CN110034279B - Preparation method of flexible lithium ion battery negative electrode material - Google Patents
Preparation method of flexible lithium ion battery negative electrode material Download PDFInfo
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- CN110034279B CN110034279B CN201910380032.1A CN201910380032A CN110034279B CN 110034279 B CN110034279 B CN 110034279B CN 201910380032 A CN201910380032 A CN 201910380032A CN 110034279 B CN110034279 B CN 110034279B
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Abstract
The invention discloses a preparation method of a flexible lithium ion negative electrode. The method comprises the steps of taking graphene oxide as an active substance, firstly adding a conductive polymer monomer, polymerizing to obtain a graphene oxide/conductive polymer composite material, then sequentially adding an elastomer, a conductive agent and a binder which can be bonded with an active site of the graphene oxide, reducing to obtain an RGO/conductive polymer/conductive agent/binder/elastomer integrated composite material, and finally carrying out vacuum filtration, drying and rolling to obtain the integrated flexible electrode plate. The flexible electrode plate prepared by the invention is bonded by chemical bonds, the intermolecular acting force is strong, the active material of the electrode plate is not easy to fall off in the bending or charging and discharging processes, and all parts are in close contact by vacuum filtration and rolling, so that the synergistic effect is achieved. The flexible electrode prepared by the invention has good flexibility and electrochemical performance, and can still maintain good rate performance and cycle performance after bending experiments.
Description
Technical Field
The invention relates to a preparation method of a flexible lithium ion battery cathode material, and belongs to the technical field of lithium ion batteries.
Technical Field
With the rapid increase of global energy consumption and the problem of environmental pollution, the search for clean and sustainable energy is an urgent need. The lithium ion battery as an important energy storage device has the advantages of environmental protection, small environmental pollution and excellent electrochemical properties such as: the advantages of long cycle life, high capacity, low self-discharge rate, no memory effect and the like are widely applied to various fields of life, such as: flexible display screen, implanted medical instrument, cell-phone etc.. The flexible lithium ion battery pole piece which has high energy density, high power density, difficult falling of active substances after bending and good cycle performance is prepared is concerned.
Traditional lithium ion battery pole piece need with thick liquids coating at metal current collector surface, active material and current collector pass through the binder to be connected promptly, and this kind of mode is not only consuming time hard, and active material often can drop from the current collector because binder intensity is not enough moreover, leads to the internal resistance of battery to increase, reduces under the electrochemical performance. The flexible battery pole piece still keeps good electrochemical performance under the condition of meeting the requirement of bending and folding, and the traditional preparation process of the lithium ion battery pole piece cannot meet the requirement.
In order to solve the problems, researchers carry out surface modification, toughening and modifying the binder or use a blending binder on the metal current collector, increase the viscosity of active substances, add an elastomer into a system, coat a conductive coating on the surface of the metal current collector, develop flexible paper electrodes, use carbon cloth as electrodes and manufacture flexible electrodes by various suction filtration film-forming technologies. And (3) dispersing graphene in CN 104810504A such as Lifeng and the like, carrying out vacuum filtration to prepare a graphene current collector layer, carrying out suction filtration on an active electrode material layer on the graphene current collector by slurry, drying and rolling to prepare the integrated flexible electrode plate. CN 108417779A of Longjia et al adopts a sodium hydroxide/urea system to dissolve nano fibers to form component chains, and then the flexible film pole piece with uniformly distributed carbon nano tubes and active substances is prepared by a method of regenerating after coagulating bath, wherein the structure of continuous distribution of all components in the electrode can provide an excellent transmission path for electrons/ions, and reduces the contact impedance among all components, thereby improving the electrochemical activity and flexibility of the electrode. According to Korea waves and the like, multiple electrode material layers, an upper coating layer and a lower coating layer are stacked layer by layer in CN 207381477U to form an electrode slice similar to a hamburger structure, so that large-scale coating is realized, the process flow is simplified, and the electrochemical performance parameters of the battery are improved.
However, in these methods, the active material is physically bonded with the binder, the conductive agent, the current collector, etc., and thus has low strength and cannot satisfy the bending stability, and the active material still falls off during the charge and discharge processes, which causes the electrochemical performance to be degraded and cannot satisfy the flexible battery that needs to be bent for a long time during the use.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a preparation method of a flexible electrode of a lithium ion battery, and the prepared flexible electrode plate is characterized in that an active material, a binder, a conductive agent, an elastomer and a current collector are combined into a whole through chemical bonds, so that the acting force among molecules is enhanced, the active material is not easy to fall off in the bending or charging and discharging process of the electrode plate, and all parts are in close contact through vacuum filtration to play a synergistic effect. The flexible electrode prepared by the invention has good flexibility and electrochemical performance, and can still maintain good rate performance and cycle performance after bending experiments.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a flexible lithium ion battery cathode material takes reduced graphene oxide as an active material, specifically, the reduced graphene oxide is taken as a raw material, a binder, a conductive agent, an elastomer and a current collector are added, multi-step polymerization is carried out, and hydroiodic acid is utilized to carry out reduction reaction, so that the reduced graphene oxide and the current collector are combined into a whole by chemical bonds; the current collector is a conductive polymer; the binder, the elastomer and the conductive agent are all functional groups capable of reacting with the graphene oxide active sites.
Preferably, the graphene oxide is used as an active material, a current collector substance in a conductive polymer monomer form is added firstly, and the graphene oxide/conductive polymer composite material is obtained through polymerization; then sequentially adding an elastomer, a conductive agent and a binder which are capable of being bonded with active sites on the graphene oxide, and then carrying out reduction reaction by using hydroiodic acid to obtain a reduced graphene oxide/conductive polymer/conductive agent/binder/elastomer integrated composite material; and finally, carrying out vacuum filtration, drying and rolling to obtain the integrated flexible electrode plate.
Preferably, the functional group capable of reacting with the graphene oxide active site is one or more selected from the group consisting of a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a carbonyl group, an acyl group, a ketone group, an ether group, a thioether group, a methoxy group, a sulfonic acid group, and an isocyanate group.
Preferably, the conductive polymer is selected from one or more of polyaniline, polyacetylene, polythiophene, polypyrrole, polyparaphenylene and polyparaphenylene ethylene.
Preferably, the conductive polymer is selected from one or more of polyaniline, polyacetylene, polythiophene, polypyrrole, polyparaphenylene and polyparaphenylene ethylene.
Preferably, in the above technical solution, the binder is one or more selected from polyvinyl alcohol, polyacrylic acid, modified polyolefin, and modified polyurethane, the modified polyolefin is carboxylated or hydroxylated polyolefin, and the modified polyurethane is polyurethane having a carboxyl group, a hydroxyl group, an amino group, or an isocyanate group.
Preferably, in the above technical solution, the conductive agent is one or more of a carboxylated, hydroxylated or aminated carbon nanotube, a carbon fiber, and a superconducting carbon.
Preferably, the elastomer is a polyurethane fiber or a polyether amide having a carboxyl group, a hydroxyl group, an amino group, or an isocyanate group, a carboxylated or hydroxylated nanofiber, or a submicron-sized hyperbranched fiber
Preferably, the method of the present invention comprises the following steps:
a. mixing graphene oxide and a solvent according to a mass ratio of 1: (1-20) mixing, uniformly dispersing, adding a conductive polymer monomer, and polymerizing to generate a graphene oxide/conductive polymer composite material, wherein the mark is A;
b. centrifuging and drying the A, adding 0.5-2.5 wt% of elastomer, a proper amount of solvent and catalyst, and heating to react to generate a graphene oxide/conductive polymer/elastomer composite material, which is marked as B;
c. adding 1-10 wt% of dispersed conductive agent into B, and heating to react to generate graphene oxide/conductive polymer/elastomer/conductive agent composite material, which is marked as C;
d. adding a binder into the C, and heating to react to generate a graphene oxide/conductive polymer/elastomer/conductive agent/binder composite material, which is marked as D;
e. carrying out vacuum filtration on the D, and drying in an oven at the temperature of 30-80 ℃ for 5-24 hours;
f. and (3) removing the dried sample containing D from the filter membrane, putting the sample into hydroiodic acid, reducing the sample in a shading mode for 6-18 hours, taking the sample out, washing the sample with deionized water, drying and rolling the product to obtain the reduced graphene oxide/conductive polymer/conductive agent/binder/elastomer integrated flexible electrode sheet, and marking the electrode sheet as E.
Preferably, the solvent for dispersing the graphene oxide in the step b is one or more of water, acetone, isopropanol, ethanol, N-methyl pyrrolidone, sodium dodecyl benzene sulfonate and triton-100; the solvent for dispersing the conductive agent in the step d is one or more of water, ethanol, N-methyl pyrrolidone, sodium dodecyl benzene sulfonate and triton-100.
Preferably, in the steps b, c and d, the reaction temperature is 45-120 ℃; the reaction time is 2-20 h.
Preferably, the microporous filter membrane used in the vacuum filtration in the step e is one selected from a polyvinylidene fluoride filter membrane, a cellulose acetate filter membrane, a mixed fiber ester microporous filter membrane and a polyamide filter membrane; the aperture of the microporous filter membrane is 0.1-1 micron.
Preferably, the graphene oxide is prepared by an improved Hummers method, wherein an oxidant adopted by the Hummers method is one or more of potassium permanganate, sodium nitrate, concentrated sulfuric acid or phosphoric acid.
Compared with the prior art, the invention has the following advantages:
1. the prepared flexible electrode plate is bonded through chemical bonds, the intermolecular acting force is strengthened, so that the active material of the electrode plate is not easy to fall off in the bending or charging and discharging processes, and the parts are in close contact through vacuum filtration and rolling, so that the synergistic effect is achieved, the bonding strength among the parts of the electrode plate is enhanced, and the cycle life and the safety of the battery are improved; meanwhile, the flexible battery has strong bending stability, keeps good rate performance and cycle performance after bending experiments, and can meet the requirement of long-term bending and folding in the use process of the flexible battery.
2. The conductive polymer is used as a current collector and is combined with the active substance and the conductive agent through chemical bonds, so that close and effective conductive contact can be realized, the conductivity between the conductive polymer and the active substance is enhanced, the interface resistance is reduced, and the internal resistance of the battery is reduced.
3. The prepared flexible electrode plate has controllable quality and thickness, and the mass energy density and the volume energy density of the electrode plate can be changed according to requirements.
4. The flexible electrode prepared by the invention is bonded by chemical bonds of the conductive polymer, the graphene oxide, the elastomer, the binder and the conductive agent to form an intercrossed three-dimensional network structure, so that the self-supporting effect is achieved, the support of a metal current collector is not needed, and the manufacturing process of the battery is greatly simplified.
5. The graphene has good heat dissipation performance, can effectively discharge heat, and improves the safety of the battery in the charging and discharging processes; the conductive polymer can also effectively inhibit the active substance from swelling and falling off in the charging and discharging processes, and improves the cycle performance and safety of the battery.
Drawings
Fig. 1 is an SEM image of the graphene oxide/polyaniline/carbon nanotube integrated composite material before membrane extraction in example 1 of the present invention.
FIG. 2 is a comparison of infrared spectra before and after bonding of the flexible electrode in example 1 of the present invention.
Fig. 3 is an SEM image of the reduced graphene oxide/polyaniline/carbon nanotube/polyvinyl alcohol integrated flexible electrode sheet with different magnifications in embodiment 1 of the invention.
FIG. 4 is a diagram of a film after reduction and bending in example 2 of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
This detailed description is to be construed as illustrative only and is not limiting, since modifications will occur to those skilled in the art upon reading the preceding specification, and it is intended to be protected by the following claims.
Example 1
A preparation method of a flexible negative electrode material of a lithium ion battery comprises the following steps:
(1) adding 0.5g of flake graphite into 50mL of concentrated sulfuric acid, stirring for 1h under the ice-water bath condition, then adding 5g of potassium permanganate, continuing stirring for 1h under the ice-water bath condition, and then sequentially stirring for 1.5h at the medium temperature of 40 ℃ and the high temperature of 90 ℃ respectively; adding 1000mL of deionized water for multiple times at 90 ℃, and adding 10mL of hydrogen peroxide after the reaction is completed to obtain a clear bright yellow graphene oxide dispersion liquid; washing the graphene oxide dispersion liquid with acid, and freeze-drying to obtain powder;
(2) taking 0.3 g of graphene oxide synthesized and dried in the step (1), dissolving the graphene oxide in 60ml of 1mol/L hydrochloric acid aqueous solution, ultrasonically dispersing for 2h, adding 0.1g of aniline monomer, magnetically stirring for 1h, adding 0.24 g of ammonium persulfate, reacting for 24h at 0 ℃, centrifuging the product, placing the product in a vacuum drying oven, setting the temperature to be 50 ℃, and vacuum-drying for 30 h for later use;
(3) taking 0.3 g of the product prepared in the step (2), placing the product in 60ml of water for ultrasonic dispersion for 40 minutes, taking 40mg of hydroxylated carbon nano tube, dispersing the hydroxylated carbon nano tube in 50ml of 0.015g/ml triton-100 aqueous solution for ultrasonic dispersion for 2 hours, mixing the two, continuing the ultrasonic dispersion for 1 hour, adding 2ml of concentrated sulfuric acid, heating in a water bath at 110 ℃, and carrying out magnetic stirring reaction for 12 hours;
(4) adding 8ml of dispersed 0.1g/ml polyvinyl alcohol into the reaction system in the step (3), heating in a water bath at 110 ℃, and reacting for 12 hours by magnetic stirring;
(5) taking the solution obtained in the step (4), controlling the total mass of each membrane to be 40mg, pouring the solution into a solvent filter for suction filtration, repeatedly washing a filter cake to be neutral by deionized water, placing the filter cake in a vacuum drying oven, and drying the filter cake for 12 hours at 50 ℃;
(6) removing the dried sample from the filter membrane, reducing the sample in hydroiodic acid, taking out the sample after shading and reducing for 12 hours, washing the sample with deionized water, drying and rolling the washed sample to obtain a reduced graphene oxide/polyaniline/carbon nano tube/polyvinyl alcohol integrated flexible electrode plate;
(7) finally, directly taking the product of the step (6) as a negative active material of the test battery, taking a lithium sheet as a positive electrode, and using commercial electrolyte and a diaphragm; then assembling a 2025 button cell in an argon atmosphere glove box, standing overnight, and carrying out electrochemical performance test on the button cell.
Fig. 1 is an SEM image of the graphene oxide/polyaniline/carbon nanotube integrated composite material before membrane extraction, and it can be known from the figure that the graphene oxide and the carbon nanotube are uniformly dispersed in the three-dimensional network structure of polyaniline, penetrate and interleave with each other to form a plurality of gaps, and the structural form is relatively loose, which is beneficial to the extraction and insertion of lithium ions.
FIG. 2 is a comparison graph of infrared before and after bonding of flexible electrodes, which shows that graphene oxide is 1720cm-1The position is C = O expansion absorption peak on carboxyl, the absorption peak of hydroxyl is gradually reduced along with the addition of the hydroxylated carbon nanotube and the polyvinyl alcohol, which indicates that the reaction is generated, and the proportion of carbon base is reduced due to the addition of reactants, so that the infrared intensity at the back is reduced. 3300cm-1The position is the absorption peak of the polyaniline secondary amine. Both show that esterification reaction occurs, and better dispersion is introduced on polyaniline, so that the graphene oxide/polyaniline/carbon nano tube/polyvinyl alcohol integrated composite material is synthesized.
Fig. 3 is an SEM image of the reduced graphene oxide/polyaniline/carbon nanotube/polyvinyl alcohol integrated flexible electrode sheet, and from fig. 3, it can be clearly seen that a sheet structure of graphene and a dendritic structure of polyaniline are folded. The large surface area of the two-dimensional nanosheets can be fully utilized, and meanwhile, the deformation caused by the separation and the embedding of lithium ions can be better relieved by gaps formed by the staggered nanosheets, so that the requirement of the nanosheets as the negative electrode material of the lithium ion battery is met, compared with a figure 1, the nanosheets are in close contact with each other through vacuum filtration, so that the active material of the electrode plate is not easy to fall off in the bending or charging and discharging process, and the addition of polyvinyl alcohol can be seen to ensure that the surface of the material is smooth and the material has good film-forming property.
Example 2
A preparation method of a flexible lithium ion battery negative electrode material comprises the following steps:
(1) adding 0.5g of flake graphite into 50mL of concentrated sulfuric acid, stirring for 1h under the ice-water bath condition, then adding 5g of potassium permanganate, continuing stirring for 1h under the ice-water bath condition, and then sequentially stirring for 1.5h at the medium temperature of 40 ℃ and the high temperature of 90 ℃ respectively; adding 1000mL of deionized water for multiple times at 90 ℃, and adding 10mL of hydrogen peroxide after the reaction is completed to obtain a clear bright yellow graphene oxide dispersion liquid; washing the graphene oxide dispersion liquid with acid, and freeze-drying to obtain powder;
(2) dissolving 0.3 g of graphene oxide synthesized and dried in the step (1) in 60ml of N-methylpyrrolidone, ultrasonically dispersing for 2h, adding 0.1g of aniline monomer, magnetically stirring for 1h, adding 0.24 g of ammonium persulfate, reacting for 24h at 0 ℃, centrifuging the product, placing the product in a vacuum drying oven, setting the temperature to be 50 ℃, and vacuum-drying for 30 h for later use;
(3) taking 0.3 g of the product prepared in the step (2), placing the product in 60ml of N-methylpyrrolidone for ultrasonic dispersion for 1 hour, adding 115 mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 35 mg of N-hydroxysuccinimide, continuing ultrasonic dispersion for 20 minutes, adding 7.5 mg of polyetherimide, reacting at room temperature for 48 hours, centrifuging and drying;
(4) taking 0.3 g of the product obtained in the step (3), placing the product in 60ml of N-methyl pyrrolidone for ultrasonic dispersion for 1 hour, taking 40mg of hydroxylated carbon nano tube to disperse in 60ml of N-methyl pyrrolidone for ultrasonic dispersion for 2 hours, mixing the two, continuing ultrasonic dispersion for 1 hour, adding 2ml of concentrated sulfuric acid, heating in a water bath at 110 ℃, and carrying out magnetic stirring reaction for 12 hours;
(5) adding 8ml of dispersed 0.05g/ml polyacrylic acid into the reaction system in the step (4), heating in a water bath at 110 ℃, and reacting for 12 hours under magnetic stirring;
(6) taking the solution obtained in the step (5), controlling the total mass of each membrane to be 40mg, pouring the solution into a solvent filter for suction filtration, repeatedly washing a filter cake to be neutral by deionized water, placing the filter cake in a vacuum drying oven, and drying the filter cake for 12 hours at 50 ℃;
(7) and removing the dried sample from the filter membrane, reducing the sample in hydroiodic acid, taking out the sample after the reduction for 12 hours in a shading mode, washing the sample with deionized water, drying and rolling the product to obtain the reduced graphene oxide/polyaniline/polyetherimide/carbon nanotube/polyacrylic acid integrated flexible electrode plate. FIG. 4 is a diagram of a film after reduction and bending.
Example 3
A preparation method of a flexible lithium ion battery negative electrode material comprises the following steps:
(1) adding 0.5g of flake graphite into 50mL of concentrated sulfuric acid, stirring for 1h under the ice-water bath condition, then adding 5g of potassium permanganate, continuing stirring for 1h under the ice-water bath condition, and then sequentially stirring for 1.5h at the medium temperature of 40 ℃ and the high temperature of 90 ℃ respectively; adding 1000mL of deionized water for multiple times at 90 ℃, and adding 10mL of hydrogen peroxide after the reaction is completed to obtain a clear bright yellow graphene oxide dispersion liquid; washing the graphene oxide dispersion liquid with acid, and freeze-drying to obtain powder;
(2) dissolving 0.3 g of graphene oxide synthesized and dried in the step (1) in 60ml of deionized water, ultrasonically dispersing for 2h, and adding monomer benzene and catalyst AlCl in a certain proportion under stirring3And an oxidant CuCl, slowly heating to 30 ℃, then keeping constant temperature, after a certain period of induction period, carrying out reaction at a higher speed, changing the color from colorless and transparent to light brown and then to coffee, reacting for 2 hours, cooling, filtering, washing and drying a reaction product for later use;
(3) taking 0.3 g of the product prepared in the step (2), placing the product in 60ml of deionized water for ultrasonic dispersion for 1 hour, taking 40mg of hydroxylated carbon nano tube for ultrasonic dispersion in 60ml of water for 2 hours, mixing the product and the water, continuing ultrasonic dispersion for 1 hour, adding 2ml of concentrated sulfuric acid, heating in a water bath at 110 ℃, and carrying out magnetic stirring reaction for 12 hours;
(4) adding 8ml of dispersed 0.1g/ml polyvinyl alcohol into the reaction system in the step (3), heating in a water bath at 110 ℃, and reacting for 12 hours by magnetic stirring;
(5) taking the solution obtained in the step (4), controlling the total mass of each membrane to be 40mg, pouring the solution into a solvent filter in batches for suction filtration, repeatedly washing a filter cake to be neutral by deionized water, placing the filter cake in a vacuum drying oven, and drying the filter cake for 12 hours at 50 ℃;
(6) and removing the dried sample from the filter membrane, reducing the sample in hydroiodic acid, taking out the sample after the reduction for 12 hours in a shading mode, washing the sample with deionized water, drying and rolling the product to obtain the reduced graphene oxide/poly-p-phenylene/carbon nano tube/polyvinyl alcohol integrated flexible electrode slice.
Claims (9)
1. A preparation method of a flexible lithium ion battery negative plate takes reduced graphene oxide as an active material, and is characterized in that: the active material, the binder, the conductive agent, the elastomer and the current collector in the flexible lithium ion battery negative plate are combined into a whole through chemical bonds; the current collector is a conductive polymer; the adhesive, the elastomer and the conductive agent are all functional groups capable of reacting with the graphene oxide active sites;
the method specifically comprises the following steps:
a. mixing graphene oxide and a solvent according to a mass ratio of 1: (1-20) mixing, uniformly dispersing, adding a conductive polymer monomer, and polymerizing to generate a graphene oxide/conductive polymer composite material, wherein the mark is A;
b. centrifuging and drying the A, adding 0.5-2.5 wt% of elastomer, a proper amount of solvent and catalyst, and heating to react to generate a graphene oxide/conductive polymer/elastomer composite material, which is marked as B;
c. adding 1-10 wt% of dispersed conductive agent into B, and heating to react to generate graphene oxide/conductive polymer/elastomer/conductive agent composite material, which is marked as C;
d. adding a binder into the C, and heating to react to generate a graphene oxide/conductive polymer/elastomer/conductive agent/binder composite material, which is marked as D;
e. carrying out vacuum filtration on the D, and drying in an oven at the temperature of 30-80 ℃ for 5-24 hours;
f. and (3) removing the dried sample containing D from the filter membrane, putting the sample into hydroiodic acid, reducing the sample in a shading mode for 6-18 hours, taking the sample out, washing the sample with deionized water, drying and rolling the product to obtain the reduced graphene oxide/conductive polymer/conductive agent/binder/elastomer integrated flexible electrode sheet, and marking the electrode sheet as E.
2. The preparation method of the negative electrode sheet of the flexible lithium ion battery according to claim 1, characterized in that: the functional group capable of reacting with the graphene oxide active site is selected from one or more of carboxyl, hydroxyl, sulfydryl, amino, carbonyl, acyl, ketone, ether, thioether, methoxyl, sulfonic group and isocyanate group.
3. The preparation method of the negative electrode sheet of the flexible lithium ion battery according to claim 1, characterized in that: the conductive polymer is selected from one or more of polyaniline, polyacetylene, polythiophene, polypyrrole, poly-p-phenylene and poly-p-phenylene ethylene.
4. The preparation method of the negative electrode sheet of the flexible lithium ion battery according to claim 1, characterized in that: the binder is selected from one or more of polyvinyl alcohol, polyacrylic acid, modified polyolefin and modified polyurethane, the modified polyolefin is carboxylated or hydroxylated polyolefin, and the modified polyurethane is polyurethane with carboxyl, hydroxyl, amino or isocyanate groups.
5. The preparation method of the negative electrode sheet of the flexible lithium ion battery according to claim 1, characterized in that: the conductive agent is one or more of carboxylated, hydroxylated or aminated carbon nanotubes, carbon fibers and superconducting carbon.
6. The preparation method of the negative electrode sheet of the flexible lithium ion battery according to claim 1, characterized in that: the elastomer is polyurethane fiber or polyether amide with carboxyl, hydroxyl, amino and isocyanate groups, and nanometer fiber or submicron level multi-branch crystal fiber after carboxylation and hydroxylation.
7. The preparation method of the negative electrode sheet of the flexible lithium ion battery according to claim 1, characterized in that: the solvent for dispersing the graphene oxide in the step b is one or more of water, acetone, isopropanol, ethanol, N-methyl pyrrolidone, sodium dodecyl benzene sulfonate and triton-100; the solvent for dispersing the conductive agent in the step d is one or more of water, ethanol, N-methyl pyrrolidone, sodium dodecyl benzene sulfonate and triton-100.
8. The preparation method of the negative electrode sheet of the flexible lithium ion battery according to claim 1, characterized in that: in the steps b, c and d, the reaction temperature is 45-120 ℃; the reaction time is 2-20 h.
9. The preparation method of the negative electrode sheet of the flexible lithium ion battery according to claim 1, characterized in that: the microporous filter membrane used in the vacuum filtration in the step e is selected from one of a polyvinylidene fluoride filter membrane, a cellulose acetate filter membrane, a mixed fiber ester microporous filter membrane and a polyamide filter membrane; the aperture of the microporous filter membrane is 0.1-1 micron.
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