLIDONE.
In a preferred embodiment, in step one, prepare homodisperse nano-silicon solution and comprise the steps: the powder of nano-silicon to join in solvent, ultrasonic disperse 10 ~ 30 minutes, obtain homodisperse nano-silicon solution.
In a preferred embodiment, described solvent is DMF, DMA, 1-METHYLPYRROLIDONE.
In a preferred embodiment, the particle diameter of described nano-silicon is 20-60nm.
In a preferred embodiment, in step 3, hydro-thermal reaction is reduced described mixed solution and is comprised the steps: described mixed solution to be placed in hydrothermal reaction kettle, react 5 ~ 10 hours at 100 ~ 150 DEG C, when question response system is cooled to room temperature, filter, obtain crude product, wash crude product repeatedly with methyl alcohol and deionized water, under room temperature, after drying, namely obtain described silicon and graphene combination electrode material.
Graphene oxide solution mixed with nano-silicon solution, then by hydro thermal method redox graphene, nano-silicon can be good at being dispersed between the lamella of Graphene, prevents Graphene from reuniting, can make the specific area that combination electrode material reaches higher; Meanwhile, this preparation technology's flow process is simple, and the reaction time is short, thus the loss of course of reaction Raw is less, and productive rate is relatively high.In obtained silicon and graphene combination electrode material, due to Graphene high conductivity can well by electrical conductivity on elemental silicon, improve conductivity, the high capacity characteristics of silicon can have been given full play to, its stability can be improved again, be suitable as the negative material of lithium ion battery.
[accompanying drawing explanation]
Fig. 1 is the silicon of an execution mode and the preparation flow figure of graphene combination electrode material;
Fig. 2 is the SEM picture of the obtained silicon of embodiment 1 and graphene combination electrode material.
[embodiment]
Mainly in conjunction with the drawings and the specific embodiments silicon and graphene combination electrode material and preparation method thereof are described in further detail below.
Present embodiments provide for a kind of silicon and graphene combination electrode material and preparation method thereof, 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 in composite material, the mass percent of nano-silicon is 10 ~ 50%.Nano-silicon and Graphene can reach other mixing of molecular level, have good consistency and uniformity; Large stretch of graphene film adsorbs nano-silicon, nano-silicon ionic conductivity can be supplied to, the electronic conductivity of nano-silicon can be significantly improved 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 homodisperse graphene oxide solution and nano-silicon solution respectively.Specifically comprise the steps:
Step S11: graphite raw material is provided.
The preferred purity of graphite raw material is not less than the natural flake graphite of 99.5%.
Step S12: graphite raw material, potassium peroxydisulfate and phosphorus pentoxide are added in the concentrated sulfuric acid of 80 DEG C, stir, cools more than 6 hours, suction filtration, and washing is to neutral, dry, obtains biased sample;
Described biased sample is added in the concentrated sulfuric acid of 0 DEG C, add potassium permanganate again, the temperature of system remains on less than 20 DEG C, then keeps after 30 minutes in the oil bath of 35 DEG C, slowly add deionized water, after 15 minutes, then add the deionized water containing hydrogen peroxide, until the color of solution becomes glassy yellow, suction filtration while hot, wash with the hydrochloric acid that concentration is 10%, suction filtration, namely 60 DEG C of vacuumizes obtain graphite oxide again.
Step S13: obtained graphite oxide to be joined in solvent ultrasonic disperse 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: join in solvent by the powder of nano-silicon, ultrasonic disperse 10 ~ 30 minutes, obtains homodisperse nano-silicon solution.
The particle diameter of nano-silicon is preferably 20-60nm.
Preferably, fully mix with graphene oxide solution for ease of nano-silicon solution, the solvent for dissolving nano-silicon is selected identical with the solvent for dissolved oxygen graphite.
Step S2: be to mix at 2 ~ 3: 1 according to graphene oxide and the mass ratio of nano-silicon by described graphene oxide solution and nano-silicon solution, obtains the mixed solution of homodisperse graphene oxide and nano-silicon.
Step S3: described mixed solution is carried out hydrothermal reduction reaction, obtains described silicon and graphene combination electrode material.
Specific as follows: the mixed solution of graphene oxide and nano-silicon is placed in hydrothermal reaction kettle, react 5 ~ 10 hours at 100 ~ 150 DEG C, when question response system is cooled to room temperature, filter, obtain crude product, wash crude product repeatedly with methyl alcohol and deionized water, under room temperature, after drying, namely obtain described silicon and graphene combination electrode material.
By graphene oxide solution is mixed with nano-silicon solution, then hydro thermal method redox graphene, nano-silicon can be good at being dispersed between the lamella of Graphene, prevents Graphene from reuniting, can make the specific area that combination electrode material reaches higher; Meanwhile, this preparation technology's flow process is simple, and the reaction time is short, thus the loss of course of reaction Raw is less, and productive rate is relatively high.In obtained silicon and graphene combination electrode material, due to Graphene high conductivity can well by electrical conductivity on elemental silicon, improve conductivity, the high capacity characteristics of silicon can have been given full play to, its stability can be improved again, be suitable as the negative material of lithium ion battery.
Be below specific embodiment part:
Embodiment 1
Silicon and the graphene combination electrode material technological process of the present embodiment 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 are added in the concentrated sulfuric acid of 80 DEG C, stir, cool more than 6 hours, suction filtration, washing is to neutral, dry, obtains biased sample;
Dried biased sample is added to 0 DEG C, in the concentrated sulfuric acid of 230mL, then adds 60g potassium permanganate, the temperature of system remains on less than 20 DEG C, then keeps, after 30 minutes, slowly adding 920mL deionized water in the oil bath of 35 DEG C;
After 15 minutes, 2.8L deionized water is added again in system, until mixture color becomes glassy yellow, suction filtration while hot, wash with the hydrochloric acid that 5L concentration is 10% again, suction filtration, within 48 hours, namely obtain graphite oxide 60 DEG C of vacuumizes, wherein, containing 50mL concentration in above-mentioned 2.8L deionized water is the hydrogen peroxide of 30%.
(3) mixed solution of graphite oxide and nano-silicon: the graphite oxide prepared to be joined in DMF (DMF) solvent ultrasonic disperse 0.5 hour, formed with the homodisperse graphene oxide solution of monolithic layer;
The nano-silicon powder taking 20g is dissolved in DMF (DMF) solvent, ultrasonic disperse 10 minutes, to form finely dispersed nano-silicon solution;
Slowly joined in graphene oxide solution by nano-silicon solution, 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, reduction reaction 10 hours at 100 DEG C, when solution is cooled to room temperature, by sample filtering, with methyl alcohol and water washing three times, under room temperature, after drying, namely obtain silicon and graphene combination electrode material.As shown in Figure 2, as can be seen 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
Silicon and the graphene combination electrode material technological process of the present embodiment 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 prepared to be joined in DMA (DMAc) solvent ultrasonic disperse 1 hour, formed with the homodisperse graphene oxide solution of monolithic layer;
The nano-silicon powder taking 10g is dissolved in DMF (DMF) solvent, ultrasonic disperse 30 minutes, to form finely dispersed nano-silicon solution;
Slowly joined in graphene oxide solution by nano-silicon solution, 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, reduction reaction 5 hours at 120 DEG C, when solution is cooled to room temperature, by sample filtering, with methyl alcohol and water washing three times, under room temperature, after drying, namely obtain silicon and graphene combination electrode material.
Embodiment 3
Silicon and the graphene combination electrode material technological process of the present embodiment 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 prepared to be joined in DMF (DMF) solvent ultrasonic disperse 0.5 hour, formed with the homodisperse graphene oxide solution of monolithic layer;
The nano-silicon powder taking 5g is dissolved in 1-METHYLPYRROLIDONE (NMP) solvent, ultrasonic disperse 10 minutes, to form finely dispersed nano-silicon solution;
Slowly joined in graphene oxide solution by nano-silicon solution, 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, reduction reaction 10 hours at 150 DEG C, when solution is cooled to room temperature, by sample filtering, with methyl alcohol and water washing three times, under room temperature, after drying, namely obtain silicon and graphene combination electrode material.
Embodiment 4
Silicon and the graphene combination electrode material technological process of the present embodiment 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 prepared to be joined in DMF (DMF) solvent ultrasonic disperse 1 hour, formed with the homodisperse graphene oxide solution of monolithic layer;
The nano-silicon powder taking 2.3g is dissolved in DMF (DMF) solvent, ultrasonic disperse 30 minutes, to form finely dispersed nano-silicon solution;
Slowly joined in graphene oxide solution by nano-silicon solution, 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, reduction reaction 5 hours at 150 DEG C, when solution is cooled to room temperature, by sample filtering, with methyl alcohol and water washing three times, under room temperature, after drying, namely obtain silicon and graphene combination electrode material.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It 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 (5)
1. a preparation method for silicon and graphene combination electrode material, is characterized in that, comprises the steps:
Step one: prepare homodisperse graphene oxide solution and nano-silicon solution respectively, wherein, prepare described graphene oxide solution and to comprise the steps: graphite oxide to join in solvent ultrasonic disperse 0.5 ~ 1 hour, to form the homodisperse graphene oxide solution of monolithic layer;
Prepare homodisperse nano-silicon solution to comprise the steps: the powder of nano-silicon to join in solvent, ultrasonic disperse 10 ~ 30 minutes, obtain homodisperse nano-silicon solution;
Described solvent is DMF, DMA, 1-METHYLPYRROLIDONE;
Step 2: be that 1 ~ 9:1 mixes according to graphene oxide and the mass ratio of nano-silicon by described graphene oxide solution and nano-silicon solution, obtains the mixed solution of homodisperse graphene oxide and nano-silicon;
Step 3: described mixed solution is carried out hydrothermal reduction reaction, obtains described silicon and graphene combination electrode material.
2. the preparation method of silicon as claimed in claim 1 and graphene combination electrode material, it is characterized in that, described graphite oxide is prepared according to following step:
Graphite raw material is provided;
Described graphite raw material, potassium peroxydisulfate and phosphorus pentoxide are added in the concentrated sulfuric acid of 80 DEG C, stir, cool more than 6 hours, suction filtration, washing is to neutral, dry, obtains biased sample;
Described biased sample is added in the concentrated sulfuric acid of 0 DEG C, add potassium permanganate again, the temperature of system remains on less than 20 DEG C, then keeps after 30 minutes in the oil bath of 35 DEG C, slowly add deionized water, after 15 minutes, then add the deionized water containing hydrogen peroxide, until the color of solution becomes glassy yellow, suction filtration while hot, wash with the hydrochloric acid that concentration is 10%, suction filtration, namely 60 DEG C of vacuumizes obtain graphite oxide again.
3. the preparation method of silicon as claimed in claim 2 and graphene combination electrode material, it is characterized in that, described graphite raw material is the natural flake graphite that purity is not less than 99.5%.
4. the preparation method of silicon as claimed in claim 1 and graphene combination electrode material, it is characterized in that, the particle diameter of described nano-silicon is 20-60nm.
5. the preparation method of silicon as claimed in claim 1 and graphene combination electrode material, it is characterized in that, in step 3, hydro-thermal reaction is reduced described mixed solution and is comprised the steps: described mixed solution to be placed in hydrothermal reaction kettle, react 5 ~ 10 hours at 100 ~ 150 DEG C, when question response system is cooled to room temperature, filters, obtain crude product, wash described crude product at least three times with methyl alcohol and deionized water, under room temperature, after drying, namely obtain described silicon and graphene combination electrode material.
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 CN103035890A (en) | 2013-04-10 |
| CN103035890B true 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) |
Families Citing this family (25)
| 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 |
| 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 |
| CN104993110B (en) * | 2015-06-11 | 2018-06-26 | 江苏大学 | A kind of preparation method of composite negative electrode material of lithium ion battery |
| 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 |
| 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 |
| 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 |
| 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 |
| CN108428883B (en) * | 2018-04-24 | 2021-06-04 | 盐城师范学院 | Preparation method of small-size edge-modified graphene and silicon composite 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 |
| 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 |
| 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 |
| 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 |
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 |
|---|
| Silicon nanoparticles-graphene paper composites for Li ion battery anodes;Jeong K. Lee et al.;《Chem. Commun.》;20100210;第46卷;第2025-2027页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103035890A (en) | 2013-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103035890B (en) | Silicon and graphene composite electrode material and preparation method thereof | |
| CN107507972B (en) | Preparation method of silicon-carbon negative electrode material, silicon-carbon negative electrode material and lithium ion battery | |
| EP3128585B1 (en) | Composite cathode material and preparation method thereof, cathode pole piece of lithium ion secondary battery, and lithium ion secondary battery | |
| CN103022436B (en) | Electrode composite material preparation method | |
| CN103165862B (en) | A kind of high performance lithium ionic cell cathode material and preparation method thereof | |
| EP3726628A1 (en) | Lithium ion battery negative electrode material and preparation method therefor | |
| US20120315550A1 (en) | Graphene-modified lithium iron phosphate positive electrode active material, preparation of the same and lithium-ion secondary cell | |
| CN106711461A (en) | Spherical porous silicon/carbon composite material as well as preparation method and application thereof | |
| CN103035881B (en) | Preparation method of graphene-silicon composite material | |
| 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 | |
| CN110085847B (en) | Germanium/carbon composite cathode material of lithium ion battery and preparation method and application thereof | |
| CN102983317A (en) | Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery | |
| CN104300129A (en) | Battery, battery cathode, battery cathode material and preparation method thereof | |
| CN110112408A (en) | A kind of graphene-silicon composite and preparation method thereof, electrode material and battery | |
| Gan et al. | Polymeric carbon encapsulated Si nanoparticles from waste Si as a battery anode with enhanced electrochemical properties | |
| CN112886000A (en) | Pre-lithiated silica negative electrode material and preparation method and application thereof | |
| CN104979540A (en) | Preparation method and application of bicontinuous-structural nanocomposite material | |
| CN108134087A (en) | Negative material and preparation method thereof used in a kind of lithium-ion-power cell | |
| 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 | |
| CN102351163A (en) | Nano carbon microsphere cathode material of lithium ion cell and its preparation method | |
| Niu et al. | High-rate lithium storage of TiNb2O7/reduced graphene oxide | |
| CN103579626A (en) | Graphene/tin composite material, preparation method of grapheme/tin composite material, lithium ion battery and preparation method of lithium ion battery | |
| CN104638248A (en) | Method for preparing graphene/lead compound composite material |
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 |