CN111362257B - Fluorinated graphene/sulfur composite material, preparation method thereof and application of fluorinated graphene/sulfur composite material in lithium battery - Google Patents
Fluorinated graphene/sulfur composite material, preparation method thereof and application of fluorinated graphene/sulfur composite material in lithium battery Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion battery materials, and provides a fluorinated graphene/sulfur composite material, a preparation method thereof and application thereof in a lithium battery. The diaphragm prepared by coating the fluorinated graphene/sulfur composite material on the surface of the substrate can generate an SEI film in situ in the charging and discharging process of the assembled lithium battery, and overcomes the defects of insufficient stability and short cycle life of the lithium battery. The process is simple and feasible, convenient to operate and strong in universality.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a fluorinated graphene/sulfur composite material, a preparation method thereof and application thereof to a lithium battery.
Background
Lithium ion batteries have a profound effect on daily life, and have been widely used in digital products such as mobile phones, digital cameras, and portable computers due to their excellent characteristics of high specific energy, good cycle performance, and no pollution, and thus have become a research hotspot in the chemical power supply world in recent years. Commercial lithium ion batteries using carbon cathodes are now substantially close to their theoretical capacity and are difficult to meet the increasingly high application requirements in portable electronic devices, electric vehicles, large-scale energy storage, and the like. The development of advanced energy storage devices with high specific energy density is one of the major challenges facing the new energy field.
In the last 5 years, with the development of research tools and nanotechnology, researchers have made a number of significant advances in the research of lithium batteries based on these technologies. Research shows that during the charge and discharge of lithium ion battery, the electrode material reacts with electrolyte at the interface of solid and liquid phases, the electrolyte is reduced and decomposed to form SEI film with thickness from tens of nanometers to hundreds of nanometers, the components are complex, and the film usually contains Li2CO3、LiF、Li2O, LiOH and ROCO2Li、ROLi、(ROCO2Li)2And various organic components. Through intensive research on lithium batteries, the excellent SEI film is found to improve the performances of the batteries, such as cycle efficiency, reversible capacity and the like. In the SEI film forming process, an unmodified metal lithium surface passivation film can react with electrolyte, so that unevenness of the metal lithium surface is caused, and uneven deposition of lithium and generation of lithium dendrites are accelerated. In addition, in the lithium battery, the SEI film is continuously broken and generated during the cycle, thereby continuously consuming the metallic lithium and the electrolyte, and finally causing the failure of the lithium battery. Therefore, removing the unstable passivation film on the surface of the lithium metal and constructing the stable SEI film are one of effective methods for solving the problems of the lithium metal negative electrode.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a fluorinated graphene/sulfur composite material, a preparation method thereof and application thereof to a lithium battery; the fluorinated graphene/sulfur composite material is coated on at least one side surface of the battery diaphragm, and a layer of compact SEI film can be formed in situ in the charging and discharging processes, so that the stability of the battery is effectively improved.
The purpose of the invention is realized by the following technical scheme:
the fluorinated graphene/sulfur composite material is prepared by taking fluorinated graphene and sulfur as raw materials and utilizing a high-temperature roasting method.
According to the invention, the high-temperature roasting method comprises the following steps: mixing fluorinated graphene and sulfur, and carrying out high-temperature treatment.
According to the invention, the composite material is prepared by the following method:
(a) uniformly mixing fluorinated graphene and sulfur powder;
(b) heating for 5-15 hours at the temperature of 150-.
According to the invention, as the fluorinated graphene and the sulfur powder are both solid, the mixing process in the step (a) can be assisted by mixing modes such as stirring, ball milling or grinding; the mass ratio of the fluorinated graphene to the sulfur powder satisfies the mass percentage content of each component in the composite material.
According to the present invention, the inert atmosphere in step (b) may be a high temperature treatment under an atmosphere of nitrogen, helium, argon, or the like; the high-temperature treatment may be performed in a device capable of performing high-temperature treatment, such as a tube furnace.
According to the present invention, the mass percentages of the fluorinated graphene and the sulfur are not particularly limited, and may be any mass percentage known to those skilled in the art that can prepare a composite material; preferably, the mass percentage of the fluorinated graphene is 10-50 wt%; the mass percentage of the sulfur is 50-90 wt%. Still preferably, the mass percentage of the fluorinated graphene is 15-35 wt%; the mass percentage of the sulfur is 65-85 wt%.
According to the present invention, the selection of the fluorinated graphene is not particularly limited, and it may be any one of fluorinated graphene known to those skilled in the art; illustratively, the preparation of the unsubstituted graphene fluoride can be any preparation method known to those skilled in the art, and for example, the preparation method can be the method disclosed in chinese patent publication No. CN 104860289a or CN 107043103 a.
Preferably, the fluorinated graphene is prepared by the following method:
1) assembling a battery by taking graphite fluoride as an electrode, taking out the pole piece containing the graphite fluoride electrode material after discharging, and carrying out ultrasonic stripping on the pole piece in an organic solvent to obtain graphite fluoride;
alternatively, the first and second electrodes may be,
2) prepared by an electrolytic graphite fluoride method: and (3) taking the graphite fluoride as an electrolytic electrode, assembling into an electrolytic cell, and electrifying for electrolysis to obtain the fluorinated graphene.
Preferably, the fluorinated graphene is prepared by the following method:
dispersing graphite fluoride in an organic solvent by using a mechanical stripping method, shearing at a high speed, ultrasonically stripping, then centrifugally separating, filtering, washing and drying to prepare the graphite fluoride.
Preferably, the method specifically comprises the following steps:
(1) dispersing graphite fluoride in an organic solvent, and heating and refluxing for 3-8 hours at 110-150 ℃;
(2) shearing the mixture obtained in the step (1) at a high speed for 3-8 hours;
(3) and (3) carrying out high-speed centrifugal treatment on the solution obtained in the step (2), collecting the upper layer part, carrying out suction filtration, washing, freezing and drying to obtain the fluorinated graphene.
According to the invention, the organic solvent of step (1) is N-methylpyrrolidone (NMP).
According to the invention, the high-speed shearing revolution number of the step (2) is 11000-15000 r/min.
In the process of preparing the fluorinated graphene/sulfur composite material, the raw material sulfur forms free radicals under the high-temperature condition, the free radicals and fluorine on the fluorinated graphene undergo nucleophilic substitution reaction, and part or all of C-F bonds are changed into C-S bonds.
The invention also provides a battery diaphragm which comprises a substrate layer and the fluorinated graphene/sulfur composite material layer, wherein the fluorinated graphene/sulfur composite material layer is positioned on at least one side surface of the substrate layer.
According to the invention, the thickness of the fluorinated graphene/sulfur composite material layer is 5-100 microns.
According to the present invention, the substrate is a separator commonly used in batteries as a substrate, which is known to those skilled in the art; separators suitable for use in lithium battery systems are preferred as substrates.
In the invention, when the diaphragm coated with the fluorinated graphene/sulfur composite material is used, namely in the charging and discharging processes, an SEI film can be generated on the surface of the diaphragm in situ, so that the defects of insufficient stability and short cycle life of a lithium battery are overcome.
The invention also provides a preparation method of the battery diaphragm, which comprises the following steps:
i) mixing the fluorinated graphene/sulfur composite material with a solvent to prepare slurry;
ii) coating the slurry obtained in the step i) on at least one side surface of the substrate layer, and drying to obtain a fluorinated graphene/sulfur composite material layer, namely, the battery diaphragm is obtained.
According to the present invention, the concentration of the fluorinated graphene/sulfur composite in the slurry is not particularly limited, and it is sufficient to facilitate coating on the surface of the base layer, and preferably, the concentration of the fluorinated graphene/sulfur composite in the slurry is 1 to 5 mg/mL.
The invention also provides a lithium ion battery, which comprises the battery diaphragm.
The invention has the beneficial effects that:
the invention provides a fluorinated graphene/sulfur composite material, a preparation method thereof and application of the fluorinated graphene/sulfur composite material to a lithium battery. The diaphragm prepared by coating the fluorinated graphene/sulfur composite material on the surface of a substrate (such as a diaphragm conventionally selected in the prior art) can generate an SEI film in situ in the charging and discharging process of an assembled lithium battery, and overcomes the defects of insufficient stability and short cycle life of the lithium battery. The process is simple and feasible, convenient to operate and strong in universality.
Drawings
Fig. 1 is an SEM image of the fluorinated graphene/sulfur composite of example 1.
Fig. 2 is an XRD pattern of the fluorinated graphene/sulfur composite of example 1.
Fig. 3 is a Raman plot of the fluorinated graphene/sulfur composite of example 1.
Figure 4 is a graph comparing the cycle performance of the separator of example 1 and a separator of Celgard2320 type.
Detailed Description
[ preparation of fluorinated graphene ]
As described above, the present invention provides an electrochemical preparation method of fluorinated graphene, including:
1) assembling a battery by taking graphite fluoride as an electrode, taking out the pole piece containing the graphite fluoride electrode material after discharging, and carrying out ultrasonic stripping on the pole piece in an organic solvent to obtain graphite fluoride;
alternatively, the first and second electrodes may be,
2) prepared by an electrolytic graphite fluoride method: and (3) taking the graphite fluoride as an electrolytic electrode, assembling into an electrolytic cell, and electrifying for electrolysis to obtain the fluorinated graphene.
According to the invention, the method comprises in particular the following steps:
(1a) assembling a battery by taking graphite fluoride as a positive electrode and a negative electrode;
(1b) discharging;
(1c) after discharging, taking out the anode, and placing the anode material on the anode in a solvent for ultrasonic stripping;
or
(2a) Assembling an electrolytic cell by taking graphite fluoride as a cathode and an anode;
(2b) and (4) electrolyzing, and separating from the electrolyte to obtain the fluorinated graphene.
According to the invention, in the step (1a), the positive electrode is a metal foil loaded with graphite fluoride;
the metal foil may be aluminum, copper, nickel, etc., such as aluminum;
preferably, the graphite fluoride may be compacted onto the metal foil, for example using a tablet press;
the negative electrode may be lithium, sodium, magnesium, potassium, such as lithium;
the battery comprises electrolyte, wherein the electrolyte comprises electrolyte and solvent;
the electrolyte may be LiPF 6;
the solvent can be one or more of Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC); for example, a mixture of EC and DMC, preferably in a volume ratio of 1: 1; for example, the volume ratio of the EC, the DEC and the DMC is preferably 1:1: 1;
according to the present invention, in the step (1b), the discharge rate of the battery may be 0.001 to 0.08C, preferably 0.01 to 0.04C;
the discharge time may be 5 to 50 hours, preferably 10 to 30 hours;
according to the invention, in the step (1c), taking out the positive electrode, scraping the positive electrode material, dispersing in the solvent and carrying out ultrasonic stripping; the solvent may be an organic solvent such as N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide;
and after ultrasonic stripping, centrifuging the dispersion liquid, separating an upper layer part, filtering, and freeze-drying to obtain the fluorinated graphene.
According to the invention, after discharge, part of fluorinated graphene is generated, and lithium is inserted between the fluorinated graphene layers, so that the interlayer spacing is increased, the fluorinated graphene can be peeled off after simple ultrasonic treatment, more fluorinated graphene can be obtained, and the yield of the fluorinated graphene is improved.
According to the invention, in step (2a), the cathode is a metal sheet loaded with graphite fluoride, such as an aluminum sheet and a nickel sheet;
preferably, graphite fluoride may be packed into the porous tube and adhered to the metal sheet;
the anode may be lithium, platinum;
the electrolytic cell comprises an electrolyte, a solvent and an optional electrolytic auxiliary agent;
the electrolyte can be one or a mixture of more of lithium chloride, lithium perchlorate, sodium chloride, potassium chloride and aluminum chloride;
the solvent can be one or a mixture of propylene carbonate, acetonitrile and dimethyl sulfoxide;
the electrolytic auxiliary agent can be one or a mixture of potassium sulfate, sodium sulfate, ammonium sulfate, potassium nitrate, ammonium nitrate and sodium nitrate;
according to the invention, in step (2b), the operating voltage for the electrolysis may be 5-25V, preferably 10-20V, for example 15V;
the time of electrolysis may be 1 to 5 hours, for example 3 hours. After the electrolysis, the graphene fluoride is separated from the electrolyte solution, and for example, the graphene fluoride is obtained by centrifugal separation, filtration, and drying.
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The method comprises the following steps: preparation of fluorinated graphene
Weighing 2g of graphite fluoride, dispersing the graphite fluoride in 200ml of NMP, heating and refluxing for 5 hours at 120 ℃, and naturally cooling; the mixture was then subjected to high-speed shearing (13000 r/min) in a high-speed shearing machine for 4 hours, and then transferred to a centrifugal tube and subjected to high-speed centrifugation for 30 to 60 minutes. Collecting supernatant, filtering, washing, and freeze drying. And collecting a sample to prepare the fluorinated graphene.
Step two: preparation of fluorinated graphene/sulfur composite material
0.2g of fluorinated graphene and 0.6g of sulfur powder are taken, ground and mixed uniformly. And (3) placing the composite material in a tubular reaction furnace, raising the temperature to 160 ℃ at a heating rate of 1 ℃/min under the protection of nitrogen, keeping the temperature for 15 hours, then continuously raising the temperature to 400 ℃ at the same heating rate, keeping the temperature for 15 hours, and then automatically cooling to obtain the fluorinated graphene/sulfur composite material.
Step three: preparation of fluorinated graphene/sulfur composite-coated separator
Weighing 50mg of fluorinated graphene-sulfur composite material, dispersing in 40ml of NMP organic solvent, and shearing and stirring to form slurry; the prepared slurry was uniformly coated on the surface of a separator (commercially available separator model Celgard2320, purchased from Celgard corporation, usa) and dried in a vacuum drying oven for 24 hours to prepare a separator coated with a fluorinated graphene/sulfur composite material layer having a thickness of 80 μm.
Step four: electrochemical testing of lithium batteries
The prepared diaphragm coated with the fluorinated graphene/sulfur composite material is moved into a glove box protected by argon atmosphere, a metal lithium sheet is used as a negative electrode, a lithium cobaltate material is used as a positive electrode, a 2025 electric shell is adopted, and a basic solvent is EC: DEC: DMC 1:1:1 (volume ratio) to assemble the button cell to test the charge and discharge performance.
Fig. 1 is an SEM image of the fluorinated graphene/sulfur composite of example 1.
Fig. 2 is an XRD pattern of the fluorinated graphene/sulfur composite of example 1.
Fig. 3 is a Raman plot of the fluorinated graphene/sulfur composite of example 1.
Figure 4 is a graph comparing the cycle performance of the separator of example 1 and a separator of Celgard2320 type. It can be seen from the figure that after the battery is assembled, the degree of capacity attenuation is reduced along with the increase of the cycle number of the diaphragm coated with the fluorinated graphene/sulfur composite material, which shows that the cycle performance is obviously improved.
Example 2
The method comprises the following steps: preparation of fluorinated graphene
30mg of graphite fluoride is weighed and compacted on an aluminum foil by a tablet press to prepare the graphite fluoride electrode material. The prepared electrode material is used as a positive electrode, and a lithium sheet is used as a negative electrode; with LiPF6Is an electrolyte, the concentration is 1M, EC and DMC in a volume ratio of 1:1 are solvents; and assembling into a battery. Discharging at a rate of 0.04C for 10 hr。
After the discharge was completed, the cell was opened, the aluminum foil was taken out, the positive electrode material was scraped off, and the aluminum foil was dispersed in NMP to be subjected to ultrasonic peeling. Centrifuging the dispersion to remove the lower precipitate, separating the upper layer, filtering, and freeze drying. The sample was collected.
Step two: the preparation of the fluorinated graphene/sulfur composite was the same as in example 1.
Step three: a graphene fluoride/sulfur composite-coated separator was prepared as in example 1, wherein the thickness of the graphene fluoride/sulfur composite layer was 15 μm.
Step four: electrochemical testing of lithium batteries was the same as in example 1.
After the separator prepared in example 2 was assembled into a battery, the degree of capacity fade decreased with the increase in the number of cycles, indicating that the cycle performance was significantly improved.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. The battery diaphragm is characterized by comprising a substrate layer and a fluorinated graphene/sulfur composite layer, wherein the fluorinated graphene/sulfur composite layer is positioned on at least one side surface of the substrate layer, and the fluorinated graphene/sulfur composite layer comprises a fluorinated graphene/sulfur composite material;
the fluorinated graphene/sulfur composite material is prepared by taking fluorinated graphene and sulfur as raw materials and utilizing a high-temperature roasting method;
under the high-temperature condition, sulfur forms free radicals, and nucleophilic substitution reaction is carried out on the free radicals and fluorine on the fluorinated graphene, so that part or all of C-F bonds are changed into C-S bonds.
2. The battery separator according to claim 1, wherein the fluorinated graphene/sulfur composite is prepared by the following method:
(a) uniformly mixing fluorinated graphene and sulfur powder;
(b) heating for 5-15 hours at the temperature of 150-.
3. The battery separator according to claim 2, wherein the mixing process of step (a) is assisted by stirring or grinding.
4. The battery separator of claim 2 wherein the inert atmosphere of step (b) is a nitrogen, helium or argon atmosphere.
5. The battery separator according to claim 1 or 2, wherein the mass percentage of the fluorinated graphene is 10-50 wt%; the mass percentage of the sulfur is 50-90 wt%.
6. The battery separator according to claim 5, wherein the mass percentage of the fluorinated graphene is 15-35 wt%; the mass percentage of the sulfur is 65-85 wt%.
7. The battery separator according to claim 1, wherein the fluorinated graphene is prepared by the following method:
1) assembling a battery by taking graphite fluoride as an electrode, taking out a pole piece containing a graphite fluoride electrode material after discharging, and carrying out ultrasonic stripping on the pole piece in an organic solvent to obtain graphite fluoride;
alternatively, the first and second electrodes may be,
2) prepared by an electrolytic graphite fluoride method: and (3) taking the graphite fluoride as an electrolytic electrode, assembling into an electrolytic cell, and electrifying for electrolysis to obtain the fluorinated graphene.
8. The battery separator according to claim 1, wherein the fluorinated graphene is prepared by the following method:
dispersing graphite fluoride in an organic solvent by using a mechanical stripping method, shearing at a high speed, ultrasonically stripping, then centrifugally separating, filtering, washing and drying to prepare the graphite fluoride.
9. The battery separator according to claim 1, wherein the preparation method of the fluorinated graphene comprises the following steps:
(1) dispersing graphite fluoride in an organic solvent, and heating and refluxing for 3-8 hours at 110-150 ℃;
(2) shearing the mixture obtained in the step (1) at a high speed for 3-8 hours;
(3) and (3) carrying out high-speed centrifugal treatment on the solution obtained in the step (2), collecting the upper layer part, carrying out suction filtration, washing, freezing and drying to obtain the fluorinated graphene.
10. The battery separator according to claim 9, wherein the organic solvent of step (1) is N-methylpyrrolidone.
11. The battery separator as claimed in claim 9, wherein the high shear rotation number of step (2) is 11000-15000 r/min.
12. The battery separator according to claim 1, wherein the thickness of the fluorinated graphene/sulfur composite layer is 5-100 microns.
13. A method of making the battery separator of any of claims 1-12, the method comprising the steps of:
i) mixing the fluorinated graphene/sulfur composite material with a solvent to prepare slurry;
ii) coating the slurry obtained in the step i) on at least one side surface of the substrate layer, and drying to obtain a fluorinated graphene/sulfur composite material layer, namely, the battery diaphragm is obtained.
14. The preparation method according to claim 13, wherein the concentration of the fluorinated graphene/sulfur composite in the slurry is 1-5 mg/mL.
15. A lithium ion battery comprising the battery separator of any of claims 1-12.
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| JP2018076196A (en) * | 2016-11-08 | 2018-05-17 | 関東電化工業株式会社 | Fluorinated graphene oxide and method for producing the same |
| CN108483432A (en) * | 2018-04-04 | 2018-09-04 | 中国科学院福建物质结构研究所 | A kind of electrochemical preparation method of fluorinated graphene material |
| CN109037662A (en) * | 2018-09-18 | 2018-12-18 | 西安交通大学 | A kind of lithium-sulfur cell sulphur carbon composite anode material preparation method |
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| JP2018076196A (en) * | 2016-11-08 | 2018-05-17 | 関東電化工業株式会社 | Fluorinated graphene oxide and method for producing the same |
| CN108039469A (en) * | 2017-12-06 | 2018-05-15 | 贵州梅岭电源有限公司 | The preparation method of fluorographite-sulfur electrode |
| CN108483432A (en) * | 2018-04-04 | 2018-09-04 | 中国科学院福建物质结构研究所 | A kind of electrochemical preparation method of fluorinated graphene material |
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