CN108270014A - A kind of supercritical carbon dioxide fluid prepares method and the application of silica/graphene composite material - Google Patents
A kind of supercritical carbon dioxide fluid prepares method and the application of silica/graphene composite material Download PDFInfo
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- CN108270014A CN108270014A CN201711498132.1A CN201711498132A CN108270014A CN 108270014 A CN108270014 A CN 108270014A CN 201711498132 A CN201711498132 A CN 201711498132A CN 108270014 A CN108270014 A CN 108270014A
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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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
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/666—Composites in the form of mixed materials
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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 present invention relates to a kind of methods that supercritical carbon dioxide fluid prepares silica/graphene composite material, include the following steps：(1) crystalline flake graphite is obtained into graphene oxide, and be freeze-dried by Hummers legal systems, it is spare；(2) ethyl orthosilicate with graphene oxide is mixed, entered in smash grinding jar and vacuumized, by CO2Smash grinding jar is pumped into, 0.5~48h is reacted under the conditions of 60~150bar of pressure, 20~70 DEG C of temperature, 100~700r/min of rotating speed；(3) after reaction, the CO in smash grinding jar is put2Reaction solution from ball grinder is taken out, is placed in polytetrafluoroethylene (PTFE) water heating kettle by gas, under the conditions of 100~200 DEG C, reacts 6~60h.(4) above-mentioned product is warming up to 400~1000 DEG C under nitrogen or argon and carries out 0.5~12h of carbonization, cooling, grinding.Product batches produced by the present invention are good, silica dioxide granule is small, be evenly distributed, lithium ion transport ability is strong, had a wide range of applications in fields such as lithium ion batteries.
Description
Technical field
The present invention relates to a kind of method and its application for preparing silica/graphene composite material, more particularly to one
Kind supercritical carbon dioxide fluid prepares silica/graphene composite material and its is used as lithium an- ode carrier material and lithium
The application of sulphur battery.
Background technology
In G20 hamburger summit in 2017, multinational established fuel vehicle prohibits selling the date, opens a new-energy automobile epoch new piece
Chapter.However, commercialized lithium rechargeable battery is too lower than energy at present, it is impossible to meet the power demand of electric vehicle.New
Secondary cell system in, using lithium metal as cathode, elemental sulfur for the lithium-sulfur cell of anode theory than energy up to 2600Wh/
Kg, the theoretical specific capacity of sulphur reach 1675mAh/g, much larger than commercial Li-ion secondary cell, and sulphur have abundance,
The features such as cheap and hypotoxicity, makes the system great commercial value.But lithium metal can form lithium in charge and discharge process
Dendrite, and the cycle life even puncture diaphragm that Li dendrite can substantially reduce battery causes security risk.Therefore, in order to improve lithium
The problem of safety of cathode and cycle life, Li dendrite, is badly in need of solving.The method of the most solution Li dendrite of report is at present
Porous carrier materials are constructed to carry lithium metal.Such as Jie Zhao et al. use lithium metal alloy method, then close lithium
The coating of the mixed pulps such as gold, graphene and SBS has obtained a kind of cathode of lithium composite material stable in an atmosphere, has had higher
Cyclical stability (Air-stable and freestanding lithium alloy/graphene foil as an
Alternative to lithium metal anodes, Nature Nanotechnology, 2017,12,993-999).But
Above-mentioned material has only delayed lithium dendrite growth, still without solving the problems, such as Li dendrite.
The present invention is with supercritical CO2Fluid is solvent and reaction medium, gives full play to that its infiltration is strong, diffusivity is good and solvent
The characteristics of change ability is strong has synthesized a kind of silica/graphene composite material of novel nano state.With other synthetic method phases
Than the silica of supercritical process synthesis is quantum dot size, using silica/graphene composite material as lithium metal
Carrier is prepared for the cathode of lithium based on silica/graphene composite material, which can reduce in lithium electrodeposition process
Unit volume current density effectively prevent the generation of Li dendrite.Meanwhile the composite material is conductive strong, it is safe with
And circulating battery stability it is good the advantages that, and preparation process is simple.
Invention content
First purpose of the present invention is to provide a kind of overcritical new side for preparing silica/graphene composite material
Method, this method have simple for process, environmentally friendly, the features such as being easy to industrializing implementation.
Second purpose of the invention is to be applied to lithium gold using the silica/graphene composite material as carrier material
Belong in cathode.
Third object of the present invention is to provide one kind and is born using the silica/graphene composite material as lithium metal
The lithium-sulfur cell of pole.
It is as follows that the present invention solves the technical solution that its technical problem uses：
Supercritical CO is utilized the present invention provides a kind of2Fluid prepares silica/graphite as solvent and reaction medium
The new method of alkene composite material plays supercritical CO2The advantages such as fluid diffusion is good, permeability is strong, make silicon source uniformly diffuse to
In graphene, silica/graphene composite material is obtained by hydro-thermal process, gained silica dioxide granule is tiny, in graphite
Alkene surface is distributed than more uniform.Specifically, the preparation method of the silica/graphene composite material includes following step
Suddenly：
S1, using crystalline flake graphite as raw material, graphene oxide, freeze-dried back are obtained by Hummers legal systems；
S2, teos solution with graphene oxide is mixed, is 1 in mass ratio by mixture and abrading-ball: (10-80)
It is fitted into smash grinding jar, after smash grinding jar vacuumizes, by CO2Smash grinding jar is pumped into, in pressure 60-150bar,
20-70 DEG C of temperature, rotational speed of ball-mill are ball milling 0.5-48h under the conditions of 100-700r/min；
S3, after reaction, is cooled to room temperature, puts the CO in smash grinding jar2Gas, by reaction solution from ball grinder
It takes out, is placed in water heating kettle, under the conditions of 100-200 DEG C, react 6-60h.Above-mentioned product is placed in 0.1M dilute hydrochloric acid solutions,
3-48h is impregnated, then filters, dry；
S4, 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 0.5-12h, carbonization postcooling, grinding obtain silica/graphene composite material.
In the present invention, crystalline flake graphite, the purity of ethyl orthosilicate are pure not less than chemistry.
In the step S2, the mass fraction of graphite oxide is preferably 15-45%, and most preferably 40%；Mixture and mill
The mass ratio of ball is 1: (40-80), more preferably 1: (40-60)；Reaction condition in smash grinding jar is preferably：Pressure is
75-100bar, temperature are 30-50 DEG C, rotational speed of ball-mill 300-400r/min, reaction time 12-16h.
In the step S3, hydrothermal condition is preferably 130-180 DEG C, and optimal conditions is 150 DEG C, and the hydro-thermal time is preferably
12-24h, optimal time is for 24 hours.Soaking time is preferably 12-16h in dilute hydrochloric acid.
In the step S3, heating rate is preferably 5-10 DEG C/min, most preferably 5 DEG C/min；Carburizing temperature is preferably
400-800 DEG C, more preferably 450-550 DEG C, most preferably 450 DEG C；Carbonization time is preferably 1-5 hours, preferably 2-4 hours,
Most preferably 4 hours.
The present invention also provides the silica/graphene composite material answering as lithium metal battery carrier material
With wherein lithium metal is compound with silica/graphene composite material in the form of electro-deposition by being assembled into half-cell.
Finally, the present invention provides a kind of using the silica/graphene/lithium composite material as negative material
Lithium-sulfur cell.
The beneficial effects of the invention are as follows：
(1) present invention makes silica in the form of quantum dot and graphene using supercritical carbon dioxide fluid as medium
Uniformly combine generation silica/graphene composite material, nanocomposite obtained it is batch it is good, oxide particle is small simultaneously
And it can be uniformly distributed in graphene film interlayer.
(2) nanocomposite made from can be as a kind of fabulous lithium metal carrier material.It is repeatedly electric in lithium metal
Unit volume current density can be reduced in deposition process, prevents Li dendrite from generating.
(3) used by silica/graphene composite material can disperse, isolating metal lithium, play fire retardation, greatly
Improve battery safety greatly.
(4) supercritical preparation process of the present invention has simple for process, controllably, is easy to industrializing implementation.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) diffraction pattern of silica/graphene composite material prepared by embodiment 1；
Fig. 2 is scanning electron microscope (SEM) figure of silica/graphene composite material prepared by embodiment 1；
Fig. 3 is the coulombic efficiency figure of the simulation lithium an- ode half-cell prepared by embodiment 1.
Specific embodiment
Below by specific embodiment, and with reference to attached drawing, technical scheme of the present invention is described in further detail.
Embodiment 1：
Graphene oxide is prepared using Hummers, it is spare.2ml teos solutions, 0.5ml ammonium hydroxide, 40ml is anhydrous
Ethyl alcohol is mixed with the graphene oxide of 0.3g, and mixture and abrading-ball are fitted into for 1: 40 in smash grinding jar in mass ratio, are pumped into
CO2Smash grinding jar internal pressure is made to reach 80bar, reacts 12h under the conditions of 35 DEG C of temperature, rotational speed of ball-mill is 350r/min；
Product is transferred in water heating kettle, fills it up with deionized water, hydro-thermal for 24 hours, then by product is immersed in the dilute salt of 0.1M under the conditions of 150 DEG C
Then 12h in acid solution is filtered, is dried.Finally above-mentioned product is risen under protection of argon gas with the heating rate of 5 DEG C/min
500 DEG C are carbonized, and keep the temperature 4h, and carbonization postcooling, grinding obtain silica/graphene composite material.
Electrode is made as follows with silica/graphene composite material obtained by embodiment 1.
Silica/graphene composite material is weighed with 80: 10: 10 mass ratio respectively：super-P：Gather inclined tetrafluoro second
Electrode is made in alkene after grinding uniformly, metal lithium sheet is to electrode, and electrolyte is 1mol/LLiN (CF3SO2)2/DOL-DME(1∶
1), polypropylene microporous film is diaphragm, is assembled into simulation lithium metal half-cell.Fig. 3 is respective battery in 1.0mA cm-2Electric current is close
The lower constant volume charge and discharge of degree, survey the coulombic efficiency of battery close to 96%, show in charge and discharge process almost without Li dendrite
It generates.
Embodiment 2：
Silica/graphene composite material is weighed respectively with 80: 10: 10 mass ratioes：super-P：Gather inclined tetrafluoroethene,
It is coated on copper sheet after grinding uniformly and electrode is made, metal lithium sheet is to electrode, and electrolyte is 1mol/L LiN (CF3SO2) 2/
DOL-DME (1: 1), polypropylene microporous film are diaphragm, are assembled into simulation lithium metal battery half-cell.In 1.0mA cm-2 electric currents
3 cycles of constant volume charge and discharge, make lithium metal be electrodeposited into silica/graphene composite carrier under density.Dismantle electricity
Lithium cathode sheet is taken out in pond, spare.Then bright sulfur powder: Super-P is weighed with 80: 10: 10 mass ratio respectively: gathers inclined tetrafluoro second
Alkene, it is spare coated in positive plate is made on aluminium flake after grinding uniformly.By above-mentioned cathode, anode, electrolyte is 1mol/L LiN
(CF3SO2) 2/DOL-DME (1: 1), polypropylene microporous film are diaphragm, the simulation full battery of lithium-sulfur cell are assembled into, in 0.2A
Under the current density of g-1 in 1.6-2.8V voltage ranges, discharge capacity is recycled close to 500mA h g-1 after 100 cycles
It has excellent performance.Under 2A g-1 heavy-current discharges, discharge capacity is up to 400mA h g-1.
Embodiment 3：
Silica/graphene/lithium composite negative pole material is prepared according to the method in example 1,2, it is spare.Then with 80:
10: 10 mass ratioes weigh LiFePO respectively4: super-P: gathers inclined tetrafluoroethene, is coated on aluminium flake and is made just after grinding uniformly
Pole piece is spare.By above-mentioned cathode, anode, electrolyte is 1mol/LLiN (CF3SO2)2/ DOL-DME (1: 1), polypropylene microporous is thin
Film is diaphragm, is assembled into simulation Li-LiFePO4The full battery of battery.
Embodiment 4：
Silica/graphene/lithium composite negative pole material is prepared according to the method in example 1,2, it is spare.Then with 80:
10: 10 mass ratio weighs V respectively2O5: super-P: gathers inclined tetrafluoroethene, is coated in after grinding uniformly on aluminium flake and anode is made
Piece is spare.By above-mentioned negative plate, positive plate, electrolyte is 1mol/L LiN (CF3SO2)2/ DOL-DME (1: 1), polypropylene microporous
Film is diaphragm, is assembled into simulation Li-V2O5The full battery of battery.
The coulombic efficiency that the lithium battery of embodiment 3-4 assemblings surveys battery is respectively 96%, 98%, is shown in charge and discharge
It is generated in journey almost without Li dendrite.
Embodiment described above is a kind of preferable scheme of the present invention, and not the present invention is made in any form
Limitation also has other variants and remodeling under the premise of without departing from the technical solution recorded in claim.
Claims (10)
1. a kind of method that supercritical carbon dioxide fluid prepares silica/graphene composite material, which is characterized in that including
Following steps：
S1, crystalline flake graphite is obtained into graphene oxide, and be freeze-dried by Hummers legal systems, it is spare；
S2, ethyl orthosilicate with graphite oxide is mixed, mixture and abrading-ball is fitted by a certain percentage in smash grinding jar, treated
After smash grinding jar vacuumizes, by CO2It is pumped into smash grinding jar ball milling certain time；
S3, after reaction, is cooled to room temperature, puts the CO in smash grinding jar2Liquid from ball grinder is taken out, put by gas
In polytetrafluoroethylene (PTFE) water heating kettle, deionized water is filled it up with, under the conditions of 100-200 DEG C, 6-60h is reacted, above-mentioned product is placed in
3-48h is impregnated in 0.1mol/L dilute hydrochloric acid solutions, then filters, dry；
S4, above-mentioned product is risen into 400-1000 DEG C of progress carbon with the heating rate of 1-20 DEG C/min under nitrogen or argon
Change, soaking time 0.5-12h, carbonization postcooling, grinding obtain silica/graphene composite material.
2. a kind of supercritical carbon dioxide fluid according to claim 1 prepares silica/graphene composite material
Method, it is characterised in that：The purity of the step S1 crystalline flake graphites is pure not less than chemistry.
3. a kind of supercritical carbon dioxide fluid according to claim 1 prepares silica/graphene composite material
Method, it is characterised in that：The purity of ethyl orthosilicate is not less than chemical pure, ethyl orthosilicate and graphite oxide in the step S2
The mass ratio of alkene is (0.1-5): 1, the mass ratio of mixture and abrading-ball is 1: (10-80).
4. a kind of supercritical carbon dioxide fluid according to claim 3 prepares silica/graphene composite material
Method, it is characterised in that：The mass ratio of mixture and abrading-ball is 1 in the step S2: (40-60).
5. a kind of supercritical carbon dioxide fluid according to claim 1 prepares silica/graphene composite material
Method, it is characterised in that：In the step S2, the reaction condition in smash grinding jar is：Pressure is 60-150bar, and temperature is
21-70 DEG C, rotational speed of ball-mill 100-700r/min, Ball-milling Time 0.5-48h.
6. a kind of supercritical carbon dioxide fluid according to claim 1 prepares silica/graphene composite material
Method, it is characterised in that：In the step S3, hydrothermal temperature is 130-180 DEG C, hydro-thermal time 12-24h, is soaked in dilute hydrochloric acid
Steep 12-16h.
7. a kind of supercritical carbon dioxide fluid according to claim 6 prepares silica/graphene composite material
Method, it is characterised in that：In the step S3, hydrothermal temperature for 150 DEG C, the hydro-thermal time for 24 hours.
8. a kind of supercritical carbon dioxide fluid according to claim 1 prepares silica/graphene composite material
Method, it is characterised in that：In the step S4,5-10 DEG C of heating rate/min, carburizing temperature is 400-800 DEG C, carbonization time
1-5 hours.
9. a kind of supercritical carbon dioxide fluid according to claim 8 prepares silica/graphene composite material
Method, it is characterised in that：In the step S4,5 DEG C/min of heating rate, carburizing temperature is 450 DEG C, carbonization time 4 hours.
10. the method as described in claim 1-9 prepares silica/graphene composite material as lithium metal battery carrier material
The application of material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109192991A (en) * | 2018-08-21 | 2019-01-11 | 广州理文能源科技有限公司 | A kind of preparation method of graphene composition metal air cell |
| CN110518195A (en) * | 2019-07-03 | 2019-11-29 | 浙江工业大学 | A kind of preparation method and application of nano-silicon/graphene composite material |
| CN114318432A (en) * | 2022-01-13 | 2022-04-12 | 江苏理工学院 | Graphene quantum dot composite plating solution, preparation method and electroplating process |
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| CN104810526A (en) * | 2015-04-02 | 2015-07-29 | 北京师范大学 | Preparation method and application of graphene based porous carbon supported metallic catalyst |
| CN104860304A (en) * | 2015-05-07 | 2015-08-26 | 中国人民解放军国防科学技术大学 | High specific surface area of silicon oxide hybridized graphene aerogel and production method thereof |
| CN105845908A (en) * | 2016-04-08 | 2016-08-10 | 浙江工业大学 | Preparation method for Si-O-C composite material and application thereof |
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| CN104810526A (en) * | 2015-04-02 | 2015-07-29 | 北京师范大学 | Preparation method and application of graphene based porous carbon supported metallic catalyst |
| CN104860304A (en) * | 2015-05-07 | 2015-08-26 | 中国人民解放军国防科学技术大学 | High specific surface area of silicon oxide hybridized graphene aerogel and production method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109192991A (en) * | 2018-08-21 | 2019-01-11 | 广州理文能源科技有限公司 | A kind of preparation method of graphene composition metal air cell |
| CN109192991B (en) * | 2018-08-21 | 2021-10-15 | 广州理文科技有限公司 | Preparation method of graphene composite metal air battery |
| CN110518195A (en) * | 2019-07-03 | 2019-11-29 | 浙江工业大学 | A kind of preparation method and application of nano-silicon/graphene composite material |
| CN114318432A (en) * | 2022-01-13 | 2022-04-12 | 江苏理工学院 | Graphene quantum dot composite plating solution, preparation method and electroplating process |
| CN114318432B (en) * | 2022-01-13 | 2024-02-02 | 江苏理工学院 | Graphene quantum dot composite plating solution, preparation method and electroplating process |
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