WO2014058279A1 - Cable-type secondary battery - Google Patents

Abstract

The present invention provides a cable-type secondary battery extending in a lengthwise direction, the secondary battery comprising: a lithium ion supply core unit including an electrolyte; an inner electrode supporter having a hollow structure, formed to wrap around an outer surface of the lithium ion supply core unit; an inner electrode which is formed on a surface of the inner electrode supporter, and which has an inner current collector and an inner electrode active material layer; a separation layer for preventing a short circuit of the electrode which is formed to wrap around an outer surface of the inner electrode; and an outer electrode which is formed to wrap around an outer surface of the separation layer, and which has an outer electrode active material layer and an outer current collector. The lithium ion supply core unit including an electrolyte of the present invention is placed inside the inner electrode supporter, and the inner electrode supporter has a hollow structure. Therefore, the electrolyte of the lithium ion supply core unit can easily permeate through an active material of an electrode, and thus allow facilitation of supply of lithium ion and exchange of lithium ion. When a large hollow fiber having flexibility is applied as the inner electrode supporter, the flexibility of the battery may be further improved.

Description

Cable type secondary battery

The present invention relates to a cable type secondary battery free of deformation, and more particularly, to a cable type secondary battery including an internal electrode support having a hollow structure capable of accommodating a lithium ion supply core part therein.

This application claims priority based on Korean Patent Application No. 10-2012-0113161, filed October 11, 2012, and all the contents disclosed in the specification and drawings of the application are incorporated in this application.

In addition, the present application claims priority based on Korean Patent Application No. 10-2013-0121487 filed on October 11, 2013, all the contents disclosed in the specification and drawings of the application are incorporated in this application.

Recently, a secondary battery is a device that converts external electrical energy into chemical energy and stores it and generates electricity when needed. The term "rechargeable battery" is also used to mean that it can be charged multiple times. Commonly used secondary batteries include lead storage batteries, nickel cadmium batteries (NiCd), nickel hydrogen storage 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. Examples are devices, handhelds, tools, and uninterruptible power supplies that help start up 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 kinds of conventional devices, and the demand for secondary batteries is exploding. In addition, hybrid vehicles and electric vehicles have been put to practical use in terms of prevention of environmental pollution, and these next-generation vehicles employ technologies that use secondary batteries to reduce value, weight, and extend life.

In general, secondary batteries are cylindrical, rectangular or pouch type batteries. This is because the secondary battery is manufactured by mounting an electrode assembly composed of a negative electrode, a positive electrode, and a separator inside a pouch-shaped case of a cylindrical or rectangular metal can or an aluminum laminate sheet, and injecting an electrolyte into the electrode assembly. Therefore, since a certain space for mounting the secondary battery is essentially required, the cylindrical, square or pouch type of the secondary battery has a problem in that it acts as a limitation for the development of various types of portable devices. Accordingly, there is a need for a new type of secondary battery that is easily deformed.

In response to this demand, a linear battery has been proposed, which is a battery having a very large ratio of length to cross-sectional diameter. Korean Patent Laid-Open Publication No. 2005-99903 discloses a variable battery including an internal electrode, an external electrode, and an electrolyte layer interposed between these electrodes, but its flexibility is not good. In addition, since the linear battery uses a polymer electrolyte to form an electrolyte layer, it is difficult to introduce electrolyte into the active material of the electrode, thereby increasing the resistance of the battery, thereby deteriorating capacity characteristics and cycle characteristics.

Accordingly, an object of the present invention is to provide a secondary battery having a novel linear structure, which is easily deformable, maintains stability and excellent performance of the secondary battery, and facilitates the introduction of an electrolyte into the active material of the electrode.

In order to solve the above problems, the present invention is a lithium ion supply core unit comprising an electrolyte; An inner electrode support having a hollow structure formed surrounding the outer surface of the lithium ion supply core; An internal electrode formed on a surface of the internal electrode support and having an internal current collector and an internal electrode active material layer; A separation layer which prevents a short circuit of the electrode formed surrounding the outer surface of the inner electrode; And an external electrode formed surrounding the outer surface of the separation layer, the external electrode including an external electrode active material layer and an external current collector.

The internal electrode support of the hollow structure may be hollow fiber.

The inner electrode support having the hollow structure may have pores on the surface of which the electrolyte may move to the inner electrode active material and the outer electrode active material.

The pores may have a diameter of 10 nm to 100 μm.

The hollow yarn is selected from the group consisting of polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, polyimide, polyethylene terephthalate, polyamide imide, polyesterimide, polyethersulfone, and polysulfone It may be formed of more than one species.

As the internal current collector, a wound wire current collector, a wound sheet current collector, or a metal coating layer may be used.

The inner electrode includes an inner electrode active material layer formed surrounding the outer surface of the inner electrode support and an inner current collector formed surrounding the outer surface of the inner electrode active material layer, or an inner surface formed surrounding the outer surface of the inner electrode support. An internal electrode active material layer formed surrounding a current collector and an outer surface of the internal current collector may be provided.

The external electrode may include an external electrode active material layer formed surrounding the outer surface of the separation layer and an external current collector formed surrounding the outer surface of the external electrode active material layer, or an external current collector formed surrounding the outer surface of the separation layer; An external electrode active material layer formed surrounding the outer surface of the outer current collector, or an outer current collector formed surrounding the outer surface of the separation layer and an outer electrode active material formed to surround the outer surface of the outer current collector and contact the separation layer An external electrode active material layer provided with a layer or surrounding the outer surface of the separation layer, and a wire-type external current collector covered with the outer electrode active material layer and surrounding the outer surface of the separation layer and spaced apart from each other. It can be provided.

 Although the shape of the external current collector is not particularly limited, it is preferable to use a pipe current collector, a wound wire current collector, a wound sheet current collector, or a mesh current collector.

The internal current collector is not particularly limited in kind, but stainless steel, aluminum, nickel, titanium, calcined carbon, copper; Stainless steel surface-treated with carbon, nickel, titanium, or silver; Aluminum-cadmium alloys; Non-conductive polymer surface-treated with a conductive material; Or a conductive polymer may be used.

Examples of the conductive material may include polyacetylene, polyaniline, polypyrrole, polythiophene and polysulfuride, ITO (Indum Thin Oxide), silver, palladium, nickel, and the like, and the conductive polymer may be polyacetylene, polyaniline, polypyrrole, The polymer etc. which are 1 type of compound chosen from polythiophene and polysulfurittride, or a mixture of 2 or more types can be used.

As the external current collector, stainless steel, aluminum, nickel, titanium, calcined carbon, copper; Stainless steel surface-treated with carbon, nickel, titanium, or silver; Aluminum-cadmium alloys; Non-conductive polymer surface-treated with a conductive material; Conductive polymers; A metal paste comprising a metal powder of Ni, Al, Au, Ag, Al, Pd / Ag, Cr, Ta, Cu, Ba, or ITO; Or a carbon paste containing carbon powder which is graphite, carbon black or carbon nanotubes.

The lithium ion supply core portion of the present invention includes an electrolyte, but the electrolyte is not particularly limited in its kind, but ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC). , Diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methyl formate (MF), gamma-butyrolactone (γ-BL; butyrolactone), sulfolane, methyl acetate Non-aqueous electrolyte using (MA; methylacetate) or methylpropionate (MP; methylpropionate); Gel polymer electrolytes using polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polymethylmethacrylate (PMMA), polyacrylonitrile (PAN) or polyvinyl acetate (PVAc); Or a solid electrolyte using PEO, polypropylene oxide (PPO), polyethylene imine (PEI), polyethylene sulphide (PES) or polyvinyl acetate (PVAc); Etc. can be used. In addition, such an electrolyte may further include a lithium salt, which may 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) it is preferred to use ₂ NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, and tetraphenyl lithium borate, etc. .

The inner electrode of the present invention may be a cathode or an anode, and the outer electrode may be an anode or a cathode corresponding to the inner electrode.

And, when the inner electrode of the present invention is a cathode, the outer electrode is a positive electrode, the inner electrode active material layer is natural graphite, artificial graphite, carbonaceous material; Metals (Me) that are lithium-containing titanium composite oxide (LTO), Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; Alloys composed of the metals (Me); Oxides of the metals (Me) (MeOx); And an anode active material layer including any one active material particles selected from the group consisting of metals (Me) and a composite of carbon or a mixture of two or more thereof, and the external electrode active material layer may be LiCoO ₂ , LiNiO ₂ , or the like. 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 independently of each other Al, Ni, Co, Fe, Mn, V, Cr, Ti, Any one selected from the group consisting of W, Ta, Mg, and Mo, and x, y, and z are each independently an atomic fraction of the elements of the oxide composition, 0 ≦ x <0.5, 0 ≦ y <0.5, 0 ≦ z <0.5, x + y + z ≦ 1), and may be a cathode active material layer including any one active material particle selected from the group consisting of two or a mixture of two or more thereof.

And, when the inner electrode is a positive electrode, the outer electrode is a negative electrode, the inner electrode active material layer is 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 from Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo, and x, y and z Is an atomic fraction of oxide composition elements, independently of each other, 0 ≦ x <0.5, 0 ≦ y <0.5, 0 ≦ z <0.5, and x + y + z ≦ 1) It may be a positive electrode active material layer comprising a mixture of two or more of the above, the external electrode active material layer is natural graphite, artificial graphite, carbonaceous material; Metals (Me) that are lithium-containing titanium composite oxide (LTO), Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; Alloys composed of the metals (Me); Oxides of the metals (Me) (MeOx); And it may be a negative electrode active material layer containing any one active material particles or a mixture of two or more thereof selected from the group consisting of a complex of the metals (Me) and carbon, but is not particularly limited thereto.

As the separation layer of the present invention, an electrolyte layer or a separator may be used.

The electrolyte layer is not particularly limited in kind, but may be a gel polymer electrolyte using PEO, PVdF, PMMA, PAN or PVAc; Or a solid electrolyte using PEO, polypropylene oxide (PPO), polyethylene imine (PEI), polyethylene sulphide (PES), or polyvinyl acetate (PVAc). The electrolyte layer may further include a lithium salt, and non-limiting examples of the lithium salt include LiCl, LiBr, LiI, LiClO ₄ , LiBF ₄ , LiB ₁₀ Cl ₁₀ , LiPF ₆ , LiCF ₃ SO ₃ , and LiCF _{3. CO 2, LiAsF 6, LiSbF 6} , LiAlCl 4, CH 3 SO 3 there is _{Li, CF 3 SO 3 Li,} (CF 3 SO 2) 2 NLi, such as chloroborane lithium, lower aliphatic carboxylic acid lithium, and tetraphenyl lithium borate .

In the case of using the separator as the separation layer, the cable-type secondary battery of the present invention requires an electrolyte solution, and the separator is not limited to ethylene homopolymer, propylene homopolymer, ethylene-butene copolymer, and ethylene. A porous substrate made of a polyolefin-based polymer selected from the group consisting of a hexene copolymer and an ethylene-methacrylate copolymer; A porous substrate made of a polymer selected from the group consisting of polyester, polyacetal, polyamide, polycarbonate, polyimide, polyether ether ketone, polyethersulfone, polyphenylene oxide, polyphenylene sulfite and polyethylene naphthalene; Alternatively, a porous substrate formed of a mixture of inorganic particles and a binder polymer may be used.

An electrolyte absorbing layer may be further provided between the internal electrode and the separation layer.

In addition, a first electrolyte absorbing layer may be further provided between the inner electrode and the separating layer, and a second electrolyte absorbing layer may be further provided between the separating layer and the outer electrode.

The wire current collector may have a structure in which two or more wires are spirally twisted with each other.

The cross section of the cable type secondary battery may be circular or polygonal.

The present invention provides a cable type secondary battery having a plurality of internal electrodes, and the present invention also provides a cable type secondary battery having a plurality of internal electrodes having a separation layer formed thereon.

Since the lithium ion supply core part including the electrolyte of the present invention is located inside the internal electrode support and the internal electrode support has a hollow structure, the electrolyte of the lithium ion supply core part easily penetrates into the active material of the electrode, thereby Supply of ions and exchange of lithium ions can be facilitated. Therefore, since the cable type secondary battery of this invention is equipped with the lithium ion supply core part, it is excellent in the capacity characteristic and cycling characteristics of a battery. In addition, since the cable type secondary battery of the present invention has an internal electrode support having a hollow structure, flexibility may be further improved.

The following drawings, which are attached to this specification, illustrate preferred embodiments of the present invention, and together with the contents of the present invention serve to further understand the technical spirit of the present invention, the present invention is limited to the matters described in such drawings. It should not be construed as limited.

1 is a view of a cable-type secondary battery according to an embodiment of the present invention.

2 is a view of a cable-type secondary battery according to an embodiment of the present invention.

3 is a view of a cable-type secondary battery according to an embodiment of the present invention.

4 is a perspective view schematically showing a spiral electrode provided in a cable type secondary battery according to an embodiment of the present invention.

5 is a cross-sectional view of FIG. 4.

6 is a cross-sectional view of a cable type secondary battery having a plurality of internal electrodes according to an embodiment of the present invention.

7 is a cross-sectional view of a cable type secondary battery having a plurality of internal electrodes according to an embodiment of the present invention.

8 is a cross-sectional view of a cable type secondary battery having a plurality of internal electrodes according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to the drawings. The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

1 schematically shows an embodiment of a cable type secondary battery according to the present invention. However, the configuration described in the embodiments and drawings described below are only the most preferred embodiment of the present invention and do not represent all of the technical idea of the present invention, which can be replaced at the time of the present application It should be understood that there may be various equivalents and variations.

Cable type secondary battery 100 of the present invention extending in the longitudinal direction, the lithium ion supply core portion 110 including an electrolyte; An inner electrode support 120 having a hollow structure formed around the outer surface of the lithium ion supply core part 110 and an inner electrode active material layer and an inner current collector formed on a surface of the inner electrode support 120 An electrode 130; Separation layer 140 to prevent the short circuit of the electrode formed surrounding the outer surface of the inner electrode; And an external electrode 150 formed surrounding the outer surface of the separation layer 140 and including an external electrode active material layer and an external current collector.

At this time, the inner electrode support of the hollow structure has a hollow structure that can accommodate the electrolyte of the lithium ion supply core unit 110, the electrolyte is free to move to the internal electrode active material and the external electrode active material to facilitate the wetting (wetting). Any structure having pores on the surface can be adopted.

Examples of the internal electrode support of the hollow structure may be hollow fiber, but are not limited thereto.

The hollow yarn is selected from the group consisting of polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, polyimide, polyethylene terephthalate, polyamide imide, polyesterimide, polyethersulfone, and polysulfone Using more than one polymer, it can be obtained by a conventional hollow fiber forming method.

The internal electrode support may have a diameter of 0.5 to 10 mm, and the internal electrode support may have pores having a diameter of 10 nm to 100 μm on its surface.

In addition, the cross section of the cable type secondary battery according to one embodiment of the present invention is not particularly limited in shape, and may be any shape that does not impair the essence of the present invention. For example, the cross section of the cable type secondary battery may be circular or polygonal, which is a geometrically perfect symmetrical circular and asymmetrical oval structure. The polygon is not particularly limited as long as it is not a two-dimensional sheet-like structure, and a non-limiting example of the polygonal structure may be a triangle, a square, a pentagon, or a hexagon.

The cable-type secondary battery of the present invention has a horizontal cross section of the above-described shape, has a linear structure elongated in the longitudinal direction with respect to the horizontal cross section, and has flexibility so that deformation is free.

The conventional cable type secondary battery has an electrolyte layer between the inner electrode and the outer electrode, and these electrolyte layers must isolate the inner electrode and the outer electrode in order to prevent a short circuit, and thus have a gel polymer electrolyte or a solid polymer having a certain level of mechanical properties. It is necessary to use an electrolyte. However, since the gel polymer electrolyte or the solid polymer electrolyte does not have excellent performance as a lithium ion source, in order to supply lithium ions to the electrode active material layer sufficiently, the thickness of the electrolyte layer must be increased, and the thickness of the electrolyte layer is increased. Due to the gap between the electrodes is widened there is a problem that leads to a decrease in battery performance due to the increase in resistance.

On the other hand, the cable-type secondary battery 100 of the present invention includes a lithium ion supply core unit 110 including an electrolyte, the internal electrode current collector of the present invention has a hollow structure, the internal electrode is also an open structure Since the internal current collector and the internal electrode active material layer having the same are applied, the electrolyte of the lithium ion supply core unit 110 passes through the internal electrode support to reach the internal current collector, the internal electrode active material layer 130 and the external electrode active material layer. can do.

Here, the open structure refers to a structure in which the open structure is used as a boundary surface, and freely moves materials from inside to outside through this boundary surface.

Therefore, it is not necessary to excessively increase the thickness of the electrolyte layer, and rather, only the separator may be selectively used since the electrolyte layer is not an essential component. That is, the cable-type secondary battery according to an embodiment of the present invention includes a lithium ion supply core unit 110 including an electrolyte, so that the electrode easily penetrates into the active material, thereby supplying lithium ions from the electrode and supplying lithium ions. Can easily be replaced, and the battery has excellent capacity characteristics and cycle characteristics.

The lithium ion supply core unit 110 includes an electrolyte, but the electrolyte is not particularly limited in its kind, but ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate ( VC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methyl formate (MF), gamma-butyrolactone (γ-BL; butyrolactone), sulfolane, Non-aqueous electrolytes using methyl acetate (MA; methylacetate) or methylpropionate (MP); Gel polymer electrolytes using PEO, PVdF, PMMA, PAN or PVAc; Or a solid electrolyte using PEO, polypropylene oxide (PPO), polyethylene imine (PEI), polyethylene sulphide (PES) or polyvinyl acetate (PVAc); Etc. can be used. In addition, such an electrolyte may further include a lithium salt, which may 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) it is preferred to use ₂ NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, and tetraphenyl lithium borate, etc. . In addition, the lithium ion supply core unit 110 may be configured only with an electrolyte, and in the case of a liquid electrolyte solution, may be configured using a porous carrier.

The inner electrode 130 may include an inner electrode active material layer formed to surround the outer surface of the inner electrode support and an inner current collector formed to surround the outer surface of the inner electrode active material layer, or surround the outer surface of the inner electrode support. The inner current collector and the inner electrode active material layer formed surrounding the outer surface of the inner current collector may be provided. Non-limiting examples of the internal current collector may be a wound wire current collector, a wound sheet current collector, or a metal coating layer.

Specifically, in the internal electrode according to the embodiment of the present invention, the internal current collector may be formed on the internal electrode support of the hollow structure, and then the internal electrode active material layer may be formed on the surface of the internal current collector. At this time, the inner electrode active material layer is formed on the surface of the open structure of the inner current collector, as well as the case where the open structure of the inner current collector is formed to surround the outer surface of the inner current collector and is not exposed to the outer surface of the inner electrode active material layer. And the open structure of the inner current collector is exposed to the outer surface of the inner electrode active material layer. For example, the case where an active material layer is formed on the surface of the wound wire-type current collector, and the case where the wire-type current collector in which the electrode active material layer was formed are used are wound.

In addition, in the internal electrode according to the exemplary embodiment of the present invention, the internal electrode active material layer may be first formed on the internal electrode support of the hollow structure, and then the internal current collector may be formed on the surface of the internal electrode active material layer. . Even in this case, the pores of the internal electrodes of the hollow structure are not closed, and the internal electrode active material layer and the internal current collector are formed to be the internal electrodes of the open structure. In this case, when the metal coating layer is applied as the internal current collector, for example, it may be formed using an electroless plating method.

The internal current collector is a surface treated with carbon, nickel, titanium, silver on the surface of stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel, aluminum-cadmium alloy, vision surface-treated with a conductive material It may be prepared using a conductive polymer, or a conductive polymer.

The current collector collects electrons generated by the electrochemical reaction of the active material or serves to supply electrons required for the electrochemical reaction. Generally, a metal such as copper or aluminum is used. In particular, in the case of using a non-conductive polymer surface-treated as a conductive material or a polymer conductor made of a conductive polymer, it is relatively more flexible than using a metal such as copper or aluminum. In addition, it is possible to achieve the light weight of the battery by using a polymer current collector in place of the metal current collector.

Such conductive materials may include polyacetylene, polyaniline, polypyrrole, polythiophene and polysulfuride, ITO (Indum Thin Oxide), silver, palladium and nickel, and the conductive polymer may be polyacetylene, polyaniline, polypyrrole, polythiol Offen, polysulfuritride and the like can be used. However, the non-conductive polymer used for the current collector is not particularly limited in kind.

The external current collector of the present invention is not particularly limited in form, but may be a pipe current collector, a wound wire current collector, a wound sheet current collector, or a mesh current collector. In addition, the external current collector may be stainless steel, aluminum, nickel, titanium, calcined carbon, copper; Stainless steel surface-treated with carbon, nickel, titanium, or silver; Aluminum-cadmium alloys; Non-conductive polymer surface-treated with a conductive material; Conductive polymers; A metal paste comprising a metal powder of Ni, Al, Au, Ag, Al, Pd / Ag, Cr, Ta, Cu, Ba, or ITO; Or a carbon paste containing carbon powder which is graphite, carbon black or carbon nanotubes.

The inner electrode may be a cathode or an anode, and the outer electrode may be an anode or a cathode corresponding to the outer 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 occlusion of ions from the electrolyte layer and release of ions into the electrolyte layer.

The electrode active material layer may be classified into a negative electrode active material layer and a positive electrode active material layer.

Specifically, when the inner electrode is a negative electrode, and the outer electrode is a positive electrode, the inner electrode active material layer is a negative electrode active material layer, natural graphite, artificial graphite, carbonaceous material; Metals (Me) that are lithium-containing titanium composite oxide (LTO), Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; Alloys composed of the metals (Me); Oxides of the metals (Me) (MeOx); And any one active material particles selected from the group consisting of metals (Me) and a composite of carbon or a mixture of two or more thereof, and the external electrode active material layer is 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 independently of each other Al, Ni, Co, Fe, Mn, V, Cr, Ti , W, Ta, Mg and Mo, and x, y and z are each independently the atomic fraction of the elements of the oxide composition 0 ≤ x <0.5, 0 ≤ y <0.5, 0 ≤ z <0.5 , x + y + z ≦ 1) and any one active material particles selected from the group consisting of 2 or a mixture of two or more thereof.

In addition, when the internal electrode is a positive electrode and the external electrode is a negative electrode, the internal electrode active material layer may be a positive electrode active material layer, and the external electrode active material layer may be a negative electrode active material layer.

As described above, the external electrode is formed surrounding the outer surface of the separation layer 140 as shown in FIG. 1, and includes an external electrode 150 including an external electrode active material layer and an external current collector. Can be.

At this time, the external electrode 150 is in contact with the separation layer, various embodiments are possible depending on the arrangement of the external electrode active material layer and the external current collector.

For example, the external electrode 150 has a structure including an external electrode active material layer formed surrounding the outer surface of the separation layer 140 and an external current collector formed surrounding the outer surface of the external electrode active material layer, the separation layer. A structure including an outer current collector formed to surround an outer surface of the outer current collector and an outer electrode active material layer formed to surround the outer surface of the outer current collector, and an outer current collector formed to surround the outer surface of the separation layer and an outer surface of the outer current collector A structure including an external electrode active material layer formed to contact the separation layer, or an external electrode active material layer formed surrounding the outer surface of the separation layer, and covered with the external electrode active material layer, and spaced apart from an outer surface of the separation layer. It is possible to have a structure having a wire-type external current collector formed in a surrounded state.

At this time, when the external current collector is wound on the outer surface of the separation layer, the contact area with the active material layer is sufficiently wide, so that a certain level of battery performance is ensured. In particular, the external electrode active material layer according to an embodiment of the present invention is manufactured in the form of an active material slurry, for example, is formed by coating on the outer surface of the external current collector, the external electrode active material layer may be in contact with the separation layer. In addition, the external current collector may be formed by covering the inside of the external electrode active material layer and surrounding the outer surface of the separation layer by being spaced apart by the external electrode active material layer. Since the electrical contact between the electrode active material can be improved, it contributes to the improvement of the characteristics of the battery.

For example, when a wired external current collector having flexibility as an external current collector is used, the wound wire external current collector has elasticity due to its shape, and the flexibility of the overall cable type secondary battery It will serve to improve In addition, even when excessive force is applied to the cable-type secondary battery of the present invention, since the wire-type external current collector of the present invention has little excessive deformation such as being wrinkled or bent due to its shape, a short circuit caused by contact with the internal current collector There is little worry.

The electrode active material layer includes an electrode active material, a binder, and a conductive material, and combines with the current collector to form an electrode. When deformation occurs, such as the electrode being folded or severely bent by an external force, detachment of the electrode active material occurs. Due to the detachment of the electrode active material, a decrease in battery performance and battery capacity occurs. However, since the wound wire-type external current collector has elasticity, it plays a role of dispersing the force during deformation due to external force, so that less deformation of the active material layer occurs, thereby preventing detachment of the active material. As the separation layer of the present invention, an electrolyte layer or a separator may be used.

The electrolyte layer serving as a passage for these ions may be a gel polymer electrolyte using PEO, PVdF, PMMA, PAN, or PVAC or PEO, polypropylene oxide (PPO), polyethylene imine (PEI), polyethylene sulphide (PES), or polyvinyl acetate (PVAc). Solid electrolyte using the same. The matrix of the solid electrolyte is preferably made of polymer or ceramic glass as a basic skeleton. In the case of a general polymer electrolyte, even if the ion conductivity is satisfied, ions may move very slowly in terms of reaction rate, and therefore, it is preferable to use an electrolyte of a gel polymer having easier movement of ions than a solid. Since the gel polymer electrolyte is not excellent in mechanical properties, it may include a pore structure support or a crosslinked polymer to compensate for this. Since the electrolyte layer of the present invention may serve as a separator, a separate separator may not be used.

The electrolyte layer of the present invention may further include a lithium salt. Lithium salts can improve ionic conductivity and reaction rate, non-limiting examples of which are 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 a kind thereof, but a porous material 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, polyethersulfone, polyphenylene oxide, polyphenylene sulfite and polyethylene naphthalene; Alternatively, a porous substrate formed of a mixture of inorganic particles and a binder polymer may be used. In particular, in order for lithium ions of the lithium ion supply core to be easily transferred to the external electrode, the polyester, polyacetal, polyamide, polycarbonate, polyimide, polyetheretherketone, polyethersulfone, polyphenylene oxide, and polyphenylene sulfone It is preferable to use a separator of a nonwoven material corresponding to a porous substrate made of a polymer selected from the group consisting of pit and polyethylene naphthalene.

The present invention includes a protective coating, which is formed on the outer surface of the outer current collector to protect the electrode against moisture and external shock in the air as an insulator. As the protective coating, a conventional polymer resin can be used. For example, PVC, HDPE or epoxy resin can be used.

Hereinafter, a cable type secondary battery and a method of manufacturing the same according to an exemplary embodiment will be briefly described with reference to FIG. 1.

Cable type secondary battery 100 of the present invention according to an embodiment includes a lithium ion supply core unit 110 including an electrolyte; An inner electrode formed on a surface of the inner electrode support 120 and the inner electrode support 120 having a hollow structure formed surrounding the outer surface of the lithium ion supply core part 110, and having an inner electrode support and an inner electrode active material 130; Separation layer 140 to prevent the short circuit of the electrode formed surrounding the outer surface of the inner electrode; And an external electrode 150 formed surrounding the outer surface of the separation layer 140 and having an external electrode active material layer and an external current collector.

First, a lithium ion supply core unit 110 is prepared by forming a wire using an extruder or the like using a polymer electrolyte. Alternatively, after preparing the internal electrode support having a hollow structure, the lithium ion supply core unit 110 may be formed by injecting a nonaqueous electrolyte into the center of the internal electrode support, and after preparing the battery assembly applied to the protective coating, the inside of the battery It can also be formed by injecting a nonaqueous electrolyte into the electrode support. As another method, after preparing the carrier in the form of a wire of sponge material, a non-aqueous electrolyte may be injected thereto to prepare the lithium ion supply core unit 110.

Subsequently, an inner electrode is provided on the inner electrode support, and as described above, an inner electrode active material layer is first formed to surround the outer surface of the inner electrode support, and then the inner electrode active material layer. An inner current collector may be formed on an outer surface of the inner current collector, or an inner current collector may be first formed on an outer surface of the inner electrode support, and an inner electrode active material layer may be formed on an outer surface of the inner current collector to provide an inner electrode.

For example, first, an internal current collector in the form of a linear wire or sheet is prepared and wound on the internal electrode current collector 120. An inner electrode active material layer is coated on a surface of the wound inner current collector. A general coating method may be applied as such a coating method. Specifically, an electroplating or an anodizing process may be used, but in order to maintain a constant interval, an electrode slurry containing an active material may be extruded. It is preferable to manufacture using a method of extrusion coating discontinuously through. In addition, in the case of the electrode slurry containing the active material, it is also possible to manufacture by using a method of extrusion coating using a dip coating or an extruder. In this case, a metal coating layer may be introduced as an internal current collector, and the metal coating layer may be formed using an electroless plating method.

Alternatively, the internal electrode active material layer may be first coated on the surface of the internal electrode current collector, and various types of internal current collectors may be introduced thereon.

Subsequently, a separation layer 140 made of a polymer electrolyte layer is formed to surround the internal electrode 130. Although the method of forming the separation layer 140, which is the electrolyte layer, is not particularly limited, it is easy to manufacture using a method of extrusion coating due to the characteristics of the linear cable-type secondary battery.

An external electrode is formed on an outer surface of the separation layer 140 which is the coated electrolyte, and the external electrode may have various structures according to the arrangement of the external electrode active material layer and the external current collector as described above.

 For example, an active material layer is coated on the outer surface of the separation layer 140, an external current collector is prepared, and introduced to the outer surface of the external electrode active material layer to form an external electrode 150.

In this case, the coating method of the inner electrode active material layer may be applied to the coating of the outer electrode active material layer.

In this case, as the external current collector, a wound wire current collector, a wound sheet current collector, a pipe current collector, or a mesh current collector may be applied.

In this case, the external electrode active material layer may be previously formed on the external current collector, and then applied to the separation layer to form the external electrode. For example, in the case of the wound sheet current collector, a sheet external electrode may be prepared by forming an external electrode active material layer on the sheet current collector and cutting the sheet to have a predetermined width. Subsequently, the external electrode may be formed on the separation layer by winding the outer surface of the separation layer on the sheet-type external electrode prepared to contact the external electrode active material layer.

On the other hand, when the external electrode has a structure having an outer current collector formed surrounding the outer surface of the separation layer and the outer electrode active material layer formed to contact the separation layer surrounding the outer surface of the outer current collector, first of the separation layer For example, a wire type or sheet type external current collector is wound on the outer surface. Although the winding method is not particularly limited, in the case of a wire-type external current collector, a winding machine may be applied to the outer surface of the separation layer. In addition, an outer electrode active material layer is formed on the outer surface of the wound wire or sheet type current collector. The external electrode active material layer is formed to surround the wound wire-type current collector and to contact the separator layer.

In addition, a structure including an external electrode active material layer formed to surround the outer surface of the separation layer, and an external current collector that is covered in the external electrode active material layer and surrounds the outer surface of the separation layer in a spaced apart state. In the case of, first, a part of the external electrode active material layer to be finally obtained on the outer surface of the separation layer is first formed, and is formed to surround the external current collector on the upper portion, and again the external electrode active material layer on the external current collector Is further formed to completely cover the external current collector. In this case, since the external current collector is spaced apart from the separation layer and is present inside the external electrode active material layer, electrical contact between the current collector and the active material can be improved, thereby contributing to improvement of characteristics of the battery.

Finally, the protective coating 160 is formed to surround the outer surface of the electrode assembly. The protective coating 160 is formed on the outermost surface to protect the electrode against moisture and external impact in the air as an insulator. As the protective coating 160, a conventional polymer resin may be used. For example, PVC, HDPE, or epoxy resin may be used.

The cable type secondary battery according to the exemplary embodiment of the present invention may further include an electrolyte absorbing layer between the internal electrode and the separation layer.

Referring to FIG. 2, the internal electrode 230 of the present invention maintains an open structure by sequentially forming the internal electrode active material layer and the internal current collector on the surface of the internal electrode support 220 having a hollow structure or in reverse order. In addition, the electrolyte absorbing layer 270 is formed on the surface of the internal electrode 220, and the electrolyte absorbing layer 270 may contain an electrolyte of the lithium ion supply core part 210, and the electrolyte absorbing layer 270. ) May contain a lithium salt, so that the supply of lithium ions and the exchange of lithium ions at the electrode can be facilitated, which can contribute to the improvement of capacity characteristics and cycle characteristics of the battery.

Although the kind is not specifically limited as the said electrolyte absorption layer, Gel-type polymer electrolyte using PEO, PVdF, PVdF-HFP, PMMA, PAN, or PVAC; Or a solid electrolyte using PEO, polypropylene oxide (PPO), polyethylene imine (PEI), polyethyle sulphide (PES), or polyvinyl acetate (PVAc); One formed of a polymer selected from among those may be used, and the electrolyte absorbing layer may further include a lithium salt.

As the method of forming the electrolyte absorbing layer, a dip coating or a method of extrusion coating using an extruder may be used.

In addition, the cable-type secondary battery according to an embodiment of the present invention may further include a first electrolyte absorbing layer between the inner electrode and the separating layer, and further include a second electrolyte absorbing layer between the separating layer and the outer electrode. have.

That is, referring to FIG. 3, the cable type secondary battery 300 includes a lithium ion supply core unit 310 including an electrolyte; An inner electrode support 320 formed to surround the outer surface of the lithium ion supply core part, an inner electrode 330 formed on the surface of the inner electrode support by forming an inner electrode active material layer and an inner current collector sequentially or in reverse order; A first electrolyte absorbing layer 370 formed on an outer surface of the inner electrode; A separation layer 340 which prevents a short circuit of an electrode formed surrounding the outer surface of the first electrolyte absorbing layer; A second electrolyte absorbing layer 380 formed on a surface of the separation layer; And an external electrode 350 formed surrounding the outer surface of the second electrolyte absorbing layer and having the external electrode active material layer and the external support disposed in various forms as described above.

In this case, the first electrolyte absorbing layer and the second electrolyte absorbing layer may be formed independently of the same material and method as the aforementioned electrolyte absorbing layer.

As such, the cable-type secondary battery according to the exemplary embodiment of the present invention includes an electrolyte absorbing layer on the outer surface of the inner electrode, or a first and second electrolyte absorbing layers on the outer surface of the inner electrode and the separation layer, respectively, thereby providing a lithium ion supply core. Since the negative electrolyte can be contained in the electrolyte absorbing layer, the supply of lithium ions and the exchange of lithium ions at the electrode can be more efficiently improved.

In addition, in the cable type secondary battery according to an embodiment of the present invention, at least one of the internal electrode and the external electrode may be a spiral electrode in which two or more wires are twisted in a spiral.

4 and 5, the spiral electrode 20 has at least two or more wire-like current collectors 21 arranged in parallel to each other and twisted in a spiral shape, and the wire-type electrode 21 is a wire-type current collector ( The electrode active material layer 23 may be coated on the surface of 22.

The spiral electrode 20 is a spiral twisted wire-like current collector 21 of several strands, but is not limited to a specific twisted shape, side by side so that the wire-like current collector 21 of several strands parallel to each other It may be twisted together after laying, or may be used to braid long hairs, while staggering several strands of wire-like current collectors 21 one by one.

Particularly, when the internal electrode is a cathode, Si or Sn-based metals or metal compounds, which are high-capacity cathode materials used as a cathode active material, are characterized by the fact that Li ions are alloyed / dealloying due to their characteristics. Since the chemical properties are realized, the volume change due to volume expansion is large, and the structure collapses when the change in volume is intensified. As a result, the electronic contact between the metal active materials worsens, and therefore, the movement of Li ions into the metal layer of the negative electrode active material is inhibited, resulting in deterioration of the cycle. In addition, when the metal of the formed negative electrode active material layer has a high density and the thickness of the layer is thick, it is difficult to diffuse Li ions to the inside of the negative electrode active material metal layer, thereby limiting the implementation of capacity and having a poor rate characteristic. However, since the spiral electrode has a plurality of negative electrode current collectors coated with a negative electrode active material layer on the surface of the wire-type current collector is twisted and overlapped, the reaction surface area with Li ions during the charge and discharge process can be increased to improve battery performance. have. In addition, the rate characteristics of the battery may be improved by using a wire-type negative electrode current collector coated with a thin layer of the negative electrode active material. In addition, there is a space between the wire-like negative electrode current collectors of several strands inside the spiral electrode, and thus buffering against stress and pressure inside the battery such as volume expansion of the active material layer accompanying charge and discharge is possible. Can be prevented and the stability can be ensured, contributing to the improvement of battery life.

The twist rate of the spiral electrode may be 0.01 to 10 mm / time. The twist rate is obtained by dividing the length of the spiral electrode by the number of twists, and the smaller the value is, the higher the degree of twist is. At this time, when the twist rate exceeds 10 mm / time, the area of contact between the wire-type current collectors is too small, so that the effect of increasing the surface area is insignificant. There is a risk of damaging the electrode such as desorption and disconnection of the current collector.

Hereinafter, another possible embodiment will be described with reference to FIGS. 6 to 8.

Referring to FIG. 6, a cable type secondary battery 400 according to an embodiment of the present invention includes two or more lithium ion supply core parts 410 including an electrolyte; The inner electrode support whole body 420 and the inner electrode support body 420 having a hollow structure formed surrounding the outer surface of each of the lithium ion supply core part 410 are formed on the inner electrode active material layer and the inner current collector. Two or more internal electrodes 430 disposed in parallel with each other; A separation layer 440 which surrounds the outer surfaces of the inner electrodes together to prevent a short circuit of the formed electrodes; And an external electrode 450 formed surrounding the outer surface of the separation layer 440 and having an external electrode active material layer and an external current collector. Since the cable type secondary battery 400 includes an internal electrode composed of a plurality of electrodes, it is easy to adjust the balance between the negative electrode and the positive electrode and includes a plurality of electrodes, thereby preventing the possibility of disconnection.

In addition, the cable-type secondary battery according to an embodiment of the present invention, two or more lithium ion supply core portion containing an electrolyte; An inner electrode support having a hollow structure formed surrounding the outer surface of each of the lithium ion supply cores; At least two inner electrode-separating layers formed on a surface of the inner electrode support body and disposed in parallel to each other, the inner electrode including an inner current collector and an inner electrode active material layer and a separation layer formed surrounding the outer surface of the inner electrode; concrete; And an outer electrode formed to surround the outer surfaces of the inner electrode-separation layer assembly and having an outer electrode active material layer and an outer current collector.

Also in the case of a cable type secondary battery having an internal electrode composed of the plurality of electrodes, as described above, an electrolyte absorbing layer is further provided between the internal electrode and the separation layer, or the first electrode is disposed between the internal electrode and the separation layer. An electrolyte absorbing layer may be further provided, and a second electrolyte absorbing layer may be further provided between the separation layer and the external electrode.

Referring to FIG. 7, a cable type secondary battery 500 according to an embodiment of the present invention includes two or more lithium ion supply core parts 510 including an electrolyte; It is formed on the surface of the internal electrode support 520 and the internal electrode support 520 of the hollow structure formed surrounding the outer surface of each of the lithium ion supply core portion 510, and has an internal electrode active material layer and an internal current collector At least two internal electrodes 530 disposed parallel to each other; An electrolyte absorbing layer 570 formed on an outer surface of the inner electrode; And a separation layer 540 formed on an outer surface of the electrolyte absorbing layer and preventing a short circuit of the electrode. And an external electrode 550 including an external electrode active material layer 551 and an external current collector 552 formed surrounding the internal electrodes on which the separation layer is formed.

In addition, referring to FIG. 8, the cable type secondary battery 600 according to an embodiment of the present invention includes two or more lithium ion supply core parts 610 including an electrolyte; The inner electrode support 620 and the inner electrode support 620 of the hollow structure formed surrounding the outer surface of each of the lithium ion supply core 610 is formed on the surface of the inner electrode active material layer and the inner current collector Two or more internal electrodes 630 disposed parallel to each other; A first electrolyte absorbing layer 670 formed on an outer surface of the inner electrode; And a separation layer 640 formed on an outer surface of the electrolyte absorbing layer and preventing a short circuit of the electrode. A second electrolyte absorbing layer 680 formed on an outer surface of the separation layer; And an external electrode 650 including an external electrode active material layer 651 and an external current collector 652 formed to surround the internal electrodes on which the second electrolyte absorption layer is formed.

In addition, a cable-type secondary battery having two or more internal electrodes according to an embodiment of the present invention may be modified in various ways.

For example, the cable type secondary battery includes two or more lithium ion supply core parts including an electrolyte; At least two inner electrodes formed on the surface of the inner electrode support having a hollow structure formed around the outer surface of each of the lithium ion supply cores, and disposed in parallel with each other including an inner electrode active material layer and an inner current collector; ; An electrolyte absorbing layer formed on an outer surface of the inner electrode; And an external electrode formed to surround the internal electrodes in which the electrolyte absorbing layer is formed, and having an external electrode active material layer and an external current collector.

In addition, the cable-type secondary battery according to an embodiment of the present invention includes at least two lithium ion supply core portion containing an electrolyte; At least two inner electrodes formed on the surface of the inner electrode support having a hollow structure formed around the outer surface of each of the lithium ion supply cores, and disposed in parallel with each other including an inner electrode active material layer and an inner current collector; ; A first electrolyte absorbing layer formed on an outer surface of the inner electrode; And a separation layer surrounding the internal electrodes on which the first electrolyte absorbing layer is formed and preventing a short circuit of the formed electrode. A second electrolyte absorbing layer formed on an outer surface of the separation layer; And an external electrode formed surrounding the outer surface of the second electrolyte absorbing layer and having an external electrode active material layer and an external current collector.

In the case of a cable type secondary battery having an internal electrode including the plurality of electrodes, as described above, the internal electrode includes an internal electrode active material layer formed around the outer surface of the internal electrode support and the internal electrode active material layer. An inner current collector formed to surround the outer surface may be provided, or an inner current collector formed to surround the outer surface of the inner electrode support and an inner electrode active material layer formed to surround the outer surface of the inner current collector.

The external electrode may be formed to surround the outer surface of the separation layer, in addition to a structure including an external electrode active material layer formed to surround the outer surface of the separation layer and an external current collector formed to surround the outer surface of the external electrode active material layer. An outer current collector and an outer electrode active material layer formed to surround the outer surface of the outer current collector and in contact with the separation layer, or covered with an outer electrode active material layer formed surrounding the outer surface of the separation layer, and the outer electrode active material layer It may have a structure having an outer current collector formed surrounding the outer surface of the separation layer in a spaced apart state.

[Description of the code]

100,200,300,400, 500, 600: Cable type secondary battery

110, 210, 310, 410, 510, 610: lithium ion supply core

120,220,320,420, 520, 620: internal electrode support

130, 230, 330, 430, 530, 630: internal electrode

140,240,340,440, 540, 640: Separation layer

150, 250, 350, 450, 550, 650: external electrode

160,260,360,460,560,660: Protective coating

270,570: electrolyte layer

370 and 670: first electrolyte layer

380 and 680: second electrolyte layer

551 and 651: external electrode active material layer

552, 652: external collector

Claims (36)

1. A lithium ion supply core unit including an electrolyte;

   An inner electrode support having a hollow structure formed surrounding the outer surface of the lithium ion supply core;

   An internal electrode formed on a surface of the internal electrode support and having an internal current collector and an internal electrode active material layer;

   A separation layer which prevents a short circuit of the electrode formed surrounding the outer surface of the inner electrode; And

   A cable type secondary battery extending in a length direction including an external electrode formed surrounding the outer surface of the separation layer and having an external electrode active material layer and an external current collector.
2. The method of claim 1,

   The internal electrode support of the hollow structure is a cable-type secondary battery, characterized in that the hollow fiber.
3. The method of claim 1,

   The inner electrode support of the hollow structure is a cable-type secondary battery, characterized in that the electrolyte has a pore on the surface to move to the internal electrode active material and the external electrode active material.
4. The method of claim 3,

   The pores have a cable type secondary battery, characterized in that having a diameter of 10 nm to 100 ㎛.
5. The method of claim 1,

   The hollow yarn is selected from the group consisting of polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, polyimide, polyethylene terephthalate, polyamide imide, polyesterimide, polyethersulfone, and polysulfone Cable type secondary battery, characterized in that formed in more than one species.
6. The method of claim 1,

   The internal current collector is a wire type current collector, a wound sheet current collector, or a cable type secondary battery, characterized in that the metal coating layer.
7. The method of claim 1,

   The inner electrode may include an inner electrode active material layer formed to surround the outer surface of the inner electrode support and an inner current collector formed to surround the outer surface of the inner electrode active material layer, or

   A cable type secondary battery comprising an inner current collector formed surrounding the outer surface of the inner electrode support and an inner electrode active material layer formed surrounding the outer surface of the inner current collector.
8. The method of claim 1,

   The external electrode may include an external electrode active material layer formed surrounding the outer surface of the separation layer and an external current collector formed surrounding the outer surface of the external electrode active material layer,

   An outer current collector formed to surround the outer surface of the separation layer and an outer electrode active material layer formed to surround the outer surface of the outer current collector;

   An outer current collector formed to surround the outer surface of the separation layer and an outer electrode active material layer formed to contact the separation layer and surrounding the outer surface of the outer current collector, or

   A cable type comprising an external electrode active material layer formed surrounding the outer surface of the separation layer, and an external current collector covered with the external electrode active material layer and surrounding the outer surface of the separation layer and spaced apart from each other. Secondary battery.
9. The method of claim 1,

   The external current collector is a pipe-type current collector, a wound wire current collector, a wound sheet current collector, or a cable-type secondary battery, characterized in that the mesh current collector.
10. The method of claim 1,

    The internal current collector is stainless steel, aluminum, nickel, titanium, calcined carbon, copper; Stainless steel surface-treated with carbon, nickel, titanium, or silver; Aluminum-cadmium alloys; Non-conductive polymer surface-treated with a conductive material; Or cable type secondary battery, characterized in that made of a conductive polymer.
11. The method of claim 10,

    The conductive material is one or a mixture of two or more selected from polyacetylene, polyaniline, polypyrrole, polythiophene and polysulfuride, ITO (Indum Thin Oxide), silver, palladium and nickel.
12. The method of claim 10,

    The conductive polymer is a cable type secondary battery, characterized in that the polymer is one or a mixture of two or more selected from polyacetylene, polyaniline, polypyrrole, polythiophene and polysulfuritride.
13. The method of claim 1,

    The external current collector is stainless steel, aluminum, nickel, titanium, calcined carbon, copper; Stainless steel surface-treated with carbon, nickel, titanium, or silver; Aluminum-cadmium alloys; Non-conductive polymer surface-treated with a conductive material; Conductive polymers; A metal paste comprising a metal powder of Ni, Al, Au, Ag, Al, Pd / Ag, Cr, Ta, Cu, Ba, or ITO; Or a carbon paste comprising carbon powder which is graphite, carbon black, or carbon nanotubes.
14. The method of claim 1,

    The electrolyte is ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methyl Non-aqueous electrolytes using formate (MF), gamma-butyrolactone (γ-BL; butyrolactone), sulfolane, methylacetate (MA), or methylpropionate (MP); Gel polymer electrolytes using PEO, PVdF, PMMA, PAN or PVAC; Or a solid electrolyte using PEO, polypropylene oxide (PPO), polyethylene imine (PEI), polyethylene sulphide (PES) or polyvinyl acetate (PVAc); Cable type secondary battery comprising an electrolyte selected from.
15. The method of claim 1,

    The electrolyte is a cable-type secondary battery further comprises a lithium salt.
16. The method of claim 15,

    The lithium salt is 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, chloroborane lithium, lower aliphatic lithium carbonate and lithium tetraphenyl borate, one or two or more selected from the cable type secondary battery.
17. The method of claim 1,

    The inner electrode is a cathode or an anode, the outer electrode is a cable-type secondary battery, characterized in that the anode or cathode corresponding to the inner electrode.
18. The method of claim 1,

    When the inner electrode is a cathode and the outer electrode is a cathode, the inner electrode active material layer may include natural graphite, artificial graphite, and carbonaceous material; Metals (Me) that are lithium-containing titanium composite oxide (LTO), Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; Alloys composed of the metals (Me); Oxides of the metals (Me) (MeOx); And one of the active material particles selected from the group consisting of a complex of the metals (Me) and carbon or a mixture of two or more thereof,

    The external electrode active material layer is 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 independently of each other Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg, and Mo, and any one selected from the group consisting of x, y and z independently of each other as the atomic fraction of the elements of the oxide composition 0 <x <0.5, 0 ≤ y <0.5, 0 ≤ z <0.5, x + y + z ≤ 1), any one active material particles selected from the group consisting of or a mixture of two or more thereof.
19. The method of claim 1,

    When the inner electrode is a positive electrode and the outer electrode is a negative electrode, the inner electrode active material layer is 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 from Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo, and x, y and z are each other Independently an active material particle selected from the group consisting of 0 ≦ x <0.5, 0 ≦ y <0.5, 0 ≦ z <0.5, and x + y + z ≦ 1 as an atomic fraction of oxide composition elements, or 2 of them Comprising at least a mixture of species,

    The external electrode active material layer is natural graphite, artificial graphite, carbonaceous material; Metals (Me) that are lithium-containing titanium composite oxide (LTO), Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; Alloys composed of the metals (Me); Oxides of the metals (Me) (MeOx); And at least one active material particle selected from the group consisting of a complex of metals (Me) and carbon, or a mixture of two or more thereof.
20. The method of claim 1,

    The separation layer is a cable type secondary battery, characterized in that the electrolyte layer or a separator.
21. The method of claim 20,

    The electrolyte layer is a gel polymer electrolyte using PEO, PVdF, PMMA, PAN or PVAC; Or a solid electrolyte using PEO, polypropylene oxide (PPO), polyethylene imine (PEI), polyethylene sulphide (PES) or polyvinyl acetate (PVAc); Cable type secondary battery comprising an electrolyte selected from.
22. The method of claim 20,

    The electrolyte layer is a cable-type secondary battery further comprises a lithium salt.
23. The method of claim 22,

    The lithium salt is 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, chloroborane lithium, lower aliphatic lithium carbonate and lithium tetraphenyl borate selected from the group consisting of one or two or more.
24. The method of claim 20,

    The separator is a porous substrate 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; A porous substrate made of a polymer selected from the group consisting of polyester, polyacetal, polyamide, polycarbonate, polyimide, polyether ether ketone, polyethersulfone, polyphenylene oxide, polyphenylene sulfite and polyethylene naphthalene; Or a porous base material formed of a mixture of inorganic particles and a binder polymer.
25. The method of claim 1,

    Cable type secondary battery further comprises an electrolyte absorbing layer between the internal electrode and the separation layer.
26. The method of claim 1,

    And a first electrolyte absorbing layer between the inner electrode and the separating layer, and a second electrolyte absorbing layer between the separating layer and the outer electrode.
27. The method of claim 1,

    At least one of the inner electrode and the outer electrode is a cable-type secondary battery, characterized in that two or more wires are spiral electrodes twisted in a spiral.
28. The method of claim 1,

    The cross section of the cable type secondary battery is a cable type secondary battery, characterized in that the circular or polygonal.
29. At least two lithium ion supply core portions comprising an electrolyte;

    An inner electrode support having a hollow structure formed surrounding the outer surface of each of the lithium ion supply cores;

    Two or more internal electrodes formed on a surface of the internal electrode support body and disposed in parallel with each other, the internal current collector and the internal electrode active material layer;

    A separation layer surrounding the outer surfaces of the inner electrodes together to prevent a short circuit of the formed electrodes; And

    A cable type secondary battery extending in a length direction including an external electrode formed surrounding the outer surface of the separation layer and having an external electrode active material layer and an external current collector.
30. At least two lithium ion supply core portions comprising an electrolyte;

    An inner electrode support having a hollow structure formed surrounding the outer surface of each of the lithium ion supply cores;

    At least two inner electrode-separating layers formed on a surface of the inner electrode support body and disposed in parallel to each other, the inner electrode including an inner current collector and an inner electrode active material layer and a separation layer formed to surround the outer surface of the inner electrode concrete; And

    And an outer electrode formed to surround the outer surfaces of the inner electrode-separation layer assembly and having an outer electrode active material layer and an outer current collector.
31. The method of claim 28 or 29,

    Cable type secondary battery further comprises an electrolyte absorbing layer on the surface of the internal electrode.
32. The method of claim 28 or 29,

    The cable type secondary battery further comprises a first electrolyte absorbing layer on the surface of the internal electrode, and further comprising a second electrolyte absorbing layer on the surface of the separation layer.
33. At least two lithium ion supply core portions comprising an electrolyte;

    At least two inner electrodes formed on the surface of the inner electrode support having a hollow structure formed around the outer surface of each of the lithium ion supply cores, and disposed in parallel with each other including an inner electrode active material layer and an inner current collector; ;

    An electrolyte absorbing layer formed on an outer surface of the inner electrode;

    A separation layer which surrounds the internal electrodes in which the electrolyte absorption layer is formed and prevents a short circuit of the formed electrodes; And

    A cable type secondary battery extending in a length direction including an external electrode formed surrounding the outer surface of the separation layer and having an external electrode active material layer and an external current collector.
34. At least two lithium ion supply core portions comprising an electrolyte;

    At least two inner electrodes formed on the surface of the inner electrode support having a hollow structure formed around the outer surface of each of the lithium ion supply cores, and disposed in parallel with each other including an inner electrode active material layer and an inner current collector; ;

    An electrolyte absorbing layer formed on an outer surface of the inner electrode; And

    And an outer electrode formed to surround the inner electrodes having the electrolyte absorbing layer formed thereon, the outer electrode having an outer electrode active material layer and an outer current collector.
35. At least two lithium ion supply core portions comprising an electrolyte;

    At least two inner electrodes formed on the surface of the inner electrode support having a hollow structure formed around the outer surface of each of the lithium ion supply cores, and disposed in parallel with each other including an inner electrode active material layer and an inner current collector; ;

    A first electrolyte absorbing layer formed on an outer surface of the inner electrode;

    A separation layer surrounding the internal electrodes on which the first electrolyte absorbing layer is formed and preventing a short circuit of the formed electrode;

    A second electrolyte absorbing layer formed on an outer surface of the separation layer; And

    And an external electrode formed surrounding the outer surface of the second electrolyte absorbing layer and having an external electrode active material layer and an external current collector.
36. 36. The method of claim 29, 30, 33, 34, or 35,

    At least one of the inner electrode and the outer electrode is a cable-type secondary battery, characterized in that two or more wires are spiral electrodes twisted in a spiral.

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