CN111384316A - Flexible lithium ion battery packaging film, lithium ion battery packaging method and battery - Google Patents
Flexible lithium ion battery packaging film, lithium ion battery packaging method and battery Download PDFInfo
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- CN111384316A CN111384316A CN201911412446.4A CN201911412446A CN111384316A CN 111384316 A CN111384316 A CN 111384316A CN 201911412446 A CN201911412446 A CN 201911412446A CN 111384316 A CN111384316 A CN 111384316A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
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- 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
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- 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 provides a flexible lithium ion battery packaging film, a lithium ion battery packaging method and a prepared integrated lithium ion battery. The packaging film consists of a polymer film outer layer, an inorganic oxide barrier layer and a polymer film inner layer from outside to inside, and the outer layer has good flexibility and certain thickness and can prevent the external damage to the battery cell; the barrier layer can prevent the penetration of moisture and oxygen in the air; the inner layer can not be dissolved by organic solvent in the battery core, has heat sealing property and the like, and ensures that the battery packaging is easy to operate. The packaging method comprises the steps of preparing a nano-layer copper foil/aluminum foil serving as a current collector on a lithium ion battery packaging film, coating an active material on the current collector, coating a solid electrolyte film on the current collector, laminating and bonding the solid electrolyte surfaces of the positive and negative electrode surfaces, and performing heat sealing to prepare the flexible lithium ion battery. The advantage is for integrating packaging material and mass flow body, effectively reduces battery thickness, increases the whole flexibility of battery, and has effectively improved packaging material's pliability and folding endurance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a flexible lithium ion battery packaging material, a preparation method of a flexible electrode and a flexible lithium ion battery, in particular to a flexible lithium ion battery packaging film, a preparation method of a lithium ion battery and an integrated flexible lithium ion battery prepared by the method.
Background
In recent years, with the rapid development of flexible/wearable devices in the fields of smart clothing, biological monitors, electronic paper, surface electronics, flexible display screens and the like, a power supply adapted to wearable electronic products must have the characteristics of light weight, small volume, random deformation, simple and rapid manufacturing process, low cost and the like. The lithium ion battery has the advantages of high safety performance, high energy density, long cycle life, wide working temperature range, wide electrochemical window, flexibility, convenience in recovery and the like.
The packaging of the traditional lithium ion battery is stacked according to a positive plate, a diaphragm and a negative plate, and the traditional lithium ion battery is packaged by a metal shell or a soft package of an aluminum plastic film, so that the traditional lithium ion battery has obstacles in the application of flexible/wearable devices. Therefore, the flexible lithium ion battery comprises a flexible positive electrode, a flexible negative electrode and a flexible diaphragm as well as a solid electrolyte and a flexible packaging material, and the bending and extending characteristics of the flexible lithium ion battery impose higher requirements on the packaging process.
The high-barrier flexible packaging material adopted by the flexible electron is from a polymer film to an aluminum plastic film soft package material taking an aluminum foil and an aluminum plated film as barrier layers, and then to a high-barrier film material taking a polymer as a base material and evaporating or depositing an inorganic oxide as the barrier layers. Wherein the polymer film has limited barrier ability to oxygen and moisture; the aluminum foil and the aluminized film are used as barrier layers, and the aluminum foil needs to have a certain thickness, but when the aluminum foil is used as a flexible packaging material, creases are easy to crack, and the barrier property of the aluminum foil is affected.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a flexible lithium ion battery packaging film and a lithium ion battery packaging method.
In order to achieve the purpose, the invention adopts the following technical scheme.
In the charging cycle process of the lithium ion battery, the packaging material of the flexible lithium ion battery needs to prevent the penetration of impurities such as moisture, air and the like, and simultaneously has higher deformation resistance.
Based on the flexible lithium ion battery packaging film, the flexible lithium ion battery packaging film is a flexible high-barrier packaging film and sequentially comprises a polymer film outer layer, an inorganic oxide barrier layer and a polymer film inner layer from outside to inside.
The outer layer of the polymer film is used for preventing damage to the battery cell from the outside, has excellent flexibility, and ensures that the flexibly packaged lithium ion battery has good deformation capability.
The outer layer of the polymer film is one of Polyimide (PI), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), ethylene/vinyl alcohol copolymer (EVOH) co-extruded film and Polydimethylsiloxane (PDMS). The thickness of the outer layer of the polymer film is 20-100 mu m.
The inorganic oxide barrier layer is Al2O3、TiO2、ZnO、HfO2Or a plurality of composite layers, which are deposited on the outer layer of the polymer film by adopting an atomic layer deposition or sputtering method. The thickness of the inorganic oxide barrier layer is 5-200 nm.
The inorganic composite barrier layer has ultrahigh barrier capability and can prevent the permeation of moisture and oxygen in the air.
The inner layer of the polymer film is a PE, PP or EOVH copolymerization layer which is coated on the inorganic oxide barrier layer by a coating method. The thickness of the inner layer of the polymer film is 20-40 μm.
The polymer inner layer film is required not to be dissolved, swelled and the like by an organic solvent in the battery cell, has heat sealing property, and enables the battery packaging to be easy to operate.
Further, the invention provides a lithium ion battery packaging method based on the flexible lithium ion battery packaging film, which comprises the following steps:
s1, preparing the flexible lithium ion battery packaging film to be used as a positive electrode packaging film and a negative electrode packaging film respectively;
s2, depositing or sputtering a nano-layer copper foil or aluminum foil on the inner sides of the inner polymer films of the anode packaging film and the cathode packaging film to respectively form an anode current collector layer and a cathode current collector layer;
s3, respectively depositing or coating the positive electrode active material and the negative electrode active material on the positive electrode current collector layer and the negative electrode current collector layer to respectively form a positive electrode active material layer and a negative electrode active material layer;
s4 coating the solid electrolyte liquid on the positive electrode active material layer and the negative electrode active material layer, respectively, to form a positive electrode solid electrolyte layer and a negative electrode solid electrolyte layer, respectively;
s5, hot pressing, bonding and packaging the solid electrolyte surfaces of the anode solid electrolyte layer and the cathode solid electrolyte layer, specifically, heating the periphery of the battery by adopting heat-sealing equipment, melting the inner layer polymer, and then cooling to finish packaging.
Specifically, the thickness of the positive electrode active material layer and the negative electrode active material layer is 20-150 microns, the thickness of the positive electrode solid electrolyte layer and the thickness of the negative electrode solid electrolyte layer are 10-100 microns, and the thickness of the negative electrode material is 20-150 microns; the thickness of the anode packaging film and the thickness of the cathode packaging film are both 40-150 mu m, and the thickness of the anode current collector layer and the thickness of the cathode current collector layer are both 8-120 mu m.
Further, according to the flexible lithium ion battery packaging method provided by the invention, the positive active material takes an NCM532 ternary material as a main material, and is matched with a polyvinylidene fluoride (PVDF) binder and a conductive agent as auxiliary materials.
When the positive pole piece is manufactured, firstly, the positive active material: adhesive: the conductive agent is as follows 93: 3: 4, mixing the mixture into slurry, and then uniformly coating the slurry on a positive current collector.
Specifically, the size of the positive pole piece of S3 is 35mm 50mm 20-150 μm, the positive active material around the positive pole piece is removed, so that a packaging area of 5-30mm flows out around the positive active material, and the tabs of the positive pole piece are respectively cut at the top end.
Further, according to the flexible lithium ion battery packaging method provided by the invention, the negative active material takes graphite as a main material, and is matched with a flexible SBR binder and a conductive agent as auxiliary materials.
When the negative pole piece is manufactured, firstly, the negative active material: adhesive: the conductive agent is prepared according to the following steps of 95: 3: 2, and then uniformly coating the mixture on a negative current collector.
Further, in the flexible lithium ion battery packaging method provided by the invention, the size of the negative pole piece of S3 is 40mm x 55mm x 20-150 μm, the negative active material around the negative pole piece is removed, so that a packaging area of 5-30mm flows out from the periphery of the negative active material, and the tabs of the negative pole piece are respectively cut at the top end.
Further, according to the flexible lithium ion battery packaging method provided by the invention, the solid electrolyte comprises ceramic powder and one or more of polypropylene oxide, polysiloxane and polyvinylidene fluoride.
Further, the heat sealing conditions of the flexible lithium ion battery packaging method provided by the invention are that the heating temperature is 150-.
Furthermore, the invention also provides an integrated flexible lithium ion battery, which is obtained by adopting the lithium ion battery packaging method.
The invention discloses an integrated flexible lithium ion battery, which comprises a polymer film outer layer (outer layer flexible polymer substrate), an inorganic oxide barrier layer (inorganic composite barrier layer), a polymer film inner layer (inner layer flexible polymer substrate), a nano current collector layer, an electrode active material layer and a solid electrolyte coating.
Specifically, an integrated flexible lithium ion battery comprises a positive electrode and a negative electrode, wherein specifically, a negative electrode packaging film comprises a negative electrode polymer film outer layer (flexible polymer film), a negative electrode inorganic oxide barrier layer (atomic layer deposition oxide composite barrier layer) is sputtered on the negative electrode polymer film outer layer (flexible polymer film), a negative electrode polymer film inner layer (composite heat-seal polymer layer) is coated on the negative electrode inorganic oxide barrier layer (atomic layer deposition oxide composite barrier layer), a negative electrode polymer film inner layer (composite heat-seal polymer layer) is sputtered on the surface of the negative electrode polymer film inner layer (composite heat-seal polymer layer) or an atomic layer deposition negative electrode current collector metal layer is welded on the negative electrode current collector layer, a negative electrode active material layer is coated on the negative electrode current collector layer, and a negative electrode solid electrolyte layer is coated on the negative.
The positive electrode packaging film comprises a positive electrode polymer film outer layer (flexible polymer film), a positive electrode inorganic oxide barrier layer (atomic layer deposition oxide composite barrier layer) is sputtered on the positive electrode polymer film outer layer (flexible polymer film), a positive electrode polymer film inner layer (composite heat-seal polymer layer) is coated on the positive electrode inorganic oxide barrier layer (atomic layer deposition oxide composite barrier layer), a positive electrode current collector metal layer is sputtered or atomic layer deposition on the surface of the positive electrode polymer film inner layer (composite heat-seal polymer layer), a positive electrode lug is welded on the positive electrode current collector layer, a positive electrode active material layer is coated on the positive electrode current collector layer, and a positive electrode solid electrolyte layer is coated on the positive electrode active material layer.
Compared with the prior art, the invention has the beneficial effects that:
1. the flexible lithium ion battery packaging film provided by the invention sequentially consists of a polymer film outer layer, an inorganic oxide barrier layer and a polymer film inner layer from outside to inside. Wherein: the outer layer of the polymer film has good flexibility and elasticity, and the polymer film has a certain thickness, so that the damage of the outside to the battery cell can be prevented; the inorganic composite barrier layer is prepared by adopting an atomic layer deposition or sputtering mode, has ultrahigh barrier capability and can prevent the permeation of moisture and oxygen in the air; the polymer inner layer film can not be dissolved, swelled and the like by organic solvents in the battery core, and has heat sealing property, so that the battery packaging is easy to operate.
2. The invention provides a lithium ion battery packaging method, which adopts a flexible polymer film atomic layer to deposit a high-barrier inorganic oxide layer, then coats a packaging film of a flexible polymer film in the interior, coats active substances on a current collector, coats a solid electrolyte film on positive and negative active materials, then presses and bonds the positive electrode surface and the solid electrolyte surface of the negative electrode surface, and heat seals the periphery to prepare an integrated flexible lithium ion battery. The packaging material and the current collector are integrated in the mode, so that the thickness of the battery is effectively reduced, the overall flexibility of the battery is improved, and the flexibility and the folding resistance of the packaging material are effectively improved.
Drawings
FIG. 1 is a schematic diagram of an integrated flexible lithium ion battery package according to the present invention;
FIG. 2 is a diagram of an integrated flexible lithium ion battery according to the present invention;
FIG. 3 is a diagram of the electrochemical performance of an integrated flexible lithium ion battery of the present invention;
the figure includes an outer layer 11 of a negative electrode polymer film, a barrier layer 12 of a negative electrode inorganic oxide, an inner layer 13 of a negative electrode polymer film, a metal layer 14 of a negative electrode current collector, an active material layer 15 of a negative electrode, a solid electrolyte layer 16 of a negative electrode, a negative electrode tab 17, an outer layer 21 of a positive electrode polymer film, a barrier layer 22 of a positive electrode inorganic oxide, an inner layer 23 of a positive electrode polymer film, a metal layer 24 of a positive electrode current collector, an active material layer 25 of a positive electrode, a solid electrolyte layer 26 of a positive electrode, and.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly apparent, the present invention is further described in detail with reference to the following embodiments; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention; reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The present invention is described in further detail below with reference to specific examples.
According to one aspect of the invention, the invention provides a flexible lithium ion battery packaging film which is composed of a polymer film outer layer, an inorganic oxide barrier layer and a polymer film inner layer from outside to inside in sequence.
The outer layer of the polymer film is one of Polyimide (PI), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), ethylene/vinyl alcohol copolymer (EVOH) co-extruded film and Polydimethylsiloxane (PDMS). The thickness of the outer layer of the polymer film is 20-100 mu m.
The inorganic oxide barrier layer is Al2O3、TiO2、ZnO、HfO2Or a plurality of composite layers, which are deposited on the outer layer of the polymer film by adopting an atomic layer deposition method. The thickness of the inorganic oxide barrier layer is 5-200 nm.
The inner layer of the polymer film is a PE, PP or EOVH copolymerization layer which is coated on the inorganic oxide barrier layer by a coating method. The thickness of the inner layer of the polymer film is 20-40 μm.
In a preferred embodiment, the polymer outer layer film is PDMS, and the thickness of the PDMS is 20 to 50 μm.
Preferably, the inorganic oxide layer is Al arranged in sequence2O3、TiO2And HfO2Composite barrier layer of Al2O3The layer is 5-10 nm TiO2A layer of 5-10 nm, HfO2The layer is 5-10 nm.
Preferably, the polymer inner layer film is polypropylene, and the thickness of the film layer is 20-30 μm.
According to an aspect of the present invention, there is provided a lithium ion battery packaging method using the above flexible lithium ion battery packaging film, the lithium ion battery packaging method including the steps of:
s1, preparing the flexible lithium ion battery packaging film to be used as a positive electrode packaging film and a negative electrode packaging film respectively;
s2, depositing or sputtering a nano-layer copper foil or aluminum foil on the inner sides of the inner polymer films of the anode packaging film and the cathode packaging film to respectively form an anode current collector layer and a cathode current collector layer;
s3, respectively depositing or coating the positive electrode active material and the negative electrode active material on the positive electrode current collector layer and the negative electrode current collector layer to respectively form a positive electrode active material layer and a negative electrode active material layer;
s4 coating the solid electrolyte liquid on the positive electrode active material layer and the negative electrode active material layer, respectively, to form a positive electrode solid electrolyte layer and a negative electrode solid electrolyte layer, respectively;
s5, hot pressing, bonding and packaging the solid electrolyte surfaces of the anode solid electrolyte layer and the cathode solid electrolyte layer, specifically, heating the periphery of the battery by adopting heat-sealing equipment, melting the inner layer polymer, and then cooling to finish packaging.
Specifically, the thickness of the positive electrode active material layer and the negative electrode active material layer is 20-150 microns, the thickness of the positive electrode solid electrolyte layer and the thickness of the negative electrode solid electrolyte layer are 10-100 microns, and the thickness of the negative electrode material is 20-150 microns; the thickness of the anode packaging film and the thickness of the cathode packaging film are both 40-200 mu m, and the thickness of the anode current collector layer and the thickness of the cathode current collector layer are both 8-120 mu m.
In a preferred embodiment of the invention, the positive active material uses an NCM532 ternary material as a main material, and is matched with a polyvinylidene fluoride (PVDF) binder and a conductive agent as auxiliary materials.
When the positive pole piece is manufactured, firstly, the positive active material: adhesive: the conductive agent is as follows 93: 3: 4, mixing the mixture into slurry, and then uniformly coating the slurry on a positive current collector.
Preferably, the size of the positive pole piece of S3 is 35mm x 50mm x 20-150 μm, the positive active material around the positive pole piece is removed, a packaging area of 5-30mm is left around the positive active material, and the tabs of the positive pole piece are cut at the top end respectively.
Further, according to the flexible lithium ion battery packaging method provided by the invention, the negative active material takes graphite as a main material, and is matched with a flexible SBR binder and a conductive agent as auxiliary materials.
When the negative pole piece is manufactured, firstly, the negative active material: adhesive: the conductive agent is prepared according to the following steps of 95: 3: 2, and then uniformly coating the mixture on a negative current collector.
Preferably, the size of the negative pole piece of S3 is 40mm x 55mm x 20-150 μm, the negative active material around the negative pole piece is removed, a packaging area of 5-30mm is flowed out from the periphery of the negative active material, and the tabs of the negative pole piece are respectively cut at the top end.
Further, according to the flexible lithium ion battery packaging method provided by the invention, the solid electrolyte comprises ceramic powder and one or a mixture of a plurality of polypropylene oxide, polysiloxane and polyvinylidene fluoride.
According to the flexible lithium ion battery packaging method provided by the invention, the heat sealing conditions comprise a heating temperature of 150-.
In the present invention, the heating temperature of the heat-sealing conditions is typically, but not limited to, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃.
In the present invention, the pressing pressure of the heat-sealing conditions is typically, but not limited to, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6 MPa.
In the present invention, the pressing time under the heat-sealing conditions is typically, but not limited to, 3s, 4s, and 5 s.
By adopting the method, the packaging material and the current collector are integrated, the thickness of the battery is effectively reduced, the overall flexibility of the battery is increased, and meanwhile, the electrode material is printed in a matrix design, so that the performance of the battery is ensured to be influenced by interface stress in the bending process of the battery.
According to one aspect of the invention, the integrated flexible lithium ion battery is obtained by adopting the lithium ion battery packaging method.
The invention discloses an integrated flexible lithium ion battery, which comprises a polymer film outer layer (outer layer flexible polymer substrate), an inorganic oxide barrier layer (inorganic composite barrier layer), a polymer film inner layer (inner layer flexible polymer substrate), a nano current collector layer, an electrode active material layer and a solid electrolyte coating.
Referring to fig. 1 and fig. 2, the integrated flexible lithium ion battery of the present invention includes a positive electrode and a negative electrode, and specifically, the negative electrode packaging film includes a negative electrode polymer film outer layer (flexible polymer film) 11, a negative inorganic oxide barrier layer (atomic layer deposition oxide composite barrier layer) 12 is sputtered on the negative polymer film outer layer (flexible polymer film) 11, the negative inorganic oxide barrier layer (atomic layer deposition oxide composite barrier layer) 12 is coated with a negative polymer film inner layer (composite heat-seal polymer layer) 13, the surface of the inner layer (composite heat-seal polymer layer) 13 of the negative electrode polymer film is sputtered or atomic layer deposited with a negative electrode current collector metal layer 14, a negative pole tab 17 is welded on the negative pole current collector layer 14, a negative pole active material layer 15 is coated on the negative pole current collector layer 14, and a negative pole solid electrolyte layer 16 is coated on the negative pole active material layer 15;
the positive electrode packaging film comprises a positive electrode polymer film outer layer (flexible polymer film) 21, a positive electrode inorganic oxide barrier layer (atomic layer deposition oxide composite barrier layer) 22 is sputtered on the positive electrode polymer film outer layer (flexible polymer film) 21, a positive electrode polymer film inner layer (composite heat-seal polymer layer) 23 is coated on the positive electrode inorganic oxide barrier layer (atomic layer deposition oxide composite barrier layer) 22, a positive electrode current collector metal layer 24 is sputtered or atomic layer deposition on the surface of the positive electrode polymer film inner layer (composite heat-seal polymer layer) 23, a positive electrode tab 27 is welded on the positive electrode current collector layer 24, a positive electrode active material layer 25 is coated on the positive electrode current collector layer 24, and a positive electrode solid electrolyte layer 26 is coated on the positive electrode active material layer 25. The flexible lithium ion battery is prepared by hot-pressing and laminating an upper packaging layer and a lower packaging layer which are coated with the solid electrolyte in the figure 1 and performing heat sealing on the periphery, and the figure is an example and does not limit the number of the layers of the core materials.
The anode polymer film outer layer 11, the anode inorganic oxide barrier layer 12, the anode polymer film inner layer 13, the anode current collector metal layer 14, the anode active material layer 15, the anode solid electrolyte layer 16, the anode tab 17, the anode polymer film outer layer 21, the anode inorganic oxide barrier layer 22, the anode polymer film inner layer 23, the anode current collector metal layer 24, the anode active material layer 25, the anode solid electrolyte layer 26, and the anode and the cathode in the anode tab 27 are relative terms, and do not represent the difference in the composition and thickness of the material layers, and the material and thickness of each layer are obtained according to the description and limitation in the foregoing method.
And (5) experiments and results.
The flexible lithium ion battery packaging film provided by the invention is different from a mature aluminum plastic film lithium battery packaging material in the market. The waterproof and oxygen-resistant performance is ensured, and the barrier cannot be damaged in the bending process.
Referring to table 1, for comparison between the water and oxygen blocking performance of the flexible lithium ion battery packaging film of the present invention and the commercial aluminum-plastic film of the prior art, during the experiment, the electrolyte was respectively packaged in the flexible lithium ion battery packaging film of the present invention and the commercial aluminum-plastic film, and the moisture content was changed before and after the test at a warm-standing state for 7 days.
Table 1 water resistance meter of flexible lithium ion battery packaging film
As seen from Table 1 Cayi, the flexible lithium ion battery packaging film has good water resistance and can not be damaged in the bending process.
Referring to fig. 3, it is a diagram of electrochemical cycle performance of the integrated flexible lithium ion battery of the present invention.
The flexible lithium ion separation membrane adopted by the integrated flexible lithium ion battery is respectively EVOH copolymer (70 mu m) TiO from outside to inside2(5 μm) PP (50 μm) as a positive electrode encapsulating film and a negative electrode encapsulating film, respectively; the positive active material takes an NCM532 ternary material as a main material, and is matched with a polyvinylidene fluoride (PVDF) binder and a conductive agent as auxiliary materials, and when the positive pole piece is manufactured, the positive active material is prepared by the following steps: adhesive: the conductive agent is as follows 93: 3: 4, mixing the mixture into slurry, and then uniformly coating the slurry on a positive current collector; the negative active material uses graphite as a main material, is matched with flexible SBR binder and conductive agent as auxiliary materials, and is prepared by the following steps: adhesive: the conductive agent is prepared according to the following steps of 95: 3: 2, then uniformly coating the mixture on a negative current collector, rolling and stamping the mixture to obtain a positive pole piece with the size of 35mm 50mm 120 mu m, removing a negative active material around the positive pole piece to enable the periphery of the positive active material to flow out of a 5mm packaging area, cutting a tab of the positive pole piece at the top end, respectively removing a negative active material around the negative pole piece with the size of 40mm 55mm 120 mu m, and enabling the periphery of the negative active material to flow out of the 5mm packaging areaAnd cutting out the tabs of the negative pole piece at the top end, coating the solid electrolyte liquid on the positive active material layer and the negative active material layer respectively to form a positive solid electrolyte layer and a negative solid electrolyte layer respectively, and hot-pressing and bonding the solid electrolyte surfaces of the positive solid electrolyte layer and the negative solid electrolyte layer under the conditions of heating temperature of 180 ℃, pressurizing pressure of 0.5MPa and pressurizing time of 5 s.
The electrochemical cycle performance test is carried out on the integrated flexible lithium ion battery, the test result is shown in fig. 3, and it can be seen from the figure that the capacity retention rate of the battery is more than 92% after 200 circles of cycles in the battery cycle bending process, which shows that the flexible lithium ion packaging film of the invention still maintains good water and oxygen resistance, the structure is not damaged, and the flexible lithium ion packaging film has better flexibility, so that the overall flexibility of the battery is indirectly improved.
The performance test and the technical effect description are carried out by the experimental example, and the performance test is carried out by adopting other embodiments of the invention, so that the results with similar effects can be obtained.
While the invention has been described with respect to specific embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention; those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and alterations of the above embodiments according to the spirit and techniques of the present invention are also within the scope of the present invention.
Claims (11)
1. A flexible lithium ion battery packaging film is characterized in that: the flexible lithium ion battery packaging film is composed of a polymer film outer layer, an inorganic oxide barrier layer and a polymer film inner layer from outside to inside in sequence.
2. The flexible lithium ion battery packaging film of claim 1, wherein: the outer layer of the polymer film is one of polyimide, polyethylene naphthalate, polyethylene terephthalate, an ethylene/vinyl alcohol copolymer film and polydimethylsiloxane;
the thickness of the outer layer of the polymer film is 20-100 mu m.
3. The flexible lithium ion battery packaging film of claim 2, wherein: the inorganic oxide barrier layer is Al2O3、TiO2、ZnO、HfO2One or more composite layers deposited on the outer layer of the polymer film by adopting an atomic layer deposition or sputtering method;
the thickness of the inorganic oxide barrier layer is 5-200 nm.
4. The flexible lithium ion battery packaging film of claim 2, wherein:
the inner layer of the polymer film is a polyethylene, polypropylene or ethylene/vinyl alcohol copolymer layer, and is coated on the inorganic oxide barrier layer by a coating method;
the thickness of the inner layer of the polymer film is 20-40 μm.
5. A flexible lithium ion battery packaging method is characterized by comprising the following steps:
s1, preparing the flexible lithium ion battery packaging film of any one of claims 1 to 4, and respectively using the flexible lithium ion battery packaging film as a positive electrode packaging film and a negative electrode packaging film;
s2, depositing or sputtering a nano-layer copper foil or aluminum foil on the inner sides of the inner polymer films of the anode packaging film and the cathode packaging film to respectively form an anode current collector layer and a cathode current collector layer;
s3, respectively depositing or coating the positive electrode active material and the negative electrode active material on the positive electrode current collector layer and the negative electrode current collector layer to respectively form a positive electrode active material layer and a negative electrode active material layer;
s4 coating the solid electrolyte liquid on the positive electrode active material layer and the negative electrode active material layer, respectively, to form a positive electrode solid electrolyte layer and a negative electrode solid electrolyte layer, respectively;
s5, hot pressing, bonding and packaging the solid electrolyte surfaces of the anode solid electrolyte layer and the cathode solid electrolyte layer, heating the periphery of the battery by adopting heat-sealing equipment, melting the inner layer polymer, and then cooling to finish packaging.
6. The flexible lithium ion battery packaging method of claim 5, wherein: the positive active material takes an NCM532 ternary material as a main material, and takes a binder and a conductive agent as auxiliary materials, and in S3, the positive active material is firstly: adhesive: the conductive agent is as follows 93: 3: 4, mixing the mixture into slurry, and then uniformly coating the slurry on a positive current collector.
7. The flexible lithium ion battery packaging method of claim 5, wherein: the negative active material uses graphite as a main material, and is matched with a binder and a conductive agent as auxiliary materials, in S3, when the negative pole piece is manufactured, the negative active material is firstly: adhesive: the conductive agent is prepared according to the following steps of 95: 3: 2, and then uniformly coating the mixture on a negative current collector.
8. The flexible lithium ion battery packaging method of claim 5, wherein: the solid electrolyte is a mixture of ceramic powder and one or more of polypropylene oxide, polysiloxane and polyvinylidene fluoride.
9. The flexible lithium ion battery packaging method of claim 5, wherein: in the S5, the heat sealing conditions are heating temperature of 150 ℃ and 190 ℃, pressurizing pressure of 0.2-0.6MPa and time of 3-5S.
10. An integrated flexible lithium ion battery, characterized in that the flexible lithium ion battery is prepared by the flexible lithium ion battery packaging method of any one of the preceding claims 4-8.
11. The flexible lithium ion battery of claim 10, wherein: the packaging film comprises a positive electrode and a negative electrode, wherein the negative electrode packaging film comprises a negative electrode polymer film outer layer (11), a negative electrode inorganic oxide barrier layer (12) is sputtered on the negative electrode polymer film outer layer (11), a negative electrode polymer film inner layer (13) is coated on the negative electrode inorganic oxide barrier layer (12), a negative electrode current collector metal layer (14) is sputtered or deposited by an atomic layer on the surface of the negative electrode polymer film inner layer (13), a negative electrode lug (17) is welded on the negative electrode current collector layer (14), a negative electrode active material layer (15) is coated on the negative electrode current collector layer (14), and a negative electrode solid electrolyte layer (16) is coated on the negative electrode active material layer (15);
the positive electrode packaging film comprises a positive electrode polymer film outer layer (21), a positive electrode inorganic oxide barrier layer (22) is sputtered on the positive electrode polymer film outer layer (21), a positive electrode polymer film inner layer (23) is coated on the positive electrode inorganic oxide barrier layer (22), a positive electrode current collector metal layer (24) is sputtered or atomic layer deposited on the surface of the positive electrode polymer film inner layer (23), a positive electrode lug (27) is welded on the positive electrode current collector layer (24), a positive electrode active material layer (25) is coated on the positive electrode current collector layer (24), and a positive electrode solid electrolyte layer (26) is coated on the positive electrode active material layer (25).
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| CN111969252A (en) * | 2020-08-31 | 2020-11-20 | 蜂巢能源科技有限公司 | Solid-state battery and method for manufacturing same |
| CN112310565A (en) * | 2020-10-30 | 2021-02-02 | 京东方科技集团股份有限公司 | Battery and display panel |
| CN112968179A (en) * | 2021-02-04 | 2021-06-15 | 珠海冠宇电池股份有限公司 | Current collector composite film and solid-state battery |
| CN114635166A (en) * | 2021-12-10 | 2022-06-17 | 南京大学 | Flexible lithium extraction device and method |
| WO2024041670A1 (en) * | 2022-08-24 | 2024-02-29 | 深圳市中睿新材料技术有限公司 | Multi-layer composite structure for lithium-ion battery packaging and preparation method therefor, and lithium-ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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