CN113078285A - Flexible battery - Google Patents

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CN113078285A
CN113078285A CN202110321269.XA CN202110321269A CN113078285A CN 113078285 A CN113078285 A CN 113078285A CN 202110321269 A CN202110321269 A CN 202110321269A CN 113078285 A CN113078285 A CN 113078285A
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active material
flexible battery
negative electrode
positive electrode
material layer
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CN113078285B (en
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江顺琼
陈稳
周旭峰
刘兆平
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention provides a flexible battery comprising: an integrated positive electrode; an integrated negative electrode; a gel electrolyte; the integrated positive electrode includes: a positive electrode base material; an aluminum atomic layer disposed on a surface of the positive electrode substrate; the positive active material layer is arranged on the surface of the aluminum atomic layer; the integrated negative electrode includes: a negative electrode base material; a copper atomic layer disposed on a surface of the negative electrode substrate; a negative electrode active material layer disposed on the surface of the copper atomic layer; the gel electrolyte is disposed between the positive electrode active material layer and the negative electrode active material layer. The flexible battery provided by the invention can effectively reduce the specific gravity of the inactive material, and is beneficial to improving the overall mass and volume energy density of the flexible battery; high flexibility is achieved by means of a substrate; the flexible battery is thin as a whole and can be widely applied to the wearable field; the size and shape of the integrated electrode can be customized.

Description

Flexible battery
Technical Field
The invention belongs to the technical field of flexible electronic devices, and particularly relates to a flexible battery.
Background
As one of flexible electronic devices, wearable equipment has been developed rapidly in recent years, and the wearable equipment not only has good application in flexible display equipment, but also has wide prospects in the field of life health. In order to meet the characteristics of flexibility and wearability, flexible batteries are also continuously and rapidly developed as important energy support devices.
The flexible battery is a novel battery with wide application prospect, and needs to give consideration to both mechanical flexibility and electrochemical performance. The existing flexible battery usually utilizes structural design such as unit assembly to realize flexibility, and the flexible battery is limited by the structural design because key materials such as internal electrodes are rigid materials, thereby causing great influence on application. However, when the battery is made thin for flexibility, the amount of active material supported is relatively reduced, and the proportion of inactive material (current collector, encapsulating film) is relatively increased, which leads to a reduction in electrochemical properties such as energy density. In a typical flexible battery with a layer-by-layer stacked sandwich structure, delamination may occur due to stress concentration during a long-term reciprocating bending process, so that the structural stability and the cycle stability of the flexible battery are further reduced. Therefore, there is a strong need for a technology that enables a flexible battery to achieve high flexibility and have high utilization efficiency of active materials.
The existing ways of designing flexible batteries can be mainly divided into three categories: one type is a battery monomer combination, and the battery is mainly made into a narrow or small unit and is flexibly connected to realize certain flexibility of the whole combination. The other type of the battery is flexible by virtue of a flexible substrate, and mainly utilizes a carbon material or a high polymer material with better flexibility as a substrate. The other is to make the conventional battery thin and light to realize relative flexibility. The flexible battery is a novel energy storage device which has both mechanical flexibility and electrochemical performance. Various factors need to be considered in design, including material selection, structural design, and device form. The flexible battery designed by means of the structure such as unit assembly is limited by the structure, and the flexibility of key materials such as internal electrodes cannot be realized, so that the flexible battery also has great influence on the application. Achieving flexibility from a mechanical point of view requires that the battery be as thin as possible, mainly for the following reasons: in the bending process, the neutral surface of the structural layer of the film material is not stressed, the outer side of the structural layer of the film material is under tensile stress, and the inner side of the structural layer of the film material is under compressive stress; in the long-term reciprocating process, the stability of the material is greatly influenced; particularly, the active materials used for the flexible battery at present are basically rigid materials, the mechanical property is poor, and the active materials can gradually fall off due to stress concentration and stress release problems in the bending process. Therefore, for realizing a flexible battery, it is desirable that the active materials are all distributed in the neutral plane, meaning that the thinner the battery, the better. However, when the battery is made thin, the amount of the active material supported is relatively decreased, thereby causing a decrease in electrochemical properties such as energy density. In addition, the existing battery design concept involves that aluminum foil and copper foil are respectively used as current collectors of positive and negative electrode materials, and an aluminum plastic film is used for packaging; however, in this design, the material components function relatively singly, i.e.: the aluminum foil and the copper foil are only used for the conduction of a current collector, and the aluminum plastic film is only used for packaging the battery; because both are inactive materials, the problem of inactive materials occupying a certain mass and volume means that the mass and volume energy density of the final device are reduced, and the problem is more serious in a flexible battery after being thinned.
Although the existing flexible battery can realize flexibility, the problem of how to consider both mechanical properties and electrochemical properties can be faced under the consideration of the dual functions of integrating a flexible electronic device and an energy storage device, which also puts higher requirements on the design of the flexible battery.
Disclosure of Invention
In view of the above, the present invention provides a flexible battery having high flexibility and high volume/mass energy density.
The present invention provides a flexible battery comprising:
an integrated positive electrode;
an integrated negative electrode;
a gel electrolyte;
the integrated positive electrode includes:
a positive electrode base material;
an aluminum atomic layer disposed on a surface of the positive electrode substrate;
the positive active material layer is arranged on the surface of the aluminum atomic layer;
the integrated negative electrode includes:
a negative electrode base material;
a copper atomic layer disposed on a surface of the negative electrode substrate;
a negative electrode active material layer disposed on the surface of the copper atomic layer;
the gel electrolyte is disposed between the positive electrode active material layer and the negative electrode active material layer.
Preferably, the positive electrode substrate and the negative electrode substrate are selected from PP films; the thickness of the anode base material and the thickness of the cathode base material are independently selected from 20-200 mu m.
Preferably, the thicknesses of the aluminum atomic layer and the copper atomic layer are independently selected from 20-100 nm.
Preferably, the thickness of the positive electrode active material layer is 500nm to 2000 μm;
the thickness of the negative electrode active material layer is 100nm to 2000 mu m.
Preferably, the positive electrode active material in the positive electrode active material layer is selected from lithium cobaltate, lithium iron phosphate or a ternary positive electrode material.
Preferably, the negative active material in the negative active material layer is selected from graphite, graphene or silicon carbon.
Preferably, the gel electrolyte includes:
a polymer, an electrolyte solvent and a lithium salt;
the dosage proportion of the high molecular substance, the electrolyte solvent and the lithium salt is (1-3) g: (10-30) mL: (0.5-2) g.
Preferably, the high molecular substance is selected from one or more of polyethylene oxide, polyvinylidene fluoride, poly (vinylidene fluoride-co-hexafluoropropylene), polyacrylonitrile and polymethyl methacrylate;
the electrolyte solvent is selected from one or more of ethylene carbonate, propylene carbonate, divinyl carbonate and dimethyl carbonate;
the lithium salt is selected from LiPF6、LiClO4Or LiTFSI.
Preferably, the high molecular substance is poly (vinylidene fluoride-co-hexafluoropropylene);
the electrolyte solution is ethylene carbonate and dimethyl carbonate, and the mass ratio of the ethylene carbonate to the dimethyl carbonate is 3: 7;
the lithium salt is LiTFSI.
Preferably, the ratio of the amount of the polymer, the electrolyte solvent and the lithium salt is 2 g: 10mL of: 1g of the total weight of the composition.
The flexible battery provided by the invention can effectively reduce the specific gravity of the inactive material, and is beneficial to improving the overall mass and volume energy density of the flexible battery; high flexibility is achieved by means of a substrate; the flexible battery is thin as a whole and can be widely applied to the wearable field; the size and shape of the integrated electrode can be customized.
Drawings
Fig. 1 is a schematic structural diagram of a PP film provided in an embodiment of the present invention;
FIG. 2 is a schematic diagram of a structure for depositing an atomic layer of aluminum and an atomic layer of copper according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of a loaded electrode active material according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other examples, which may be modified or appreciated by those of ordinary skill in the art based on the examples given herein, are intended to be within the scope of the present invention. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. In the examples, the methods used were all conventional methods unless otherwise specified.
The present invention provides a flexible battery comprising:
an integrated positive electrode;
an integrated negative electrode;
a gel electrolyte;
the integrated positive electrode includes:
a positive electrode base material;
an aluminum atomic layer disposed on the substrate surface;
the positive active material layer is arranged on the surface of the aluminum atomic layer;
the integrated negative electrode includes:
a negative electrode base material;
a copper atomic layer disposed on a surface of the negative electrode substrate;
a negative electrode active material layer disposed on the surface of the copper atomic layer;
the gel electrolyte is disposed between the positive electrode active material layer and the negative electrode active material layer.
In the present invention, the positive electrode substrate is preferably a PP film (polypropylene film); the thickness of the positive electrode substrate is preferably 20 to 200 μm, more preferably 50 to 150 μm, more preferably 80 to 120 μm, and most preferably 100 μm. In the embodiment of the present invention, the thickness of the cathode substrate is preferably 20 μm.
In the present invention, the thickness of the aluminum atomic layer is preferably 20 to 100nm, more preferably 40 to 80nm, more preferably 50 to 60nm, and most preferably 50 nm. In an embodiment of the invention, the thickness of the atomic layer of aluminum is preferably 20 nm.
In the present invention, the method for preparing the aluminum atomic layer preferably includes:
and depositing a compact aluminum atomic layer on the surface of the cathode substrate by adopting a PVD method.
In the present invention, the positive electrode active material in the positive electrode active material layer is preferably selected from lithium cobaltate, lithium iron phosphate, or a ternary positive electrode material; the ternary cathode material is preferably an NCM811 ternary cathode material.
In the present invention, the thickness of the positive electrode active material layer is preferably 500nm to 2000. mu.m, more preferably 800nm to 1500. mu.m, more preferably 10 μm to 1000. mu.m, more preferably 50 μm to 800. mu.m, and most preferably 400 μm to 600. mu.m. In the embodiment of the present invention, the thickness of the positive electrode active material layer is preferably 600 μm.
In the present invention, the method for preparing the positive electrode active material layer preferably includes:
mixing a positive electrode active material, a binder, a conductive additive and a solvent to obtain positive electrode slurry;
and coating the positive electrode slurry on the surface of the aluminum atomic layer, and drying to obtain a positive electrode active material layer.
In the present invention, the positive electrode active material is the same as the positive electrode active material described in the above technical solution, and is not described herein again.
In the present invention, the binder in the positive electrode slurry is preferably selected from PVDF (polyvinylidene fluoride), more preferably a PVDF solution; the mass concentration of the PVDF solution is preferably 3-7%, more preferably 4-6%, and most preferably 5%.
In the present invention, the conductive additive in the positive electrode slurry is preferably selected from graphene, conductive carbon black or carbon nanotubes, and more preferably conductive carbon black.
In the present invention, the solvent in the positive electrode material is preferably selected from NMP (N-methylpyrrolidone).
In the invention, the mass ratio of the positive electrode active material, the binder and the conductive additive in the positive electrode slurry is preferably (7-9): (0.1-3): (0.1 to 3), more preferably (8 to 9): (0.1-2): (0.1-2), most preferably 8:1: 1.
in the present invention, the thickness of the coated positive electrode slurry is preferably 500nm to 2000. mu.m, more preferably 800nm to 1500. mu.m, more preferably 10 μm to 1000. mu.m, more preferably 50 μm to 800. mu.m, more preferably 100 μm to 600. mu.m, more preferably 200 μm to 500. mu.m, and most preferably 300 μm to 400. mu.m. In the embodiment of the present invention, the thickness of the coated positive electrode slurry is preferably 600 μm.
In the present invention, the method of drying during the preparation of the positive electrode active material layer is preferably oven drying; the drying time is preferably 2 to 8 hours, more preferably 3 to 6 hours, and most preferably 6 hours.
In the present invention, the negative electrode substrate is preferably a PP film (polypropylene film); the thickness of the negative electrode substrate is preferably 20 to 200 μm, more preferably 50 to 150 μm, more preferably 80 to 120 μm, and most preferably 100 μm. In the embodiment of the present invention, the thickness of the negative electrode base material is preferably 20 μm.
In the present invention, the thickness of the copper atomic layer is preferably 20 to 100nm, more preferably 30 to 80nm, more preferably 40 to 70nm, and most preferably 50 to 60 nm. In an embodiment of the invention, the thickness of the copper atomic layer is preferably 20 nm.
In the present invention, the method for preparing the copper atomic layer preferably includes:
and depositing a compact copper atomic layer on the surface of the cathode substrate by adopting a PVD method.
In the present invention, the negative electrode active material in the negative electrode active material layer is preferably selected from graphite, graphene, or silicon carbon, and more preferably graphite.
In the present invention, the thickness of the negative electrode active material layer is preferably 100nm to 2000 μm, more preferably 500nm to 1500 μm, more preferably 1 μm to 1000 μm, more preferably 10 μm to 800 μm, more preferably 100 μm to 600 μm, more preferably 200 μm to 500 μm, more preferably 300 μm to 400 μm, and most preferably 350 μm.
In the present invention, the method for preparing the anode active material layer preferably includes:
mixing a negative electrode active material, a binder, a conductive additive and a solvent to obtain negative electrode slurry;
and coating the negative electrode slurry on the surface of the copper atomic layer and then drying to obtain a negative electrode active material layer.
In the present invention, the negative active material is preferably selected from graphite, graphene or silicon carbon, and more preferably graphite.
In the present invention, the binder in the negative electrode slurry is preferably selected from PVDF, more preferably a PVDF solution; the mass concentration of the PVDF solution is preferably 3-7%, more preferably 4-6%, and most preferably 5%.
In the present invention, the solvent in the anode slurry is preferably selected from NMP.
In the present invention, the conductive additive in the negative electrode slurry is preferably selected from graphene, conductive carbon black, or carbon nanotubes, and more preferably conductive carbon black.
In the invention, the mass ratio of the negative electrode active material, the binder and the conductive additive in the negative electrode slurry is preferably (7-9): (0.1-3): (0.1 to 3), more preferably (8 to 9): (0.1-2): (0.1-2), most preferably 8:1: 1.
in the present invention, the thickness of the coated anode slurry is preferably 100nm to 2000. mu.m, more preferably 500nm to 1500. mu.m, more preferably 1 μm to 1000. mu.m, more preferably 10 μm to 800. mu.m, more preferably 50 μm to 600. mu.m, more preferably 100 μm to 500. mu.m, more preferably 200 μm to 400. mu.m, and most preferably 350. mu.m.
In the present invention, the method of drying during the preparation of the anode active material layer is preferably oven drying; the drying time is preferably 2 to 8 hours, more preferably 3 to 6 hours, and most preferably 6 hours.
In the present invention, the gel electrolyte preferably includes:
a polymer, an electrolyte solvent and a lithium salt.
In the present invention, the high molecular substance is preferably one or more selected from the group consisting of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), Polyacrylonitrile (PAN), and polymethyl methacrylate (PMMA), and more preferably PVDF-HFP.
In the present invention, the electrolyte solvent is preferably selected from one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), diethylene carbonate (DEC) and dimethyl carbonate (DMC), more preferably from EC and DMC; the mass ratio of the EC to the DMC is preferably (2-4): (6-8), more preferably (2.5-3.5): (6.5 to 7.5), most preferably 3: 7.
in the present invention, the lithium salt is preferably selected from LiPF6、LiClO4Or LiTFSI, more preferably LiTFSI.
In the present invention, the ratio of the amount of the polymer, the electrolyte solvent and the lithium salt is preferably (1 to 3) g: (10-30) mL: (0.5-2) g, more preferably (1.5-2.5): (10-20) mL: (1-1.5) g, most preferably 2 g: 10mL of: 1g of the total weight of the composition.
In the present invention, the thickness of the gel electrolyte is preferably 15 to 25 μm, more preferably 18 to 22 μm, and most preferably 20 μm.
In the present invention, the preparation method of the gel electrolyte preferably includes:
mixing and heating to dissolve the high molecular substance, the electrolyte solvent and the lithium salt to obtain the gel electrolyte.
In the invention, the heating and dissolving temperature is preferably 45-55 ℃, more preferably 48-52 ℃ and most preferably 50 ℃; the time for heating and dissolving is preferably 10 to 15 hours, more preferably 11 to 13 hours, and most preferably 12 hours.
In the invention, the thickness of the flexible battery is preferably 80-120 μm, more preferably 90-110 μm, and most preferably 100 μm.
In the present invention, the method for manufacturing the flexible battery preferably includes:
and coating the surface of the negative electrode active material layer and/or the surface of the positive electrode active material layer with gel electrolyte, and then pressing to enable the integrated positive electrode, the gel electrolyte and the integrated negative electrode to be integrally bonded together to prepare the flexible battery.
In the present invention, it is preferable that the pressing is completed by further including:
and (5) performing edge sealing to prepare the flexible battery.
In the present invention, the method of pressing is preferably roll pressing.
In the present invention, the method for manufacturing a flexible battery more preferably includes:
designing an integrated positive electrode and an integrated negative electrode into a required shape (such as the shape shown in fig. 1), and reserving a part of the integrated positive electrode and the integrated negative electrode as tabs;
respectively coating gel electrolytes on the surface of the positive active material layer and the surface of the negative active material layer in a scraping way, and relatively sticking the two surfaces coated with the gel electrolytes together to form a whole when the surfaces are dried to be in a semi-solid state;
rolling the whole body to obtain a tightly combined device;
and then, carrying out heat sealing by using the base materials (PP films) with the exposed outer edges of the integrated anode and the integrated cathode to obtain the flexible battery with high flexibility and high active material ratio.
The flexible battery provided by the invention can effectively reduce the specific gravity of the inactive material, and is beneficial to improving the overall mass and volume energy density of the flexible battery; high flexibility is achieved by means of a substrate; the flexible battery is thin as a whole and can be widely applied to the wearable field; the size and shape of the integrated electrode can be customized.
The raw materials used in the following examples of the present invention are all commercially available products
Example 1
Ternary high nickel series NCM811 is selected as a positive active material, and graphite is selected as a negative active material.
The integrated positive electrode adopts a PVD (physical vapor deposition) technology to deposit a compact aluminum atomic layer (shown in figure 2) on the PP film (shown in figure 1) with the cut shape; wherein the thickness of the PP film is 20 mu m, and the thickness of the aluminum atomic layer is 20 nm; coating the surface of the aluminum atomic layer with positive electrode slurry, and drying to form a positive electrode active material layer (shown in figure 3); the positive electrode slurry is composed of a positive electrode active material, conductive carbon black, a binder and a solvent, wherein the mass ratio of the positive electrode active material to the conductive carbon black to the binder is 8:1: 1; coating the positive electrode slurry to the thickness of 600 mu m; the binder is a PVDF solution with the mass concentration of 5%, and the solvent is NMP; the drying time is 6 hours.
The integrated negative electrode adopts a PVD (physical vapor deposition) technology to deposit a compact copper atomic layer on the PP film cut into a shape; wherein the thickness of the PP film is 20 mu m, and the thickness of the copper atomic layer is 20 nm; coating the surface of the copper atomic layer with negative electrode slurry and then drying to form a negative electrode active material layer; the negative electrode slurry is composed of a negative electrode active material graphite, conductive carbon black, a binder and a solvent, wherein the mass ratio of the graphite to the conductive carbon black to the binder is 8:1: 1; the coating thickness of the negative electrode slurry is 350 mu m; the binder is a PVDF solution with the mass concentration of 5%, and the solvent is NMP; the drying time was 6 hours.
The preparation method of the gel electrolyte comprises the following steps: dissolving a high molecular substance poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), a lithium salt LiTFSI and an electrolyte solvent (a mixed solvent (EC: DMC mass ratio is 3: 7)) at 50 ℃ for 12 hours by heating; the dosage ratio of the high molecular substance, the electrolyte solvent and the lithium salt is 2 g: 10mL of: 1g of the total weight of the composition.
Assembling the flexible battery: respectively blade-coating gel electrolyte with the thickness of 10 mu m on the surfaces of the positive electrode active material layer and the negative electrode active material layer, and relatively sticking the two surfaces coated with the gel electrolyte together to form a whole when the surfaces are dried to be semi-solid; pressing the whole roller to obtain a tightly combined device; and then, carrying out heat sealing by using a PP film exposed on the outer side edge of the electrode to obtain the flexible battery with the thickness of 100 mu m and high flexibility and high active material ratio.
When the cycle stability test of the flexible battery prepared in example 1 was performed by using the novyi battery tester, the 500-cycle capacity retention rate was 81%.
The flexible battery prepared in the embodiment 1 of the invention is bent for 180 degrees by adopting an epoch supergroup CM35D series controller, and the bending is performed for 5 ten thousand times according to the detection result, so that the performance is not attenuated.
Examples 2 to 8
A flexible battery was manufactured according to the method of example 1, except that the gel electrolyte composition of example 1 was replaced with the gel electrolyte composition of table 1.
The flexible batteries prepared in examples 2 to 8 of the present invention were tested according to the method of example 1, and the test results are shown in table 1.
Table 1 gel electrolyte for preparing flexible battery in embodiments 2 to 8 of the present invention and performance test results of the flexible battery
Figure BDA0002993015650000091
As can be seen from table 1, the selection of the solvent in the gel electrolyte and the selection of the lithium salt have a great influence on the electrochemical performance, and the cycle performance of the flexible batteries prepared from different gel electrolytes in different proportions and different types has a significant difference, so that the flexible battery prepared in example 1 has a better effect. In addition, the content of the high polymer in the gel electrolyte also has great influence on the mechanical property of the flexible battery, when the content of the high polymer is low (very dilute), the flexible battery cannot form a film, the cohesiveness is poor, the mechanical property is influenced, and the structural stability of a device is influenced; when concentrated, it is too viscous to dissolve in the solvent, and higher crystallinity reduces the ion transport efficiency, and example 1 has the most excellent effect.
According to the embodiment, the specific gravity of the inactive material can be effectively reduced, and the overall mass and the volume energy density of the flexible battery can be improved; high flexibility is achieved by means of a substrate; the flexible battery is thin as a whole and can be widely applied to the wearable field; the size and shape of the integrated electrode can be customized.
While only the preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.

Claims (10)

1. A flexible battery, comprising:
an integrated positive electrode;
an integrated negative electrode;
a gel electrolyte;
the integrated positive electrode includes:
a positive electrode base material;
an aluminum atomic layer disposed on a surface of the positive electrode substrate;
the positive active material layer is arranged on the surface of the aluminum atomic layer;
the integrated negative electrode includes:
a negative electrode base material;
a copper atomic layer disposed on a surface of the negative electrode substrate;
a negative electrode active material layer disposed on the surface of the copper atomic layer;
the gel electrolyte is disposed between the positive electrode active material layer and the negative electrode active material layer.
2. The flexible battery of claim 1, wherein the positive and negative substrates are selected from PP films;
the thickness of the anode base material and the thickness of the cathode base material are independently selected from 20-200 mu m.
3. The flexible battery according to claim 1, wherein the thickness of the aluminum atomic layer and the copper atomic layer is independently selected from 20nm to 100 nm.
4. The flexible battery according to claim 1, wherein the thickness of the positive electrode active material layer is 500nm to 2000 μm;
the thickness of the negative electrode active material layer is 100nm to 2000 mu m.
5. The flexible battery according to claim 1, wherein the positive active material in the positive active material layer is selected from lithium cobaltate, lithium iron phosphate or ternary positive material.
6. The flexible battery of claim 1, wherein the negative active material in the negative active material layer is selected from graphite, graphene, or silicon carbon.
7. The flexible battery of claim 1, wherein the gel electrolyte comprises:
a polymer, an electrolyte solvent and a lithium salt;
the dosage proportion of the high molecular substance, the electrolyte solvent and the lithium salt is (1-3) g: (10-30) mL: (0.5-2) g.
8. The flexible battery according to claim 8, wherein the polymer substance is selected from one or more of polyethylene oxide, polyvinylidene fluoride, poly (vinylidene fluoride-co-hexafluoropropylene), polyacrylonitrile, and polymethyl methacrylate;
the electrolyte solvent is selected from one or more of ethylene carbonate, propylene carbonate, divinyl carbonate and dimethyl carbonate;
the lithium salt is selected from LiPF6、LiClO4Or LiTFSI.
9. The flexible battery according to claim 8, wherein the polymer substance is poly (vinylidene fluoride-co-hexafluoropropylene);
the electrolyte solution is ethylene carbonate and dimethyl carbonate, and the mass ratio of the ethylene carbonate to the dimethyl carbonate is 3: 7;
the lithium salt is LiTFSI.
10. The flexible battery according to claim 7, wherein the polymer substance, the electrolyte solvent, and the lithium salt are used in a ratio of 2 g: 10mL of: 1g of the total weight of the composition.
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