CN110808406A - Integrated flexible lithium ion battery and preparation method thereof - Google Patents
Integrated flexible lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN110808406A CN110808406A CN201911188571.1A CN201911188571A CN110808406A CN 110808406 A CN110808406 A CN 110808406A CN 201911188571 A CN201911188571 A CN 201911188571A CN 110808406 A CN110808406 A CN 110808406A
- Authority
- CN
- China
- Prior art keywords
- ion battery
- lithium ion
- slurry
- layer
- substrate
- 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.)
- Pending
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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses an integrated flexible lithium ion battery and a preparation method thereof, wherein the preparation method comprises the following steps: dispersing graphene and a binder in a solvent to prepare graphene current collector slurry; dispersing the material of the negative electrode active material layer in a first solvent to prepare negative electrode slurry; stacking a graphene current collector slurry layer and a negative electrode slurry layer on a substrate, drying, and removing the substrate to obtain a negative electrode sheet; dispersing the material of the positive active material layer in a second solvent to prepare positive slurry, stacking a positive slurry layer and a graphene current collector slurry layer on one surface of the flexible substrate, drying, and forming a positive plate on one surface of the flexible substrate; arranging a diaphragm slurry layer on the surface of one side of the flexible substrate, which is far away from the positive plate; then the negative plate is stuck on the diaphragm slurry layer and dried; and then packaging, adding electrolyte and sealing. The preparation method is simple and easy to implement, and the prepared integrated flexible lithium ion battery is stable in electrochemical performance, safe, reliable and high in reliability.
Description
Technical Field
The invention relates to the technical field of flexible energy storage devices, in particular to an integrated flexible lithium ion battery and a preparation method thereof.
Background
In recent years, the market of wearable electronic products is very explosive, and sales volumes of products such as smart watches, smart bracelets and smart glasses are increasing year by year. Because most wearable electronic products have certain shapes or radians, the traditional lithium ion batteries are fixed in shape and can only utilize the limited space of the electronic products, the energy density is low, and in the process of repeated wearing, the appearance of the batteries cannot be bent, so that the experience of consumers is reduced. Therefore, it is necessary to develop a flexible lithium ion battery for flexible and wearable electronic products.
In the past decades, scientists have made many efforts to realize the flexibility of lithium ion batteries, but most of the existing flexible batteries have relatively complex design schemes and preparation processes, which are not favorable for realizing future industrial production. In addition, when the conventional flexible lithium ion battery is deformed by extrusion and the like, the electrochemical performance of the conventional flexible lithium ion battery is deteriorated, and even the safety problem of the battery is caused. This is because the relative positions of the separator and the electrodes in the internal structure of the battery change when the battery is deformed. Under some extreme situations, the relative positions of the diaphragm and the electrode change to cause the contact of the anode and the cathode, so that the internal short circuit of the battery is caused, and the lithium ion battery cannot work normally. In addition, the mismatch of the positive and negative electrodes of the flexible lithium ion battery caused by the relative change of the positions of the positive and negative electrodes can also cause the instability of the battery performance and the attenuation of the battery capacity. And because the flexible lithium ion battery works in a dynamic environment (such as bending, twisting, folding and the like), the battery is very frequently deformed, so that the structure of the battery is also very frequently changed, the chemical performance of the battery is unstable, and the reliability is low.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides an integrated flexible lithium ion battery and a preparation method thereof, the preparation method is simple and feasible, and the electrochemical performance of the prepared integrated flexible lithium ion battery is stable.
The technical scheme adopted by the invention is as follows:
the invention provides a preparation method of an integrated flexible lithium ion battery, which comprises the following steps:
(1) dispersing graphene and a binder in a solvent to prepare graphene current collector slurry;
(2) dispersing the material of the negative electrode active material layer in a first solvent to prepare negative electrode slurry; stacking a graphene current collector slurry layer and a negative electrode slurry layer on a substrate, drying, and removing the substrate to obtain a negative electrode sheet;
(3) dispersing the material of the positive active material layer in a second solvent to prepare positive slurry, stacking a positive slurry layer and a graphene current collector slurry layer on one surface of the flexible substrate, drying, and forming a positive plate on one surface of the flexible substrate;
(4) arranging a diaphragm slurry layer on the surface of one side, which is far away from the positive plate, of the flexible substrate; then, the negative plate is stuck on the diaphragm slurry layer and dried; and then packaging, adding electrolyte and sealing.
According to some embodiments of the invention, in the step (2), the materials of the negative active material layer include a lithium ion battery negative electrode material, a first conductive agent and a first binder; in the step (3), the material of the positive active material layer comprises a lithium ion battery positive material, a second conductive agent and a second binder.
According to some embodiments of the invention, the mass ratio of the lithium ion battery negative electrode material, the first conductive agent and the first binder is (6-8): (1-3): 1; the mass ratio of the lithium ion battery positive electrode material to the second conductive agent to the second binder is (6-8): (1-3): 1.
according to some embodiments of the invention, the lithium ion battery negative electrode material is selected from at least one of lithium titanate, titanium dioxide, iron oxide, cobalt oxide, natural graphite, artificial graphite, metallic lithium, silicon-based alloy, silicon-based oxide, tin-based alloy, tin-based oxide;
the lithium ion battery anode material is selected from at least one of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium manganese phosphate, lithium vanadium phosphate, lithium nickel manganese and nickel cobalt manganese ternary materials;
the first conductive agent and the second conductive agent are respectively and independently selected from at least one of graphite, conductive carbon black, activated carbon, carbon nanotubes, carbon fibers and graphene;
the binder, the binder I and the binder II are respectively and independently selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene, epoxy resin, polyacrylate, sodium carboxymethyl cellulose, sodium alginate, LA series binders and modified styrene butadiene rubber.
According to some embodiments of the invention, in the step (1), the mass ratio of the graphene to the binder is (8-10): 1. further, the concentration of the graphene current collector slurry can be 0.8-1.0 g of graphene per 10g of solvent.
According to some embodiments of the invention, in step (2), the substrate is made of an alkali-soluble material; and removing the substrate, in particular, soaking the substrate in an alkaline solution to dissolve the substrate. The substrate can be made of at least one of aluminum foil, iron foil and zinc foil; the alkaline solution can be at least one of NaOH solution and KOH solution, and the concentration of the alkaline solution is generally 0.8-1.2 mol/L, preferably 1 mol/L. After the substrate is removed, the negative plate can be further cleaned and dried to remove the alkaline solution on the surface of the negative plate.
In addition, in the step (2), the thickness of the graphene current collector slurry layer arranged on the substrate is generally 40-60 μm, and preferably 50 μm; the thickness of the negative electrode slurry layer is generally 140 to 160 μm, preferably 150 μm. The graphene current collector slurry layer and the negative electrode slurry layer can be arranged on the substrate in a coating or printing mode respectively.
According to some embodiments of the invention, in the step (4), a separator slurry layer is firstly disposed on a surface of the flexible substrate, which is away from the positive electrode plate, and then a separator slurry layer is disposed after drying, and then the negative electrode plate is adhered to the separator slurry layer. The concentration of the membrane slurry on the membrane slurry layer is generally 10 wt%, and the solvent can adopt at least one of ethanol, acetone and methyl pyrrolidone. The thickness range of the diaphragm slurry layers arranged twice is generally 80-120 mu m.
According to some embodiments of the invention, in the step (4), the material of the separator slurry layer includes at least one of polyvinylidene fluoride, polypropylene, and polyethylene.
According to some embodiments of the invention, in step (3), the flexible substrate is selected from at least one of printing paper, a glass fiber substrate, and a Celgard separator.
In addition, the graphene and the binder are dispersed in the solvent in the step (1), the material of the negative electrode active material layer is dispersed in the solvent I in the step (2), and the material of the positive electrode active material layer is dispersed in the solvent II in the step (3), so that the dispersion effect can be improved by means of at least one of ultrasonic dispersion, high-speed shear dispersion and mechanical stirring. Wherein, the solvent, the first solvent and the second solvent can be respectively and independently selected from at least one of ethanol, acetone and methyl pyrrolidone. In the steps (2) - (4), the drying temperature is generally 70-100 ℃, and preferably 80 ℃. The arrangement of the positive electrode slurry layer and the graphene current collector slurry layer in the step (3) and the arrangement of the diaphragm slurry layer in the step (4) can also be arranged in a coating or printing mode.
In a second aspect of the present invention, an integrated flexible lithium ion battery is provided, which is prepared by any one of the methods for preparing an integrated flexible lithium ion battery provided in the first aspect of the present invention.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a preparation method of an integrated flexible lithium ion battery, which integrates a positive plate, a diaphragm and a negative plate together through the integrated design of the internal structure of the battery, so that the internal structure of the battery is not easy to change even if the prepared integrated flexible lithium ion battery is frequently deformed, the chemical stability and the safety of the battery are improved, and the problem that the electrochemical performance of the flexible battery is unstable when the conventional flexible battery is frequently deformed can be solved; the preparation method is simple and easy to implement, is beneficial to the realization of industrial production, and can solve the problem that the existing flexible battery preparation technology is inconvenient for industrial production.
Drawings
Fig. 1 is a schematic process flow diagram of a method of making an integrated flexible lithium ion battery of example 1;
FIG. 2 is a schematic structural diagram of an integrated flexible battery material in the integrated flexible lithium ion battery in example 1;
FIG. 3 is an electronic scanning image of the integrated flexible battery material in the integrated flexible lithium ion battery of example 1;
FIG. 4 is a graph of the electrochemical performance characterization results of the integrated flexible lithium ion battery of example 1.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
Referring to fig. 1, the preparation method of the integrated flexible lithium ion battery includes the following steps:
(1) preparing graphene current collector slurry, comprising: by an ultrasonic method, 0.9g of graphene and 0.1g of polyvinylidene fluoride are uniformly dispersed in 10g of methyl pyrrolidone solvent to prepare graphene current collector slurry.
(2) Preparing a negative plate, comprising: uniformly dispersing lithium titanate, carbon black and polyvinylidene fluoride in a mass ratio of 8:1:1 in a methyl pyrrolidone solvent by a stirring method to prepare lithium titanate cathode slurry; sequentially coating graphene current collector slurry with the thickness of 50 microns and lithium titanate negative electrode slurry with the thickness of 150 microns on an aluminum foil substrate by a round rod coating method to respectively form a graphene current collector slurry layer and a negative electrode slurry layer, and drying at 80 ℃ to correspondingly form a graphene current collector layer and a negative electrode active material layer; then soaking the aluminum foil substrate in 1mol/L sodium hydroxide solution to dissolve and remove the aluminum foil substrate, and preparing a negative electrode sheet substrate; and then, cleaning the negative plate substrate with deionized water for 3 times, and drying at 80 ℃ to obtain the final negative plate, which comprises a graphene current collector layer and a negative active material layer.
(3) Preparing a positive plate, comprising: uniformly dispersing lithium iron phosphate, carbon black and polyvinylidene fluoride in a mass ratio of 8:1:1 in a methyl pyrrolidone solution by a stirring method to prepare the lithium iron phosphate anode slurry. The method comprises the steps of sequentially coating lithium iron phosphate anode slurry with the thickness of 100 microns and graphene current collector slurry with the thickness of 50 microns on the surface of one side of printing paper by a round rod coating method, respectively forming an anode slurry layer and a graphene current collector slurry layer, drying at 80 ℃, and forming an anode plate on the printing paper, wherein the anode plate comprises an anode active material layer and a graphene current collector layer.
(4) Preparing an integrated flexible battery material, comprising: coating polyvinylidene fluoride slurry (the concentration is 1g of polyvinylidene fluoride/10 g of methyl pyrrolidone) with the thickness of 100 microns on the surface of one side, which is far away from the positive plate, of the printing paper to form a first diaphragm slurry layer, drying at 80 ℃ to form a first diaphragm layer, coating polyvinylidene fluoride slurry with the thickness of 100 microns on the first diaphragm layer to form a second diaphragm slurry layer, pasting the negative plate on the second diaphragm slurry layer, specifically, pasting a negative active material layer on the negative plate and the second diaphragm slurry layer, and drying at 80 ℃ to obtain the integrated flexible battery material. The structure of the integrated flexible battery material is shown in fig. 2, and specifically comprises a graphene current collector layer 1, a negative electrode active material layer 2, a separator layer 3, printing paper 4, a positive electrode active material layer 5 and a graphene current collector layer 6 which are sequentially stacked.
(5) Assembling, comprising: and (5) packaging the integrated flexible battery material prepared in the step (4) in a glove box by using a polyethylene film, adding an electrolyte, and then carrying out sealing treatment to obtain the integrated flexible lithium ion battery.
And (3) observing and characterizing the integrated flexible battery material prepared in the step (4) by using a Scanning Electron Microscope (SEM), wherein the obtained result is shown in figure 3. FIG. 3 (A) is an electronic scanning image of the integrated flexible battery material; (B) is an enlarged view at M in (A); (C) is an enlarged view of N in (A); (D) in the figure, the boundary between the layers is shown by a dotted line in an enlarged view at P in (a). Specifically, as shown in fig. 3 (a), the integrated flexible battery material prepared by the above preparation method comprises a negative plate, a printing Paper layer, a diaphragm layer and a positive plate, wherein the total thickness is about 200 μm, in the figure, Graphene/LTO (i.e. Graphene/lithium titanate) represents the negative plate, PVDF layer (i.e. polyvinylidene fluoride layer) represents the diaphragm layer, Paper (i.e. Paper) represents the printing Paper layer, and LFP/Graphene (i.e. lithium iron phosphate/Graphene) represents the positive plate; as shown in fig. 3 (B), the positive electrode sheet includes a positive electrode active material layer and a Graphene current collector layer, where LFP (i.e., lithium iron phosphate) represents the positive electrode active material layer, and Graphene (i.e., Graphene) represents the Graphene current collector layer; as shown in fig. 3 (C), the separator layer and the negative electrode active material layer are closely combined, in which LTO (i.e., lithium titanate) represents the negative electrode active material layer, and PVDF (i.e., polyvinylidene fluoride) represents the separator layer; as shown in fig. 3 (D), the separator layer is tightly combined with the printing paper layer. By the above, in the setting process of the diaphragm layer, the polyvinylidene fluoride layer realized by the two coating processes can well obstruct the contact between the lithium iron phosphate particles in the positive active material layer and the lithium titanate particles in the negative active material layer, so that the problem of internal short circuit of the battery caused by the penetration of the lithium iron phosphate particles in printing paper in the coating process can be solved.
The electrochemical performance of the integrated flexible lithium ion battery prepared above is subjected to characterization test, and the obtained result is shown in fig. 4. Specifically, firstly, the integrated flexible battery material prepared in the step (4) is assembled and tested in the button cell. The prepared button cell was clamped in a blue light test system, and after standing overnight, charge and discharge tests were performed, and the obtained results are shown in fig. 4 (a), the first coulombic efficiency at 0.5C test current was 87%, and after 140 times of charge and discharge, the capacity of the cell was stabilized at 110mAh g-1. The integrated flexible lithium ion battery prepared in the embodiment is tested and characterized, and the obtained result is shown in fig. 4 (B), and the integrated flexible lithium ion battery packaged by the polyethylene film is 50mA g-1The first charge-discharge efficiency at the test current was about 87%, and the capacity of the battery was maintained at 108mAh g after 20 cycles of charge-discharge-1And shows better cycle performance. In addition, after the prepared integrated flexible lithium ion battery is folded and bent, the positive electrode and the negative electrode are respectively clamped on the positive electrode and the negative electrode of the blue test system to perform charge and discharge tests, and the obtained result is shown as (C) in fig. 4.
In addition, the integrated flexible lithium ion battery manufactured in this embodiment is used as an experimental battery, a flexible battery (not designed based on an integrated structure) directly purchased from the market is used as a comparison battery, and the open-circuit voltages of the experimental battery and the comparison battery before and after the bending test (100 bending operations) are tested and compared. The test shows that the open-circuit voltage of the experimental battery is 1.827V before the bending test, and the open-circuit voltage of the experimental battery is 1.825V after 100 times of bending operation, so that the integrated flexible lithium ion battery prepared by the embodiment keeps a very stable open-circuit voltage state, and further shows the stability of the internal structure of the battery. And after the comparison battery is subjected to 100 times of bending test operation, the open-circuit voltage of the battery is reduced from the initial 2.381V to 0.434V, and the instability of the internal structure of the flexible battery with the traditional structure is shown. And then the LED lamps of the same model are lighted by adopting the experimental batteries and the comparison batteries before and after the bending test, and the test experiment shows that: before the bending test, the LED lamp can be well lightened by the experimental battery and the comparison battery, but after 100 times of bending operation, the LED lamp can still be well lightened by the experimental battery, and the LED lamp cannot be lightened by the comparison battery, which further shows that the integrated flexible lithium ion battery prepared by the embodiment has good stability of the internal structure under the dynamic working environment.
Example 2
The preparation method of the integrated flexible lithium ion battery comprises the following steps:
(1) preparing graphene current collector slurry, comprising: by an ultrasonic method, 0.9g of graphene and 0.1g of polyvinylidene fluoride are uniformly dispersed in 10g of methyl pyrrolidone solvent to prepare graphene current collector slurry.
(2) Preparing a negative plate, comprising: uniformly dispersing lithium titanate, carbon black and polyvinylidene fluoride in a mass ratio of 8:1:1 in a methyl pyrrolidone solvent by a stirring method to prepare lithium titanate cathode slurry; sequentially coating graphene current collector slurry with the thickness of 50 microns and lithium titanate negative electrode slurry with the thickness of 150 microns on an aluminum foil substrate by a round rod coating method to respectively form a graphene current collector slurry layer and a negative electrode slurry layer, and drying at 80 ℃ to correspondingly form a graphene current collector layer and a negative electrode active material layer; then soaking the aluminum foil substrate in 1mol/L sodium hydroxide solution to dissolve and remove the aluminum foil substrate, and preparing a negative electrode sheet substrate; and then, cleaning the negative electrode sheet substrate with deionized water for 3 times, and drying at 80 ℃ to obtain the final negative electrode sheet, which comprises a negative electrode graphene current collector layer and a negative electrode active material layer.
(3) Preparing a positive plate, comprising: uniformly dispersing lithium iron phosphate, carbon black and polyvinylidene fluoride in a mass ratio of 8:1:1 in a methyl pyrrolidone solution by a stirring method to prepare the lithium iron phosphate anode slurry. The method comprises the steps of sequentially coating lithium iron phosphate anode slurry with the thickness of 100 microns and graphene current collector slurry with the thickness of 50 microns on the surface of one side of printing paper by a round rod coating method to form an anode slurry layer and a graphene current collector slurry layer, drying at 80 ℃, and forming an anode plate comprising an anode active material layer and an anode graphene current collector layer on the printing paper.
(4) Preparing an integrated flexible battery material, comprising: coating polyvinylidene fluoride slurry (the concentration is 1g of polyvinylidene fluoride/10 g of methyl pyrrolidone) with the thickness of 100 microns on the surface of one side, which is far away from the positive plate, of the printing paper to form a first diaphragm slurry layer, drying at 80 ℃ to form a first diaphragm layer, coating polyvinylidene fluoride slurry with the thickness of 100 microns on the first diaphragm layer to form a second diaphragm slurry layer, pasting the negative plate on the second diaphragm slurry layer, specifically, pasting a negative active material layer on the negative plate and the second diaphragm slurry layer, and drying at 80 ℃ to obtain the integrated flexible battery material.
(5) Assembling, comprising: and (4) packaging the integrated flexible battery material prepared in the step (4) with a polydimethylsiloxane membrane in a glove box, adding electrolyte, and then carrying out sealing treatment to obtain the integrated flexible lithium ion battery.
Example 3
The preparation method of the integrated flexible lithium ion battery comprises the following steps:
(1) preparing graphene current collector slurry, comprising: by an ultrasonic method, 1.0g of graphene and 0.1g of sodium carboxymethyl cellulose are uniformly dispersed in 10g of acetone solvent to prepare graphene current collector slurry.
(2) Preparing a negative plate, comprising: uniformly dispersing lithium titanate, graphite and sodium carboxymethyl cellulose in a mass ratio of 7:2:1 in an acetone solvent by a stirring method to prepare cathode slurry; sequentially coating graphene current collector slurry with the thickness of 40 microns and negative electrode slurry with the thickness of 150 microns on an aluminum foil substrate by a round rod coating method to respectively form a graphene current collector slurry layer and a negative electrode slurry layer, and drying at 80 ℃ to correspondingly form a graphene current collector layer and a negative electrode active material layer; then soaking the aluminum foil substrate in 0.8mol/L sodium hydroxide solution to dissolve and remove the aluminum foil substrate, and preparing a negative electrode sheet substrate; and then, cleaning the negative electrode sheet substrate with deionized water for 3 times, and drying at 80 ℃ to obtain the final negative electrode sheet, which comprises a negative electrode graphene current collector layer and a negative electrode active material layer.
(3) Preparing a positive plate, comprising: uniformly dispersing lithium cobaltate, graphite and polyacrylate in a mass ratio of 7:2:1 in an acetone solution by a stirring method to prepare the anode slurry. The printing paper is coated with positive electrode slurry with the thickness of 100 microns and graphene current collector slurry with the thickness of 60 microns in sequence on one side surface of the printing paper through a round rod coating method to form a positive electrode slurry layer and a graphene current collector slurry layer, and the positive electrode slurry layer and the graphene current collector slurry layer are dried at 80 ℃ to form a positive electrode plate on the printing paper, wherein the positive electrode plate comprises a positive electrode active material layer and a positive electrode graphene current collector layer.
(4) Preparing an integrated flexible battery material, comprising: coating 90-micrometer-thickness sodium carboxymethyl cellulose slurry on the surface of one side, which is far away from the positive plate, of printing paper to form a first diaphragm slurry layer, drying at 80 ℃ to form a first diaphragm layer, coating 100-micrometer-thickness sodium carboxymethyl cellulose slurry on the first diaphragm layer to form a second diaphragm slurry layer, pasting the negative plate on the second diaphragm slurry layer, specifically, laminating a negative active material layer on the negative plate and the second diaphragm slurry layer, and drying at 80 ℃ to obtain the integrated flexible battery material.
(5) Assembling, comprising: and (4) packaging the integrated flexible battery material prepared in the step (4) with a polydimethylsiloxane membrane in a glove box, adding electrolyte, and then carrying out sealing treatment to obtain the integrated flexible lithium ion battery.
Claims (10)
1. A preparation method of an integrated flexible lithium ion battery is characterized by comprising the following steps:
(1) dispersing graphene and a binder in a solvent to prepare graphene current collector slurry;
(2) dispersing the material of the negative electrode active material layer in a first solvent to prepare negative electrode slurry; stacking a graphene current collector slurry layer and a negative electrode slurry layer on a substrate, drying, and removing the substrate to obtain a negative electrode sheet;
(3) dispersing the material of the positive active material layer in a second solvent to prepare positive slurry, stacking a positive slurry layer and a graphene current collector slurry layer on one surface of the flexible substrate, drying, and forming a positive plate on one surface of the flexible substrate;
(4) arranging a diaphragm slurry layer on the surface of one side, which is far away from the positive plate, of the flexible substrate; then, the negative plate is stuck on the diaphragm slurry layer and dried; and then packaging, adding electrolyte and sealing.
2. The method for preparing the integrated flexible lithium ion battery according to claim 1, wherein in the step (2), the materials of the negative electrode active material layer comprise a lithium ion battery negative electrode material, a first conductive agent and a first binder; in the step (3), the material of the positive active material layer comprises a lithium ion battery positive material, a second conductive agent and a second binder.
3. The preparation method of the integrated flexible lithium ion battery according to claim 2, wherein the mass ratio of the lithium ion battery negative electrode material, the first conductive agent and the first binder is (6-8): (1-3): 1; the mass ratio of the lithium ion battery positive electrode material to the second conductive agent to the second binder is (6-8): (1-3): 1.
4. the method for preparing the integrated flexible lithium ion battery according to claim 2, wherein the lithium ion battery negative electrode material is selected from at least one of lithium titanate, titanium dioxide, iron oxide, cobalt oxide, natural graphite, artificial graphite, metallic lithium, silicon-based alloy, silicon-based oxide, tin-based alloy and tin-based oxide;
the lithium ion battery anode material is selected from at least one of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium manganese phosphate, lithium vanadium phosphate, lithium nickel manganese and nickel cobalt manganese ternary materials;
the first conductive agent and the second conductive agent are respectively and independently selected from at least one of graphite, conductive carbon black, activated carbon, carbon nanotubes, carbon fibers and graphene;
the binder, the binder I and the binder II are respectively and independently selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene, epoxy resin, polyacrylate, sodium carboxymethyl cellulose, sodium alginate, LA series binders and modified styrene butadiene rubber.
5. The preparation method of the integrated flexible lithium ion battery according to claim 1, wherein in the step (1), the mass ratio of the graphene to the binder is (8-10): 1.
6. the method according to claim 1, wherein in the step (2), the substrate is made of alkali-soluble material; and removing the substrate, in particular, soaking the substrate in an alkaline solution to dissolve the substrate.
7. The method for preparing the integrated flexible lithium ion battery according to claim 1, wherein in the step (4), a membrane slurry layer is firstly arranged on the surface of one side of the flexible substrate, which is far away from the positive plate, and then a membrane slurry layer is arranged after drying, and then the negative plate is adhered to the membrane slurry layer.
8. The method for preparing the integrated flexible lithium ion battery according to claim 1, wherein in the step (4), the material of the separator slurry layer comprises at least one of polyvinylidene fluoride, polypropylene and polyethylene.
9. The method for preparing an integrated flexible lithium ion battery according to any one of claims 1 to 8, wherein in the step (3), the flexible substrate is at least one selected from printing paper, glass fiber substrate and Celgard diaphragm.
10. An integrated flexible lithium ion battery, characterized by being prepared by the preparation method of the integrated flexible lithium ion battery of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911188571.1A CN110808406A (en) | 2019-11-28 | 2019-11-28 | Integrated flexible lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911188571.1A CN110808406A (en) | 2019-11-28 | 2019-11-28 | Integrated flexible lithium ion battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110808406A true CN110808406A (en) | 2020-02-18 |
Family
ID=69491839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911188571.1A Pending CN110808406A (en) | 2019-11-28 | 2019-11-28 | Integrated flexible lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110808406A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785898A (en) * | 2020-07-13 | 2020-10-16 | 南京林业大学 | Cellulose-based integrated zinc ion battery and preparation method thereof |
| CN112542569A (en) * | 2020-12-04 | 2021-03-23 | 宁德新能源科技有限公司 | Electrode assembly, electrochemical device comprising same and electronic device |
| CN114335410A (en) * | 2021-12-29 | 2022-04-12 | 蜂巢能源科技(无锡)有限公司 | Dry-process anode containing diaphragm, and preparation method and application thereof |
| CN115249848A (en) * | 2021-09-15 | 2022-10-28 | 青岛大学 | Ultra-tensile fiber-based water-based zinc ion battery and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120183863A1 (en) * | 2008-12-22 | 2012-07-19 | Taiwan Textile Research Institute | Lithium Phosphate Thin Film, Method for Manufacturing the Same and Application Thereof |
| CN103682368A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院金属研究所 | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery |
| CN104810504A (en) * | 2014-01-24 | 2015-07-29 | 中国科学院金属研究所 | Flexible graphene current collector and active material integrated electrode pole piece and preparation method thereof |
| KR101671421B1 (en) * | 2014-04-16 | 2016-11-01 | 주식회사 엘지화학 | Flexible Electrode Assembly Comprising Electrode Pattern-Coated |
| CN106252659A (en) * | 2016-09-30 | 2016-12-21 | 上海空间电源研究所 | Integrated flexible thin film lithium sulfur or lithium ion battery cell, battery and preparation method |
| CN106549185A (en) * | 2015-09-17 | 2017-03-29 | 中国科学院金属研究所 | A kind of lithium ion battery with integral structure and preparation method thereof |
| CN107819153A (en) * | 2016-09-12 | 2018-03-20 | 中国科学院金属研究所 | A kind of new structure lithium ion battery and preparation method thereof |
| CN109638357A (en) * | 2018-11-23 | 2019-04-16 | 浙江衡远新能源科技有限公司 | A kind of integrated preparation method of electrodes of lithium-ion batteries/diaphragm |
-
2019
- 2019-11-28 CN CN201911188571.1A patent/CN110808406A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120183863A1 (en) * | 2008-12-22 | 2012-07-19 | Taiwan Textile Research Institute | Lithium Phosphate Thin Film, Method for Manufacturing the Same and Application Thereof |
| CN103682368A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院金属研究所 | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery |
| CN104810504A (en) * | 2014-01-24 | 2015-07-29 | 中国科学院金属研究所 | Flexible graphene current collector and active material integrated electrode pole piece and preparation method thereof |
| KR101671421B1 (en) * | 2014-04-16 | 2016-11-01 | 주식회사 엘지화학 | Flexible Electrode Assembly Comprising Electrode Pattern-Coated |
| CN106549185A (en) * | 2015-09-17 | 2017-03-29 | 中国科学院金属研究所 | A kind of lithium ion battery with integral structure and preparation method thereof |
| CN107819153A (en) * | 2016-09-12 | 2018-03-20 | 中国科学院金属研究所 | A kind of new structure lithium ion battery and preparation method thereof |
| CN106252659A (en) * | 2016-09-30 | 2016-12-21 | 上海空间电源研究所 | Integrated flexible thin film lithium sulfur or lithium ion battery cell, battery and preparation method |
| CN109638357A (en) * | 2018-11-23 | 2019-04-16 | 浙江衡远新能源科技有限公司 | A kind of integrated preparation method of electrodes of lithium-ion batteries/diaphragm |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785898A (en) * | 2020-07-13 | 2020-10-16 | 南京林业大学 | Cellulose-based integrated zinc ion battery and preparation method thereof |
| CN111785898B (en) * | 2020-07-13 | 2022-12-16 | 南京林业大学 | Cellulose-based integrated zinc ion battery and preparation method thereof |
| CN112542569A (en) * | 2020-12-04 | 2021-03-23 | 宁德新能源科技有限公司 | Electrode assembly, electrochemical device comprising same and electronic device |
| CN115249848A (en) * | 2021-09-15 | 2022-10-28 | 青岛大学 | Ultra-tensile fiber-based water-based zinc ion battery and preparation method thereof |
| CN114335410A (en) * | 2021-12-29 | 2022-04-12 | 蜂巢能源科技(无锡)有限公司 | Dry-process anode containing diaphragm, and preparation method and application thereof |
| CN114335410B (en) * | 2021-12-29 | 2024-02-02 | 蜂巢能源科技(无锡)有限公司 | Dry-method positive electrode containing diaphragm, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110808406A (en) | Integrated flexible lithium ion battery and preparation method thereof | |
| CN104600240B (en) | Electrode assemblie and the lithium secondary battery comprising it | |
| Praveen et al. | 3D-printed architecture of Li-ion batteries and its applications to smart wearable electronic devices | |
| CN104681857B (en) | Foldable lithium ion battery and manufacturing method thereof | |
| KR101618218B1 (en) | An Electrochemical Device Comprising The Nano-Fiber Membrane Cellulose And Preparation Method Thereof | |
| CN110178252A (en) | The prelithiation method of cathode for secondary cell | |
| CN109585850A (en) | Slurry containing negative electrode active material, the cathode using the slurry and the electrochemical appliance comprising the cathode | |
| WO2015100414A1 (en) | Deformable origami batteries | |
| JP6408137B2 (en) | Electrode, electrode group and non-aqueous electrolyte battery | |
| JP5675519B2 (en) | Secondary battery negative electrode, non-aqueous electrolyte secondary battery using secondary battery negative electrode, and methods for producing the same | |
| WO2013132592A1 (en) | Solid sulfide battery system and method for controlling solid sulfide battery | |
| CN110416637A (en) | A kind of preparation method and applications of solid state battery buffer layer | |
| KR20130054872A (en) | Electrode assembly, manufacturing the samem, and method of charging and discharging a battery | |
| CN106532055A (en) | Lithium ion battery binder and lithium ion battery | |
| JP2018106984A (en) | All-solid-state lithium ion battery | |
| CN113614951A (en) | Method for preparing negative electrode for secondary battery | |
| CN104704663B (en) | Secondary cell conductive material and electrode of lithium secondary cell comprising the conductive material | |
| KR20180000605A (en) | Peparing method for lithium secondary battery comprising high temperature and pressurization condition during formation process | |
| CN115699397A (en) | Secondary battery and method for manufacturing same | |
| CN114284507B (en) | Negative electrode sandwich structure, preparation method and application thereof | |
| KR101606958B1 (en) | Collector, electrode and secondary battery having the same | |
| WO2022000308A1 (en) | Bipolar current collector, electrochemical device, and electronic device | |
| JP2013239358A (en) | Nonaqueous electrolyte secondary battery anode, nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery system, and manufacturing method thereof | |
| CN106063021A (en) | Rolled electrode set and nonaqueous-electrolyte battery | |
| CN216054799U (en) | Zinc electrode protected by fiber membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200218 |