Secondary battery and method for manufacturing same

Abstract

The present invention relates to a secondary battery comprising: an electrode assembly in which a positive electrode plate, a negative electrode plate, and a separator interposed between the positive electrode plate and the negative electrode plate are wound in one direction and impregnated with an electrolyte; a hollow center pin positioned on a winding axis of the electrode assembly and having a plurality of holes formed through the outer circumferential surface thereof; an electrolytic solid body disposed inside the hollow of the center pin and including a first polymer electrolyte having a melting point of 60℃ to 73℃; a battery case in which the electrode assembly and the center pin are received; and a sealing body for sealing the open end of the battery case. By applying the electrolytic solid body to the secondary battery, a secondary battery having an improved electrolytic impregnation property can be implemented.

Description

Secondary battery and its manufacturing method Cross-citation with related applications This application claims the benefit of priority to Korean Patent Application No. 10-2023-0176098, filed December 6, 2023, and Korean Patent Application No. 10-2024-0172904, filed November 27, 2024, the entire contents of which are incorporated herein by reference. Technical field The present invention relates to a secondary battery, and more specifically, to a secondary battery with improved output stability and impregnation properties. With the advancement of technology in electric vehicles and portable devices, the demand for secondary batteries as an energy source is rapidly increasing. In particular, as the scope of application of secondary batteries expands to electric vehicles (EVs) and hybrid electric vehicles (HEVs), the demand for secondary batteries with excellent capacity and output stability is increasing. In particular, in order to implement high-capacity secondary batteries, secondary batteries are being manufactured in larger sizes. As the capacity and size of the secondary battery increase, more electrolyte needs to be injected into the secondary battery. At this time, it is important that the enlarged electrode assembly is sufficiently impregnated with the electrolyte. If the electrode assembly of the secondary battery is not sufficiently impregnated with the electrolyte, the capacity of the secondary battery may decrease, and the deterioration of the electrode may be accelerated, which may cause a problem in that the lifespan of the secondary battery is shortened. In addition, the above problems may occur even when the amount of electrolyte is insufficient. For example, the amount of electrolyte is determined by the initial injection amount of electrolyte, but if charging and discharging are repeated during use of the secondary battery, the amount of electrolyte may decrease, which may cause electrolyte loss. Therefore, a technology that can supplement the electrolyte impregnation property and electrolyte amount of a secondary battery is required. In order to solve the above-described problem, the first technical problem to be solved by the present invention is to provide a secondary battery having improved electrolyte impregnation property and output stability by arranging a polymer electrolyte that can melt above a certain temperature inside a center pin having a plurality of holes. In order to solve the above-described problem, the second technical problem to be solved by the present invention is to provide a method for manufacturing a secondary battery with improved electrolyte impregnation property and output stability by arranging a polymer electrolyte that can melt at a certain temperature or higher inside a center pin having a plurality of holes. [1] The present invention provides a secondary battery including an electrode assembly in which a positive electrode plate, a negative electrode plate, and a separator interposed between the positive electrode plate and the negative electrode plate are wound in one direction and impregnated with an electrolyte; a hollow center pin positioned on a winding axis of the electrode assembly and having a plurality of holes formed on an outer peripheral surface; an electrolyte solid body disposed inside the hollow interior of the center pin and including a first polymer electrolyte having a melting point of 60°C to 73°C; a battery case in which the electrode assembly and the center pin are accommodated; and a sealing body sealing an open end of the battery case. [2] The present invention, in the above [1], the first polymer electrolyte comprises a main component including lithium ethylene oxide (PEO); and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and aluminum oxide (Al 2 O 3 ) and a secondary battery including at least one component selected from the group consisting of: [3] The present invention, in the above [1] or [2], the diameter (D) of the center pin c ) and the diameter (D) of each of the plurality of holes h ) provides a secondary battery satisfying the following equation 1: [Formula 1] D c / 10 ≤ D h ≤ Dc / 3. [4] The present invention provides a secondary battery in which the plurality of holes are arranged at a constant interval along the circumferential direction in at least one of the above [1] to [3]. [5] The present invention provides a secondary battery in which, in at least one of the above [1] to [4], the plurality of holes are arranged at a constant interval along a direction perpendicular to the circumferential direction. [6] The present invention provides a secondary battery in which, in at least one of the above [1] to [5], the electrolyte solid body further includes a second polymer electrolyte, and the melting point of the second polymer electrolyte is lower than the melting point of the first polymer electrolyte. [7] The present invention provides a secondary battery in which the melting point of the second polymer electrolyte in the above [6] is 35°C to 55°C. [8] The present invention provides a secondary battery including, in the above [6], a main component including the second polymer electrolyte succinonitrile (SN); and a secondary component including at least one selected from the group consisting of polycarboxylate ether (PCE), polyethylene oxide (PEO), polyvinylpyrrolidone (PVP), polyethylene carbonate (PEC), and polyacrylonitrile (PAN). [9] The present invention provides a secondary battery, wherein in at least one of the above [1] to [8], the secondary battery further includes a first electrolyte sheet including a first polymer electrolyte, and the first electrolyte sheet is disposed on at least one surface selected from the surface of the separator and the outermost surface of the electrode assembly.

[0010] The present invention provides a secondary battery according to the above [9], wherein the secondary battery further includes a second electrolyte sheet including the second polymer electrolyte, the second electrolyte sheet is arranged on at least one surface selected from the surface of the separator and the outermost surface of the electrode assembly, and the melting point of the second polymer electrolyte is lower than the melting point of the first polymer electrolyte.

[0011] The present invention provides a secondary battery, wherein the secondary battery is a cylindrical secondary battery, in at least one of the above [1] to

[0010] .

[0012] The present invention provides a method for manufacturing a secondary battery, comprising: a step of manufacturing an electrode assembly by winding a positive electrode plate, a negative electrode plate, and a separator interposed between the positive and negative electrode plates in one direction; a step of housing the electrode assembly in a battery case; a step of injecting an electrolyte solid including a first polymer electrolyte into a hollow center pin located on a winding axis of the electrode assembly; and a step of preparing an inactive secondary battery by injecting the electrolyte into the battery case and sealing the electric case with a sealant; wherein the melting point of the first polymer electrolyte is 60°C to 73°C.

[0013] The present invention provides a method for manufacturing a secondary battery, wherein, in the above

[0012] , the electrolyte solid body further includes a second polymer electrolyte, and the melting point of the second polymer electrolyte is 35°C to 55°C.

[0014] The present invention provides a method for manufacturing a secondary battery, wherein, in the above

[0013] , the step of activating the inactive secondary battery is further included, the center pin includes a plurality of holes, and during the step of activating the inactive secondary battery, the second polymer electrolyte melts and moves into the gap of the electrode assembly through the plurality of holes.

[0015] The present invention provides a method for manufacturing a secondary battery, wherein, in the above

[0013] , the step of manufacturing the electrode assembly includes at least one step selected from the steps of: manufacturing a first electrolyte sheet including a first polymer electrolyte, and arranging the first electrolyte sheet on at least one surface selected from the surface of the separator and the outermost surface of the electrode assembly; and manufacturing a second electrolyte sheet including a second polymer electrolyte, and arranging the second electrolyte sheet on at least one surface selected from the surface of the separator and the outermost surface of the electrode assembly. The secondary battery according to the present invention aims to provide a secondary battery in which a polymer electrolyte capable of melting at a certain temperature or higher is disposed inside a center pin, thereby replenishing an electrolyte reduced during a secondary battery charge / discharge process and improving electrolyte impregnation properties. In addition, by disposing first and second electrolyte sheets having different melting points in an electrode assembly, the present invention aims to provide a secondary battery having excellent electrolyte impregnation properties and output stability despite its large size. The effects obtainable from the exemplary embodiments of the present invention are not limited to the effects mentioned above, and other effects not mentioned can be clearly derived and understood by those skilled in the art to which the exemplary embodiments of the present disclosure belong from the following description. That is, unintended effects resulting from practicing the exemplary embodiments of the present disclosure can also be derived by those skilled in the art from the exemplary embodiments of the present disclosure. FIG. 1 is a perspective view showing a secondary battery according to one embodiment. FIG. 2 is a drawing for explaining a secondary battery according to one embodiment. FIG. 3a is a projection diagram showing a center pin according to one embodiment. FIG. 3b is a projection diagram showing a center pin according to one embodiment. FIG. 3C is a projection drawing showing a center pin according to one embodiment. FIG. 4 is a drawing showing a first electrolyte sheet disposed on a separator surface according to one embodiment. FIG. 5 is a drawing showing a first electrolyte sheet and a second electrolyte sheet arranged on an electrode assembly according to one embodiment. The terms or words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as having meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term in order to explain his or her own invention in the best manner. In this specification, “electrolyte solid” and “electrolyte sheet” mean materials that can function as an electrolyte of a secondary battery as their constituents, such as a polymer electrolyte, and have a sheet-like shape by maintaining a solid state at room temperature. In this specification, the “polymer electrolyte” may mean a material that maintains a solid state at room temperature, can be formed into a shape such as a sheet or band, and changes into an amorphous state by transitioning into a liquid or gel at a melting temperature (Tm) or higher, and the polymer electrolyte may also be referred to as a solid polymer electrolyte (SPE) or a solid electrolyte. It should be understood that the terms “comprise,” “include,” or “have,” as used herein, are intended to specify the presence of a feature, number, step, component, or combination thereof, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof. Each of the phrases "A or B", "at least one of A and B", "at least one of A or B", "A, B, or C", "at least one of A, B, and C", and "at least one of A, B, or C" can include any one of the items listed in that phrase, or all possible combinations of them. Terms such as "first" or "second" may be used merely to distinguish one component from another, and do not qualify the components in any other respect (e.g., importance or order). Hereinafter, the present invention will be described in detail. A secondary battery according to the present invention comprises at least one of the configurations disclosed below, and may comprise any combination between technically possible configurations among the configurations below. A secondary battery according to the present invention comprises: an electrode assembly in which a positive electrode plate, a negative electrode plate, and a separator interposed between the positive electrode plate and the negative electrode plate are wound in one direction and impregnated with an electrolyte; a hollow center pin positioned on a winding axis of the electrode assembly and having a plurality of holes formed on an outer peripheral surface; an electrolyte solid body disposed inside the hollow interior of the center pin and including a first polymer electrolyte having a melting point of 60° C. to 73° C.; a battery case in which the electrode assembly and the center pin are accommodated; and a sealing body sealing an open end of the battery case. The secondary battery according to the present invention can supplement the amount of electrolyte in the secondary battery by applying an electrolyte solid including a first polymer electrolyte that can melt within the normal operating temperature range of the secondary battery to the inside of a hollow center pin, thereby improving output stability. In addition, the electrolyte solid body may further include a second polymer electrolyte, and the melting point of the second polymer electrolyte may be 35° C. to 55° C. lower than the melting point of the first polymer electrolyte. By applying the second polymer electrolyte that can melt during the activation process to the electrolyte solid body, a secondary battery having excellent electrolyte impregnation property can be implemented. That is, the impregnation property of the center of the electrode assembly can be improved through the electrolyte solid body positioned inside the center pin, thereby realizing a secondary battery having a high capacity and excellent electrolyte impregnation property. Meanwhile, each of the first electrolyte sheet including the first polymer electrolyte and the second electrolyte sheet including the second polymer electrolyte may be disposed on at least one surface selected from the surface of the separator and the outermost surface of the electrode assembly. For example, the first electrolyte sheet may be disposed on the surface of the separator, and the second electrolyte sheet may be disposed on the outermost surface of the electrode assembly. Accordingly, the first electrolyte sheet positioned on the separator of the electrode assembly may improve the electrolyte impregnation property of the electrode assembly and supplement the amount of electrolyte, thereby improving output stability. In addition, the second electrolyte sheet positioned on the outer surface of the electrode assembly may improve the electrolyte impregnation property of the electrode assembly. In this way, when the electrolyte solid and electrolyte sheet are utilized as a means for replenishing or impregnating the electrolyte during the activation process or between charge and discharge of the secondary battery, the means for replenishing or impregnating the electrolyte exist both inside and outside the electrode assembly, so that the electrolyte can be impregnated and supplied uniformly throughout, and stable performance can be expected. <Secondary battery> FIG. 1 is a perspective view showing a secondary battery (100) according to one embodiment. Referring to FIG. 1, the secondary battery (100) includes an electrode assembly (200), a battery case (400), and a sealing body (410). The external shape of the secondary battery (100) is not particularly limited, and may be a cylindrical shape, a square shape, etc. using a can. For example, the secondary battery (100) may be a cylindrical secondary battery, and the battery case (400) may be a cylindrical can. In this case, the electrode assembly (200) may be a coiled type, and may be a jelly-roll type electrode assembly. The battery case (400) may be a container made of a metal material, and may include, for example, aluminum or an aluminum alloy. The open top of the battery case (400) may be covered with a sealant (410). The sealant (410) is for sealing the open end of the battery case (400) and may be coupled with the open end of the battery case (400). According to another embodiment of the present invention, a battery module including a secondary battery (100) as a unit cell and a battery pack including the same can be provided. Since the battery module and the battery pack include the secondary battery having high capacity, high rate characteristics and cycle characteristics, they can be used as a power source for medium and large-sized devices selected from the group consisting of electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles and power storage systems. Electrode assembly FIG. 2 is a drawing for explaining a secondary battery (100) according to one embodiment. Referring to FIG. 2, a secondary battery (100) according to the present invention includes an electrode assembly (200) in which a positive electrode plate (210), a negative electrode plate (220), and a separator (230) interposed between the positive electrode plate (210) and the negative electrode plate (220) are wound in one direction. The electrode assembly (200) may be formed in a jelly-roll shape in which the positive electrode plate (210), the negative electrode plate (220), and the separator (230) are wound. The electrode assembly (200) includes a winding shaft in the center, and the winding center is an empty space in which a center pin (300) may be positioned. In addition, the electrode assembly (200) may be impregnated with an electrolyte (not shown) that is injected into a battery case (400). (1) Bipolar plate The positive electrode plate (210) according to the present invention may include a positive electrode current collector and a positive electrode active material layer (not shown) applied on the positive electrode current collector. The positive electrode plate (210) may have a structure in which a positive electrode active material layer is formed on a positive electrode current collector. The positive electrode current collector is not particularly limited as long as it is conductive and does not cause a chemical change in the battery, and for example, stainless steel, aluminum, nickel, titanium, sintered carbon, or aluminum or stainless steel surface-treated with carbon, nickel, titanium, silver, etc. may be used. The above-mentioned positive electrode active material layer includes a positive electrode active material, a positive electrode conductive material, and a positive electrode binder. The positive electrode active material may be a commonly used positive electrode active material. Specifically, the positive electrode active material may be lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ) or a layered compound substituted with one or more transition metals; LiFe 3 O 4 Lithium iron oxide; chemical formula Li 1+a1 Mn 2-a1 O 4 (0≤a1≤0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO2 Lithium manganese oxide, etc.; lithium copper oxide (Li 2 CuO 2 ); LiV 3 O 8 , V 2 O 5 , Cu 2 V 2 O 7 Vanadium oxide, chemical formula LiNi 1 -a 2 Mc 2 O 2 (wherein, M is at least one selected from the group consisting of Co, Mn, Al, Cu, Fe, Mg, B, and Ga, and satisfies 0.01≤a2≤0.3) Ni-site type lithium nickel oxide; chemical formula LiMn 2-a3 M c3 O 2 (wherein, M is at least one selected from the group consisting of Co, Ni, Fe, Cr, Zn, and Ta, and satisfies 0.01≤a3≤0.1) or Li 2 Mn 3 MO 8 (wherein, M is at least one selected from the group consisting of Fe, Co, Ni, Cu, and Zn); LiMn, a lithium manganese composite oxide expressed by the chemical formula, wherein a portion of Li is replaced by an alkaline earth metal ion. 2 O 4　 These may include, but are not limited to, the anode. The anode may be Li-metal. The above-mentioned positive electrode conductive material is used to provide conductivity to the electrode, and in the battery to be formed, as long as it does not cause a chemical change and has electronic conductivity, it can be used without special restrictions. Specific examples include graphite such as natural graphite or artificial graphite; carbon-based materials such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, summer black, carbon fiber, and carbon nanotube; metal powder or metal fiber such as copper, nickel, aluminum, and silver; conductive whiskers such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; or conductive polymers such as polyphenylene derivatives, and the like. One of these may be used alone or a mixture of two or more may be used. Next, the positive electrode binder serves to improve the adhesion between positive electrode active material particles and the adhesion between the positive electrode active material and the positive electrode current collector. Specific examples thereof include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer rubber (EPDM rubber), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, or various copolymers thereof, and one of these may be used alone or a mixture of two or more thereof may be used. The positive electrode plate (210) can be manufactured according to a conventional electrode manufacturing method. For example, a positive electrode slurry can be manufactured by mixing a positive electrode active material, a positive electrode binder, and / or a positive electrode conductive material in a positive electrode slurry solvent, and the positive electrode slurry can be applied onto a positive electrode current collector, followed by drying and rolling to manufacture a positive electrode current collector having a positive electrode active material layer (222) formed thereon. Meanwhile, solvents commonly used in the relevant technical field can be used as solvents for the positive electrode slurry, and for example, dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, water, etc. can be used alone or in a mixture of two or more. (2) Negative plate The negative electrode plate (220) according to the present invention may have a structure in which a negative electrode active material layer (not shown) is formed on a negative electrode current collector (not shown). The negative electrode current collector is not particularly limited as long as it has high conductivity without causing a chemical change in the battery, and for example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, silver, etc., aluminum-cadmium alloy, etc. may be used. As the negative electrode active material, compounds capable of reversible intercalation and deintercalation of lithium, which are generally used in the relevant technical field, can be used, and the type is not particularly limited. Specific examples of the negative electrode active material include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber, and amorphous carbon; Si, Si-Me alloy (wherein, Me is at least one selected from the group consisting of Al, Sn, Mg, Cu, Fe, Pb, Zn, Mn, Cr, Ti, and Ni), SiOy (wherein, 0 <y<2), Si-C 복합체 등과 같은 실리콘계 물질; 리튬 금속 박막; Sn, Al 등과 같이 리튬과 합금화가 가능한 금속 물질; 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 혼합물이 사용될 수 있다. The above negative electrode conductive material is used to provide conductivity to the negative electrode, and can be used without special restrictions in the battery being composed, as long as it does not cause a chemical change and has electronic conductivity. The negative electrode conductive material may be the same as the positive electrode conductive material. The above negative electrode binder serves to improve the adhesion between negative electrode active material particles and the adhesive strength between the negative electrode active material and the negative electrode current collector. The above negative electrode binder may be the same as the above positive electrode binder. Meanwhile, the negative electrode plate (220) can be manufactured according to a conventional electrode manufacturing method. For example, a negative electrode slurry can be manufactured by mixing a negative electrode active material, a negative electrode binder, and / or a negative electrode conductive material in a negative electrode slurry solvent, and the negative electrode slurry can be applied onto a negative electrode current collector, followed by drying and rolling to manufacture a negative electrode current collector having a negative electrode active material layer (212) formed thereon. As the solvent of the above cathode slurry, solvents generally used in the relevant technical field can be used, and for example, dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, water, etc. can be used alone or in a mixture of two or more. (3) Membrane The separator (230) according to the present invention is positioned between the electrodes and can provide a passage for lithium ions to move. Any separator that is commonly used in secondary batteries can be used without special restrictions. Specifically, the separator may be a porous polymer film, for example, a porous polymer film made of a polyolefin polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer, and an ethylene / methacrylate copolymer, or a laminated structure of two or more layers thereof. In addition, a conventional porous nonwoven fabric, for example, a nonwoven fabric made of high-melting-point glass fibers, polyethylene terephthalate fibers, etc. may be used. In addition, a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength. Center pin FIGS. 3A to 3C are drawings showing a center pin according to one embodiment. Referring to FIG. 2 and FIGS. 3a to 3c, a hollow center pin (300) is positioned on the winding axis of the electrode assembly (200). The center pin (300) is positioned at the center of the electrode assembly (200) and may be formed in a hollow cylindrical shape. The center pin (300) may be inserted into the winding axis of the electrode assembly (200) to prevent the electrode assembly (200) from being deformed. In addition, a plurality of holes (320) may be arranged on the outer surface of the center pin (300), and an electrolyte solid (310) may be arranged inside the hollow space. When the electrolyte solid (310) melts above a certain temperature and undergoes a phase transition to an amorphous state such as a liquid or gel, the plurality of holes (320) may serve as a passage through which the electrolyte solid (310) moves from the inside of the center pin (300) toward the electrode assembly (200). Specifically, referring to FIG. 3a, a plurality of holes (320) may be arranged at regular intervals along a circumferential direction, and referring to FIG. 3b, a plurality of holes (320) may be arranged at regular intervals along a direction perpendicular to the circumferential direction. Referring to FIG. 3c, a plurality of holes (320) may be arranged on an outer surface of a center pin (300) along a circumferential direction and a direction perpendicular to the circumferential direction. A plurality of holes (320) may be arranged in an appropriate number on the center pin (300) as needed, and the direction and speed of movement of the electrolyte may be controlled by the arrangement positions and number of the plurality of holes (320), so the arrangement positions and number of the plurality of holes (320) may be controlled depending on the type of the electrolyte solid body (320). Also, the diameter of the center pin (D c ) and the diameter (D) of each of the plurality of holes (320) h ) can satisfy the following equation 1. [Formula 1] D c / 10 ≤ D h ≤ D c / 3 The diameter (D) of each of the multiple holes (320) h ) is the center pin diameter (D c ) is 1 / 10 or more, it may be easy for the electrolyte solid (310) located inside the center pin (300) to move to the electrode assembly (200). In addition, the diameter (D) of each of the plurality of holes (320) h ) is the center pin diameter (D c ) is less than 1 / 3 of the center pin (300), the durability of the center pin (300) can be designed so that the movement speed of the electrolyte solid (310) is not excessively fast. A secondary battery that can maintain electrolyte impregnation and output stability can be implemented through the center pin (300) to which a plurality of holes (320) satisfying the above range are applied. Accordingly, preferably, the diameter (D) of each of the plurality of holes (320) is h ) is the center pin diameter (D c) may be 1 / 10 or more, 1 / 9 or more, 1 / 8 or more, or 1 / 7 or more, and preferably, the diameter (D) of each of the plurality of holes (320) h ) is the center pin diameter (D c ) may be less than 1 / 3, less than 1 / 4, less than 1 / 5, or less than 1 / 6. Electrolyte solid The electrolyte solid (310) according to the present invention is placed inside the hollow center pin (300). The shape of the electrolyte solid (310) is not particularly limited as long as it can be placed inside the center pin (300). For example, the shape of the electrolyte solid (310) may be a cylinder, a prismatic cylinder, or an irregular shape. In addition, the electrolyte solid (310) may include one or more lumps, and for example, may include two lumps having different compositions. In addition, the electrolyte solid (310) includes a first polymer electrolyte having a melting point of 60° C. to 73° C. The first polymer electrolyte may include polyethylene oxide (PEO), and preferably includes a main component including polyethylene oxide (PEO); and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and aluminum oxide (Al 2 O 3 ) may include a secondary component including at least one selected from the group consisting of; If polyethylene oxide (PEO) having a melting point of about 75°C is used alone as the first polymer electrolyte, it may not melt at the normal operating temperature of the secondary battery. Therefore, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or aluminum oxide (Al) may be added to polyethylene oxide (PEO). 2 O 3 ) can be mixed, the electrolyte solid (310) including the first polymer electrolyte can be melted during operation of the secondary battery. Accordingly, the electrolyte can be supplemented to the electrode assembly (200), the electrolyte impregnation property can be improved, and a secondary battery (100) having excellent performance can be implemented. Specifically, the first polymer electrolyte may include the polyethylene oxide (PEO) and the lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in a weight ratio of 40:1 to 80:1, and preferably 40:1 to 60:1. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) can change the structure of the polyethylene oxide (PEO) from crystalline to amorphous, thereby lowering the melting point of the first polymer electrolyte. When the weight ratio of the polyethylene oxide (PEO) and the lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) satisfies the above range, the first electrolyte sheet can melt during the operation of the secondary battery (100) without melting during the manufacturing process of the secondary battery (100). In addition, the melting point of the first polymer electrolyte may be 60° C. to 73° C., preferably 60° C. to 70° C., and more preferably 60° C. to 66° C. If the melting point of the first polymer electrolyte is lower than 60° C., it completely melts during the manufacturing process of the secondary battery (100) and does not exist inside the center pin (300) after the secondary battery (100) is completed, so that the electrolyte cannot be replenished after the manufacturing of the secondary battery (100) is completed. On the other hand, if the melting point of the first polymer electrolyte is higher than 73° C., the first electrolyte sheet (230_1) does not melt in the normal operating temperature range of the secondary battery (100), so that it cannot perform the role of replenishing the electrolyte. Accordingly, preferably, the melting point of the first polymer electrolyte may be 60°C or higher, 61°C or higher, or 62°C or higher, and the melting point of the first polymer electrolyte may be 73°C or lower, 71°C or lower, 70°C or lower, 68°C or lower, or 66°C or lower. The above first polymer electrolyte may be partially melted during the secondary battery activation process, and the remainder may be melted during the secondary battery operation. That is, the first polymer electrolyte included in the electrolyte solid body may be positioned within the hollow space of the center pin (300) when the secondary battery is manufactured. In addition, the electrolyte solid (310) may further include a second polymer electrolyte. The second polymer electrolyte may include a main component including succinonitrile (SN); and a secondary component including at least one selected from the group consisting of polycarboxylate ether (PCE), polyethylene oxide (PEO), polyvinylpyrrolidone (PVP), polyethylene carbonate (PEC), and polyacrylonitrile (PAN). In exemplary embodiments, the second polymer electrolyte may include, as the auxiliary component, a combination of polycarboxylate (PCE) and polyethylene oxide (PEO), a combination of polycarboxylate (PCE) and polyvinylpyrrolidone (PVP), a combination of polycarboxylate (PCE) and polyethylene carbonate (PEC), or a combination of polycarboxylate (PCE) and polyacrylonitrile (PAN). In exemplary embodiments, the molecular weight of the polycarboxylate (PCE) may be about 165 g / mol, the molecular weight of the polyethylene oxide (PEO) may be about 100 g / mol, and the molecular weight of the polyvinylpyrrolidine (PVP) may be about 25 g / mol. The melting point of the second polymer electrolyte may be lower than the melting point of the first polymer electrolyte. Specifically, the melting point of the second polymer electrolyte may be about 35°C to 55°C, preferably about 35°C to 53°C, and more preferably about 40°C to 50°C. The second polymer electrolyte may melt during the manufacturing process of the secondary battery (100), and after the second polymer electrolyte melts during the process, it may be impregnated into the positive electrode plate (210), the negative electrode plate (220), and the separator (230) within the electrode assembly (200), and may not return to the original state even if the temperature is lowered again, thereby improving the electrolyte impregnation property of the secondary battery (100) during the manufacturing process. Accordingly, preferably, the melting point of the second polymer electrolyte may be 35°C or higher, 37°C or higher, 40°C or higher, or 42°C or higher, and the melting point of the second polymer electrolyte may be 55°C or lower, 53°C or lower, 52°C or lower, 50°C or lower, or 48°C or lower. That is, the second polymer electrolyte included in the above-mentioned electrolyte solid can be dissolved during the activation process of the secondary battery (100), thereby enabling the implementation of a secondary battery (100) with improved electrolyte impregnation properties. In conclusion, the electrolyte solid (310) may include at least one selected from the group consisting of a first polymer electrolyte and a second polymer electrolyte. By applying the first polymer electrolyte and the second polymer electrolyte having different melting points to the electrolyte solid (310), the electrolyte impregnation property of the secondary battery (100) can be improved during the secondary battery manufacturing process and during the operation of the manufactured secondary battery. In particular, as the electrolyte solid located inside the center pin (300) melts and moves to the center of the electrode assembly (200), the electrode assembly (200) can be impregnated up to the center of the enlarged electrode assembly (200). Through this, the electrolyte impregnation property of the enlarged secondary battery can be improved without an additional process. In addition, the electrolyte solid (310) to which the first polymer electrolyte is applied can improve output stability by replenishing the electrolyte reduced during operation of the manufactured secondary battery. Electrolyte sheet FIG. 4 is a drawing showing a first electrolyte sheet disposed on a separator according to one embodiment. FIG. 5 is a drawing showing a first electrolyte sheet and a second electrolyte sheet arranged on an electrode assembly according to one embodiment. The first electrolyte sheet (240_1) includes a first polymer electrolyte, and since the first polymer electrolyte is the same as described above, a detailed description thereof will be omitted. The second electrolyte sheet (240_2) includes a second polymer electrolyte, and since the second polymer electrolyte is the same as described above, a detailed description thereof will be omitted. Referring to FIGS. 4 and 5, each of the first electrolyte sheet (240_1) and the second electrolyte sheet (240_2) may be positioned on at least one surface selected from the surface of the separator (230) and the outermost surface of the electrode assembly (200). Specifically, the first electrolyte sheet (240_1) and the second electrolyte sheet (240_2) may be alternately positioned on the surface of the separator (230). In addition, the first electrolyte sheet (240_1) may be positioned on the upper side of the outermost surface of the electrode assembly (200), and the second electrolyte sheet (240_2) may be positioned on the lower side of the outermost surface of the electrode assembly (200). At this time, the first electrolyte sheet (240_1) and the second electrolyte sheet (240_2) may play a role in maintaining the shape of the electrode assembly (200) before the electrode assembly (200) is stored in the battery case (400). Since the first electrolyte sheet (240_1) may melt during operation of the secondary battery (100), when a swelling phenomenon occurs in which the electrode assembly (200) expands, the first electrolyte sheet (240_1) may not press the electrode assembly (200). The second electrolyte sheet (240_2) may melt during the activation process of the secondary battery (100) after the electrode assembly (200) is housed in the battery case (400). Meanwhile, the first electrolyte sheet (240_1) and the second electrolyte sheet (240_2) according to the present invention may be placed at different positions within the secondary battery (100). Specifically, the first electrolyte sheet (240_1) may be placed on the surface of the separator (230), and the second electrolyte sheet (240_2) may be placed on the outermost surface of the electrode assembly (200). At this time, the number of first electrolyte sheets (240_1) may be two or more, and a plurality of first electrolyte sheets (240_1) may be arranged at a constant interval on the surface of the separator. In addition, a plurality of first electrolyte sheets (240_1) may be arranged on both sides of the separator. That is, since the first electrolyte sheet (240_1) is positioned on the surface of the separator (230), the first electrolyte sheet (240_1) can provide electrolyte to the positive electrode plate (210) and the negative electrode plate (220) inside the electrode assembly (200) during operation of the secondary battery (100). As a result, a secondary battery (100) with improved lifespan of the positive electrode plate (210) and the negative electrode plate (220) can be implemented. In addition, the second electrolyte sheet (240_2) may be positioned in the center based on the height of the electrode assembly (200). In addition, the number of second electrolyte sheets (240_2) may be plural. For example, each of the plurality of second electrolyte sheets (240_2) may be positioned close to each of the two ends of the electrode assembly (200). That is, the first electrolyte sheet (240_1) and the second electrolyte sheet (240_2) can stably maintain the output performance of the secondary battery by being a means for replenishing or impregnating the electrolyte during the activation process or between charging and discharging of the secondary battery. Electrolyte The secondary battery (100) according to the present invention further includes an electrolyte (not shown) that is poured inside the battery case (400). The electrolyte is for moving lithium ions generated by an electrochemical reaction of an electrode during charging / discharging of the secondary battery, and may include a non-aqueous organic electrolyte that is a mixture of a lithium salt and an organic solvent. As the organic solvent, any solvent that can act as a medium through which ions involved in the electrochemical reaction of the battery can move may be used without particular limitation. Specifically, the organic solvent may include: ester solvents such as methyl acetate, ethyl acetate, γ-butyrolactone, and ε-caprolactone; ether solvents such as dibutyl ether or tetrahydrofuran; ketone solvents such as cyclohexanone; aromatic hydrocarbon solvents such as benzene and fluorobenzene; carbonate solvents such as dimethylcarbonate (DMC), diethylcarbonate (DEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), and propylene carbonate (PC); Alcohol solvents such as ethyl alcohol, isopropyl alcohol, etc. can be used. Among these, a carbonate solvent is preferable, and a mixture of a cyclic carbonate (e.g., ethylene carbonate or propylene carbonate) having high ionic conductivity and high dielectric constant that can improve the charge / discharge performance of the battery and a low-viscosity linear carbonate compound (e.g., ethyl methyl carbonate, dimethyl carbonate, or diethyl carbonate) is more preferable. The above lithium salt can be used without any special limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery. Specifically, the above lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN(C 2 F 5 SO 3 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , LiCl, LiI, or LiB(C 2 O 4 ) 2 The above lithium salt concentration is preferably used within the range of 0.1 M to 2.0 M. When the concentration of the lithium salt is within the above range, the electrolyte has appropriate conductivity and viscosity, so that it can exhibit excellent electrolyte performance, and lithium ions can move effectively. <Method for manufacturing secondary batteries> A method for manufacturing a secondary battery (100) according to the present invention includes the steps of: manufacturing an electrode assembly (200) by winding a positive electrode plate (210), a negative electrode plate (220), and a separator (230) interposed between the positive electrode plate (210) and the negative electrode plate (220) in one direction; storing the electrode assembly (200) in a battery case (400); introducing an electrolyte solid (310) including a first polymer electrolyte into a hollow center pin (300) located on a winding shaft of the electrode assembly (200); and introducing the electrolyte into the battery case (400) and sealing the electrical case (400) with a sealant (410) to prepare an inactive secondary battery. At this time, the melting point of the first polymer electrolyte is 60°C to 73°C. Meanwhile, the electrolyte solid (310) may further include a second polymer electrolyte, and the melting point of the second polymer electrolyte may be 35°C to 55°C. Steps for manufacturing an electrode assembly The step of manufacturing the electrode assembly (200) may include at least one selected from the following steps: manufacturing a first electrolyte sheet (240_1) including a first polymer electrolyte, and arranging the first electrolyte sheet (240_1) on at least one surface selected from the surface of the separator (230) and the outermost surface of the electrode assembly (200); and manufacturing a second electrolyte sheet (240_2) including a second polymer electrolyte, and arranging the second electrolyte sheet (240_2) on at least one surface selected from the surface of the separator (230) and the outermost surface of the electrode assembly (200). If the first electrolyte sheet (240_1) and the second electrolyte sheet each include the first polymer electrolyte and the second polymer electrolyte, the molding method may be a conventional method used to manufacture the first electrolyte sheet (240_1) or the second electrolyte sheet (240_2). Step of storing the electrode assembly in the battery case The step of storing the electrode assembly (200) in the battery case (400) may be inserting the electrode assembly (200) through the open end of the battery case (400). The electrode assembly (200) can be inserted and removed through the open end of the battery case (400). A step of injecting an electrolyte solid body containing a first polymer electrolyte into the hollow center pin. The step of injecting an electrolyte solid body containing a first polymer electrolyte into the hollow center pin may include a step of manufacturing an electrolyte solid body (310), and if the first polymer electrolyte is included as a component, the molding method may be applied to manufacture the electrolyte solid body (310). In addition, the electrolyte solid body may further include a second polymer electrolyte, and the characteristics of the second polymer electrolyte are the same as those of the second polymer electrolyte described above. Therefore, the step of introducing the electrolyte solid body may include a step of preparing an electrolyte solid body including the second polymer electrolyte. Steps for preparing an inactive secondary battery The step of preparing an inactive secondary battery may be to inject an electrolyte into a battery case (400) and seal the battery case (400) with a sealant (410). The sealant (410) may be combined with the battery case (400). By sealing the battery case (400) with the sealant (410), the electrode assembly (200) may be prevented from being deformed or damaged by an external environment. Steps to activate an inactive secondary battery Meanwhile, the method for manufacturing a secondary battery (100) may further include a step of activating an inactive secondary battery. The activation step may be to perform charging and discharging of the secondary battery (100) at a temperature of 45° C. to 59° C. In exemplary embodiments, the temperature of the activation step may be 50° C. to 59° C. In addition, the activation step may include a step in which the electrolyte solid (310) including the second polymer electrolyte is melted within the battery case (400). Specifically, during the activation step, the second polymer electrolyte may be melted and moved into the pores of the electrode assembly through the plurality of holes (320) of the center pin (300). The pores of the electrode assembly (200) may include pores of the positive electrode plate (210), the negative electrode plate (220), and the separator (230). Through this, even though the electrode assembly (200) is enlarged, the electrolyte impregnation property of the central portion of the electrode assembly (200) may be improved. Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein. Example 1 (1) Preparation of electrolyte solid containing first polymer electrolyte Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, purity 99.9%) stored in a dry room at 110°C for more than 24 hours and polyethylene oxide (PEO) stored at 45°C for 48 hours were prepared. Thereafter, polyethylene oxide:LiTFSI were mixed at a weight ratio of 50:1 and stirred for 12 hours to prepare a first polymer electrolyte. Using the first polymer electrolyte, a cylindrical electrolyte solid having a melting point of about 60°C and capable of being placed inside a center pin was prepared. (2) Manufacturing of secondary batteries A jelly-roll type electrode assembly was manufactured by interposing a separator between a positive and negative plate and winding it, storing the electrode assembly in a battery case, and placing a hollow center pin on the winding shaft of the electrode assembly. An electrolyte solid containing the first polymer electrolyte was injected into the hollow center pin, and ethylene carbonate (EC): ethyl methyl carbonate (EMC) were mixed in a volume ratio of 30:70, and then LiPF 6 The electrolyte dissolved to a concentration of 1.0 M was injected into the battery case. Thereafter, the open end of the battery case was sealed with a sealant to prepare a non-activated secondary battery. After that, the inactivated secondary battery was subjected to an activation process at 45°C to 59°C, and then subjected to additional aging for 3 days to manufacture a secondary battery. Example 2 A secondary battery was manufactured in the same manner as in Example 1, except that the first polymer electrolyte was manufactured as follows. Lithium salt (LiTFSI) with polyethylene oxide (PEO) and aluminum oxide (Al 2 O 3 ) were mixed in a mass ratio of 9:1 and stirred for 12 hours to produce a first polymer electrolyte having a melting point of approximately 73°C. Example 3 A secondary battery was manufactured in the same manner as in Example 1, except that an electrolyte solid body including a second polymer electrolyte was manufactured as follows and additionally inserted into the center pin. (1) Preparation of electrolyte solid containing second polymer electrolyte Polycarboxylate (PCE) and polyethylene oxide (PEO) were prepared by drying in a dry room for 24 hours. Then, polycarboxylate (PCE) and polyethylene oxide (PEO), which were mixed in a mass ratio of 9:1 to a mixture of lithium bis(trifluoromethanesulfonyl)imide (99.9% purity LiTFSI) and succinonitrile (SN), were added so that 10 wt% of the polycarboxylate (PCE) and polyethylene oxide (PEO) were mixed, and stirred at 70°C to prepare a second polymer electrolyte. Using the second polymer electrolyte, a cylindrical electrolyte solid having a melting point of 42°C and capable of being placed inside a center pin was prepared. Example 4 A secondary battery was manufactured in the same manner as in Example 3, except that the second polymer electrolyte was manufactured as follows. Polycarboxylate (PCE) and polyvinylpyrrolidine (PVP) were prepared by drying in a dry room for 24 hours. Then, polycarboxylate (PCE) and polyvinylpyrrolidine (PVP), which were mixed in a mass ratio of 9:1 to a mixture of lithium bis(trifluoromethanesulfonyl)imide (99.9% purity LiTFSI) and succinonitrile (SN), were added so that 10 wt% of the mixture was obtained, and then stirred at 70°C to produce a second polymer electrolyte having a melting point of approximately 52°C. Example 5 A secondary battery was manufactured in the same manner as in Example 3, except that a first electrolyte sheet was manufactured and placed on the outermost surface of the electrode assembly, and a second electrolyte sheet was manufactured and placed on the surface of the separator. The above first electrolyte sheet was manufactured in the form of a film by casting an electrolyte solid containing the first polymer electrolyte into a glass container and drying it in a vacuum oven at 50°C for 24 hours. The second electrolyte sheet was manufactured in the form of a film by casting an electrolyte solid containing the second polymer electrolyte into a glass container and drying it in a vacuum oven at 35°C for 24 hours. Comparative Example 1 A secondary battery was manufactured in the same manner as in Example 1, except that the electrolyte solid was not applied. Experimental Example 1: Impregnation Evaluation Each of the secondary batteries manufactured in Examples 1 to 5 and Comparative Example 1 was charged and discharged at a 1C-rate as one cycle, and after 100 cycles, they were disassembled to relatively evaluate the electrolyte impregnation properties, which are shown in Table 1 below. In Table 1 below, the “○” mark means good, meaning that the electrolyte impregnation area is 80% or more compared to the entire surface of the electrode and separator. The “△” mark means normal, meaning that the electrolyte impregnation area is 50% to 80% compared to the entire surface of the electrode and separator. Experimental Example 2: Evaluation of electrolyte reduction during use of secondary batteries Each of the secondary batteries manufactured in Examples 1 to 5 and Comparative Example 1 was charged and discharged at 1C-rate as 1 cycle, and after 100 cycles, the batteries were disassembled and the battery cases were opened. Thereafter, the weights of the secondary batteries before and after 100 cycles were compared to determine the amount of remaining electrolyte. The performance for electrolyte reduction was evaluated by evaluating the state of the amount of remaining electrolyte, and the results are shown in Table 1 below. In Table 1 below, the “○” mark indicates that the remaining electrolyte result of the pouch-type secondary battery manufactured in Example 1 is 90% or more, and the “X” mark indicates that the remaining electrolyte result is less than 80% based on the result of Example 1. Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Impregnation Evaluation ○○○○○△ Residual Electrolyte Evaluation ○○○○○Х Referring to Table 1 above, it can be confirmed that the secondary batteries of Examples 1 to 5 have better electrolyte impregnation properties and a larger amount of residual electrolyte than the secondary battery of Comparative Example 1. It is believed that this is because an electrolyte solid capable of replenishing electrolyte or impregnating an electrode assembly during the activation process or between charge and discharge of the secondary battery was applied. [Explanation of symbols] 100: Secondary battery 200: Electrode assembly 210: Bipolar plate 220: Negative plate 230: Membrane 240_1: 1st electrolyte sheet 240_2: Second electrolyte sheet 300: Center pin 310: Electrolyte solid 320: Multiple holes 400: Battery Case 410: Seal

Claims

1. An electrode assembly comprising a positive electrode plate, a negative electrode plate, and a separator interposed between the positive and negative electrode plates, which are wound in one direction and impregnated with an electrolyte; A hollow center pin positioned on the winding axis of the electrode assembly and having a plurality of holes formed on the outer surface thereof; An electrolyte solid body disposed within the hollow interior of the center pin and including a first polymer electrolyte having a melting point of 60°C to 73°C; A battery case in which the electrode assembly and the center pin are stored; and A secondary battery including a sealing body that seals the open end of the battery case.

2. In paragraph 1, The first polymer electrolyte is a main component comprising polyethylene oxide; and A secondary battery comprising an auxiliary component including at least one selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide and aluminum oxide.

3. In paragraph 1, Diameter of the above center pin (D) c ) and the diameter (D) of each of the plurality of holes h ) A secondary battery satisfying the following equation 1: [Formula 1] D c / 10 ≤ D h ≤ D c / 3.

4. In paragraph 1, A secondary battery in which the above plurality of holes are arranged at regular intervals along the circumference.

5. In paragraph 1, A secondary battery in which the above plurality of holes are arranged at regular intervals along a direction perpendicular to the circumferential direction.

6. In paragraph 1, The above electrolyte solid further comprises a second polymer electrolyte, A secondary battery wherein the melting point of the second polymer electrolyte is lower than the melting point of the first polymer electrolyte.

7. In paragraph 6, A secondary battery wherein the melting point of the second polymer electrolyte is 35°C to 55°C.

8. In paragraph 6, The second polymer electrolyte is a main component comprising succinonitrile; and A secondary battery comprising an auxiliary component including at least one selected from the group consisting of polycarboxylate, polyethylene oxide, polyvinyl pyrrolidine, polyethylene carbonate, and polyacrylonitrile.

9. In paragraph 1, The secondary battery further comprises a first electrolyte sheet comprising a first polymer electrolyte, A secondary battery in which the first electrolyte sheet is disposed on at least one surface selected from the surface of the separator and the outermost surface of the electrode assembly.

10. In paragraph 9, The secondary battery further comprises a second electrolyte sheet including the second polymer electrolyte, The second electrolyte sheet is disposed on at least one surface selected from the surface of the separator and the outermost surface of the electrode assembly, A secondary battery wherein the melting point of the second polymer electrolyte is lower than the melting point of the first polymer electrolyte.

11. In paragraph 1, The above secondary battery is a cylindrical secondary battery.

12. A step of manufacturing an electrode assembly by winding a positive electrode plate, a negative electrode plate, and a separator interposed between the positive and negative electrode plates in one direction; A step of housing the above electrode assembly in a battery case; A step of injecting an electrolyte solid body containing a first polymer electrolyte into the hollow center pin located on the winding axis of the electrode assembly; and A step of preparing an inactive secondary battery by injecting an electrolyte into the battery case and sealing the electric case with a sealant; A method for manufacturing a secondary battery wherein the melting point of the first polymer electrolyte is 60°C to 73°C.

13. In paragraph 12, The above electrolyte solid further comprises a second polymer electrolyte, A method for manufacturing a secondary battery wherein the melting point of the second polymer electrolyte is 35°C to 55°C.

14. In paragraph 13, Further comprising a step of activating the above-deactivated secondary battery, The above center pin includes a plurality of holes, A method for manufacturing a secondary battery, wherein during the step of activating the above-described inactive secondary battery, the second polymer electrolyte melts and moves into the pores of the electrode assembly through the plurality of holes.

15. In paragraph 13, The step of manufacturing the above electrode assembly is: A step of manufacturing a first electrolyte sheet including a first polymer electrolyte and arranging the first electrolyte sheet on at least one surface selected from the surface of the separator and the outermost surface of the electrode assembly; and A method for manufacturing a secondary battery, comprising the steps of: manufacturing a second electrolyte sheet including a second polymer electrolyte, and disposing the second electrolyte sheet on at least one surface selected from the surface of the separator and the outermost surface of the electrode assembly;

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