KR101654680B1 - Electrode for a secondary battery and cable-type secondary battery including the same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode for a secondary battery and a cable-type secondary battery including the same, and more particularly, An electrode active material layer formed on at least one surface or the entire outer surface of the current collector; And a porous coating layer formed on an upper surface of the electrode active material layer, the porous coating layer including a polymer binder, wherein the current collector includes a hollow current collector, a wire-shaped current collector, a wound wire- To an electrode for a secondary battery which is a full or mesh-shaped current collector, and a cable-type secondary battery including the same.
According to the present invention, it is possible to prevent detachment of the electrode active material layer, which may occur due to stress due to external force due to deformation of a cable type secondary battery or the like, or rapid expansion of the electrode active material layer during charge / It is possible to improve the cycle life characteristics and at the same time to smoothly flow the electrolyte into the electrode active material layer, thereby preventing the increase in resistance of the electrode, thereby improving the performance of the battery.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an electrode for a secondary battery and a cable-

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an electrode for a secondary battery and a cable-type secondary battery including the same, and more particularly, to an electrode for a secondary battery and a cable-type secondary battery including the same, wherein the electrode active material layer is prevented from desorption, .

Recently, a secondary cell is a device that converts external electrical energy into a form of chemical energy, stores it, and produces electricity when needed. The term "rechargeable battery" also means that the battery can be recharged several times. Common secondary batteries include lead acid batteries, NiCd batteries, NiMH batteries, Li-ion batteries, and Li-ion polymer batteries. Secondary batteries provide both economic and environmental advantages over single-use primary batteries.

Secondary cells are currently used for low power applications. Such as a device that assists the starting of a vehicle, a portable device, a tool, and an uninterruptible power supply. Background Art [0002] Recent developments in wireless communication technology have led to the popularization of portable devices and the tendency to wirelessize many types of conventional devices, and demand for secondary batteries is exploding. In addition, hybrid vehicles and electric vehicles are being put to practical use in terms of prevention of environmental pollution, and these next generation vehicles employ secondary battery technology to reduce the value and weight and increase the life span.

Generally, a secondary battery is a cylindrical, square, or pouch type battery. This is because the secondary battery is manufactured by inserting an electrode assembly composed of a cathode, an anode, and a separator into 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 indispensably required, there is a problem that the cylindrical shape, the square shape, or the pouch shape of the secondary battery acts as a constraint on the development of various types of portable devices. Therefore, there is a demand for a new type secondary battery which is easy to deform in shape.

With respect to this demand, a cable-type secondary battery which is a battery having a very large length-to-diameter diameter ratio has been proposed. However, such a cable-type secondary battery is liable to cause deterioration of capacity and cycle life characteristics due to stress due to an external force due to a deformation of shape, or desorption of an electrode active material layer due to rapid expansion of the electrode active material layer during charging and discharging have.

In order to solve this problem, a polymeric binder coating layer may be further formed on the upper surface of the electrode active material layer. In this case, the cycle life characteristics of the battery can be improved. However, since the polymeric binder coating layer has almost no pores therein, it may interfere with the flow of the electrolyte solution into the electrode active material layer, .

Accordingly, it is an object of the present invention to provide a positive electrode active material composition capable of preventing detachment of an electrode active material layer, improving cycle life characteristics of the battery, facilitating the flow of an electrolyte solution into the electrode active material layer, An electrode for a secondary battery, and a cable-type secondary battery including the same.

According to an aspect of the present invention, there is provided a current collector comprising: a current collector; An electrode active material layer formed on at least one surface or the entire outer surface of the current collector; And a porous coating layer formed on an upper surface of the electrode active material layer, the porous coating layer including a polymer binder, wherein the current collector includes a hollow current collector, a wire-shaped current collector, a wound wire- There is provided an electrode for a secondary battery which is a whole or a mesh-shaped current collector.

At this time, the size of pores formed in the porous coating layer may be 0.01 μm to 10 μm and the porosity may be 5 to 95%.

The porous coating layer may further include inorganic particles.

Here, the weight ratio of the inorganic particles and the polymeric binder may be 10:90 to 80:20.

The inorganic particles may be inorganic particles having a dielectric constant of 5 or more, inorganic particles having lithium ion transporting ability, or a mixture thereof.

At this time, the inorganic particles is greater than or equal to the dielectric constant of _{5, BaTiO 3, Pb (Zr x} , Ti 1 -x) O 3 (PZT, where, 0 <x <1 _{Im), Pb 1 - x La x} Zr 1 -y Ti _y O ₃ (PLZT, where, 0 <x <1, 0 <y <1 Im), (1-x) Pb (Mg 1/3 Nb 2/3) O 3 -xPbTiO 3 (PMN-PT, where , 0 <x <1), hafnia (HfO ₂ ), SrTiO ₃ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , SiC, SiO ₂ , AlOOH, Al (OH) ₃ and TiO ₂ , or a mixture of two or more thereof.

The inorganic particles having the lithium ion transferring ability include lithium phosphate (Li ₃ PO ₄ ), lithium titanium phosphate (Li _x Ti _y (PO ₄ ) ₃ , 0 <x <2, 0 <y < (Li _x Al _y Ti _z (PO ₄ ) ₃ , 0 <x <2, 0 <y <1, 0 <z <3), (LiAlTiP) _x O _y- 0 <y <13), lithium lanthanum titanate (Li _x La _y TiO _{3 ,} 0 <x <2, 0 <y <3), lithium germanium thiophosphate (Li _x Ge _y P _z S _w , x <4, 0 <y < 1, 0 <z <1, 0 <w <5), lithium nitrides _{(Li x N y, 0 <} x <4, 0 <y <2), SiS 2 (Li x _{Si y S z, 0 <x} <3, 0 <y <2, 0 <z <4) based glass, and _{P 2 S 5 (Li x P} y S z, 0 <x <3, 0 <y <3, 0 < z < 7) series glass, or a mixture of two or more thereof.

The average particle diameter of the inorganic particles may be 10 nm to 5 탆.

On the other hand, the polymer binder may be selected from the group consisting of polyvinylidene fluoride (PVDF), hexafluoro propylene (HFP), polyvinylidene fluoride-co- hexafluoro propylene, polyvinylidene fluoride-co-trichlorethylene, polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone, But are not limited to, polyvinylacetate, polyethylene-co-vinyl acetate, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate cellulose acetate propionate, cyanoethylpullulan, , Cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, carboxyl methyl cellulose, acrylonitrile styrene butadiene copolymer (acrylonitrile-styrene-butadiene copolymer) and polyimide, or a mixture of two or more thereof.

The electrode for secondary battery is a cathode and the electrode active material is at least one selected from the group consisting of Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Metals (Me) which are Ni or Fe; An alloy composed of the metal (Me); And an oxide of the metal (Me) (MeOx), or a mixture of two or more thereof.

According to another aspect of the present invention, there is provided a lithium ion secondary battery comprising: a lithium ion supply core portion including an electrolyte; An inner current collector formed on an outer surface of the internal current collector, and a porous coating layer formed on an outer surface of the internal electrode active material layer and including a polymeric binder, the internal current collector having an open structure surrounding the outer surface of the lithium ion supply core, An internal electrode; A separating layer surrounding the outer surface of the inner electrode to prevent short-circuiting of the electrode; And an outer electrode surrounding the outer surface of the separating layer and including an outer collector and an outer electrode active material layer. The cable-type secondary battery has a horizontal cross section and extends in the longitudinal direction.

At this time, the inner current collector of the open structure may be a wire-wound current collector, a wound sheet-like collector, or a mesh-like current collector.

The internal electrode is a cathode and the internal electrode active material layer is made of at least one selected from the group consisting of Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Metals (Me) which are Ni or Fe; An alloy composed of the metal (Me); And an oxide of the metal (Me) (MeOx), or a mixture of two or more thereof.

The outer electrode may include an outer electrode active material layer formed to surround the outer surface of the separation layer and an outer current collector surrounding the outer surface of the outer electrode active material layer, And an outer electrode active material layer formed to surround the outer surface of the outer current collector, or an outer electrode active material layer surrounding the outer surface of the outer current collector, and an outer electrode active material layer surrounding the outer surface of the outer current collector, An outer electrode active material layer formed on the outer surface of the separating layer and having an electrode active material layer or an outer electrode active material layer formed on the outer electrode active material layer and surrounding the outer surface of the separating layer, .

According to another aspect of the present invention, there is provided a lithium ion secondary battery comprising: a lithium ion supply core portion including an electrolyte; An internal electrode including an internal current collector having an open structure formed to surround an outer surface of the lithium ion supply core portion and an internal electrode active material layer formed on an outer surface of the internal current collector; A separating layer surrounding the outer surface of the inner electrode to prevent short-circuiting of the electrode; And an outer electrode surrounding the outer surface of the separating layer and including a porous coating layer including an outer current collector, an outer electrode active material layer, and a polymeric binder, the cable type secondary battery having a horizontal cross- Is provided.

The external electrode is a cathode and the external electrode active material layer is made of at least one selected from the group consisting of Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Metals (Me) which are Ni or Fe; An alloy composed of the metal (Me); And an oxide of the metal (Me) (MeOx), or a mixture of two or more thereof.

The outer electrode includes a porous coating layer including a polymer binder formed around the outer surface of the separating layer, an outer electrode active material layer surrounding the outer surface of the porous coating layer, and an outer electrode active material layer surrounding the outer surface of the outer electrode active material layer. An outer electrode active material layer surrounding the outer surface of the outer current collector, and an outer electrode active material layer surrounding the outer surface of the outer electrode active material layer, wherein the outer electrode active material layer surrounds the outer surface of the separator layer, An outer electrode active material layer formed to surround the outer surface of the outer current collector and contacting the separating layer, and an outer electrode active material layer formed on the outer surface of the outer electrode active material layer, And has a porous coating layer including a polymeric binder, or An outer electrode active material layer formed to surround the outer surface of the separating layer; an outer current collector formed to surround the outer electrode active material layer and surrounding the outer surface of the separating layer, And a porous coating layer comprising a polymeric binder.

Meanwhile, the separation layer may be an electrolyte layer or a separator.

At this time, the electrolyte layer may be a gel-type polymer electrolyte using PEO, PVdF, PVdF-HFP, PMMA, PAN, or PVAC; Or solid electrolytes using PEO, polypropylene oxide (PPO), polyethylene imine (PEI), polyethylene sulphide (PES) or polyvinyl acetate (PVAc); The electrolyte may be selected from the group consisting of:

The electrolyte layer may further include a lithium salt.

In this case, the lithium salt, 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, lithium lower aliphatic carboxylate and lithium tetraphenylborate.

The separator may be a porous substrate made of a polyolefin-based polymer selected from the group consisting of an ethylene homopolymer, a propylene homopolymer, an ethylene-butene copolymer, an ethylene-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, polyphenylsulfite and polyethylene naphthalene; Or a porous substrate formed of a mixture of inorganic particles and a binder polymer.

According to another aspect of the present invention, there is provided a lithium ion secondary battery comprising: at least two lithium ion supply core parts including an electrolyte; An internal current collector formed on an outer surface of the internal current collector, and an electrode active material layer formed on an external surface of the internal electrode active material layer and having a porous structure including a polymeric binder, At least two internal electrodes arranged parallel to each other and having a coating layer; A separating layer surrounding the outer surfaces of the inner electrodes to prevent short-circuiting of the electrodes; And an outer electrode surrounding the outer surface of the separating layer and including an outer collector and an outer electrode active material layer. The cable-type secondary battery has a horizontal cross section and extends in the longitudinal direction.

According to another aspect of the present invention, there is provided a lithium ion secondary battery comprising: at least two lithium ion supply core parts including an electrolyte; An inner electrode active material layer formed on an outer surface of the inner current collector, an inner electrode active material layer formed on an outer surface of the inner electrode active material layer, and a porous binder layer formed on an outer surface of the inner electrode active material layer, At least two internal electrodes arranged parallel to each other and having a coating layer and a separating layer for preventing short-circuiting of the electrodes formed around the outer surface of the porous coating layer; And an outer electrode that is formed to surround the outer surfaces of the inner electrodes and includes an outer collector and an outer electrode active material layer, the cable type secondary battery having a horizontal section and extending in the longitudinal direction.

According to another aspect of the present invention, there is provided a lithium ion secondary battery comprising: at least two lithium ion supply core parts including an electrolyte; At least two internal electrodes arranged parallel to each other and having an internal current collector of an open structure formed to surround an outer surface of each of the lithium ion supply core parts and an internal electrode active material layer formed to surround an outer surface of the internal current collector; A separating layer surrounding the outer surfaces of the inner electrodes to prevent short-circuiting of the electrodes; And an outer electrode surrounding the outer surface of the separating layer, the outer electrode including a porous coating layer including an outer collector, an outer electrode active material layer, and a polymer binder, A battery is provided.

According to another aspect of the present invention, there is provided a lithium ion secondary battery comprising: at least two lithium ion supply core parts including an electrolyte; An internal current collector having an open structure surrounding the external surface of each of the lithium ion supply core parts, an internal electrode active material layer formed to surround the external surface of the internal current collector, and an electrode formed surrounding the external surface of the internal electrode active material layer, Two or more internal electrodes disposed parallel to each other and having a separation layer for preventing the electrodes from being separated from each other; And an outer electrode which is formed to surround the outer surfaces of the inner electrodes and has a porous coating layer including an outer collector, an outer electrode active material layer, and a polymer binder, and a cable type A secondary battery is provided.

According to the present invention, it is possible to suppress the detachment of the electrode active material layer, which may occur due to external stress due to deformation of the shape of a cable-type secondary battery or the like, or rapid expansion of the electrode active material layer during charge / The cycle life characteristics can be improved.

At the same time, it is possible to improve the performance of the battery by preventing the increase of the resistance of the electrode by facilitating the inflow of the electrolyte into the electrode active material layer.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate preferred embodiments of the invention and, together with the description of the invention given above, serve to further the understanding of the technical idea of the invention, It should not be construed as limited.
1 is a perspective view of an electrode for a cable-type secondary battery including a wire-shaped current collector according to an embodiment of the present invention.
2 is a perspective view of an electrode for a cable-type secondary battery including a hollow current collector according to an embodiment of the present invention.
3 is a perspective view of a cable-type secondary battery including one internal electrode according to an embodiment of the present invention.
4 is a perspective view of a cable-type secondary battery including one internal electrode according to another embodiment of the present invention.
5 is a cross-sectional view of a cable-type secondary battery including two or more internal electrodes according to an embodiment of the present invention.
6 is a cross-sectional view of a cable-type secondary battery including two or more internal electrodes according to another embodiment of the present invention.
7 is a SEM photograph showing a cross section of a porous coating layer prepared according to an embodiment of the present invention.
8 is a graph showing a first charge / discharge profile of a battery according to an embodiment of the present invention and a comparative example.
9 is a graph showing cycle life characteristics of a battery according to an embodiment and a comparative example of the present invention.

Hereinafter, the present invention will be described in detail with reference to the drawings. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

In addition, since the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention, It is to be understood that equivalents and modifications are possible.

An electrode for a secondary battery according to the present invention includes: a current collector; An electrode active material layer formed on at least one surface or the entire outer surface of the current collector; And a porous coating layer formed on an upper surface of the electrode active material layer, the porous coating layer including a polymer binder, wherein the current collector includes a hollow current collector, a wire-shaped current collector, a wound wire- It is a full or mesh-like collector.

At this time, when the current collector is a hollow current collector, the electrode active material layer may be formed on at least one surface of the current collector and a surface existing outside the current collector. The electrode active material layer may be formed on the entire surface of the whole body. In the case of the wound wire-like current collector, the wound sheet-like current collector or the mesh-shaped current collector, the surface present inside the current collector and the surface present outside The electrode active material layer may be formed on at least one side of the current collector, or may be formed to surround the entire surface of the current collector.

FIG. 1 is a perspective view of an electrode for a cable-type secondary battery including a wire-shaped current collector according to an embodiment of the present invention. FIG. 2 is a perspective view illustrating a hollow current collector according to an embodiment of the present invention. Fig. 2 is a perspective view of an electrode for a cable-type secondary battery.

1, an electrode 10 for a cable-type secondary battery according to the present invention includes a wire-shaped current collector 11; An electrode active material layer 12 formed to surround the entire surface of the wire-like current collector 11; And a porous coating layer 13 formed on the upper surface of the electrode active material layer 12 and including a polymeric binder, and extends in the longitudinal direction. At this time, the electrode 10 for a cable-type secondary battery may be constructed such that at least one wire is wound in a coil shape, or at least one wire composite formed by twining two or more wires in a spiral shape is wound in a coil shape, .

2, the electrode 20 for a cable-type secondary battery according to the present invention includes a hollow current collector 21; An electrode active material layer 22 formed on a surface existing outside the hollow current collector 21; And a porous coating layer 23 surrounding the upper surface of the electrode active material layer 22 and including a polymer binder, and extending in the longitudinal direction. At this time, the electrode 20 for the cable-type secondary battery can be used as an external electrode of the cable-type secondary battery.

As electrode for a cable-type secondary battery, the electrode active material layer formed on the current collector may cause desorption of the electrode active material layer due to a rapid volume expansion during charge and discharge or stress due to external force due to deformation of the shape. Particularly, in the case of a metallic anode active material layer formed by an electroplating method or an anodic oxidation method, since the polymer binder and the conductive material are not present, the desorption phenomenon may be more serious.

In order to prevent such a phenomenon, in the present invention, by forming a porous coating layer made of a polymeric binder on the outer surface of the electrode active material layer, desorption phenomenon of the electrode active material layer is prevented, and capacity reduction and cycle life characteristics of the battery can be improved . Even if a strong external force is applied due to a bending or the like, desorption phenomenon of the electrode active material layer is suppressed, which contributes to improvement of the fluidity of the cable-type secondary battery. Furthermore, the pores existing in the porous coating layer can smoothly flow the electrolyte into the electrode active material layer, thereby preventing an increase in resistance of the electrode, thereby improving the performance of the battery.

At this time, the porous coating layer may form a porous pore structure through phase separation or phase change during the manufacturing process.

The pores formed in the porous coating layer should be smaller than the size of the particles constituting the electrode active material layer in order to suppress the detachment of the electrode active material layer and should be larger than the solvation radius of the lithium ion of the electrolyte solution in order to activate the electrolyte solution into the electrode . In order to satisfy such a condition, the pore size formed in the porous coating layer may be 0.01 탆 to 10 탆.

In order to achieve the above-mentioned effect, the porosity of the porous coating layer may be 5 to 95%.

On the other hand, the porous coating layer may further include inorganic particles.

In this case, the pores are formed due to the interstitial volume between the inorganic particles formed by connecting and fixing the inorganic particles by the polymer binder.

At this time, the weight ratio of the inorganic particles and the polymeric binder may be 10:90 to 80:20 to ensure proper porosity.

The inorganic particles usable in the present invention are not particularly limited as long as they are electrochemically stable. That is, the inorganic particles usable in the present invention are not particularly limited as long as oxidation and / or reduction reaction does not occur in the operating voltage range of the applied electrochemical device (for example, 0 to 5 V based on Li / Li ⁺ ). Particularly, when inorganic particles having a high dielectric constant are used as the inorganic particles, the dissociation of the electrolyte salt, for example, the lithium salt in the liquid electrolyte, can be increased, and the ion conductivity of the electrolyte can be improved.

For the reasons stated above, the inorganic particles may include high-permittivity inorganic particles having a dielectric constant of 5 or more, or 10 or more. Nonlimiting examples of inorganic particles having a dielectric constant of 5 or more include BaTiO ₃ , Pb (Zr _x , Ti _{1 -x} ) O ₃ (PZT, where 0 <x <1), Pb _{1 -x} La _x Zr _{1- y} Ti _y O ₃ (PLZT, where, 0 <x <1, 0 <y <1 Im), (1-x) Pb (Mg 1/3 Nb 2/3) O 3 -xPbTiO 3 (PMN-PT, where, 0 <x <1), hafnia _{(HfO 2), SrTiO 3,} SnO 2, CeO 2, MgO, NiO, CaO, ZnO, ZrO 2, Y 2 O 3, Al 2 O 3, SiC, SiO 2 , AlOOH, Al (OH) ₃ and TiO ₂ , or a mixture of two or more thereof.

As the inorganic particles, inorganic particles having a lithium ion transferring ability, that is, inorganic particles containing a lithium element but having a function of transferring lithium ions without storing lithium can be used. Non-limiting examples of inorganic particles having lithium ion transferring ability include lithium phosphate (Li ₃ PO ₄ ), lithium titanium phosphate (Li _x Ti _y (PO ₄ ) ₃ , 0 <x <2, 0 <y < (Li _x Al _y Ti _z (PO ₄ ) ₃ , 0 <x <2, 0 <y <1, 0 <z <3), 14Li ₂ O-9Al ₂ O ₃ -38TiO ₂ -39P ₂ O ₅ (0 <x <4, 0 <y <13), lithium lanthanum titanate (Li _x La _y TiO ₃ , 0 <x <2, 0 <y <3), Li (LiAlTiP) _x O _y series glass _{3 .25} Ge _{0 .25} P _{0 .75} S ₄ Lithium, such as germanium Mani help thiophosphate lithium nitro, such as _{(Li x Ge y P z S} w, 0 <x <4, 0 <y <1, 0 <z <1, 0 <w <5), Li 3 N (Li _x N _y , 0 <x <4, 0 <y <2), Li ₃ PO ₄ -Li ₂ S-SiS ₂ SiS ₂ based glass, such as _{(Li x Si y S z,} 0 <x <3, 0 <y <2, 0 <z <4), LiI-Li 2 SP 2 S 5 There is P ₂ S ₅ based glass _{(Li x P y S z,} 0 <x <3, 0 <y <3, 0 <z <7) or a mixture thereof as such.

The size of the inorganic particles is not limited. However, for proper porosity of the porous coating layer, the average particle size may be 10 nm to 5 탆.

The polymer binder may be at least one selected from the group consisting of polyvinylidene fluoride (PVDF), hexafluoro propylene (HFP), polyvinylidene fluoride-co- hexafluoro propylene, polyvinylidene fluoride-co-trichlorethylene, polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone, But are not limited to, polyvinylacetate, polyethylene-co-vinyl acetate, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate cellulose acetate propionate, cyanoethylpullulane, an anion selected from the group consisting of cyanoethylpolyvinyl alcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, carboxyl methyl cellulose, acrylonitrile styrene butadiene Acrylonitrile-styrene-butadiene copolymer, polyimide, or a mixture of two or more thereof. However, the present invention is not limited thereto.

Meanwhile, the current collector may be made of stainless steel, aluminum, nickel, titanium, sintered carbon, copper; Stainless steel surface-treated with carbon, nickel, titanium or silver; Aluminum-cadmium alloy; A nonconductive polymer surface-treated with a conductive material; Or an electrically conductive polymer, and the external current collector of the open structure may be made of a material selected from the group consisting of stainless steel, aluminum, nickel, titanium, sintered carbon, copper; Stainless steel surface-treated with carbon, nickel, titanium or silver; Aluminum-cadmium alloy; A nonconductive polymer surface-treated with a conductive material; Conductive polymer; A metal paste containing a metal powder of Ni, Al, Au, Ag, Al, Pd / Ag, Cr, Ta, Cu, Ba or ITO; Or a carbon paste comprising graphite, carbon black or carbon powder which is a carbon nanotube.

The collector collects electrons generated by the electrochemical reaction of the electrode active material or supplies electrons necessary for the electrochemical reaction and generally uses a metal such as copper or aluminum. In particular, when a nonconductive polymer surface-treated with a conductive material or a polymeric conductor made of a conductive polymer is used, it is more flexible than when a metal such as copper or aluminum is used. Further, the lightweight property of the battery can be achieved by using the polymer current collector in place of the metal current collector.

Examples of the conductive material include polyacetylene, polyaniline, polypyrrole, polythiophene, polysulfuronitride, ITO (Indium Thin Oxide), silver, palladium and nickel, and conductive polymers include polyacetylene, polyaniline, polypyrrole, Polyphenylene sulfide, opene and polysulfuronitrile. However, the kind of the nonconductive polymer used in the current collector is not particularly limited.

The electrode for the secondary battery may be a negative electrode, and the electrode active material layer may include at least one selected from the group consisting of Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Metals (Me) which are Cu, Co, Ni or Fe; An alloy composed of the metal (Me); And an oxide of the metal (Me) (MeOx), or a mixture of two or more thereof.

The electrode active material layer of the present invention acts to transfer ions through a current collector, and the movement of these ions is due to interactions of ions from the electrolyte and release of ions to the electrolyte.

Meanwhile, a cable type secondary battery having a horizontal cross section and extending in the longitudinal direction according to an aspect of the present invention includes: a lithium ion supply core portion including an electrolyte; An inner current collector formed on an outer surface of the internal current collector, and a porous coating layer formed on an outer surface of the internal electrode active material layer and including a polymeric binder, the internal current collector having an open structure surrounding the outer surface of the lithium ion supply core, An internal electrode; A separating layer surrounding the outer surface of the inner electrode to prevent short-circuiting of the electrode; And an outer electrode surrounding the outer surface of the separating layer and including an outer collector and an outer electrode active material layer.

In this case, the open structure refers to a structure in which the open structure is an interface, and the material is allowed to move from the inside to the outside through the interface, and the outer current collector of the open structure is a wire- But it is not limited to the whole, the wound sheet-like collector, or the mesh-shaped collector.

And, the horizontal section may be circular or polygonal, wherein the circular shape is a geometrically perfectly symmetrical circular shape and an asymmetric elliptical shape. The polygon is not particularly limited as long as it is a structure that is not a two-dimensional sheet type. Non-limiting examples of such a polygonal structure include a triangle, a rectangle, a pentagon, or a hexagon.

The porous coating layer may further include inorganic particles as described above.

The inner electrode is a cathode and the inner electrode active material layer is an anode active material such as Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, , Metals (Me) which are Co, Ni or Fe; An alloy composed of the metal (Me); And an oxide of the metal (Me) (MeOx), or a mixture of two or more thereof.

In this case, the external electrode is an anode, and the external electrode active material layer is made of 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 (Wherein M 1 and M ₂ are independently selected from the group consisting of Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo, Wherein 0 <x <0.5, 0 <y <0.5, 0 <z <0.5 and x + y + z <1) as the atomic fraction of the oxide composition elements, or two or more And mixtures thereof.

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

3 is a perspective view of a cable-type secondary battery including one internal electrode according to an embodiment of the present invention.

Referring to FIG. 3, a cable-type secondary battery 100 includes a lithium ion supply core 110 including an electrolyte; An internal electrode active material layer 130 formed on an outer surface of the internal current collector 120 and an internal electrode active material layer 130 formed on an external surface of the internal current collector 120, 130), an inner electrode having a porous coating layer (131) including a polymeric binder; A separation layer (140) surrounding the outer surface of the inner electrode to prevent short-circuiting of the electrode; An outer electrode active material layer 150 formed to surround the outer surface of the separation layer 140 and an outer electrode 160 formed to surround the outer surface of the outer electrode active material layer 150 .

In addition to the above structure, the external electrode may have various structures depending on the positions of the external current collector and the external electrode active material layer. The external electrode includes an outer current collector surrounding the outer surface of the separating layer, A structure having an electrode active material layer; An outer current collector surrounding the outer surface of the separating layer, and an outer electrode active material layer surrounding the outer surface of the outer current collector and contacting the separating layer; An outer electrode active material layer formed to surround the outer surface of the separating layer, and an outer current collector coated within the outer electrode active material layer and surrounded by the outer surface of the separating layer so as to surround the outer electrode active material layer; And so on.

According to another aspect of the present invention, there is provided a cable-type secondary battery having a horizontal section and extending in the longitudinal direction, the cable-type secondary battery comprising: a lithium ion supply core unit including an electrolyte; An internal electrode including an internal current collector having an open structure formed to surround an outer surface of the lithium ion supply core portion and an internal electrode active material layer formed on an outer surface of the internal current collector; A separating layer surrounding the outer surface of the inner electrode to prevent short-circuiting of the electrode; And an outer electrode surrounding the outer surface of the separating layer and including a porous coating layer including an outer collector, an outer electrode active material layer, and a polymeric binder.

Here, the porous coating layer may further include inorganic particles as described above.

At this time, the external electrode is a cathode, and the external electrode active material layer includes a negative electrode active material, as described above.

4 is a perspective view of a cable-type secondary battery having a porous coating layer formed on an outer electrode according to an embodiment of the present invention.

Referring to FIG. 4, the cable-type secondary battery 200 includes a lithium ion supply core 210 including an electrolyte; An inner electrode 220 having an open structure formed around the outer surface of the lithium ion supply core 210 and an inner electrode active material layer 230 formed on an outer surface of the inner current collector 220; A separation layer (240) surrounding the outer surface of the inner electrode to prevent shorting of the electrode; And an outer electrode active material layer 250 surrounding the outer surface of the porous coating layer 251. The outer electrode active material layer 250 and the outer electrode active material layer 250 are formed on the outer surface of the separator layer 240, And an outer electrode 260 formed around the outer surface of the outer collector 260.

In addition to the above structure, the outer electrode may have various structures according to the position of the porous coating layer. The outer electrode may include an outer current collector surrounding the outer surface of the separation layer, an outer electrode active material layer surrounding the outer surface of the outer current collector, A structure formed surrounding the outer surface of the outer electrode active material layer and including a porous coating layer comprising a polymeric binder; An external current collector surrounding the outer surface of the separating layer, an outer electrode active material layer surrounding the outer surface of the outer current collector and contacting the separating layer, and an outer electrode active material layer surrounding the outer surface of the outer electrode active material layer, A structure comprising a porous coating layer comprising: An outer electrode active material layer formed to surround the outer surface of the separating layer; an outer current collector formed to surround the outer electrode active material layer and surrounding the outer surface of the separating layer, A structure comprising a porous coating layer comprising a polymeric binder; And so on.

On the other hand, the separating layer of the present invention can use an electrolyte layer or a separator.

Examples of the electrolyte layer that serves as a passage of ions include a gel-type polymer electrolyte using PEO, PVdF, PVdF-HFP, PMMA, PAN, or PVAC; Or solid electrolytes using PEO, polypropylene oxide (PPO), polyethylene imine (PEI), polyethylene sulphide (PES) or polyvinyl acetate (PVAc); . The matrix of the solid electrolyte is preferably made of a polymer or a ceramic glass as a basic skeleton. In the case of a general polymer electrolyte, it is preferable to use an electrolyte of a gel type polymer in which ions can move more easily than in a solid state because ions can move very slowly in terms of reaction rate even if ion conductivity is satisfied. Since the gel type polymer electrolyte is not excellent in mechanical properties, it may include a pore structure support or a crosslinked polymer in order to compensate for the mechanical property. Since the electrolyte layer of the present invention can 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 salt may enhance the ion conductivity and the reaction rate, these non-limiting examples, 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 available borane lithium, lower aliphatic carboxylic acid lithium, and tetraphenyl lithium borate, etc. have.

The separator is not limited in its kind, but may be made of 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, polyphenylsulfite and polyethylene naphthalene; Or a porous substrate formed of a mixture of inorganic particles and a binder polymer.

And, the present invention has a protective coating, which is formed on the outer surface of the external electrode to protect the electrode against moisture and external impact 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.

Meanwhile, the cable-type secondary battery according to another embodiment of the present invention includes two or more internal electrodes.

Here, in the case where the internal electrode is a cathode, at least two lithium ion supply core parts including an electrolyte; An internal current collector formed on an outer surface of the internal current collector, and an electrode active material layer formed on an external surface of the internal electrode active material layer and having a porous structure including a polymeric binder, At least two internal electrodes arranged parallel to each other and having a coating layer; A separating layer surrounding the outer surfaces of the inner electrodes to prevent short-circuiting of the electrodes; And an outer electrode surrounding the outer surface of the separating layer, the outer electrode comprising an outer collector and an outer electrode active material layer, or at least two lithium ion supply cores including an electrolyte; An inner electrode active material layer formed on an outer surface of the inner current collector, an inner electrode active material layer formed on an outer surface of the inner electrode active material layer, and a porous binder layer formed on an outer surface of the inner electrode active material layer, At least two internal electrodes arranged parallel to each other and having a coating layer and a separating layer for preventing short-circuiting of the electrodes formed around the outer surface of the porous coating layer; And an outer electrode formed to surround the outer surfaces of the inner electrodes and including an outer current collector and an outer electrode active material layer.

At this time, the porous coating layer may further include inorganic particles as described above.

This will be described in detail with reference to Fig.

Referring to FIG. 5, a cable-type secondary battery 300 including a plurality of internal electrodes according to the present invention includes at least two lithium ion supply core portions 310 including an electrolyte; An internal current collector 320 of an open structure formed to surround the outer surface of each lithium ion supply core 310, an internal electrode active material layer 330 formed on an outer surface of the internal current collector 320, Two or more internal electrodes formed on the outer surface of the layer 330 and arranged parallel to each other and having a porous coating layer 331 comprising a polymeric binder; A separation layer (340) for preventing short-circuiting of the electrodes formed by surrounding the outer surfaces of the internal electrodes together; An outer electrode active material layer 350 formed around the outer surface of the isolation layer 340 and an outer electrode 360 formed around the outer surface of the outer electrode active material layer 350 .

When the external electrode is a cathode, at least two lithium ion supply core parts including an electrolyte; At least two internal electrodes arranged parallel to each other and having an internal current collector of an open structure formed to surround an outer surface of each of the lithium ion supply core parts and an internal electrode active material layer formed to surround an outer surface of the internal current collector; A separating layer surrounding the outer surfaces of the inner electrodes to prevent short-circuiting of the electrodes; And an outer electrode surrounding the outer surface of the separating layer and including a porous coating layer including an outer current collector, an outer electrode active material layer, and a polymeric binder, or at least two lithium ion supply core parts ; An internal current collector having an open structure surrounding the external surface of each of the lithium ion supply core parts, an internal electrode active material layer formed to surround the external surface of the internal current collector, and an electrode formed surrounding the external surface of the internal electrode active material layer, Two or more internal electrodes disposed parallel to each other and having a separation layer for preventing the electrodes from being separated from each other; And an outer electrode including an outer collector, an outer electrode active material layer, and a polymeric binder, the outer electrode being formed to surround the outer surfaces of the inner electrodes together.

At this time, the porous coating layer may further include inorganic particles as described above.

Hereinafter, this will be described in detail with reference to Fig.

Referring to FIG. 6, there are shown at least two lithium ion supply core portions 410 including an electrolyte; An internal current collector 420 of an open structure formed to surround the outer surface of each of the lithium ion supply core portions 410 and an internal electrode active material layer 430 formed to surround the external surface of the internal current collector 420 At least two internal electrodes arranged in parallel to each other; A separating layer 440 for preventing short-circuiting of the electrodes formed by surrounding the outer surfaces of the inner electrodes together; And an outer electrode active material layer 450 surrounding the outer surface of the porous coating layer 451. The outer electrode active material layer 450 is formed on the outer surface of the separator layer 440. The outer electrode active material layer 450 is formed on the outer surface of the separator layer 440, And an outer electrode 460 formed around the outer surface of the outer collector 460.

In addition to the formation of the external electrode shown here, more specific details are as described above.

Since the cable type secondary batteries 300 and 400 have internal electrodes composed of a plurality of electrodes, balance between the cathode and the anode can be easily adjusted, and a plurality of electrodes can be provided, thereby preventing the possibility of disconnection.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

Example

(1) Preparation of electrode

Using an electroplating method, an electrode active material including nickel and tin having a thickness of 2.5 占 퐉 was coated on a wire-type copper current collector having a diameter of 125 占 퐉 to form an electrode active material layer.

Subsequently, a mixture prepared by mixing silicon oxide (SiO ₂ ) as inorganic particles and polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP 5%) as a polymer binder at a weight ratio of 10:90 was dissolved in acetone To a solvent so as to have a weight ratio of 10%.

Water was added as a non-solvent to the prepared solution at 5 wt% of the total solution. The prepared solution was coated on the entire outer surface of the wire electrode active material layer, and the acetone solvent was evaporated at room temperature, and then dried in a vacuum oven at a temperature of 100 ° C for 10 hours to form a porous coating layer.

FIG. 7 is a SEM photograph showing the shape of the porous coating layer formed by this process.

(2) Production of coin type half cell

The wire-type electrode manufactured in the above-mentioned Example (1) was wound in a horizontal plane to produce a plate-like shape, which was used as a negative electrode, and a metallic lithium foil was used as the positive electrode. An electrode assembly was manufactured through a polyethylene separator.

After the electrode assembly was placed in a battery case, an electrolytic solution to which 1 M of LiPF ₆ was added was added to a nonaqueous solvent in which a volume ratio of ethylene carbonate (EC) and diethyl carbonate (DEC) was 1: 2, .

Comparative Example  One

(1) Preparation of electrode

Using an electroplating method, an electrode active material including nickel and tin having a thickness of 2.5 占 퐉 was coated on a wire-type copper current collector having a diameter of 125 占 퐉 to form an electrode active material layer.

(2) Production of coin type half cell

The wire-type electrode prepared in Comparative Example 1- (1) was wound up on a horizontal plane to produce a plate-like shape and used as a negative electrode, A battery was prepared.

Comparative Example  2

(1) Preparation of electrode

Using an electroplating method, an electrode active material including nickel and tin having a thickness of 2.5 占 퐉 was coated on a wire-type copper current collector having a diameter of 125 占 퐉 to form an electrode active material layer.

Subsequently, a solution was prepared by mixing polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP 5%) as a polymer binder in an acetone solvent to a weight ratio of 10%.

The prepared solution was coated on the entire outer surface of the wire electrode active material layer, and the acetone solvent was evaporated at room temperature. Then, the solvent was dried in a vacuum oven at 100 ° C for 10 hours to form a dense polymer binder To form a coating layer.

(2) Production of coin type half cell

The wire-shaped electrode prepared in Comparative Example 2- (1) was wound up on a horizontal plane to produce a plate-like shape, and was used as a negative electrode. In the same manner as in Example (2) .

Charging and discharging  Character rating

Charge-discharge characteristics were evaluated using the coin-type half-cell produced in the above-mentioned Examples, Comparative Examples 1 and 2.

The battery was charged at a current density of 0.1 C at a constant current of 5 mV, and then kept constant at a constant voltage of 5 mV. When the current density reached 0.005 C, charging was terminated. The discharge was completed in a constant current mode up to 1.5 V at a current density of 0.5 C during discharging. Charging and discharging were repeated 30 times under the same conditions.

FIG. 8 is a graph showing a first charge / discharge profile of a battery according to an embodiment and a comparative example of the present invention, and FIG. 9 is a graph showing cycle life characteristics of a battery according to an embodiment and a comparative example of the present invention.

Referring to FIG. 8, it can be seen that the embodiment in which the porous coating layer is formed is superior in the capacity implementation rate as compared with Comparative Example 1 and Comparative Example 2. In particular, in Comparative Example 2 in which a dense polymeric binder coating layer having almost no pores was formed, it was difficult to flow the electrolyte solution into the electrode layer, so that the battery resistance was high and the constant current period was short during the first charge, It can be seen that the section is very long.

Also, referring to FIG. 9, it can be seen that the cycle life characteristics of the embodiment are superior to those of the comparative example.

Meanwhile, Table 1 shows the measured efficiency after the first cycle. In the case of the embodiment, it is understood that the initial efficiency and capacity are excellent.

Charging capacity (mAh / g) Discharge capacity (mAh / g) First cycle efficiency (%) Example 1 817.5 701.8 85.8 Comparative Example 1 792.8 624.3 78.7 Comparative Example 2 786.2 588.6 74.9

As a result, the porous coating layer formed on the metal-based high-capacity anode active material layer inhibits the active material from being separated from the surface of the collector due to the volume expansion during charging and discharging, and the electrolyte can be introduced into the electrode through the porous structure. Rate and cycle life characteristics.

It should be noted that the embodiments of the present invention disclosed in the present specification and drawings are only illustrative of specific examples for the purpose of understanding and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.

10, 20: Electrode for cable type secondary battery 11: Wire type current collector
12, 22: electrode active material layer 13, 23: porous coating layer
21: Hollow type collector
100, 200, 300, 400: Cable type secondary battery
110, 210, 310, 410: lithium ion supply core portion
120, 220, 320, 420: internal current collector
130, 230, 330, 430: internal electrode active material layer
140, 240, 340, 440: separation layer
150, 250, 350, 450: external electrode active material layer
160, 260, 360, 460: Outer collector
170, 270, 370, 470: protective sheath
131, 251, 331, 451: Porous coating layer

Claims (27)

delete delete delete delete delete delete delete delete delete delete delete A lithium ion supply core portion including an electrolyte;
An inner current collector formed on an outer surface of the internal current collector, and a porous coating layer formed on an outer surface of the internal electrode active material layer and including a polymeric binder, the internal current collector having an open structure surrounding the outer surface of the lithium ion supply core, An internal electrode;
A separating layer surrounding the outer surface of the inner electrode to prevent short-circuiting of the electrode; And
And an outer electrode surrounding the outer surface of the separating layer and including an outer collector and an outer electrode active material layer. 13. The method of claim 12,
Wherein the internal current collector of the open structure is a wire wound current collector, a wound sheet current collector, or a mesh current collector. 13. The method of claim 12,
The internal electrode is a cathode,
Wherein the internal electrode active material layer is made of at least one metal selected from the group consisting of Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Ce, Cu, Co, Ni or Fe; An alloy composed of the metal (Me); And an oxide of the metal (Me) (MeOx), or a mixture of two or more thereof. The cable-type secondary battery has a horizontal cross section and extends in the longitudinal direction. 13. The method of claim 12,
Wherein the external electrode includes an external electrode active material layer formed to surround the outer surface of the separating layer and an external current collector surrounding the outer surface of the external electrode active material layer,
An outer current collector formed to surround the outer surface of the separating layer, and an outer electrode active material layer surrounding the outer surface of the outer current collector,
An external current collector surrounding the outer surface of the separating layer, and an external electrode active material layer surrounding the outer surface of the external current collector and contacting the separating layer, or
An outer electrode active material layer formed to surround the outer surface of the separating layer and an outer current collector coated in the outer electrode active material layer and surrounding the outer surface of the separating layer so as to be spaced apart from each other, battery. A lithium ion supply core portion including an electrolyte;
An internal electrode including an internal current collector having an open structure formed to surround an outer surface of the lithium ion supply core portion and an internal electrode active material layer formed on an outer surface of the internal current collector;
A separating layer surrounding the outer surface of the inner electrode to prevent short-circuiting of the electrode; And
And an outer electrode surrounding the outer surface of the separating layer and having a porous coating layer including an outer collector, an outer electrode active material layer, and a polymer binder, and extending in the longitudinal direction with a horizontal section. 17. The method of claim 16,
Wherein the external electrode is a cathode,
Wherein the external electrode active material layer is made of a metal (Me), wherein the external electrode active material layer is made of Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Ce, Cu, An alloy composed of the metal (Me); And an oxide of the metal (Me) (MeOx), or a mixture of two or more thereof. The cable-type secondary battery has a horizontal cross section and extends in the longitudinal direction. 17. The method of claim 16,
The outer electrode includes a porous coating layer including a polymer binder formed around the outer surface of the separating layer, an outer electrode active material layer surrounding the outer surface of the porous coating layer, and an outer electrode active material layer surrounding the outer surface of the outer electrode active material layer. Respectively,
An outer electrode active material layer surrounding the outer surface of the outer current collector, and a porous coating layer surrounding the outer surface of the outer electrode active material layer, the porous coating layer including a polymeric binder do or,
An external current collector surrounding the outer surface of the separating layer, an outer electrode active material layer surrounding the outer surface of the outer current collector and contacting the separating layer, and an outer electrode active material layer surrounding the outer surface of the outer electrode active material layer, Or a porous coating layer containing
An outer electrode active material layer formed to surround the outer surface of the separating layer; an outer current collector formed to surround the outer electrode active material layer and surrounding the outer surface of the separating layer, And a porous coating layer including a polymer binder. 17. The method according to claim 12 or claim 16,
Wherein the separating layer is an electrolyte layer or a separator. 20. The method of claim 19,
The electrolyte layer may be a gel-type polymer electrolyte using PEO, PVdF, PVdF-HFP, PMMA, PAN, or PVAC; or
Solid electrolytes using PEO, polypropylene oxide (PPO), polyethylene imine (PEI), polyethylene sulphide (PES) or polyvinyl acetate (PVAc); Wherein the electrolyte is selected from the group consisting of an electrolyte and a non-aqueous electrolyte. 21. The method of claim 20,
Wherein the electrolyte layer further comprises a lithium salt. 22. The method of claim 21,
The lithium salt, 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, lithium lower aliphatic carboxylate and lithium tetraphenylborate. 20. The method of claim 19,
Wherein the separator is a porous substrate made of a polyolefin-based polymer selected from the group consisting of an ethylene homopolymer, a propylene homopolymer, an ethylene-butene copolymer, an ethylene-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, polyphenylsulfite and polyethylene naphthalene; Or a mixture of inorganic particles and a binder polymer. At least two lithium ion supply core parts including an electrolyte;
An internal current collector formed on an outer surface of the internal current collector, and an electrode active material layer formed on an external surface of the internal electrode active material layer and having a porous structure including a polymeric binder, At least two internal electrodes arranged parallel to each other and having a coating layer;
A separating layer surrounding the outer surfaces of the inner electrodes to prevent short-circuiting of the electrodes; And
And an outer electrode surrounding the outer surface of the separating layer and including an outer collector and an outer electrode active material layer. At least two lithium ion supply core parts including an electrolyte;
An inner electrode active material layer formed on an outer surface of the inner current collector, an inner electrode active material layer formed on an outer surface of the inner electrode active material layer, and a porous binder layer formed on an outer surface of the inner electrode active material layer, At least two internal electrodes arranged parallel to each other and having a coating layer and a separating layer for preventing short-circuiting of the electrodes formed around the outer surface of the porous coating layer; And
And an outer electrode formed on the outer surface of the inner electrode, the outer electrode including an outer collector and an outer electrode active material layer. At least two lithium ion supply core parts including an electrolyte;
At least two internal electrodes arranged parallel to each other and having an internal current collector of an open structure formed to surround an outer surface of each of the lithium ion supply core parts and an internal electrode active material layer formed to surround an outer surface of the internal current collector;
A separating layer surrounding the outer surfaces of the inner electrodes to prevent short-circuiting of the electrodes; And
And an outer electrode surrounding the outer surface of the separating layer and including a porous coating layer including an outer collector, an outer electrode active material layer, and a polymer binder, the cable type secondary battery having a horizontal cross- . At least two lithium ion supply core parts including an electrolyte;
An internal current collector having an open structure surrounding the external surface of each of the lithium ion supply core parts, an internal electrode active material layer formed to surround the external surface of the internal current collector, and an electrode formed surrounding the external surface of the internal electrode active material layer, Two or more internal electrodes disposed parallel to each other and having a separation layer for preventing the electrodes from being separated from each other; And
And a porous coating layer formed on the outer surface of the inner electrodes and including an outer collector, an outer electrode active material layer, and a polymeric binder, the outer electrode having a horizontal cross section and a cable- battery.

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