WO2020080919A1 - Compartiment de batterie secondaire souple et batterie secondaire souple le comprenant - Google Patents

Compartiment de batterie secondaire souple et batterie secondaire souple le comprenant Download PDF

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WO2020080919A1
WO2020080919A1 PCT/KR2019/013847 KR2019013847W WO2020080919A1 WO 2020080919 A1 WO2020080919 A1 WO 2020080919A1 KR 2019013847 W KR2019013847 W KR 2019013847W WO 2020080919 A1 WO2020080919 A1 WO 2020080919A1
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graphene oxide
layer
secondary battery
reduced graphene
flexible secondary
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PCT/KR2019/013847
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English (en)
Korean (ko)
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권요한
임준원
엄인성
이재헌
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주식회사 엘지화학
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Publication of WO2020080919A1 publication Critical patent/WO2020080919A1/fr

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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
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • 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
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • H01M10/04—Construction or manufacture in general
    • 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
    • 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
    • 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
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • 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
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • 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
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • 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
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H01M50/133—Thickness
    • 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
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H01M50/136—Flexibility or foldability
    • 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
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/141—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against humidity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—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
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
    • H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
    • 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

Definitions

  • the present invention relates to a flexible secondary battery packaging and a flexible secondary battery comprising the same.
  • a secondary battery is a device that converts and stores external electrical energy into chemical energy and then generates electricity when needed.
  • the name "rechargeable battery” is also used to mean that it can be charged multiple times.
  • Commonly used secondary batteries include lead-acid batteries, nickel-cadmium batteries (NiCd), nickel-metal hydride batteries (NiMH), lithium-ion batteries (Li-ion), and lithium-ion polymer batteries (Li-ion polymer). Secondary batteries offer both economic and environmental advantages over primary batteries that are used once and discarded.
  • Secondary batteries are currently used where low power is used. For example, there are devices, portable devices, tools, and uninterruptible power supplies to help start the car. Recently, the development of wireless communication technology has led to the popularization of portable devices, and there is also a tendency to wirelessize many types of conventional devices, and the demand for secondary batteries is exploding. In addition, hybrid vehicles and electric vehicles have been put into practical use in terms of prevention of environmental pollution, and these next-generation vehicles employ technology that reduces the value, weight, and extends the life span by using a secondary battery.
  • Cylindrical, prismatic, and pouch-type secondary batteries are known as secondary battery types, and recently, flexible secondary batteries featuring flexibility, including a cable-type secondary battery, which is a battery having a very large ratio to the cross-sectional diameter, are proposed. Became.
  • the flexible secondary battery 50 is provided with a negative electrode 10 wound around a coil and provided in a cylindrical shape, and provided with a negative electrode 10 on one side to surround the other side of the negative electrode 10. It includes a separator 20, an anode 30 provided on the other side of the separator 20, and a packaging 40 provided in a cylindrical shape and provided with an anode 30 on one side. That is, the flexible secondary battery 50 is prepared by sequentially winding the separator 20, the anode 30, and the packaging 40 on the other side of the cathode 10 provided in a coil shape. In this way, the flexible secondary battery 50 is provided in a cable shape so that it can be bent.
  • FIG. 2 is a packaging for a flexible secondary battery including a laminate film and a heat shrink tube, a state before applying heat to the packaging for the flexible secondary battery.
  • a laminate film 50 including a sealant polymer layer 2 on both sides of a predetermined support layer 1 and the support layer 1 surrounds the outer surface of the electrode assembly so that a predetermined portion overlaps.
  • the outer heat shrink tube 60 is present. When heat is applied after this, the heat-shrinkable tube contracts tightly and tightly wraps the laminate film surrounding the electrode assembly and the heat-shrinkable tube.
  • the heat-shrinkable tube is generally made of a polymer material as a main component. Since these polymers are made porous due to their structural characteristics, there is a problem that moisture, air, and the like are easily introduced into the battery. The inflow of moisture into the battery is a major cause of deterioration of the performance of the battery by reaction with moisture in the electrolyte solution using LiPF 6 as a lithium salt.
  • one problem to be solved in the present invention is to improve the moisture barrier properties of the heat-shrinkable tube when the heat-shrinkable tube is included in the flexible secondary battery packaging.
  • Another problem to be solved in the present invention is to improve the moisture barrier properties of the heat-shrinkable tube while ensuring flexibility of the flexible secondary battery.
  • Another problem to be solved in the present invention is to provide a flexible secondary battery with improved moisture barrier properties of the heat shrink tube.
  • the packaging for the flexible secondary battery is in the form of a tube surrounding the outer surface of the electrode assembly, the packaging for the flexible secondary battery, A moisture barrier film comprising a reduced graphene oxide (rGO) layer comprising a plurality of reduced graphene oxide sheets and a sealant layer located on at least one of the one side and the other side of the reduced graphene oxide; And a polymer heat shrink tube surrounding the outermost side of the moisture barrier film, wherein the plurality of reduced graphene oxide sheets in the reduced graphene oxide layer form electrostatic interactions between the reduced graphene oxide sheets adjacent to each other.
  • Packaging for a flexible secondary battery is provided, which is characterized in that.
  • the reduced graphene oxide sheet is provided with a flexible secondary battery packaging, characterized in that it has a layer structure of 1 to 3 reduced graphene oxide particles.
  • the reduced graphene oxide sheet in the first aspect or the second aspect, is provided with a packaging for a flexible secondary battery, characterized in that it has a thickness in the range of 0.1 to 10 ⁇ m.
  • the reduced graphene oxide sheet in any one of the first to third aspects is Li + , K + , Ag + , Mg 2 + , Ca 2 + , Cu 2 + , Pb 2 + , Co 2+ , Al 3 + , Cr 3 + , Fe 3 + or two or more of these are provided for packaging a flexible secondary battery, characterized in that it forms an electrostatic interaction with the adjacent reduced graphene oxide sheet. .
  • the moisture barrier film includes a sealant layer located on one side of the reduced graphene oxide, and the reduced graphene oxide layer Further comprising a mechanical support layer located on the other side of the, both ends are formed in a tubular shape surrounding the outer surface of the electrode assembly in the form of overlapping, the opposite sealant layers of the water barrier film overlapping each other are heat-pressed and sealed Packaging is provided for a flexible secondary battery, characterized in that the sealing portion forms a folded wing portion along the periphery of the moisture barrier film.
  • At least one of the mechanical support layer and the reduced graphene oxide layer, and between the reduced graphene oxide layer and the sealant layer in any one of the first to fifth aspects Packaging for a flexible secondary battery further comprising an adhesive layer is provided.
  • the moisture barrier film includes two sealant layers located on one side and the other side of the reduced graphene oxide layer,
  • the two sealant layers are a first sealant layer located on one side of the reduced graphene oxide layer and a second sealant layer located on the other side of the reduced graphene oxide layer, and a first of one end surface of the moisture barrier film
  • a packaging for a flexible secondary battery is provided in which a sealant layer and a second sealant layer on the other end of the other end overlap and adhere to each other.
  • packaging for a flexible secondary battery is further provided, further comprising a mechanical support layer between the reduced graphene oxide layer and the second sealant layer.
  • the mechanical support layer and the second sealant layer Packaging for a flexible secondary battery further comprising an adhesive layer on at least one of the gaps is provided.
  • the packaging for a flexible secondary battery in which the reduced graphene oxide layer has a thickness in the range of 20 nm to 30 ⁇ m in any one of the first to ninth aspects.
  • a method of manufacturing a packaging for a flexible secondary battery surrounding an outer surface of the flexible secondary battery electrode assembly
  • Graphene oxide Graphene Oxide (GO) coated with a dispersion composition in which particles and metal salts are dispersed and dried on the sealant layer to form a reduced graphene oxide (rGO), the sealant Forming a moisture barrier film having a reduced graphene oxide layer formed on one surface of the layer;
  • a method of manufacturing a packaging for a flexible secondary battery according to the first aspect comprising a.
  • a method for manufacturing a flexible secondary battery packaging method in which the graphene oxide layer is reduced by iodic acid or vitamin C in the twelfth aspect is provided.
  • the moisture barrier film includes two sealant layers located on one side and the other side of the reduced graphene oxide layer, and the two sealant layers are the reduced graphene A first sealant layer located on one side of the pin oxide layer and a second sealant layer located on the other side of the reduced graphene oxide layer, and a first sealant layer on one end of the moisture barrier film and a second sealant on the other end A method of manufacturing a flexible secondary battery packaging in which a sealant layer is adhered to each other by overlapping a predetermined portion is provided.
  • the electrode assembly in the thirteenth aspect of the invention, the electrode assembly; A flexible secondary battery including; packaging for the flexible secondary battery of claim 1 surrounding the outer surface of the electrode assembly is provided.
  • a moisture barrier film is present between the electrode assembly and the heat shrink tube, so that moisture and / or gas flowing into the secondary battery can be prevented.
  • the packaging for a flexible secondary battery of the present invention includes a reduced graphene oxide layer in the moisture barrier film.
  • the reduced graphene oxide layer in contrast to the fact that several water monolayers exist between the graphene oxide interlayers, such that moisture and / or gas molecules cannot be blocked, the reduced graphene oxide layer according to the present invention Silver, an electrostatic interaction is formed between the reduced graphene oxide sheets constituting the reduced graphene oxide layer, thereby effectively blocking a path through which moisture and / or gas can be introduced.
  • the packaging material for the flexible secondary battery itself may have flexibility, and thus stress generated when the flexible secondary battery is bent can be alleviated.
  • FIG. 1 is a view showing the structure of an embodiment of a general flexible secondary battery.
  • FIG. 2 is a cross-sectional view schematically showing an embodiment of a general flexible secondary battery inserted into a heat-shrinkable tube but before being heat-treated.
  • FIG 3 is a cross-sectional view schematically showing a moisture barrier film according to an embodiment of the present invention.
  • FIG. 4 is a cross-sectional view schematically showing a moisture barrier film according to an embodiment of the present invention.
  • FIG. 5 is a cross-sectional view schematically showing a moisture barrier film according to an embodiment of the present invention.
  • FIG. 6 is an internal cross-sectional view schematically showing a reduced graphene oxide layer according to an embodiment of the present invention.
  • FIG. 7 is a cross-sectional view schematically showing an embodiment in which a moisture barrier film and a heat shrinkable tube are applied to an electrode assembly according to an embodiment of the present invention.
  • FIG. 8 is a cross-sectional view schematically showing an embodiment in which a moisture barrier film and a heat shrinkable tube are applied to an electrode assembly according to an embodiment of the present invention.
  • Example 9 is a graph showing the cycle performance of the secondary battery produced in Example 3 and Comparative Example 4.
  • graphene means that a plurality of carbon atoms are covalently linked to each other to form a polycyclic aromatic molecule, wherein the covalently linked carbon atoms form a six-membered ring as a basic repeating unit. It forms, but it is also possible to further include a 5-membered ring and / or a 7-membered ring. Therefore, the sheet formed by the graphene may be seen as a single layer of carbon atoms covalently bonded to each other, but may not be limited thereto.
  • the sheet formed by the graphene may have various structures, and such a structure may vary depending on the content of the 5-membered ring and / or 7-membered ring that may be included in the graphene.
  • a structure may vary depending on the content of the 5-membered ring and / or 7-membered ring that may be included in the graphene.
  • the sheet formed by the graphene when they is composed of a single layer, they may be stacked with each other to form a plurality of layers, and the side ends of the graphene sheet may be saturated with hydrogen atoms, but may not be limited thereto.
  • graphene oxide is also called graphene oxide and may be abbreviated as "GO”.
  • the monolayer graphene may include a structure in which a functional group containing oxygen, such as a carboxyl group, a hydroxy group, or an epoxy group, is combined, but may not be limited thereto.
  • reduced graphene oxide refers to graphene oxide having a reduced oxygen ratio through a reduction process, and may be abbreviated as “rGO”, but may not be limited thereto.
  • oxygen content included in the reduced graphene oxide may include 0.01 to 30 atomic% (at.%) Of oxygen relative to 100% of carbon atoms, but is not limited thereto.
  • the interlayer spacing of the reduced graphene oxide sheet may be measured using an XRD device and calculated by calculating the Brag equation, and the XRD device may use Bruker's D4 Endeavor.
  • the thickness of the reduced graphene oxide layer may be determined by observing the cross section of the synthesized reduced graphene oxide layer using an SEM device, and Hitachi 4800 may be used as the SEM device.
  • the thickness of the reduced graphene oxide sheet may be measured using an atomic force microscope (AFM) device after spin-casting the reduced graphene oxide sheet on an SiO 2 substrate, and the Park Systems' NX10 can be used as the AFM device.
  • AFM atomic force microscope
  • the packaging for the flexible secondary battery is in the form of a tube surrounding the outer surface of the electrode assembly, and the packaging for the flexible secondary battery is a plurality of reduction A moisture barrier film comprising a reduced graphene oxide (rGO) layer comprising a graphene oxide sheet and a sealant layer located on at least one of the one side and the other side of the reduced graphene oxide; And a polymer heat shrink tube surrounding the outermost side of the moisture barrier film, wherein the plurality of reduced graphene oxide sheets in the reduced graphene oxide layer form electrostatic interactions between the reduced graphene oxide sheets adjacent to each other.
  • Packaging for a flexible secondary battery is provided, which is characterized in that.
  • the packaging for the flexible secondary battery is in the form of a tube surrounding the outer surface of the electrode assembly, and packaging for the flexible secondary battery
  • a moisture barrier film comprising a reduced graphene oxide (rGO) layer comprising a plurality of reduced graphene oxide sheets and a sealant layer located on one side of the reduced graphene oxide layer
  • a mechanical support layer located on the other side of the moisture barrier film
  • a polymer heat-shrinkable tube surrounding the outermost side of the moisture barrier film, wherein opposing sealant layers at both ends of the moisture barrier film are thermocompressed to form a sealing portion, and the sealing portion is around the moisture barrier film.
  • the packaging for the flexible secondary battery comprising a plurality of reducing graphene oxide sheets (reduced A moisture barrier film comprising a graphene oxide (rGO) layer and two sealant layers located on one side and the other side of the reduced graphene oxide layer; And a polymer heat shrink tube surrounding the outermost side of the moisture barrier film, wherein the two sealant layers are located on one side of the reduced graphene oxide layer and on the other side of the reduced graphene oxide layer.
  • the first sealant layer on one end of the moisture barrier film and the second sealant layer on the other end of the other end are adhered to each other by overlapping each other, and in the reduced graphene oxide layer, the plurality of The reduced graphene oxide sheet is provided with a packaging for a flexible secondary battery, characterized in that it forms an electrostatic interaction between the reducing graphene oxide sheet adjacent to each other.
  • electrostatic interaction is understood to include ionic bonding.
  • the packaging for the flexible secondary battery of the present invention comprises i) a moisture barrier film and ii) a heat shrink tube.
  • the mechanical support layer 110 An adhesive layer 120a located on the other side of the mechanical support layer 110; A reduced graphene oxide layer 130 located on the other side of the adhesive layer 120a; And an adhesive layer 120b located on the other side of the reduced graphene oxide layer 130. And a sealant layer 150 positioned on the other side of the adhesive layer 120a sequentially positioned in the thickness direction. At least one layer of the adhesive layers 120a and 120b may be omitted. For example, when the affinity between the mechanical support layer 110 and the reduced graphene oxide layer 130 is good or excellent, the adhesive layer 120a between the mechanical support layer 110 and the reduced graphene oxide layer 130 may be omitted. .
  • the moisture barrier film F of FIG. 4 includes a first sealant layer 240a, a first adhesive layer 220a, a mechanical support layer 210, a second adhesive layer 220b, a reduced graphene oxide layer 230, and 3 may have a structure in which the adhesive layer 220c and the second sealant layer 240b are sequentially positioned in the thickness direction.
  • At least one layer of the adhesive layers 220a, 220b, and 220c may be omitted.
  • the adhesive layer 220b between the mechanical support layer 210 and the reduced graphene oxide layer 230 may be omitted.
  • the moisture barrier film (F) of the present invention may not include a mechanical support layer. That is, as shown in Figure 5, another embodiment of the moisture barrier film (F) of the present invention is a first sealant layer (340a), the first adhesive layer located on the other side of the first sealant layer (340a) ( 320a), a reduced graphene oxide layer 330 located on the other side of the first adhesive layer 320a, a second adhesive layer 320b located on the other side of the reduced graphene oxide layer 330, and the second adhesive layer
  • the second sealant layer 340b positioned on the other side of the 320b may have a structure sequentially positioned in the thickness direction.
  • the mechanical support layer serves to prevent the moisture barrier film from being torn or damaged against external stress or impact, and can be used without limitation as long as it is a material having such a mechanical property.
  • Non-limiting examples of materials constituting the mechanical support layer high density polyethylene, low density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, polyolefins such as polypropylene; Polyesters such as polyethylene terephthalate and polybutylene terephthalate; Polyacetal; Polyamide; Polycarbonate; Polyimide; Polyetheretherketone; Polyethersulfone; Polyphenylene oxide; Polyphenylenesulfide; And polyethylene naphthalate (polyethylenenaphthalate); may be mentioned one or a mixture of two or more selected from the group consisting of, but is not limited thereto.
  • the mechanical support layer can optionally be modified to a hydrophilic surface by oxygen or nitrogen plasma treatment.
  • a hydrophilic surface by oxygen or nitrogen plasma treatment.
  • surface energy is generated due to a difference between the hydrophobicity of the surface of the mechanical support layer and the hydrophilicity of graphene oxide, and as a result, graphene oxide is formed on one surface of the mechanical support layer. It may be difficult to ensure a uniform coating of the layer.
  • the surface of a mechanical support layer having a hydrophobic surface can be surface modified with hydrophilicity.
  • the surface modification may be performed by UV-ozone treatment, plasma surface treatment using oxygen or nitrogen, chemical treatment using a silane coupling agent such as amino silane, or surface coating using a polymer or organic compound, but is not limited thereto. .
  • the reduced graphene oxide layer may be formed directly on one surface of the mechanical support layer or with an adhesive layer therebetween.
  • the reduced graphene oxide layer is a component that enables the packaging for a flexible secondary battery according to the present invention to block the inflow of moisture and / or gas.
  • the blocking effect may be influenced by factors such as the thickness of the graphene oxide layer and the degree of graphene oxide alignment, and these may be determined according to process conditions for producing reduced graphene oxide.
  • the process conditions include, but are not limited to, the purity of the graphene oxide, the concentration of the graphene oxide dispersion composition, the coating time and the number of coatings, the evaporation rate of the solvent after coating, the presence or absence of shear force, and the like.
  • the reduced graphene oxide layer may directly or directly disperse a dispersion composition in which graphene oxide (GO) particles and metal salts are dispersed on one surface of a mechanical support layer. It can be obtained by coating and drying the adhesive layer therebetween to form a graphene oxide layer, and reducing the formed graphene oxide layer.
  • the mechanical barrier is not included in the moisture barrier film
  • the graphene oxide particles and the metal salt are dispersed to coat and dry the graphene oxide dispersion composition directly on one surface of the sealant layer or with an adhesive layer therebetween and reduce it. Can be obtained.
  • a plurality of reduced graphene oxide particles 2310 for example, reduced graphene oxide flat particles are stacked to reduce graphene oxide
  • a sheet 2320 is formed, and a plurality of reduced graphene oxide sheets 2320 formed as described above form a reduced graphene oxide layer.
  • the reduced graphene oxide sheet 2320 is adjacent to a metal cation. It forms an electrostatic interaction 2320 with the reduced graphene oxide sheet.
  • the metal cation interacts electrostatically with oxygen functional groups present at the edge portion of the reduced graphene oxide particles. Since the oxygen functional group has a (-) charge and a metal cation has a (+) charge, a cation having an oxidation number of 2+ or more to have sufficient attraction due to electrostatic interaction between two or more reduced graphene oxide particles This is preferred. In addition, since the attraction force between the metal cation and the reduced graphene oxide particles is an interaction occurring at the edge of the reduced graphene oxide particles, the spacing between the reduced graphene oxide sheets in the basal plane portion is maintained.
  • the reduced graphene oxide sheet may be in the form of a layer structure of 1 to 3 reduced graphene oxide particles, for example, reduced graphene oxide platelet particles.
  • the layer structure of the reduced graphene oxide should be made before the reduction reaction of the graphene oxide.
  • graphene oxide is synthesized after oxidizing graphite through an ultrasonic dispersion process. By controlling the degree of oxidation of graphite in the step of oxidizing graphite, it is possible to control the number of stacked graphene oxide particles.
  • the layer structure of the reduced graphene oxide particles is as described above, the probability of occurrence of defects when coating the reduced graphene oxide is significantly reduced, and an effect of improving the mechanical properties of the prepared reduced graphene oxide layer occurs. .
  • the reduced graphene oxide sheet may have a thickness in the range of 0.002 to 10 ⁇ m, or 0.005 to 1 ⁇ m, or 0.01 to 0.1 ⁇ m.
  • the reduced graphene oxide sheet may have flexible mechanical properties and effective moisture blocking effect.
  • graphene oxide having a certain level of purity or more it is preferable to use graphene oxide having a certain level of purity or more to obtain a dense interlayer spacing.
  • graphene oxide having a purity of 93% or higher, or a purity of 97.5% or higher, or 99.5% or higher may be used.
  • the term “purity” in the present specification means a weight ratio of graphene oxide to weight combined with graphene oxide and metal residue.
  • the graphene oxide is dispersed in a dispersion medium such as water to obtain a dispersion composition.
  • a metal salt and graphene oxide are dispersed in a dispersion medium such as water or deionized water to obtain a dispersion composition.
  • the metal cation constituting the metal salt is Li + , K + , Ag + , Mg 2 + , Ca 2 + , Cu 2 + , Pb 2 + , Co 2 + , Al 3 + , Cr 3 + , Fe 3 + or two or more of them.
  • the metal cation Al 3 + , Cr 3 + , or Fe 3 + is particularly preferable because it has a high oxidation number and can effectively exhibit electrostatic attraction.
  • Anion constituting the metal salt with said metal cation is not particularly limited as to meet the object of the present invention, non-limiting examples of Cl - may be, or SO 4 2- -, NO 3.
  • the metal salt may be added to the dispersion medium in an amount ranging from 0.01 to 10% by weight or 0.01 to 1% by weight based on the weight of the graphene oxide particles.
  • the metal salt is used in an amount in the above-described range, when an excessive amount of metal cations is introduced, a nanometer-level gap between reducing graphene sheets is prevented due to formation of metal particles, and at the same time, proper electrostatic interaction is obtained. You can.
  • the dispersion composition may include graphene oxide in an amount of about 0.0001 parts by weight to about 0.01 parts by weight based on 100 parts by weight of the dispersion medium.
  • the amount of graphene oxide is included in an amount in the above numerical range, it is contained more than 0.0001 parts by weight to induce the alignment of graphene oxide when the graphene oxide layer is formed, and is used in an amount of 0.01 parts by weight or less to disperse It can obtain the effect of securing.
  • the graphene oxide dispersion composition is about 0.0001 parts by weight to about 0.01 parts by weight, about 0.0004 parts by weight to about 0.01 parts by weight, about 0.0004 parts by weight to about 0.008 parts by weight, based on 100 parts by weight of the dispersion medium, Or it may be prepared to include from about 0.0004 parts by weight to about 0.006 parts by weight, but may not be limited thereto.
  • the dispersion may be an ultrasonic generator such as an ultrasonic disperser, but may not be limited thereto.
  • the graphene oxide dispersion composition may further include an organic solvent capable of graphene oxide dispersion.
  • organic solvent include alcohol, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), N-methyl pyrrolidone (N-methyl pyrrolidone), methyl phenol (methyl phenol, It may be a cresol (cresol) or a mixture of two or more of them, but may not be limited to this.
  • the graphene oxide dispersion composition is less than about 100% by volume of the graphene oxide dispersion with respect to 100% by volume of the dispersion medium It may be to further include this possible organic solvent, for example, the graphene oxide dispersion composition is about 1% by volume to about 100% by volume, about 20% by volume to about 100% by volume relative to 100% by volume of the dispersion medium, 20% by volume to about 60% by volume, or about 40% by volume to about 60% by volume, may be to further include an organic solvent capable of dispersing the graphene oxide, but
  • the graphene oxide dispersion composition is coated on a mechanical support layer or a sealant layer.
  • Non-limiting examples of the coating method bar coating (rod coating), spin casting (spin-casting), drop-casting (drop-casting), vacuum filtering (vacuum filtering), deep coating (dip-coating) or electrophoretic coating (electrophoretic coating) may be used.
  • the coating induces alignment of graphene oxide by securing a coating time of 1 second or longer to obtain a dense film, and 1 second to 30 minutes, or 3 seconds in order to expect an effect to obtain a uniform film with a coating time within 30 minutes. To 10 minutes, or 5 seconds to 5 minutes.
  • the coating can securely form a sufficient graphene oxide layer by securing the number of coatings one or more times, and in order to expect an effect for suppressing the formation of a thick layer unnecessarily with the number of coatings within 30 times, 1 to It may be coated over 30 times, or 1 to 10 times, or 1 to 5 times.
  • the amount of graphene oxide dispersion composition 1 mL to 1000 mL, or 3 mL to 200 mL, or 10 mL to 100 mL may be used in one coating.
  • the dried graphene oxide layer has an effect of securing moisture barrier properties by having a thickness of 20 nm or more, and securing mechanical properties by having a thickness of 30 ⁇ m or less, and this effect
  • the dried graphene oxide layer may have a thickness in the range of 20 nm to 30 ⁇ m, or 100 nm to 10 ⁇ m, or 500 nm to 5 ⁇ m.
  • the obtained graphene oxide layer is reduced to maximize the moisture barrier properties of the moisture barrier film, thereby forming a reduced graphene oxide layer.
  • a reduction method using iodic acid (HI) or a reduction method using vitamin C may be performed.
  • the container containing the iodic acid solution and the prepared graphene oxide layer are put together in a closed space, such as a glass petri dish, for 1 minute to 1 hour at a temperature in the range of 10 ° C to 100 ° C
  • the graphene oxide is converted into reduced graphene oxide by the step of vaporizing iodic acid, and maintaining the graphene oxide layer together with the vaporized iodic acid for 2 minutes to 3 hours, thereby reducing the graphene oxide layer.
  • a closed space such as a glass petri dish
  • the graphene oxide layer is impregnated with a solution of iodic acid at 10 to 100 ° C, such as 90 ° C, so that the graphene oxide layer is converted into a reduced graphene oxide layer, and washing the reduced graphene oxide layer with distilled water.
  • a reduced graphene oxide layer can be obtained.
  • the reduced graphene oxide layer obtained can be washed with ethanol.
  • the reduced graphene oxide layer obtained from the above has a structure capable of blocking the inflow of moisture and / or gas, for example, a reduced graphene oxide sheet interlayer spacing in the range of 0.3 nm to 5.0 nm, or 0.3 nm to 0.7 nm.
  • a reduced graphene oxide sheet interlayer spacing in the range of 0.3 nm to 5.0 nm, or 0.3 nm to 0.7 nm.
  • interlayer spacing refers to the spacing between sheets of reduced graphene oxide, that is, the spacing between sheets of reduced graphene oxide.
  • the electrode assembly may be blocked from the outside after surrounding the outer surface of the electrode assembly.
  • the sealant layer has a heat-adhesive or heat-sealable adhesive adhered by heat, and each independently polypropylene-acrylic acid copolymer, polyethylene-acrylic acid copolymer, polypropylene chloride, polypropylene-butylene-ethylene terpolymer, poly It may include at least one or more selected from the group consisting of propylene, polyethylene and ethylene propylene copolymer, but is not limited thereto.
  • the mechanical support layer, the reduced graphene oxide A layer may further include an adhesive layer between the sealant layers facing each other.
  • the material of the adhesive layer includes, for example, a composition containing a urethane-based material, an acrylic material, and a thermoplastic elastomer, but is not limited thereto.
  • the moisture barrier film having the above-described structure may have a thickness in the range of 1 ⁇ m to 1000 ⁇ m, or 10 ⁇ m to 500 ⁇ m, or 20 ⁇ m to 200 ⁇ m.
  • 10 -6 g / m 2 / day to 10 -3 g / m 2 / day, or 10 -6 g / m 2 / day to 10 -4 g / m 2 / day, or 10 -6 g / It may have a water vapor transmission rate (WVTR) in the range of m 2 / day to 10 -5 g / m 2 / day. Therefore, it is possible to meet the moisture barrier properties required in secondary battery packaging.
  • WVTR water vapor transmission rate
  • WVTR water vapor permeation rate
  • the packaging for the flexible secondary battery further includes a heat shrink tube in addition to the moisture barrier film, and non-limiting embodiments thereof are illustrated in FIGS. 8 and 9.
  • the outer surface of the electrode assembly (C) is surrounded by a moisture barrier film (F), the sealant layer 400 is disposed to face the electrode assembly.
  • the moisture barrier film forms a tube that surrounds the outer surface of the electrode assembly in a form in which predetermined portions of both ends overlap, and opposing sealant layers of both ends overlapping each other of the moisture barrier film are thermally compressed to form a sealing portion.
  • the sealing portion forms a folded wing portion along the periphery of the moisture barrier film. Then, a heat shrink tube (T) is applied.
  • the outer surface of the electrode assembly (C) is surrounded by a moisture barrier film (F), the first sealant layer (not shown) and the second sealant layer (not shown) on each side of the other side of the moisture barrier film It is equipped.
  • the moisture barrier film is in the form of a tube surrounding the outer surface of the electrode assembly, and the first sealant layer on one end of the moisture barrier film and the second sealant layer on the other end of the other end portion are adhered to each other by overlapping each other. Then, a heat shrink tube (T) is applied.
  • the term 'predetermined portion' means that when the moisture barrier film surrounds the outer surface of the electrode assembly, the length of the moisture barrier film is longer than the circumference of the electrode assembly, so that the sealant layer of the moisture barrier film overlaps. It means to exist.
  • the predetermined portion may be 1 to 99%, or 1 to 70%, or 3 to 50%, or 5 to 30% around the outer surface of the electrode assembly.
  • the heat-shrinkable tube is a tube that contracts when heated, and means a material that tightly wraps a terminal or a material having a different shape or size.
  • the moisture barrier film is partially wrapped on the outer surface of the electrode assembly, and when heat is applied after being inserted into the heat shrink tube, the sealing polymer of the moisture barrier film is melted by heat transmitted through the heat shrink tube and the moisture barrier film melts. The sealing proceeds, and at the same time, the heat-shrinkable tube is shrunk while being heated, thereby providing tight packaging tightly between the heat-shrinkable tube and the moisture barrier film surrounding the outer surface of the electrode assembly.
  • the moisture barrier performance of the packaging is further improved, and the effect of insulation can be obtained simultaneously through the heat shrink tube.
  • the heat-shrinkable tube is a commercialized heat-shrinkable tube having various materials and shapes, it can be easily obtained and used for the purpose of the present invention.
  • the temperature of the shrinking process To avoid thermal damage to the secondary battery, it is necessary to reduce the temperature of the shrinking process to a low temperature, and generally shrink to a temperature of 70 to 200 ° C, or 70 to 150 ° C, or 100 to 150 ° C, or 70 to 120 ° C It is required to be completed.
  • the heat shrink layer is selected from the group consisting of polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, fluororesins such as polyvinylidene fluoride and polytetrafluoroethylene, and polyvinyl chloride. It can be formed from any one, or a polymer modified two or more of them.
  • a flexible secondary battery including the packaging for the flexible secondary battery is provided.
  • the flexible secondary battery according to the present invention has a horizontal cross section of a predetermined shape including an internal electrode, a separation layer to prevent shorting of an electrode formed surrounding the internal electrode, and an external electrode formed around an outer surface of the separation layer. Electrode assembly extended to; And packaging for a flexible type flexible secondary battery according to the present invention, which is in close contact with the entire outer surface of the electrode assembly.
  • the term 'predetermined shape' means that the shape is not particularly limited, and that any shape that does not impair the essence of the present invention is possible.
  • the horizontal cross-section of the predetermined shape may be circular or polygonal, and the circular structure is a geometrically complete symmetrical circular shape and an asymmetrical oval shape.
  • the polygonal structure is not particularly limited, and non-limiting examples of the polygonal structure may be triangular, square, pentagonal or hexagonal.
  • the flexible secondary battery of the present invention has a horizontal cross-section of a predetermined shape, has a linear structure elongated in the longitudinal direction of the horizontal cross-section, has flexibility and is free from deformation.
  • the internal electrode of the electrode assembly is a lithium ion supply core portion including an electrolyte, an internal current collector having an open structure formed surrounding an outer surface of the lithium ion supply core portion, and an internal electrode formed on the surface of the internal current collector.
  • An active material layer may be provided.
  • the open structure refers to a structure in which the open structure is used as a boundary surface, and the material can be freely moved from inside to outside through the boundary surface.
  • the lithium ion supply core portion may include an electrolyte, and the type of the electrolyte is not particularly limited, but ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC) are not limited.
  • EC ethylene carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • VC vinylene carbonate
  • DEC Diethyl carbonate
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • MF gamma-butyrolactone
  • ⁇ -BL gamma-butyrolactone
  • MP methyl propionate
  • PEO Polypropylene oxide
  • PI polyethylene imine
  • PES polyethylene sulphide
  • PVAc polyvinyl acetate
  • the electrolyte may further include a lithium salt, such as LiCl, LiBr, LiI, LiClO4, LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, chloroboranlithium, lower aliphatic lithium carboxylate, lithium tetraphenylborate, and the like are preferably used.
  • the lithium ion supply core portion may be composed of only an electrolyte, and in the case of a liquid electrolyte, it may also be configured using a porous carrier.
  • the internal current collector of the present invention has an open structure to facilitate the penetration of the electrolyte in the lithium ion supply core, and such an open structure can be adopted as long as the structure has an easy penetration of the electrolyte.
  • the internal current collector is a surface treated with carbon, nickel, titanium, or silver on the surface of stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel, and a vision treated with aluminum-cadmium alloy and a conductive material. It is preferable to use a conductive polymer or a conductive polymer.
  • the current collector serves to collect electrons generated by the electrochemical reaction of the active material or to supply electrons necessary for the electrochemical reaction, and generally metals such as copper or aluminum are used.
  • metals such as copper or aluminum are used.
  • a non-conductive polymer surface-treated with a conductive material or a polymer conductor made of a conductive polymer it is relatively more flexible than a metal such as copper or aluminum.
  • the conductive material examples include polyacetylene, polyaniline, polypyrrole, polythiophene and polysulfurnitride, ITO (Indum Thin Oxide), silver, palladium, and nickel, and conductive polymers include polyacetylene, polyaniline, polypyrrole, and polyt Offen and polysulfuride can be used.
  • the non-conductive polymer used in the current collector is not particularly limited.
  • the inner electrode active material layer of the present invention is formed on the surface of the inner current collector. At this time, it is formed around the outer surface of the inner current collector, as well as when the inner current collector open structure is not exposed to the outer surface of the inner electrode active material layer, the inner electrode active material layer is formed on the surface of the open structure of the inner current collector Also included is the case where the open structure of the inner current collector is exposed to the outer surface of the inner electrode active material layer. For example, a case where an active material layer is formed on the surface of a wound wire-type current collector and a case where a wire-type current collector having an electrode active material layer is formed by winding are used.
  • the external current collector of the present invention is not particularly limited in form, but a pipe-type current collector, a wound wire-type current collector, or a mesh-type current collector can be used.
  • the external current collector may include stainless steel, aluminum, nickel, titanium, calcined carbon, and copper; Stainless steel surface-treated with carbon, nickel, titanium or silver; Aluminum-cadmium alloy; A non-conductive polymer surface-treated with a conductive material; Conductive polymers; A metal paste containing a metal powder that is Ni, Al, Au, Ag, Al, Pd / Ag, Cr, Ta, Cu, Ba or ITO; Alternatively, a carbon paste containing carbon powder that is graphite, carbon black, or carbon nanotubes may be used.
  • the internal electrode may be a cathode or an anode
  • the external electrode may be an anode or a cathode corresponding to the external electrode
  • the electrode active material layer of the present invention functions to move ions through a current collector, and the movement of these ions is caused by interaction through absorption of ions from the electrolyte layer and release of ions to the electrolyte layer.
  • the electrode active material layer is natural graphite, artificial graphite, carbonaceous material; Lithium-containing titanium composite oxides (LTO), metals (Me) which are Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; Alloys composed of the metals (Me); Oxides (MeO x ) of the metals (Me); And may include a complex of the metal (Me) and carbon, as a positive electrode active material layer LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiCoPO 4 , LiFePO 4 , LiNiMnCoO 2 And LiNi 1 -xyz Co x M1 y M2 z O 2 (M1 and M2 are each independently selected
  • the separation layer of the present invention may use an electrolyte layer or a separator.
  • the electrolyte layer used as a passage for these ions is a gel polymer electrolyte or PEO, polypropylene oxide (PPO), polyethylene imine (PEI), polyethylene sulphide (PES), or polyvinyl acetate (PVAc) using PEO, PVdF, PMMA, PAN or PVAC
  • PEO polypropylene oxide
  • PEI polyethylene imine
  • PES polyethylene sulphide
  • PVAc polyvinyl acetate
  • the matrix of the solid electrolyte is preferably a polymer or ceramic glass as a basic skeleton. In the case of a general polymer electrolyte, even if the ionic conductivity is satisfied, the ions can move very slowly in terms of reaction rate.
  • an electrolyte of a gel polymer that facilitates ionic movement than a solid. Since the gel polymer electrolyte is not excellent in mechanical properties, a pore structure support or a crosslinked polymer may be included to compensate for this. Since the electrolyte layer of the present invention can function as a separator, a separate separator may not be used.
  • the electrolyte layer of the present invention may further include a lithium salt.
  • Lithium salt may improve the ionic conductivity and reaction rate, and non-limiting examples of these include LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloro may borane lithium, lower aliphatic carboxylic acid lithium, and tetraphenyl lithium borate available .
  • the separator is not limited to the type, but is made of a polyolefin-based polymer selected from the group consisting of ethylene homopolymer, propylene homopolymer, ethylene-butene copolymer, ethylene-hexene copolymer and ethylene-methacrylate copolymer. materials;
  • a porous substrate made of a polymer selected from the group consisting of polyester, polyacetal, polyamide, polycarbonate, polyimide, polyether ether ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfite and polyethylene naphthalene;
  • a porous substrate formed of a mixture of inorganic particles and a binder polymer may be used.
  • a porous coating layer including a mixture of inorganic particles and a binder polymer may be further provided on at least one surface of the porous substrate made of the above-described polymer.
  • the polyester, polyacetal, polyamide, polycarbonate, polyimide, polyether ether ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide It is preferable to use a separator made of a non-woven material corresponding to a porous substrate made of a polymer selected from the group consisting of pits and polyethylene naphthalene.
  • the method of manufacturing a flexible secondary battery according to an aspect of the present invention includes: (S1) an internal electrode, a separation layer preventing a short circuit of the electrode formed surrounding the internal electrode, and an external electrode formed surrounding the outer surface of the separation layer. Preparing an electrode assembly having a horizontal cross-section having a predetermined shape and extending in a longitudinal direction;
  • the flexible secondary battery according to an embodiment of the present invention has no wrinkle due to skin-tight packaging of the electrode assembly, thereby improving the flexibility of the battery.
  • a heat-shrinkable tube in the packaging can exhibit better battery flexibility.
  • a polypropylene film (Yulchon Chemical) was prepared as a sealant layer.
  • graphene oxide particles graphene oxide powder, Standard Graphen Co.
  • energy was added with an ultrasonic disperser to prepare a graphene oxide dispersion composition having a concentration of 1 mg / mL.
  • metal salt CuCl 2 Sigma Aldrich, CuCl 2
  • a coating was performed with a bar coating, followed by drying to prepare a graphene oxide layer.
  • the prepared graphene oxide layer was immersed in a solution of iodic acid at 90 ° C (TCI, 57% Hydriodic acid) and maintained for at least 12 hours.
  • the formed reduced graphene oxide layer was washed with distilled water and dried at room temperature.
  • the reduced graphene oxide sheet of the reduced graphene oxide layer included in the reduced graphene oxide layer had an interulator spacing of about 0.3 to 0.4 nm, and the reduced graphene oxide layer had a thickness of about 100 nm, and
  • the graphene oxide sheet constituting the layer was found to have a thickness of 1 to 4 nm.
  • the interlayer spacing of the reduced graphene oxide sheet was measured using an XRD device and calculated using the Brag equation.
  • XRD device D4 Endeavor from Bruker was used.
  • the thickness of the reduced graphene oxide layer was determined by observing the cross section of the synthesized reduced graphene oxide layer with an SEM device, and Hitachi 4800 was used as the SEM device.
  • the thickness of the reduced graphene oxide sheet was measured using an atomic force microscope (AFM) device after spin-casting the reduced graphene oxide sheet onto an SiO 2 substrate.
  • AFM atomic force microscope
  • the negative electrode slurry was coated and dried on a wire-shaped copper current collector having a diameter of 250 ⁇ m with a loading of 3.8 mAh / cm 2 to prepare a wire-type negative electrode having a negative electrode active material layer.
  • the four prepared wire-type negative electrodes were wound to produce a spring, thereby forming an internal negative electrode part of an open structure with an empty interior and a lithium ion supply core.
  • a separation layer was formed by winding a polyolefin film separator on the other side of the internal cathode.
  • LiCoO 2 as a positive electrode active material, Denka Black as a conductive material, and polyvinylidene fluoride (PVdF) as a binder were added to N-methylpyrrolidone (NMP) as a solvent at a weight ratio of 85: 5: 15 to prepare a positive electrode active material slurry.
  • NMP N-methylpyrrolidone
  • the positive electrode active material slurry was coated on a sheet-shaped aluminum current collector and dried to form a positive electrode active material layer.
  • Conductive layer slurry was prepared by dispersing carbon black, which is a conductive material, and PVdF binder in a NMP solvent in a 1: 1 weight ratio.
  • a conductive layer slurry was applied on the positive electrode active material layer, and after placing the porous polymer nonwoven fabric substrate on the conductive layer slurry, the conductive layer slurry was dried to prepare a sheet-like external positive electrode.
  • the prepared positive electrode was prepared by designing the N / P ratio to 108% compared to the negative electrode discharge capacity (final positive electrode loading amount: 3.3 mAh / cm 2 ). After cutting the sheet-like outer anode to have a width of 2 mm, an electrode assembly was manufactured by winding around the inner cathode and the separation layer.
  • the moisture barrier film produced above encloses the outer surface of the electrode assembly manufactured as described above so that a predetermined portion overlaps, and at this time, the outer surface of the electrode assembly is in contact with the sealant layer.
  • heat shrink tube Yulchon Chemical, a modified polyvinylidene fluoride tube
  • a non-aqueous electrolyte solution (1M LiPF 6 , ethylene carbonate (EC) / propylene carbonate (PC) / diethyl carbonate (DEC)
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • a water barrier film was obtained in the same manner as in Example 1, except that CuCl 2 was not added to the dispersion composition.
  • the reduced graphene oxide sheet of the reduced graphene oxide layer in the prepared moisture barrier film had an interlayer spacing of about 0.3 to 0.4 nm, and the reduced graphene oxide layer had a thickness of about 100 nm, and the graphene The oxide sheet was found to have a thickness of 1 to 4 nm.
  • PET polyethylene terephthalate
  • the packaging for the flexible secondary battery made of the polyethylene terephthalate (PET) film and the heat-shrinkable tube in the same manner as in Example 1, and the packaging for the flexible secondary battery forming a tube that surrounds the outer surface of the flexible secondary battery electrode assembly All secondary batteries were obtained.
  • PET polyethylene terephthalate
  • a moisture barrier film was prepared by applying a polypropylene film, a sealant layer, by a bar coating method to both sides of a polyethylene terephthalate (PET) film (Ramiace Co., Ltd., a laminating film).
  • PET polyethylene terephthalate
  • each of the moisture barrier films prepared in Example 1 and Comparative Examples 1 and 2 were prepared in a size of 10 x 10 cm, and after being cut, a moisture permeability tester (manufacturer: Sejin Test Technology Co., Ltd.) , Model name: SJTM-014), respectively. Then, dry nitrogen gas containing no water vapor was introduced into one side of the packaging for the flexible secondary battery, and water vapor was introduced into the other side. At this time, the two spaces into which the respective gases were introduced were separated from each other so that the gases flowing into both sides of the packaging for the flexible secondary battery did not mix. On the other hand, during the experiment, the temperature was set at 38 ° C. and the humidity was maintained at 100% RH.
  • Example 1 As a result, as shown in Table 1 below, it was confirmed that the water vapor transmission rate of the moisture barrier film of Example 1 was significantly improved compared to the packaging film for secondary batteries of Comparative Examples 1 and 2, respectively.
  • the packaging film for secondary batteries in which the reduced graphene oxide sheet constituting the reducing graphene oxide layer forms an electrostatic interaction can effectively block moisture compared to the packaging film for secondary batteries without the electrostatic interaction. I could confirm.

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Abstract

L'objectif de la présente invention est d'améliorer les propriétés de barrière à l'humidité et la flexibilité d'une batterie secondaire souple, et concerne un compartiment de batterie secondaire souple pour englober la surface extérieure d'un ensemble d'électrodes pour la batterie secondaire souple, et une batterie secondaire souple le comprenant, le compartiment de batterie secondaire souple ayant une forme de tuyau pour entourer la surface extérieure d'un ensemble d'électrodes, et comprenant : un film de barrière contre l'humidité comprenant une couche d'oxyde de graphène réduit (rGO), qui comprend une pluralité de feuilles de rGO, et une couche d'agent d'étanchéité située sur un côté et/ou l'autre côté du rGO ; et un tube de rétraction thermique polymère destiné à entourer la partie la plus à l'extérieur du film barrière contre l'humidité, des interactions électrostatiques se produisant entre des feuilles de rGO adjacentes parmi la pluralité de feuilles de rGO de la couche de rGO.
PCT/KR2019/013847 2018-10-19 2019-10-21 Compartiment de batterie secondaire souple et batterie secondaire souple le comprenant WO2020080919A1 (fr)

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KR101190219B1 (ko) * 2011-01-26 2012-10-16 성균관대학교산학협력단 바닥 접촉식 그래핀옥사이드를 이용한 환원그래핀옥사이드 전계효과 트랜지스터 제조방법
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