Secondary battery

Abstract

The present invention relates to a secondary battery that undergoes charging and discharging through the oxidation and reduction of metal ions dissolved in an electrolyte. A secondary battery according to an embodiment of the present invention comprises a plurality of layers stacked in one direction, each of the plurality of layers comprising: an anode liquid electrode in which an anode half-reaction occurs; a cathode liquid electrode in which a cathode half-reaction occurs; and a separator disposed between the anode liquid electrode and the cathode liquid electrode and having an ion-selective polymer layer applied to one surface of a porous substrate layer, wherein, in any one of the plurality of layers, the ion-selective polymer layer of the separator is in contact with the cathode liquid electrode and the porous substrate layer of the separator is in contact with the anode liquid electrode.

Description

secondary batteries

[0001] The present invention relates to a secondary battery, and more specifically, to a secondary battery in which metal ions dissolved in an electrolyte are oxidized and reduced to charge and discharge.

[0002] Redox Flow Battery (RFB), unlike conventional secondary batteries, is an electrochemical storage device that stores electrical energy as the chemical energy of the electrolyte by charging and discharging the active material within the electrolyte through oxidation and reduction. Redox flow batteries operate by continuously circulating the electrolyte inside the tank within the stack using a fluid pump, while the actual electrochemical reaction occurs in the stack. While these redox flow batteries have the advantages of long life, high output, and high capacity, they have suffered from space constraints and design difficulties due to the tank that stores the electrolyte and the fluid pump that circulates the electrolyte. Therefore, the inventors of the present invention developed a redox secondary battery that eliminates the electrolyte tank and fluid pump. However, there was a problem that the crossover phenomenon, in which the active materials pass through the separator during charging and discharging, occurred, and the pressure of one electrode increased, causing the separator to deform or break.

[0003] The problem to be solved by the present invention is to provide a secondary battery with high efficiency and performance while applying a separator with increased tensile strength.

[0004] The tasks of the present invention are not limited to the tasks mentioned above, and other tasks not mentioned will be clearly understood by those skilled in the art from the description below.

[0005] In order to achieve the above object, a secondary battery according to an embodiment of the present invention includes a plurality of layers stacked in one direction, each of the plurality of layers including: an anode liquid electrode in which an anode half-reaction occurs; a cathode liquid electrode in which a cathode half-reaction occurs; and a separator disposed between the anode liquid electrode and the cathode liquid electrode and having an ion-selective polymer layer applied to one surface of a porous substrate layer, wherein at least one layer of the plurality of layers is such that the ion-selective polymer layer of the separator is in contact with the cathode liquid electrode and the porous substrate layer of the separator is in contact with the anode liquid electrode.

[0006] In order to achieve the above object, a secondary battery according to an embodiment of the present invention includes a plurality of layers stacked in one direction, each of the plurality of layers including: an anode solid electrode impregnated with an anode liquid electrode in which an anode half-reaction occurs; a cathode solid electrode impregnated with a cathode liquid electrode in which a cathode half-reaction occurs; and a separator disposed between the anode solid electrode and the cathode solid electrode and having an ion-selective polymer layer applied to one surface of a porous substrate layer, wherein at least one layer of the plurality of layers is such that the ion-selective polymer layer of the separator is in contact with the cathode solid electrode and the porous substrate layer of the separator is in contact with the anode solid electrode.

[0007] In order to achieve the above object, a secondary battery according to an embodiment of the present invention includes a plurality of layers stacked in one direction, each of the plurality of layers including: an anode carbon current collector; a cathode carbon current collector spaced apart from the anode carbon current collector; and a separator disposed between the first current collector and the second current collector and having an ion-selective polymer layer applied to one surface of a porous substrate layer, wherein at least one of the plurality of layers is such that the ion-selective polymer layer of the separator is disposed toward the cathode carbon current collector, and the porous substrate layer of the separator is disposed toward the anode carbon current collector.

[0008] In order to achieve the above object, a secondary battery according to an embodiment of the present invention includes a plurality of layers stacked in one direction, each of the plurality of layers including: an anode carbon current collector; a cathode carbon current collector spaced apart from the anode carbon current collector; and a separator disposed between the first current collector and the second current collector and having an ion-selective polymer layer applied to one surface of a porous substrate layer, wherein one of the plurality of layers includes a cathode electrode receiving portion formed by the ion-selective polymer layer and the cathode carbon current collector, and an anode electrode receiving portion formed by the porous substrate layer and the anode carbon current collector.

[0009] Specific details of other embodiments are included in the detailed description and drawings.

[0010] According to the secondary battery of the present invention, one or more of the following effects are present.

[0011] First, there is an advantage in that the tensile strength of the membrane is increased by using a membrane in which an ion-selective polymer layer is applied to one surface of the porous substrate layer.

[0012] Second, there is also the advantage of improving charging performance by using a separator with an ion-selective polymer layer applied to one side of the porous substrate layer.

[0013] Third, there is also the advantage of increasing energy efficiency by cross-arranging membranes with ion-selective polymer layers applied to one side of the porous substrate layer.

[0014] The effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.

[0015] Figure 1 is a perspective view of a secondary battery according to one embodiment of the present invention.

[0016] FIG. 2 is a perspective view of a layer of a secondary battery according to one embodiment of the present invention.

[0017] Figure 3 is an exploded perspective view of a layer of a secondary battery according to one embodiment of the present invention.

[0018] FIG. 4 is a transparent plan view of a frame of a layer according to one embodiment of the present invention.

[0019] Figure 5 is a structural diagram of a layer separation membrane according to one embodiment of the present invention.

[0020] Figure 6 is a 6-6 cross-sectional view of the layer illustrated in Figure 2.

[0021] Figure 7 is a partial cross-sectional view of a secondary battery according to one embodiment of the present invention.

[0022] Figure 8 is a graph showing the charging energy amount of each of a secondary battery (Example 1) according to one embodiment of the present invention and a secondary battery (Comparative Example 1) including a separator composed only of an ion-selective polymer layer.

[0023] Figure 9 is a partial cross-sectional view of a secondary battery according to another embodiment of the present invention.

[0024] The advantages and features of the present invention, and the methods for achieving them, will become clearer with reference to the embodiments described in detail below together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below and may be implemented in various different forms. These embodiments are provided only to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention, and the present invention is defined only by the scope of the claims. Like reference numerals designate like elements throughout the specification.

[0025] Although terms like "first" and "second" are used to describe various components, these components are not limited by these terms. These terms are used merely to distinguish one component from another, and unless otherwise specified, a "first" component may also be a "second" component.

[0026] Throughout the specification, unless otherwise specifically stated, each element may be singular or plural.

[0027] Hereinafter, the phrase "any configuration is placed on (or below)" a component or "on (or below)" a component may mean that any configuration is placed in contact with the upper surface (or lower surface) of said component, and that other configurations may be interposed between said component and any configuration placed on (or below) said component.

[0028] Additionally, when it is described that a component is "connected," "coupled," or "connected" to another component, it should be understood that the components may be directly connected or connected to one another, but that other components may also be "interposed" between the components, or that each component may be "connected," "coupled," or "connected" through another component.

[0029] As used herein, singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, terms such as "consisting of" or "comprising" should not necessarily be construed to include all of the components or steps described in the specification, and should be construed to mean that some of the components or steps may not be included, or that additional components or steps may be included.

[0030] Throughout the specification, when we refer to "A and / or B", this means A, B, or A and B, unless otherwise stated, and when we refer to "C to D", this means C or more and D or less, unless otherwise stated.

[0031] Hereinafter, the present invention will be described with reference to drawings for explaining a secondary battery according to embodiments of the present invention.

[0032] Figure 1 is a perspective view of a secondary battery according to one embodiment of the present invention.

[0033] A secondary battery according to one embodiment of the present invention includes a plurality of layers (100) in which each redox reaction occurs and which are stacked in one direction.

[0034] The layer (100) accumulates or releases electrical energy through a redox reaction of a redox couple dissolved in an electrolyte. The layer (100) has a short rectangular parallelepiped shape. A plurality of layers (100) are stacked in the height direction. It is preferable that the plurality of layers (100) stacked in the height direction have a tall rectangular parallelepiped shape.

[0035] A pair of end plates (not shown) may be arranged at both ends of the stacking direction (height direction) of the stacked plurality of layers (100). A pair of bus bars (not shown) that electrically connect the plurality of layers (100) in parallel may be arranged on the stacked plurality of layers (100).

[0036] FIG. 2 is a perspective view of a layer of a secondary battery according to an embodiment of the present invention, FIG. 3 is an exploded perspective view of a layer of a secondary battery according to an embodiment of the present invention, FIG. 4 is a transparent plan view of a frame of a layer according to an embodiment of the present invention, FIG. 5 is a structural diagram of a separator of a layer according to an embodiment of the present invention, and FIG. 6 is a 6-6 cross-sectional view of the layer illustrated in FIG. 2.

[0037] A layer (100) according to one embodiment of the present invention comprises: a hollow frame (110) forming an anode liquid electrode in which an anode redox couple is dissolved, a cathode liquid electrode in which a cathode redox couple is dissolved, an anode electrode receiving portion (111a) which is a space in which the anode liquid electrode is stored, and a cathode electrode receiving portion (111b) which is a space in which the cathode liquid electrode is stored; a separator (120) which is coupled to the frame (110) and is arranged between the anode electrode receiving portion (111a) and the cathode electrode receiving portion (111b); an anode solid electrode (150a) which is arranged in the anode electrode receiving portion (111a) and impregnated with the anode liquid electrode; a cathode solid electrode (150b) which is arranged in the cathode electrode receiving portion (111b) and impregnated with the cathode liquid electrode; An anode carbon collector (130a) disposed on one side of a frame (110) and electrically connected to an anode liquid electrode, a cathode carbon collector (130b) disposed on the other side of the frame (110) and electrically connected to a cathode liquid electrode, an anode adhesive member (160a) connecting the anode carbon collector (130a) and the frame (110), a cathode adhesive member (160b) connecting the cathode carbon collector (130b) and the frame (110), an anode metal collector (140a) that contacts the anode carbon collector (130a) to transfer electrons from the outside to the anode liquid electrode or to emit electrons from the anode liquid electrode, and a cathode that contacts the cathode carbon collector (130b) to transfer electrons from the outside to the cathode liquid electrode or to emit electrons from the cathode liquid electrode. Includes a metal collector (140b).

[0038] The anode liquid electrode is an electrolyte in which an anode redox couple is dissolved. The anode redox couple can be implemented with a material including at least one of vanadium (V), zinc (Zn), bromine (Br), chromium (Cr), manganese (Mn), titanium (Ti), iron (Fe), cerium (Ce), and cobalt (Co), and in this embodiment, V 2+ / V 3+It is a redox couple. The anode liquid electrode may be an acidic aqueous solution that conducts current through ionization, preferably containing sulfuric acid. In the present embodiment, the anode liquid electrode may be manufactured by dissolving VOSO4 (vanadylsulfate) or V2O5 (vanadium pentoxide) in an H2SO4 aqueous solution.

[0039] The anode liquid electrode causes the anode half-reaction. The anode half-reaction is as follows, where → indicates the direction of the discharge reaction and ← indicates the direction of the charge reaction.

[0040] V 2+ ←→ V 3+ + e -

[0041] During discharge, vanadium 2 ions are oxidized to vanadium 3 ions, and during charge, vanadium 3 ions are reduced to vanadium 2 ions.

[0042] The anode liquid electrode is surrounded by a frame (110), an anode carbon current collector (130a), and a separator (120). The anode liquid electrode is prevented from flowing out in an in-plane direction between the anode carbon current collector (130a) and the frame (110) by the anode adhesive member (160a). Hereinafter, the in-plane direction means a direction parallel to a plane formed by the separator (120). In addition, the out-of-plane direction means a direction penetrating the in-plane direction (a direction parallel to a plane formed by the separator (120), and includes the through-thickness direction of the frame (110), but does not mean only a direction perpendicular to the in-plane direction. The anode liquid electrode is accommodated in the anode electrode receiving portion (111a). It is preferable that the anode liquid electrode is impregnated in the anode solid electrode (150a).

[0043] The anode liquid electrode is electrically connected to the anode carbon collector (130a), so that when discharging, electrons move to the anode carbon collector (130a), and when charging, electrons of the anode carbon collector (130a) move to the anode liquid electrode. The anode liquid electrode is in contact with the separator (120), so that hydrogen cations (protons) move through the separator (120).

[0044] The cathode liquid electrode is an electrolyte in which a cathode redox couple is dissolved. The cathode redox couple can be implemented with a material including at least one of vanadium (V), zinc (Zn), bromine (Br), chromium (Cr), manganese (Mn), titanium (Ti), iron (Fe), cerium (Ce), and cobalt (Co), and in this embodiment, V 4+ / V 5+ It is a redox couple. The cathode liquid electrode may be an acidic aqueous solution that conducts current through ionization, preferably containing sulfuric acid. In the present embodiment, the cathode liquid electrode may be prepared by dissolving VOSO4 (vanadylsulfate) or V2O5 (vanadium pentoxide) in an H2SO4 aqueous solution.

[0045] The cathode liquid electrode causes the cathode half-reaction. The cathode half-reaction is as follows, where → indicates the direction of the discharge reaction and ← indicates the direction of the charge reaction.

[0046] V 5+ + e- ←→ V 4+

[0047] During discharge, vanadium pentavalent ions are reduced to vanadium tetravalent ions, and during charge, vanadium tetravalent ions are oxidized to vanadium pentavalent ions.

[0048] The cathode liquid electrode is provided surrounded by a frame (110), a cathode carbon collector (130b), and a separator (120). The cathode liquid electrode is prevented from flowing out in an in-plane direction, etc., between the cathode carbon collector (130b) and the frame (110) by a cathode adhesive member. The cathode liquid electrode is accommodated in a cathode electrode receiving portion (111b). It is preferable that the cathode liquid electrode is impregnated in the cathode solid electrode (150b).

[0049] The cathode liquid electrode is electrically connected to the cathode carbon collector (130b), so that when charging, electrons move to the cathode carbon collector (130b), and when discharging, electrons from the cathode carbon collector (130b) move to the cathode liquid electrode. The cathode liquid electrode is in contact with the separator (120), so that hydrogen cations (protons) move through the separator (120).

[0050] As previously discussed, the anode liquid electrode and cathode liquid electrode contain redox couples (vanadium ions) of different valences in an electrolyte of the same composition. Hereinafter, the anode liquid electrode and cathode liquid electrode are collectively referred to as the liquid electrode.

[0051] The anode electrode receiving portion (111a) is a space where the anode solid electrode (150a) and the anode liquid electrode are received, and is formed by the anode carbon current collector (130a), the frame (110), and the separator (120).

[0052] The cathode electrode receiving portion (111b) is a space where the cathode solid electrode (150b) and the cathode liquid electrode are received, and is formed by a cathode carbon collector (130b), a frame (110), and a separator (120).

[0053] The anode carbon current collector (130a) is arranged on one side of the frame (110) to form an anode electrode receiving portion (111a) together with the frame (110) and the separator (120). The anode carbon current collector (130a) is arranged parallel to and spaced apart from the cathode carbon current collector (130b). The anode carbon current collector (130a) is bonded to the frame (110) by an anode adhesive member (160a). The anode carbon current collector (130a) is electrically connected to the anode liquid electrode, and electrons move to cause current to flow during charging and discharging.

[0054] The anode carbon current collector (130a) is formed of a material such as graphite, carbon, carbon plastic, etc., and has high electrical conductivity and high acid resistance. The anode carbon current collector (130a) is placed between the anode liquid electrode and the anode metal current collector (140a) to allow electrons to move between each other, but prevent the anode metal current collector (140a) from being oxidized. The anode carbon current collector (130a) may be formed in a rectangular plate shape or may be formed by being applied to the anode metal current collector (140a).

[0055] When a plurality of layers (100) are stacked to form a secondary battery (200) as shown in Fig. 1, two anode carbon collectors (130a) of two adjacent layers (100) are arranged to face each other, and one anode metal collector (140a) is arranged between the two anode carbon collectors (130a).

[0056] The cathode carbon collector (130b) is disposed on the other side of the frame (110) (the opposite side of the side where the anode carbon collector (130a) is disposed) to form a cathode electrode receiving portion (111b) together with the frame (110) and the separator (120). The cathode carbon collector (130b) is disposed parallel to and spaced apart from the anode carbon collector (130a). The cathode carbon collector (130b) is bonded to the frame (110) by a cathode adhesive member (160b). The cathode carbon collector (130b) is electrically connected to the cathode liquid electrode, and electrons move to cause current to flow during charging and discharging.

[0057] The cathode carbon current collector (130b) is formed of a material such as graphite, carbon, or carbon plastic, and has high electrical conductivity and high acid resistance. The cathode carbon current collector (130b) is placed between the cathode liquid electrode and the cathode metal current collector (140b) to allow electrons to move between each other, but prevent the cathode metal current collector (140b) from being oxidized. The cathode carbon current collector (130b) may be formed in a rectangular plate shape or may be formed by being applied to the cathode metal current collector (140b).

[0058] When a plurality of layers (100) are stacked to form a secondary battery (200) as shown in Fig. 1, two cathode carbon collectors (130b) of two adjacent layers (100) are arranged to face each other, and one cathode metal collector (140b) is arranged between the two cathode carbon collectors (130b).

[0059] The anode metal collector (140a) is formed of a metal with high electrical conductivity, such as copper or aluminum. The anode metal collector (140a) is formed in a rectangular plate shape, with a portion protruding so that it can be connected to a bus bar.

[0060] The anode metal current collector (140a) may be formed as a flexible thin film or a rigid plate. An anode carbon current collector (130a) is disposed on one surface of the anode metal current collector (140a). When a plurality of layers (100) are laminated to form a secondary battery (200) as shown in Fig. 1, an anode carbon current collector (130a) is disposed on both surfaces of the anode metal current collector (140a).

[0061] The cathode metal current collector (140b) is formed of a metal with high electrical conductivity, such as copper or aluminum. The cathode metal current collector (140b) is formed in a rectangular plate shape, with a portion protruding so that it can be connected to a bus bar.

[0062] The cathode metal current collector (140b) may be formed as a flexible thin film or a rigid plate. A cathode carbon current collector (130b) is disposed on one surface of the cathode metal current collector (140b). When a plurality of layers (100) are laminated to form a secondary battery (200) as shown in Fig. 1, cathode carbon current collectors (130b) are disposed on both surfaces of the cathode metal current collector (140b).

[0063] The anode solid electrode (150a) is impregnated with an anode liquid electrode and placed in an anode electrode receiving portion (111a). The anode solid electrode (150a) is placed surrounded by a frame (110), an anode carbon current collector (130a), and a separator (120). The anode solid electrode (150a) includes carbon-based materials such as carbon or graphite felt, carbon cloth, carbon black, graphite powder, or graphene.

[0064] The anode solid electrode (150a) may be formed in a porous hexahedral shape. Before being accommodated in the anode electrode receiving portion (111a), the anode solid electrode (150a) may have a thickness greater than the thickness in the out-of-plane direction of the anode electrode receiving portion (111a). In this case, the anode solid electrode (150a) may be accommodated by being pressed into the anode electrode receiving portion (111a). The anode solid electrode (150a) is in close contact with the anode carbon current collector (130a) and the separator (120).

[0065] The cathode solid electrode (150b) is impregnated with a cathode liquid electrode and is placed in a cathode electrode receiving portion (111b). The cathode solid electrode (150b) is placed surrounded by a frame (110), a cathode carbon current collector (130b), and a separator (120). The cathode solid electrode (150b) includes carbon-based materials such as carbon or graphite felt, carbon cloth, carbon black, graphite powder, or graphene.

[0066] The cathode solid electrode (150b) may be formed in a porous hexahedral shape. Before being accommodated in the cathode electrode receiving portion (111b), the cathode solid electrode (150b) may have a thickness greater than the thickness in the out-of-plane direction of the cathode electrode receiving portion (111b). In this case, the cathode solid electrode (150b) may be accommodated by being pressed into the cathode electrode receiving portion (111b). The cathode solid electrode (150b) is in close contact with the cathode carbon current collector (130b) and the separator (120).

[0067] Each of the anode adhesive member (160a) and the cathode adhesive member (160b) includes at least one of an acrylate adhesive, an acrylate-ester adhesive, an acrylate-ethylene adhesive, a polycarbonate adhesive, a polyethylene adhesive, an epoxy adhesive, and an isocyanate adhesive. Each of the anode adhesive member (160a) and the cathode adhesive member (160b) is one or a combination of a solvent-based adhesive, an emulsion-based adhesive, a hot melt-based adhesive, a liquid-curable adhesive, and a film-based adhesive.

[0068] The anode adhesive member (160a) connects the anode carbon collector (130a) and the frame (110) and seals the space between the anode carbon collector (130a) and the frame (110). The anode adhesive member (160a) is laminated between the anode carbon collector (130a) and the frame (110). The anode adhesive member (160a) is adhered to one edge of the frame (110) in the out-of-plane direction. The anode adhesive member (160a) can be applied to the anode carbon collector (130a) and adhered to the frame (110).

[0069] The cathode adhesive member (160b) connects the cathode carbon collector (130b) and the frame (110) and seals the space between the cathode carbon collector (130b) and the frame (110). The cathode adhesive member (160b) is laminated between the cathode carbon collector (130b) and the frame (110). The cathode adhesive member (160b) is adhered to the other edge of the frame (110) in the out-of-plane direction. The cathode adhesive member (160b) can be applied to the cathode carbon collector (130b) and adhered to the frame (110).

[0070] The frame (110) is formed in a hollow square shape. Depending on the embodiment, the frame (110) may be formed in a rhombus, circle, triangle, or polygon larger than a pentagon. The frame (110) has a predetermined thickness in the out-of-plane direction to form an anode electrode receiving portion (111a) and a cathode electrode receiving portion (111b).

[0071] The frame (110) has an anode carbon collector (130a) arranged on one side in the out-of-plane direction and a cathode carbon collector (130b) arranged on the other side. The hollow portion of the frame (110) is closed by the anode carbon collector (130a) and the cathode carbon collector (130b). It is preferable that the frame (110) be arranged between the anode carbon collector (130a) and the cathode carbon collector (130b) to prevent the anode liquid electrode and the cathode liquid electrode from leaking in the in-plane direction, etc. The frame (110) is coupled to the anode carbon collector (130a) by the anode adhesive member (160a) and is coupled to the cathode carbon collector (130b) by the cathode adhesive member (160b).

[0072] A separator (120) is placed in the hollow space of the frame (110). The hollow space of the frame (110) is divided into two spaces by the separator (120). The frame (110) can be bonded to the separator (120) using an adhesive having the same composition as the anode adhesive member (160a) or the cathode adhesive member (160b).

[0073] The frame (110) forms an anode electrode receiving portion (111a) between the anode carbon current collector (130a) and the separator (120), and forms a cathode electrode receiving portion (111b) between the cathode carbon current collector (130b) and the separator (120).

[0074] The frame (110) accommodates an anode liquid electrode and a cathode liquid electrode. An anode solid electrode (150a) and a cathode solid electrode (150b) are arranged inside the frame (110). An anode adhesive member (160a) is adhered to one edge in the out-of-plane direction of the frame (110), and a cathode adhesive member (160b) is adhered to the other edge in the out-of-plane direction.

[0075] Referring to FIG. 4, a frame (110) according to one embodiment of the present invention includes a hollow rectangular frame body (119), a hollow membrane support member (115) that protrudes inward from the hollow portion of the frame body (119) and is combined with a membrane (120), a frame reinforcement member (116) that is arranged in the hollow portion of the membrane support member (115) to prevent the frame body (119) and / or the membrane support member (115) from being deformed, an electrode connection member (112) that connects an anode electrode receiving member (111a) and a cathode electrode receiving member (111b), and an injection member (114) that is formed in the frame (110) and into which an anode liquid electrode and / or a cathode liquid electrode are injected.

[0076] The frame body (119) is formed in a hollow rectangular shape consisting of four sides. The hollow portion of the frame body (119) forms an anode electrode receiving portion (111a) and a cathode electrode receiving portion (111b). The frame body (119) is formed with a separator support portion (115) that protrudes in the plane direction in the hollow portion. An electrode connection portion (112) is formed in the frame body (119).

[0077] The frame body (119) has an anode adhesive member (160a) adhered to one side in the out-of-plane direction and a cathode adhesive member (160b) adhered to the other side in the out-of-plane direction. The frame body (119) has one side in the out-of-plane direction bonded to an anode carbon current collector (130a) by the anode adhesive member (160a) and the other side in the out-of-plane direction bonded to a cathode carbon current collector (130b) by the cathode adhesive member (160b).

[0078] The membrane support (115) is formed in a rectangular shape by protruding toward the center in the plane direction from the hollow portion of the frame body (119). Referring to Fig. 6, the membrane support (115) is positioned at the center in the thickness direction of the frame body (119).

[0079] The membrane support (115) has a predetermined thickness capable of supporting the membrane (120). The membrane support (115) serves as a rib that reinforces the in-plane direction of the frame body (119), so that the frame body (119) is not deformed in the in-plane direction, etc. even when the anode liquid electrode or cathode liquid electrode expands or contracts, gas is generated within the liquid electrode, or an external impact occurs.

[0080] To prevent the anode liquid electrode or cathode liquid electrode from leaking between the membrane support (115) and the membrane (120), one side of the membrane support (115) is completely bonded to the membrane (120). The membrane support (115) can be bonded to the porous substrate layer (121) or the ion-selective polymer layer (122) of the membrane (120), and in the present embodiment, it is bonded to the porous substrate layer (121).

[0081] An adhesive that binds the membrane support (115) and the membrane (120) (porous substrate layer (121) or ion-selective polymer layer (122)) may be laminated between the membrane support (115) and the membrane (120) (porous substrate layer (121) or ion-selective polymer layer (122)). The membrane support (115) and the membrane (120) (porous substrate layer (121) or ion-selective polymer layer (122)) may be bonded by an adhesive that includes at least one of an acrylate-based adhesive, an acrylate-ester-based adhesive, an acrylate-ethylene-based adhesive, a polycarbonate-based adhesive, a polyethylene-based adhesive, an epoxy-based adhesive, and an isocyanate-based adhesive.

[0082] The frame reinforcement member (116) is formed to connect one side of the membrane support member (115) (or the frame body (119)) to the other side or to connect one vertex to the other vertex. The frame reinforcement member (116) connects at least two sides or two vertices across the hollow portion to prevent the rectangular frame body (119) and the membrane support member (115) from being deformed into a diamond or circle. In the present embodiment, the frame reinforcement member (116) is formed in a + shape to connect two opposing sides of the membrane support member (115). The frame reinforcement member (116) has a predetermined thickness, and preferably, it is the same thickness as the membrane support member (115).

[0083] The frame reinforcement (116) can be in contact with the porous substrate layer (121) or the ion-selective polymer layer (122) of the separator (120), and in this embodiment, it is in contact with the porous substrate layer (121).

[0084] The electrode connection portion (112) is where the anode liquid electrode and / or the cathode liquid electrode flows. The separator (120) must prevent the anode liquid electrode and the cathode liquid electrode from mixing with each other. However, a crossover phenomenon may occur in which vanadium ions and water contained in the anode liquid electrode and the cathode liquid electrode pass through the separator (120) during charging or discharging. Accordingly, an imbalance occurs in the amount of the anode liquid electrode and the amount of the cathode liquid electrode, which affects the performance and lifespan of the secondary battery. In the case of a conventional redox flow secondary battery having a liquid electrode tank and a pump, the imbalance of the liquid electrodes within the stack can be resolved. However, in the case of the present invention, where the liquid electrode exists only within the layer (100), even a small imbalance affects the performance and lifespan of the secondary battery. The electrode connection (112) resolves the imbalance caused by this crossover, and the anode liquid electrode or cathode liquid electrode with increased volume is temporarily stored in the electrode connection (112) or moves to the cathode liquid electrode or anode liquid electrode with reduced volume through the electrode connection (112).

[0085] The electrode connection part (112) connects the anode electrode receiving part (111a) and the cathode electrode receiving part (111b) so that the imbalance between the amount of the anode liquid electrode and the amount of the cathode liquid electrode due to crossover occurring during charging or discharging is resolved, and the anode liquid electrode or cathode liquid electrode flows inside during charging or discharging.

[0086] The electrode-to-electrode connection portion (112) is formed in a direction (out-of-plane direction (thickness direction) of the frame (110)) that penetrates at least a portion of the plane formed by the separator (120). The electrode-to-electrode connection portion (112) can be bent at least twice. The electrode-to-electrode connection portion (112) is bent from the in-plane direction of the frame (110) to the out-of-plane direction (or from the out-of-plane direction to the in-plane direction), and is bent from the in-plane direction of the frame (110) to the in-plane direction.

[0087] The electrode connection portion (112) is formed on a part of the frame body (119) surrounding the anode solid electrode (150a) or the cathode solid electrode (150b) and is arranged on a part of the periphery of the anode solid electrode (150a) or the cathode solid electrode (150b).

[0088] The electrode connection portion (112) is positioned on the outer side in the in-plane direction relative to the separator support portion (115). The electrode connection portion (112) is positioned on the inner side in the in-plane direction relative to the anode adhesive member (160a) or the cathode adhesive member (160b). The electrode connection portion (112) is covered with the anode adhesive member (160a) or the cathode adhesive member (160b).

[0089] In this embodiment, the electrode connection portion (112) is described as being formed in the frame body (119) of the frame (11), but depending on the embodiment, the electrode connection portion (112) may be formed in the separator (120), the separator support portion (115), or the frame reinforcement portion (116).

[0090] The injection part (114) is formed in the frame (110) so that a liquid electrode is injected from the outside and flows into the anode electrode receiving part (111a) and the cathode electrode receiving part (111b). One end of the injection part (114) is opened to the outside in the frame (110), and the other end is connected to the electrode connection part (112). The injection part (114) is formed so that the anode liquid electrode is injected into the anode electrode receiving part (111a) and the cathode liquid electrode is injected into the cathode electrode receiving part (111b). When the liquid electrode is injected from the outside through the injection part (114), it is received into the anode electrode receiving part (111a) and the cathode electrode receiving part (111b) through the electrode connection part (112). The liquid electrode injected into the anode electrode receiving portion (111a) through the injection portion (114) becomes the anode liquid electrode, and the liquid electrode injected into the cathode electrode receiving portion (111b) through the injection portion (114) becomes the cathode liquid electrode. The injection portion (114) is closed after the anode liquid electrode and / or the cathode liquid electrode are injected.

[0091] A separator (120) is arranged inside the frame (110) to separate the anode liquid electrode and the cathode liquid electrode and to allow hydrogen cations (protons) to move between the anode liquid electrode and the cathode liquid electrode. The separator (120) divides the hollow space of the frame (110) in the thickness direction to separate the anode electrode receiving portion (111a) and the cathode electrode receiving portion (111b).

[0092] The separator (120) is placed between the anode carbon collector (130a) and the cathode carbon collector (130b).

[0093] Hydrogen cations move from the anode liquid electrode to the cathode liquid electrode through the separator (120) during discharge, and move from the cathode liquid electrode to the anode liquid electrode through the separator (120) during charge.

[0094] The separator (120) is joined at its edge to the separator support (115) so as to be stretched out tautly. Referring to FIG. 6, the separator (120) is preferably joined to the cathode electrode receiving portion (111b) side of the separator support (115). In addition, the separator (120) is preferably in contact with the cathode electrode receiving portion (111b) side of the frame reinforcement portion (116). That is, in the present embodiment, the separator (120) is not arranged in the center of the thickness direction of the frame (110), but is arranged offset toward the cathode electrode receiving portion (11b) in the thickness direction of the frame (110).

[0095] Referring to Fig. 5, the separation membrane (120) is formed by applying an ion-selective polymer layer (122) to one surface of a porous substrate layer (121). The porous substrate layer (121) and the ion-selective polymer layer (122) are not clearly divided into two layers, and a layer in which the ion-selective polymer layer (122) is impregnated into the porous substrate layer (121) may exist in the intervening portion.

[0096] The ion-selective polymer layer (122) is preferably a polybenzimidazole-based (polybenzimidazole (PBI)-based) polymer having excellent ion selectivity and excellent impregnation and coating properties for a polyolefin-based polymer substrate, for example, ab-PBI (Poly(2,5-benzimidazole)), O-PBI (Poly[2,2'-(4,4'-oxybis(1,4-phenylene))-5,5'-bibenzimidazole), m-PBI (meta-polybenzimidazole), p-PBI (para-polybenzimidazole), s-PBI (sulfonated polybenzimidazole), f-PBI (fluorine-containing polybenzimidazole), 2OH-PBI (Dihydroxy polybenzimidazole), PIPBI (Phenylindane-polybenzimidazole), It may be one or more mixtures or copolymers selected from the group including, but not necessarily limited to, PBI-OO(poly[(1-(4,4'-diphenylether)-5-oxybenzimidazole)-benzimidazole]), Py-PBI(poly[2,2'-(2,6-pyridine)-5,5'-bibenzimidazole]), biphenyl-PBI(biphenyl-linked polybenzimidazole), terphenyl-PBI(terphenyl-linked polybenzimidazole), and HMT-PBI(poly[2,2'-(2,2'',4,4'',6,6''-hexamethyl-p-terphenyl-3,3''-diyl)-5,5'-bibenzimidazole]).

[0097] The porous substrate layer (121) is preferably a material that exhibits high tensile strength (e.g., 100 MPa or more) even with a thin thickness and has excellent impregnation and coating properties of a polybenzimidazole-based polymer. The porous substrate layer (121) is preferably a polyolefin-based polymer substrate such as polyethylene (PE) or polypropylene (PP), and according to an embodiment, may be a fluorine-based resin such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), or polychlorotrifluoroethylene (PCTFE), or a copolymer or mixture of any one or two or more of polysulfone (PSf), polyethersulfone (PES), polyimide (PI), or polyetherimide (PEI). The thickness of the porous substrate layer (121) may be, for example, 5 to 500 μm, preferably 20 to 80 μm, but is not necessarily limited thereto.

[0098] In this embodiment, the separation membrane (120) is formed by dissolving an ion-selective polymer in an organic solvent, applying (or impregnating) the dissolved solution to one surface of a porous substrate layer (121), and then drying at room temperature to form a coating film. Depending on the embodiment, the coating film may be formed by drying at a temperature higher than room temperature, such as 50 to 80°C. The organic solvent may be a polar solvent, such as NMP (N-methyl-2-pyrrolidone) or N,N-dimethylacetamide (DMAc).

[0099] Referring to FIG. 6, a separator (120) composed of two layers of an ion-selective polymer layer (122) and a porous substrate layer (121) is disposed between an anode liquid electrode and a cathode liquid electrode (between an anode solid electrode (150a) and a cathode solid electrode (150b)), so that one of the ion-selective polymer layer (122) and the porous substrate layer (121) forms an anode electrode receiving portion (111a) and is in contact with the anode liquid electrode and the anode solid electrode (150a), and the other forms a cathode electrode receiving portion (111b) and is in contact with the cathode liquid electrode and the cathode solid electrode (150b).

[0100] The arrangement direction of the ion-selective polymer layer (122) and the porous substrate layer (121) can determine the characteristics of the secondary battery, and the arrangement direction will be described later with reference to FIGS. 7 and 8.

[0101] In the present embodiment, among the plurality of layers (100) of the secondary battery (200), one layer (100) has an ion-selective polymer layer (122) of a separator (120) in contact with the cathode liquid electrode, and a porous substrate layer (121) of the separator (120) in contact with the anode liquid electrode. The porous substrate layer (121) of the separator (120) is in contact with the anode solid electrode (150a), and the ion-selective polymer layer (122) of the separator (120) is in contact with the cathode solid electrode (150b). The porous substrate layer (121) of the separator (120) is arranged toward the anode carbon current collector (130a), and the ion-selective polymer layer (122) of the separator (120) is arranged toward the cathode carbon current collector (130b). The porous substrate layer (121) of the separator (120) forms an anode electrode receiving portion (111a) together with the frame (110) and the anode carbon collector (130a), and the ion-selective polymer layer (122) of the separator (120) forms a cathode electrode receiving portion (111b) together with the frame (110) and the cathode carbon collector (130b).

[0102] It is preferable that the porous substrate layer (121) of the separator (120) is connected at the edge with the separator support member (115). It is preferable that the porous substrate layer (121) of the separator (120) is in contact with the frame reinforcement member (116).

[0103] According to an embodiment, the arrangement direction of the separator (120) of all of the plurality of layers (100) may be such that the ion-selective polymer layer (122) is in contact with the cathode liquid electrode (cathode solid electrode (150b)) and the porous substrate layer (121) is in contact with the anode liquid electrode (anode solid electrode (150a)), as shown in FIG. 6. In this case, all of the separator support parts (115) of the plurality of layers (100) are combined with the porous substrate layer (121). In addition, all of the frame reinforcement parts (116) of the plurality of layers (100) may be in contact with the porous substrate layer (121).

[0104] In addition, according to an embodiment, the arrangement direction of the separation membrane (120) of some of the plurality of layers (100) may be such that the ion-selective polymer layer (122) is in contact with the anode liquid electrode (anode solid electrode (150a)) and the porous substrate layer (121) is in contact with the cathode liquid electrode (cathode solid electrode (150b)). In this case, the separation membrane support (115) of some of the layers (100) among the plurality of layers (100) is bonded to the porous substrate layer (121), and the rest are bonded to the ion-selective polymer layer (122). In addition, the frame reinforcement (116) of some of the layers (100) among the plurality of layers (100) may be in contact with the porous substrate layer (121), and the rest may be in contact with the ion-selective polymer layer (122).

[0105] FIG. 7 is a partial cross-sectional view of a secondary battery according to one embodiment of the present invention, and FIG. 8 is a graph showing the charging energy amounts of each of a secondary battery (Example 1) according to one embodiment of the present invention and a secondary battery (Comparative Example 1) including a separator composed only of an ion-selective polymer layer.

[0106] In a secondary battery (200) according to one embodiment of the present invention, all of the plurality of layers (100) may have the arrangement direction of the separator (120) as shown in FIG. 6. That is, in all of the plurality of layers (100), the ion-selective polymer layer (122) of the separator (120) is in contact with the cathode liquid electrode (cathode solid electrode (150b)), and the porous substrate layer (121) of the separator (120) is in contact with the anode liquid electrode (cathode solid electrode (150b)). In this case, the separator support portion (115) of all of the plurality of layers (100) may be combined with the porous substrate layer (121), and the frame reinforcement portion (116) of all of the plurality of layers (100) may be in contact with the porous substrate layer (121). According to an embodiment, the ion-selective polymer layer (122) of some layers (100) among the plurality of layers (100) may be combined with the porous substrate layer (121) and may be in contact with the frame reinforcement (116).

[0107] In FIG. 8, Example 1 is a case where all separators (120) of a secondary battery (200) are composed of a porous substrate layer (121) and an ion-selective polymer layer (122), and the ion-selective polymer layer (122) is in contact with a cathode liquid electrode, and Comparative Example 1 is a case where all separators of a secondary battery are composed only of an ion-selective polymer.

[0108] As confirmed in Fig. 8, the secondary battery including the asymmetric separator according to Example 1 exhibited a higher charging energy amount in all ranges compared to the secondary battery including the polyimidazole separator according to Comparative Example 1. In particular, it was confirmed that the difference in the charging energy amount between Example 1 and Comparative Example 1 increased as the C-rate increased.

[0109] Here, C-rate stands for Current Rate, and it represents the speed at which a battery is charged, discharged, or both. This is also called the "charge / discharge rate," and its unit is "C," which stands for Capacity. C-rate is calculated by dividing the charge / discharge current (A) by the battery's rated capacity (Ah). The standard value is 1.0C, and it can be calculated as follows.

[0110] C-rate = charge / discharge current (A) / rated capacity of battery (Ah)

[0111] An increase in C-rate means that the charging current increases, which means that the charging conditions are harsh, and yet Example 1 showed a result in which the loss (decrease) of the charging energy amount was significantly less than that of Comparative Example 1.

[0112] Therefore, it was confirmed that the secondary battery of Example 1 had an overall improved charging performance compared to the secondary battery of Comparative Example 1, and it was confirmed that it could be usefully used, especially under conditions of high C-rate, i.e., rapid charging.

[0113] Figure 9 is a partial cross-sectional view of a secondary battery according to another embodiment of the present invention.

[0114] In a secondary battery (200) according to another embodiment of the present invention, the arrangement direction of the separator (120) of some layers among a plurality of layers (100) may be different from the arrangement direction of the separator (120) of the remaining layers (100).

[0115] That is, some of the plurality of layers (100) have the ion-selective polymer layer (122) of the separator (120) in contact with the cathode liquid electrode (cathode solid electrode (150b)) and the porous substrate layer (121) of the separator (120) in contact with the anode liquid electrode (anode solid electrode (150a)), and the remainder of the plurality of layers (100) have the ion-selective polymer layer (122) of the separator (120) in contact with the anode liquid electrode (anode solid electrode (150a)) and the porous substrate layer (121) of the separator (120) in contact with the cathode liquid electrode (cathode solid electrode (150b)). In this case, some of the plurality of layers (100) may have the membrane support (115) bonded to the porous substrate layer (121), and the remainder of the plurality of layers (100) may have the membrane support (115) bonded to the ion-selective polymer layer (122). In addition, some of the plurality of layers (100) may have the frame reinforcement (116) in contact with the porous substrate layer (121), and the remainder of the plurality of layers (100) may have the frame reinforcement (116) in contact with the ion-selective polymer layer (122).

[0116] In Table 1 below, Example 1 is a case where all ion-selective polymer layers (122) of a secondary battery (200) are in contact with the cathode liquid electrode, as shown in FIG. 7, Example 2 is a case where the layer (100) in which the ion-selective polymer layer (122) is in contact with the cathode liquid electrode and the layer (100) in which the ion-selective polymer layer (122) is in contact with the anode liquid electrode are arranged in an alternating manner, as shown in FIG. 9, and Comparative Example 2 is a case where all ion-selective polymer layers (122) of a secondary battery (200) are in contact with the anode liquid electrode.

[0117] Example 0.2C0.5C1.0CC-rate star energy efficiency (%) Example 195.3692.0884.12 Example 297.3293.6988.39 Comparative example 296.4892.7187.92 C-rate star charge energy (Wh) Example 14.084.063.87 Example 24.044.023.65 Comparative example 23.943.773.04 C-rate star discharge energy (Wh) Example 13.893.743.26 Example 23.953.763.16 Comparative example 23.793.512.68

[0118] In the case of Example 1, the charging energy is the highest, but the energy efficiency is low. In the case of Example 2, the energy efficiency is high, and the discharge energy is high. In the case of Comparative Example 2, both the charging energy and the discharge energy are low. Therefore, when high charging performance is required, it is preferable to configure all ion-selective polymer layers (122) to be in contact with the cathode liquid electrode, as in Example 1 (Fig. 7). In addition, when high energy efficiency is required, it is preferable to arrange the layer (100) in which the ion-selective polymer layer (122) is in contact with the cathode liquid electrode and the layer (100) in which the ion-selective polymer layer (122) is in contact with the anode liquid electrode in an alternating manner, as in Example 2 (Fig. 9). In the case of Example 2, the discharge energy is high at 0.2 C-rate and 0.5 C-rate, and the charging energy is not much different from that of Example 1, so that it can be used in relatively general charge / discharge situations that do not require high output or high input.

[0119] As in another embodiment of the present invention, it is preferable that the layer (100) in which the ion-selective polymer layer (122) is in contact with the cathode liquid electrode (cathode solid electrode (150b)) and the layer (100) in which the ion-selective polymer layer (122) is in contact with the anode liquid electrode (anode solid electrode (150a)) are arranged in an alternating manner. However, regardless of the arrangement of the layers (100), if the ratio of the layer (100) in which the ion-selective polymer layer (122) is in contact with the cathode liquid electrode (cathode solid electrode (150b)) and the layer (100) in which the ion-selective polymer layer (122) is in contact with the anode liquid electrode (anode solid electrode (150a)) is 4:6 to 6:4, excellent results in energy efficiency and discharge characteristics can be obtained.

[0120] Although the preferred embodiments of the present invention have been illustrated and described above, the present invention is not limited to the specific embodiments described above, and various modifications may be made by a person skilled in the art without departing from the gist of the present invention as claimed in the claims. Furthermore, such modifications should not be understood individually from the technical idea or prospect of the present invention.

Claims

1. Contains multiple layers stacked in one direction, Each of the above multiple layers, Anode liquid electrode where the anode half reaction occurs; A cathode liquid electrode where the cathode half-reaction occurs; and It comprises a plurality of layers arranged between the anode liquid electrode and the cathode liquid electrode and laminated in an ion-selective high-density direction on one surface of the porous substrate layer, Each of the above multiple layers, Anode liquid electrode where the anode half reaction occurs; A cathode liquid electrode where the cathode half-reaction occurs; and A separator is disposed between the anode liquid electrode and the cathode liquid electrode and includes an ion-selective polymer layer applied to one surface of a porous substrate layer, A secondary battery in which one of the plurality of layers, the ion-selective polymer layer of the separator is in contact with the cathode liquid electrode, and the porous substrate layer of the separator is in contact with the anode liquid electrode.

2. In paragraph 1, The above porous substrate layer is a secondary battery having a polyolefin-based polymer substrate.

3. In paragraph 1, A secondary battery in which the above ion-selective polymer layer is a polybenzimidazole-based polymer.

4. In paragraph 3, The polybenzimidazole polymers include ab-PBI (Poly(2,5-benzimidazole)), O-PBI (Poly[2,2'-(4,4'-oxybis(1,4-phenylene))-5,5'-bibenzimidazole), m-PBI (meta-polybenzimidazole), p-PBI (para-polybenzimidazole), and s-PBI (sulfonated). polybenzimidazole), f-PBI(fluorine-containing polybenzimidazole), 2OH-PBI(Dihydroxy polybenzimidazole), PIPBI(Phenylindane-polybenzimidazole), PBI-OO(poly[(1-(4,4'-diphenylether)-5-oxybenzimidazole)-benzimidazole]), Py-PBI(poly[2,2'-(2,6-pyridine)-5,5'-bibenzimidazole]), biphenyl-PBI(biphenyl-linked A secondary battery comprising one or more mixtures or copolymers selected from the group consisting of polybenzimidazole), terphenyl-PBI (terphenyl-linked polybenzimidazole), and HMT-PBI (poly[2,2'-(2,2'',4,4'',6,6''-hexamethyl-p-terphenyl-3,3''-diyl)-5,5'-bibenzimidazole]).

5. In paragraph 1, A secondary battery in which the ion-selective polymer layer of the separator is in contact with the anode liquid electrode and the porous substrate layer of the separator is in contact with the cathode liquid electrode among the plurality of layers.

6. In paragraph 5, A secondary battery in which the plurality of layers are arranged such that the layer in which the ion-selective polymer layer is in contact with the cathode liquid electrode and the layer in which the ion-selective polymer layer is in contact with the anode liquid electrode are intersecting each other.

7. In paragraph 5, A secondary battery in which the above plurality of layers have a ratio of the layer in which the ion-selective polymer layer is in contact with the cathode liquid electrode and the layer in which the ion-selective polymer layer is in contact with the anode liquid electrode of 4:6 to 6:

4.

8. In paragraph 1, A secondary battery in which the ion-selective polymer layer of the separator is in contact with the cathode liquid electrode and the porous substrate layer of the separator is in contact with the anode liquid electrode.

9. In paragraph 1, A secondary battery in which the ion-selective polymer layer of the separator is in contact with the anode liquid electrode and the porous substrate layer of the separator is in contact with the cathode liquid electrode, among the plurality of layers.

10. In paragraph 1, A secondary battery in which the ion-selective polymer layer of the separator is in contact with the cathode liquid electrode and the porous substrate layer of the separator is in contact with the anode liquid electrode, among the plurality of layers.

11. Contains multiple layers stacked in one direction, Each of the above multiple layers, An anode solid electrode impregnated with an anode liquid electrode where an anode half-reaction occurs; A cathode solid electrode impregnated with a cathode liquid electrode where a cathode half-reaction occurs; and A separator is disposed between the anode solid electrode and the cathode solid electrode and includes an ion-selective polymer layer applied to one surface of a porous substrate layer, A secondary battery in which one of the plurality of layers is in contact with the cathode solid electrode, and the porous substrate layer of the separator is in contact with the anode solid electrode.

12. Contains multiple layers stacked in one direction, Each of the above multiple layers, Anode carbon collector; A cathode carbon collector disposed spaced apart from the anode carbon collector; and A separator is disposed between the anode carbon collector and the cathode carbon collector and includes an ion-selective polymer layer applied to one surface of the porous substrate layer, A secondary battery in which one of the plurality of layers is arranged such that the ion-selective polymer layer of the separator is positioned toward the cathode carbon collector, and the porous substrate layer of the separator is positioned toward the anode carbon collector.

13. Contains multiple layers stacked in one direction, Each of the above multiple layers, Anode carbon collector; A cathode carbon collector disposed spaced apart from the anode carbon collector; and A separator is disposed between the anode carbon collector and the cathode carbon collector and includes an ion-selective polymer layer applied to one surface of the porous substrate layer, Any one of the plurality of layers, wherein the ion-selective polymer layer and the cathode carbon collector form a cathode electrode receiving portion, A secondary battery in which the porous substrate layer and the anode carbon collector form an anode electrode receiving portion.

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