CN110518195A - A kind of preparation method and application of nano-silicon/graphene composite material - Google Patents
A kind of preparation method and application of nano-silicon/graphene composite material Download PDFInfo
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- CN110518195A CN110518195A CN201910593711.7A CN201910593711A CN110518195A CN 110518195 A CN110518195 A CN 110518195A CN 201910593711 A CN201910593711 A CN 201910593711A CN 110518195 A CN110518195 A CN 110518195A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of new methods of nano-silicon/graphene composite material: first obtaining silica/graphene composite material, under vacuum or protective atmosphere, composite material and metal hydride is ground uniformly, and mixture is transferred to closed reactor；Reactor is heated to 350~800 DEG C with the heating rate of 0.2~20 DEG C/min, and keeps the temperature 0.5~20h.It is cooled to room temperature after reaction to above-mentioned, takes out the product in reactor, successively impregnate 3h, 10% hydrofluoric acid dips half an hour, deionized water and ethanol wash three times through 1M dilute hydrochloric acid.Then it filters, vacuum drying obtains nano-silicon/graphene composite material under the conditions of 80 DEG C.The features such as present invention has preparation process simple, environmentally friendly, is easy to industrializing implementation.Obtained product morphology keeps good, as lithium ion battery negative material electrochemical performance, in 0.2Ag‑1Discharge capacity after recycling 100 times under current density is close to 1000mAh/g.
Description
Technical field
Nano-silicon/graphene is prepared using metal hydride direct-reduction silica/graphene the present invention relates to a kind of
The method of composite material.
Background technique
Electric car is one of the research hotspot of current science and technology and industrial circle, and the key of electric vehicle engineering is to develop height
The power lithium-ion battery of new generation of performance, currently, be applied to lithium-ion-power cell negative electrode material be still graphite, it is soft
Carbon, hard carbon etc., the theoretical specific capacity of graphite cathode about 372mAh/g are not able to satisfy lasting high current required by power battery and put
Electric energy power and course continuation mileage.Therefore, the silicon materials with superelevation theoretical specific capacity (4200mAh/g) are favored, but silicon is negative
Pole there is also lithium ionic mobility it is low and be recycled in Volumetric expansion it is big, limit its commercial applications.Graphene tool
Conductive height, fast (the about 5000cm of carrier mobility rate2V-1s-1) and the series of advantages such as large specific surface area, as one kind
Good carrier material is widely used in various fields.
2012, Xin etc. reported A 3D porous architecture of Si/graphene
nanocompositeas high-performance anode materials for Li-ion batteries(Journal
Of Materials Chemistry, 2012,22:7724-7730), three-dimensional porous silicon/graphene framework is synthesized by design,
Nano-silicon is firmly riveted in graphene sheet layer, good structural stability is shown in charge and discharge process, while three-dimensional
Graphene network structure also enhances the electric conductivity of composite material.In previous research, mostly use the method for magnesiothermic reduction will greatly
Reducing silica is silicon to construct silicon/graphene composite material, but this method reaction temperature is high (650 DEG C of >), and reacts
It is highly exothermic in journey to cause reaction temperature uncontrollable, it is larger to the destruction of silica/graphene pattern, while high temperature will lead to
Graphene degree of graphitization becomes larger.The present invention, which provides, a kind of to be reduced directly silica using metal hydride and constructs nanometer
Ghost/graphene composite material new method not only has the characteristics that reaction condition is mild, controllable, and advantage more outstanding is gained
To composite material can preferably keep originally silica/graphene pattern and structure, show excellent electrochemistry storage
Lithium performance has the potentiality of large-scale commercial.
Summary of the invention
It is prepared the first purpose of the invention is to provide a kind of using metal hydride direct-reduction silica/graphene
Nano-silicon/graphene composite material method, this method have reaction condition mild, simple process, pattern and micro-structure it is controllable,
It is environmentally friendly, the features such as being easy to industrializing implementation.
Second purpose of the invention is to provide the nano-silicon/graphene composite material as lithium ion battery negative material
Application.
Technical solution of the present invention is specifically described below:
The present invention provide it is a kind of using metal hydride direct-reduction silica/graphene prepare nano-silicon/graphene
The method of composite material.During magnesium reduction process prepares nano-silicon/graphene composite material, since reaction temperature is uncontrollable
It will lead to silica/graphene template to be destroyed, obtained composite material pattern is uneven, consistency is poor.The present invention
Innovative point be that using metal hydride as reducing agent, reaction condition is mild, simple process, available pattern and micro- knot
The controllable composite material of structure.Specifically, the preparation method of the nano-silicon/graphene composite material includes the following steps:
(1) using crystalline flake graphite as raw material, graphite oxide is first made by Hummers method, freeze-drying is spare；By positive silicon
Acetate solution is mixed with the graphite oxide that mass fraction is 25~85%, is in mass ratio 1 by mixture and abrading-ball: (10~
80) it is fitted into smash grinding jar, vacuumizes CO then2It is pumped into smash grinding jar, until internal pressure reaches 60~150bar, In
21~70 DEG C of temperature, rotational speed of ball-mill react 0.5~48h under the conditions of being 100~700r/min；After reaction, it is cooled to room temperature,
Put the CO in smash grinding jar2Liquid is taken out from ball grinder, is placed in water heating kettle, adds a certain amount of deionized water by gas,
Under the conditions of 100~200 DEG C, 6~60h is reacted.Above-mentioned product is placed in 0.1M dilute hydrochloric acid solution and impregnates 3~48h, is then taken out
Filter, drying；By above-mentioned product under nitrogen or argon with the heating rate of 1~20 DEG C/min rise to 400~1000 DEG C into
Row carbonization, soaking time are 0.5~12h, and cooling after carbonization, grinding obtains silica/graphene composite material, spare；
(2) under vacuum or protective atmosphere, a certain proportion of above-mentioned composite material and metal hydride are ground uniformly, and
Mixture is transferred to closed reactor；Reactor is heated to 350~800 DEG C with the heating rate of 0.2~20 DEG C/min,
And keep the temperature 0.5~20h；
(3) it is cooled to room temperature after reaction to above-mentioned, takes out the product in reactor, successively impregnated through 1M dilute hydrochloric acid
3h, 10% hydrofluoric acid dips half an hour, deionized water and ethanol wash three times, filter, and vacuum drying obtains under the conditions of 80 DEG C
Nano-silicon/graphene composite material.
Preferably, in the present invention, the purity of crystalline flake graphite, butyl titanate and metal hydride is pure not less than chemistry.
Preferably, in the step (1), metal hydride can be selected from one of llowing group of materials or any several mixed
It closes: lithium hydride, magnesium hydride, sodium hydride, calcium hydride.
Preferably, in the step (1), silica/graphene composite material preparation process is preferably Chinese invention
Patent CN108258211A the method.
Preferably, in the step (2), the mass ratio of silica/graphene composite material and metal hydride is preferred
It is 1: (1~10), most preferably 1: 1.5.
Preferably, in the step (2), heating rate is preferably 0.5~5 DEG C/min；Heating temperature is preferably 350~
800 DEG C, most preferably 500 DEG C；Soaking time is preferably 1~20 hour, and most preferably 5 hours.
Compared with prior art, the present invention its advantages are mainly reflected in:
(1) silica/graphene system is reduced directly using metal hydride as reducing agent the present invention provides a kind of
The new method of standby nano-silicon/graphene composite material.
(2) method provided by the invention has reaction temperature compared with traditional magnesiothermic reduction method, and process conditions are controllable,
Outstanding advantages of pattern of reaction template can preferably be kept.
(3) nano-silicon/graphene composite material provided by the present invention has specific capacity as lithium ion battery negative material
The characteristics of height, good cycle.
Detailed description of the invention
Fig. 1 is nano-silicon/graphene composite material X-ray diffraction diffraction pattern (XRD) prepared by embodiment 1；
Fig. 2 is nano-silicon/graphene composite material electron scanning micrograph (SEM) prepared by embodiment 1；
Fig. 3 is nano-silicon/graphene composite material cycle performance prepared by embodiment 1.
Specific embodiment
With specific embodiment, technical scheme is described further below, but protection scope of the present invention is unlimited
In this.
Embodiment 1
Silica/graphene composite material is prepared according to Chinese invention patent CN108258211A the method,
It is spare.Under vacuum or protective atmosphere, above-mentioned 1g composite material and 1g magnesium hydride are ground uniformly, and mixture is transferred to close
The reactor closed；Reactor is heated to 500 DEG C with the heating rate of 5 DEG C/min, and keeps the temperature 5h；To it is above-mentioned after reaction,
Be cooled to room temperature, take out reactor in product, successively through 1M dilute hydrochloric acid impregnate 3h, 10% hydrofluoric acid dips half an hour, go from
Sub- water and ethanol wash are three times.Then it filters, vacuum drying obtains silicon/graphene composite material under the conditions of 80 DEG C.Nano-silicon/
Graphene composite material.Fig. 1 is prepared nano-silicon/graphene composite material X-ray diffractogram (XRD), reference standard
Card is monocrystalline silicon.Fig. 2 is prepared nano-silicon/graphene composite material scanning electron microscope (SEM) photograph (SEM).
Electrode is made in nano-silicon/graphene composite material obtained by embodiment 1 as follows.
Nano-silicon/graphene composite material: Super-P is weighed respectively with 80: 10: 10 mass ratio: gathering inclined tetrafluoroethene,
Electrode is made after grinding uniformly, metal lithium sheet is to electrode, and electrolyte is 1mol/L LiPF6/ EC-DMC (1: 1), polypropylene is micro-
Hole film is diaphragm, is assembled into simulation lithium ion battery.Fig. 3 is respective battery in 1A g-1, in 0.01-3.0V voltage range
Cycle performance curve shows surveyed battery in 0.2A g-1Have good cycle performance, capacity retention ratio and close to 99% coulomb
Efficiency, it can be seen that the nano-silicon/graphene composite material being made by embodiment 1 is in 0.2A g-1Electric discharge after circulation 100 times is held
For amount close to 1000mAh/g (Fig. 3), cycle performance is excellent.
Embodiment 2
Silica/graphene composite material is prepared according to Chinese invention patent CN108258211A the method,
It is spare.Under vacuum or protective atmosphere, above-mentioned 1g composite material and 0.8g lithium hydride are ground uniformly, and mixture is transferred to
Closed reactor；Reactor is heated to 550 DEG C with the heating rate of 5 DEG C/min, and keeps the temperature 5h；To the end of above-mentioned reaction
Afterwards, it is cooled to room temperature, takes out the product in reactor, successively impregnate 3h through 1M dilute hydrochloric acid, 10% hydrofluoric acid dips half an hour, go
Ionized water and ethanol wash are three times.Then it filters, vacuum drying obtains nano-silicon/graphene composite material under the conditions of 80 DEG C.
Embodiment 3
Silica/graphene composite material is prepared according to Chinese invention patent CN108258211A the method,
It is spare.Under vacuum or protective atmosphere, a certain proportion of above-mentioned 1g composite material and 2g calcium hydride are ground uniformly, and will mixing
Object is transferred to closed reactor；Reactor is heated to 700 DEG C with the heating rate of 5 DEG C/min, and keeps the temperature 5h；To above-mentioned anti-
It after answering, is cooled to room temperature, takes out the product in reactor, successively impregnate 3h, 10% hydrofluoric acid dips half through 1M dilute hydrochloric acid
Hour, deionized water and ethanol wash are three times.Then it filters, it is multiple to obtain nano-silicon/graphene for vacuum drying under the conditions of 80 DEG C
Condensation material.
Embodiment 4
Silica/graphene composite material is prepared according to Chinese invention patent CN108258211A the method,
It is spare.Under vacuum or protective atmosphere, a certain proportion of above-mentioned 1g composite material and 1.2g sodium hydride are ground uniformly, and will mix
It closes object and is transferred to closed reactor；Reactor is heated to 400 DEG C with the heating rate of 5 DEG C/min, and keeps the temperature 5h；To above-mentioned
After reaction, it is cooled to room temperature, takes out the product in reactor, successively impregnate 3h, 10% hydrofluoric acid dips through 1M dilute hydrochloric acid
Half an hour, deionized water and ethanol wash are three times.Then it filters, vacuum drying obtains nano-silicon/graphene under the conditions of 80 DEG C
Composite material.
Embodiment 5
Silica/graphene composite material is prepared according to Chinese invention patent CN108258211A the method,
It is spare.Under vacuum or protective atmosphere, a certain proportion of above-mentioned 1g composite material and 1.5g hydrofining are ground uniformly, and will mix
It closes object and is transferred to closed reactor；Reactor is heated to 400 DEG C with the heating rate of 5 DEG C/min, and keeps the temperature 5h；To above-mentioned
After reaction, it is cooled to room temperature, takes out the product in reactor, successively impregnate 3h, 10% hydrofluoric acid dips through 1M dilute hydrochloric acid
Half an hour, deionized water and ethanol wash are three times.Then it filters, vacuum drying obtains nano-silicon/graphene under the conditions of 80 DEG C
Composite material.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (7)
1. a kind of preparation method of nano-silicon/graphene composite material, which is characterized in that steps are as follows for the preparation method:
(1) using crystalline flake graphite as raw material, graphite oxide is first made using Hummers method, by teos solution and quality point
Number mixes for 25~85% graphite oxide, is in mass ratio 1 by mixture and abrading-ball: (10~80) are packed into smash grinding jar
In, after vacuumizing, by CO2It is pumped into smash grinding jar to internal pressure and reaches 60~150bar, be in 21~70 DEG C of temperature, revolving speed
0.5~48h is reacted under the conditions of 100~700r/min；After reaction, it is cooled to room temperature, puts the CO in smash grinding jar2Gas
Liquid is taken out from ball grinder, is placed in water heating kettle, adds a certain amount of deionized water by body, under the conditions of 100~200 DEG C, reaction
6~60h；Above-mentioned product is placed in 0.1M dilute hydrochloric acid solution and impregnates 3~48h, then filters, dry；By above-mentioned product in nitrogen
Under gas or argon gas protection 400~1000 DEG C are risen to the heating rate of 1~20 DEG C/min be carbonized, soaking time is 0.5~
12h, cooling after carbonization, grinding obtains silica/graphene composite material, spare；
(2) under vacuum or protective atmosphere, a certain proportion of above-mentioned composite material and metal hydride are ground uniformly, and will mix
It closes object and is transferred to closed reactor；Reactor is heated to 350~800 DEG C with the heating rate of 0.2~20 DEG C/min, and is protected
0.5~20h of temperature；
(3) be cooled to room temperature after reaction to above-mentioned, take out reactor in product, successively through 1M dilute hydrochloric acid impregnate 3h,
10% hydrofluoric acid dips half an hour, deionized water and ethanol wash three times, filter, and vacuum drying obtains nanometer under the conditions of 80 DEG C
Silicon/graphene composite material.
2. the preparation method of nano-silicon/graphene composite material as described in claim 1, it is characterised in that: institute in step (1)
The purity of crystalline flake graphite, butyl titanate and the metal hydride stated is pure not less than chemistry, and metal hydride is selected from llowing group of materials
One of or any several mixing: lithium hydride, magnesium hydride, sodium hydride, calcium hydride.
3. the preparation method of nano-silicon/graphene composite material as described in claim 1, it is characterised in that: the step (1)
In, silica/graphene composite material preparation process is using method disclosed in Chinese invention patent CN108258211A.
4. the preparation method of nano-silicon/graphene composite material as described in claim 1, it is characterised in that: the step (2)
In, the mass ratio of silica/graphene composite material and metal hydride is 1: (1~10).
5. the preparation method of nano-silicon/graphene composite material as claimed in claim 4, it is characterised in that: the step (2)
In, the mass ratio of silica/graphene composite material and metal hydride is 1: 1.5.
6. the preparation method of nano-silicon/graphene composite material as described in claim 1, it is characterised in that: the step (2)
In, heating temperature is 500 DEG C；Soaking time is 5 hours.
7. nano-silicon/graphene composite material that preparation method described in claim 1-6 any one is prepared as lithium from
The application of sub- cell negative electrode material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114079045A (en) * | 2020-08-14 | 2022-02-22 | 昱瓴新能源科技(浙江)有限公司 | Porous silicon/carbon composite material synthesized in situ by taking porous polymer microspheres as template, preparation method and lithium ion battery |
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| CN108258211A (en) * | 2017-12-29 | 2018-07-06 | 浙江工业大学 | A kind of supercritical carbon dioxide fluid prepares method and the application of titanium dioxide/graphene composite material |
| CN108270014A (en) * | 2017-12-29 | 2018-07-10 | 浙江工业大学 | A kind of supercritical carbon dioxide fluid prepares method and the application of silica/graphene composite material |
| CN109081350A (en) * | 2018-09-11 | 2018-12-25 | 浙江工业大学 | A kind of method that watery fusion salt medium prepares nano-silicon |
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| CN106946259A (en) * | 2017-04-17 | 2017-07-14 | 浙江工业大学 | A kind of non-crystalline silicon raw powder's production technology |
| CN108258211A (en) * | 2017-12-29 | 2018-07-06 | 浙江工业大学 | A kind of supercritical carbon dioxide fluid prepares method and the application of titanium dioxide/graphene composite material |
| CN108270014A (en) * | 2017-12-29 | 2018-07-10 | 浙江工业大学 | A kind of supercritical carbon dioxide fluid prepares method and the application of silica/graphene composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114079045A (en) * | 2020-08-14 | 2022-02-22 | 昱瓴新能源科技(浙江)有限公司 | Porous silicon/carbon composite material synthesized in situ by taking porous polymer microspheres as template, preparation method and lithium ion battery |
| CN114079045B (en) * | 2020-08-14 | 2024-03-15 | 上海昱瓴新能源科技有限公司 | Porous silicon/carbon composite material synthesized in situ by taking porous polymer microspheres as templates, preparation method and lithium ion battery |
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