CN103035888B - Preparation method of silicon and graphene composite material - Google Patents
Preparation method of silicon and graphene composite material Download PDFInfo
- Publication number
- CN103035888B CN103035888B CN201110301951.9A CN201110301951A CN103035888B CN 103035888 B CN103035888 B CN 103035888B CN 201110301951 A CN201110301951 A CN 201110301951A CN 103035888 B CN103035888 B CN 103035888B
- Authority
- CN
- China
- Prior art keywords
- silicon
- composite material
- graphene composite
- preparation
- gaseous
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
- Silicon Compounds (AREA)
Abstract
The invention relates to a preparation method of a silicon and graphene composite material. The silicon and graphene composite material is prepared by placing graphite oxide solids in a silicon-containing gas atmosphere for reduction reaction. The preparation process is relatively simple. Since impurities produced during reaction are gas substances and can be directly discharged, complex drying and purifying steps are not needed and the product can be directly obtained, the preparation efficiency is higher, the purity of the prepared composite material is high and the performance is guaranteed.
Description
[technical field]
The present invention relates to lithium ion battery, hybrid super capacitor field, particularly relate to the preparation method of a kind of silicon, graphene composite material.
[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 silicon, the graphene combination electrode material prepared has good electrochemical stability with silicon.Traditional silicon, graphene combination electrode material mostly adopt wet-layer preparation, and the product obtained needs to carry out strict purification removal of impurities, and process is loaded down with trivial details, and efficiency is low, and product is usually mixed with impurity, affects the performance of electrode material.
[summary of the invention]
Based on this, be necessary to provide a kind of process relative ease, directly can obtain the silicon of product, the preparation method of graphene composite material.
A preparation method for silicon, graphene composite material, comprises the steps:
There is provided or prepare graphite oxide;
Described graphite oxide is placed in siliceous reducibility gas atmosphere, slowly be heated to 200 ~ 1200 DEG C with 10 ~ 100 DEG C/min and carry out reduction reaction, obtain described silicon, graphene composite material after cooling, wherein, silicon accounts for 1 ~ 50% of described composite weight.
Preferably, described graphite oxide of preparing comprises the steps: graphite raw material, potassium peroxydisulfate and phosphorus pentoxide to be added in the concentrated sulfuric acid of 80 DEG C, stirs, 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 2 hours 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.Preferred further, above-mentioned graphite raw material is the natural flake graphite that purity is more than or equal to 99.5%.
Preferably, described siliceous reducibility gas is the mixture of gaseous silicon compound and reducibility gas, or described siliceous reducibility gas is the one-component of the gaseous silicon compound with reproducibility or the mixture of many components.
Preferably, described gaseous silicon compound is gaseous silane, gaseous state halosilanes, gaseous state alkyl silane or gaseous state alkoxy silane.
Preferably, described halosilanes is SiF
4, SiCl
4or SiHCl
3.
Preferably, described alkyl silane is Si (CH
3)
4or Si (CH
2cH
3)
4.
Preferably, described alkoxy silane is tetramethoxy-silicane, a methoxytrimethylsilane, tetraethoxysilane.
Preferably, described reducibility gas is hydrogen.
Carry out reduction reaction obtain silicon, graphene composite material by oxidation graphite solid being placed in siliceous atmosphere in this preparation process, preparation process is relatively simple, because the impurity produced in course of reaction is gaseous matter, can directly discharge, without the need to the dry purification step of complexity, directly can obtain product, thus preparation efficiency is higher, obtained composite material purity is high, and performance is guaranteed.
[accompanying drawing explanation]
Fig. 1 is the SEM photo of the obtained silicon of embodiment 1, graphene composite material;
Fig. 2 is the XRD figure of the obtained silicon of embodiment 1, graphene composite material.
[embodiment]
Mainly in conjunction with the drawings and the specific embodiments the preparation method of silicon, graphene composite material is described in further detail below.
Present embodiment provides the preparation method of a kind of silicon, graphene composite material, and this composite material is comprise the nanometer of silicon and Graphene or the particle of micron level.Wherein, in composite material, the mass fraction of silicon is 1 ~ 50%.Graphene is layer structure, and silicon particle dispersion is among the lamellar structure of Graphene, and silicon particle and Graphene can reach other mixing of molecular level, have good consistency and uniformity; Large stretch of graphene film adsorbs silicon grain, silicon particle ionic conductivity can be supplied to, the electronic conductivity of silicon particle can be significantly improved simultaneously.
The silicon of present embodiment, the preparation method of graphene composite material, preparation technology's flow process is as follows:
Reduction → silicon, graphene composite material in the reducibility gas atmosphere of graphite → graphite oxide → siliceous
Specifically comprise the steps:
Step S1: prepare graphite oxide.
Preferably, following method can be adopted to prepare, comprise the steps: graphite raw material, potassium peroxydisulfate and phosphorus pentoxide to be 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; Again 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 2 hours 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.
Wherein, graphite raw material is preferably the natural flake graphite that purity is more than or equal to 99.5%.
Step S2: graphite oxide obtained in step S1 is placed in siliceous reducibility gas atmosphere, slowly be heated to 200 ~ 1200 DEG C with 10 ~ 100 DEG C/min and carry out reduction reaction, silicon, graphene composite material is obtained after cooling again under reproducibility atmosphere, wherein, in composite material, the mass fraction of silicon controls between 1 ~ 50%.
Siliceous reducibility gas is as silicon source, and graphite oxide redox reaction occurs in siliceous reducibility gas atmosphere and generates Graphene and elementary silicon, and Graphene forms layer structure, and elementary silicon is dispersed in the layer structure of Graphene.
Wherein, siliceous reducibility gas can be the mixture of gaseous silicon compound and reducibility gas, if gaseous silicon compound self has reproducibility, then siliceous reducibility gas can also select the one-component of the gaseous silicon compound with reproducibility or multi-component mixture.Gaseous silicon compound can be gaseous silane (SiH
4), gaseous state halosilanes, gaseous state alkyl silane or gaseous state alkoxy silane etc.Silane itself has stronger reproducibility, when use silane as silicon source time, in a heated condition, its can directly and graphite oxide generation redox reaction generate Graphene and elementary silicon.Halosilanes can be the monosubstituted or polysubstituted silane such as fluorine, chlorine, bromine, iodine, as silicon tetrafluoride (SiF
4), silicon tetrachloride (SiCl
4), four bromo-silicane (SiBr
4), a chlorine silicofluoroform (SiClF
3), trichlorosilane (SiHCl
3) etc., preferably prepare the silicon tetrafluoride of easy advantage of lower cost, silicon tetrachloride or trichlorosilane.Alkyl silane can be C
1~ C
4the monosubstituted or polysubstituted silane of alkyl, as tetramethylsilane (Si (CH
3)
4) or tetraethyl silane (Si (CH
2cH
3)
4) etc.Alkoxy silane can be C
1~ C
4monosubstituted or the polysubstituted silane of alkoxyl, as tetramethoxy-silicane, a methoxytrimethylsilane, tetraethoxysilane etc.The hydrogen that reducibility gas is preferably commonly used.
Carry out reduction reaction obtain silicon, graphene composite material by oxidation graphite solid being placed in siliceous atmosphere in the preparation process of above-mentioned silicon, graphene composite material, preparation process is relatively simple, because the impurity produced in course of reaction is gaseous matter, can directly discharge, without the need to the dry purification step of complexity, thus preparation efficiency is higher, obtained composite material purity is high, and performance is guaranteed.In the composite material obtained, nano-micrometre grade silicon can be good at being dispersed between the lamella of Graphene; Graphene due to sheet has larger specific area, so composite material has good porosity, has good ionic conduction characteristic, can be widely used as lithium ion battery, and the negative material of ultracapacitor makes field.
It is below specific embodiment part
Wherein, gaseous silicon compound selects silane simple and easy to get, silicon tetrachloride, silicon tetrafluoride, trichlorosilane, tetramethylsilane, tetramethoxy-silicane etc., in other embodiments, can also be above-mentioned introduction siliceous reducibility gas in one or more combination.Reducibility gas is selected and is easy to get and free of contamination H
2, in other embodiments, can also the gases such as CO be selected.
Embodiment 1
Preparation technology's flow process is as follows:
Reduction → silicon, graphene composite material in the reducibility gas atmosphere of graphite raw material → graphite oxide → siliceous
(1) graphite raw material: 50 order purity are the natural flake graphite of 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, cools more than 6 hours, suction filtration, and 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 2 hours, 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) reduce in siliceous reducibility gas atmosphere: the graphite oxide powder that step (2) is obtained is put into and is connected with SiH
4200 DEG C of reactions 10 hours are warming up to the slow speed of 10 DEG C/min in the tube furnace of gas; Again by reacted powder at H
2atmosphere under cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 1%, and as shown in Figure 1, its XRD photo as shown in Figure 2 for its SEM photo, wherein, be the characteristic peak of silicon 28.4 ° and 47.6 ° as can be seen from Figure 2,26 ° and 42.8 ° is Graphene characteristic peak, shows that the material obtained is silicon and graphene composite material.
In composite material, the mass fraction of silicon adopts calcination method, and in the Muffle furnace of 500 DEG C, calcination 3 hours, makes quality no longer reduce, Graphene is converted into gas completely, remaining is silica solid, is weighed by remaining solid, the mass fraction according to formulae discovery silicon:
Mass fraction=(quality × 28/60 of remaining solid) × 100%/initial mass of silicon
Embodiment 2
The preparation of graphite oxide is with embodiment 1.
Obtained graphite oxide powder is put into and is connected with SiH
4with H
2400 DEG C of reactions 1 hour is warming up to the slow speed of 100 DEG C/min in the tube furnace of mist, then by reacted powder at H
2atmosphere cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 20%.
Embodiment 3
The preparation of graphite oxide is with embodiment 1.
Obtained graphite oxide powder is put into and is connected with SiF
4with H
2mist tube furnace in be warming up to 400 DEG C of reactions 10 hours, then by reacted powder at H with the slow speed of 20 DEG C/min
2atmosphere cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 27.8%.
Embodiment 4
The preparation of graphite oxide is with embodiment 1.
Obtained graphite oxide powder is put into and is connected with SiHCl
3with H
2mist tube furnace in be warming up to 800 DEG C of reactions 8 hours, then by reacted powder at H with the slow speed of 50 DEG C/min
2atmosphere cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 42.5%.
Embodiment 5
The preparation of graphite oxide is with embodiment 1.
Obtained graphite oxide powder is put into the tube furnace being connected with tetramethylsilane and be warming up to 400 DEG C of reactions 10 hours with the slow speed of 40 DEG C/min, then by reacted powder at H
2atmosphere cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 28.5%.
Embodiment 6
The preparation of graphite oxide is with embodiment 1.
Obtained graphite oxide powder is put into the tube furnace being connected with tetramethoxy-silicane and be warming up to 500 DEG C of reactions 10 hours with the slow speed of 40 DEG C/min, then by reacted powder at H
2atmosphere cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 30.7%.
Embodiment 7
The preparation of graphite oxide is with embodiment 1.
Obtained graphite oxide powder is put into and is connected with SiCl
4with H
2mist tube furnace in be warming up to 1200 DEG C of reactions 5 hours, then by reacted powder at H with the slow speed of 100 DEG C/min
2atmosphere cool to room temperature with the furnace, obtain silicon, graphene composite material, wherein, the mass fraction of silicon is 50%.
Sample powder the various embodiments described above obtained becomes disk at the pressure of 10MPa, with the two electrical measurement four-point probe testing conductivity of D41-11D/ZM type under room temperature.When measuring current is shown as probe coefficient, press the button of electricalresistivityρ, then screen directly shows electricalresistivityρ's value, directly calculates conductivity according to γ=l/ ρ.By four probe method measure silicon that each embodiment obtains, graphene composite material conductivity as shown in table 1 below, the silicon of various embodiments of the present invention, the graphene composite material conductivity (6.7 × 10 relative to silicon can be found out from table 1 numerical value
-2s/m) improve a lot.
Table 1
The silicon of various embodiments of the present invention, the graphene composite material conductivity (6.7 × 10 relative to silicon can be found out from table 1 numerical value
-2s/m) improve a lot.
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 (8)
1. a preparation method for silicon, graphene composite material, is characterized in that, comprises the steps:
Prepare graphite oxide: 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 2 hours 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;
Described graphite oxide is placed in the atmosphere of siliceous reducibility gas, slowly be heated to 200 ~ 1200 DEG C with 10 ~ 100 DEG C/min and carry out reduction reaction, obtain described silicon, graphene composite material after cooling, wherein, silicon account for described silicon, graphene composite material weight 1 ~ 50%.
2. the preparation method of silicon as claimed in claim 1, graphene composite material, it is characterized in that, described graphite raw material is the natural flake graphite that purity is more than or equal to 99.5%.
3. the preparation method of silicon as claimed in claim 1, graphene composite material, it is characterized in that, described siliceous reducibility gas is the mixture of gaseous silicon compound and reducibility gas, or described siliceous reducibility gas is the one-component of the gaseous silicon compound with reproducibility or the mixture of many components.
4. the preparation method of silicon as claimed in claim 3, graphene composite material, it is characterized in that, described gaseous silicon compound is gaseous silane, gaseous state halosilanes, gaseous state alkyl silane or gaseous state alkoxy silane.
5. the preparation method of silicon as claimed in claim 4, graphene composite material, it is characterized in that, described gaseous state halosilanes is SiF
4, SiCl
4or SiHCl
3.
6. the preparation method of silicon as claimed in claim 4, graphene composite material, it is characterized in that, described gaseous state alkyl silane is Si (CH
3)
4or Si (CH
2cH
3)
4.
7. the preparation method of silicon as claimed in claim 4, graphene composite material, it is characterized in that, described gaseous state alkoxy silane is tetramethoxy-silicane, a methoxytrimethylsilane, tetraethoxysilane.
8. the silicon as described in claim 3 or 4, the preparation method of graphene composite material, is characterized in that, described reducibility gas is hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110301951.9A CN103035888B (en) | 2011-09-28 | 2011-09-28 | Preparation method of silicon and graphene composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110301951.9A CN103035888B (en) | 2011-09-28 | 2011-09-28 | Preparation method of silicon and graphene composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103035888A CN103035888A (en) | 2013-04-10 |
| CN103035888B true CN103035888B (en) | 2015-07-08 |
Family
ID=48022552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110301951.9A Active CN103035888B (en) | 2011-09-28 | 2011-09-28 | Preparation method of silicon and graphene composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103035888B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103715405B (en) * | 2013-12-25 | 2017-02-01 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-graphene lithium-ion composite electrode material and preparation method thereof |
| CN105016330B (en) * | 2015-07-08 | 2017-12-22 | 常州市诚天电子有限公司 | A kind of preparation method of graphene |
| CN105355892A (en) * | 2015-12-15 | 2016-02-24 | 中南大学 | Preparation method of lithium ion battery cathode |
| CN106058207A (en) * | 2016-08-02 | 2016-10-26 | 中国科学技术大学 | Silicon-carbon composite material, preparation method thereof and negative pole for lithium-ion battery |
| CN111392719B (en) * | 2020-03-12 | 2021-02-09 | 兰州大学 | Silicon-doped graphene, preparation method thereof and silicon-doped graphene-based chemical resistance type nitrogen oxide room temperature sensor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145887A (en) * | 2011-05-18 | 2011-08-10 | 中国科学院长春应用化学研究所 | Method for preparing and purifying graphene oxide |
-
2011
- 2011-09-28 CN CN201110301951.9A patent/CN103035888B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145887A (en) * | 2011-05-18 | 2011-08-10 | 中国科学院长春应用化学研究所 | Method for preparing and purifying graphene oxide |
Non-Patent Citations (3)
| Title |
|---|
| Nanosilicon-Coated Graphene Granules as Anodes for Li-Ion Batteries;Kara Evanoff et al.;《Advanced Energy Materials》;20110421;第1卷;第495-498页 * |
| Silicon nanoparticles–graphene paper composites for Li ion battery anodes;Jeong K. Lee et al.;《Chemical Communications》;20100210;第46卷;第2025–2027页 * |
| 蔡珣 等.硅烷.《现代薄膜材料与技术》.华东理工大学出版社,2007, * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103035888A (en) | 2013-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103022436B (en) | Electrode composite material preparation method | |
| Sun et al. | A hybrid ZnO/Si/porous-carbon anode for high performance 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 | |
| CN103035890B (en) | Silicon and graphene composite electrode material and preparation method thereof | |
| CN104347857B (en) | Negative electrode of lithium ionic secondary battery and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery | |
| Wu et al. | Carbon coated mesoporous Si anode prepared by a partial magnesiothermic reduction for lithium-ion batteries | |
| Shen et al. | Si/mesoporous carbon composite as an anode material for lithium ion batteries | |
| CN103035881B (en) | Preparation method of graphene-silicon composite material | |
| Song et al. | Porous nano-Si/carbon derived from zeolitic imidazolate frameworks@ nano-Si as anode materials for lithium-ion batteries | |
| Guo et al. | Optimum synthesis of Li2Fe1− xMnxSiO4/C cathode for lithium ion batteries | |
| He et al. | Optimal microstructural design of pitch-derived soft carbon shell in yolk-shell silicon/carbon composite for superior lithium storage | |
| Feng et al. | Enabling the ability of Li storage at high rate as anodes by utilizing natural rice husks-based hierarchically porous SiO2/N-doped carbon composites | |
| Huang et al. | Synergetic restriction to polysulfides by hollow FePO4 nanospheres wrapped by reduced graphene oxide for lithium–sulfur battery | |
| CN103035888B (en) | Preparation method of silicon and graphene composite material | |
| Xiao et al. | 3D interconnected mesoporous Si/SiO2 coated with CVD derived carbon as an advanced anode material of Li-ion batteries | |
| CN107565136B (en) | A kind of porous Si-C composite material preparation method and products thereof based on rectorite | |
| Zou et al. | Microwave-assisted preparation of hollow porous carbon spheres and as anode of lithium-ion batteries | |
| Tang et al. | Novel scalable synthesis of porous silicon/carbon composite as anode material for superior lithium-ion batteries | |
| CN104347858B (en) | Negative electrode of lithium ionic secondary battery and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery | |
| CN102983317A (en) | Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery | |
| Zhang et al. | Nitrogen-doped-carbon coated lithium iron phosphate cathode material with high performance for lithium-ion batteries | |
| CN106252622B (en) | A kind of silica/carbon composite nano line negative electrode material, preparation method and lithium ion battery | |
| CN108134087A (en) | Negative material and preparation method thereof used in a kind of lithium-ion-power cell | |
| CN105206802B (en) | Rich lithium sulfonated graphene nano silicon oxide negative material and its preparation method and application | |
| CN104282894B (en) | A kind of preparation method of porous Si/C complex microsphere |
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 |