WO2014081227A1 - Corrosion-resistant washer, and secondary battery comprising same - Google Patents

Corrosion-resistant washer, and secondary battery comprising same Download PDF

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Publication number
WO2014081227A1
WO2014081227A1 PCT/KR2013/010635 KR2013010635W WO2014081227A1 WO 2014081227 A1 WO2014081227 A1 WO 2014081227A1 KR 2013010635 W KR2013010635 W KR 2013010635W WO 2014081227 A1 WO2014081227 A1 WO 2014081227A1
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WIPO (PCT)
Prior art keywords
washer
secondary battery
rust
nano
present
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Application number
PCT/KR2013/010635
Other languages
French (fr)
Korean (ko)
Inventor
김도균
황보광수
이향목
정상석
Original Assignee
주식회사 엘지화학
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Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2014551216A priority Critical patent/JP6007447B2/en
Priority to CN201380002416.0A priority patent/CN103959514B/en
Publication of WO2014081227A1 publication Critical patent/WO2014081227A1/en

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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/571—Methods or arrangements for affording protection against corrosion; Selection of materials therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/147—Lids or covers
    • H01M50/166—Lids or covers characterised by the methods of assembling casings with lids
    • H01M50/167—Lids or covers characterised by the methods of assembling casings with lids by crimping
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/147—Lids or covers
    • H01M50/166—Lids or covers characterised by the methods of assembling casings with lids
    • H01M50/171—Lids or covers characterised by the methods of assembling casings with lids using adhesives or sealing agents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/184—Sealing members characterised by their shape or structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/191—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/193—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/195—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
    • H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/598—Guarantee labels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • 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

Definitions

  • the present invention relates to a rust-proof washer comprising a vaporizable rust inhibitor and a secondary battery comprising the same.
  • secondary batteries are classified into cylindrical batteries and rectangular batteries in which the electrode assembly is embedded in a cylindrical or rectangular metal can, and pouch-type batteries in which the electrode assembly is embedded in a pouch type case of an aluminum laminate sheet. .
  • a secondary battery in general, includes a can and an electrode assembly accommodated in the can; A cap assembly coupled to the top opening of the can; And a washer mounted to the top of the cap assembly.
  • the washer attached to the cap assembly basically serves to supplement the electrical insulation state, and also serves to protect the battery cell from external shock and to supplement the mechanical strength of the members mounted on the top of the battery cell. do. In addition, it also serves to improve the safety of the battery cell by preventing the internal short circuit of the battery that may be caused by the corrosion of the battery cell and the electronic devices such as PCM (current blocking device).
  • PCM current blocking device
  • polymer resin layers such as polypropylene, polyethylene, rayon, blended yarns, polyviscose, polynosics, and synthetic resins thereof have been used as washers for cylindrical batteries.
  • FIG. 1 there is a problem that rust occurs in a crimping portion of a cylindrical battery in a high temperature and high humidity atmosphere, and an improvement therefor is required.
  • the problem to be solved by the present invention is to provide a secondary battery comprising a rust-proof washer that can prevent the occurrence of rust or corrosion of the crimping portion of the battery.
  • the present invention provides a rust-proof washer for a secondary battery including a vaporizing rust inhibitor (VCI; Volatile Corrosion Inhibitor) and a base resin (base resin).
  • VCI vaporizing rust inhibitor
  • base resin base resin
  • the present invention is a secondary battery in which the electrode assembly of the anode / separator / cathode structure is embedded in the metal can, the washer (mounter) is mounted on the top of the cap assembly mounted on the open top of the metal can containing the electrode assembly
  • the washer provides a secondary battery including an anti-rust washer including a base resin and a vaporizable anti-corrosive agent.
  • the secondary battery including the rust-proof washer of the present invention can prevent the occurrence of rust or corrosion of the crimping portion of the battery to improve the safety of the battery.
  • 1 is a photograph showing a rusting image of the crimping portion of the cylindrical battery.
  • Figure 2 shows the manufacturing process of the anticorrosive wash washer according to an embodiment of the present invention.
  • FIG 3 is a schematic cross-sectional view showing an upper structure of a cylindrical secondary battery according to an embodiment of the present invention.
  • FIG. 4 shows an actual picture of a cylindrical battery equipped with an anti-rust washer according to an embodiment of the present invention.
  • FIG. 5 and 6 are photographs of the cylindrical battery manufactured according to one embodiment of the present invention stored in a sealed state in vinyl to test whether rust occurs.
  • An anti-rust washer for a secondary battery includes a vapor-proof rust inhibitor (VCI; Volatile Corrosion Inhibitor) and a base resin.
  • VCI vapor-proof rust inhibitor
  • base resin a vapor-proof rust inhibitor
  • the anti-corrosive washer is excellent in rust prevention property to prevent the occurrence of rust or corrosion of the crimping portion of the secondary battery can improve the safety of the battery.
  • the rust preventive property is a property of preventing the formation of a compound mainly composed of a hydroxide or an oxide on the metal surface, and means a property of preventing the generation of decay products on the metal surface.
  • the vaporizable rust inhibitor according to an embodiment of the present invention may include a polymer resin and NaNO 2 or NaNO 3 .
  • the vaporizable rust preventive agent may be composed of a mixture based on NaNO 2 or NaNO 3 or a compound having sublimation at room temperature and having rust resistance.
  • the polymer resin used in the present invention may be a polymer resin or a polymer synthetic resin that is commonly used.
  • polypropylene (PP), polybutylene terephthalate, polyethylene, PET, Teflon, polytetrafluoroethylene, rayon, blended yarn, polyviscose and polynostic, or a mixture of two or more thereof may be, but is not limited to these.
  • the anti-corrosive washer of the present invention may be obtained by mixing the vaporizing anti-corrosive agent and the base resin, and extruding it in an extruder to form a desired washer shape.
  • the base resin may be a polymer resin or polymer synthetic resin that is commonly used, for example, polypropylene (PP), polybutylene terephthalate, polyethylene, PET, Teflon, polytetrafluoroethylene, rayon, blended yarn It may be one or a mixture of two or more selected from the group consisting of polyviscos and polynosic.
  • NaNO 2 or NaNO 3 is finely ground until a uniform appearance.
  • the pulverized NaNO 2 or NaNO 3 can be mixed with the polymer resin to obtain a vaporizable rust inhibitor. After mixing and extruding it with the base resin, it can be punched out in the shape of a washer to produce an antirust washer.
  • the grinding process of NaNO 2 or NaNO 3 may be performed at room temperature and atmospheric pressure.
  • NaNO 2 or NaNO 3 must be uniformly dispersed in a uniform state to produce a rust preventive washer containing a uniform vaporizable rust inhibitor, further improving the rust resistance of the battery.
  • the NaNO 2 or NaNO 3 may be used in 3 to 30% by weight based on 100% by weight of the polymer resin, but is not limited thereto.
  • the pulverized NaNO 2 or NaNO 3 may be mixed with the molten polymer resin, preferably the molten polypropylene resin. At this time, it is possible to use a solvent and other additives when mixing, which can be used as commonly known in the art. At this time, the vaporizable rust preventive agent, for example, can be pelletized so that it can be easily stored and used, it can be made at room temperature, atmospheric pressure.
  • the vaporizable rust inhibitor produced in this way may be mixed with the base resin at a predetermined ratio according to the use, and for example, the vaporizable rust preventive agent may be used in an amount of 1 to 30 wt% based on 100 wt% of the base resin.
  • the mixture may be extruded at a constant temperature to obtain an extruded sheet, and the extruded sheet may be punched into a desired washer shape using a mold to obtain a rust preventive washer for secondary batteries of the present invention.
  • the washer preferably has a thickness of 0.1 mm to 0.8 mm.
  • the anti-corrosive washer it can be used by further adding a solvent and other additives used in the art, the method is only one example, it does not limit the present invention.
  • the present invention includes a secondary battery including the anti-rust washer.
  • a secondary battery according to an embodiment of the present invention is a secondary battery in which an electrode assembly having a cathode / separation membrane / cathode structure is embedded in a metal can, and a washer at the top of a cap assembly mounted on an open top of the metal can in which the electrode assembly is embedded.
  • a washer may be mounted, and the washer may be an anticorrosive washer including a base resin and a vaporizable rust inhibitor as described above.
  • the anti-corrosive washer may function by the following principle.
  • NaNO 2 or NaNO 3 can be dispersed in crystals inside the rust-proof washer, and slowly oxidized in the air to form NaNO 3 , so that NaNO 2 and NaNO 3 coexist in the rust-proof washer.
  • the NaNO 2 and NaNO 3 meet with moisture in the air to form HNO 2 (nitrous acid; nitrous acid) and HNO 3 (nitric acid; nitric acid), where HNO 3 is finely formed on the metal surface of the metal can of the secondary battery. Corrosion can be prevented by oxidizing.
  • these HNO 2 and HNO 3 when reacted with the iron surface of the metal can, the VCI gas (gas) action at the end of the metal can is 10 kPa to 1000 kPa thickness
  • Gamma iron trioxide ( ⁇ -Fe 2 O 3 ) may be formed.
  • the gamma iron trioxide ( ⁇ -Fe 2 O 3 ) formed at the end of the metal can further prevent rusting of the battery cell.
  • the metal can may be a cylindrical can or a rectangular can.
  • the cap assembly in the case of a cylindrical can, the cap assembly includes a positive electrode protruding terminal connected to an electrode assembly, a cap plate is connected to a positive electrode terminal, and the can forms a negative terminal. It may be a structure.
  • the cap assembly may have a cathode protruding terminal connected to an electrode terminal at a center thereof, and the rectangular can and the cap plate may have a structure in which an anode terminal is formed in an insulated state from the cathode terminal.
  • the secondary battery according to the present invention may preferably be a lithium secondary battery having a high energy density, discharge voltage, and output stability.
  • Such lithium secondary batteries are composed of a positive electrode, a negative electrode, a separator, a lithium salt-containing nonaqueous electrolyte, and the like.
  • the positive electrode is prepared by, for example, applying a mixture of a positive electrode active material, a conductive material, and a binder onto a positive electrode current collector, followed by drying, and further, a filler may be further added as necessary.
  • the negative electrode is also manufactured by coating and drying a negative electrode material on a negative electrode current collector, and if necessary, the components as described above may be further included.
  • the separator is interposed between the cathode and the anode, and an insulating thin film having high ion permeability and mechanical strength is used as the separator.
  • the lithium salt-containing non-aqueous electrolyte solution consists of a nonaqueous electrolyte solution and a lithium salt, and a liquid nonaqueous electrolyte solution, a solid electrolyte, an inorganic solid electrolyte, and the like are used as the nonaqueous electrolyte solution.
  • the electrode active material As the current collector, the electrode active material, the conductive material, the binder, the filler, the separator, the electrolyte, the lithium salt, and the like, conventional ones known in the art may be used.
  • the secondary battery according to the present invention can be produced by conventional methods known in the art. That is, it may be prepared by inserting a porous separator between the anode and the cathode and injecting the electrolyte therein.
  • the positive electrode may be manufactured by applying a slurry containing a lithium transition metal oxide active material, a conductive material, and a binder as a positive electrode active material onto a current collector, followed by drying and rolling.
  • the negative electrode can be produced by, for example, applying a slurry containing a carbon active material, a conductive material, and a binder as a negative electrode active material on a thin current collector, as described above, and then drying.
  • FIG 3 is a partial cross-sectional view schematically showing an upper structure of a cylindrical secondary battery according to one embodiment of the present invention.
  • the battery 100 inserts an electrode assembly 300 as a power generator into the can 200, injects an electrolyte solution therein, and cans (
  • the cap assembly 400 is mounted on the upper opening of the 200, and the can 200 is inserted into the heat shrinkable tubing 220 while applying the predetermined heat while the cap assembly 400 is mounted.
  • the cap assembly 400 may include a positive temperature coefficient (PTC) element 420 for preventing an overcurrent and a safety vent 430 for maintaining a pressure inside a battery in a normal state.
  • PTC positive temperature coefficient
  • the PTC device 420 and the safety vent 430 are in close contact with each other in the airtight gasket mounted on the upper beading part 210 of the can 200 to block overcurrent to the upper cap 410. Is installed.
  • the upper cap 410 protrudes upward, and serves as a positive electrode terminal by connection with an external circuit.
  • the safety vent 430 has a lower end thereof connected to the anode of the power generator 300 through the current blocking member 440 and the anode lead 310.
  • the safety vent 430 is a conductive thin plate, the center of which forms a downward indentation 432, and two notches having different depths are formed in the upper and lower bending portions of the indentation 432. It is.
  • the washer 500 is formed of a disc structure as a whole so as to be mounted on the bead 210 while surrounding the top cap 410 of the cap assembly 400. Meanwhile, when the heat shrinkable tubing 220 is contracted, the heat shrinkable tubing 220 surrounds the outer circumferential surface of the washer 500 while mounting the washer 500 to the cap assembly 400.
  • the thickness of the washer 500 may vary depending on its material, but is not particularly limited, and may preferably be 0.1 mm to 0.8 mm. Since the thickness of the washer affects its mechanical rigidity, elasticity, etc., if the washer thickness is too thin, it does not exhibit the desired mechanical rigidity and can be destroyed by a weak external impact. On the contrary, if the washer thickness is too thick, The increase in size of the battery is remarkable, which is undesirable. Therefore, these points can be considered in combination, and can be appropriately determined within the above range.
  • the washer 500 mounted to the cap assembly may be fixed to the corresponding parts in various ways.
  • a heat shrinkable tubing fixed to the outer circumferential surface of the washer or mounted on the outer surface of the can during crimping of the cap assembly may be provided.
  • a mechanical coupling method of fixing the outer circumferential surface of the washer while being contracted, an adhesive method of adding an adhesive to the lower surface of the washer or the upper surface of the cap assembly, and the like may be used.
  • the washer 500 may prevent the internal short from occurring when the upper cap 410 as the positive terminal contacts the can 200 as the negative terminal.
  • Figure 4 shows an actual picture of the cylindrical battery equipped with the washer.
  • the cylindrical battery according to an embodiment of the present invention can be provided with tubing (tubing) on the outside of the rust-proof washer can wrap the outer peripheral surface of the washer.
  • NaNO 2 was mixed well until it reached a uniform property at room temperature and atmospheric pressure, and then finely ground.
  • the pulverized NaNO 2 was mixed with the molten polypropylene resin to obtain a vaporizable rust inhibitor (VCI).
  • VCI vaporizable rust inhibitor
  • the pelletized vaporizable rust preventive agent was mixed with a polypropylene resin as a base resin in a ratio of about 0.5: 10, and extruded at a predetermined temperature to obtain an extruded sheet, which was punched into a washer shape using a mold to prepare an rust preventive washer.
  • Ni-plated SPCE cold rolled steel sheet
  • the electrode assembly was mounted on the cylindrical can, and then the anti-corrosive washer was wrapped around the upper cap of the cap assembly as shown in FIG. It was mounted on, and sealed the upper end of the cap assembly while wrapping the outer surface of the can with heat shrinkable tubing to prepare a cylindrical secondary battery.
  • a cylindrical secondary battery was produced in the same manner as in Example 1, except that a washer made of YUPO synthetic resin was used as the base resin without using a vaporizing rust inhibitor.
  • a cylindrical secondary battery was produced in the same manner as in Example 1, except that a washer made of polypropylene was used as the base resin without using a vaporizing rust inhibitor.
  • electrode assembly 310 anode lead
  • cap assembly 410 cap 420: PTC element
  • the secondary battery including the rust-proof washer according to an embodiment of the present invention can prevent the rust or corrosion of the crimping portion of the battery to improve the safety of the secondary battery, it can be usefully applied to the secondary battery field .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Connection Of Batteries Or Terminals (AREA)
  • Bolts, Nuts, And Washers (AREA)

Abstract

According to one embodiment of the present invention, provided are a corrosion-resistant washer for a secondary battery, and a secondary battery comprising same, wherein the corrosion-resistant washer is characterized by including a volatile corrosion inhibitor (VCI) and a base resin. The corrosion-resistant washer of the present invention can improve the stability in a battery by preventing the occurrence of corrosion or the occurrence of rust in the crimping part of a battery cell.

Description

방청성 와셔 및 이를 포함하는 이차전지 Anti-corrosive washer and secondary battery comprising the same
본 발명은 기화성 방청제를 포함하는 방청성 와셔 및 이를 포함하는 이차전지에 관한 것이다. The present invention relates to a rust-proof washer comprising a vaporizable rust inhibitor and a secondary battery comprising the same.
모바일 기기에 대한 기술 개발과 수요가 증가함에 따라 에너지원으로서의 이차전지의 수요가 급격히 증가하고 있다. 또한 그러한 이차전지 중 높은 에너지 밀도와 방전 전압의 리튬 이차전지에 대해 많은 연구가 행해졌고, 상용화되어 널리 사용되고 있다. As technology development and demand for mobile devices increase, the demand for secondary batteries as an energy source is rapidly increasing. In addition, many studies have been conducted on lithium secondary batteries of high energy density and discharge voltage among such secondary batteries, and have been commercialized and widely used.
이차전지는 전지케이스의 형상에 따라, 전극조립체가 원통형 또는 각형의 금속 캔에 내장되어 있는 원통형 전지 및 각형 전지와, 전극조립체가 알루미늄 라미네이트 시트의 파우치형 케이스에 내장되어 있는 파우치형 전지로 분류된다.According to the shape of the battery case, secondary batteries are classified into cylindrical batteries and rectangular batteries in which the electrode assembly is embedded in a cylindrical or rectangular metal can, and pouch-type batteries in which the electrode assembly is embedded in a pouch type case of an aluminum laminate sheet. .
일반적으로 이차전지는 캔과, 상기 캔의 내부에 수용되는 전극 조립체; 상기 캔의 상단개부에 결합되는 캡(cap) 조립체; 및 상기 캡 어셈블리의 상단에 장착되는 와셔를 포함한다.In general, a secondary battery includes a can and an electrode assembly accommodated in the can; A cap assembly coupled to the top opening of the can; And a washer mounted to the top of the cap assembly.
일반적으로, 캡 어셈블리에 장착된 와셔는 기본적으로 전기적 절연상태를 보완하는 역할을 수행하며, 전지셀을 외부의 충격으로부터 보호하고 전지셀 상단에 장착되는 부재들에 대한 기계적 강도를 보완하는 역할도 수행한다. 또한, 전지셀의 부식 및 PCM(전류차단 소자) 등과 같은 전자소자들의 부식으로 인해 초래될 수 있는 전지의 내부단락을 방지하여 전지셀의 안전성을 향상시키는 역할도 병행한다.In general, the washer attached to the cap assembly basically serves to supplement the electrical insulation state, and also serves to protect the battery cell from external shock and to supplement the mechanical strength of the members mounted on the top of the battery cell. do. In addition, it also serves to improve the safety of the battery cell by preventing the internal short circuit of the battery that may be caused by the corrosion of the battery cell and the electronic devices such as PCM (current blocking device).
일반적으로 원통형 전지의 와셔로서 폴리프로필렌, 폴리에틸렌, 레이온, 혼방사, 폴리비스코스, 폴리노직 및 이들의 합성수지 등의 고분자 수지층을 사용하여 왔다. 그러나, 도 1과 같이, 고온고습 분위기에서 원통형 전지의 크림핑부(crimping)에 녹발생이 일어나는 문제가 있으며, 이에 대한 개선이 요구되고 있다.Generally, polymer resin layers such as polypropylene, polyethylene, rayon, blended yarns, polyviscose, polynosics, and synthetic resins thereof have been used as washers for cylindrical batteries. However, as shown in FIG. 1, there is a problem that rust occurs in a crimping portion of a cylindrical battery in a high temperature and high humidity atmosphere, and an improvement therefor is required.
본 발명의 해결하고자 하는 과제는 전지의 크림핑부의 녹발생 또는 부식이 발생하는 것을 방지할 수 있는 방청성 와셔 및 이를 포함하는 이차전지를 제공하는 것이다. The problem to be solved by the present invention is to provide a secondary battery comprising a rust-proof washer that can prevent the occurrence of rust or corrosion of the crimping portion of the battery.
상기와 같은 목적을 달성하기 위하여, 본 발명은 기화성 방청제(VCI; Volatile Corrosion Inhibitor)와 베이스 수지(base resin)를 포함하는 이차전지용 방청성 와셔를 제공한다.In order to achieve the above object, the present invention provides a rust-proof washer for a secondary battery including a vaporizing rust inhibitor (VCI; Volatile Corrosion Inhibitor) and a base resin (base resin).
또한, 본 발명은 양극/분리막/음극 구조의 전극조립체가 금속 캔에 내장되어 있는 이차전지로서, 전극조립체가 내장된 금속 캔의 개방 상단에 장착되는 캡 어셈블리의 상단에 와셔(washer)가 탑재되어 있으며, 상기 와셔는 베이스 수지와 기화성 방청제를 포함하는 방청성 와셔를 포함하는 이차전지를 제공한다.In addition, the present invention is a secondary battery in which the electrode assembly of the anode / separator / cathode structure is embedded in the metal can, the washer (mounter) is mounted on the top of the cap assembly mounted on the open top of the metal can containing the electrode assembly The washer provides a secondary battery including an anti-rust washer including a base resin and a vaporizable anti-corrosive agent.
본 발명의 방청성 와셔가 포함되는 이차전지는 전지의 크림핑부의 녹발생 또는 부식이 발생하는 것을 방지하여 전지의 안전성을 향상시킬 수 있다.The secondary battery including the rust-proof washer of the present invention can prevent the occurrence of rust or corrosion of the crimping portion of the battery to improve the safety of the battery.
본 명세서에 첨부되는 다음의 도면들은 본 발명의 바람직한 실시예를 예시하는 것이며, 전술한 방명의 내용과 함께 본 발명의 기술사상을 더욱 이해시키는 역할을 하는 것이므로, 본 발명은 그러한 도면에 기재된 사항에만 한정되어 해석되어서는 아니된다.The following drawings, which are attached to this specification, illustrate preferred embodiments of the present invention, and together with the contents of the foregoing description, serve to further understand the technical spirit of the present invention. It should not be construed as limited.
도 1은 원통형 전지의 크림핑부의 녹발생 이미지를 나타낸 사진이다.1 is a photograph showing a rusting image of the crimping portion of the cylindrical battery.
도 2는 본 발명의 하나의 실시예에 따른 방성청 와셔의 제조과정을 나타낸 것이다.Figure 2 shows the manufacturing process of the anticorrosive wash washer according to an embodiment of the present invention.
도 3은 본 발명의 하나의 실시예에 따른 원통형 이차전지의 상부 구조를 보여주는 단면 모식도이다.3 is a schematic cross-sectional view showing an upper structure of a cylindrical secondary battery according to an embodiment of the present invention.
도 4는 본 발명의 하나의 실시예에 따른 방청성 와셔가 장착된 원통형 전지의 실제 사진을 나타낸 것이다.4 shows an actual picture of a cylindrical battery equipped with an anti-rust washer according to an embodiment of the present invention.
도 5 및 6은 본 발명의 하나의 실시예에 따라 제조된 원통형 전지를 비닐에 밀봉한 상태로 보관하여 녹발생 여부를 실험한 사진이다. 5 and 6 are photographs of the cylindrical battery manufactured according to one embodiment of the present invention stored in a sealed state in vinyl to test whether rust occurs.
이하, 본 발명에 대한 이해를 돕기 위해 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.
본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
본 발명의 일 실시예에 따르는 이차전지용 방청성 와셔는 기화성 방청제(VCI; Volatile Corrosion Inhibitor) 및 베이스 수지(base resin)를 포함한다.An anti-rust washer for a secondary battery according to an embodiment of the present invention includes a vapor-proof rust inhibitor (VCI; Volatile Corrosion Inhibitor) and a base resin.
본 발명의 일 실시예에 따르면, 상기 방청성 와셔는 방청성이 우수하여 이차전지의 크림핑부의 녹발생 또는 부식이 발생하는 것을 방지하여 전지의 안전성을 향상시킬 수 있다.According to one embodiment of the present invention, the anti-corrosive washer is excellent in rust prevention property to prevent the occurrence of rust or corrosion of the crimping portion of the secondary battery can improve the safety of the battery.
본 발명에 있어서, 방청성이란 금속 표면에서 수산화물 또는 산화물을 주체로 하는 화합물이 생성되는 것을 방지하는 성질로서, 금속 표면에서 부패 생성물의 발생을 방지하는 성질을 의미한다. In the present invention, the rust preventive property is a property of preventing the formation of a compound mainly composed of a hydroxide or an oxide on the metal surface, and means a property of preventing the generation of decay products on the metal surface.
본 발명의 일 실시예에 따르는 상기 기화성 방청제는 고분자 수지, 및 NaNO2 또는 NaNO3를 포함할 수 있다. 상기 기화성 방청제는 상온에서 승화성이 있고, 방청성을 가지는 NaNO2 또는 NaNO3 또는 그 화합물을 주성분으로 하는 혼합물로 이루어질 수 있다. The vaporizable rust inhibitor according to an embodiment of the present invention may include a polymer resin and NaNO 2 or NaNO 3 . The vaporizable rust preventive agent may be composed of a mixture based on NaNO 2 or NaNO 3 or a compound having sublimation at room temperature and having rust resistance.
또한, 본 발명에서 사용되는 고분자 수지는 통상적으로 사용되는 고분자 수지 또는 고분자 합성수지를 사용할 수 있다. 예를 들어 폴리프로필렌(PP), 폴리부틸렌테레프탈레이트, 폴리에틸렌, 페트, 테플론, 폴리테트라플루오로에틸렌, 레이온, 혼방사, 폴리비스코스 및 폴리노직으로 이루어진 군에서 선택되는 하나 또는 이들 중 2종 이상의 혼합물일 수 있으나, 이들로 한정되는 것은 아니다.In addition, the polymer resin used in the present invention may be a polymer resin or a polymer synthetic resin that is commonly used. For example, polypropylene (PP), polybutylene terephthalate, polyethylene, PET, Teflon, polytetrafluoroethylene, rayon, blended yarn, polyviscose and polynostic, or a mixture of two or more thereof It may be, but is not limited to these.
본 발명의 일 실시예에 따르면, 본 발명의 방청성 와셔는 상기 기화성 방청제와 베이스 수지를 혼합하고, 이를 압출기에서 압출하여 원하는 와셔 모양으로 타발하여 얻을 수 있다. According to one embodiment of the present invention, the anti-corrosive washer of the present invention may be obtained by mixing the vaporizing anti-corrosive agent and the base resin, and extruding it in an extruder to form a desired washer shape.
이때, 상기 베이스 수지는 통상적으로 사용되는 고분자 수지 또는 고분자 합성수지를 사용할 수 있으며, 예를 들어 폴리프로필렌(PP), 폴리부틸렌테레프탈레이트, 폴리에틸렌, 페트, 테플론, 폴리테트라플루오로에틸렌, 레이온, 혼방사, 폴리비스코스 및 폴리노직으로 이루어진 군에서 선택되는 하나 또는 이들 중 2종 이상의 혼합물일 수 있다.In this case, the base resin may be a polymer resin or polymer synthetic resin that is commonly used, for example, polypropylene (PP), polybutylene terephthalate, polyethylene, PET, Teflon, polytetrafluoroethylene, rayon, blended yarn It may be one or a mixture of two or more selected from the group consisting of polyviscos and polynosic.
상기 제조 과정을 일례로서 도 2에 나타내었으나, 이들로 한정되는 것은 아니다.Although the manufacturing process is shown in FIG. 2 as an example, the present invention is not limited thereto.
도 2를 살펴보면, NaNO2 또는 NaNO3를 균일한 성상을 이를 때까지 곱게 분쇄시킨다. 분쇄된 NaNO2 또는 NaNO3를 고분자 수지와 혼합하여 기화성 방청제를 얻을 수 있다. 이를 베이스 수지와 혼합하고 압출한 후, 와셔 모양으로 타발하여 방청성 와셔를 제조할 수 있다. Referring to Figure 2, NaNO 2 or NaNO 3 is finely ground until a uniform appearance. The pulverized NaNO 2 or NaNO 3 can be mixed with the polymer resin to obtain a vaporizable rust inhibitor. After mixing and extruding it with the base resin, it can be punched out in the shape of a washer to produce an antirust washer.
구체적으로, 상기 NaNO2 또는 NaNO3의 분쇄 공정은 상온 및 상압에서 이루어 질 수 있다. NaNO2 또는 NaNO3가 균일한 상태로 고루 분산되어야 균일한 기화성 방청제를 함유하는 방청성 와셔를 생산할 수 있어서, 전지의 방청성을 더욱 향상시킬 수 있다. 상기 NaNO2 또는 NaNO3는 고분자 수지 100 중량%에 대해 3 내지 30 중량%로 사용될 수 있으나, 이에 한정되는 것은 아니다. Specifically, the grinding process of NaNO 2 or NaNO 3 may be performed at room temperature and atmospheric pressure. NaNO 2 or NaNO 3 must be uniformly dispersed in a uniform state to produce a rust preventive washer containing a uniform vaporizable rust inhibitor, further improving the rust resistance of the battery. The NaNO 2 or NaNO 3 may be used in 3 to 30% by weight based on 100% by weight of the polymer resin, but is not limited thereto.
상기 분쇄된 NaNO2 또는 NaNO3를 용융된 고분자 수지, 바람직하게는 용융된 폴리프로필렌 수지와 혼합할 수 있다. 이때, 혼합시 용매 및 기타 첨가제들을 사용할 수 있으며, 이는 당 분야에서 공지된 통상적으로 사용되는 것을 사용할 수 있다. 이때, 기화성 방청제는 보관 및 사용이 용이할 수 있도록, 예를 들어 펠렛화 시킬 수 있으며, 이는 상온, 상압에서 이루어질 수 있다.The pulverized NaNO 2 or NaNO 3 may be mixed with the molten polymer resin, preferably the molten polypropylene resin. At this time, it is possible to use a solvent and other additives when mixing, which can be used as commonly known in the art. At this time, the vaporizable rust preventive agent, for example, can be pelletized so that it can be easily stored and used, it can be made at room temperature, atmospheric pressure.
이와 같이 생성된 기화성 방청제를 용도에 따라 베이스 수지와 일정비율로 혼합하여 사용할 수 있으며, 예를 들어 상기 기화성 방청제를 베이스 수지 100 중량%에 대해 1 내지 30 중량%로 사용할 수 있다. 상기 혼합물을 일정 온도에서 압출시켜 압출 시트를 얻고, 이 압출 시트를 금형을 이용하여 원하는 와셔 모양으로 타발하여 본 발명의 이차전지용 방청성 와셔를 얻을 수 있다. 이때 와셔는 0.1 mm 내지 0.8mm의 두께를 갖는 것이 바람직하다.The vaporizable rust inhibitor produced in this way may be mixed with the base resin at a predetermined ratio according to the use, and for example, the vaporizable rust preventive agent may be used in an amount of 1 to 30 wt% based on 100 wt% of the base resin. The mixture may be extruded at a constant temperature to obtain an extruded sheet, and the extruded sheet may be punched into a desired washer shape using a mold to obtain a rust preventive washer for secondary batteries of the present invention. In this case, the washer preferably has a thickness of 0.1 mm to 0.8 mm.
상기 방청성 와셔의 제조 공정에 있어서, 당분야에서 사용되는 용매 및 기타 첨가제를 추가로 첨가하여 사용될 수 있으며, 상기 방법은 일례에 불과할 뿐, 이들로 본 발명을 한정하는 것은 아니다.In the manufacturing process of the anti-corrosive washer, it can be used by further adding a solvent and other additives used in the art, the method is only one example, it does not limit the present invention.
또한, 본 발명은 상기 방청성 와셔를 포함하는 이차전지를 포함한다.In addition, the present invention includes a secondary battery including the anti-rust washer.
본 발명의 일 실시예에 따른 이차전지는 양극/분리막/음극 구조의 전극조립체가 금속 캔에 내장되어 있는 이차전지로서, 전극조립체가 내장된 금속 캔의 개방 상단에 장착되는 캡 어셈블리의 상단에 와셔(washer)가 탑재될 수 있으며, 상기 와셔는 상술한 바와 같이 베이스 수지와 기화성 방청제를 포함하는 방청성 와셔일 수 있다.A secondary battery according to an embodiment of the present invention is a secondary battery in which an electrode assembly having a cathode / separation membrane / cathode structure is embedded in a metal can, and a washer at the top of a cap assembly mounted on an open top of the metal can in which the electrode assembly is embedded. A washer may be mounted, and the washer may be an anticorrosive washer including a base resin and a vaporizable rust inhibitor as described above.
본 발명의 일 실시예에 있어서, 상기 방청성 와셔는 하기와 같은 원리에 의해 방청 기능을 할 수 있다.In one embodiment of the present invention, the anti-corrosive washer may function by the following principle.
구체적으로 살펴보면, NaNO2 또는 NaNO3는 방청성 와셔 내부에 크리스탈(crystals) 상태로 분산될 수 있으며, 공기중에서 천천히 산화되어 일부는 NaNO3를 형성함으로써, 방청성 와셔 내부에 NaNO2와 NaNO3가 공존할 수 있다. 상기 NaNO2와 NaNO3는 공기중의 수분과 만나서 HNO2(nitrous acid; 아질산)와 HNO3(nitric acid; 질산)을 형성하게 되는데, 이때 HNO3는 이차전지의 금속 캔의 금속 표면을 미세하게 산화시킴으로써 부식을 방지할 수 있다.Specifically, NaNO 2 or NaNO 3 can be dispersed in crystals inside the rust-proof washer, and slowly oxidized in the air to form NaNO 3 , so that NaNO 2 and NaNO 3 coexist in the rust-proof washer. Can be. The NaNO 2 and NaNO 3 meet with moisture in the air to form HNO 2 (nitrous acid; nitrous acid) and HNO 3 (nitric acid; nitric acid), where HNO 3 is finely formed on the metal surface of the metal can of the secondary battery. Corrosion can be prevented by oxidizing.
한편, 본 발명의 일 실시예에 따르면, 이들 HNO2와 HNO3는 예를 들어, 금속 캔의 철 표면과 반응할 경우, VCI 가스(gas) 작용으로 금속 캔 끝단에 10 Å 내지 1000 Å 두께로 감마 삼산화철(γ-Fe2O3)이 형성될 수 있다.On the other hand, according to one embodiment of the invention, these HNO 2 and HNO 3 , for example, when reacted with the iron surface of the metal can, the VCI gas (gas) action at the end of the metal can is 10 kPa to 1000 kPa thickness Gamma iron trioxide (γ-Fe 2 O 3 ) may be formed.
이렇게 금속 캔 끝단에 형성된 감마 삼산화철(γ-Fe2O3)은 추가적으로 전지셀의 녹 발생을 방지할 수 있다.The gamma iron trioxide (γ-Fe 2 O 3 ) formed at the end of the metal can can further prevent rusting of the battery cell.
본 발명에 있어서, 상기 금속 캔은 원통형 캔일 수도 있고, 각형 캔일 수도 있다. 본 발명의 하나의 실시예에 따르는 이차전지는, 원통형 캔인 경우, 상기 캡 어셈블리에는 전극조립체에 연결된 양극 돌출 단자가 중앙에 형성되어 있고, 캡플레이트는 양극 단자와 연결되고, 캔은 음극 단자를 형성하는 구조일 수 있다. In the present invention, the metal can may be a cylindrical can or a rectangular can. In the secondary battery according to an embodiment of the present invention, in the case of a cylindrical can, the cap assembly includes a positive electrode protruding terminal connected to an electrode assembly, a cap plate is connected to a positive electrode terminal, and the can forms a negative terminal. It may be a structure.
또 다른 예로서 각형 캔인 경우, 상기 캡 어셈블리에는 전극단자에 연결된 음극 돌출 단자가 중앙에 형성되어 있고, 각형 캔과 캡 플레이트는 상기 음극 단자와 절연된 상태에서 양극 단자를 형성하는 구조일 수 있다.As another example, in the case of a rectangular can, the cap assembly may have a cathode protruding terminal connected to an electrode terminal at a center thereof, and the rectangular can and the cap plate may have a structure in which an anode terminal is formed in an insulated state from the cathode terminal.
본 발명에 따른 상기 이차전지는 바람직하게는 높은 에너지 밀도, 방전 전압, 및 출력 안정성의 리튬 이차전지일 수 있다. 그러한 리튬 이차전지는 양극, 음극, 분리막, 리튬염 함유 비수 전해액 등으로 구성되어 있다.The secondary battery according to the present invention may preferably be a lithium secondary battery having a high energy density, discharge voltage, and output stability. Such lithium secondary batteries are composed of a positive electrode, a negative electrode, a separator, a lithium salt-containing nonaqueous electrolyte, and the like.
상기 양극은, 예를 들어, 양극 집전체 상에 양극 활물질, 도전재 및 바인더의 혼합물을 도포한 후 건조하여 제조되며, 필요에 따라서는, 충진제를 더 첨가하기도 한다. 상기 음극은 또한 음극 집전체 상에 음극 재료를 도포, 건조하여 제작되며, 필요에 따라, 앞서 설명한 바와 같은 성분들이 더 포함될 수도 있다.The positive electrode is prepared by, for example, applying a mixture of a positive electrode active material, a conductive material, and a binder onto a positive electrode current collector, followed by drying, and further, a filler may be further added as necessary. The negative electrode is also manufactured by coating and drying a negative electrode material on a negative electrode current collector, and if necessary, the components as described above may be further included.
상기 분리막은 음극과 양극 사이에 개재되며, 이러한 분리막으로는 높은 이온 투과도와 기계적 강도를 가지는 절연성의 얇은 박막이 사용된다.The separator is interposed between the cathode and the anode, and an insulating thin film having high ion permeability and mechanical strength is used as the separator.
리튬염 함유 비수계 전해액은, 비수 전해액과 리튬염으로 이루어져 있으며, 비수 전해액으로는 액상 비수 전해액, 고체 전해질, 무기 고체 전해질 등이 사용된다.The lithium salt-containing non-aqueous electrolyte solution consists of a nonaqueous electrolyte solution and a lithium salt, and a liquid nonaqueous electrolyte solution, a solid electrolyte, an inorganic solid electrolyte, and the like are used as the nonaqueous electrolyte solution.
상기 집전체, 전극 활물질, 도전재, 바인더, 충진제, 분리막, 전해액, 리튬염 등은 당업계에 공지되어 있는 통상적인 것을 사용할 수 있다.As the current collector, the electrode active material, the conductive material, the binder, the filler, the separator, the electrolyte, the lithium salt, and the like, conventional ones known in the art may be used.
본 발명에 따른 이차전지는 당업계에 공지되어 있는 통상적인 방법에 의해 제조될 수 있다. 즉, 양극과 음극 사이에 다공성 분리막을 삽입하고 거기에 전해액을 주입하여 제조할 수 있다.The secondary battery according to the present invention can be produced by conventional methods known in the art. That is, it may be prepared by inserting a porous separator between the anode and the cathode and injecting the electrolyte therein.
양극은, 예를 들어, 앞서 설명한 바와 같이, 양극 활물질로서의 리튬 전이금속 산화물 활물질과 도전재 및 바인더를 함유한 슬러리를 집전체 위에 도포한 후 건조 및 압연하여 제조할 수 있다. 마찬가지로 음극은, 예를 들어, 앞서 설명한 바와 같이, 음극 활물질로서 탄소 활물질과 도전재 및 바인더를 함유한 슬러리를 얇은 집전체 위에 도포한 후 건조하여 제조할 수 있다.For example, as described above, the positive electrode may be manufactured by applying a slurry containing a lithium transition metal oxide active material, a conductive material, and a binder as a positive electrode active material onto a current collector, followed by drying and rolling. Similarly, the negative electrode can be produced by, for example, applying a slurry containing a carbon active material, a conductive material, and a binder as a negative electrode active material on a thin current collector, as described above, and then drying.
이하, 본 발명의 하나의 실시예에 따른 도면을 참조하여 본 발명의 내용을 더욱 상술하지만, 본 발명의 범주가 그것에 의해 한정되는 것은 아니다.Hereinafter, the content of the present invention will be described in more detail with reference to the drawings according to an embodiment of the present invention, but the scope of the present invention is not limited thereto.
도 3은 본 발명의 하나의 실시예에 따른 원통형 이차전지의 상부 구조를 보여주는 부분 단면도가 모식적으로 도시되어 있다. 3 is a partial cross-sectional view schematically showing an upper structure of a cylindrical secondary battery according to one embodiment of the present invention.
구체적으로, 도 3을 참조하면 본 발명의 일 실시예에 따른 전지(100)는, 캔(200)의 내부에 발전소자로서의 전극조립체(300)를 삽입하고, 여기에 전해액을 주입하며, 캔(200)의 상단 개구부에 캡 어셈블리(400)를 장착하고, 이와 같이 캡 어셈블리(400)가 장착된 상태에서 캔(200)을 열수축성 튜빙(220)에 삽입하여 소정의 열을 가함으로써 제조된다.Specifically, referring to FIG. 3, the battery 100 according to the exemplary embodiment of the present invention inserts an electrode assembly 300 as a power generator into the can 200, injects an electrolyte solution therein, and cans ( The cap assembly 400 is mounted on the upper opening of the 200, and the can 200 is inserted into the heat shrinkable tubing 220 while applying the predetermined heat while the cap assembly 400 is mounted.
상기 캡 어셈블리(400)는 과전류 방지용 PTC(Positive Temperature Coefficient) 소자(420) 및 전지 내부 압력을 정상적인 상태로 유지하기 위한 안전벤트(430)를 포함할 수 있다. 구체적으로, 캔(200)의 상부 비딩부(210)에 실장되는 기밀유지용 가스켓 내부에, 상단 캡(410)으로의 과전류를 차단하기 위한 PTC 소자(420)와 안전벤트(430)가 밀착되어 설치된다. 상단 캡(410)은 중앙이 상향 돌출되어 있어서 외부 회로와의 접속에 의한 양극 단자로서의 역할을 수행한다. 안전벤트(430)는 그것의 하단이 전류차단부재(440) 및 양극리드(310)를 통해 발전소자(300)의 양극에 연결되어 있다.The cap assembly 400 may include a positive temperature coefficient (PTC) element 420 for preventing an overcurrent and a safety vent 430 for maintaining a pressure inside a battery in a normal state. In detail, the PTC device 420 and the safety vent 430 are in close contact with each other in the airtight gasket mounted on the upper beading part 210 of the can 200 to block overcurrent to the upper cap 410. Is installed. The upper cap 410 protrudes upward, and serves as a positive electrode terminal by connection with an external circuit. The safety vent 430 has a lower end thereof connected to the anode of the power generator 300 through the current blocking member 440 and the anode lead 310.
안전벤트(430)는 도전성의 얇은 판재로서, 그것의 중앙부는 하향 만입부(432)를 형성하고 있고, 만입부(432)의 상절곡 및 하절곡 부위에는 각각 깊이를 달리하는 2 개의 노치들이 형성되어 있다.The safety vent 430 is a conductive thin plate, the center of which forms a downward indentation 432, and two notches having different depths are formed in the upper and lower bending portions of the indentation 432. It is.
와셔(500)는 캡 어셈블리(400)의 상단 캡(410)을 감싸면서 비딩부(210) 상부에 탑재될 수 있도록 전체적으로 원판 구조로 이루어져 있다. 한편, 열수축성 튜빙(220)이 수축될 때, 상기 열수축성 튜빙(220)이 와셔(500)의 외주면을 감싸면서 캡 어셈블리(400)에 대한 와셔(500)의 장착이 이루어진다.The washer 500 is formed of a disc structure as a whole so as to be mounted on the bead 210 while surrounding the top cap 410 of the cap assembly 400. Meanwhile, when the heat shrinkable tubing 220 is contracted, the heat shrinkable tubing 220 surrounds the outer circumferential surface of the washer 500 while mounting the washer 500 to the cap assembly 400.
상기 와셔(500)의 두께는 그것의 소재에 따라 달라질 수 있으므로 특별히 한정되지는 않으나, 바람직하게는 0.1 mm 내지 0.8 mm일 수 있다. 와셔의 두께는 그것의 기계적 강성, 탄성력 등에 영향을 미치므로, 와셔의 두께가 너무 얇을 경우 소망하는 기계적 강성 등을 나타내지 못하고 약한 외부 충격에 의해서도 파괴될 수 있지만, 반대로, 와셔의 두께가 너무 두꺼우면, 전지의 크기 증가가 현저하여 바람직하지 않다. 따라서, 이러한 점들을 복합적으로 고려하여 상기 범위 내에서 적절히 결정할 수 있다.The thickness of the washer 500 may vary depending on its material, but is not particularly limited, and may preferably be 0.1 mm to 0.8 mm. Since the thickness of the washer affects its mechanical rigidity, elasticity, etc., if the washer thickness is too thin, it does not exhibit the desired mechanical rigidity and can be destroyed by a weak external impact. On the contrary, if the washer thickness is too thick, The increase in size of the battery is remarkable, which is undesirable. Therefore, these points can be considered in combination, and can be appropriately determined within the above range.
캡 어셈블리에 탑재되는 와셔(500)는 다양한 방식으로 해당 부위에 고정될 수 있는 바, 예를 들어, 캡 어셈블리의 크림핑 과정에서 와셔의 외주면을 함께 고정하거나 캔의 외면에 장착되는 열수축성 튜빙이 수축되면서 와셔의 외주면을 함께 고정하는 기계적 결합 방식, 와셔의 하면 또는 캡 어셈블리의 상면에 접착제를 부가하여 상호 결합시키는 접착 방식 등이 사용될 수 있다. The washer 500 mounted to the cap assembly may be fixed to the corresponding parts in various ways. For example, a heat shrinkable tubing fixed to the outer circumferential surface of the washer or mounted on the outer surface of the can during crimping of the cap assembly may be provided. A mechanical coupling method of fixing the outer circumferential surface of the washer while being contracted, an adhesive method of adding an adhesive to the lower surface of the washer or the upper surface of the cap assembly, and the like may be used.
상기 와셔(500)는 양극 단자로서의 상단 캡(410)이 음극 단자로서의 캔(200)과 접촉되면서 내부 단락(short)이 유발되는 것을 방지할 수 있다. The washer 500 may prevent the internal short from occurring when the upper cap 410 as the positive terminal contacts the can 200 as the negative terminal.
한편, 도 4는 상기 와셔가 장착된 원통형 전지의 실제 사진을 나타낸 것이다.On the other hand, Figure 4 shows an actual picture of the cylindrical battery equipped with the washer.
도 4를 살펴보면, 본 발명의 일 실시예에 따르는 원통형 전지는 방청성 와셔의 외부에 튜빙(tubing)이 구비되어 와셔의 외주면을 감쌀 수 있다. Referring to Figure 4, the cylindrical battery according to an embodiment of the present invention can be provided with tubing (tubing) on the outside of the rust-proof washer can wrap the outer peripheral surface of the washer.
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예에 한정되는 것으로 해석되어서는 안 된다. 본 발명의 실시예는 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되는 것이다.Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
실시예Example
이하 실시예 및 실험예를 들어 더욱 설명하나, 본 발명이 이들 실시예 및 실험예에 의해 제한되는 것은 아니다.Although the following Examples and Experimental Examples will be further described, the present invention is not limited to these Examples and Experimental Examples.
실시예 1Example 1
<방청성 와셔의 제조><Preparation of anti-rust washer>
NaNO2를 상온, 상압에서 균일한 성상을 이를 때까지 잘 섞은 후 곱게 분쇄시켰다. 상기 분쇄된 NaNO2를 용융된 폴리프로필렌 수지와 혼합시켜 기화성 방청제(VCI)를 얻었다.NaNO 2 was mixed well until it reached a uniform property at room temperature and atmospheric pressure, and then finely ground. The pulverized NaNO 2 was mixed with the molten polypropylene resin to obtain a vaporizable rust inhibitor (VCI).
그 다음, 상기 기화성 방청제를 펠렛화시킨 후, 상온으로 냉각시켜서 펠렛형 기화성 방청제를 얻었다. 이렇게 얻은 펠렛형 기화성 방청제를 베이스 수지로서 폴리프로필렌 수지와 약 0.5:10의 비율로 섞어서 일정 온도에서 압출시켜 압출 시트를 얻고, 이를 금형을 이용하여 와셔 모양으로 타발하여 방청성 와셔를 제조하였다.Then, after pelletizing the vaporizable rust inhibitor, the mixture was cooled to room temperature to obtain a pellet-type vaporizable rust inhibitor. The pelletized vaporizable rust preventive agent was mixed with a polypropylene resin as a base resin in a ratio of about 0.5: 10, and extruded at a predetermined temperature to obtain an extruded sheet, which was punched into a washer shape using a mold to prepare an rust preventive washer.
<원통형 이차전지 제조><Manufacture of Cylindrical Secondary Battery>
Ni을 도금한 SPCE(냉간압연강판)을 사용하여 상단 캡 및 원통형 캔을 제작하였고, 원통형 캔에 전극조립체를 장착한 다음, 도 3과 같이 방청성 와셔를 캡 어셈블리의 상단 캡을 감싸면서 비딩부 상단에 탑재하고, 열수축성 튜빙으로 캔의 외면을 감싸면서 캡 어셈블리의 상단부를 밀봉하여 원통형 이차전지를 제작하였다.Ni-plated SPCE (cold rolled steel sheet) was used to fabricate the upper cap and the cylindrical can. The electrode assembly was mounted on the cylindrical can, and then the anti-corrosive washer was wrapped around the upper cap of the cap assembly as shown in FIG. It was mounted on, and sealed the upper end of the cap assembly while wrapping the outer surface of the can with heat shrinkable tubing to prepare a cylindrical secondary battery.
비교예 1Comparative Example 1
기화성 방청제를 사용하지 않고, 베이스 수지로서 YUPO 합성수지 소재의 와셔를 사용하였다는 점을 제외하고는, 실시예 1과 동일한 방법으로 원통형 이차전지를 제작하였다.A cylindrical secondary battery was produced in the same manner as in Example 1, except that a washer made of YUPO synthetic resin was used as the base resin without using a vaporizing rust inhibitor.
비교예 2Comparative Example 2
기화성 방청제를 사용하지 않고, 베이스 수지로서 폴리프로필렌 소재의 와셔를 사용하였다는 점을 제외하고는, 실시예 1과 동일한 방법으로 원통형 이차전지를 제작하였다.A cylindrical secondary battery was produced in the same manner as in Example 1, except that a washer made of polypropylene was used as the base resin without using a vaporizing rust inhibitor.
실험예 1Experimental Example 1
비교예 1과 2 및 실시예 1에서 제조된 와셔를 각각 50개씩 원통형 전지에 조립하여 도 5와 같이 비닐에 밀봉한 상태로 항온항습 챔버에서 약 65℃, 90% R.H 조건으로 7일 동안 보관한 후, 전지의 크림핑부의 녹발생 개수를 살펴보고 비교하였다. 50 washers prepared in Comparative Examples 1 and 2 and Example 1, respectively, were assembled in a cylindrical cell and stored in a vinyl sealed state as shown in FIG. 5 for 7 days in a constant temperature and humidity chamber at about 65 ° C. and 90% RH. After that, the number of rusting occurrences of the crimping part of the battery was examined and compared.
그 결과, 도 6에서 알 수 있는 바와 같이, 7일 보관 후 육안으로 확인한 결과, 비교예 1의 YUPO 합성지로 제조된 와셔를 포함하는 전지는 50개중 46개 정도 녹발생 현상이 일어났으며, 비교예 2의 폴리프로필렌 수지로 제조된 와셔를 포함하는 전지는 44개 정도 녹발생 현상이 일어났다. 반면, 본 발명의 방청성 와셔를 사용한 전지의 경우 14개 정도 밖에 녹발생 현상이 일어나지 않았음을 확인할 수 있었다. 이로부터, 본 발명의 실시예 1에서 제조된 방청성 와셔는 우수한 방청 기능을 가지고 있음을 알 수 있다.As a result, as can be seen in Figure 6, after 7 days of storage and visually confirmed, the battery containing a washer made of YUPO synthetic paper of Comparative Example 1, about 46 out of 50 rust occurred phenomenon was compared, The battery including the washer made of the polypropylene resin of Example 2 occurred about 44 rusting phenomenon. On the other hand, in the case of the battery using the anti-corrosive washer of the present invention was confirmed that only about 14 rust occurred. From this, it can be seen that the anti-rust washer prepared in Example 1 of the present invention has an excellent anti-rust function.
본 발명이 속한 분야에서 통상의 지식을 가진 자라면, 상기 내용을 바탕으로 본 발명의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다.Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above contents.
부호의 설명Explanation of the sign
100:전지 100: battery
200:캔 210: 비딩부 220:튜빙 200: can 210: beading portion 220: tubing
300:전극조립체 310:양극리드 300: electrode assembly 310: anode lead
400:캡 어셈블리 410:캡 420:PTC 소자400: cap assembly 410: cap 420: PTC element
430:안전벤트 432:만입부 440:전류차단부재 430: safety vent 432: indent 440: current blocking member
500:와셔500: Washer
본 발명의 일 실시예에 따른 방청성 와셔가 포함되는 이차전지는 전지의 크림핑부의 녹발생 또는 부식이 발생하는 것을 방지하여 이차전지의 안전성을 향상시킬 수 있으므로, 이차전지 분야에 유용하게 적용될 수 있다.The secondary battery including the rust-proof washer according to an embodiment of the present invention can prevent the rust or corrosion of the crimping portion of the battery to improve the safety of the secondary battery, it can be usefully applied to the secondary battery field .

Claims (13)

  1. 기화성 방청제(VCI; Volatile Corrosion Inhibitor)와 베이스 수지(base resin)를 포함하는 것을 특징으로 하는 이차전지용 방청성 와셔.A rust preventive washer for secondary batteries, comprising a vaporizable rust inhibitor (VCI; Volatile Corrosion Inhibitor) and a base resin.
  2. 제 1 항에 있어서, The method of claim 1,
    상기 기화성 방청제는 고분자 수지, 및 NaNO2 또는 NaNO3를 포함하는 것을 특징으로 하는 이차전지용 방청성 와셔.The vaporizable rust inhibitor comprises a polymer resin, and NaNO 2 or NaNO 3 anti-rust washer for a secondary battery.
  3. 제 2 항에 있어서, The method of claim 2,
    상기 NaNO2 또는 NaNO3는 고분자 수지 100 중량%에 대해 3 내지 30 중량%인 것을 특징으로 하는 이차전지용 방청성 와셔.NaNO 2 or NaNO 3 is an anti-rust washer for secondary batteries, characterized in that 3 to 30% by weight based on 100% by weight of the polymer resin.
  4. 제 1 항에 있어서, The method of claim 1,
    상기 기화성 방청제는 베이스 수지 100 중량%에 대해 1 내지 30 중량%인 것을 특징으로 하는 이차전지용 방청성 와셔.The vaporizable rust preventive agent is a corrosion resistant washer for secondary batteries, characterized in that 1 to 30% by weight based on 100% by weight of the base resin.
  5. 제 1 항에 있어서, The method of claim 1,
    상기 베이스 수지는 폴리프로필렌(PP), 폴리부틸렌테레프탈레이트, 폴리에틸렌, 페트, 테플론, 폴리테트라플루오로에틸렌, 레이온, 혼방사, 폴리비스코스 및 폴리노직으로 이루어진 군에서 선택되는 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 이차전지용 방청성 와셔.The base resin is one or two or more selected from the group consisting of polypropylene (PP), polybutylene terephthalate, polyethylene, pet, teflon, polytetrafluoroethylene, rayon, blended yarn, polyviscos and polynosic An anti-rust washer for secondary batteries, characterized in that the mixture.
  6. 제 2 항에 있어서, The method of claim 2,
    상기 고분자 수지는 폴리프로필렌(PP), 폴리부틸렌테레프탈레이트, 폴리에틸렌, 페트, 테플론, 폴리테트라플루오로에틸렌, 레이온, 혼방사, 폴리비스코스 및 폴리노직으로 이루어진 군에서 선택되는 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 이차전지용 방청성 와셔.The polymer resin is one or two or more selected from the group consisting of polypropylene (PP), polybutylene terephthalate, polyethylene, pet, teflon, polytetrafluoroethylene, rayon, blended yarn, polyviscose and polynosic An anti-rust washer for secondary batteries, characterized in that the mixture.
  7. 양극/분리막/음극 구조의 전극조립체가 금속 캔에 내장되어 있는 이차전지로서, 전극조립체가 내장된 금속 캔의 개방 상단에 장착되는 캡 어셈블리의 상단에 와셔(washer)가 탑재되어 있으며, 상기 와셔는 제 1 항의 방청성 와셔를 포함하는 것을 특징으로 하는 이차전지. A secondary battery in which an electrode assembly having a cathode / membrane / cathode structure is embedded in a metal can, and a washer is mounted on an upper end of a cap assembly mounted on an open top of the metal can in which the electrode assembly is embedded. A secondary battery comprising the anti-rust washer of claim 1.
  8. 제 7 항에 있어서, The method of claim 7, wherein
    상기 금속 캔의 끝단에 감마 삼산화철(γ-Fe2O3)이 형성되는 것을 특징으로 하는 이차전지. Gamma iron trioxide (γ-Fe 2 O 3 ) is formed on the end of the metal can secondary battery.
  9. 제 8 항에 있어서, The method of claim 8,
    상기 감마 삼산화철이 10 Å 내지 1000 Å 두께로 형성되는 것을 특징으로 하는 이차전지.Secondary battery, characterized in that the gamma iron trioxide is formed in a thickness of 10 Å to 1000 Å.
  10. 제 7 항에 있어서, The method of claim 7, wherein
    상기 금속 캔은 원통형 캔이며, 상기 캡 어셈블리에는 전극조립체에 연결된 양극 돌출 단자가 중앙에 형성되어 있는 것을 특징으로 하는 이차전지.The metal can is a cylindrical can, and the cap assembly is a secondary battery, characterized in that the positive electrode projecting terminal connected to the electrode assembly is formed in the center.
  11. 제 7 항에 있어서, The method of claim 7, wherein
    상기 금속 캔은 각형 캔이며, 상기 캡 어셈블리에는 전극단자에 연결된 음극 돌출 단자가 중앙에 형성되어 있는 것을 특징으로 하는 이차전지.The metal can is a rectangular can, and the cap assembly has a cathode protruding terminal connected to an electrode terminal at the center thereof.
  12. 제 7 항에 있어서, The method of claim 7, wherein
    상기 와셔는 접착 방식 또는 기계적 결합 방식으로 캡 어셈블리의 상단면에 고정되는 것을 특징으로 하는 이차전지.The washer is characterized in that the secondary battery is fixed to the top surface of the cap assembly by an adhesive method or a mechanical coupling method.
  13. 제 7 항에 있어서, The method of claim 7, wherein
    상기 와셔의 두께는 0.1 mm 내지 0.8 mm인 것을 특징으로 하는 이차전지.The thickness of the washer is a secondary battery, characterized in that 0.1 mm to 0.8 mm.
PCT/KR2013/010635 2012-11-23 2013-11-21 Corrosion-resistant washer, and secondary battery comprising same WO2014081227A1 (en)

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