CN111653780A - Flexible graphene-based composite scaffold material and preparation method and application thereof - Google Patents
Flexible graphene-based composite scaffold material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a flexible graphene-based composite scaffold material and a preparation method and application thereof. The flexible graphene-based composite support material comprises a support substrate and a graphene-based thin film loaded on the surface of the support substrate, wherein the thickness of the graphene-based thin film is 10-900 nm. The preparation method comprises the following steps: and attaching the graphene-based dispersion liquid to the surface of the stent matrix in a dipping mode, and drying to obtain the graphene-based dispersion liquid. The flexible graphene-based composite support material is arranged between a metal lithium cathode and a diaphragm as a flexible interlayer to assemble a lithium metal battery, so that lithium ions can be effectively guided to deposit on the surface of the cathode, the growth of lithium dendrites is inhibited, the cycling stability of the lithium metal cathode is improved, and the service life and the safety performance of the battery are improved.
Description
Technical Field
The invention relates to the field of lithium metal batteries, in particular to a flexible graphene-based composite support material for protecting metal lithium and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
At present, the performance of commercial lithium ion batteries is approaching the limit, people's urgent demand for high-specific energy batteries makes the development of metallic lithium negative electrodes necessary, and metallic lithium is widely considered by researchers to be the ultimate choice of lithium battery negative electrode materials. Due to the extremely high chemical activity of lithium metal, the lithium metal is faced with a plurality of challenges in the use process, such as serious side reaction with the electrolyte, irreversible consumption of the electrolyte, gradual damage to an SEI (solid electrolyte interface) film between a lithium cathode and the electrolyte, and continuous loss of the lithium metal; in addition, during the electrochemical cycle process of the lithium metal battery, due to the action of large polarization and strong electric field, non-uniform deposition of lithium ions is caused, severe nucleation and growth of lithium dendrites are formed, the coulomb efficiency of the battery is reduced, the service life of the battery is prolonged, and when the lithium dendrites grow to pierce through a diaphragm and contact with a positive electrode, the internal short circuit of the battery causes serious potential safety hazard.
In order to solve the problems of the lithium metal, the stability of the lithium metal negative electrode can be improved by using electrolyte additives to generate an SEI film in situ, manually manufacturing an SEI protective film, using a three-dimensional host substrate to prepare a lithium metal composite electrode and the like. Therefore, a preparation method for simply and efficiently stabilizing the lithium metal negative electrode and inhibiting the growth of lithium dendrites is indispensable.
The prior art discloses an application of a graphene film in a lithium metal battery cathode, a symmetric battery, a full battery and a preparation method, wherein a graphene solid is dispersed in a solvent, a binder is used for carrying out vacuum filtration, drying and rolling to obtain a 47-53 micron graphene film, and the graphene film is used as an interlayer and is introduced between the lithium metal cathode and a diaphragm to regulate and control the nucleation uniformity of lithium ions and prolong the service life of the battery. The inventors found that the drawbacks of this technique are: the thickness of the graphene film, which is a key material, is dozens of microns in the preparation process, and the graphene film is directly used as an interlayer due to the large thickness, so that the internal impedance of the battery can be increased to a great extent, the rapid transmission of lithium ions is not facilitated, and the method is not easy to prepare the thin graphene film.
The prior art also discloses a high-performance composite lithium metal cathode based on graphene and a preparation method thereof, wherein a Graphene Oxide (GO) film is obtained through suction filtration, Reduced Graphene Oxide (RGO) is obtained through thermal reduction under argon, then metal lithium in a high-temperature molten state is pre-embedded into the RGO, and the three-dimensional layered lithium metal composite cathode is obtained after cooling. The inventors found that the drawbacks of this technique are: the preparation method of the three-dimensional composite lithium metal cathode based on the graphene film is complex and the structure is not easy to maintain, and in the GO suction filtration preparation process, the suction filtration process is very slow due to rich functional groups on the surface of GO; during the high-temperature reduction process of the GO film under inert gas, the RGO is easy to crack and incomplete, and the flexibility of the film is reduced; and finally, the process of embedding lithium at high temperature in the glove box has high operation difficulty.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a flexible graphene-based composite scaffold material and a preparation method and application thereof. According to the invention, the graphene-based dispersion liquid is attached to the surface of the support matrix in a dipping mode, and is dried and then placed between the metal lithium cathode and the diaphragm as the flexible interlayer to assemble the lithium metal battery, so that the uniform distribution of an electric field on the surface of the lithium metal cathode can be effectively regulated, lithium ions are induced to be deposited on the surface of the cathode, the growth of lithium dendrites is inhibited, the circulation stability of the lithium metal cathode is improved, and the service life and the safety performance of the battery are improved.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a flexible graphene-based composite scaffold material, comprising: the graphene-based thin film structure comprises a support substrate and a graphene-based thin film loaded on the surface of the support substrate, wherein the thickness of the graphene-based thin film is 10-900 nm.
The support matrix is made of flexible netted support base materials such as non-woven fabrics, carbon nanotube fiber cloth and the like.
The graphene-based film is a graphene oxide film, a graphene film, and a graphene oxide film and a graphene film with metal and metal oxide nanoparticles or doped atoms N, S or P loaded on the surface.
The invention also provides a preparation method of the flexible graphene-based composite scaffold material, which comprises the following steps:
1) placing the graphene-based powder material in a solvent, and performing ultrasonic dispersion to prepare a graphene-based dispersion liquid;
2) dipping a support matrix in the graphene-based dispersion liquid obtained in the step 1);
3) placing the support matrix attached with the dispersion liquid in the step 2) in a drying oven for drying to obtain a flexible graphene-based composite support material;
and 2) the graphene-based dispersion liquid can be attached to the surface of the stent matrix in a dropping or electrostatic spraying mode.
The invention also provides an application of the flexible graphene-based composite support material in the aspect of protecting a lithium metal cathode, and the specific method comprises the following steps:
and cutting the composite support material into a shape which is the same as that of the lithium metal and has the size not smaller than that of the lithium metal electrode, and placing the composite support material between the lithium metal electrode and the diaphragm as an interlayer to assemble the lithium metal battery.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) according to the invention, the strong ion conductivity and mechanical strength of the graphene material are used as a support material, so that the electric field on the surface of the lithium metal is effectively dispersed, the uniform deposition of lithium ions on the surface of a lithium metal negative electrode is promoted, the growth of lithium dendrites is inhibited, and the cycle stability and safety of the lithium metal battery are greatly improved.
(2) The invention uses the flexible material as the support substrate and covers the flexible graphene oxide-based film, so that the composite support material maintains extremely strong flexibility, has simple preparation process and no toxicity, can be widely applied to lithium-sulfur batteries and lithium-air batteries, and is easy to realize the industrialized and flexible design of lithium metal batteries.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is an optical photograph of the graphene oxide @ non-woven fabric composite scaffold material prepared in example 1 in a flat state;
fig. 2 is an optical photograph of the graphene oxide @ non-woven fabric composite scaffold material prepared in example 1 in a folded state;
FIG. 3 is a scanning electron microscope photograph of the surface of the graphene oxide @ non-woven fabric composite scaffold material prepared in example 1;
FIG. 4 is a high-power scanning electron micrograph of the surface of the graphene oxide @ non-woven fabric composite scaffold material prepared in example 1;
FIG. 5 is a long cycle plot of a lithium metal-on-battery fabricated from the graphene oxide @ nonwoven composite scaffold prepared in example 1 versus the lithium metal-on-battery of comparative examples 1 and 2;
fig. 6 is an optical photograph of the graphene oxide @ non-woven fabric composite scaffold material prepared in example 1 after being cycled in a battery for one cycle;
FIG. 7 shows the cycle performance of the graphene oxide @ non-woven fabric composite scaffold material prepared in example 2 when applied to a lithium oxygen battery;
FIG. 8 is an electron microscope picture of the surface of a lithium metal negative electrode after the graphene oxide @ non-woven fabric composite support material prepared in example 2 is applied to a lithium oxygen battery and cycled for 50 cycles;
fig. 9 is a graph showing the cycle life of the lithium oxygen battery formed by the graphene oxide @ non-woven fabric composite scaffold material in example 2 and the lithium oxygen battery in comparative examples 3 and 4.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. When the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
As introduced in the background art, in the prior art, the thickness of the graphene film is micron-sized in the preparation process, the preparation method is complex, the structure is not easy to maintain, and in order to solve the above technical problems, the invention provides a flexible graphene-based composite scaffold material, which comprises: the graphene-based thin film structure comprises a support substrate and a graphene-based thin film loaded on the surface of the support substrate, wherein the thickness of the graphene-based thin film is 10-900 nm.
In some embodiments of this embodiment, the graphene-based thin film has a thickness of 10-100 nm.
In some examples of this embodiment, the scaffold matrix is a mesh scaffold base material such as a non-woven fabric, a carbon nanotube fiber fabric, or the like.
In some embodiments of this embodiment, the scaffold substrate is a nonwoven.
In some examples of this embodiment, the thickness of the stent matrix is 10 to 1000 microns.
In some examples of this embodiment, the graphene-based thin film is a graphene oxide thin film, a graphene thin film, and a graphene oxide, graphene thin film with metal, metal oxide nanoparticles, or doping atoms N, S or P loaded on the surface.
In some embodiments of this embodiment, the graphene-based film is a graphene oxide film.
The invention also provides a preparation method of the flexible graphene-based composite scaffold material, which comprises the following steps:
1) placing a certain mass of graphene-based powder material in a solvent, and performing ultrasonic dispersion to prepare a graphene-based dispersion liquid;
2) dipping a support matrix in the graphene-based dispersion liquid obtained in the step 1);
3) placing the support matrix attached with the dispersion liquid in the step 2) in a drying oven for drying to obtain a flexible graphene-based composite support material;
in some examples of this embodiment, in step 1), the solvent is one of deionized water, absolute ethanol, or isopropanol.
In some examples of this embodiment, in step 1), the mass to volume ratio of graphene-based powder material to solvent is (1-100) mg: 10 mL.
In some examples of the embodiment, in the step 1), the power of the ultrasonic wave is 50W-800W, and the ultrasonic frequency is 40KHZ-80 KHZ; the ultrasonic dispersion time is 30-120 min.
In some examples of this embodiment, the immersion time in step 2) is 1 to 30 minutes, more preferably 2 to 6 minutes.
In some examples of this embodiment, the graphene-based dispersion may be drop-coated or electrostatic-sprayed on the surface of the stent substrate in step 2).
In some examples of this embodiment, the drying temperature in step 3) is 50 to 160 ℃.
The invention also provides application of the flexible graphene-based composite support material in the aspect of protecting a lithium cathode, and the specific method comprises the following steps:
cutting the composite support material into a shape which is the same as that of the lithium metal and the size of which is not smaller than that of the lithium metal electrode, and placing the composite support material between the lithium metal electrode and the diaphragm as an interlayer to assemble the lithium ion battery.
In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the technical solution of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1
1) Placing 10mg of graphene oxide powder into 10mL of deionized water, and ultrasonically dispersing for 60min under the condition of 100W of power and 60KHZ of frequency to prepare corresponding 1mg/mL of graphene oxide dispersion liquid;
2) soaking a commercial non-woven fabric material with the thickness of 100 micrometers in the graphene oxide dispersion liquid for 2 minutes, and drying in a 60 ℃ blast oven for 2 hours to obtain a graphene oxide @ non-woven fabric composite support material, wherein the thickness of a graphene oxide film on the surface of the non-woven fabric is 20 nm;
3) cutting the graphene oxide @ non-woven fabric composite support material into a wafer with the diameter of 16mm, placing the wafer as an interlayer between a lithium metal electrode plate (with the diameter of 14.5mm) and a glass fiber diaphragm, taking 1M LiTFSI/TEGDME as electrolyte, arranging a pair of batteries, and testing the lithium metal content to be 0.2mA/cm2Current density of 0.2mA/cm2Is tested in an electrochemical cycling process, wherein graphene oxide is reduced to graphene in situ during the electrochemical cycling process.
Fig. 1 and 2 are optical photographs of the graphene oxide @ non-woven fabric composite stent material prepared by the method in a flat and folded state, and it can be found from fig. 1 and 2 that the composite stent material is in a flat and straight state after being dried, the graphene oxide is uniformly coated on the surface of the non-woven fabric, and the composite stent has strong flexibility and can be arbitrarily bent and folded into a fan shape. Fig. 3 is a scanning electron microscope picture of the surface of the graphene oxide @ non-woven fabric composite scaffold material prepared by the method, wherein the picture can clearly show that the graphene oxide covers the surface of the non-woven fabric. Fig. 4 is a high-power scanning electron microscope photograph of the surface of the graphene oxide @ non-woven fabric composite scaffold material prepared by the method, which shows that the graphene oxide is coated on the surface of a single non-woven fabric fiber and is in a wrinkled state. Fig. 6 is an optical photograph of the graphene oxide @ non-woven fabric composite scaffold material prepared by the method after a cycle of battery cycle, and it can be seen that yellow graphene oxide is reduced into a black graphene material through a cycle of electrochemical cycle, so that an ion conduction function is realized.
Example 2
1) Placing 20mg of graphene oxide powder into 10mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 120min under the condition of 100W of power and 60KHZ of frequency to prepare a corresponding 2mg/mL graphene oxide dispersion liquid;
2) soaking a commercial non-woven fabric material with the thickness of 100 micrometers in the graphene oxide dispersion liquid for 2 minutes, and drying in a 60 ℃ blast oven for 2 hours to obtain a graphene oxide @ non-woven fabric composite support material, wherein the thickness of a graphene oxide film on the surface of the non-woven fabric is 30 nm;
3) the graphene oxide @ non-woven fabric composite support material is cut into a wafer with the diameter of 18mm, the wafer is used as an interlayer and is placed between a lithium metal electrode plate (with the diameter of 16mm) and a glass fiber diaphragm, 1M LiTFSI/TEGDME is used as electrolyte, graphene aerogel is an air anode, porous carbon paper is used as a current collector, and the device is a lithium oxygen battery, wherein graphene oxide is reduced into graphene in situ in the electrochemical circulation process.
FIG. 7 shows the cycle performance of the graphene oxide @ non-woven fabric composite stent material prepared by the method when applied to a lithium oxygen battery; it can be seen that under the protection of the composite support, the lithium-air battery can stably circulate for 500 cycles, the discharge voltage is not lower than 2.0V, and the strong stability of the lithium metal cathode under the protection of the support is reflected.
FIG. 8 is an electron microscope picture of the surface of a lithium metal cathode after the graphene oxide @ non-woven fabric composite support material prepared by the method is applied to a lithium oxygen battery and circulates for 50 cycles; it can be seen that after 50 cycles of cycling, the lithium metal negative electrode interface remained smooth and flat with no apparent lithium dendrites or dead lithium.
Example 3
1) Placing 60mg of graphene powder in 10mL of isopropanol solvent, and ultrasonically dispersing for 120min under the condition of 600W power and 100KHZ frequency to prepare corresponding 6mg/mL graphene oxide dispersion liquid;
2) soaking a commercial non-woven fabric material with the thickness of 100 micrometers in the graphene oxide dispersion liquid for 2 minutes, and drying in a 60 ℃ blast oven for 2 hours to obtain a graphene oxide @ non-woven fabric composite support material, wherein the thickness of a graphene oxide film on the surface of the non-woven fabric is 100 nm;
3) the graphene oxide @ non-woven fabric composite support material is cut into a wafer with the diameter of 16mm, the wafer is used as an interlayer and is placed between a lithium metal electrode plate (with the diameter of 14.5mm) and a glass fiber diaphragm, and the lithium sulfur battery is formed by the device.
Example 4
1) Placing 20mg of nano-silver particle loaded graphene material (Ag @ GN) in 10mL of deionized water, and performing ultrasonic dispersion for 120min under the condition of 100W of power and 60KHZ of frequency to prepare a corresponding 2mg/mL graphene oxide dispersion liquid;
2) soaking a commercial non-woven fabric material with the thickness of 100 micrometers in the Ag @ GN dispersion liquid for 2 minutes, and drying in a blast oven at the temperature of 60 ℃ for 2 hours to obtain a graphene oxide @ non-woven fabric composite support material, wherein the thickness of a graphene oxide film on the surface of the non-woven fabric is 50 nm;
3) cutting the Ag @ GN @ non-woven fabric composite support material into a wafer with the diameter of 18mm, using the wafer as an interlayer, placing the wafer between a lithium metal electrode plate (with the diameter of 16mm) and a glass fiber diaphragm, and adding 1M LiClO4And the/DMSO is electrolyte, the carbon nano tube is an air anode, the porous carbon paper is a current collector, and the device is a lithium oxygen battery.
Example 5:
1) placing 10mg of graphene oxide powder in 10mL of isopropanol, and ultrasonically dispersing for 120min under the condition of 100W of power and 60KHZ of frequency to prepare a corresponding 1mg/mL graphene oxide dispersion liquid;
2) soaking carbon nanotube fiber cloth with the thickness of 50 micrometers in the graphene oxide dispersion liquid for 6 minutes, and drying in a 60 ℃ blast oven for 2 hours to obtain a graphene oxide @ carbon nanotube composite support material, wherein the thickness of a graphene oxide film on the surface of the non-woven fabric is 100 nm;
3) the graphene oxide @ carbon nanotube composite support material is cut into a wafer with the diameter of 18mm, the wafer is used as an interlayer and is placed between a lithium metal electrode plate (with the diameter of 16mm) and a glass fiber diaphragm, 1M LiTFSI/TEGDME is used as electrolyte, graphene aerogel is an air anode, porous carbon paper is used as a current collector, and the device is a lithium oxygen battery, wherein graphene oxide is reduced into graphene in situ in the electrochemical cycle process.
Example 6:
1) placing 5mg of graphene oxide powder in 10mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 120min under the condition of 100W of power and 60KHZ of frequency to prepare corresponding 0.5mg/mL of graphene oxide dispersion liquid;
2) placing the graphene oxide dispersion liquid in a spraying gun, uniformly spraying the GO dispersion liquid on the surface of a commercial non-woven fabric material with the thickness of 500 micrometers by adopting the atomization pressure of 0.40MPa, and drying in a blast oven at 60 ℃ for 2 hours to obtain a graphene oxide @ non-woven fabric composite support material, wherein the thickness of a graphene oxide film on the surface of the non-woven fabric is 100 nm;
3) the graphene oxide @ non-woven fabric composite support material is cut into a wafer with the diameter of 18mm, the wafer is used as an interlayer and is placed between a lithium metal electrode plate (with the diameter of 16mm) and a glass fiber diaphragm, 1M LiTFSI/TEGDME is used as electrolyte, activated carbon is used as an air anode, porous carbon paper is used as a current collector, and the device is a lithium oxygen battery, wherein graphene oxide is reduced into graphene in situ in the electrochemical cycle process.
Comparative example 1: cutting a commercial non-woven fabric material (NWF) with the thickness of 100 micrometers into a round piece with the diameter of 18mm, using the round piece as an interlayer, placing the round piece between a lithium metal electrode plate (with the diameter of 14.5mm) and a glass fiber diaphragm, using 1M LiTFSI/TEGDME as electrolyte, arranging a pair of batteries, and testing the lithium metal content to be 0.2mA/cm2Current density of 0.2mA/cm2Electrochemical cycling tests were performed at the deposition capacity of (a).
Comparative example 2: directly arranging a lithium metal pole piece (Pure Li, the diameter of which is 14.5mm), a glass fiber diaphragm (containing 1M LiTFSI/TEGDME as electrolyte) and the lithium metal pole piece (Pure Li, the diameter of which is 14.5mm) into a lithium metal pair battery without adding any bracket material, and testing that the lithium metal is 0.2mA/cm2Current density of 0.2mA/cm2Electrochemical cycling tests were performed at the deposition capacity of (a).
Fig. 5 is a long cycle diagram of a lithium metal-to-battery cell assembled by graphene oxide @ non-woven fabric composite scaffold material (GO @ WNF) in example 1 and a lithium metal-to-battery cell in comparative examples 1 and 2, and it can be seen that GO @ WNF shows the lowest lithium ion deposition voltage plateau for the lithium metal-to-battery cell as the composite scaffold and has high stability.
Comparative example 3: a commercial non-woven fabric material (NWF) with the thickness of 100 micrometers is used as a support material and cut into a wafer with the diameter of 18mm, the wafer is used as an interlayer and is placed between a lithium metal electrode plate (with the diameter of 16mm) and a glass fiber diaphragm, 1MLiTFSI/TEGDME is used as electrolyte, graphene aerogel is used as an air anode, porous carbon paper is used as a current collector, the device is used for forming a lithium oxygen battery, and the cycle life of the battery is tested.
Comparative example 4: the method is characterized in that no support material is added, a lithium metal pole piece (Pure Li, the diameter is 14.5mm), a glass fiber diaphragm (containing 1M LiTFSI/TEGDME as electrolyte), graphene aerogel (air anode), porous carbon paper (current collector) are directly assembled into a lithium oxygen battery, and the cycle life of the battery is tested.
Fig. 9 is a cycle life chart of the lithium oxygen battery formed by the graphene oxide @ non-woven fabric composite support material in example 2 and the lithium oxygen batteries in comparative examples 3 and 4, and it can be seen from the chart that when the limited capacity is 500mAh/g and the working current is 500mA/g, the lithium oxygen battery protected by the GO @ NWF support can stably cycle for more than 500 cycles, and the discharge termination voltage is more than 2.0V; compared with the Pure Li lithium oxygen battery without the bracket, the cycle life of the battery only using the non-woven fabric NWF as the bracket is reduced to 90 periods only by circulating 166 periods; the important significance of the GO @ NWF composite structure on prolonging the cycle life of the lithium-air battery is shown.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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 (10)
1. A flexible graphene-based composite scaffold material, comprising: the graphene-based thin film structure comprises a support substrate and a graphene-based thin film loaded on the surface of the support substrate, wherein the thickness of the graphene-based thin film is 10-900 nm.
2. The flexible graphene-based composite scaffold material of claim 1, wherein the graphene-based thin film has a thickness of 10-100 nm.
3. The flexible graphene-based composite scaffold material according to claim 1, wherein the scaffold substrate is a mesh scaffold base material such as non-woven fabric, carbon nanotube fiber cloth, or the like;
preferably, the support matrix is non-woven fabric;
preferably, the thickness of the stent matrix is 10-1000 microns.
4. The flexible graphene-based composite scaffold material according to claim 1, wherein the graphene-based thin film is a graphene oxide thin film, a graphene thin film, and a graphene oxide, graphene thin film with metal, metal oxide nanoparticles or doping atoms N, S or P loaded on the surface;
preferably, the graphene-based thin film is a graphene oxide thin film.
5. The method for preparing a flexible graphene-based composite scaffold material according to any one of claims 1 to 4, specifically comprising:
1) placing the graphene-based powder material in a solvent, and performing ultrasonic dispersion to prepare a graphene-based dispersion liquid;
2) dipping a support matrix in the graphene-based dispersion liquid obtained in the step 1);
3) and (3) placing the support matrix attached with the dispersion liquid in the step 2) in a drying oven for drying to obtain the flexible graphene-based composite support material.
6. The method of claim 5, wherein in step 1), the solvent is one of deionized water, absolute ethanol or isopropanol.
7. The method according to claim 5, wherein in step 1), the mass-to-volume ratio of the graphene-based powder material to the solvent is 1-100 mg: 10 mL.
8. The preparation method according to claim 5, wherein in the step 1), the power of the ultrasonic wave is 50W-800W, and the ultrasonic frequency is 40KHZ-80 KHZ; the ultrasonic dispersion time is 30-120 min.
9. The method according to claim 5, wherein in step 2), the immersion time is 1 to 30 minutes, preferably 2 to 6 minutes; in the step 2), the graphene-based dispersion liquid can be attached to the surface of the stent matrix in a dropping or electrostatic spraying manner;
in the step 3), the drying temperature is 50-160 ℃.
10. The application of the flexible graphene-based composite scaffold material of claim 1 in the aspect of protecting a lithium negative electrode is characterized in that the specific application method is as follows:
the flexible graphene-based composite support material is cut into a shape which is the same as that of lithium metal and the size of which is not smaller than that of a lithium metal electrode, and the flexible graphene-based composite support material is used as an interlayer and is arranged between the lithium metal electrode and a diaphragm to assemble the lithium metal battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114284635A (en) * | 2021-12-28 | 2022-04-05 | 厦门大学 | Diaphragm modification method for lithium metal negative electrode protection |
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| CN114284635A (en) * | 2021-12-28 | 2022-04-05 | 厦门大学 | Diaphragm modification method for lithium metal negative electrode protection |
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