CN109309221A - A kind of preparation method of silicon particle/graphene quantum dot core-shell structure - Google Patents
A kind of preparation method of silicon particle/graphene quantum dot core-shell structure Download PDFInfo
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- CN109309221A CN109309221A CN201811194662.1A CN201811194662A CN109309221A CN 109309221 A CN109309221 A CN 109309221A CN 201811194662 A CN201811194662 A CN 201811194662A CN 109309221 A CN109309221 A CN 109309221A
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The present invention provides a kind of preparation method of silicon particle/graphene quantum dot core-shell structure.Silicon particle is added to graphene oxide quantum dot/be closely sized in the small lamella graphene oxide solution of graphene quantum dot, after ultrasonic disperse is uniform, continues stir process, obtains silicon particle/graphene oxide core-shell structure；Residual solvent is removed in naturally dry, heating, forms silicon particle/fold graphene oxide structure, silicon particle/graphene quantum dot core-shell structure is obtained after reduction.The method of the invention selects graphene quantum dot and small size graphene more can readily wrap silicon particle, overlapping and the slight distortion of lamella and protuberance on a large amount of boundaries can form fold abundant, fold graphene coated layer has elasticity, it can be compressed, can effectively buffer the volume expansion of silicon.Graphene quantum dot clad and silicon particle contact area are bigger, can carry out charge and discharge faster, consume energy low, and easy to control, synthesis step is simple, and the requirement to equipment is lower, are suitable for industry or laboratory operation.
Description
Technical field
The present invention relates to electrode material preparation field more particularly to a kind of silicon particle/graphene quantum dot core-shell structures
Preparation method.
Background technique
Reserves of the silicon in the earth's crust are very rich, are only second to oxygen.Silicon has high volume and capacity ratio and specific discharge capacity, high
Removal lithium embedded current potential can effectively avoid the precipitation of lithium during high rate charge-discharge, can be improved the safety of battery, will not
Solvent occurs with electrolyte to be embedded in altogether, and then wider to the scope of application of electrolyte, therefore, silicon is considered most potential new
Generation cathode material for high capacity lithium ion battery.There are serious volume expansion (~300%), silicon electricity in charge and discharge process for silicon
Pole material is understood dusting in charge and discharge process and is peeled off from collector, active material and active material, active material and afflux
Lose electrical contact between body, while constantly forming new solid-phase electrolyte layer, eventually lead to the low reversible capacity of silicium cathode material,
The cyclical stability and high rate performance of difference.Huge bulk effect and lower conductivity limit the commercialization of silicium cathode technology
Using.
However, in order to overcome these deficiencies, using Composite technology, " cushioning frame " compensating material is utilized to expand.Carbon anode
Volume change is small in material charge and discharge process, has good stable circulation performance and excellent electric conductivity, and Carbon anode material
Material is the mixed conductor of ion and electronics in itself；In addition, silicon is close with carbon geochemistry property, the two can combine closely, and therefore, carbon exists
Therefore it is often used to carry out with silicon compound.Hud typed silicon/carbon composite is uniformly to coat using silicon particle as core in core outer surface
One layer of carbon-coating.The presence of carbon-coating not only contributes to increase the conductivity of silicon, buffers partial volume effect of silicon during removal lithium embedded
It answers, silicon face can also be reduced to greatest extent and contacted with the direct of electrolyte, and then alleviate electrolyte decomposition, be remarkably improved silicon
The cyclical stability and reversible capacity of sill.Zhang etc. coats polypropylene on nano silicon particles surface using emulsion polymerization
Nitrile obtains silicon-carbon composite material of core-shell structure through 800 DEG C of heat treatments.Amorphous carbon layer inhibits silicon particle in charge and discharge process
Reunite, core-shell structure capacity after circulation 20 times maintains 50% or so of initial capacity.However, when in silicon-carbon core-shell structure
When being coated on silicon particle surface to carbon-coating tight, since the bulk effect of silicon core lithiumation process is too big, entire nucleocapsid will lead to
Particle expansion even results in carbon layer on surface and ruptures, and composite structure collapses, and cyclical stability declines rapidly.To solve
This problem, researcher start with from shell mechanical properties are strengthened, and have devised double shell structurres.Cui Yi etc. is outside Si particle
One layer of SiO is prepared first2, then coated with carbon material, it is prepared for Si/SiO from inside to outside2/ C composite construction, utilizes salt
Sour eating away middle layer SiO2, hollow core-shell structure is formed, the volume expansion of silicon is effectively relieved in this space being available； Wei
Zhai etc. has wrapped up silico-aluminum using graphene oxide, forms Si-Al/C core-shell structure, falls aluminium using hcl corrosion, in
Between form Porous Silicon structures, the volume expansion of silicon can also be effectively relieved in the space being available.But prepare the side of hollow structure
Method step is complicated, needs accurately to control and the consuming time is more, the part eroded forms waste, is badly in need of a kind of more simple
Effective method solves the bulk effect of silicon.
Summary of the invention
Propose a kind of preparation method of silicon particle/graphene quantum dot core-shell structure.Graphene quantum dot is tied in the form of sheets
Structure, the overlapping protuberance at slight distortion and edge can form fold in additive process, and fold graphene coated layer has bullet
Property, it can be compressed, can effectively buffer the volume expansion of silicon, save the design of hollow layer, and compared with hollow core-shell structure,
Graphene coated layer and silicon particle contact area are bigger, can carry out charge and discharge faster.In addition, the graphene with tens microns
The size of difference, graphene quantum dot is less than 100nm, is more prone to form the core-shell structure of cladding, rather than silicon particle is equal
It is even to be dispersed in graphene film layer surface.
The present invention adopts the following technical scheme:
A kind of preparation method of silicon particle/graphene quantum dot core-shell structure, includes the following steps:
(1) the small lamella that silicon particle is added to graphene oxide quantum dot/be closely sized to graphene quantum dot is aoxidized into stone
In black alkene solution, after ultrasonic disperse is uniform, continues stir process, obtain silicon particle/graphene oxide core-shell structure；
(2) by silicon particle/graphene oxide core-shell structure naturally dry, residual solvent is removed in heating, forms silicon particle/pleat
Graphene oxide structure of wrinkling obtains silicon particle/graphene amount using hydroiodic acid solution reduction graphene oxide after being cleaned with ethyl alcohol
Son point core-shell structure.
The small lamella of silicon particle in step (1) and graphene oxide quantum dot/be closely sized to graphene quantum dot aoxidizes
The mass ratio of graphene is 0.1-10.
For graphene quantum spot size in step (1) in 40-100nm, edge and surface modification have oxygen-containing group, lead to
The graphite nanoparticles size that control is used to prepare graphene quantum dot is crossed, and to the graphene quantum dot solution being prepared
Regulate and control pH centrifugal treating, gets rid of undersized graphene quantum dot in solution.
The small lamella graphene size for being closely sized to graphene quantum dot in step (1) is in 100-200nm.
The ultrasonic disperse time in step (1) is 0.5-2h, and the stir process time is 1-12h.
Heating temperature in step (2) is 70 DEG C, continues 4-12h.
Hydroiodic acid solution concentration in step (2) is 10-30%, recovery time 0.5-6h.
The present invention has the advantage that
(1) the method for the invention selects graphene quantum dot and small size graphene more can readily wrap silicon
Particle, overlapping and the slight distortion of lamella and protuberance on a large amount of boundaries can form fold abundant, fold graphene coated layer tool
It is flexible, it can be compressed, can effectively buffer the volume expansion of silicon.
(2) of the present invention compared with silicon particle in hollow core-shell structure only partially contacts the carbon-coating of its periphery package
Graphene quantum dot clad and silicon particle contact area are bigger in method, can carry out charge and discharge faster.
(3) the method for the invention energy consumption is low, and easy to control, synthesis step is simple, and the requirement to equipment is lower, is suitable for industry
Or laboratory operation, hollow etching method step complexity is overcome, more, heavy-polluted disadvantage is expended.
Detailed description of the invention
Fig. 1 is 1 graphene quantum dot structural schematic diagram of embodiment of the present invention method.
Fig. 2 is that embodiment of the present invention method 1 prepares silicon particle/graphene quantum dot transmission electron microscope picture.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for helping to understand the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
(1) 0.1g silicon nanoparticle is added in the aqueous solution containing 0.1g graphene oxide quantum dot, ultrasonic disperse
1h。
(2) stir process 2h.
(3) powder, naturally dry are taken out after solution centrifugal treating.
(4) powder is heated at a temperature of 70 DEG C, continues 4h.
(5) powder is put into hydroiodic acid solution and restores 1h, silicon particle/graphene quantum dot core is obtained after being cleaned with ethyl alcohol
Shell structure.
Embodiment 2
(1) 0.1g silicon nanoparticle is added in the aqueous solution containing 0.2g graphene oxide quantum dot, ultrasonic disperse
1h。
(2) stir process 2h.
(3) powder, naturally dry are taken out after solution centrifugal treating.
(4) powder is heated at a temperature of 70 DEG C, continues 4h.
(5) powder is put into hydroiodic acid solution and restores 1h, silicon particle/graphene quantum dot core is obtained after being cleaned with ethyl alcohol
Shell structure.
Embodiment 3
(1) 0.1g silicon nanoparticle is added in the aqueous solution containing 0.1g graphene oxide quantum dot, ultrasonic disperse
0.5h。
(2) stir process 4h.
(3) powder, naturally dry are taken out after solution centrifugal treating.
(4) powder is heated at a temperature of 70 DEG C, continues 4h.
(5) powder is put into hydroiodic acid solution and restores 1h, silicon particle/graphene quantum dot core is obtained after being cleaned with ethyl alcohol
Shell structure.
Embodiment 4
(1) 0.1g silicon nanoparticle is added in the aqueous solution containing 0.1g graphene oxide quantum dot, ultrasonic disperse
1h。
(2) stir process 2h.
(3) powder, naturally dry are taken out after solution centrifugal treating.
(4) powder is heated at a temperature of 70 DEG C, continues 4h.
(5) powder is put into reductase 12 h in hydroiodic acid solution, silicon particle/graphene quantum dot core is obtained after being cleaned with ethyl alcohol
Shell structure.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (7)
1. a kind of silicon particle/graphene quantum dot core-shell structure preparation method, includes the following steps:
(1) silicon particle is added to the small lamella graphene oxide of graphene oxide quantum dot/be closely sized to graphene quantum dot
In solution, after ultrasonic disperse is uniform, continues stir process, obtain silicon particle/graphene oxide core-shell structure；
(2) by silicon particle/graphene oxide core-shell structure naturally dry, residual solvent is removed in heating, forms silicon particle/fold oxygen
Graphite alkene structure obtains silicon particle/graphene quantum dot using hydroiodic acid solution reduction graphene oxide after being cleaned with ethyl alcohol
Core-shell structure.
2. preparation method according to claim 1, which is characterized in that silicon particle and graphene oxide amount in step (1)
The mass ratio of the small lamella graphene oxide of sub- point/be closely sized to graphene quantum dot is 0.1-10.
3. preparation method according to claim 1, which is characterized in that the graphene quantum spot size in step (1) is in 40-
In 100nm, edge and surface modification have oxygen-containing group, and the graphite nanoparticles of graphene quantum dot are used to prepare by controlling
Size, and pH centrifugal treating is regulated and controled to the graphene quantum dot solution being prepared, get rid of undersized stone in solution
Black alkene quantum dot.
4. preparation method according to claim 1, which is characterized in that be closely sized to graphene quantum dot in step (1)
Small lamella graphene size in 100-200nm.
5. preparation method according to claim 1, which is characterized in that the ultrasonic disperse time in step (1) is 0.5-2h,
The stir process time is 1-12h.
6. preparation method according to claim 1, which is characterized in that the heating temperature in step (2) is 70 DEG C, continues 4-
12h。
7. preparation method according to claim 1, which is characterized in that the hydroiodic acid solution concentration in step (2) is 10-
30%, recovery time 0.5-6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811194662.1A CN109309221A (en) | 2018-09-29 | 2018-09-29 | A kind of preparation method of silicon particle/graphene quantum dot core-shell structure |
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| CN201811194662.1A CN109309221A (en) | 2018-09-29 | 2018-09-29 | A kind of preparation method of silicon particle/graphene quantum dot core-shell structure |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110085852A (en) * | 2019-05-28 | 2019-08-02 | 中国科学院重庆绿色智能技术研究院 | Conductive structure and electrode |
| CN111435736A (en) * | 2019-12-31 | 2020-07-21 | 蜂巢能源科技有限公司 | Silicon-carbon negative electrode material, preparation method and lithium ion battery |
| CN113415804A (en) * | 2021-07-29 | 2021-09-21 | 厦门海辰新能源科技有限公司 | Carbon-silicon three-dimensional structure composite material and preparation method thereof |
-
2018
- 2018-09-29 CN CN201811194662.1A patent/CN109309221A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110085852A (en) * | 2019-05-28 | 2019-08-02 | 中国科学院重庆绿色智能技术研究院 | Conductive structure and electrode |
| CN111435736A (en) * | 2019-12-31 | 2020-07-21 | 蜂巢能源科技有限公司 | Silicon-carbon negative electrode material, preparation method and lithium ion battery |
| CN111435736B (en) * | 2019-12-31 | 2022-05-27 | 蜂巢能源科技有限公司 | Silicon-carbon negative electrode material, preparation method and lithium ion battery |
| CN113415804A (en) * | 2021-07-29 | 2021-09-21 | 厦门海辰新能源科技有限公司 | Carbon-silicon three-dimensional structure composite material and preparation method thereof |
| US11817574B2 (en) | 2021-07-29 | 2023-11-14 | Xiamen Hithium Energy Storage Technology Co., Ltd. | Carbon-silicon three-dimensional structural composite material and preparation method thereof |
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