CN110364687B - Preparation method of flexible thin film electrode, prepared electrode and application - Google Patents
Preparation method of flexible thin film electrode, prepared electrode and application Download PDFInfo
- Publication number
- CN110364687B CN110364687B CN201910693346.7A CN201910693346A CN110364687B CN 110364687 B CN110364687 B CN 110364687B CN 201910693346 A CN201910693346 A CN 201910693346A CN 110364687 B CN110364687 B CN 110364687B
- Authority
- CN
- China
- Prior art keywords
- polyacrylic acid
- sodium carboxymethylcellulose
- graphene oxide
- film electrode
- flexible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a flexible film electrode, which comprises the steps of firstly preparing an aqueous composite adhesive from graphene oxide, sodium carboxymethylcellulose and polyacrylic acid in water, adding active particles such as nano silicon particles and silicon monoxide particles, preparing a flexible graphene oxide-sodium carboxymethylcellulose-polyacrylic acid-active particle composite film through vacuum filtration and vacuum freeze drying, and then carrying out liquid phase reduction and vacuum thermal polycondensation reaction to obtain the flexible film electrode. The method uses water as a solvent to prepare the adhesive, and the conductive agent can generate molecular crosslinking effect with the adhesive, has good conductive effect, can still keep the stability of the electrode structure after a plurality of cycles, has slow capacity decay, and has good mechanical strength and flexibility. The prepared flexible film electrode can be used for manufacturing electrodes of lithium ion batteries, capacitors or other energy storage systems.
Description
Technical Field
The invention relates to the field of electrode materials, in particular to a preparation method of a flexible thin film electrode, the prepared electrode and application.
Background
Aiming at the problems of energy crisis, resource shortage, environmental pollution and the like which are increasingly aggravated at present, the development of clean and renewable energy becomes a major strategy for the social and economic development of China, and the strategy is listed as a key and preferential development direction in the national medium-long scientific and technological development planning outline. Lithium Ion Batteries (LIBs) have attracted wide attention worldwide as a primary power source for portable energy storage devices due to their advantages of high energy density, long cycle life, and environmental friendliness. In order to meet the increasing energy consumption requirements of portable electronic equipment, wearable flexible electronic equipment, electric vehicles, hybrid vehicles and the like, how to further realize efficient energy storage and conversion of lithium ion batteries and simultaneously have the advantages of high safety, low cost, environmental friendliness and the like become an important challenge facing the present stage.
The lithium storage performance of lithium ion batteries depends greatly on the performance of positive and negative electrodes, and currently, research and development on lithium ion batteries are in progressDuring the development, researchers have concentrated much on the positive and negative electrode active materials, and have not paid sufficient attention to the important components of the electrode, i.e., the binder and the conductive agent. Currently, in the production of commercial lithium ion batteries, polyvinylidene fluoride (PVDF) is widely used as a binder for positive and negative electrodes due to its good electrochemical stability, adhesion and wide electrochemical stability window. However, the expensive price of PVDF binder increases the production cost of lithium ion batteries; meanwhile, in the application process, a toxic volatile organic solvent N-methyl pyrrolidone (NMP) is also required to be used as a slurry dispersing agent, so that the environment is polluted, and the health of operators is harmed. In addition, the production process has strict requirement on the environmental humidity, and the lithium metal complex can easily react with the lithium metal to generate stable LiF6An exothermic reaction occurs. In order to overcome the above disadvantages of PVDF binder, researchers have recently proposed a method of replacing the oil-based binder PVDF with an aqueous binder based on the requirements of eco-friendliness, low cost, enhanced lithium storage performance of the electrode, solvent recycling, and the like. The water-based binder can avoid the use of NMP, and has the advantages of low cost, easy acquisition, environmental friendliness, safe use and the like. Moreover, the process of simply using water as a dispersant to manufacture the electrode is simpler and more convenient, so that the electrode becomes an ideal binder of a safe and environment-friendly lithium ion battery. In recent years, in the course of active development of polymer binders replacing PVDF, a great deal of work has focused on designing and developing new aqueous polymer binders with specific molecular compositions and structures.
The chains of the PVDF, sodium carboxymethylcellulose (CMC), polyacrylic acid (PAA), and other linear binder molecules that are commonly used at present can only be connected through a physical crosslinking manner (such as van der waals force and hydrogen bonds) with weak binding force, and after a short number of continuous cycles, irreversible slippage with active material particles is inevitable, so that the electrical connectivity between the active material and the current collector and the conductive additive is lost, and the degradation of the structural stability of the electrode and the rapid attenuation of the capacity are caused. Meanwhile, the conductive agent and the active material are not adhered, and the conductive agent is easily separated from the active material in the charging/discharging process, so that the electric connectivity is lost to interrupt an electron transmission path. In addition, the conventional binder lacks sufficient mechanical strength and cannot withstand the large volume change of the electrode material such as silicon-based, tin-based, and oxide-based materials during the lithium desorption/insertion process, which accelerates the mechanical breakage and peeling of the electrode material, resulting in the loss of electron conduction path.
How to select the conductive agent and the adhesive to enable the conductive agent and the adhesive to be mutually subjected to molecular crosslinking better and enhance the conductivity of the conductive agent is beneficial to better coating an electrode material, enhancing the mechanical strength and flexibility of a prepared electrode and improving the cyclability and the service life of a battery, and is a practical problem expected to be solved in the field.
Disclosure of Invention
The invention aims to provide a preparation method of a flexible film electrode, which uses water as a solvent to prepare an adhesive, can generate molecular crosslinking action with the adhesive, has good conductive effect, can still keep the stability of an electrode structure after a plurality of cycles, has slow capacity attenuation, and has good mechanical strength and flexibility.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a flexible film electrode is characterized by comprising the following steps:
(a) respectively dispersing graphene oxide and sodium carboxymethylcellulose in water to obtain a graphene oxide dispersion liquid and a sodium carboxymethylcellulose dispersion liquid, adding polyacrylic acid and the sodium carboxymethylcellulose dispersion liquid into the graphene oxide dispersion liquid, uniformly mixing and performing molecular crosslinking to obtain a water-based composite adhesive, wherein the mass percentage content of the graphene oxide is 10-35%, the mass percentage content of the sodium carboxymethylcellulose is 5-10%, the mass percentage content of the polyacrylic acid is 55-85%, and the sum of the mass percentage contents of the graphene oxide, the sodium carboxymethylcellulose and the polyacrylic acid is 100%;
(b) adding active particles into the aqueous composite adhesive, and uniformly dispersing the active particles to obtain an active particle mixed solution, wherein the active particles are silicon nano particles or silicon oxide particles, the mass percentage content of the active particles is 60-90%, the sum of the mass percentages of the graphene oxide, the sodium carboxymethylcellulose and the polyacrylic acid is 10-40%, and the sum of the mass percentages of the active particles, the graphene oxide, the sodium carboxymethylcellulose and the polyacrylic acid is 100%;
(c) performing vacuum filtration and vacuum freeze drying on the active particle mixed solution to prepare a flexible graphene oxide-sodium carboxymethylcellulose-polyacrylic acid-active particle composite film;
(d) reducing the flexible graphene oxide-sodium carboxymethylcellulose-polyacrylic acid-active particle composite film into a flexible graphene-sodium carboxymethylcellulose-polyacrylic acid-active particle composite film in a liquid phase;
(e) and (2) soaking the flexible graphene-sodium carboxymethylcellulose-polyacrylic acid-active particle composite film in water, washing, freezing and drying, then carrying out vacuum thermal polycondensation reaction, and obtaining the flexible film electrode after the reaction.
Preferably, the sodium carboxymethylcellulose is Japanese cellosolve DAICEL CMC2200, the viscosity (1% aqueous solution @25 ℃ C. 60rpm) is 1500-3000 mPas, the pH value (1% aqueous solution @25 ℃ C.) is 6.0-8.5, the minimum substitution degree is 0.8, the polyacrylic acid is an aqueous solution with the mass percentage concentration of 45-55%, and the average molecular weight of the polyacrylic acid is 2800-3200.
Preferably, the purity of the silicon nano particles is not lower than 99.9%, and the particle size is 20-100 nm; the average particle size of the silicon oxide particles is 3.5-5 microns.
Preferably, the reduction in step (d) is performed by using a liquid-phase reducing agent, and the liquid-phase reducing agent is hydrazine hydrate or an aqueous solution of sodium borohydride.
Preferably, the thickness of the flexible thin film electrode obtained in the step (e) is 5-200 microns.
Preferably, the temperature of the vacuum thermal polycondensation reaction in the step (e) is 120-.
The method takes water as a solvent, is simple to operate, is green and environment-friendly, and is easy to prepare the flexible thin film electrode in a large area. According to the method, the graphene oxide is bonded with sodium carboxymethylcellulose (CMC) and polyacrylic acid (PAA), the bonded part still keeps good connection after the graphene oxide is reduced to graphene, and polymerization is carried out through vacuum thermal polycondensation, so that the bonding force of the graphene serving as a conductive agent with the sodium carboxymethylcellulose and the polyacrylic acid is effectively enhanced, the continuous effective contact of the conductive agent with electrode active materials, namely silicon oxide nanoparticles and silicon nanoparticles is enhanced, the irreversible slippage which is easy to occur between the electrode active materials and the conductive agent in the past is avoided, the structural stability, the mechanical strength and the cycle performance of the electrode are improved, and the excessively fast attenuation of the battery capacity is avoided.
Another object of the present invention is to provide a flexible thin film electrode, which is prepared by the above method, and which has a layered network structure as a whole, and improves electron transfer and ion diffusion inside the electrode, and at the same time, the binder covers the surface of the active material, so as to reduce oxidation of the nano active material, not only inhibit deposition of the electrolyte on the surface of the active material from generating an irreversible reaction, but also effectively alleviate volume expansion of the material during charge/discharge, and improve cycle life and rate performance of the battery.
The flexible film electrode can be used for manufacturing electrodes of lithium ion batteries, capacitors or other energy storage systems.
Based on organic-inorganic micro-nano multi-level layer-by-layer assembly structures and interface interaction, the layered graphene is used as a framework structure, the sodium carboxymethyl cellulose enhances the bonding performance of the layered graphene, polyacrylic acid is introduced to be capable of carrying out molecular crosslinking with molecular chains of the graphene and the sodium carboxymethyl cellulose, meanwhile, the-COOH groups in the polyacrylic acid are uniformly distributed and can be connected with electrochemical active material particles in three dimensions through chemical bonds (hydrogen bonds or covalent bonds), and the bonding force with active materials is enhanced; polyacrylic acid molecules and sodium carboxymethyl cellulose molecules can be successfully embedded into channels among graphene oxide layers, more hydrogen bonds can be formed among graphene oxide layers, and sodium carboxymethyl cellulose has the effect of connecting graphene oxide layers and polyacrylic acid molecules, so that the interlayer acting force is further increased. Polyacrylic acid molecules and sodium carboxymethyl cellulose can generate thermal polycondensation reaction under the vacuum condition, and the mutual binding force of the polyacrylic acid molecules and the sodium carboxymethyl cellulose is increased. Due to the unique molecular structure of the sodium carboxymethyl cellulose, hydrogen bonds are formed with polyacrylic acid in the transverse direction, so that the material has better tensile strength. Meanwhile, a polyacrylic acid layer with high amorphous degree is crosslinked with graphene, and the polyacrylic acid layer is easier to cover the surface of the active material than PVDF with high crystallinity, so that a bifunctional conformal coating similar to an SEI film is formed, and the bifunctional conformal coating is similar to the polar hydrogen bond action of carboxyl of some binders and hydroxyl on the surface of the active material. The conformal coating similar to the SEI film can inhibit the irreversible reaction of the electrolyte on the surface of the active material, effectively relieve the volume expansion of the material in the charge/discharge process, provide a three-dimensional continuous electron conduction path, and be beneficial to maintaining the structural integrity of the electrode in the charge/discharge process and the reversibility of the cycle process.
According to the invention, graphene oxide is used as an inorganic reinforcing material, a graphene/sodium carboxymethylcellulose/polyacrylic acid aqueous binder is constructed by covalent bond crosslinking between polyacrylic acid, graphene oxide and sodium carboxymethylcellulose, and simultaneously, the components of the binder and an active material can be subjected to mutual bonding, so that the preparation of the integrated electrochemical energy storage composite flexible thin film electrode with strong, tough, high electron and ion transmission is realized. In addition, the composite material structure of the graphene oxide is more complete after the graphene oxide is subjected to liquid-phase chemical reduction, so that the graphene oxide composite material has good electrochemical energy storage performance.
The invention has the following beneficial effects:
(1) the invention adopts water-soluble macromolecule derivative-sodium carboxymethyl cellulose as raw material, which has wide source and low cost. And the sodium carboxymethyl cellulose has biodegradability and is green and pollution-free.
(2) The graphene oxide adopted by the invention is used as a precursor of a binder conductive agent material and is applied to a water-based binder system. Graphene oxide can form a stable suspension in water. Meanwhile, the graphene sheets are kept at the micron level, which is beneficial to the long-range conductivity thereof; the formed conductive film has ductility, can inhibit large volume change of some active materials in the charging and discharging processes to a certain extent, is favorable for improving the rate performance of the battery and prolonging the service life of the battery. According to the invention, graphene is added to replace a commercial conductive carbon material, so that the defects of poor wettability, easy agglomeration and difficult dispersion of the commercial conductive carbon material in an aqueous system are overcome to a certain extent.
(3) Introducing sodium carboxymethylcellulose and polyacrylic acid to be uniformly dispersed on the surface of silicon particles in the vacuum filtration process to form effective coverage and protection and reduce the oxidation of nano silicon; and can play a role in stabilizing silicon particles.
(4) The invention avoids the additional use of a binder and a conductive additive in the traditional electrode preparation process. Therefore, the method is expected to become a very suitable alternative process of the traditional coating process technology, and the interface performance between the electrode material and the electrolyte is improved, so that the coulombic efficiency of the electrode material and the cycling stability and rate capability of the battery are improved.
(5) The technology of the invention is green and environment-friendly, the scheme is simple, the operation is easy, the repeatability is good, the application range is wide, and an effective way is provided for the research of the high-capacity lithium ion battery.
Drawings
FIG. 1 is a photo of a nano silicon-based flexible thin film electrode prepared in example 3 of the present invention;
FIG. 2 is an XRD spectrum of the nano silicon-based flexible thin film electrode prepared in example 3 of the present invention;
fig. 3 to 6 are SEM images of nano silicon-based flexible thin film electrodes prepared in example 3 of the present invention at different magnifications;
FIG. 7 is a cyclic voltammetry curve of a nano silicon-based flexible thin film electrode prepared in example 3 of the present invention;
fig. 8 is a charge-discharge curve of the nano silicon-based flexible thin film electrode prepared in example 3 of the present invention.
Detailed Description
For further explanation of the present invention, the following detailed description of the present invention is provided with reference to the accompanying drawings.
Example 1 method for manufacturing flexible thin film electrode 1
(1) Firstly, weighing 10 mg of graphene oxide by using a balance, placing the graphene oxide in 20 ml of deionized water, continuously stirring for 30 min, and then carrying out ultrasonic treatment for 60 min to obtain a uniform graphene oxide dispersion liquid; weighing 5mg of sodium carboxymethylcellulose, placing the sodium carboxymethylcellulose in 10 ml of deionized water, and stirring and ultrasonically preparing a uniform sodium carboxymethylcellulose dispersion liquid; slowly adding 0.2ml of polyacrylic acid solution containing 85mg of polyacrylic acid into the graphene oxide dispersion liquid, magnetically stirring at room temperature for 30 min, and performing ultrasonic treatment for 30 min; and then adding the sodium carboxymethylcellulose dispersion liquid into the graphene oxide dispersion liquid, and stirring and ultrasonically treating until the graphene oxide dispersion liquid is uniform. In the stirring ultrasonic process, polyacrylic acid, carboxyl and epoxy groups on the surfaces of graphene oxide and sodium carboxymethyl cellulose are subjected to covalent crosslinking to generate the aqueous composite binder.
(2) Adding 150 mg of silicon nano particles into the aqueous composite binder, magnetically stirring for 30 min, and then performing ultrasonic dispersion for 30 min to obtain a uniform active particle mixed solution;
(3) filtering the obtained active particle mixed solution on a vacuum filtration device by using a microporous filter membrane with micropores of 0.22 mu m by using vacuum auxiliary filtration; then cleaning the filtered product by using 100-300 ml of deionized water; the filters were then placed in a refrigerator for freezing. Freezing for 5h, and then freezing and drying for 8h by using a vacuum freezing dryer to obtain the flexible graphene oxide-sodium carboxymethylcellulose-polyacrylic acid-nano silicon composite film.
(4) And (3) placing the dried composite film in a watch glass, adding a hydrazine hydrate solution for reduction, and standing for 6 hours to obtain the flexible graphene-sodium carboxymethylcellulose-polyacrylic acid-nano silicon composite film.
(5) Taking out the composite membrane obtained in the step (4), and washing the composite membrane for a plurality of times by using deionized water; after cleaning, immediately putting the mixture into a refrigerator, and freezing for 5 hours; and putting the nano silicon-based flexible thin film electrode into a vacuum freeze dryer again, freeze-drying for 8h, and then carrying out vacuum thermal polycondensation reaction for 6h at the temperature of 120 ℃, wherein the pressure of the reaction is not higher than 0.1Mpa, thus obtaining the nano silicon-based flexible thin film electrode.
Example 2 method for manufacturing flexible thin film electrode 2
(1) Firstly, weighing 35 mg of graphene oxide by using a balance, placing the graphene oxide in 50 ml of deionized water, continuously stirring for 30 min, and then carrying out ultrasonic treatment for 60 min to obtain a uniform graphene oxide dispersion liquid; weighing 10 mg of sodium carboxymethylcellulose, placing the sodium carboxymethylcellulose in 10 ml of deionized water, and stirring and ultrasonically preparing a uniform sodium carboxymethylcellulose dispersion liquid; slowly adding 0.13ml of polyacrylic acid solution containing 55mg of polyacrylic acid into the graphene oxide dispersion liquid, magnetically stirring at room temperature for 30 min, and performing ultrasonic treatment for 30 min; and then adding the sodium carboxymethylcellulose dispersion liquid into the graphene oxide dispersion liquid, and stirring and ultrasonically treating until the graphene oxide dispersion liquid is uniform. In the stirring ultrasonic process, polyacrylic acid, carboxyl and epoxy groups on the surfaces of graphene oxide and sodium carboxymethyl cellulose are subjected to covalent crosslinking to generate the aqueous composite binder.
(2) Adding 900 mg of nano silicon into the aqueous composite binder, magnetically stirring for 30 min, and then ultrasonically dispersing for 30 min to obtain a uniform active particle mixed solution;
(3) filtering the obtained active particle mixed solution on a vacuum filtration device by using a microporous filter membrane with micropores of 0.22 mu m by using vacuum auxiliary filtration; then cleaning the filtered product by using 100-300 ml of deionized water; the filters were then placed in a refrigerator for freezing. Freezing for 5h, and then freezing and drying for 8h by using a vacuum freezing dryer to obtain the flexible graphene oxide-sodium carboxymethylcellulose-polyacrylic acid-nano silicon composite film.
(4) And placing the dried composite film in a watch glass, adding a sodium borohydride aqueous solution for reduction, and standing for 6 hours to obtain the flexible graphene-sodium carboxymethylcellulose-polyacrylic acid-nano silicon composite film.
(5) Taking out the composite membrane obtained in the step (4), and washing the composite membrane for a plurality of times by using deionized water; after cleaning, immediately putting the mixture into a refrigerator, and freezing for 5 hours; and putting the nano silicon-based flexible thin film electrode into a vacuum freeze dryer again, freeze-drying for 8h, and then carrying out vacuum thermal polycondensation reaction for 1h at the temperature of 180 ℃, wherein the pressure intensity of the reaction is not higher than 0.1Mpa, thus obtaining the nano silicon-based flexible thin film electrode.
Example 3 method for manufacturing flexible thin film electrode 3
(1) Firstly, weighing 25 mg of graphene oxide by using a balance, placing the graphene oxide in 20 ml of deionized water, continuously stirring for 30 min, and then carrying out ultrasonic treatment for 60 min to obtain a uniform graphene oxide dispersion liquid; weighing 8 mg of sodium carboxymethylcellulose, placing the sodium carboxymethylcellulose in 10 ml of deionized water, and stirring and ultrasonically preparing a uniform sodium carboxymethylcellulose dispersion liquid; slowly adding 0.16ml of polyacrylic acid solution containing 67mg of polyacrylic acid into the graphene oxide dispersion liquid, magnetically stirring at room temperature for 30 min, and performing ultrasonic treatment for 30 min; and then adding the sodium carboxymethylcellulose dispersion liquid into the graphene oxide dispersion liquid, and stirring and ultrasonically treating until the graphene oxide dispersion liquid is uniform. In the stirring ultrasonic process, polyacrylic acid, carboxyl and epoxy groups on the surfaces of graphene oxide and sodium carboxymethyl cellulose are subjected to covalent crosslinking to generate the aqueous composite binder.
(2) Adding 240 mg of nano silicon into the aqueous composite binder, magnetically stirring for 30 min, and then performing ultrasonic dispersion for 30 min to obtain a uniform active particle mixed solution;
(3) filtering the obtained active particle mixed solution on a vacuum filtration device by using a microporous filter membrane with micropores of 0.22 mu m by using vacuum auxiliary filtration; then cleaning the filtered product by using 100-300 ml of deionized water; the filters were then placed in a refrigerator for freezing. Freezing for 5h, and then freezing and drying for 8h by using a vacuum freezing dryer to obtain the flexible graphene oxide-sodium carboxymethylcellulose-polyacrylic acid-nano silicon composite film.
(4) And (3) placing the dried composite film in a watch glass, adding a hydrazine hydrate solution for reduction, and standing for 6 hours to obtain the flexible graphene-sodium carboxymethylcellulose-polyacrylic acid-nano silicon composite film.
(5) Taking out the composite membrane obtained in the step (4), and washing the composite membrane for a plurality of times by using deionized water; after cleaning, immediately putting the mixture into a refrigerator, and freezing for 5 hours; and putting the nano silicon-based flexible thin film electrode into a vacuum freeze dryer again, freeze-drying for 8h, and then carrying out vacuum thermal polycondensation reaction for 4h at 160 ℃, wherein the pressure of the reaction is not higher than 0.1Mpa, thus obtaining the nano silicon-based flexible thin film electrode.
Example 4 method for manufacturing flexible thin film electrode 4
(1) Firstly, weighing 10 mg of graphene oxide by using a balance, placing the graphene oxide in 20 ml of deionized water, continuously stirring for 30 min, and then carrying out ultrasonic treatment for 60 min to obtain a uniform graphene oxide dispersion liquid; weighing 5mg of sodium carboxymethylcellulose, placing the sodium carboxymethylcellulose in 10 ml of deionized water, and stirring and ultrasonically preparing a uniform sodium carboxymethylcellulose dispersion liquid; slowly adding 0.2ml of polyacrylic acid solution containing 85mg of polyacrylic acid into the graphene oxide dispersion liquid, magnetically stirring at room temperature for 30 min, and performing ultrasonic treatment for 30 min; and then adding the sodium carboxymethylcellulose dispersion liquid into the graphene oxide dispersion liquid, and stirring and ultrasonically treating until the graphene oxide dispersion liquid is uniform. In the stirring ultrasonic process, polyacrylic acid, carboxyl and epoxy groups on the surfaces of graphene oxide and sodium carboxymethyl cellulose are subjected to covalent crosslinking to generate the aqueous composite binder.
(2) Adding 150 mg of silicon monoxide into the aqueous composite binder, magnetically stirring for 30 min, and then performing ultrasonic dispersion for 30 min to obtain a uniform active particle mixed solution;
(3) filtering the obtained active particle mixed solution on a vacuum filtration device by using a microporous filter membrane with micropores of 0.22 mu m by using vacuum auxiliary filtration; then cleaning the filtered product by using 100-300 ml of deionized water; the filters were then placed in a refrigerator for freezing. Freezing for 5h, and then freezing and drying for 8h by using a vacuum freezing dryer to obtain the flexible graphene oxide-sodium carboxymethylcellulose-polyacrylic acid-silicon oxide composite film.
(4) And (3) placing the dried composite film in a watch glass, adding a hydrazine hydrate solution for reduction, and standing for 6 hours to obtain the flexible graphene-sodium carboxymethylcellulose-polyacrylic acid-silicon oxide composite film.
(5) Taking out the composite membrane obtained in the step (4), and washing the composite membrane for a plurality of times by using deionized water; after cleaning, immediately putting the mixture into a refrigerator, and freezing for 5 hours; and putting the membrane into a vacuum freeze dryer again, freeze drying for 8h, and then carrying out vacuum thermal polycondensation reaction for 6h at the temperature of 120 ℃, wherein the pressure of the reaction is not higher than 0.1Mpa, thus obtaining the silicon protoxide-based flexible membrane electrode.
Example 5 method for manufacturing flexible thin film electrode 5
(1) Firstly, weighing 35 mg of graphene oxide by using a balance, placing the graphene oxide in 50 ml of deionized water, continuously stirring for 30 min, and then carrying out ultrasonic treatment for 60 min to obtain a uniform graphene oxide dispersion liquid; weighing 10 mg of sodium carboxymethylcellulose, placing the sodium carboxymethylcellulose in 10 ml of deionized water, and stirring and ultrasonically preparing a uniform sodium carboxymethylcellulose dispersion liquid; slowly adding 0.13ml of polyacrylic acid solution containing 55mg of polyacrylic acid into the graphene oxide dispersion liquid, magnetically stirring at room temperature for 30 min, and performing ultrasonic treatment for 30 min; and then adding the sodium carboxymethylcellulose dispersion liquid into the graphene oxide dispersion liquid, and stirring and ultrasonically treating until the graphene oxide dispersion liquid is uniform. In the stirring ultrasonic process, polyacrylic acid, carboxyl and epoxy groups on the surfaces of graphene oxide and sodium carboxymethyl cellulose are subjected to covalent crosslinking to generate the aqueous composite binder.
(2) Adding 900 mg of silicon monoxide into the aqueous composite binder, magnetically stirring for 30 min, and then ultrasonically dispersing for 30 min to obtain a uniform active particle mixed solution;
(3) filtering the obtained active particle mixed solution on a vacuum filtration device by using a microporous filter membrane with micropores of 0.22 mu m by using vacuum auxiliary filtration; then cleaning the filtered product by using 100-300 ml of deionized water; the filters were then placed in a refrigerator for freezing. Freezing for 5h, and then freezing and drying for 8h by using a vacuum freezing dryer to obtain the flexible graphene oxide-sodium carboxymethylcellulose-polyacrylic acid-silicon oxide composite film.
(4) And placing the dried composite film in a watch glass, adding a sodium borohydride aqueous solution for reduction, and standing for 6 hours to obtain the flexible graphene-sodium carboxymethylcellulose-polyacrylic acid-silicon oxide composite film.
(5) Taking out the composite membrane obtained in the step (4), and washing the composite membrane for a plurality of times by using deionized water; after cleaning, immediately putting the mixture into a refrigerator, and freezing for 5 hours; and putting the membrane into a vacuum freeze dryer again, freeze drying for 8h, and then carrying out vacuum thermal polycondensation reaction for 1h at 180 ℃ under the pressure not higher than 0.1Mpa to obtain the silicon protoxide-based flexible membrane electrode.
Example 6 method for manufacturing flexible thin film electrode 6
(1) Firstly, weighing 25 mg of graphene oxide by using a balance, placing the graphene oxide in 20 ml of deionized water, continuously stirring for 30 min, and then carrying out ultrasonic treatment for 60 min to obtain a uniform graphene oxide dispersion liquid; weighing 8 mg of sodium carboxymethylcellulose, placing the sodium carboxymethylcellulose in 10 ml of deionized water, and stirring and ultrasonically preparing a uniform sodium carboxymethylcellulose dispersion liquid; slowly adding 0.16ml of polyacrylic acid solution containing 67mg of polyacrylic acid into the graphene oxide dispersion liquid, magnetically stirring at room temperature for 30 min, and performing ultrasonic treatment for 30 min; and then adding the sodium carboxymethylcellulose dispersion liquid into the graphene oxide dispersion liquid, and stirring and ultrasonically treating until the graphene oxide dispersion liquid is uniform. In the stirring ultrasonic process, polyacrylic acid, carboxyl and epoxy groups on the surfaces of graphene oxide and sodium carboxymethyl cellulose are subjected to covalent crosslinking to generate the aqueous composite binder.
(2) Adding 240 mg of silicon monoxide into the aqueous composite binder, magnetically stirring for 30 min, and then performing ultrasonic dispersion for 30 min to obtain a uniform active particle mixed solution;
(3) filtering the obtained active particle mixed solution on a vacuum filtration device by using a microporous filter membrane with micropores of 0.22 mu m by using vacuum auxiliary filtration; then cleaning the filtered product by using 100-300 ml of deionized water; the filters were then placed in a refrigerator for freezing. Freezing for 5h, and then freezing and drying for 8h by using a vacuum freezing dryer to obtain the flexible graphene oxide-sodium carboxymethylcellulose-polyacrylic acid-silicon oxide composite film.
(4) And (3) placing the dried composite film in a watch glass, adding a hydrazine hydrate solution for reduction, and standing for 6 hours to obtain the flexible graphene-sodium carboxymethylcellulose-polyacrylic acid-silicon oxide composite film.
(5) Taking out the composite membrane obtained in the step (4), and washing the composite membrane for a plurality of times by using deionized water; after cleaning, immediately putting the mixture into a refrigerator, and freezing for 5 hours; and putting the membrane into a vacuum freeze dryer again, freeze drying for 8 hours, and then carrying out vacuum thermal polycondensation reaction for 4 hours at 160 ℃, wherein the pressure intensity of the reaction is not higher than 0.1Mpa, thus obtaining the silicon protoxide-based flexible membrane electrode.
The sodium carboxymethylcellulose can be Japanese cellosolve DAICEL CMC2200, viscosity (1% aqueous solution @25 deg.C. at 60rpm) is 1500-3000 mPas, pH value (1% aqueous solution @25 deg.C.) is 6.0-8.5, and substitution degree is at least 0.8.
The polyacrylic acid can adopt an aqueous solution with the mass percentage concentration of 45-55%, and the average molecular weight of the polyacrylic acid is 2800-3200.
The purity of the silicon nano particles is not lower than 99.9%, and the particle size is 20-100 nanometers; the average particle size of the silicon oxide particles is 3.5-5 microns.
The thickness of the flexible film electrode is 5-200 microns.
Example 7 Effect verification
The using effect of the prepared flexible thin film electrode is verified by taking example 3 as an example, as shown in fig. 1, the diameter of the flexible thin film is about 5cm, the obtained flexible thin film electrode sheet can be cut into electrode slices with the diameter of 12 mm, and the electrode slices can be directly used as working electrodes to complete the assembly of button cells without adding any conductive additives and polymer adhesives.
FIG. 2 is an XRD spectrum of the flexible thin film electrode, and as can be seen from FIG. 2, the rGO-Si-CMC-PAA thin film (i.e. the nano silicon-based flexible thin film electrode) shows characteristic peaks (located at 2) of crystalline silicon (JCPDS number 27-1402) and grapheneθ(002) characteristic diffraction peak of 19.58 °). The results show that: the raw material graphene oxide is positioned at 2 after liquid phase reductionθThe (001) diffraction peak of = 10.1 ° disappears, and a large amount of oxygen-containing functional groups on the surface and between layers of graphene oxide are removed. The graphene oxide is reduced to graphene. Referring to the characteristic diffraction peak of graphene and related documents, the peak is positioned at 2θThe (002) characteristic diffraction peak of = 19.58 ° indicates that PAA and CMC molecules enter the lamellar gaps of adjacent graphene.
Fig. 3 to 6 are SEM images at different magnifications, wherein fig. 3 and 4 are SEM images of the surface of the rGO-Si-CMC-PAA film at magnifications of 9 ten thousand and 20 ten thousand respectively, and it can be seen from fig. 3 and 4 that graphene sheets in the prepared rGO-Si-CMC-PAA film are connected with each other to form a three-dimensional continuous nanoporous network structure, and the porous structure is composed of two-dimensional graphene nanosheets loaded with Si nanoparticles. The grain size range of Si nano-particles contained in the film is about 50nm, almost all the Si nano-particles are embedded and uniformly distributed in the layered graphene network, and meanwhile, the surface of the silicon nano-particles is coated by a layer of thinner organic matter. Fig. 5 and 6 are SEM images of cross-sections of rGO-Si-CMC-PAA films, respectively, at different magnifications, from which it can be seen that most of the graphene sheets constituting the film are relatively horizontal, and many new pores exist between the layers, and the film exhibits a three-dimensional structure of a loose typical layer. Meanwhile, the silicon nanoparticles are attached to the graphene, so that the nanoparticles are effectively prevented from being agglomerated. Compared with a tightly packed structure, the open nano porous network structure is beneficial to full contact between the active material and the electrolyte, electrolyte ions are quickly diffused to the surface of the electrode active material/electrolyte solution interface, a large number of electrochemical reaction active sites are added, the diffusion path of lithium ions is shortened, and the huge volume change of the active material in the continuous charging/discharging process is effectively relieved.
Manufacturing the battery: using a lithium sheet as a counter electrode, and preparing 1mol L of ethylene carbonate and dimethyl carbonate (EC/DMC) according to a volume ratio of 1:1-1LiPF of6The solution is electrolyte, Celgard 2400 microporous polypropylene membrane is used as lithium ion battery diaphragm to assemble button cell (CR 2025) to perform cyclic voltammetry, constant current charge/discharge and alternating current impedance test, and the voltage test range is 0.005-3.0V (vs. Li)+Li), the current density was 200-1000 mA/g. The frequency range adopted by the AC impedance test is 100m Hz-100 kHz, and the voltage amplitude is 5 mV. The test temperature was 25. + -. 0.5 ℃.
Fig. 7 is a cyclic voltammetry curve of a button cell assembled by taking the prepared rGO-Si-CMC-PAA film as a negative electrode, and it can be seen from the graph that the first cyclic voltammetry curve of the electrode is greatly different from the second and subsequent cyclic voltammetry curves, and the curves from the second cycle to the third cycle are almost completely overlapped, indicating that irreversible reaction occurs during the first cyclic voltammetry process and excellent reversibility after the first cycle. The irreversible capacity in the first cycle can be attributed to the decomposition of the organic electrolyte and the generation of an SEI film at the electrode/electrolyte interface. The peak intensity and overall integration area of the third and subsequent cycles of the electrode are nearly similar to the second cycle, but are significantly reduced compared to the first cycle. These results indicate that the electrochemical reversibility of the rGO-Si-CMC-PAA electrode is built up gradually after the first cycle.
FIG. 8 is a graph of rGO-Si-CMC-PAA electrodes at 420 mA g-1Current density of (1) initiallyst、2nd、3rd、5th、200thConstant current charge/discharge curve for each cycle. As can be seen from the figure, the coulombic efficiency of the rGO-Si-CMC-PAA electrode for the second cycle rapidly increased to 95.65% and remained above 99% after several subsequent cycles, indicating that the electrode forms a relatively stable SEI film after the first discharge process. After 200 cycles, the high charge and discharge capacity is maintained.
Table 1 shows the initial voltage and the voltage change after 15 days for five batteries, and it can be seen from table 1 that the prepared film is used as an electrode, and the assembled battery has a stable voltage, a small voltage drop, and a stable battery interior.
The experiment proves that the nano silicon-based flexible film electrode prepared by the invention is suitable for manufacturing electrodes of lithium ion batteries, capacitors or other energy storage systems, and has excellent performance. The performance of the nano silicon-based flexible membrane electrode prepared in the embodiments 1 and 2 is similar to that prepared in the embodiment 3, and the nano silicon-based flexible membrane electrode can also be used for manufacturing electrodes of lithium ion batteries, capacitors or other energy storage systems.
When the active particles are the silicon oxide particles, the performance is proved to be equivalent to the experimental performance of the silicon nanoparticles through experiments, and the silicon oxide particles can be used for manufacturing electrodes of lithium ion batteries, capacitors or other energy storage systems.
Claims (9)
1. A preparation method of a flexible film electrode is characterized by comprising the following steps:
(a) respectively dispersing graphene oxide and sodium carboxymethylcellulose in water to obtain a graphene oxide dispersion liquid and a sodium carboxymethylcellulose dispersion liquid, adding polyacrylic acid and the sodium carboxymethylcellulose dispersion liquid into the graphene oxide dispersion liquid, uniformly mixing and performing molecular crosslinking to obtain a water-based composite adhesive, wherein the mass percentage content of the graphene oxide is 10-35%, the mass percentage content of the sodium carboxymethylcellulose is 5-10%, the mass percentage content of the polyacrylic acid is 55-85%, and the sum of the mass percentage contents of the graphene oxide, the sodium carboxymethylcellulose and the polyacrylic acid is 100%;
(b) adding active particles into the aqueous composite adhesive, and uniformly dispersing the active particles to obtain an active particle mixed solution, wherein the active particles are silicon nano particles or silicon oxide particles, the mass percentage content of the active particles is 60-90%, the sum of the mass percentages of the graphene oxide, the sodium carboxymethylcellulose and the polyacrylic acid is 10-40%, and the sum of the mass percentages of the active particles, the graphene oxide, the sodium carboxymethylcellulose and the polyacrylic acid is 100%;
(c) performing vacuum filtration and vacuum freeze drying on the active particle mixed solution to prepare a flexible graphene oxide-sodium carboxymethylcellulose-polyacrylic acid-active particle composite film;
(d) reducing the flexible graphene oxide-sodium carboxymethylcellulose-polyacrylic acid-active particle composite film into a flexible graphene-sodium carboxymethylcellulose-polyacrylic acid-active particle composite film in a liquid phase;
(e) and (2) soaking the flexible graphene-sodium carboxymethylcellulose-polyacrylic acid-active particle composite film in water, washing, freezing and drying, then carrying out vacuum thermal polycondensation reaction, and obtaining the flexible film electrode after the reaction.
2. The method for preparing a flexible thin-film electrode according to claim 1, wherein the sodium carboxymethylcellulose is japanese cellosolve DAICEL CMC2200, the viscosity is 1500-3000 mPa · s, the pH value is 6.0-8.5, the substitution degree is 0.8 at the minimum, the polyacrylic acid is an aqueous solution with a mass percentage concentration of 45-55%, and the average molecular weight of the polyacrylic acid is 2800-3200.
3. The method for preparing the flexible thin film electrode according to claim 1, wherein the purity of the silicon nanoparticles is not less than 99.9%, and the particle size is 20-100 nm; the average particle size of the silicon oxide particles is 3.5-5 microns.
4. The method for preparing a flexible thin film electrode according to claim 1, wherein the liquid phase reduction is performed in the step (d) by using a liquid phase reducing agent, and the liquid phase reducing agent is hydrazine hydrate or an aqueous solution of sodium borohydride.
5. The method for preparing a flexible thin film electrode according to claim 1, wherein the thickness of the flexible thin film electrode obtained in the step (e) is 5 to 200 μm.
6. The method as claimed in claim 1, wherein the temperature of the vacuum thermal polycondensation reaction in step (e) is 120-180 ℃, the time is 1-6 h, and the vacuum degree is not higher than 0.1 MPa.
7. A flexible thin film electrode, characterized in that it is manufactured using the manufacturing method of any one of claims 1 to 6.
8. The flexible thin film electrode of claim 7, wherein the flexible thin film electrode exhibits a layered network structure as a whole, and the active particles are coated with graphene, sodium carboxymethyl cellulose, and polyacrylic acid molecules.
9. Use of a flexible thin film electrode according to claim 7, in the manufacture of a lithium ion battery or a supercapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910693346.7A CN110364687B (en) | 2019-07-30 | 2019-07-30 | Preparation method of flexible thin film electrode, prepared electrode and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910693346.7A CN110364687B (en) | 2019-07-30 | 2019-07-30 | Preparation method of flexible thin film electrode, prepared electrode and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110364687A CN110364687A (en) | 2019-10-22 |
| CN110364687B true CN110364687B (en) | 2021-05-18 |
Family
ID=68222570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910693346.7A Active CN110364687B (en) | 2019-07-30 | 2019-07-30 | Preparation method of flexible thin film electrode, prepared electrode and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110364687B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110993895B (en) * | 2019-12-04 | 2022-04-19 | 绍兴文理学院 | Preparation method of Si/graphene composite flexible electrode of lithium ion battery |
| CN111477844A (en) * | 2020-04-16 | 2020-07-31 | 陕西科技大学 | Stable conductive sponge body electrode prepared by reduction method and preparation method thereof |
| CN111676541B (en) * | 2020-06-10 | 2022-10-11 | 浙江恒逸石化研究院有限公司 | Preparation method of antistatic low-temperature far-infrared polyester fiber |
| CN114470335A (en) * | 2020-10-26 | 2022-05-13 | 天津理工大学 | Preparation method of safe, nontoxic and environment-friendly intelligent bionic skin |
| CN113072731A (en) * | 2021-04-06 | 2021-07-06 | 朱铁寨 | Carbon crystal plate |
| CN114678575A (en) * | 2022-03-30 | 2022-06-28 | 福建农林大学 | Large-area microbial film moisture power generation device and preparation method and application thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8956688B2 (en) * | 2011-10-12 | 2015-02-17 | Ut-Battelle, Llc | Aqueous processing of composite lithium ion electrode material |
| US20140030590A1 (en) * | 2012-07-25 | 2014-01-30 | Mingchao Wang | Solvent-free process based graphene electrode for energy storage devices |
| CN107369835B (en) * | 2016-05-12 | 2020-12-25 | 华为技术有限公司 | Conductive adhesive for lithium ion battery and preparation method thereof, lithium ion battery electrode plate and preparation method thereof, and lithium ion battery |
| CN107039646A (en) * | 2017-04-18 | 2017-08-11 | 合肥工业大学 | Flexible negative material of a kind of lithium ion battery and preparation method thereof |
| CN108063258B (en) * | 2017-12-26 | 2020-02-18 | 成都新柯力化工科技有限公司 | Preparation method of binder for improving cycle stability of lithium battery silicon electrode |
| CN109192543A (en) * | 2018-08-16 | 2019-01-11 | 中国科学院成都有机化学有限公司 | A kind of graphene oxide based binder and preparation method thereof and electrode slice |
| CN109301184A (en) * | 2018-09-10 | 2019-02-01 | 江苏塔菲尔新能源科技股份有限公司 | Modified composite material, preparation method and the purposes in lithium ion battery of siliceous substrates material |
| CN109524641A (en) * | 2018-10-19 | 2019-03-26 | 西安科技大学 | Lithium ion battery flexible self-supporting silicon/graphene negative electrode material preparation method |
| CN109461937B (en) * | 2018-10-19 | 2021-06-22 | 深圳市优宝新材料科技有限公司 | Three-dimensional mixed conductive adhesive for lithium battery and battery comprising same |
| CN109616645B (en) * | 2018-12-07 | 2021-08-13 | 武汉工程大学 | Flexible silicon negative electrode material for lithium ion battery and preparation method thereof |
| CN109860577A (en) * | 2019-03-07 | 2019-06-07 | 上海电气集团股份有限公司 | A kind of carbon/ferriferous oxide composite and flexible electrode material and preparation method thereof |
-
2019
- 2019-07-30 CN CN201910693346.7A patent/CN110364687B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110364687A (en) | 2019-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110364687B (en) | Preparation method of flexible thin film electrode, prepared electrode and application | |
| CN107799699B (en) | Clay mineral composite lithium battery diaphragm and preparation method thereof | |
| US9911976B2 (en) | Negative electrode active material for secondary battery, conductive composition for secondary battery, negative electrode material comprising same, negative electrode structure and secondary battery comprising same, and method for manufacturing same | |
| EP1903628A2 (en) | A Negative Electrode Active Material for an Electricity Storage Device and Method for Manufacturing the Same | |
| WO2014087992A1 (en) | Graphene sheet composition | |
| CN111540868A (en) | Preparation method and application of two-dimensional manganese dioxide modified polypropylene diaphragm | |
| CN108390064A (en) | A kind of graphene-based flexible self-supporting mixed gel electrode and preparation method thereof | |
| CN112103509B (en) | Positive electrode current collector, positive electrode plate, lithium ion battery and battery module | |
| KR102567300B1 (en) | Pre-lithiated negative electrode, manufacturing method thereof, lithium ion battery including pre-lithiated negative electrode, and supercapacitor | |
| CN108539280B (en) | Composite current collector and preparation method thereof | |
| KR101451354B1 (en) | Free-standing carbon nanotube/metal oxide particle composite film and the manufacturing method | |
| Zhu et al. | A novel UV-cured semi-IPN structure PEO@ nano-SiO2 composite polymer electrolyte for lithium metal batteries | |
| WO2013067280A1 (en) | Carbon film and method of production thereof | |
| WO2017177960A1 (en) | Electrolyte solution, battery, and battery pack | |
| CN113471405A (en) | Pre-lithiated negative electrode, preparation method thereof, lithium ion battery containing pre-lithiated negative electrode and super capacitor | |
| KR20210006897A (en) | All-solid-state battery current collector layer, all-solid-state battery and carbon material | |
| CN105226251A (en) | A kind of pure carbon compound cathode materials and preparation method thereof | |
| Li et al. | Chitosan derived carbon membranes as protective layers on zinc anodes for aqueous zinc batteries | |
| CN110120499B (en) | Graphite nanosheet and preparation method and application thereof | |
| KR20190039155A (en) | Flexible electrode-separator element and manufacturing method thereof | |
| CN115917818A (en) | Sheet for all-solid-state secondary battery, method for producing all-solid-state secondary battery, sheet for all-solid-state secondary battery, and all-solid-state secondary battery | |
| CN112582752A (en) | Porous boron nitride fiber/reduced graphene oxide composite lithium-sulfur battery diaphragm material | |
| CN111916704A (en) | Negative electrode material, preparation method, negative plate and battery | |
| Wang et al. | Cyclodextrin polymers as effective water-soluble binder with enhanced cycling performance for Li2ZnTi3O8 anode in lithium-ion batteries | |
| JP2015056282A (en) | Polymer solid electrolyte battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220914 Address after: 064204 bigou village, Jianming Town, Zunhua City, Tangshan City, Hebei Province Patentee after: HEBEI LINGDIAN NEW ENERGY TECHNOLOGY CO.,LTD. Address before: 063000 No.9 University West Road, Tangshan City, Hebei Province Patentee before: TANGSHAN College |
|
| TR01 | Transfer of patent right |