WO2024071934A1 - 젤리-롤형 전극조립체, 젤리-롤형 전극조립체 제조방법 및 이를 포함하는 이차전지 - Google Patents
젤리-롤형 전극조립체, 젤리-롤형 전극조립체 제조방법 및 이를 포함하는 이차전지 Download PDFInfo
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- WO2024071934A1 WO2024071934A1 PCT/KR2023/014720 KR2023014720W WO2024071934A1 WO 2024071934 A1 WO2024071934 A1 WO 2024071934A1 KR 2023014720 W KR2023014720 W KR 2023014720W WO 2024071934 A1 WO2024071934 A1 WO 2024071934A1
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- Prior art keywords
- electrode
- jelly
- electrode assembly
- roll type
- swelling tape
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Images
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- H01M10/04—Construction or manufacture in general
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/0431—Cells with wound or folded electrodes
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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- H—ELECTRICITY
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- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a jelly-roll type electrode assembly, a method of manufacturing a jelly-roll type electrode assembly, and a secondary battery including the same. More specifically, a jelly-roll type electrode assembly including a swelling tape, a method of manufacturing a jelly-roll type electrode assembly, and It relates to a cylindrical secondary battery including this.
- a jelly roll-shaped electrode assembly is manufactured by rolling long electrodes with a fixed width into a roll.
- a cylindrical battery manufactured by inserting such a jelly-roll type electrode assembly into a battery case repeats contraction/expansion of the electrode during charging and discharging.
- a tab In tab
- the degree of contraction/expansion of the electrode assembly increases due to the addition of silicon-based active material in the negative electrode, the pressure acting on the core portion of the electrode assembly increases significantly. I do it.
- the present invention seeks to provide a jelly-roll type electrode assembly with a modified design of the jelly-roll type electrode assembly, a method for manufacturing the jelly-roll type electrode assembly, and a secondary battery including the same.
- One embodiment of the present invention includes a first electrode; first separator; A jelly-roll type electrode assembly in which a second electrode and a second separator are sequentially stacked and wound, comprising a swelling tape attached to at least one surface of the first electrode, wherein the first electrode is wound along the longitudinal direction.
- the first end begins; and a second end where winding ends, wherein the swelling tape is attached so that one end coincides with the first end of the first electrode.
- Another embodiment of the present invention includes a first electrode; first separator; A method of manufacturing a jelly-roll type electrode assembly in which a second electrode and a second separator are sequentially stacked and wound, comprising: (a) transferring the first electrode in a roll-to-roll manner; (b) attaching a swelling tape on at least one side of a slitting area included in the first electrode; and (c) slitting the longitudinal center of the first electrode slitting area, wherein the step (b) includes the longitudinal center of the swelling tape being the longitudinal center of the first electrode slitting area.
- the step (c) includes: a first end at which winding of the first electrode begins along the longitudinal direction; and a jelly-roll type electrode assembly manufacturing method of slitting the longitudinal center of the slitting area to provide a second end where winding ends, and a jelly-roll type electrode assembly manufactured by the manufacturing method.
- Another embodiment of the present invention includes the jelly-roll type electrode assembly; and a battery case for accommodating the electrode assembly.
- the jelly-roll type electrode assembly includes a swelling tape that expands when impregnated with an electrolyte and is attached to cover one longitudinal end of the positive electrode, thereby causing the electrode assembly to contract/expand during charging and discharging of the battery. Damage to the anode and separator can be prevented from deformation, and even if separator damage occurs, the swelling tape prevents internal short circuit between the anode and cathode, thereby improving battery stability and lifespan characteristics.
- the jelly-roll type electrode assembly manufacturing method is a jelly-roll type electrode assembly including a swelling tape that expands when impregnated with the electrolyte and is attached to cover one longitudinal end of the positive electrode.
- Productivity and economic efficiency can be secured by enabling production in a continuous process using roll to roll processing equipment.
- the secondary battery according to the present invention can improve battery stability and lifespan characteristics by preventing internal short circuit between the positive and negative electrodes even when the electrode assembly is deformed due to contraction/expansion of the electrodes during charging and discharging of the battery.
- Figure 1 shows a jelly-roll type electrode assembly including a swelling tape according to an exemplary embodiment of the present invention.
- Figure 2 shows a schematic diagram of a method of manufacturing a jelly-roll type electrode assembly including a swelling tape and a method of manufacturing a jelly-roll type electrode assembly including a PET tape according to an embodiment of the present invention.
- Figure 3 is an image showing an implementation example of a jelly-roll type electrode assembly manufacturing method according to an embodiment of the present invention.
- Figure 4 shows the results of a swelling test of a swelling tape included in a jelly-roll type electrode assembly according to an exemplary embodiment of the present invention.
- Figures 5 and 6 are images showing the first end of the first electrode before and after activation of the jelly-roll type electrode assembly according to Example 1 and Comparative Example 1.
- Figure 7 shows the change in coulombic efficiency of the secondary batteries manufactured in Example 1 and Comparative Example 2 as the cycle progresses and the results of room temperature-voltage tracking evaluation over time.
- Figure 8 is an image showing the state of the first electrode facing portion of the separator included in the secondary battery manufactured in Example 1 and Comparative Example 2.
- Figure 9 is an image showing the roundness evaluation results of the secondary batteries manufactured in Example 1 and Comparative Example 3.
- One embodiment of the present invention includes a first electrode; first separator; A jelly-roll type electrode assembly in which a second electrode and a second separator are sequentially stacked and wound, comprising a swelling tape attached to at least one surface of the first electrode, wherein the first electrode is wound along the longitudinal direction.
- the first end begins; and a second end where winding ends, wherein the swelling tape is attached so that one end coincides with the first end of the first electrode.
- the jelly-roll type electrode assembly includes a swelling tape that expands when impregnated with an electrolyte and is attached to cover one longitudinal end of the positive electrode, thereby causing the electrode assembly to contract/expand during charging and discharging of the battery. Damage to the anode and separator can be prevented from deformation, and even if separator damage occurs, the swelling tape prevents internal short circuit between the anode and cathode, thereby improving battery stability and lifespan characteristics.
- the jelly-roll type electrode assembly may include a swelling tape attached to at least one surface of the first electrode.
- the swelling tape may be attached to one side facing the winding axis of the first electrode, or to the opposite side of the side facing the winding axis, or to both sides of the first electrode.
- the swelling tape may expand and increase in length when impregnated with an electrolyte, and when the swelling tape is attached to one side of the first electrode, after expansion, the swelling tape may be attached to the first electrode.
- the swelling tape when the swelling tape is attached to one surface opposite to the winding axis of the first electrode, it can more efficiently perform the role of preventing internal short circuit between the anode and cathode when the separator is damaged.
- the swelling tape when the swelling tape is attached to both sides of the first electrode, after expansion, the ends of the swelling tape come into contact with each other while surrounding the end of the first electrode, so that the effect of protecting the longitudinal ends of the first electrode is increased. It can be better.
- the swelling tape surrounds the longitudinal end of the first electrode after expansion, the effect of relieving internal stress and improving the roundness of the core portion may be excellent due to the porous material characteristics of the swelling tape.
- the first electrode includes a first end at which winding begins along the longitudinal direction; And it may include a second end where winding ends.
- the winding of the first electrode may begin from the first end and be wound toward the second end. That is, the first end may refer to one end in the longitudinal direction located in the core portion of the jelly-roll type electrode assembly after winding, and the second end may refer to a length located in the outer portion of the jelly-roll type electrode assembly after winding. It may mean one end of the direction.
- the swelling tape may be attached so that one end in the longitudinal direction of the first electrode coincides with one end.
- the swelling tape may be attached so that one end coincides with the first end of the first electrode.
- the swelling tape may be attached so that one end coincides with one longitudinal end located in the core portion of the first electrode.
- the swelling tape may prevent deformation of the electrode assembly due to contraction/expansion of the electrode during charging and discharging of the battery, especially damage to the separator due to sliding of the first end of the first electrode of the core part.
- one end of the swelling tape wraps around the end of the first electrode, or the ends of the swelling tape attached to both sides of the first end of the first electrode wrap around the ends of the first electrode. Since they are in contact, they can effectively perform the role of preventing internal short circuit between the anode and cathode even if the separator is damaged.
- the width direction length of the swelling tape may be 60% or more and 100% or less based on 100% of the width of the first electrode.
- the width direction length of the swelling tape is 70% to 100%, 80% to 100%, 60% to 90%, 60% to 80%, based on 100% of the width of the first electrode.
- it may be 60% or more and 70% or less, or 70% or more and 90% or less.
- the width length of the swelling tape is less than the above-mentioned range, the protection effect of the first end of the first electrode is inferior, and damage to the separator may occur by exposing one end of the first electrode, and when the separator is damaged, the first end of the first electrode is exposed. An internal short circuit may occur due to direct contact between the electrode and the second electrode.
- the width direction length of the swelling tape exceeds the above-mentioned range, the manufacturing cost may increase due to excessive use of materials, and after expansion, one end of the swelling tape is formed in the width direction of the jelly-roll type electrode assembly.
- the width direction length of the preferred swelling tape may be adjusted according to the physical properties of the swelling tape, particularly the rate of change in length before/after expansion.
- the longitudinal length of the swelling tape may be 250% or more and 3500% or less based on 100% of the thickness of the first electrode.
- the longitudinal length of the swelling tape may be 300% or more, 350% or more, 400% or more, 450% or more, or 500% or more based on 100% of the thickness of the first electrode, and the swelling
- the longitudinal length of the tape may be 3000% or less, 2500% or less, 2000% or less, or 1500% or less, based on 100% of the thickness of the first electrode, and is preferably 1000% or less, 850% or less, or 700%. It may be below.
- the longitudinal length of the swelling tape When the longitudinal length of the swelling tape satisfies the above-mentioned range, the longitudinal length of the swelling tape after expansion may correspond to the thickness of the first electrode, and one end of the swelling tape may be connected to the first electrode.
- the longitudinal length of the swelling tape after expansion may correspond to the thickness of the first electrode, and one end of the swelling tape may be connected to the first electrode.
- the swelling tape may expand on both sides by more than 40% in the width and length directions, and may expand by more than 20% on one side. That is, when the longitudinal length of the swelling tape attached to both sides of the first electrode is 250% or more based on 100% of the thickness of the first electrode, the sum of the longitudinal lengths of the expanded swelling tape is It may correspond to the thickness of the first electrode, and one end of the swelling tape attached to both sides of the first electrode can come into contact with each other to effectively wrap one end of the first electrode in the longitudinal direction.
- the longitudinal length of the swelling tape is 500% or more based on 100% of the thickness of the first electrode, even if the swelling tape is attached only on one side opposite the winding axis of the first electrode, it expands.
- the longitudinal length of the swelling tape may correspond to the thickness of the first electrode, and may efficiently serve to prevent internal short circuit between the anode and cathode when the separator is damaged.
- the longitudinal length of the swelling tape is less than 250% based on 100% of the thickness of the first electrode, the swelling tape may not fully cover one end of the first electrode after expansion and a portion may be exposed. Therefore, the effect of preventing damage to the separator and the effect of preventing internal short circuit between the anode and cathode when the separator is damaged may be inferior.
- the longitudinal length of the swelling tape attached to both sides of the first electrode is 1000% or less based on 100% of the thickness of the first electrode, one end of the swelling tape is located in the longitudinal direction of the first electrode. This can minimize defects caused by overlapping areas of the swelling tape that may be caused by excessive exposure.
- the deactivated area that can be formed in the swelling tape attachment area is adjusted to an appropriate level to It is possible to achieve the above-described effect of preventing damage to the separator and internal short while minimizing the impact on electrochemical properties, such as the capacity reduction rate of the battery included.
- the first end of the first electrode may be formed at the same position as the current collector of the first electrode and the active material layer of the first electrode.
- the first end of the first electrode may be in a free-edge shape.
- the swelling tape may be expanded or softened by an electrolyte solution.
- the swelling tape may include a portion made of a polymer material, as will be described later, and when the swelling tape is impregnated with an electrolyte solution, the portion made of the polymer material absorbs the electrolyte solution and expands or becomes flexible. You can. More specifically, one characteristic of the polymer material may be that solvent molecules penetrate between the chains of the polymer material, thereby increasing the volume. Accordingly, the swelling tape may expand or become flexible when it absorbs electrolyte.
- the swelling tape is expanded by an electrolyte solution, and after expansion, the swelling tape may surround the first end of the first electrode.
- the swelling tape may be expanded by absorbing an electrolyte solution containing an organic solvent, as described later, and the longitudinal length may increase, and after expansion, one longitudinal end of the swelling tape is extended and the first 1 It may be bent to surround the first end of the electrode.
- the swelling tape may increase in longitudinal length and be bent to cover at least one edge of the first end of the first electrode.
- the sharp free-edge of the anode can be prevented from directly contacting the separator or cathode, thereby preventing damage to the anode and separator from deformation of the electrode assembly due to contraction/expansion of the electrode during battery charging and discharging. Even when damage to the separator occurs, the swelling tape prevents internal short circuit between the anode and cathode, thereby improving battery stability and lifespan characteristics.
- Figure 1 shows a jelly-roll type electrode assembly including a swelling tape according to an exemplary embodiment of the present invention.
- Figure 1 (a) shows a first electrode including swelling tape attached to both sides of the first electrode before impregnation with an electrolyte solution
- Figure 1 (b) shows a first electrode after impregnation with an electrolyte solution. It shows a first electrode including a swelling tape attached to both sides
- Figure 1(c) shows a first electrode including a swelling tape attached to one side of the first electrode after impregnating the electrolyte.
- the swelling tape may be attached to both sides of the first electrode so that the first end of the first electrode coincides with one end, and (b) of FIG. 1
- the swelling tape is expanded by the electrolyte when impregnated with the electrolyte, and after expansion, the swelling tape may surround the first end of the first electrode.
- the swelling tape may be attached to one surface of the first electrode so that the first end of the first electrode coincides with one end, and the swelling tape may be When impregnated with an electrolyte, it is expanded by the electrolyte, and after expansion, the swelling tape may surround the first end of the first electrode.
- the swelling tape is impregnated for 60 minutes in an electrolyte solution containing 45 wt% of dimethyl carbonate, 20 wt% of ethylene carbonate, 15 wt% of ethylmethyl carbonate, and 15 wt% of LiPF 6 as an electrolyte.
- the length may be 120% or more and 160% or less based on 100% of the length of the swelling tape before expansion.
- the length of the swelling tape after expansion is 120% or more and 150% or less, 120% or more and 140% or less, 120% or more and 130% or less, and 130% or more based on 100% of the length of the swelling tape before expansion. It may be 160% or less, 140% or more and 160% or less, 150% or more and 160% or less, or 130% or more and 150% or less.
- the length of the swelling tape after expansion may include both the longitudinal direction and the width direction. That is, the ratio of the length of the swelling tape after expansion and the length of the swelling tape before expansion may be the same in the longitudinal direction and the width direction. Additionally, the length of the swelling tape may mean measuring the length from one end to the other end of the swelling tape in a specific direction. For example, when measuring the length from one end in the longitudinal direction of the swelling tape to the other end after expansion, it may be 120% or more and 160% or less, and after expansion based on the longitudinal center of the swelling tape before expansion. When measuring the length to one end in the longitudinal direction, it may be 110% or more and 130% or less.
- the swelling tape after expansion When the length of the swelling tape after expansion satisfies the above-mentioned range, even if the swelling tape is attached on at least one side of the first electrode so that one end coincides with the first end of the first electrode, the electrolyte solution is then By being impregnated, the swelling tape may be expanded to a length suitable for effectively surrounding the first end of the first electrode. Accordingly, the effect of protecting the first end of the first electrode may be excellent, and the effect of preventing internal short circuit and improving battery stability may be more excellent.
- the swelling tape may include a part made of a polymer material that absorbs electrolyte and expands or becomes flexible, and a part having adhesiveness for attaching the swelling tape to the first electrode.
- the swelling tape includes a base layer and an adhesive layer, and the adhesive layer may be provided on at least one side of the base layer.
- the swelling tape may include a multilayer structure of a base layer that absorbs and expands the electrolyte when impregnated with an electrolyte and an adhesive layer that attaches the swelling tape to the first electrode, and the adhesive layer is It may be provided on one or both sides of the base layer.
- the adhesive layer may include a pressure-sensitive adhesive containing a polyacrylic resin. That is, the adhesive strength of the adhesive layer may be affected by the amount of pressure applied to the surface of the swelling tape.
- the adhesive layer may include one or more comonomers selected from the group consisting of poly methyl methacrylate (PMMA), poly ethyl methacrylate (PEMA), and poly butyl methacrylate (PBMA).
- the adhesive layer is composed of monomers such as EA (Ethyl acrylate), BA (Butyl acrylate), and 2-EHA (2-Ethylhexyl acrylate), PMMA (poly methyl methacrylate), PEMA (poly ethyl methacrylate), and PBMA (poly butyl). It may include a polyacrylic resin manufactured by copolymerizing a comonomer selected from the group consisting of methacrylate).
- the adhesive layer includes the above-described material, the adhesive force of the swelling tape can be maintained at an appropriate level while minimizing the impact on the electrochemical properties of the battery including the swelling tape.
- the base layer may include a urethane-based resin.
- the base layer may include polyurethane resin, etc.
- the electrolyte absorption of the swelling tape may be easier, and when impregnated with the electrolyte solution, the swelling tape has a length suitable to effectively surround the first end of the first electrode. It may be expanded to .
- the electrolyte solution may include an organic solvent.
- the organic solvent is any of ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and mixtures thereof. It may contain more than 70 wt% of one.
- the electrolyte may contain a mixed organic solvent containing 45 wt% or more of dimethyl carbonate.
- the electrolyte solution may include 45 wt% of dimethyl carbonate, 20 wt% of ethylene carbonate, and 15 wt% of ethylmethyl carbonate. It may contain a mixed organic solvent containing.
- the base layer when the base layer contains a urethane-based resin, the base layer may expand by absorbing the electrolyte solution, and when the electrolyte solution contains the above-mentioned type of organic solvent, the base layer containing the urethane-based resin may be expanded. Inflation may be easier. That is, the expansion of the swelling tape including the base layer may be easier, and the expanded swelling may effectively surround the first end of the first electrode to prevent damage to the separator.
- the electrolyte solution may further include an electrolyte.
- the electrolyte may include, but is not limited to, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, or a molten inorganic electrolyte that can be used when manufacturing a lithium secondary battery.
- the electrolyte may contain a metal salt such as LiPF 6 as an electrolyte, for example, 45 wt% of dimethyl carbonate, 20 wt% of ethylene carbonate, 15 wt% of ethylmethyl carbonate, and 15 wt of LiPF 6 as an electrolyte. It may be that an electrolyte containing % is used.
- the electrolyte further contains the above-described type of electrolyte, the swelling characteristics of the swelling tape may be superior compared to the case where the electrolyte is not included, and the expanded swelling of the first end of the first electrode This may effectively protect the separator and prevent damage to the separator.
- the first electrode may be an anode
- the second electrode may be a cathode
- the jelly-roll type electrode assembly includes a positive electrode; first separator; It may be a jelly-roll type electrode assembly in which a cathode and a second separator are sequentially laminated and wound, and includes a swelling tape attached to at least one side of the anode, wherein the anode is formed by an electrode assembly that begins to be wound along the longitudinal direction. 1 end; and a second end where winding ends, and the swelling tape may be attached so that one end coincides with the first end of the positive electrode.
- the first electrode may include a current collector and an active material layer provided on the current collector. That is, the positive electrode may include a positive electrode current collector and a positive electrode active material layer provided on the positive electrode current collector. Specifically, the positive electrode may include a positive electrode current collector and a positive electrode active material layer formed on one or both sides of the positive electrode current collector and containing a positive electrode active material. In other words, the positive electrode active material layer is formed on the positive electrode holding portion of the positive electrode current collector, and the surface not provided with the positive active material layer may be expressed as a positive electrode uncoated region.
- the positive electrode current collector may include a positive electrode holding portion to which the positive electrode active material is applied and a positive electrode uncoated portion to which the positive electrode active material is not applied, and may include a tab on the positive electrode uncoated portion.
- the positive electrode current collector may include a positive electrode uncoated region, and may include a positive electrode tab formed on the positive electrode uncoated region.
- the positive electrode current collector is not particularly limited as long as it is conductive without causing chemical changes in the battery.
- the positive electrode current collector includes stainless steel, aluminum, nickel, and titanium. , fired carbon, or surface treatment of aluminum or stainless steel with carbon, nickel, titanium, silver, etc. can be used. That is, the positive electrode current collector may be provided in the form of surface-treated stainless steel, aluminum foil, etc.
- the positive electrode current collector may typically have a thickness of 3 to 50 ⁇ m, but is not limited to this, and fine irregularities may be formed on the surface of the current collector to increase the adhesion of the positive electrode active material.
- it can be used in various forms such as films, sheets, foils, nets, porous materials, foams, and non-woven materials.
- the positive electrode active material may be a commonly used positive electrode active material.
- the positive electrode active material is a layered compound such as lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), or a compound substituted with one or more transition metals; Lithium iron oxide such as LiFe 3 O 4 ; Lithium manganese oxide with the formula Li 1+x Mn 2-x O 4 (0 ⁇ x ⁇ 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2 , etc.; lithium copper oxide (Li 2 CuO 2 ); Vanadium oxides such as LiV 3 O 8 , V 2 O 5 , and Cu 2 V 2 O 7 ; With the chemical formula LiNi 1-y M y O 2 (where M is at least one selected from the group consisting of Co, Mn, Al, Cu, Fe, Mg, B and Ga, and satisfies 0.01 ⁇ y ⁇ 0.3) Ni site type lithium nickel oxide expressed;
- the positive electrode active material layer may further include a positive electrode conductive material and a positive electrode binder.
- the anode conductive material is used to provide conductivity to the electrode, and can be used without particular restrictions in the battery being constructed as long as it does not cause chemical change and has electronic conductivity.
- the anode conductive material includes 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, and carbon fiber; Metal powders or metal fibers such as copper, nickel, aluminum, and silver; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Alternatively, conductive polymers such as polyphenylene derivatives may be used, and one type of these may be used alone or a mixture of two or more types may be used.
- 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, and carbon fiber
- Metal powders or metal fibers such as copper, nickel, aluminum, and silver
- Conductive whiskeys such as zinc oxide and potassium titanate
- Conductive metal oxides such as titanium oxide
- conductive polymers such as polyphenylene
- the positive electrode binder serves to improve adhesion between positive electrode active material particles and adhesion between the positive electrode active material and the positive electrode current collector.
- Specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, and carboxymethyl cellulose (CMC). ), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber. (SBR), fluorine rubber, or various copolymers thereof, and one type of these may be used alone or a mixture of two or more types may be used.
- PVDF polyvinylidene fluoride
- PVDF-co-HFP vinylidene flu
- the second electrode may include a current collector and an active material layer provided on the current collector. That is, the negative electrode may include a negative electrode current collector and a negative electrode active material layer provided on the negative electrode current collector. Specifically, the negative electrode may include a negative electrode current collector and a negative electrode active material layer formed on one or both sides of the negative electrode current collector and containing a negative electrode active material. In other words, the negative electrode active material layer is formed on the negative electrode holding portion of the negative electrode current collector, and the side not provided with the negative electrode active material layer can be expressed as a negative electrode uncoated region.
- the negative electrode current collector may include a negative electrode holding portion on which the negative electrode active material layer is formed and a negative electrode uncoated portion on which the negative electrode active material layer is not formed, and may include a tab on the negative electrode uncoated portion.
- the negative electrode current collector may include a negative electrode uncoated portion and may include a negative electrode tab formed on the negative electrode uncoated portion.
- the manufactured electrode assembly may include one or more negative electrode tabs.
- the negative electrode active material layer may include a negative electrode active material containing at least one selected from the group consisting of silicon-based materials and carbon-based materials.
- the negative electrode active material layer may further include a negative electrode conductive material and a negative electrode binder, and may include the negative electrode active material; cathode conductive material; And the cathode binder may be any material used in the art without limitation.
- the negative electrode current collector can be any conductive material without causing chemical changes in the battery, and is not particularly limited.
- the negative electrode current collector may be copper, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel surface treated with carbon, nickel, titanium, silver, etc. .
- a transition metal that adsorbs carbon well such as copper or nickel, can be used as the negative electrode current collector.
- the thickness of the negative electrode current collector may be 6 ⁇ m or more and 80 ⁇ m or less, but the thickness of the negative electrode current collector is not limited thereto.
- the negative electrode binder is polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride, polyacrylonitrile, Polymethylmethacrylate, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene.
- PVDF-co-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
- EPDM propylene-diene monomer
- SBR styrene butadiene rubber
- fluororubber poly acrylic acid
- materials whose hydrogen is replaced with Li, Na, or Ca etc. It may include at least one of the following, and may also include various copolymers thereof.
- the anode conductive material is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
- graphite such as natural graphite or artificial graphite
- Carbon black such as acetylene black, Ketjen black, channel black, Paneth black, lamp black, and thermal black
- Conductive fibers such as carbon fiber and metal fiber
- Conductive tubes such as carbon nanotubes
- Metal powders such as fluorocarbon, aluminum, and nickel powder
- Conductive whiskers such as zinc oxide and potassium titanate
- Conductive metal oxides such as titanium oxide
- Conductive materials such as polyphenylene derivatives may be used.
- One embodiment of the present invention includes a first electrode; first separator; A method of manufacturing a jelly-roll type electrode assembly in which a second electrode and a second separator are sequentially stacked and wound, comprising: (a) transferring the first electrode in a roll-to-roll manner; (b) attaching a swelling tape on at least one surface of a slitting area included in the first electrode; and (c) slitting the longitudinal center of the first electrode slitting area, wherein the step (b) includes the longitudinal center of the swelling tape being the longitudinal center of the first electrode slitting area. and the step (c) includes: a first end at which winding of the first electrode begins along the longitudinal direction; and slitting the longitudinal center of the slitting area to provide a second end where winding ends.
- the jelly-roll type electrode assembly manufacturing method is a jelly-roll type electrode assembly including a swelling tape that expands when impregnated with the electrolyte and is attached to cover one longitudinal end of the positive electrode.
- Productivity and economic efficiency can be secured by enabling production in a continuous process using roll to roll processing equipment.
- the jelly-roll type electrode assembly manufactured by the above manufacturing method includes a swelling tape that expands when impregnated with electrolyte and is attached to cover one longitudinal end of the positive electrode, thereby causing the electrode assembly to shrink/expand during battery charging and discharging. Damage to the anode and separator can be prevented from deformation, and even if separator damage occurs, the swelling tape prevents internal short circuit between the anode and cathode, thereby improving battery stability and lifespan characteristics.
- the method of manufacturing the jelly-roll type electrode assembly may include the step of (a) transferring the first electrode in a roll to roll method.
- step (a) may be performed using a roll-to-roll processing method in which several bendable metal foils, etc. are processed while moving between rollers.
- the electrode current collector is supplied by unwinding a roll winding a flexible, thin metal sheet-shaped electrode current collector, and an electrode slurry containing an electrode active material is applied to at least one side of the electrode current collector.
- This may mean a method of drying to form an electrode mixture layer and then rewinding and recovering the processed electrode current collector on another roll. That is, step (a) may be a step of transferring the first electrode for processing in the roll-to-roll method, and may be expressed as a first electrode transfer step (S11).
- the jelly-roll type electrode assembly manufacturing method includes the step of (b) attaching a swelling tape on at least one surface of the slitting area included in the first electrode.
- the slitting area may mean an area for cutting the first electrode by a slitting process of cutting the first electrode or the electrode assembly including the same to a set length, and the slitting area may be It may refer to a partial area in the longitudinal direction including the first electrode current collector and the first electrode active material layer included in the first electrode, and the slitting area may have a longitudinal length adjusted according to process conditions. Additionally, the length and position of the slitting area may change depending on the length and position of the swelling tape to which it is attached. That is, the slitting area may be set by changing the length and position of the swelling tape attached to one or both sides of the first electrode according to process conditions.
- step (b) may be attaching the swelling tape such that the longitudinal center of the swelling tape coincides with the longitudinal center of the first electrode slitting area.
- the swell is performed on at least one side of the slitting area included in the first electrode so that the longitudinal center of the swelling tape coincides with the longitudinal center of the first electrode slitting area. This may be by attaching a ring tape.
- the first electrode in the subsequent step of slitting the longitudinal center of the slitting area, includes a first end at which winding begins along the longitudinal direction; and providing a second end where winding is completed, and the first electrode is provided with a swelling tape of a predetermined length attached to at least one surface of the first end and the second end after the slitting step. It may be possible.
- step (b) may be a step of attaching a swelling tape on at least one surface of the slitting area included in the first electrode, and specifically, step (b) may be a step of attaching a swelling tape on one or both sides of the slitting area included in the first electrode, and may be expressed as a swelling tape attachment step (S12).
- the method of manufacturing the jelly-roll type electrode assembly may include the step of (c) slitting the longitudinal center of the first electrode slitting area.
- step (c) may be a step of cutting the first electrode or an electrode assembly including the same to a set length, and the cutting may be performed using a cutting knife or the like, but is not particularly limited. .
- step (c) includes: a first end at which winding of the first electrode begins along the longitudinal direction; and slitting the longitudinal center of the slitting area to provide a second end where winding ends.
- step (c) includes: a first end at which winding of the first electrode or the first electrode included in the electrode assembly begins along the longitudinal direction; and slitting the longitudinal center of the slitting area to provide a second end where winding ends.
- Step (c) may be performed in plural steps, and when performed during the first electrode preparation process (S10), step (c) may be expressed as a slitting step (S13).
- steps (a) and (b) may be performed during the first electrode preparation process (S10), and step (c) may be performed during the first electrode preparation process (S10). Alternatively, it may be performed after the first electrode preparation process (S10). Specifically, step (c) may be performed before or after the winding process (S50). More specifically, step (c) may be performed after the winding process (S50).
- a separate process is required to check the position of the slitted electrode end after the electrode is slitted and properly attach the protective tape to cover it. This is necessary, and after attaching the protective tape to the end of the electrode, an inspection process, for example, a vision inspection step, to rule out attachment defects may be additionally required.
- an inspection process for example, a vision inspection step, to rule out attachment defects may be additionally required.
- the winding process is performed only after the vision inspection step to reduce defects in the electrode assembly, the production speed of the jelly-roll type electrode assembly is greatly reduced, and the roll-to-roll process is virtually impossible.
- the jelly-roll type electrode assembly manufacturing method involves manufacturing the jelly-roll type electrode assembly including the swelling tape in a continuous process using existing roll to roll process equipment. It may be something that can be produced.
- the jelly-roll type electrode assembly manufacturing method includes a swelling tape attachment step (S12) in the first electrode preparation process (S10), so that step (c) is performed during the first electrode preparation process (S10) or It may be performed after the first electrode preparation process (S10), and therefore the entire process may be performed by a roll-to-roll process used in the industry.
- the method of manufacturing a jelly-roll type electrode assembly includes a jelly-roll type electrode assembly including a swelling tape that expands when impregnated with the electrolyte and is attached to cover one longitudinal end of the positive electrode, using an existing roll.
- a jelly-roll type electrode assembly including a swelling tape that expands when impregnated with the electrolyte and is attached to cover one longitudinal end of the positive electrode, using an existing roll.
- -Productivity and economic efficiency can be secured by enabling production in a continuous process using roll to roll process equipment.
- Figure 2 shows a schematic diagram of a method of manufacturing a jelly-roll type electrode assembly including a swelling tape and a method of manufacturing a jelly-roll type electrode assembly including a PET tape according to an embodiment of the present invention.
- Figure 2 (a) is a method of manufacturing a jelly-roll type electrode assembly including a swelling tape according to an embodiment of the present invention, a jelly-roll type electrode including the step (S12) of attaching the swelling tape.
- a method for manufacturing an assembly is schematically shown
- Figure 2(b) is a method for manufacturing a jelly-roll type electrode assembly including a PET tape, wherein a PET protective tape instead of the swelling tape surrounds the first end of the first electrode. This schematically shows the manufacturing method of the attached jelly-roll type electrode assembly.
- a protective tape to surround the first end of the first electrode, such as a jelly-roll type electrode assembly including a swelling tape according to an embodiment of the present invention
- an additional process is required. This may be what you need. That is, if a protective tape (PET) attachment step (S12') is included instead of the swelling tape attachment step (S12), an additional process may be required to produce an electrode with a similar structure.
- PET protective tape
- a protective tape (PET) attachment step (S12') is included instead of the swelling tape attachment step (S12), a step of slitting the first electrode (S11') after the first electrode transfer step (S12). ; And in order to attach a protective tape made of PET, a first electrode spacing step (S11'') of spacing the slit first electrode by a predetermined distance may be necessary, and by slitting the attached protective tape. An additional slitting step (S13') to surround the longitudinal end of the first electrode may be necessary.
- the slitting step (S11') is performed after stopping the winder of the running first electrode. It may be necessary, and a step (S11'') of spacing the first electrodes apart in consideration of the thickness of the first electrode so as to sufficiently surround the first end of the slitted first electrode may be further necessary. . Thereafter, attaching a protective tape on both sides of the spaced apart first electrode (S12'); And an additional slitting step (S13') of cutting the attached protective tape may be further required.
- the jelly-roll type electrode assembly manufacturing method includes a swelling tape attachment step (S12), thereby minimizing separate additional processes and attaching it to cover one end in the longitudinal direction of the positive electrode.
- a jelly-roll type electrode assembly including a swelling tape can be provided.
- productivity and economic efficiency can be secured by enabling production in a continuous process using existing roll-to-roll processing equipment.
- Figure 3 is an image showing an implementation example of a jelly-roll type electrode assembly manufacturing method according to an embodiment of the present invention.
- Figure 3 (a) shows a state in which the swelling tape is attached to the slitting area included in the first electrode in the winding process (S50) after the swelling tape attachment step (S12).
- Figure 3(b) shows a state in which the swelling tape is attached so that one end coincides with the first end of the first electrode after the slitting step (S13), and
- Figure 3(c) shows the winding
- This image shows the disassembled jelly-roll type electrode assembly after the process (S50) and the swelling tape attached.
- the jelly-roll type electrode assembly manufacturing method includes a supply process (S20), a placement process (S30), a lamination process (S40), a winding process (S50), It may further include a tapping process (S60) and an inspection process (S70).
- the supply process (S20) may be to supply the first electrode and the second electrode together with the first separator and the second separator after the first electrode preparation process (S10), and the arrangement process (S30) ) may be to sequentially arrange the first electrode, first separator, second electrode, and second separator supplied in the supply process (S20) and form a laminate.
- the lamination process (S40) pressurizes and heats the laminate manufactured in the batch process (S30), that is, the laminate including the first electrode, the first separator, the second electrode, and the second separator.
- the electrode assembly may be provided by fusion.
- the winding process (S50) may involve winding the electrode assembly on which the lamination process has been performed, and may further include a slitting process of cutting the electrode assembly to a set length before or after the winding process.
- the taping process (S60) may be to finish the outer surface of the electrode assembly wound in the winding process (S50) with a thread tape, and the taping process may be performed on the first electrode, the first separator, and the second electrode. And, the longitudinal ends of the second separator may be spaced apart to prevent defects such as the electrode assembly coming loose.
- the inspection process (S70) is a vision inspection step of determining defects by inspecting the shape, arrangement, damage, etc. of the first electrode, first separator, second electrode, and second separator included in the electrode assembly, the electrode assembly It may include a withstand voltage test step of supplying power to and measuring the withstand voltage to determine defects.
- the swelling tape used in the jelly-roll type electrode assembly manufacturing method may be the same as the swelling tape described above with respect to the jelly-roll type electrode assembly.
- the width direction length of the swelling tape may be 60% or more and 100% or less based on 100% of the width of the first electrode.
- the width direction length of the swelling tape is 70% to 100%, 80% to 100%, 60% to 90%, 60% to 80%, based on 100% of the width of the first electrode.
- it may be 60% or more and 70% or less, or 70% or more and 90% or less.
- the longitudinal length of the swelling tape may be 500% or more and 7000% or less based on 100% of the thickness of the first electrode.
- the longitudinal length of the swelling tape may be 600% or more, 700% or more, 800% or more, or 1000% or more based on 100% of the thickness of the first electrode.
- the length may be 6000% or less, 5000% or less, 4000% or less, or 3000% or less, preferably 2000% or less, 1700% or less, or 1400% or less, based on 100% of the thickness of the first electrode. .
- the length of the swelling tape slit after step (c) is within an appropriate range, that is, 250% based on 100% of the thickness of the first electrode. It may be 3500% or less, preferably 250% or more and 1000% or less, and the longitudinal length of the swelling tape after expansion may correspond to the thickness of the first electrode, and one end of the swelling tape may be the first electrode. 1 It effectively wraps one end of the electrode in the longitudinal direction, minimizing the impact on electrochemical properties such as the capacity reduction rate of the battery including the swelling tape, while also preventing internal short circuit between the anode and cathode even if the separator is damaged. can be performed more efficiently.
- the longitudinal length of the swelling tape may be 0.75 mm or more and 10 mm or less.
- the longitudinal length of the swelling tape may be 1 mm or more, 1.25 mm or more, 1.5 mm or more, 1.75 mm or more, or 2 mm or more, and the longitudinal length of the swelling tape may be 2.75 mm or less, 2.5 mm or more. It may be less than or equal to 2.25 mm or less than or equal to 2 mm.
- the first electrode may be an anode
- the second electrode may be a cathode.
- the anode and cathode used in the jelly-roll type electrode assembly manufacturing method may be the same as those described above with respect to the jelly-roll type electrode assembly.
- One embodiment of the present invention provides a jelly-roll type electrode assembly manufactured by the above-described jelly-roll type electrode assembly manufacturing method.
- the jelly-roll type electrode assembly includes a swelling tape that expands when impregnated with an electrolyte and is attached to cover one longitudinal end of the positive electrode, thereby causing the electrode assembly to contract/expand during charging and discharging of the battery. Damage to the anode and separator can be prevented from deformation, and even if separator damage occurs, the swelling tape prevents internal short circuit between the anode and cathode, thereby improving battery stability and lifespan characteristics. Additionally, when the swelling tape surrounds the longitudinal end of the first electrode, the effect of relieving internal stress and improving the roundness of the core portion may be excellent due to the porous material characteristics of the swelling tape.
- One embodiment of the present invention includes the jelly-roll type electrode assembly; and a battery case for accommodating the electrode assembly.
- the secondary battery may include an electrode assembly according to the above-described embodiment and a battery case for accommodating the electrode assembly.
- the secondary battery according to the present invention can improve battery stability and lifespan characteristics by preventing internal short circuit between the positive and negative electrodes even when the electrode assembly is deformed due to contraction/expansion of the electrodes during charging and discharging of the battery.
- the battery case may be cylindrical.
- the battery case may be cylindrical, square, or pouch-shaped depending on the purpose, but is not limited thereto.
- the interior of the battery case may contain electrolyte.
- the electrolyte may include, but is not limited to, an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, or a molten inorganic electrolyte that can be used in the manufacture of a lithium secondary battery.
- the electrolyte may include a non-aqueous organic solvent and a metal salt.
- the non-aqueous organic solvent includes, for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and ethylmethyl.
- the metal salt may be a lithium salt
- the lithium salt is a material that is easily soluble in the non-aqueous electrolyte solution.
- anions of the lithium salt include F - , Cl - , I - , NO 3 - , N(CN) 2- , BF 4 - , ClO 4 - , PF 6 - , (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF
- the electrolyte in addition to the electrolyte components, includes, for example, halo such as difluoroethylene carbonate for the purpose of improving battery life characteristics, suppressing battery capacity reduction, and improving battery discharge capacity.
- halo such as difluoroethylene carbonate
- One or more additives such as dinon, N,N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol, or aluminum trichloride may be further included.
- An Al foil with a thickness of 15 ⁇ m and a width direction of 63.9 mm was prepared as a positive electrode current collector, and an NMCA (Ni-Mn-Co-Al) composite with a Ni content of 92% or more as a positive electrode active material and a conductive material were placed on the positive electrode current collector.
- a positive electrode active material layer was formed by applying and drying a positive electrode active material slurry containing CNTs, thereby producing a positive electrode with a total thickness of 154 ⁇ m.
- a swelling tape with a thickness of 52 ⁇ m was prepared with an adhesive layer containing a copolymer of ethyl acrylate (EA) and polyethyl methacrylate (PEMA) on one side of the base layer made of polyurethane (PU), A swelling tape was attached to one side of the slitting area of the anode to have a length of 62 mm in the width direction and 10 mm in the longitudinal direction.
- EA ethyl acrylate
- PEMA polyethyl methacrylate
- a Cu foil with a thickness of 10 ⁇ m and a length of 62 mm in the width direction as a negative electrode current collector
- a negative electrode active material slurry containing 50 parts by weight of artificial graphite and natural graphite as a negative electrode active material on the negative electrode current collector.
- a negative electrode active material layer was formed by drying, thereby producing a negative electrode with a total thickness of 187 ⁇ m.
- the anode, the first separator, the cathode, and the second separator are sequentially placed to form a laminate, then pressurized and heat-sealed, the center of the slitting area is slit, and the first end where the winding of the anode begins.
- the laminate is wound to be located in the core portion, and a seal tape made of PET is attached and finished to the second end where the winding ends to cover the upper and lower outer peripheral surfaces of the jelly-roll to form a jelly-roll type electrode.
- the assembly was manufactured.
- the seal tape was used with a length of 62 mm in the longitudinal direction, a length of 10 mm in the width direction, and a thickness of 22 ⁇ m, and the length of the swelling tape after slitting was 5 mm.
- ethylene carbonate (EC): dimethyl carbonate (DMC): ethyl methyl carbonate (EMC) was mixed in a ratio of 4:9:3.
- An electrolyte solution containing 15 wt% of LiPF 6 was mixed by weight and injected, and a cylindrical battery can was sealed with a cap assembly to manufacture a secondary battery.
- a jelly-roll type electrode assembly and a secondary battery were prepared in the same manner as in Example 1, except that swelling tapes were attached on both sides of the slitting area of the positive electrode to have a width of 62 mm and a longitudinal length of 5 mm. was manufactured.
- a jelly-roll type electrode assembly and a secondary battery were manufactured in the same manner as Example 1, except that a PET tape was attached to one side of the slitting area of the positive electrode to have a width of 62 mm and a longitudinal length of 10 mm. did.
- a jelly-roll type electrode assembly and a secondary battery were manufactured in the same manner as Example 1, except that the swelling tape was not attached to the slitting area of the positive electrode.
- a jelly-roll type electrode assembly and a secondary battery were made in the same manner as in Example 1, except that PET tape was attached to each to be 10 mm and then the center was additionally slitted to have the structure shown in (b) of FIG. 1. Manufactured.
- Example 1 Prepare a sample of the same material as the swelling tape used in Example 1 and Example 2 (10 mm in longitudinal direction, 62 mm in width direction), and add ethylene carbonate (EC) and dimethyl carbonate. , DMC) and ethyl methyl carbonate (EMC) were prepared by dissolving LiPF 6 as an electrolyte in a mixed solvent. Thereafter, the swelling tape sample was immersed in the electrolyte solution for 60 minutes, and the length of the swelling tape before expansion and the length of the swelling tape after expansion were measured, respectively.
- the composition of the electrolyte solution used for swelling evaluation is shown in Table 1 below.
- Table 1 The swelling characteristics of the swelling tape samples were evaluated in the same manner as in Experimental Examples 1-1 to 1-6, except that they were impregnated with electrolyte solutions of the compositions shown in Table 1 below.
- Figure 4 shows DMC and the composition of Experimental Example 1-1. After impregnating the swelling tape sample in the electrolyte solution for 60 minutes, the ratio of the transverse direction (TD) and machine direction (MD) length of the swelling tape after expansion to the length of the swelling tape before expansion was calculated, respectively. It is calculated and shown.
- TD transverse direction
- MD machine direction
- the longitudinal and width directions of the swelling tape after expansion were about 140% of the length of the swelling tape before expansion.
- the longitudinal expansion of the swelling tape occurred at the same rate in both the longitudinal and width directions, and it was confirmed that the swelling tape expanded by about 120% on one side from the center to one end before expansion.
- Example 1 The secondary batteries prepared in Example 1 and Comparative Example 1 were activated by performing 2 cycles of 4.2 V-2.5 V, 0.2 C charging, and 0.2 C discharging, respectively, and then disassembled to produce jelly-roll type electrode assemblies before and after activation. Prepared, the anode end of the jelly-roll type electrode assembly was observed with the naked eye, and the evaluation results are shown in Figures 5 and 6 below.
- Figure 5(a) shows the first end of the first electrode before activation of the jelly-roll type electrode assembly according to Example 1
- Figure 5(b) shows the jelly-roll type electrode according to Example 1. It shows the first end of the first electrode after activation of the assembly
- Figure 6 (a) shows the first end of the first electrode before activation of the jelly-roll type electrode assembly according to Comparative Example 1
- Figure 6 (a) shows the first end of the first electrode before activation of the jelly-roll type electrode assembly according to Comparative Example 1.
- b) shows the first end of the first electrode after activation of the jelly-roll type electrode assembly according to Comparative Example 1.
- the swelling tape attached so that one end coincides with the first end of the first electrode before activation is expanded after activation to form the first end of the first electrode. It was confirmed that the end was wrapped.
- the length (2L) of the swelling tape attached to at least one side of the slitting area included in the first electrode is 10 mm, and the step of slitting the longitudinal center of the first electrode slitting area.
- the length of the swelling tape before expansion (L) was measured to be 5 mm
- the length of the swelling tape after expansion (L') was 7 mm
- the expansion length of the swelling tape (L -s ) was measured to be a total of 2 mm.
- the length (L') of the swelling tape after expansion expanded to about 140% of the length (L) of the swelling tape before expansion, and the swelling tape stretched to one end based on the center before expansion.
- the jelly-roll type electrode assembly including the swelling tape according to the present invention is expanded by the electrolyte solution, and after expansion, the swelling tape effectively surrounds the first end of the first electrode.
- Example 1 The secondary batteries manufactured in Example 1 and Comparative Example 2 were tested for battery characteristics through a 25°C Cycle Test.
- Figure 7 (a) shows the change in coulombic efficiency of the secondary battery manufactured in Example 1 and Comparative Example 2 as the cycle progresses
- Figure 7 (b) shows the change in coulombic efficiency of the secondary battery manufactured in Example 1 and Comparative Example 2. This shows the results of room temperature-voltage tracking evaluation over time of the secondary battery.
- the secondary battery according to Example 1 did not exhibit any special abnormal behavior, but the secondary battery according to Comparative Example 2 exhibited abnormal coulombic efficiency behavior, that is, the occurrence of leak current. Confirmed.
- the secondary battery according to Example 1 maintained a voltage of 1.0 V or more even after 12 hours, but the secondary battery according to Comparative Example 2 failed to maintain a constant voltage and decreased over time. It was confirmed that the voltage gradually decreased. Through this, it can be seen that the separator was damaged and an internal short circuit occurred.
- each secondary battery according to Example 1 was disassembled and visually evaluated for damage to the separator, and the results are shown in FIG. 8 below.
- Figure 8 (a) is an image showing the state of the first electrode facing portion of the separator included in the secondary battery manufactured in Example 1
- Figure 8 (b) is an image showing the state of the secondary battery manufactured in Comparative Example 2. This is an image showing the state of the first electrode facing portion of the included separator.
- the secondary battery according to the present invention improves battery stability and lifespan characteristics by preventing internal short circuit between the anode and cathode even when the electrode assembly is deformed due to contraction/expansion of the electrode during battery charging and discharging.
- Figure 9 is an image showing the roundness evaluation results of the secondary batteries manufactured in Example 1 and Comparative Example 3. Referring to Table 2, by wrapping the longitudinal end of the positive electrode using a PET protective tape, swelling after expansion was achieved. In the case of the secondary battery according to Comparative Example 3, which has a similar structure to the secondary battery according to Example 1 including a tape, the takt time is about 2 times increased to 3.0 s compared to the secondary battery according to Example 1. It was confirmed that productivity was inferior.
- the jelly-roll type electrode assembly manufacturing method includes the step of attaching a swelling tape, thereby minimizing separate additional processes, and a swelling tape attached to cover one end in the longitudinal direction of the positive electrode. It can be seen that a jelly-roll type electrode assembly containing a can be provided, and productivity and economic efficiency can be secured by enabling production in a continuous process using existing roll-to-roll processing equipment.
- the secondary battery according to the present invention includes a structure where the swelling tape surrounds the longitudinal end of the first electrode after expansion, so that even when the electrode assembly is deformed due to contraction/expansion of the electrode during charging and discharging, the positive electrode and
- the swelling tape surrounds the longitudinal end of the first electrode after expansion, so that even when the electrode assembly is deformed due to contraction/expansion of the electrode during charging and discharging, the positive electrode and
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Abstract
Description
용매 | 염 | 팽창정도 | |||||
EC(wt%) | PC(wt%) | DMC(wt%) | EMC(wt%) | LiPF6(wt%) | TD(%) | MD(%) | |
참고예 1-1 |
- | - | 100 | - | - | 118 | 117 |
실험예 1-1 | 18.53 | - | 45.01 | 14.31 | 15.95 | 136 | 138 |
실험예 1-2 | 27.12 | 4.11 | 47.59 | - | 15.48 | 137 | 136 |
실험예 1-3 | 28.02 | 4.24 | 49.18 | - | 15.56 | 140 | 140 |
실험예 1-4 | 26.33 | 3.99 | 46.2 | - | 7.61 | 141 | 140 |
실험예 1-5 | 27.37 | 4.14 | 48.03 | - | 15.46 | 138 | 140 |
실험예 1-6 | 27.58 | 4.18 | 48.4 | - | 15.54 | 140 | 139 |
택 타임(sec) | 진원도(%) | |
실시예 1 | 1.55 | 91 |
비교예 3 | 3.0 | 89.0-89.9 |
Claims (19)
- 제1 전극; 제1 분리막; 제2 전극 및 제2 분리막이 차례대로 적층되어 권취된 젤리-롤형 전극조립체에 있어서,상기 제1 전극의 적어도 일면 상에 부착되는 스웰링 테이프를 포함하고,상기 제1 전극은 길이방향을 따라 권취가 시작되는 제1 단부; 및 권취가 종료되는 제2 단부를 포함하고,상기 스웰링 테이프는 상기 제1 전극의 제1 단부와 일 단부가 일치하도록 부착되는 것인 젤리-롤형 전극조립체.
- 제1항에 있어서,상기 스웰링 테이프의 폭방향 길이는 상기 제1 전극의 폭 100 %를 기준으로, 60 % 이상 100 % 이하인 것인 젤리-롤형 전극조립체.
- 제1항에 있어서,상기 스웰링 테이프의 길이방향 길이는 상기 제1 전극의 두께 100 %를 기준으로, 250 % 이상 3500 % 이하인 것인 젤리-롤형 전극조립체.
- 제1항에 있어서,상기 스웰링 테이프는 전해액에 의해 팽창되고,팽창 후 상기 스웰링 테이프는 상기 제1 전극의 제1 단부를 감싸는 것인 젤리-롤형 전극조립체.
- 제4항에 있어서,상기 전해액은 에틸렌카보네이트(ethylene carbonate, EC), 프로필렌카보네이트(propylene carbonate, PC), 디메틸카보네이트(dimethyl carbonate, DMC), 에틸메틸카보네이트(ethyl methyl carbonate, EMC) 및 이들의 혼합물 중 어느 하나를 70 wt% 이상 포함하는 것인 젤리-롤형 전극조립체.
- 제4항에 있어서,디메틸카보네이트 45 wt%, 에틸렌카보네이트 20 wt%, 에틸메틸카보네이트 15 wt% 및 전해질로서 LiPF6를 15 wt% 포함하는 전해액에 60 분 동안 함침 후 상기 스웰링 테이프의 길이는,팽창 전 상기 스웰링 테이프의 길이 100 %를 기준으로 120 % 이상 160 % 이하인 것인 젤리-롤형 전극조립체.
- 제1항에 있어서,상기 스웰링 테이프는 기재층 및 점착층을 포함하고,상기 점착층은 상기 기재층의 적어도 일면 상에 구비되는 것인 젤리-롤형 전극조립체.
- 제7항에 있어서,상기 점착층은 폴리아크릴계 수지를 포함하는 감압성 접착제를 포함하는 것인 젤리-롤형 전극조립체.
- 제7항에 있어서,상기 점착층은 PMMA(poly methyl methacrylate), PEMA(poly ethyl methacrylate), PBMA(poly butyl methacrylate)로 이루어진 군에서 선택되는 공단량체를 1 이상 포함하는 것인 젤리-롤형 전극조립체.
- 제7항에 있어서,상기 기재층은 우레탄계 수지를 포함하는 것인 젤리-롤형 전극조립체.
- 제1항에 있어서,상기 제1 전극은 양극이고, 상기 제2 전극은 음극인 것인 젤리-롤형 전극조립체.
- 제1항에 있어서,상기 제1 전극은 집전체 및 상기 집전체 상에 구비된 활물질층을 포함하는 것인 젤리-롤형 전극조립체.
- 제1 전극; 제1 분리막; 제2 전극 및 제2 분리막이 차례대로 적층되어 권취된 젤리-롤형 전극조립체를 제조하는 방법으로서,(a) 롤-투-롤(roll to roll) 방식으로 상기 제1 전극을 이송하는 단계;(b) 상기 제1 전극에 포함되는 슬리팅(slitting) 영역의 적어도 일면 상에 스웰링 테이프를 부착하는 단계; 및(c) 상기 제1 전극 슬리팅 영역의 길이방향 중심부를 슬리팅하는 단계를 포함하고,상기 (b) 단계는 상기 스웰링 테이프의 길이방향 중심부가 상기 제1 전극 슬리팅 영역의 길이 방향 중심부와 일치하도록 부착하는 것이고,상기 (c) 단계는 상기 제1 전극을 길이방향을 따라 권취가 시작되는 제1 단부; 및 권취가 종료되는 제2 단부를 제공하도록 상기 슬리팅 영역의 길이방향 중심부를 슬리팅하는 것인 젤리-롤형 전극조립체 제조방법.
- 제13항에 있어서,상기 스웰링 테이프의 폭방향 길이는 상기 제1 전극의 폭 100 %를 기준으로, 60 % 이상 100 % 이하인 것인 젤리-롤형 전극조립체 제조방법.
- 제13항에 있어서,상기 스웰링 테이프의 길이방향 길이는 상기 제1 전극의 두께 100 %를 기준으로, 500 % 이상 7000 % 이하인 것인 젤리-롤형 전극조립체 제조방법.
- 제13항에 있어서,상기 제1 전극은 양극이고, 상기 제2 전극은 음극인 것인 젤리-롤형 전극조립체 제조방법.
- 제13항에 따른 제조방법에 의하여 제조되는 것인 젤리-롤형 전극조립체.
- 제1항 내지 제12항 및 제17항 중 어느 한 항에 따른 젤리-롤형 전극조립체; 및상기 전극조립체를 수용하기 위한 전지케이스를 포함하는 것인 이차전지.
- 제18항에 있어서,상기 전지케이스는 원통형인 것인 이차전지.
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EP23873049.3A EP4407739A1 (en) | 2022-09-26 | 2023-09-26 | Jelly-roll type electrode assembly, manufacturing method for jelly-roll type electrode assembly, and secondary battery comprising same |
CN202380014433.XA CN118235279A (zh) | 2022-09-26 | 2023-09-26 | 卷绕型电极组件、用于卷绕型电极组件的制造方法以及包括该卷绕型电极组件的二次电池 |
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KR20220121663A (ko) | 2021-02-25 | 2022-09-01 | 인하대학교 산학협력단 | ArF 위상반전 블랭크 마스크용 차광막 제조 방법 및 장치 |
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KR20140065592A (ko) * | 2012-11-16 | 2014-05-30 | 주식회사 엘지화학 | 간극 충진용 스웰링 테이프 |
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KR20220121663A (ko) | 2021-02-25 | 2022-09-01 | 인하대학교 산학협력단 | ArF 위상반전 블랭크 마스크용 차광막 제조 방법 및 장치 |
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