CN108270014B - Method for preparing silicon dioxide/graphene composite material by supercritical carbon dioxide fluid and application - Google Patents
Method for preparing silicon dioxide/graphene composite material by supercritical carbon dioxide fluid and application Download PDFInfo
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- CN108270014B CN108270014B CN201711498132.1A CN201711498132A CN108270014B CN 108270014 B CN108270014 B CN 108270014B CN 201711498132 A CN201711498132 A CN 201711498132A CN 108270014 B CN108270014 B CN 108270014B
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- 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
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H—ELECTRICITY
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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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- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- 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
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Abstract
The invention relates to a method for preparing a silicon dioxide/graphene composite material by using supercritical carbon dioxide fluid, which comprises the following steps: (1) preparing graphene oxide from flake graphite by a Hummers method, and freeze-drying the graphene oxide for later use; (2) mixing tetraethoxysilane and graphene oxide, putting the mixture into a high-pressure ball milling tank, vacuumizing, and adding CO2Pumping into a high-pressure ball milling tank, and reacting for 0.5-48h under the conditions that the pressure is 60-150bar, the temperature is 20-70 ℃ and the rotating speed is 100-700 r/min; (3) after the reaction is finished, releasing CO in the high-pressure ball milling tank2And (3) taking the reaction liquid out of the ball milling tank, placing the reaction liquid in a polytetrafluoroethylene hydrothermal kettle, and reacting for 6-60 hours at the temperature of 100-200 ℃. (4) And heating the product to 400-1000 ℃ under the protection of nitrogen or argon, carbonizing for 0.5-12h, cooling and grinding. The product prepared by the invention has good batch property, small silicon dioxide particles, uniform distribution and strong lithium ion transmission capability, and has wide application in the fields of lithium ion batteries and the like.
Description
Technical Field
The invention relates to a method for preparing a silicon dioxide/graphene composite material and application thereof, in particular to a silicon dioxide/graphene composite material prepared by supercritical carbon dioxide fluid and application thereof as a lithium metal negative electrode carrier material and a lithium sulfur battery.
Background
In G20 hamburger meeting in 2017, sale prohibition dates of fuel vehicles are established in many countries, and a new chapter in the new energy automobile era is opened. However, the specific energy of the lithium ion secondary battery currently commercialized is too low to satisfy the power requirement of the electric vehicle. In a new secondary battery system, the theoretical specific energy of a lithium-sulfur battery taking metal lithium as a negative electrode and elemental sulfur as a positive electrode can reach 2600Wh/kg, the theoretical specific capacity of sulfur reaches 1675mAh/g, which is far greater than that of a commercial lithium ion secondary battery, and the sulfur has the characteristics of rich source, low price, low toxicity and the like, so that the system has high commercial value. However, lithium metal forms lithium dendrites during charging and discharging, which can greatly reduce the cycle life of the battery and even puncture the separator to cause safety hazards. Therefore, in order to improve the safety and cycle life of the lithium negative electrode, the problem of lithium dendrites is urgently needed to be solved. The most reported solution to lithium dendrites is to construct a porous support material to support the lithium metal. For example, JieZhao et al, which uses a metallic lithium alloying process, and then slurry-coats a mixture of lithium alloy, graphene and SBS, etc., have resulted in an atmospheric stable lithium negative electrode composite material with high cycle stability (Air-stable free standing lithium alloy/graphene film anode synthesis, nature nanotechnology, 2017, 12, 993-999). However, the above materials merely retard the growth of lithium dendrites and still do not solve the problem of lithium dendrites.
The invention uses supercritical CO2The fluid is a solvent and a reaction medium, the characteristics of strong penetration, good diffusivity and strong solvation capacity are fully exerted, and the novel nano-state silicon dioxide/graphene composite material is synthesized. Compared with other synthesis methods, the silicon dioxide synthesized by the supercritical method is in the size of quantum dots, the silicon dioxide/graphene composite material is used as a carrier of metal lithium, and the lithium cathode based on the silicon dioxide/graphene composite material is prepared. Meanwhile, the composite material has the advantages of strong conductivity, high safety, good battery cycle stability and the like, and the preparation process is simple.
Disclosure of Invention
The invention aims to provide a novel method for preparing a silicon dioxide/graphene composite material in a supercritical manner, which has the characteristics of simple process, environmental friendliness, easiness in industrial implementation and the like.
The second purpose of the invention is to apply the silicon dioxide/graphene composite material as a carrier material to a lithium metal negative electrode.
The third purpose of the invention is to provide a lithium-sulfur battery using the silicon dioxide/graphene composite material as a lithium metal negative electrode.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a method for utilizing supercritical CO2Novel method for preparing silicon dioxide/graphene composite material by using fluid as solvent and reaction medium and exerting supercritical CO2The silicon source is uniformly diffused into the graphene, the silicon dioxide/graphene composite material is obtained through hydrothermal treatment, and the obtained silicon dioxide particles are fine and are uniformly distributed on the surface of the graphene. Specifically, the preparation method of the silicon dioxide/graphene composite material comprises the following steps:
s1, preparing graphene oxide by using flake graphite as a raw material through a Hummers method, and freeze-drying the graphene oxide for later use;
s2, mixing the ethyl orthosilicate solution with the graphene oxide, filling the mixture and grinding balls into a high-pressure ball-milling tank according to the mass ratio of 1 to (10-80), vacuumizing the high-pressure ball-milling tank, and then, adding CO into the high-pressure ball-milling tank2Pumping into a high-pressure ball milling tank, and ball milling for 0.5-48h at the pressure of 60-150bar and the ball milling rotation speed of 100-700r/min at the temperature of 20-70 ℃;
s3, cooling to room temperature after the reaction is finished, and discharging CO in the high-pressure ball milling tank2And gas, taking the reaction liquid out of the ball milling tank, placing the reaction liquid in a hydrothermal kettle, and reacting for 6-60h at the temperature of 100-200 ℃. Putting the obtained product into 0.1M dilute hydrochloric acid solution, soaking for 3-48h, then carrying out suction filtration and drying;
s4, raising the temperature of the product obtained in the step S3 to 400-1000 ℃ at the heating rate of 1-20 ℃/min under the protection of nitrogen or argon, carbonizing the product, keeping the temperature for 0.5-12h, cooling the carbonized product, and grinding the carbonized product to obtain the silicon dioxide/graphene composite material.
In the invention, the purities of the crystalline flake graphite and the tetraethoxysilane are not lower than chemical purity.
In the step S2, the mass fraction of graphite oxide is preferably 15 to 45%, and most preferably 40%; the mass ratio of the mixture to the grinding balls is 1: 40-80, and more preferably 1: 40-60; the reaction conditions in the high-pressure ball milling tank are preferably: the pressure is 75-100bar, the temperature is 30-50 ℃, the ball milling rotation speed is 300-400r/min, and the reaction time is 12-16 h.
In the step S3, the hydrothermal condition is preferably 130-180 ℃, the optimal condition is 150 ℃, the hydrothermal time is preferably 12-24h, and the optimal time is 24 h. The soaking time in dilute hydrochloric acid is preferably 12-16 h.
In the step S3, the heating rate is preferably 5-10 ℃/min, and most preferably 5 ℃/min; the carbonization temperature is preferably 400-800 ℃, more preferably 450-550 ℃, and most preferably 450 ℃; the carbonization time is preferably 1 to 5 hours, preferably 2 to 4 hours, most preferably 4 hours.
The invention also provides application of the silicon dioxide/graphene composite material as a lithium metal battery carrier material, wherein lithium metal is assembled into a half battery to be compounded with the silicon dioxide/graphene composite material in an electrodeposition mode.
Finally, the invention provides a lithium-sulfur battery using the silicon dioxide/graphene/lithium composite material as a negative electrode material.
The invention has the beneficial effects that:
(1) according to the invention, supercritical carbon dioxide fluid is used as a medium, so that silicon dioxide and graphene are uniformly combined in a quantum dot form to generate the silicon dioxide/graphene composite material, and the prepared nano composite material has good batch property and small oxide particles and can be uniformly distributed among graphene lamella.
(2) The prepared nano composite material can be used as an excellent lithium metal carrier material. The unit volume current density can be reduced in the repeated electrodeposition process of the lithium metal, and lithium dendrite is prevented from being generated.
(3) The silicon dioxide/graphene composite material can disperse and isolate metal lithium, has a flame retardant effect, and greatly improves the safety performance of the battery.
(4) The supercritical preparation method adopted by the invention has the advantages of simple process, controllability and easy industrial implementation.
Drawings
Fig. 1 is an X-ray diffraction (XRD) diffractogram of the silica/graphene composite prepared in example 1;
fig. 2 is a Scanning Electron Microscope (SEM) image of the silica/graphene composite prepared in example 1;
fig. 3 is a graph of coulombic efficiency for a simulated lithium metal negative half cell prepared in example 1.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples in conjunction with the accompanying drawings.
Example 1:
graphene oxide was prepared by Hummers for use. Mixing 2ml of ethyl orthosilicate solution, 0.5ml of ammonia water, 40ml of absolute ethyl alcohol and 0.3g of graphene oxide, putting the mixture and grinding balls into a high-pressure ball milling tank according to the mass ratio of 1: 40, pumping CO into the high-pressure ball milling tank, and pumping CO into the high-pressure ball milling tank2The internal pressure of the high-pressure ball milling tank reaches 80bar, and the reaction is carried out for 12 hours at the temperature of 35 ℃ and the ball milling rotating speed of 350 r/min; transferring the product into a hydrothermal kettle, filling deionized water, carrying out hydrothermal reaction at 150 ℃ for 24 hours, soaking the product in 0.1M dilute hydrochloric acid solution for 12 hours, carrying out suction filtration, and drying. And finally, under the protection of argon, raising the temperature of the dried product to 500 ℃ at the heating rate of 5 ℃/min for carbonization, preserving the temperature for 4 hours, cooling after carbonization, and grinding to obtain the silicon dioxide/graphene composite material.
An electrode was fabricated using the silica/graphene composite material prepared in example 1 as follows.
Weighing the silicon dioxide/graphene composite material according to the mass ratio of 80: 10: super-P: grinding polyvinylidene fluoride uniformly to obtain electrode, using metal lithium sheet as counter electrode and electrolyte as 1mol/LLIN (CF)3SO2)2the/DOL-DME (1: 1) and the polypropylene microporous film are taken as a diaphragm to assemble a simulated lithium metal half cell. FIG. 3 shows the corresponding cell at 1.0mAcm-2The coulomb efficiency of the battery measured by constant capacity charging and discharging under current density is close to 96 percent, which shows that almost no lithium dendrite is generated in the charging and discharging process.
Example 2:
weighing the silicon dioxide/graphene composite material according to the mass ratio of 80: 10: super-P: grinding polyvinylidene fluoride uniformly, coating the ground polyvinylidene fluoride on a copper sheet to prepare an electrode, taking a metal lithium sheet as a counter electrode, and taking electrolyte as 1mol/LLIN (CF)3SO2)2the/DOL-DME (1: 1) and the polypropylene microporous film are taken as a diaphragm to assemble a simulated lithium metal battery half cell. At 1.0mAcm-2And (3) constant-capacity charge and discharge cycles under current density, so that the metal lithium is electrodeposited on the silicon dioxide/graphene composite carrier. And disassembling the battery and taking out the lithium negative plate for later use. Then weighing pure sulfur powder, Super-P and polyvinylidene fluoride according to the mass ratio of 80: 10 respectively, grinding uniformly and coating on an aluminum sheet to prepare a positive plate for later use. The above negative electrode, positive electrode and electrolyte are 1mol/LLIN (CF)3SO2)2the/DOL-DME (1: 1) and the polypropylene microporous film are membranes which are assembled into a simulated lithium-sulfur battery full cell, the discharge capacity is close to 500mAhg < -1 > after 100 cycles in the voltage range of 1.6-2.8V under the current density of 0.2Ag < -1 >, and the cycle performance is excellent. Under the condition of 2Ag-1 heavy current discharge, the discharge capacity can reach 400 mAhg-1.
Example 3:
a silica/graphene/lithium composite anode material was prepared according to the method in examples 1 and 2, and was ready for use. Then LiFePO4, super-P and polyvinylidene fluoride are respectively weighed according to the mass ratio of 80: 10, and are coated on an aluminum sheet after being uniformly ground to prepare a positive plate for later use. The cathode, the anode, the electrolyte of 1mol/LLIN (CF3SO2)2/DOL-DME (1: 1) and the polypropylene microporous film as the diaphragm are assembled into the simulated Li-LiFePO4 full cell.
Example 4:
a silica/graphene/lithium composite anode material was prepared according to the method in examples 1 and 2, and was ready for use. Then weighing V2O5, super-P and polyvinylidene fluoride according to the mass ratio of 80: 10 respectively, grinding uniformly and coating on an aluminum sheet to prepare a positive plate for later use. The cathode plate, the anode plate, the electrolyte of 1mol/LLIN (CF3SO2)2/DOL-DME (1: 1) and the polypropylene microporous film as the diaphragm are assembled into the simulated Li-V2O5 battery full cell.
The coulombic efficiencies of the assembled lithium batteries of examples 3-4 were 96% and 98%, respectively, indicating that almost no lithium dendrites were generated during the charge and discharge processes.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (7)
1. A method for preparing a silicon dioxide/graphene composite material by using supercritical carbon dioxide fluid is characterized by comprising the following steps:
s1, preparing graphene oxide from the flake graphite by a Hummers method, and freeze-drying the graphene oxide for later use;
s2, mixing tetraethoxysilane and graphite oxide, putting the mixture and grinding balls into a high-pressure ball-milling tank according to a certain proportion, vacuumizing the high-pressure ball-milling tank, and then adding CO2Pumping into a high-pressure ball-milling tank for ball milling for a certain time, wherein the purity of the ethyl orthosilicate is not lower than that of chemical purity, the mass ratio of the ethyl orthosilicate to the graphene oxide is (0.1-5) to 1, and the mass ratio of the mixture to the grinding balls is 1 to (10-80);
s3, cooling to room temperature after the reaction is finished, and discharging CO in the high-pressure ball milling tank2Taking out the liquid from the ball milling tank, placing the liquid in a polytetrafluoroethylene hydrothermal kettle, adding deionized water, reacting for 6-60h at the temperature of 100-200 ℃, placing the obtained product in 0.1mol/L dilute hydrochloric acid solution for soaking for 3-48h, then carrying out suction filtration and drying;
s4, raising the temperature of the product obtained in the step S3 to 400-;
the purity of the flake graphite in the step S1 is not lower than chemical purity;
in the step S2, the mass ratio of the mixture to the grinding balls is 1: 40-60.
2. The method for preparing the silica/graphene composite material by using the supercritical carbon dioxide fluid as claimed in claim 1, wherein the supercritical carbon dioxide fluid comprises the following steps: in the step S2, the reaction conditions in the high-pressure ball milling tank are as follows: the pressure is 60-150bar, the temperature is 21-70 ℃, the ball milling speed is 100-700r/min, and the ball milling time is 0.5-48 h.
3. The method for preparing the silica/graphene composite material by using the supercritical carbon dioxide fluid as claimed in claim 1, wherein the supercritical carbon dioxide fluid comprises the following steps: in the step S3, the hydrothermal temperature is 130-180 ℃, the hydrothermal time is 12-24h, and the soaking is carried out in dilute hydrochloric acid for 12-16 h.
4. The method for preparing the silica/graphene composite material by using the supercritical carbon dioxide fluid as claimed in claim 3, wherein the supercritical carbon dioxide fluid comprises the following steps: in the step S3, the hydrothermal temperature is 150 ℃ and the hydrothermal time is 24 h.
5. The method for preparing the silica/graphene composite material by using the supercritical carbon dioxide fluid as claimed in claim 1, wherein the supercritical carbon dioxide fluid comprises the following steps: in the step S4, the temperature rise rate is 5-10 ℃/min, the carbonization temperature is 400-800 ℃, and the carbonization time is 1-5 hours.
6. The method for preparing the silica/graphene composite material by using the supercritical carbon dioxide fluid as claimed in claim 5, wherein the supercritical carbon dioxide fluid comprises the following steps: in the step S4, the temperature rise rate is 5 ℃/min, the carbonization temperature is 450 ℃, and the carbonization time is 4 hours.
7. Use of the silica/graphene composite material prepared by the method according to any one of claims 1 to 6 as a support material for lithium metal batteries.
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| 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 |
| 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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| 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 |
| 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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