CN114792779A - Flexible battery pole piece and battery - Google Patents
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- CN114792779A CN114792779A CN202111408146.6A CN202111408146A CN114792779A CN 114792779 A CN114792779 A CN 114792779A CN 202111408146 A CN202111408146 A CN 202111408146A CN 114792779 A CN114792779 A CN 114792779A
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/022—Electrodes made of one single microscopic fiber
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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
Abstract
The invention relates to a flexible battery pole piece which comprises carbon nanofiber and graphene, wherein the carbon nanofiber is prepared from polyacrylonitrile through electrostatic spinning and carbonization in sequence, the diameter of the carbon nanofiber is 200-500nm, the weight fraction of the graphene is 5-40% of that of the flexible battery pole piece, and the thickness of the flexible battery pole piece is 0.2-2 mm. According to the invention, the size of the carbon nanofiber, the content of graphene and carbonization parameters are regulated and controlled to prepare the flexible battery pole piece with high specific capacity and flexibility, the flexible battery pole piece has a large bending angle and is free from powder falling in the bending process, and the pole piece serving as a negative electrode can meet the high energy density requirement of a lithium/sodium ion battery and can ensure good flexibility when being applied to the field of power batteries.
Description
Technical Field
The invention relates to the field of battery cathode materials, in particular to a flexible battery pole piece and a battery.
Background
At present, power batteries on the market mainly comprise lithium ion batteries and sodium ion batteries, the lithium ion batteries are widely applied due to high specific capacity and energy density, and the sodium ion batteries also have huge application potential due to rich sodium resource reserves and high power density. However, the shape and structure of the conventional lithium/sodium ion battery pole piece are generally fixed and lack flexibility, which limits the application of the conventional lithium/sodium ion battery pole piece in flexible electronic devices to a certain extent. Compared with the traditional electronic device, the flexible device has higher flexibility, can adapt to different working environments to a certain extent, and meets the deformation requirement of equipment, so that the flexible energy storage device receives more and more extensive attention and has huge market potential in the fields of information, energy, medical treatment, national defense and the like.
The traditional coating process comprises the steps of firstly crushing an electrode material into powder, then adding auxiliaries such as a conductive agent and a binder, and finally coating and drying to obtain the battery pole piece.
The electrostatic spinning technology is a technical means for preparing carbon nanofibers, and the electrostatic spinning technology takes high molecular polymers as raw materials to prepare the carbon nanofibers. The carbon nanofiber can form a conductive network and has certain flexibility, the carbon nanofiber prepared by the electrostatic spinning technology can be subjected to carbonization treatment to obtain a negative pole piece, the pole piece has a self-supporting structure, no binder or conductive agent needs to be additionally added, and the preparation process is simple. The method adopts an electrostatic spinning technology and a carbonization process as a feasible way for preparing the flexible battery pole piece, but the battery pole piece taking carbon nanofibers as the cathode cannot have high energy/power density and high flexibility at the same time, usually the specific capacity of the conventional flexible pole piece is lower than that of graphite, the performance on the flexibility needs to be improved, if the bending angle is small, the pole piece is subjected to powder falling in the bending process, and the like, so that the lithium/sodium ion battery pole piece still has flexibility and still has great difficulty under the condition of keeping the high energy/power density.
Disclosure of Invention
In order to solve the technical problems in the prior art, in a first aspect, the invention provides a flexible battery pole piece, which comprises carbon nanofibers and graphene, wherein the carbon nanofibers are prepared from polyacrylonitrile through electrostatic spinning and carbonization in sequence, the diameter of the carbon nanofibers is 200-500nm, the weight fraction of the graphene is 5-40% of that of the flexible battery pole piece, and the thickness of the flexible battery pole piece is 0.2-2 mm.
Further, the flexible battery pole piece is prepared by the following steps:
s1, dissolving the polyacrylonitrile in a dimethylformamide solution, adding the graphene, and stirring to prepare an electrostatic spinning solution;
s2, preparing the electrostatic spinning solution into a graphene composite nanofiber sheet by taking an aluminum foil as a receiving substrate;
and S3, carbonizing the graphene compounded nanofiber sheet to obtain the flexible battery pole piece.
Further, in step S1, the weight ratio of the graphene to the polyacrylonitrile is (5-40): (60-95).
Further, in step S2, the electrospinning solution is injected into a 10ml syringe having a pushing speed of 0.002mm/S, a voltage of 15 to 20kv, and a receiving distance of 10 to 15 cm.
Further, the graphene-composited nanofiber sheet is subjected to a pre-oxidation treatment before the carbonization treatment. The purpose of pre-oxidation is to maintain the stability of the nanofiber sheet structure.
Further, the pre-oxidation treatment is to oxidize the graphene composite nanofiber sheet for 2-3h under the conditions of air atmosphere and temperature of 200-220 ℃.
Further, the carbonization is carried out for 2-3h under the conditions of nitrogen atmosphere and temperature of 700-800 ℃.
Further, the flexible battery pole piece is used as a negative electrode in a lithium ion battery or a sodium ion battery.
Furthermore, the bending angle of the flexible battery pole piece is 0-180 degrees under the action of external force.
In a second aspect, the present invention provides a battery comprising the flexible battery pole piece.
Compared with the prior art, the technical scheme of the invention has at least the following beneficial effects:
1. the graphene is compounded with the carbon nanofibers, and the graphene is attached to the carbon nanofibers, so that the stability of the carbon nanofiber structure is improved, the flexibility and the conductivity of the carbon nanofiber structure are enhanced, and the electrochemical performance of the flexible battery pole piece is improved;
2. the size of the carbon nanofiber is regulated, the uniformity and the stability of the size of the carbon nanofiber are improved, the carbon nanofiber is contacted with each other to form a three-dimensional net structure, and the flexibility and the specific discharge capacity of the flexible battery pole piece are improved;
3. the carbonization parameters are optimized to reduce the brittleness of the carbon nanofibers, prevent the flexible battery pole piece from being broken in the bending process and improve the flexibility of the flexible battery pole piece;
4. the flexible battery pole piece has a large bending angle and does not fall off powder in the bending process, and the flexible battery pole piece serving as a negative electrode can meet the high energy density requirement of the lithium/sodium ion battery and can ensure good flexibility when being applied to the field of power batteries.
Drawings
The figures further illustrate the invention, but the examples in the figures do not constitute any limitation of the invention.
FIG. 1 is a digital photograph of a flexible battery pole piece;
FIG. 2 is a digital photograph of a flexible battery pole piece being bent;
FIG. 3 is a scanning electron microscope image of a flexible battery pole piece;
FIG. 4 is a multiplying power performance test chart of a flexible battery pole piece for a lithium ion battery;
fig. 5 is a multiplying power performance test chart of the flexible battery pole piece used for the sodium-ion battery.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Compared with the traditional electronic device, the flexible device has higher flexibility, can adapt to different working environments to a certain extent, and meets the deformation requirement of equipment, so that the flexible energy storage device is concerned more and more widely, and has huge market potential in the fields of information, energy, medical treatment, national defense and the like. The battery pole piece manufactured by the traditional technology is relatively fixed in appearance and structure, generally has no flexibility or poor flexibility, namely the battery pole piece manufactured by the traditional technology is difficult to apply to a flexible energy storage device, so that in order to promote the development of the flexible energy storage device, a flexible pole piece of a lithium/sodium ion battery, which can maintain high energy/power density and has flexibility, needs to be developed. Graphene as a new material has excellent electronic conductivity, mechanical strength and flexibility, and an electronic device prepared from graphene can deform to a certain extent without being damaged, so that the graphene has great application potential in the aspect of energy storage devices.
The invention provides a flexible battery pole piece which is a material compounded by carbon nanofibers and graphene, wherein the carbon nanofibers are prepared by sequentially carrying out electrostatic spinning and carbonization on polyacrylonitrile, the diameter of the carbon nanofibers is 200-500nm, the carbon nanofibers are uniformly distributed and have certain mechanical properties within the range, and when the diameter of the carbon nanofibers is less than 200nm, the carbon nanofibers are easily bonded with one another, so that the thickness of fibers in the flexible battery pole piece is not uniform, the uniformity and the stability of the material are reduced, and the specific capacity of the flexible battery pole piece is further reduced; when the diameter of the carbon nanofiber is larger than 500nm, the mechanical property of the fibers in the flexible battery pole piece is easily insufficient, so that the flexibility of the macroscopic flexible battery pole piece is reduced, the bending angle of the flexible battery pole piece is small, and the phenomena of fracture, powder falling and the like are easily generated in the bending process.
The inventor determines through theoretical calculation and multiple tests that the weight fraction of the graphene is 5-40% of that of the flexible battery pole piece, in the range, the graphene and the carbon nanofiber are compounded, so that the flexibility of the carbon nanofiber is improved, the conductivity of the carbon nanofiber is also improved, when the weight fraction of the graphene is less than 5%, the mechanical and electrochemical properties of the carbon nanofiber cannot be improved due to too small addition amount of the graphene, and when the weight fraction of the graphene is more than 40%, the graphene and polyacrylonitrile cannot form uniform spinning solution, so that the flexibility and the electrochemical properties of the flexible battery pole piece are influenced.
The thickness of the flexible battery pole piece is 0.2-2mm, the length is 20-100mm, the width is 10-80mm, the length and the width of the flexible battery pole piece are regulated and controlled according to the actual battery assembly requirement, the length and the width can meet the lithium batteries or sodium batteries with various sizes and specifications on the market at present in the range, and the length and the width of the flexible battery pole piece prepared by the invention can be bent and do not fall powder in the size range; the thickness of the flexible battery pole piece is obtained according to actual tests, and the inventor finds that when the thickness is smaller than 0.2mm, an independent nanofiber membrane cannot be prepared in the actual operation process, and when the thickness is larger than 2mm, the flexibility of the flexible battery pole piece is reduced, and winding bending cannot be achieved.
The flexible battery pole piece is prepared by the following three steps:
s1: dissolving polyacrylonitrile in a dimethylformamide solution, adding graphene, and stirring to prepare an electrostatic spinning solution;
in the flexible battery pole piece, the weight fraction of graphene is 5-40%, the weight fraction of carbon nanofiber is 60-95%, the carbon nanofiber is derived from polyacrylonitrile, namely in the electrostatic spinning solution, the weight ratio of graphene to polyacrylonitrile is (5-40): (60-95), the electrostatic spinning solution prepared according to the proportion has uniformity, and the graphene and the polyacrylonitrile are uniformly dispersed in the solution, so that the composite fiber material with the graphene uniformly distributed on the nanofiber can be prepared, and the flexibility and the specific capacity of the finally prepared flexible battery pole piece can be further improved.
S2, preparing the electrostatic spinning solution into a graphene composite nanofiber sheet by taking an aluminum foil as a receiving substrate;
the diameter of the nanofiber is influenced in the electrostatic spinning process, and then the thickness and the area of the nanofiber sheet are influenced, and the inventor confirms through a plurality of tests that the operation and the parameters of the electrostatic spinning process are as follows: injecting the electrostatic spinning solution into a 10ml injector, wherein the pushing speed of the injector is 0.002mm/s, the voltage is 15-20kv, the receiving distance is 10-15cm, the diameter of the prepared nanofiber is within 200-500nm under the conditions, and the size of the finally prepared flexible battery pole piece meets the following requirements: the thickness is 0.2-2mm, the length is 20-100mm, and the width is 10-80 mm.
And S3, carbonizing the graphene compounded nanofiber sheet to obtain the flexible battery pole piece.
The carbonization comprises preoxidation and high-temperature carbonization, wherein the preoxidation is firstly carried out and then the high-temperature carbonization is carried out, and the purpose of the preoxidation is to keep the stability of the structure of the nanofiber sheet and avoid the deformation of a fiber membrane caused by direct carbonization; the high-temperature carbonization is used for removing hydrogen, oxygen and other elements from polyacrylonitrile, which are remained in the nanofiber sheet, so that the prepared carbon material can realize energy storage characteristics.
The carbonization parameters influence the fiber structure and the performance of the flexible battery pole piece, and in the invention, the nano fiber piece which is subjected to pre-oxidation treatment and is compounded by graphene is oxidized for 2-3h in a high-temperature furnace with the air atmosphere and the temperature of 200-220 ℃; and (3) treating the graphene composite nanofiber sheet for 2-3h under the conditions of nitrogen atmosphere and temperature of 700-800 ℃ by high-temperature carbonization, and carbonizing the graphene composite nanofiber sheet under the parameters, so that the conditions that the fibers are easy to be fragile and bend and fall off powder in the prepared flexible battery pole piece can be avoided.
Example 1
Dissolving 1g of polyacrylonitrile in 10ml of dimethylformamide solvent, adding 0.5g of graphene, uniformly stirring, injecting the solution into a 10ml injector, propelling at the speed of 0.002mm/s, carrying out electrostatic spinning on the solution under the conditions of voltage of 20kv and receiving distance of 15cm to prepare nanofiber, placing the nanofiber in a tube furnace, pre-oxidizing the nanofiber at the temperature of 200 ℃ for 2 hours, and carbonizing the pre-oxidized nanofiber at the temperature of 800 ℃ under the protection of nitrogen for 2 hours to prepare the flexible battery pole piece.
As shown in fig. 1-2, the flexible battery electrode sheet prepared in this embodiment has a thickness of 0.2mm, a length of 50mm, and a width of 25mm, and under the action of an external force, the bending angle of the flexible battery electrode sheet can reach 180 ℃, and the powder falling phenomenon does not occur in the bending process.
As shown in fig. 3, the internal structure of the flexible battery pole piece is formed by compounding criss-cross carbon nanofibers and graphene segments, the graphene is attached to the carbon nanofibers to enhance the flexibility of the carbon nanofibers, the carbon nanofibers are in close contact with each other to ensure the macroscopic flexibility of the flexible battery pole piece, the three-dimensional conductive network increases the specific surface area inside the material, the specific discharge capacity of the electrode material is favorably improved, meanwhile, the graphene with strong conductivity can accelerate the conduction of electrons and ions in the pole piece, and the multiplying power performance of the material is improved.
The flexible battery plate prepared in example 1 was placed in a vacuum oven and dried at 100 ℃ for 12 hours, then the flexible battery plate was fixed between two pieces of weighing paper, and the flexible battery plate was punched with a microtome into a circular sheet with a diameter of 14mm as a negative electrode for assembling a button cell. Using a metal lithium sheet as a counter electrode, Celgard2500 as a diaphragm and 1.0M LiPF 6 Dissolving in EC: DEC: EMC (volume ratio is 1:1:1) as electrode solution, and assembling into CR2032 type button cell in a glove box filled with argon.
And under a constant environment with the temperature of 25 ℃, carrying out electrochemical performance test on the assembled button cell in a blue cell test system (Land, 2001A), and carrying out constant current charge and discharge test under the conditions that the charge and discharge voltage range is 0.01-3V and the current density is 0.1-5C.
The test result is shown in fig. 4, the specific capacity of the flexible battery pole piece at 0.1C is greater than 400mAh/g, the specific values are 421mAh/g at 0.1C, 383mAh/g at 0.2C, 349mAh/g at 0.5C, 314mAh/g at 1C, 266mAh/g at 2C and 191mAh/g at 5C, and the specific capacity is attenuated slowly and has higher retention rate as the current density is increased from 0.1C to 5C. The specific capacity of the graphite serving as a common negative electrode material in the lithium battery is 372mAh/g, and the specific capacity of the flexible battery in the embodiment is superior to that of the graphite under the current densities of 0.1C and 0.2C.
The flexible battery pole piece prepared in example 1 was placed in a vacuum drying oven and dried at 100 ℃ for 12 hours, then the flexible battery pole piece was fixed between two pieces of weighing paper, and the flexible battery pole piece was punched with a microtome into a circular piece with a diameter of 14mm as a negative electrode for assembling a button cell. A metal sodium sheet is taken as a counter electrode, glass fiber is taken as a diaphragm, and 1.0M NaPF 6 Dissolving in EC (EC) and DEC (volume ratio 1:1) as electrode solution, and assembling into a CR2032 type button cell in a glove box filled with argon.
And under the constant environment with the temperature of 25 ℃, carrying out electrochemical performance test on the assembled button cell in a blue cell test system (Land, 2001A), and carrying out constant current charge and discharge test under the conditions that the charge and discharge voltage range is 0.01-3V and the current density is 0.1-5C.
The test result is shown in fig. 5, the specific capacity of the flexible battery pole piece under 0.1C is more than 200mAh/g, the specific values are 214mAh/g under 0.1C, 184mAh/g under 0.2C, 171mAh/g under 0.5C, 151mAh/g under 1C, 137mAh/g under 2C, and 117mAh/g under 5C, and the specific capacity is attenuated slowly and has higher retention rate with the increase of the current density from 0.1C to 5C. When the current density is recovered to 0.1C from 5C, the specific capacity of the flexible battery pole piece is recovered to 186mAh/g, which shows that the flexible battery pole piece has higher structural stability.
The flexible battery pole piece provided by the invention has the following advantages:
1. the method is simple to operate, low in cost and high in applicability: the size-controllable flexible battery pole piece is prepared by electrostatic spinning technology and carbonization, and the size of the flexible battery pole piece prepared in the mode can meet the requirements of lithium batteries or sodium batteries with various sizes and specifications on the market at present;
2. has high specific capacity and flexibility: graphene is added to be compounded with the carbon nanofibers, and the graphene is attached to the carbon nanofibers, so that the structure of the carbon nanofibers is improved, and the flexibility and the conductivity of the carbon nanofibers are enhanced; the size of the carbon nanofiber is regulated and controlled to form a three-dimensional network structure which is connected with each other, so that the discharge specific capacity of the electrode material is improved; the carbonization parameters are optimized to avoid the brittleness of the fibers and improve the flexibility of the fibers, and the three dimensions are jointly regulated and optimized to prepare the flexible battery pole piece with good flexibility and electrochemical performance;
3. the bending angle is large, powder does not fall off in the bending process, and the lithium/sodium ion battery anode material serving as the cathode can meet the high energy density requirement of the lithium/sodium ion battery and can ensure good flexibility when being applied to the field of power batteries.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. The flexible battery pole piece is characterized by comprising carbon nanofiber and graphene, wherein the carbon nanofiber is prepared from polyacrylonitrile through electrostatic spinning and carbonization in sequence, the diameter of the carbon nanofiber is 200-500nm, the weight fraction of the graphene is 5-40% of that of the flexible battery pole piece, and the thickness of the flexible battery pole piece is 0.2-2 mm.
2. The flexible battery pole piece of claim 1, wherein the flexible battery pole piece is made by the steps of:
s1, dissolving the polyacrylonitrile in a dimethylformamide solution, adding the graphene, and stirring to prepare an electrostatic spinning solution;
s2, preparing the electrostatic spinning solution into a graphene composite nanofiber sheet by taking an aluminum foil as a receiving substrate;
and S3, carbonizing the graphene composite nanofiber sheet to obtain the flexible battery pole piece.
3. The flexible battery pole piece of claim 2, wherein in step S1, the weight ratio of the graphene to the polyacrylonitrile is (5-40): (60-95).
4. The flexible battery pole piece of claim 2, wherein in step S2, the electrospinning solution is injected into a 10ml syringe with a pushing speed of 0.002mm/S, a voltage of 15-20kv and a receiving distance of 10-15 cm.
5. The flexible battery pole piece of claim 2, wherein the graphene-composited nanofiber sheet is subjected to a pre-oxidation treatment prior to the carbonization treatment.
6. The flexible battery pole piece as claimed in claim 5, wherein the pre-oxidation treatment is to oxidize the graphene composite nanofiber sheet for 2-3h in an air atmosphere at a temperature of 200-220 ℃.
7. The flexible battery pole piece as claimed in claim 2, wherein the carbonization is performed on the graphene composite nanofiber sheet for 2-3h under the conditions of nitrogen atmosphere and temperature of 700-800 ℃.
8. The flexible battery pole piece of claim 1, wherein the flexible battery pole piece is used as a negative electrode in a lithium ion battery or a sodium ion battery.
9. The flexible battery pole piece of claim 1, wherein the flexible battery pole piece is bent at an angle of 0-180 ° under an external force.
10. A battery comprising the flexible battery sheet of any one of claims 1-9.
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