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WO2019146927A1 - Plaque d'isolation pour batterie rechargeable et son procédé de fabrication - Google Patents

Plaque d'isolation pour batterie rechargeable et son procédé de fabrication Download PDF

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Publication number
WO2019146927A1
WO2019146927A1 PCT/KR2019/000113 KR2019000113W WO2019146927A1 WO 2019146927 A1 WO2019146927 A1 WO 2019146927A1 KR 2019000113 W KR2019000113 W KR 2019000113W WO 2019146927 A1 WO2019146927 A1 WO 2019146927A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicone rubber
glass fiber
insulating plate
fabric
secondary battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2019/000113
Other languages
English (en)
Korean (ko)
Inventor
이병구
김도균
정상석
신항수
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180125530A external-priority patent/KR102268405B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to CN201980003502.0A priority Critical patent/CN110870091B/zh
Priority to EP19743871.6A priority patent/EP3644393B1/fr
Priority to JP2019569935A priority patent/JP6947362B2/ja
Priority to PL19743871.6T priority patent/PL3644393T3/pl
Priority to ES19743871T priority patent/ES2977188T3/es
Priority to US16/632,694 priority patent/US11552358B2/en
Publication of WO2019146927A1 publication Critical patent/WO2019146927A1/fr
Anticipated expiration legal-status Critical
Priority to US18/085,431 priority patent/US12334571B2/en
Ceased legal-status Critical Current

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Classifications

    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/494—Tensile strength
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • 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
    • 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
    • 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 an insulating plate for a secondary battery and a manufacturing method thereof, and more particularly, to an insulating plate for a secondary battery which improves properties such as heat resistance and chemical resistance and suppresses generation of dust upon punching, and a method of manufacturing the same.
  • the secondary battery includes a nickel cadmium battery, a nickel metal hydride battery, a lithium ion battery, and a lithium ion polymer battery.
  • a secondary battery is not limited to small-sized products such as a digital camera, a P-DVD, an MP3P, a mobile phone, a PDA, a portable game device, a power tool and an e-bike, It is also applied to power storage devices that store power and renewable energy, and backup power storage devices.
  • an electrode assembly (electrode assembly) of a predetermined shape is prepared by first coating an electrode active material slurry on a positive electrode current collector and a negative electrode current collector to prepare a positive electrode and a negative electrode, and laminating them on both sides of a separator. . Then, the electrode assembly is housed in the battery case, and the electrolyte solution is injected and sealed.
  • the secondary battery is classified into a pouch type and a can type according to the material of the case housing the electrode assembly.
  • the pouch type accommodates the electrode assembly in a pouch made of a flexible polymer material having a non-uniform shape.
  • the can type accommodates the electrode assembly in a case made of a material such as metal or plastic having a constant shape.
  • Such a can type secondary battery is classified into a prismatic type whose case has a shape of a polygonal shape and a cylindrical type whose case has a cylindrical shape according to the shape of the battery case.
  • 1 is a partial cross-sectional view of a conventional cylindrical secondary battery 2.
  • the cylindrical rechargeable battery 2 includes a cylindrical battery can 12, a jelly-roll type electrode assembly 13 housed inside the battery can 12, a battery can 12, A beading portion 14 provided at the front end of the battery can 12 for mounting the cap assembly 11 and a crimping portion 15 for sealing the battery can 12 to attach the cap assembly 11 .
  • the cap assembly 11 includes a top cap 111 for sealing the opening of the battery can 12 and forming a positive terminal, a PTC element 112 for blocking current due to an increase in resistance in the inside of the battery, A CID gasket 114 for electrically isolating the safety vent 113 from the CID filter 115, except for a specific part, a safety vent 113 for interrupting the current when the pressure inside the cell rises and exhausting the gas inside, And a CID filter 115 connected to the positive electrode lead 131 connected to the positive electrode and blocking current when a high voltage is generated in the battery are sequentially stacked.
  • the cap assembly 11 is mounted to the beading portion 14 of the battery can 12 while being mounted on the crimping gasket 116. Therefore, under normal operating conditions, the positive electrode of the electrode assembly 13 is connected to the top cap 111 via the positive electrode lead 131, the CID filter 115, the safety vent 113 and the PTC element 112, It accomplishes.
  • An insulating plate 26 is disposed at the upper and lower ends of the electrode assembly 13, respectively.
  • the upper insulating plate 26 disposed at the upper end insulates the electrode assembly 13 from the cap assembly 11 and the lower insulating plate (not shown) disposed at the lower end electrically insulates the electrode assembly 13 from the battery can 12, As shown in Fig.
  • the material of the insulating plate 26 is made of a thermoplastic resin such as polyethylene or polypropylene having an insulating property and excellent electrolyte resistance and excellent punching workability .
  • a thermoplastic resin has a melting point which is considerably low at 200 ° C to 250 ° C.
  • the insulating plate 26 is melted and short-circuiting occurs because of the thermoplastic resin.
  • the insulating plate 26 is manufactured by coating phenol (Phenol), which is a thermosetting resin, on a raw material of glass fiber.
  • phenol Phenol
  • the melting point of phenol itself was very low at 40 ° C, and even if it was coated on the glass fiber fabric, there was a problem of mass reduction due to oxidation to carbon dioxide or carbon monoxide at 600 ° C.
  • dust is generated frequently, which makes it difficult to continuously produce the product, resulting in a decrease in the production amount and an increase in the manufacturing cost.
  • An object of the present invention is to provide an insulating plate for a secondary battery which improves properties such as heat resistance and chemical resistance and suppresses generation of dust upon punching, and a method for manufacturing the same.
  • a method of manufacturing an insulating plate inserted into a case of a secondary battery comprising the steps of: inserting glass fiber yarns into a glass fiber cloth Coating a silicone rubber on at least one side of the insulating sheet fabric to produce an insulation sheet fabric; And touching the insulation plate fabric.
  • the step of fabricating the insulation plate fabric includes coating a first silicone rubber, wherein coating the first silicone rubber comprises applying on the at least one side a first silicone polymer to the first solvent Applying the first solution prepared by dissolving; And drying the coated first solution to coat the first silicone rubber.
  • the step of fabricating the insulation panel further comprises coating a second silicone rubber, wherein coating the second silicone rubber further comprises, after coating the first silicone rubber, Applying a second solution prepared by dissolving a second silicone polymer in a second solvent to the surface of the second silicone polymer; And drying the coated second solution to coat the second silicone rubber.
  • the coating of the first silicone rubber may be performed such that the first silicone rubber is adhered to the glass fiber yarn and a gap is formed between the glass fiber yarns.
  • the void may be a gap formed between the glass fiber yarns which are orthogonal to each other.
  • the step of coating the second silicone rubber may insert the second silicone rubber into the generated gap.
  • the first solution may have a lower viscosity than the second solution.
  • the first silicone rubber and the second silicone rubber may be laminated on at least one side of the glass fiber fabric.
  • the first silicone rubber when the step of coating the first silicone rubber is performed, the first silicone rubber may be laminated on at least one side of the glass fiber fabric.
  • the thickness of the glass fiber fabric and the insulation plate may be the same.
  • the glass fiber may be formed into a disc shape.
  • the silicone rubber may be coated on both sides of the glass fiber fabric.
  • an insulating plate for a secondary battery comprising glass fibers formed by crossing glass fiber yarns with weft yarns and warp yarns; And a silicone rubber coated on at least one side of the glass fiber.
  • the mass loss due to thermal decomposition may be 10 to 15 wt%.
  • the mass loss when heated to a temperature of 950 ⁇ ⁇ or more, the mass loss may be 10 to 15 wt%.
  • the mass loss may be 12 to 14 wt%.
  • the lithium bis (fluorosulfonyl) imide Sulfonyl) imide may be 1 to 3 wt% or less.
  • the reduction amount of the lithium bis (fluorosulfonyl) imide (LIFSI) may be 1.5 to 2.5 wt% or less.
  • pin holes may not be formed in the battery case when the secondary battery explodes.
  • the tensile strength may be 120 to 150 N / mm 2 and the elongation may be 5 to 10%.
  • the tensile strength may be 130 to 140 N / mm 2 , and the elongation may be 7 to 8%.
  • the properties such as heat resistance and chemical resistance can be improved by coating the glass fiber fabric with a silicone rubber to prepare an insulating plate for a secondary battery.
  • the insulating plate fabric is manufactured by using the insulating plate fabric, the generation of dust is suppressed, continuous production is possible, the production amount is increased, and the manufacturing cost can be reduced.
  • the insulating plate fabric has flexibility, and it is wound up to easily form a mother roll, so that an insulating plate for a secondary battery can be easily manufactured.
  • FIG. 1 is a partial cross-sectional view of a conventional cylindrical secondary battery.
  • FIG. 2 is a flowchart illustrating a method of manufacturing an insulating plate according to an embodiment of the present invention.
  • FIG 3 is a partial cross-sectional view of a cylindrical rechargeable battery according to an embodiment of the present invention.
  • FIG. 4 is a plan view of an insulating plate according to an embodiment of the present invention.
  • FIG. 5 is a side view of an insulating plate according to an embodiment of the present invention.
  • FIG. 6 is a flowchart illustrating a method of manufacturing an insulating plate according to another embodiment of the present invention.
  • FIG. 7 is a partial cross-sectional view of a cylindrical rechargeable battery according to another embodiment of the present invention.
  • FIG. 8 is a side view of an insulating plate according to another embodiment of the present invention.
  • FIG. 9 is a partial cross-sectional view of a cylindrical secondary battery according to another embodiment of the present invention.
  • FIG. 10 is a schematic view of a glass fiber fabric according to another embodiment of the present invention in which a first silicone rubber is coated.
  • FIG. 11 is a schematic view of a glass fiber fabric according to another embodiment of the present invention coated with a second silicone rubber.
  • FIG. 12 is a cross-sectional view of the insulating plate taken along line A-A 'in FIG. 11 according to another embodiment of the present invention.
  • FIG. 13 is an SEM photograph of an actually manufactured insulating plate according to another embodiment of the present invention and magnifying it at a magnification of 1500 times.
  • FIG. 14 is a SEM photograph of an actually manufactured insulation plate according to another embodiment of the present invention, and magnified by 1000 times.
  • FIG. 14 is a SEM photograph of an actually manufactured insulation plate according to another embodiment of the present invention, and magnified by 1000 times.
  • FIG. 15 is a SEM photograph of an actually manufactured insulating plate according to still another embodiment of the present invention and magnified 200 times.
  • FIG. 15 is a SEM photograph of an actually manufactured insulating plate according to still another embodiment of the present invention and magnified 200 times.
  • FIG. 16 is a SEM photograph of an actually manufactured insulating plate according to still another embodiment of the present invention and magnifying it 40 times.
  • FIG. 16 is a SEM photograph of an actually manufactured insulating plate according to still another embodiment of the present invention and magnifying it 40 times.
  • 17 is a graph showing the heat resistance test results of the insulating plate according to the production example of the present invention.
  • 19 is a photograph showing the state of each electrolyte sample after the chemical resistance test.
  • FIG. 20 is a graph showing the result of GC-MS test for each of the electrolyte samples.
  • 21 is a photograph showing an exploded view of a secondary battery in which an insulating plate is assembled according to a production example of the present invention after stability test.
  • FIG. 22 is a photograph showing an exploded view of a secondary battery in which the insulating plate of Comparative Example 1 is assembled after the stability test.
  • FIG. 23 is a photograph showing an exploded view of the secondary battery in which the insulating plate of Comparative Example 2 is assembled after the stability test.
  • FIG. 2 is a flowchart illustrating a method of manufacturing the insulating plate 16 according to an embodiment of the present invention.
  • the insulating plate 16 according to an embodiment of the present invention is manufactured by coating a glass fiber cloth 161 with a silicone rubber 162. Accordingly, when the insulating plate 16 for a secondary battery is manufactured by using the insulating plate fabric, it is possible to suppress the generation of dust, to continuously produce the product, to increase the production amount, and to increase the manufacturing cost . In addition, the insulating plate fabric has flexibility, and it is wound up to easily form a mother roll, so that the insulating plate 16 for a secondary battery can be easily manufactured.
  • FIG. 2 Specific details of each step shown in the flowchart of FIG. 2 will be described with reference to FIGS. 3 to 5.
  • FIG 3 is a partial cross-sectional view of a cylindrical rechargeable battery 1 according to an embodiment of the present invention.
  • the cylindrical rechargeable battery 1 includes a battery can 12, a jelly-roll type electrode assembly 13 accommodated in the battery can 12, A cap assembly 11 coupled to the upper portion of the battery can 12, a beading portion 14 provided at the tip of the battery can 12 for mounting the cap assembly 11, And a crimping portion 15.
  • a cylindrical secondary battery 1 can be used as a power source for a mobile phone, a notebook computer, an electric car, or the like which stably supplies a constant output.
  • the battery can 12 is made of a lightweight conductive metal such as aluminum, nickel, stainless steel, or an alloy thereof, and may have an open top and an open bottom facing the open. An electrolyte solution is contained in the inner space of the battery can 12 together with the electrode assembly 13.
  • the battery can 12 may be formed in a cylindrical shape, but may be formed in various shapes other than a cylindrical shape such as a square shape.
  • the electrode assembly 13 includes two electrode plates, such as a positive electrode plate and a negative electrode plate, each of which has a large plate shape in the form of a roll, and a separator interposed between the electrode plates for separating the electrode plates from each other, Or the like.
  • the laminated structure may be wound in the form of a jelly roll, and may have various shapes without limitation, such as a laminate of a positive electrode plate and a negative electrode plate of a predetermined size sandwiching the separating film.
  • the two electrode plates have a structure in which an active material slurry is applied to a metal foil or metal mesh type current collector including aluminum and copper, respectively.
  • the slurry may be usually formed by agitating a granular active material, auxiliary conductor, binder and plasticizer with a solvent added.
  • the solvent is removed in the subsequent process.
  • a pair of leads corresponding to the respective electrode plates are attached to the non-coated portion.
  • the positive electrode lead 131 attached to the upper end of the electrode assembly 13 is electrically connected to the cap assembly 11 and the negative electrode lead (not shown) attached to the lower end of the electrode assembly 13 contacts the battery can 12 .
  • the positive electrode lead 131 and the negative electrode lead may both be drawn out in the direction toward the cap assembly 11.
  • an insulating plate 16 for insulating the electrode assembly 13 is disposed.
  • the upper insulating plate 16 disposed at the upper end is disposed between the electrode assembly 13 and the cap assembly 11 to insulate the electrode assembly 13 and a lower insulating plate (not shown) 13 and the bottom of the battery can 12 to insulate the electrode assembly 13.
  • the insulating plate 16 according to an embodiment of the present invention may be an upper insulating plate 16 disposed on the upper portion of the electrode assembly as shown in FIG. (Not shown). A detailed description of the insulating plate 16 according to an embodiment of the present invention will be described later.
  • a center pin (not shown) is inserted in the center of the battery can 12 to prevent the electrode assembly 13 wound in the form of a jelly roll from being unwound and to serve as a gas passage for the inside of the secondary battery 1 It is possible.
  • the electrolytic solution filled in the battery can 12 is for transferring lithium ions generated by the electrochemical reaction of the electrode plate during charging and discharging of the secondary battery 1.
  • the electrolytic solution is a mixture of a lithium salt and a high purity organic solvent, Based organic electrolytic solution or a polymer electrolyte.
  • the cap assembly 11 is coupled to an opening formed in the upper end of the battery can 12 to seal the opening of the battery can 12.
  • the cap assembly 11 may be formed in various shapes, such as a circular shape or a square shape, depending on the shape of the battery can 12. According to an embodiment of the present invention, since the battery can 12 is formed in a cylindrical shape, in this case, it is preferable that the cap assembly 11 is also formed in a disk shape corresponding to the shape.
  • the cap assembly 11 includes a top cap 111 which seals an opening of the battery can 12 and forms a positive terminal, a current which is interrupted when a pressure inside the battery rises due to an abnormal current
  • a safety vent 113 for exhausting gas inside and a positive electrode lead 131 connected to the positive electrode of the electrode assembly 13 and a current blocking member for blocking current when a high voltage is generated in the battery are sequentially stacked .
  • the cap assembly 11 is mounted on the beading portion 14 of the battery can 12 while being mounted on the crimping gasket 116. Therefore, under normal operating conditions, the positive electrode of the electrode assembly 13 is connected to the top cap 111 via the positive electrode lead 131, the current blocking member, the safety vent 113, and the PTC element 112,
  • the top cap 111 is disposed on the uppermost portion of the cap assembly 11 in an upwardly projecting shape to form a positive terminal.
  • the top cap 111 can be electrically connected to an external device such as a load or a charging device.
  • a gas hole 1111 through which the gas generated inside the secondary battery 1 is discharged may be formed in the top cap 111. Therefore, when gas is generated from the electrode assembly 13 side due to overcharging or the like and the internal pressure is increased, the CID filter 115 and the safety vent 113 of the current blocking member are ruptured, And the gas hole 1111, as shown in Fig. Therefore, the charge and discharge can be prevented from further proceeding and the safety of the secondary battery 1 can be ensured.
  • the top cap 111 may be made of a metal material such as stainless steel or aluminum.
  • the thickness of the portion of the top cap 111 that is in contact with the safety vent 113 is not particularly limited as long as it can protect various components of the cap assembly 11 from external pressure, 0.3 to 0.5 mm. If the thickness of the top cap 111 is too thin, it is difficult to exhibit mechanical rigidity. On the other hand, if the top cap 111 is too thick, the capacity of the battery can be reduced to the same standard by increasing the size and weight.
  • the safety vent 113 serves to cut off the current when the pressure inside the battery rises due to an abnormal current or exhaust gas, and may be made of a metal material.
  • the thickness of the safety vent 113 may vary depending on material, structure, etc., and is not particularly limited as long as it can discharge gas while rupturing when a predetermined high pressure is generated in the battery. For example, it may be 0.2 to 0.6 mm.
  • a current interrupt device is positioned between the safety vent 113 and the electrode assembly 13 to electrically connect the electrode assembly 13 and the safety vent 113.
  • the current blocking member includes a CID filter 115 that contacts the safety vent 113 to transmit a current and a CID gasket 115 that spatially separates and isolates the CID filter 115 from the safety vent 113 except for a part of the area. (114).
  • the current generated from the electrode assembly 13 flows to the safety vent 113 via the cathode lead 131, the CID filter 115, and the discharge of the secondary battery 1 can be performed.
  • the safety vent 113 and the CID filter 114 Is detached or the CID filter 114 is ruptured. Thereby, the electrical connection between the safety vent 113 and the electrode assembly 13 is cut off, and safety can be ensured.
  • the cap assembly 11 may further include a PTC element (Positive Temperature Coefficient Element) 112 between the safety vent 113 and the top cap 111.
  • the PTC element 112 increases the resistance of the battery when the temperature inside the battery rises and cuts off the current. That is, the PTC element 112 electrically connects the top cap 111 and the safety vent 113 in a normal state. However, when the abnormal state, for example, the temperature rises abnormally, the PTC element 112 disconnects the electrical connection between the top cap 111 and the safety vent 113.
  • the thickness of the PTC device 112 may also vary depending on material, structure, etc., and may be, for example, 0.2 to 0.4 mm.
  • the thickness of the PTC element 112 is larger than 0.4 mm, the internal resistance is increased and the size of the battery is increased, thereby reducing the battery capacity to the same standard.
  • the thickness of the PTC element 112 is thinner than 0.2 mm, it is difficult to exert a current-blocking effect at a high temperature and can be broken even by a weak external impact. Therefore, the thickness of the PTC element 112 can be appropriately determined within the above-mentioned thickness range in view of these points in combination.
  • the secondary battery 1 including the cap assembly 11 can instantaneously provide a high output and can be used for external physical shocks such as vibration, It can be stable.
  • a bead portion 14 bent from the outside to the inside is formed on the upper portion of the battery can 12.
  • the beading portion 14 is formed by positioning the cap assembly 11 having the top cap 111, the PTC device 112, the safety vent 113 and the current blocking member stacked on the top of the battery can 12, (13) in the vertical direction.
  • the cap assembly 11 is installed in the beading portion 14 of the battery can 12 while being mounted on the crimping gasket 116.
  • the crimping gasket 116 has a cylindrical shape with both open ends.
  • One end of the crimping gasket 116 facing the inside of the battery can 12 is first bent substantially vertically toward the central axis as shown in FIG. 2, Bent in a substantially vertical direction toward the inside of the battery can 12 and seated in the bead 14.
  • the other end of the crimping gasket 116 is initially extended in a direction parallel to the central axis.
  • the process of forming the crimping portion 15 by the pressing of the upper outer wall of the cell can 12 and then joining the cap assembly 11 is performed, And it is directed to the central axis.
  • the inner peripheral surface of the crimping gasket 116 is in close contact with the inner peripheral surface of the battery can 12 and the outer peripheral surface thereof is in close contact with the inner peripheral surface of the battery can 12.
  • FIG. 4 is a plan view of the insulating plate 16 according to an embodiment of the present invention.
  • the insulating plate 16 for the secondary battery 1 is an insulating plate 16 inserted into the case of the secondary battery 1 in such a manner that the glass fibers 161 are crossed with each other Shaped glass fibers 161 formed by the process of forming the glass fibers; And a silicone rubber 162 coated on at least one side of the glass fiber 161.
  • the silicon rubber 162 is laminated on at least one surface of the glass fiber 161.
  • Glass fiber 161 is produced by melting a glass in a platinum furnace and then drawing it through a small-diameter hole to form a long fiber. It is excellent in heat resistance, durability, sound-absorbing property, electrical insulation, rust-proof, easy to process and is mainly used for building insulation, air filter material, According to an embodiment of the present invention, the fabric of the glass fiber 161 in the form of a fabric formed by crossing the yarns of the glass fiber 161 with the weft yarns and the warp yarns is provided, The rubber 162 is coated. It is preferable that the diameter of a cross section of one strand from which the glass fiber 161 yarn is loosened is approximately 4 to 15 mu m.
  • Silicone rubber (Si Rubber, 162) is a silicone-containing rubber. Heat resistance and cold resistance. Therefore, even if left at 250 ⁇ ⁇ for 3 days, the change in strength and elongation can be kept within 10%, and the elasticity can be maintained even at -45 ⁇ ⁇ . Since electrical characteristics are not sensitive to temperature, they are widely used in electric, electronic and communication fields requiring heat resistance. In the silicone rubber 162, a variety of materials are mixed and manufactured.
  • silicone polymers such as organopolysiloxanes used as main raw materials, silica fillers, extender for increasing the volume and improving oil resistance, vulcanizing agents such as organic peroxides, processing aids such as low-molecular-weight silicone oligomers, or BaO, CaO , MgO, ZnO, and the like may be mixed.
  • a flame retardant such as Al (OH) 3 , Mg (OH) 2 , BH 3 O 3 or the like may be further contained, or a pigment may be further included for easy quality inspection.
  • the silicone rubber 162 may be prepared by mixing and heating the above materials, followed by vulcanization and drying.
  • the peroxide such as benzoyl peroxide, dicumyl peroxide, etc. may be used for the vulcanization step.
  • the various materials including the silicone polymer are mixed and cured before they are dissolved in a specific solvent to prepare a solution.
  • the solvent is preferably an organic solvent capable of easily dissolving the above materials, for example, toluene, xylene, MEK, and the like.
  • the prepared solution has a different viscosity depending on the concentration of the silicone polymer dissolved therein.
  • the viscosity is too low, the warp yarns and warp yarns of the glass fiber 161 can be loosened, and the effect of coating may not be conspicuous.
  • the viscosity is too high, the glass fibers 161 do not penetrate into the gap 3 between the warp yarns of the fabric and the warp yarns, and the void 3 may not be filled.
  • the viscosity of such a solution can be selected experimentally as an optimum viscosity.
  • the prepared solution is coated on the raw glass fiber 161 (S201) and dried (S202).
  • the solution may be sprayed onto the glass fiber 161 by spraying or the like, but it is preferable to immerse the glass fiber 161 raw material in the container containing the solution. Thereby, a large amount of the solution can be quickly applied to the glass fiber 161 fabric.
  • the solvent evaporates, and the silicone rubber 162 is coated on the glass fiber 161 to form the insulation panel fabric (S203). Then, the insulation plate 16 according to an exemplary embodiment of the present invention is manufactured (S204).
  • the insulating plate 16 is installed in the cylindrical rechargeable battery 1, in order to easily insert the insulating plate 16 into the battery can 12 of the cylindrical rechargeable battery 1, It is preferable to engage in a shape.
  • the insulating plate 16 is formed by coating the glass fiber 161 having a disc shape as a whole with the silicone rubber 162.
  • FIG 5 is a side view of the insulating plate 16 according to an embodiment of the present invention.
  • the insulating plate 16 is formed by coating a silicon rubber 162 on at least one surface of a glass fiber 161, Layered structure.
  • the solution may be applied only to one side of the glass fiber 161, it is preferable that the solution is applied to both sides of the glass fiber 161 according to one embodiment of the present invention.
  • the silicon rubber 162 is coated on both sides of the glass fiber 161, so that the insulating plate 16 according to an embodiment of the present invention can have a laminated shape of a plurality of layers. In FIG. 5, three layers are shown as being laminated, but the present invention is not limited thereto, and a separate layer may be further included between the glass fiber 161 and the silicone rubber 162.
  • FIG. 6 is a flowchart illustrating a method of manufacturing the insulating plate 16a according to another embodiment of the present invention.
  • the insulating plate 16 according to an embodiment of the present invention is manufactured by coating a silicon rubber 162 on at least one side of the glass fiber 161 once.
  • the insulating plate 16a according to another embodiment of the present invention is manufactured by coating a plurality of times of the silicone rubber 162a on at least one surface of the glass fiber 161a.
  • FIG. 6 Specific details of the steps shown in the flowchart of FIG. 6 will be described with reference to FIGS. 7 to 8.
  • FIG. 7 is a partial cross-sectional view of a cylindrical secondary battery 1a according to another embodiment of the present invention.
  • an insulating plate 16a for insulating the electrode assembly 13 is disposed.
  • the insulating plate 16a according to another embodiment of the present invention may be an upper insulating plate 16a disposed on the upper portion of the electrode assembly as shown in FIG. (Not shown).
  • the insulating plate 16a is inserted into the case of the secondary battery 1a.
  • the insulating plate 16a includes glass fibers 161a formed by crossing glass fibers 161a with weft and warp yarns; And a silicone rubber 162a coated on at least one surface of the glass fiber 161a.
  • the silicone rubber 162a may include a first silicone rubber 1621a coated on at least one surface of the glass fiber 161a; And a second silicone rubber 1622a coated on the first silicone rubber 1621a.
  • the first and second solutions are prepared by first mixing the various materials including the silicone polymer and then curing the mixture in a specific solvent.
  • a first solution is prepared by dissolving a first silicone polymer in a first solvent
  • a second solution is prepared by dissolving a second silicone polymer in a second solvent.
  • the prepared solution has a different viscosity depending on the concentration of the silicone polymer dissolved therein. At this time, it is preferable that the viscosity of the first solution is lower than that of the second solution.
  • the prepared first solution is coated on at least one surface of the glass fiber 161a (S601) and dried (S602).
  • the first solution may be applied only to one side of the glass fiber 161a, it is preferable that the first solution is applied to both sides of the glass fiber 161a according to another embodiment of the present invention.
  • the first solvent evaporates and the first silicone rubber 1621a is coated on the glass fiber 161a (S603).
  • the prepared second solution is coated on at least one surface coated with the first silicone rubber 1621a (S604) and dried (S605).
  • the second solvent evaporates and the second silicone rubber 1622a is coated on the first silicone rubber 1621a (S606). Thereby, an insulating plate fabric is produced.
  • the first solution is low in viscosity and can easily penetrate into the gap 3 between the warp yarns of the glass fibers 161a and the warp yarns to fill the void 3.
  • the viscosity of the second solution is high, so that the weft and warp of the glass fiber 161a can be fixed so that the weft and warp threads do not loosen each other, so that the holding force can be increased. Therefore, in the insulating plate 16a according to another embodiment of the present invention, the holding force can be increased while the silicone rubber 162a is mixed with the glass fiber 161a more well.
  • the insulation plate 16a is fabricated by stamping the insulation plate fabric in a specific shape (S607). At this time, if the insulating plate 16a is installed in the cylindrical secondary battery 1a, it is preferable that the insulating plate raw material is punched out in the form of a disk in order to be easily inserted into the battery can of such a cylindrical secondary battery 1a.
  • FIG 8 is a side view of the insulating plate 16a according to another embodiment of the present invention.
  • the insulating plate 16a is manufactured by stacking a first silicone rubber 1621a on at least one surface of the glass fiber 161a, A second silicone rubber 1622a is laminated on the rubber 1621a. That is, the first and second silicone rubbers 1621a and 1622a are sequentially coated and laminated in a plurality of layers.
  • the first and second solutions may be applied to only one side of the raw glass fiber 161a, according to another embodiment of the present invention, the first and second solutions are preferably applied on both sides.
  • the first and second silicone rubbers 1621a and 1622a are coated on both sides of the glass fiber 161a, and the insulating plate 16a according to another embodiment of the present invention has a laminated shape of a plurality of layers .
  • the first silicone rubber 1621a is coated before the second silicone rubber 1622a
  • the first silicone rubber 1621a is further laminated inside
  • the second silicone rubber 1622a is laminated further on the outside, do.
  • five layers are shown as being laminated, but the present invention is not limited thereto.
  • a separate layer may be further included between the glass fiber 161a and the first and second silicone rubbers 1621a and 1622a.
  • FIG. 9 is a partial cross-sectional view of a cylindrical rechargeable battery 1b according to another embodiment of the present invention.
  • the insulating plate 16 according to one embodiment of the present invention and the insulating plate 16a according to another embodiment of the present invention are all coated with at least one surface of the glass fibers 161 and 161a with silicone rubber 162 and 162a So that a plurality of layers are stacked.
  • the thickness of the silicon rubber 162b is equal to the thickness of the glass fiber 161b since the silicon rubber 162b is not laminated on the glass fiber 161a.
  • the manufacturing method of the insulating plate 16b according to another embodiment of the present invention is similar to the manufacturing method of the insulating plate 16a according to another embodiment of the present invention, Specific details will be described again with reference to Figs. 9 to 16. Fig. Hereinafter, the contents of the cylindrical secondary battery 1b and the insulating plate 16b according to still another embodiment of the present invention will be omitted. This is for convenience of explanation and is not intended to limit the scope of rights.
  • the insulating plate 16b is inserted into a case of a secondary battery.
  • the insulating plate 16b includes glass fibers 161b formed by crossing glass fibers 161b with weft and warp yarns; And a silicone rubber 162b coated on at least one side of the glass fiber 161b.
  • the silicone rubber 162b may include: a first silicone rubber 1621b attached to the glass fibers 161b; And a second silicone rubber 1622b inserted into the gap 3 formed between the yarns of the glass fibers 161b.
  • the first solution is applied to at least one surface of the raw glass fiber 161b (S601) and dried (S602). According to another embodiment of the present invention, it is preferable to apply both of the both surfaces of the raw glass fiber 161b.
  • FIG 10 is a schematic view in which the first silicone rubber 1621b is coated on the glass fiber 161b according to another embodiment of the present invention.
  • the glass fibers 161b are formed so as to intersect with each other in such a manner that the yarns of the glass fibers 161b are orthogonal to each other, and the voids 3 are formed between the yarns of the orthogonal glass fibers 161b.
  • the viscosity of the first solution is lower than that of the second solution, which is lower than the viscosity of the first solution according to another embodiment of the present invention. Therefore, only the periphery of the glass fibers 161b yarns forming the glass fiber 161b is adhered to the first solution.
  • the surface of the glass fiber 161b is scraped off with a knife or the like. Thereby, the thickness of the glass fiber 161b can be adjusted and the surface of the glass fiber 161b can be smoothed.
  • the first solution is dried (S602), the first solvent is evaporated, and the first silicone rubber 1621b is coated on the glass fiber 161b as shown in FIG. 10 (S603). According to another embodiment of the present invention, since the first silicone rubber 1621b adheres only to the yarn of the glass fiber 161b, the gap 3b formed between the yarns of the orthogonal glass fiber 161b ).
  • FIG 11 is a schematic view in which a glass fiber 161b according to another embodiment of the present invention is coated with a second silicone rubber 1622b.
  • the second solution is applied to at least one surface of the glass fiber 161b (S604) and dried (S605).
  • the viscosity of the second solution is higher than that of the first solution, but lower than that of the second solution according to another embodiment of the present invention. Therefore, the second solution is inserted into the gap 3 formed between the yarns of the glass fibers 161b.
  • the second solution After the second solution is applied, the surface of the glass fiber 161b is scraped off with a knife or the like. Thereby, the thickness of the glass fiber 161b can be adjusted and the surface of the glass fiber 161b can be smoothed.
  • the second solution is dried (S605), the second solvent is evaporated, and the second silicone rubber 1622b is coated on the glass fiber 161b as shown in FIG. 11 (S606).
  • the second silicone rubber 1622b may be inserted into the gap 3 formed between the yarns of the orthogonal glass fibers 161b to fill the gap 3 . Thereby, an insulating plate fabric is produced.
  • the insulating plate 16b When the insulating plate raw material is punched out in a specific shape, the insulating plate 16b according to another embodiment of the present invention is manufactured (S607). At this time, if the insulating plate 16b is installed in the cylindrical secondary battery 1b, it is preferable that the insulating plate raw material is punched out in the form of a disk in order to be easily inserted into the battery can 12 of the cylindrical secondary battery 1b.
  • FIG. 12 is a cross-sectional view of the insulating plate 16b taken along line A-A 'in FIG. 11 according to another embodiment of the present invention.
  • the first and second silicon rubbers 162b do not form a separate layer. That is, the first silicone rubber 1621b is adhered to only the glass fibers 161b and the second silicone rubber 1622b is inserted into the gap 3 formed between the yarns of the orthogonal glass fibers 161b do. Therefore, since the first and second silicon rubbers 162b do not have separate layers, the thickness of the completed insulating plate 16b is equal to the thickness of the glass fiber 161b when the silicone rubber 162b is not coated Or almost similar.
  • the insulating plate 16b may be an upper insulating plate 16b disposed on an upper portion of the electrode assembly as shown in FIG. And may be an insulating plate (not shown).
  • the insulating plate 16b according to another embodiment of the present invention When the insulating plate 16b according to another embodiment of the present invention is used as the upper insulating plate, heat and chemical stability can be secured since properties such as heat resistance and chemical resistance are improved. On the other hand, when used as a lower insulating plate, thermal and chemical stability can be ensured, as well as the heat transfer path spreading from the lower portion of the electrode assembly 13 is blocked. Conventionally, the lower separator of the electrode assembly 13 can be lost due to the heat spreading through the negative electrode tab of the electrode assembly 13, thereby causing the edge short of the lower portion of the electrode assembly 13 I could. However, since the insulating plate 16b according to another embodiment of the present invention is used as a lower insulating plate to block the heat transfer path spreading from the lower portion of the electrode assembly 13, the edge of the lower portion of the electrode assembly 13 Short) can be prevented.
  • FIG. 13 is a SEM photograph of an actually manufactured insulating plate 16b according to another embodiment of the present invention and magnified by a factor of 1500
  • FIG. 14 is a cross-sectional view of the insulating plate 16b according to another embodiment of the present invention
  • FIG. 15 is a SEM photograph of an actually manufactured insulating plate 16b according to still another embodiment of the present invention and magnified 200 times
  • FIG. 16 is a SEM photograph showing an enlarged photograph of a still further embodiment of the present invention Is actually manufactured and enlarged by 40 times, is an SEM photograph.
  • the large rounded shapes are the cross-sections of the yarns of the glass fibers 161b, and the materials attached around the yarns of the glass fibers 161b are the silicone rubber 162b.
  • the first silicone rubber 1621b is adhered and adhered between the yarns of the glass fibers 161b. 15 and 16, the silicon rubber 162b does not form a separate layer.
  • the composition ratio is measured as follows.
  • Material name Composition ratio (wt%) Glass Fiber (Fabric) 70 ⁇ 80 Siloxanes and silicones, di-Me, vinyl group-terminated 10 to 15 Dimethylvinylated and trimethylated silica 0-5 Aluminum trihydroxide 10 to 15 Titanium dioxide 0-5
  • Table 1 shows the composition ratio of the insulating plate in the Production Example.
  • the glass fibers have a composition ratio of 70 to 80 wt%
  • the silicone rubber has a composition ratio of 20 to 30 wt%.
  • the major chains of silicon polymers are 10-15 wt% of siloxanes and silicones, di-Me, vinyl group-terminated, and 0-5 wt% of dimethylvinylated and trimethylated silica. That is, the composition ratio of the silicone polymer is 10 to 20 wt%.
  • Aluminum trihydroxide, which is a flame retardant, is 10 ⁇ 15 wt% and titanium dioxide is 0 ⁇ 5 wt%. In other words, dimethylvinylated and trimethylated silica and titanium dioxide are not included at all because they are minimum 0 wt%.
  • an insulation plate for a secondary battery the insulation plate being inserted into a case of a secondary battery, the insulation plate comprising: glass fibers formed by crossing glass fiber yarns with weft and warp; And a silicone rubber coated on at least one side of the glass fiber.
  • the mass loss due to thermal decomposition may be 10 to 15 wt%, preferably 12 to 14 wt%. Therefore, the insulating plate for a secondary battery according to an embodiment of the present invention is excellent in heat resistance.
  • the insulating plate for a secondary battery When the insulating plate for a secondary battery is impregnated with an electrolyte containing lithium bis (fluorosulfonyl) imide (LIFSI, lithium bis (fluorosulfonyl) imide) at 72 ° C. for 1 week or more,
  • the reduction amount of lithium bis (fluorosulfonyl) imide (LIFSI) may be 1 to 3 wt% or less, preferably 1.5 to 2.5 wt% or less. Therefore, the insulating plate for a secondary battery according to an embodiment of the present invention is excellent in chemical resistance.
  • the insulating plate for a secondary battery according to an embodiment of the present invention when the secondary battery is manufactured using the insulating plate for a secondary battery according to an embodiment of the present invention, pinholes may not be formed in the battery case when the secondary battery is heated to a temperature of 600 ° C or higher. Therefore, the insulating plate for a secondary battery according to an embodiment of the present invention is excellent in safety.
  • the insulating plate for a secondary battery according to an embodiment of the present invention has tensile strength of 120 to 150 N / mm 2 , preferably tensile strength of 130 to 140 N / mm 2 , elongation of 5 to 10 N / 10%, preferably an elongation of 7 to 8%. Therefore, the insulating plate for a secondary battery according to an embodiment of the present invention has excellent tensile strength and elongation.
  • a glass fiber cloth having a width of 1,040 mm, a length of 300,000 mm and a thickness of 0.3 mm was provided. 12 kg of siloxanes and silicones, di-Me, vinyl group-terminated and 4 kg of dimethylvinylated and trimethylated silica were added as main chain of silicone polymer to 20 kg of toluene solvent. Aluminum trihydroxide 13 kg. Further, 3 kg of titanium dioxide was further added as a coloring matter to prepare 52 kg of the first solution.
  • the rollers were placed on both sides of the glass fiber fabric, knives were placed on top of each roller. Then, the first solution was put in a barrel, and the roller was rotated to immerse the glass fiber fabric in the first solution. While the rollers were reversely rotated to take out the glass fiber fabric, the first solution remaining on the surface of the glass fiber fabric was scraped off by the knife. Then, the glass fiber fabric was inserted into the drying furnace, and the first solution was dried at 170 DEG C for 5 minutes.
  • the insulating plate fabric was manufactured as described above, the insulating plate was inserted into a punching machine and pulverized in a disc shape having a diameter of 20 mm to prepare an insulating plate of a production example.
  • PET was prepared by using an electrospinning method and 30 mm in width, 30 mm in length, and 0.3 mm in thickness as a nonwoven fabric raw material.
  • the insulating plate fabric was manufactured as described above, the insulating plate of Comparative Example 1 was prepared by inserting it into a punching machine and pulverizing it into a disc having a diameter of 20 mm.
  • the insulating plate fabric was manufactured as described above, it was inserted into a punching machine and punched into a disc having a diameter of 20 mm to produce an insulating plate of Comparative Example 2.
  • Insulation plates of the above-mentioned production example, comparative example 1 and comparative example 2 were inserted into a heat resistance tester (model: TGA Q500) manufactured by TA Instruments Co., and heat was gradually applied at a temperature range of 25 to 950 DEG C and a temperature increase rate of 10 DEG C / min. Then, the mass of each insulating plate was measured in real time, and the amount of mass loss due to pyrolysis was confirmed.
  • a heat resistance tester model: TGA Q500 manufactured by TA Instruments Co.
  • a salt and an additive are mixed in a solvent to prepare an electrolytic solution.
  • the solvent is prepared by mixing EC (Ethylene Carbonate), DMC (Dimethyl Carbonate), EMC (Ethyl Methyl Carbonate), and a salt such as LiPF6 (Lithium hexafluorophosphate), LiFSI (Lithium bis (fluorosulfonyl) imide, lithium bis (fluorosulfonyl) imide) and various additives were mixed.
  • the thus prepared electrolytic solution was impregnated with the insulating plates of the above Preparation Example, Comparative Example 1 and Comparative Example 2, respectively, and stored at 72 ⁇ for one week. After removing the respective insulating plates, the above electrolyte samples were injected into NMR equipment (manufacturer Varian, model name EQC-0279) and GC-MS equipment (manufacturer SHIMADZU, model GC2010 Plus / QP2020, EQC-0291) , The composition ratio of each electrolyte sample and reaction byproducts were analyzed.
  • an insulation plate of a manufacturing example is installed in equipment having a main heat source and an auxiliary heat source, and a flame is applied.
  • a main heat source a flame is generated with a methane gas of 99.99% purity as a fuel on a radiating hot plate of 483 mm in width and 284 mm in length.
  • the heat is 50.5 kW / m 2 at 50 mm and 23.9 kW / m 2 at 350 mm.
  • the length of the pilot flame is about 230 mm, and propane gas is used as a fuel to generate a flame.
  • the insulating plate of the production example is removed and a standard test piece is again set. A total of three insulating plates of the above production example were prepared, and this process was repeated three times in total.
  • the secondary batteries were manufactured using the insulating plates of the above Production Examples, Comparative Examples 1 and 2, and were fully charged. When the secondary batteries are put in a heating furnace maintaining the temperature of 600 ° C and heated for 3 minutes to 5 minutes, the secondary batteries explode. Then, the detonated secondary batteries were cooled at room temperature, and then the cap assembly was disassembled to confirm whether pin holes were formed in the upper corner of the battery can.
  • the upper and lower jigs of an Instron universal testing machine (UTM, model 3340) were fixed to the above-mentioned insulating plates of the production example, the comparative example 1 and the comparative example 2, respectively. Then, the required force was measured while being stretched at a speed of 300 mm / min, and this force was evaluated by the tensile strength. In addition, the ratio of the stretched length by the tensile strength was evaluated by the elongation.
  • FIG. 17 is a graph showing the heat resistance of the insulating plate according to the production example of the present invention
  • FIG. 18 is a graph showing the heat resistance of the insulating plate according to Comparative Example 2.
  • Table 2 shows the amount of mass loss and the mass loss of each insulating plate according to the temperature range.
  • the insulating plate of the production example gradually decreased gradually in mass.
  • the reduced mass width is shown in Table 2 above.
  • the insulating plate of the production example had a mass loss of 3.8 wt% in the range of 0-320 ° C, 9.3 wt% in the range of 320-600 ° C, and 0.3 wt% in the range of 600-700 ° C.
  • the insulating plate of Comparative Example 2 continuously decreased its mass up to 600 ° C, and the mass rapidly decreased especially in the range of 320 to 600 ° C.
  • the insulating plate of Comparative Example 2 had a mass loss of 40.5 wt% in the range of 0 to 600 ° C.
  • the insulation plate of the production example has the least amount of mass loss of 13.4 wt% due to pyrolysis at 600 ° C or higher, and even has heat stability up to 950 ° C.
  • FIG. 19 is a photograph showing the state of each electrolyte sample after the chemical resistance test
  • FIG. 20 is a graph showing a result of GC-MS experiment of each electrolyte sample.
  • Table 3 is the composition ratio of the components of each electrolyte sample analyzed.
  • LiPF6 and LiFSI are relatively decreased in all the samples, and the remaining components tend to increase relatively. However, this does not mean that the LiPF6 or LiFSI has been decomposed and changed into the remaining components of the electrolytic solution since the absolute mass is not changed. Since the numerical values shown in Table 3 are relative mass ratios, it means that LiPF6 and LiFSI are relatively more decomposed than the other components.
  • the insulating plate according to the production example of the present invention was manufactured by Ref. Compared with the electrolytic solution, LiPF6 was reduced by 3 wt% and LiFSI was decreased by 2.1 wt%. However, in the insulating plate according to Comparative Example 1, LiPF6 and LiFSI were reduced by 0.1 wt% and 0.3 wt%, respectively. In the insulating plate according to Comparative Example 2, LiPF6 and LiFSI were decreased by 1.7 wt% and 10.6 wt%, respectively. That is, LiFSI was most reduced in the insulating plate of Comparative Example 2, which indicates that the insulating plate of Comparative Example 2 was the most active.
  • the insulating plate of Comparative Example 1 had the highest chemical resistance. However, in the above heat resistance test, it was confirmed that the insulating plate of Comparative Example 1 had the lowest heat resistance, so that the insulating plate of Production Example was excellent in heat resistance and chemical resistance.
  • Table 4 shows the results of the critical radiant heat flux, the total heat emission, the maximum heat release rate, and the flame dropping rate during the extinguishment for the insulating plate of the production example
  • Table 5 is the result of the average combustion duration column for the insulating plate of the production example.
  • the combustion sustained heat is the time from the initial exposure of the specimen to the point at which the flame tip reaches each point multiplied by the radiant heat flux viewed through the incombustible calibration plate at the same point.
  • the average combustion duration column is the average of the characteristic values measured at different locations by the continuous heat sequence. As shown in Table 5, the average burning heat of the insulating plate of the production example was less than the standard value of 1.5 when the flame reach distance was 50 mm and 100 mm, respectively.
  • Critical radiant heat flux during extinguishing means the flow rate of heat at the position where the flame propagates farthest from the centerline of the specimen to be burned and stopped.
  • the recorded heat flux is the value obtained by the calibration test of the testing machine using the calibration plate.
  • the average value of the critical radiant heat flux during the extinguishing of the insulating plate of the production example is 48.6 kW / m 2 , which is larger than the reference value of 20.0 kW / m 2 and thus satisfies the criterion.
  • the total heat release refers to the total heat release during the test period
  • the maximum heat release rate refers to the maximum heat release during the test period.
  • the average of the total heat emission amount of the insulating plate of the manufacturing example is 0.03 MJ, which is smaller than the reference 0.7 MJ and the average of the maximum heat release rate is 0.21 kW, which is smaller than the reference 4.0 kW. .
  • FIG. 21 is a photograph showing an exploded view of a secondary battery in which an insulating plate is assembled according to the production example of the present invention after the stability test
  • FIG. 22 is an exploded view of the secondary battery in which the insulating plate of Comparative Example 1 is assembled after the stability test
  • FIG. 23 is a photograph showing an exploded view of the secondary battery in which the insulating plate of Comparative Example 2 is assembled after the stability test.
  • Table 6 shows the number and ratio of pinholes generated in each of the insulating plates.
  • Table 7 shows the tensile strength and elongation of the respective insulating plates.
  • the insulating plate of the production example was broken at an average tensile strength of 133.64 N / mm < 2 & gt ;.
  • the average elongation at this time was 7.13%.
  • the insulating plate of Comparative Example 2 was not stretched to 1000N which is the maximum allowable weight of the universal testing machine. Therefore, the tensile strength could not be measured, and the elongation was accordingly 0% on average.
  • the insulating plate of Comparative Example 1 has a problem of being easily deformed by a small force because of low tensile strength and high elongation. Since the insulating plate of Comparative Example 2 does not have a stretching property, it can not be made into a roll type and can not be fed into a line, so continuous production is impossible and production speed may be lowered. However, the insulating plate of the production example can be made into a roll type rolled up to one side because of its high tensile strength and low elongation, and can be stretched to some extent.
  • the insulating plate 16 for a secondary battery is manufactured, compared with coating with a conventional thermoplastic resin or phenol or the like, so that the properties such as heat resistance and chemical resistance Can be improved.
  • the phenol has a chain bonding form in which the central element is carbon (C)
  • the silicone polymer as a main raw material of the silicone rubber 162 has a chain bonding form in which the central element is silicon (Si). Therefore, it can have high thermal stability. Further, generation of dust is suppressed when the insulating plate 16 for a secondary battery is punched, so that continuous production is possible, production amount increases, and manufacturing cost can be reduced.
  • the insulating plate 16 for the secondary battery can be easily manufactured by forming the mother roll easily by winding the insulating plate raw material before the insulating plate 16 for secondary battery has flexibility.

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Abstract

Selon un mode de réalisation de la présente invention, un procédé de fabrication d'une plaque d'isolation pour une batterie rechargeable, afin de résoudre ce problème, est un procédé de fabrication d'une plaque d'isolation insérée dans un boîtier d'une batterie rechargeable, et comprend les étapes consistant à : fabriquer un tissu de plaque d'isolation par revêtement de caoutchouc de silicone sur au moins une surface d'un tissu de fibre de verre formé en croisant des fils de trame et de fibre de verre de chaîne ; et découper le tissu de plaque d'isolation.
PCT/KR2019/000113 2018-01-29 2019-01-03 Plaque d'isolation pour batterie rechargeable et son procédé de fabrication Ceased WO2019146927A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CN201980003502.0A CN110870091B (zh) 2018-01-29 2019-01-03 用于二次电池的顶部绝缘体及其制造方法
EP19743871.6A EP3644393B1 (fr) 2018-01-29 2019-01-03 Plaque d'isolation pour batterie rechargeable et son procédé de fabrication
JP2019569935A JP6947362B2 (ja) 2018-01-29 2019-01-03 二次電池用絶縁板及びその製造方法
PL19743871.6T PL3644393T3 (pl) 2018-01-29 2019-01-03 Izolator górny dla baterii akumulatorowej oraz sposób jego wytwarzania
ES19743871T ES2977188T3 (es) 2018-01-29 2019-01-03 Elemento de aislamiento superior para batería secundaria y método de fabricación del mismo
US16/632,694 US11552358B2 (en) 2018-01-29 2019-01-03 Top insulator for secondary battery and method for manufacturing the same
US18/085,431 US12334571B2 (en) 2018-01-29 2022-12-20 Top insulator for secondary battery and method for manufacturing the same

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KR10-2018-0010900 2018-01-29
KR20180010900 2018-01-29
KR1020180125530A KR102268405B1 (ko) 2018-01-29 2018-10-19 이차 전지용 절연판 및 그의 제조 방법
KR10-2018-0125530 2018-10-19

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US18/085,431 Division US12334571B2 (en) 2018-01-29 2022-12-20 Top insulator for secondary battery and method for manufacturing the same

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CN111628133A (zh) * 2020-05-25 2020-09-04 大连中比能源科技有限公司 一种锂离子电池复合隔膜及其制备方法
CN113601774A (zh) * 2021-08-14 2021-11-05 许绝电工股份有限公司 一种高导热绝缘板的生产工艺

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