WO2018133030A1 - Agent d'étanchéité de languette - Google Patents

Agent d'étanchéité de languette Download PDF

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Publication number
WO2018133030A1
WO2018133030A1 PCT/CN2017/071918 CN2017071918W WO2018133030A1 WO 2018133030 A1 WO2018133030 A1 WO 2018133030A1 CN 2017071918 W CN2017071918 W CN 2017071918W WO 2018133030 A1 WO2018133030 A1 WO 2018133030A1
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WO
WIPO (PCT)
Prior art keywords
layer
comonomer
tab sealant
monomer
polyolefin
Prior art date
Application number
PCT/CN2017/071918
Other languages
English (en)
Inventor
Changsheng Liang
Tylor ZHOU
Xinhui Zhang
Original Assignee
Avery Dennison Corporation
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
Application filed by Avery Dennison Corporation filed Critical Avery Dennison Corporation
Priority to PCT/CN2017/071918 priority Critical patent/WO2018133030A1/fr
Priority to TW106146596A priority patent/TWI655280B/zh
Priority to CN201810048542.4A priority patent/CN108274869A/zh
Publication of WO2018133030A1 publication Critical patent/WO2018133030A1/fr

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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
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • 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
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    • H01M50/19—Sealing members characterised by the material
    • H01M50/197—Sealing members characterised by the material having a layered structure
    • H—ELECTRICITY
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    • 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
    • H01M50/198—Sealing members characterised by the material characterised by physical properties, e.g. adhesiveness or hardness
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    • B32B2307/00—Properties of the layers or laminate
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    • 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
    • H01M50/172—Arrangements of electric connectors penetrating the casing
    • H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
    • H01M50/178—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for pouch or flexible bag cells
    • 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
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    • 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 generally to tab sealants.
  • the tab sealants comprise three layers and in particular, at least one of the first and third layer contains a base polymer grafted with a monomer and comonomer comprising a benzene ring.
  • Tab sealants also referred to as terminal covering resin films, are generally used for covering tabs in battery cells.
  • the tabs have metal leads serving as a metal terminal and the tabs serve as electrode terminals to which electric power is supplied to a cell body.
  • Tab sealants desirably have good adhesion between the tab sealant and the metal lead to prevent peeling off of the tab sealant.
  • Tab sealants also desirably secure insulation of the lead with other parts of the cell body.
  • tab sealants desirably have good corrosion resistance.
  • US Pat. No. 7,972,722 discloses a lead sealant film and a non-aqueous electrolyte battery.
  • the lead sealant film includes a laminated structure composed of an inner layer, an intermediate layer, and an outer layer.
  • the intermediate layer includes a first acid-modified polypropylene having a high melting-point
  • each of the inner layer and the outer layer includes a second acid-modified polypropylene having a low melting-point.
  • a difference between the melting point of the first acid-modified polypropylene and the melting point of the second acid-modified polypropylene is from 20°C to 25°C.
  • US Pat. No. 9,123,922 discloses a lithium ion battery exterior material, including a base material layer and a sequentially laminated adhesive layer, aluminum foil layer provided with a corrosion prevention treated layer, and an adhesive resin layer on one surface of the base material layer; wherein, the adhesive resin layer contains an acid-modified polyolefin resin and a miscible elastomer dispersed in the acid-modified polyolefin at a dispersed phase size of 1 nm to less than 1 ⁇ m.
  • US Pub. No. 2010/0221601 discloses an electrical part comprising a lead conductor and a sealed vessel including a metal layer, the lead conductor extending from the inside of the sealed vessel to the outside, wherein the lead conductor and the sealed vessel are fusion-bonded through a thermal adhesive layer at the sealing portion, and wherein a softening-resistant layer having through holes made in the thickness direction is provided between the lead conductor and the metal layer at the sealing portion.
  • a nonaqueous electrolyte cell comprising an electrode and a nonaqueous electrolyte are both enclosed inside the sealed vessel. Both the sealed vessel and a lead conductor having an insulating coating layer can be used in the electrical part or the like.
  • US Pub. No. 2015/0311483 discloses a secondary battery metal terminal coating resin film having improved overall performance. It is capable of securing filling ability, adhesive properties, insulating properties of a lead end portion, and shape retention properties of a sealant. Also disclosed is a manufacturing method for the same. Also disclosed is a battery pack using the secondary battery metal terminal coating resin film provided in the lead end portion of a tab used for a laminate-type packaging material for a secondary battery. The secondary battery metal terminal coating resin film is laminated and a coating metal terminal is connected to a positive electrode or a negative electrode of a secondary battery. The melt flow rate of at least one layer of a resin that constitutes the resin film is within a range from about 0.1 g/10 minutes to about 2.5 g/10 minutes.
  • US Pub. No. 2016/0099446 discloses a resin film, which is adapted for use in a packaging material for secondary cell.
  • the secondary cell has a sealant layer formed of a polyolefin resin.
  • the resin film is disposed between the sealant layer and leads that are connected to a positive electrode and a negative electrode.
  • the layer includes a first layer disposed at a position close to the leads and a second layer disposed at a position close to the sealant layer.
  • a heat quantity of the second layer measured according to JIS K 7122, is larger than a heat quantity of fusion of the first layer.
  • US Pub. No. 2016/0099447 discloses a terminal covering resin film for a secondary cell, which is attached so as to cover part of an outer surface of a terminal connected to a power generation element of a secondary cell.
  • the film comprises an innermost layer contacting the terminal and an outermost layer forming a surface opposite to the innermost layer, wherein the innermost layer is a layer of not less than 20 ⁇ m in thickness containing an acid-modified polyolefin and a melt flow rate of the innermost layer is not less than 2.0 g/10 minutes.
  • JP 2016091939 discloses tensile storage modulus, dynamic viscoelasticity and melt flow rate values for a resin film.
  • the invention relates to a tab sealant comprising: (a) a first layer comprising a polyolefin grafted with a monomer; (b) a second layer comprising a polyolefin; and (c) a third layer comprising a polyolefin grafted with a monomer; wherein the second layer is disposed between the first layer and the third layer, and further wherein the polyolefin in at least one of the first layer and the third layer is grafted with a monomer and a comonomer containing a benzene ring.
  • the polyolefin of the first layer, second layer, and third layer may be independently selected from the group consisting of homo polypropylene, block polypropylene, and random polypropylene.
  • the monomer in the first layer and/or the third layer may be selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, ⁇ -methacrylic acid, methyl methacrylate, and glycidyl methacrylate.
  • the polyolefin in the first layer may be grafted with the monomer and a comonomer.
  • the polyolefin in the third layer may be grafted with the monomer and a comonomer.
  • the polyolefin in the first layer and the third layer may be grafted with the monomer and a comonomer.
  • the comonomer in the first layer is different than the comonomer in the second layer.
  • the comonomer in the first layer is the same as the comonomer in the second layer.
  • the comonomer may be selected from the group consisting of styrene, dipropyl phthalate, diallyl phthalate, allylbenzene, methyleugenol, and ⁇ -methylstyrene.
  • the monomer may be present in the first layer from 1 to 20 wt. %.
  • the comonomer may be present in the first layer from 1 to 10 wt. %.
  • the monomer may be present in the third layer from 1 to 20 wt. %.
  • the comonomer may be present in the third layer from 1 to 10 wt. %.
  • the first layer and third layer may have substantially the same composition.
  • the thickness of the first layer may be from 1 to 50 ⁇ m.
  • the thickness of the second layer may be from 30 to 100 ⁇ m.
  • the first layer may have a melting point from 130 to 160°C.
  • the second layer may have a melting point from 130 to 190°C.
  • the third layer may have a melting point from 130 to 160°C.
  • the first layer may have a melt flow rate of 2 to 20 g/10 min.
  • the second layer may have a melt flow rate of 2 to 20 g/10 min.
  • the third layer may have a melt flow rate of 2 to 20 g/10 min.
  • the first layer may further comprise an additive.
  • FIG. 1 shows a perspective view of a cell pack in accordance with aspects of the invention
  • FIG. 2 shows a perspective view of a tab in accordance with aspects of the invention.
  • FIG. 3 shows a cross-sectional view of a tab sealant in accordance with aspects of the invention.
  • the present invention is directed to tab sealants that have superior adhesion, insulation, and corrosion resistance as compared to conventional tab sealants.
  • the tab sealant according to the present invention is a three layer film.
  • the first and third layers each (individually) comprise a polyolefin grafted with a monomer.
  • the second layer comprises a polyolefin.
  • the polyolefin is grafted with the monomer and with a comonomer comprising a benzene ring.
  • the first layer comprises a polyolefin grafted with a monomer and a comonomer comprising a benzene ring, also referred to as a benzene ring comonomer.
  • the third layer comprises a polyolefin grafted with a monomer and a benzene ring comonomer.
  • both the first layer and the third layer comprise a polyolefin grafted with a monomer and a benzene ring comonomer, and the composition of the first layer and third layer may be substantially the same.
  • the overall compositions of the first and third layers may vary widely (as long as the benzene ring comonomer is included in at least one of the layers) .
  • the base polymer may be the same in each layer while the monomer and/or inclusion of a comonomer may differ.
  • Further embodiments may include the same monomer in each layer but with a different base polymer.
  • the base polymer, monomer, and optional comonomer may be the same, but the weight percentages and/or molecular weights of each component may differ between the first and third layer.
  • FIG. 1 illustrates a cell pack 10 comprising a cell body 11, packaging material 12, tabs 13 and 14, lead 15, and tab sealant 16.
  • FIG. 2 shows tab 13 with a lead 15 serving as a metal terminal, and tab sealant 16.
  • the lead 15 has a first end portion 15A electrically connected to a power generation element inside of packaging material 12 (shown in FIG. 1) , and a second end portion 15B which is electrically conductive and which has an outer surface that is at least partially exposed to permit connection with an external device to which electric power may be supplied.
  • FIG. 3 shows a cross-sectional view of tab sealant 16.
  • tab sealant 16 contains a first layer 17 (an inner layer) , a second layer 18 (an intermediate layer) , and a third layer 19 (an outer layer) .
  • first layer 17 an inner layer
  • second layer 18 an intermediate layer
  • third layer 19 an outer layer
  • the tab sealant may be prepared by a co-extrusion casting process, a co-extrusion blowing process, or other processes known in the art.
  • the first, second, and third layer may be co-extruded together in a three-layer co-extrusion machine.
  • the processing temperature may depend on the tab sealant components. Generally, the processing temperature is in the range of 230 to 250°C.
  • the first layer 17, also referred to as an inner layer, is the layer which seals the outer surface of the lead 15 and is therefore in contact with the outer surface of the lead.
  • the first layer may be comprised of a base polymer grafted with a monomer.
  • the base polymer may be an olefin polymer.
  • the olefin polymer may include, but is not limited to, polyethylene, including low, medium and high density polyethylenes; polypropylene, including homo, block or random polypropylene; polymethylpentene, polybutene-1; and ethylene- ⁇ -olefin copolymers.
  • the olefin polymer is polypropylene.
  • the base polymer may be grafted with a monomer.
  • the monomer may include, but is not limited to acrylic acid, methacrylic acid, maleic acid, and maleic anhydride, ⁇ -methacrylic acid, methyl methacrylate, and glycidyl methacrylate. In some aspects, the monomer is maleic anhydride.
  • the base polymer in the first layer may also be grafted with a comonomer, e.g., a monomer containing a benzene ring.
  • a comonomer e.g., a monomer containing a benzene ring.
  • the comonomer may be an olefin monomer containing a benzene ring, such as styrene, dipropyl phthalate, diallyl phthalate, allylbenzene, methyleugenol, and ⁇ -methylstyrene.
  • the inventors have now discovered that by including a comonomer with a benzene ring when grafting the base polymer and monomer, the grafting reaction rate is surprisingly increased, resulting in improved adhesion of the tab sealant. Additionally, the inclusion of a comonomer with a benzene ring when grafting the base polymer and monomer has been found to unexpectedly improve corrosion resistance of the base polymer, e.g., polypropylene.
  • the base polymer may be present in the first layer in an amount from to 70 to 98 wt. %, based on the entire weight of the first layer, e.g., from 78.5 to 96.5 wt. %or from 85 to 95 wt. %.
  • the first layer comprises at least 70 wt. % base polymer, based on the entire weight of the first layer, e.g., at least 78.5 wt. %or at least 85 wt. %.
  • the first layer comprises no more than 98 wt. % base polymer, based on the entire weight of the first layer, e.g., no more than 96.5 wt. % or no more than 95 wt. %.
  • the monomer may be present in the first layer in an amount from 1 to 20 wt.%, e.g., from 2 to 15 wt. %or from 3 to 10 wt. %, based on the entire weight of the first layer.
  • the first layer comprises at least 1 wt. %monomer, based on the entire weight of the first layer, e.g., at least 2 wt. %or at least 3 wt. %.
  • the first layer comprises no more than 20 wt. %monomer, based on the entire weight of the first layer, e.g., no more than 15 wt. %or no more than 10 wt. %.
  • the first layer may comprise from 1 to 10 wt.%comonomer, based on the entire weight of the first layer, e.g., from 1.5 to 7.5 wt. % or from 2 to 5 wt. %.
  • the first layer comprises at least 1 wt. % comonomer, based on the entire weight of the first layer, e.g., at least 1.5 wt. %or at least 2 wt. %.
  • the first layer comprises no more than 20 wt. % monomer, based on the entire weight of the first layer, e.g., no more than 15 wt. %or no more than 10 wt. %.
  • the first layer may comprise an additive.
  • the additive may be present from 1 to 15 wt. %, based on the entire weight of the first layer, e.g., from 1 to 12 wt. %or from 1 to 10 wt. %.
  • Additives known in the art may be included, such as antioxidants.
  • the first layer may be thinner than those of conventional tab sealants.
  • the first layer has a thickness ranging from 1 to 50 microns, e.g., from 5 to 25 microns, or from 10 to 20 microns. In terms of lower limits, the first layer may have a thickness of at least 1 micron, e.g., at least 5 microns, or at least 10 microns. It has now been discovered that a thinner first layer may lead to improved corrosion resistance as compared to a thicker first layer. In some cases, the thickness of the first layer may be selected based on the desired corrosion resistance. Without being bound by theory, it is believed that the existence of the polar groups in the first (and/or third layer) reduce corrosion resistance.
  • the second layer may not contain polar groups, its corrosion resistance is better as compared to the first and/or third layer. Therefore, by having a thinner first layer (and/or third layer) , the impact of the first (and/or third layer) on the corrosion resistance of the tab sealant is reduced.
  • the first layer may have a melting point from 130 to 160°C, e.g., from 130 to 150°C, or from 130 to 140°C. In terms of lower limits, the first layer may have a melting point of at least 130°C, e.g., at least 133°C or at least 135°C . In terms of upper limits, the first layer may have a melting point no greater than 160°C, e.g., no greater than 150°C or 140°C. A melting point below 130°C may not provide satisfactory heat resistance while a melting point above 160°C may require too much heat to seal the first layer to the lead, resulting in decreased adhesion and insulation.
  • the melt flow rate of the first layer may range from 2 to 20 g/10 minutes, e.g., from 3 to 10 g/10 minutes or from 5 to 6 g/10 minutes. In terms of lower limits, the first layer may have a melt flow rate of at least 2 g/10 minutes, e.g., at least 3 g/10 minutes or at least 5 g/10 minutes. In terms of upper limits, the first layer may have a melt flow rate of no greater than 20 g/10 minutes, e.g., no greater than 10 g/10 minutes or no greater than 6 g/10 minutes.
  • the melt flow rate is an index showing the fluidity of the layer during heating. If the melt flow rate is less than 2 g/10 minutes, sealing of the tab sealant around the lead may be insufficient due to reduced fluidity. If the melt flow rate is greater than 20 g/10 minutes, the first layer may flow too easily, resulting in thinning of the layer during sealing.
  • the second layer 18 may also be referred to as an intermediate layer, and is disposed between the first layer 17 and third layer 19 of the tab sealant.
  • the second layer may be comprised of a polyolefin.
  • the polyolefin film may vary widely.
  • the polyolefin may include polyethylene, including low, medium and high density polyethylenes; polypropylene, including homo, block or random polypropylene; polymethylpentene, polybutene-1; and ethylene- ⁇ -olefin copolymers.
  • the olefin polymer is polypropylene, and may be a casting polypropylene film.
  • the polyolefin film may comprise any polyolefin material that exhibits good mechanical strength and heat resistance.
  • Exemplary polyolefin films may comprise at least one of a polyimide, a polyester, a polyetherimide (PEI) , a polyethylene naphthalate (PEN) , a polyether sulfone (PES) , a polysulfone, polymethylpentene (PMP) , a polyvinylidene fluoride (PVDF) , an ethylene-chlorotrifluoroethylene (ECTFE) , or combinations thereof.
  • the polyolefin in the second layer may be the same polyolefin as in the first layer, though the molecular weight and/or melting point may differ.
  • Exemplary polyolefin films made of polyimide include available from DuPont, and available from Kaneka Texas Corporation, Exemplary polyolefin films made of polyester include avai lable from DuPont, and 2600 polyethylene terephthalate film, available from American Hoechst.
  • Other commercially available polyolefin films include Tempalux TM (PEI) , available from Westlake Plastics Company; Superio-UT TM (PEI) , available from Mitsubishi Plastics, Kaladex TM ; (PEN) and Teonex (PEN) , both available from DuPont.
  • the second layer may be thicker than the first layer and/or third layer.
  • the second layer may be at least 10%thicker, e.g., at least 20%thicker, at least 30%thicker, or at least 40%thicker than at least one of the first and third layer.
  • the second layer may have a thickness ranging from 30 to 100 microns, e.g., from 45 to 90 microns or from 60 to 80 microns.
  • the second layer may have a thickness of at least 30 microns, e.g., at least 45 microns, or at least 60 micros.
  • the second layer may have a thickness of no more than 100 microns, e.g., no more than 90 microns or no more than 80 microns.
  • the second layer may have a melting point from 130 to 190°C, e.g., from 140 to 180°C, or from 150 to 170°C. In terms of lower limits, the second layer may have a melting point of at least 130°C, e.g., at least 140°C or at least 150°C . In terms of upper limits, the second layer may have a melting point no greater than 190°C, e.g., no greater than 180°C or 170°C. As compared to at least one of the first and third layer, the melting point of the second layer may be at least 10°C greater, e.g., at least 20°C greater or at least 30°C greater.
  • the melt flow rate of the second layer may range from 2 to 20 g/10 minutes, e.g., from 5 to 10 g/10 minutes or from 7 to 9 g/10 minutes. In terms of lower limits, the second layer may have a melt flow rate of at least 2 g/10 minutes, e.g., at least 5 g/10 minutes or at least 7 g/10 minutes. In terms of upper limits, the second layer may have a melt flow rate of no greater than 20 g/10 minutes, e.g., no greater than 10 g/10 minutes or no greater than 9 g/10 minutes.
  • the tensile strength and flexural modulus of the second layer may be selected based on the desired heat and moisture resistance of the layer, since the second layer provides insulation for the tab sealant.
  • the tensile strength at yield ranges from 25 to 35 MPa, e.g., from 28 to 34 MPa or from 30 to 32 MPa.
  • the flexural modulus may range from 800 to 1500 MPa, e.g., from 900 to 1450 MPa or from 1100 to 1400 MPa.
  • the third layer 19 also referred to as an outer layer, is in contact with the second layer 18.
  • the third layer may be the same, substantially the same, or different than the first layer.
  • the third layer may be comprised of a base polymer grafted with a monomer.
  • the base polymer may be an olefin polymer.
  • the olefin polymer may include, but is not limited to, polyethylene, including low, medium and high density polyethylenes; polypropylene, including homo, block or random polypropylene; polymethylpentene, polybutene-1; and ethylene- ⁇ -olefin copolymers.
  • the olefin polymer is polypropylene.
  • the base polymer may be grafted with a monomer.
  • the monomer may include, but is not limited to acrylic acid, methacrylic acid, maleic acid, maleic anhydride, ⁇ -methacrylic acid, methyl methacrylate, and glycidyl methacrylate. In some aspects, the monomer is maleic anhydride.
  • the base polymer in the third layer may also be grafted with a comonomer, e.g., a monomer containing a benzene ring.
  • the comonomer may be an olefin monomer containing a benzene ring, such as styrene, dipropyl phthalate, diallyl phthalate, allylbenzene, methyleugenol, and ⁇ -methylstyrene.
  • the base polymer may be present in the third layer in an amount from to 70 to 98 wt. %, based on the entire weight of the third layer, e.g., from 78.5 to 96.5 wt. %or from 85 to 95 wt. %.
  • the third layer comprises at least 70 wt. % base polymer, based on the entire weight of the third layer, e.g., at least 78.5 wt. %or at least 85 wt. %.
  • the third layer comprises no more than 98 wt. % base polymer, based on the entire weight of the third layer, e.g., no more than 96.5 wt.%or no more than 95 wt.
  • the base polymer in the third layer may be the same base polymer as in the first layer, or it may be substantially the same due to differences in melting point or molecular weight. In some aspects, a different base polymer is used in the third layer as compared to the first layer. In further aspects, the base polymer in the third layer may be the same as the polyolefin in the second layer or it may be substantially the same due to differences in melting point or molecular weight. In still further aspects, a different base polymer is used in the third layer as compared to the polyolefin in the second layer.
  • the monomer may be present in the third layer in an amount from 1 to 20 wt.%, e.g., from 2 to 15 wt. %or from 3 to 10 wt. %, based on the entire weight of the third layer.
  • the third layer comprises at least 1 wt. %monomer, based on the entire weight of the third layer, e.g., at least 2 wt. %or at least 3 wt. %.
  • the third layer comprises no more than 20 wt. %monomer, based on the entire weight of the third layer, e.g., no more than 15 wt. %or no more than 10 wt.%.
  • the monomer polymer in the third layer may be the same monomer as in the first layer, or it may be substantially the same due to differences in melting point or molecular weight. In some aspects, a different monomer is used in the third layer as compared to the first layer.
  • the third layer may comprise from 1 to 10 wt.%comonomer, based on the entire weight of the third layer, e.g., from 1.5 to 7.5 wt.%or from 2 to 5 wt. %. In terms of lower limits, the third layer comprises at least 1 wt.%comonomer, based on the entire weight of the third layer, e.g., at least 1.5 wt. %or at least 2 wt. %. In terms of upper limits, the third layer comprises no more than 20 wt. % monomer, based on the entire weight of the third layer, e.g., no more than 15 wt. %or no more than 10 wt. %.
  • the comonomer in the third layer may be the same comonomer as in the first layer, or it may be substantially the same due to differences in melting point or molecular weight. In some aspects, a different comonomer is used in the third layer as compared to the first layer.
  • the third layer may comprise an additive.
  • the additive may be present from 1 to 15 wt. %, based on the entire weight of the third layer, e.g., from 1 to 12 wt. %or from 1 to 10 wt. %.
  • Additives known in the art may be included, such as antioxidants.
  • the third layer may have a thickness ranging from 1 to 50 microns, e.g., from 5 to 25 microns, or from 10 to 20 microns. In terms of lower limits, the third layer may have a thickness of at least 1 micron, e.g., at least 5 microns, or at least 10 micros.
  • the thickness of the third layer may be selected based on the desired corrosion resistance. Without being bound by theory, it is believed that a thinner first layer leads to improved corrosion resistance as compared to a thicker first layer.
  • the thickness of the third layer may be the as the first layer, or it may be different. In some aspects, the thickness of the third layer is within ⁇ 30%of the thickness of the first layer, e.g., within ⁇ 20%or ⁇ 10%.
  • the total thickness of the first and third layer combined may range from 2 to 100 microns, e.g., from 10 to 80 microns, or from 20 to 40 microns.
  • the total thickness of the first layer, second layer, and third layer, combined may range from 32 to 200 microns, e.g., from 55 to 190 microns, or from 80 to 120 microns.
  • the third layer may have a melting point from 130 to 160°C, e.g., from 130 to 150°C, or from 130 to 140°C. In terms of lower limits, the third layer may have a melting point of at least 130°C, e.g., at least 133°C or at least 135°C. In terms of upper limits, the first layer may have a melting point no greater than 160°C, e.g., no greater than
  • the melting point of the third layer is within 10°C of the melting point of the first layer, e.g., within 5°C or within 3°C. In further aspects, the melting point of the third layer is within 40°C of the melting point of the first layer, e.g., within 35°C or within 30°C.
  • the melt flow rate of the third layer may range from 2 to 20 g/10 minutes, e.g., from 3 to 10 g/10 minutes or from 5 to 6 g/10 minutes. In terms of lower limits, the third layer may have a melt flow rate of at least 2 g/10 minutes, e.g., at least 3 g/10 minutes or at least 5 g/10 minutes. In terms of upper limits, the third layer may have a melt flow rate of no greater than 20 g/10 minutes, e.g., no greater than 10 g/10 minutes or no greater than 6 g/10 minutes. In some aspects, the melt flow rate of the third layer is within 3 g/10 minutes of the melt flow rate of the first layer, e.g., within 2 g/10 minutes or within 1 g/10 minutes. In some aspects, the melt flow rate of the third layer may be within 5 g/10 minutes of the melt flow rate of the second layer, e.g., within 4 g/10 minutes or within 3 g/10 minutes.
  • Embodiment 1 A tab sealant comprising: (a) a first layer comprising a polyolefin grafted with a monomer; (b) a second layer comprising a polyolefin; and (c) a third layer comprising a polyolefin grafted with a monomer; wherein the second layer is disposed between the first layer and the third layer, and further wherein the polyolefin in at least one of the first layer and the third layer is grafted with a monomer and a comonomer containing a benzene ring.
  • Embodiment 2 An embodiment of embodiment 1, wherein the polyolefin of the first layer, second layer, and third layer is independently selected from the group consisting of homo polypropylene, block polypropylene, and random polypropylene.
  • Embodiment 3 An embodiment of any one of the embodiments of embodiments 1-2, wherein the monomer in the first layer and/or the third layer is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, ⁇ -methacrylic acid, methyl methacrylate, and glycidyl methacrylate.
  • Embodiment 4 An embodiment of any one of the embodiments of embodiments 1-3, wherein the polyolefin in the first layer is grafted with the monomer and a comonomer.
  • Embodiment 5 An embodiment of any one of the embodiments of embodiments 1-4, wherein the polyolefin in the third layer is grafted with the monomer and a comonomer.
  • Embodiment 6 An embodiment of any one of the embodiments of embodiments 1-5, wherein the comonomer in the first layer is different than the comonomer in the second layer.
  • Embodiment 7 An embodiment of any one of the embodiments of embodiments 1-5, wherein the comonomer in the first layer is the same as the comonomer in the second layer.
  • Embodiment 8 An embodiment of any one of the embodiments of embodiments 1-7, wherein the comonomer is selected from the group consisting of styrene, dipropyl phthalate, diallyl phthalate, allylbenzene, methyleugenol, and ⁇ -methylstyrene.
  • Embodiment 9 An embodiment of any one of the embodiments of embodiments 1-8, wherein the monomer is present in the first layer from 1 to 20 wt. %.
  • Embodiment 10 An embodiment of any one of the embodiments of embodiments 1-9, wherein the comonomer is present in the first layer from 1 to 10 wt. %.
  • Embodiment 11 An embodiment of any one of the embodiments of embodiments 1-10, wherein the monomer is present in the third layer from 1 to 20 wt. %.
  • Embodiment 12 An embodiment of any one of the embodiments of embodiments 1-11, wherein the comonomer is present in the third layer from 1 to 10 wt. %.
  • Embodiment 13 An embodiment of any one of the embodiments of embodiments 1-12, wherein the first layer and third layer have substantially the same composition.
  • Embodiment 14 An embodiment of any one of the embodiments of embodiments 1-13, wherein the thickness of the first layer is from 1 to 50 ⁇ m.
  • Embodiment 15 An embodiment of any one of the embodiments of embodiments 1-14, wherein the thickness of the second layer is from 30 to 100 ⁇ m.
  • Embodiment 16 An embodiment of any one of the embodiments of embodiments 1-15, wherein the thickness of the third layer is from 1 to 50 ⁇ m.
  • Embodiment 17 An embodiment of any one of the embodiments of embodiments 1-16,
  • Embodiment 18 An embodiment of any one of the embodiments of embodiments 1-17, wherein the first layer has a melting point from 130 to 160°C.
  • Embodiment 19 An embodiment of any one of the embodiments of embodiments 1-18: wherein the second layer has a melting point from 130 to 190°C.
  • Embodiment 20 An embodiment of any one of the embodiments of embodiments 1-19: wherein the third layer has a melting point from 130 to 160°C.
  • Embodiment 21 An embodiment of any one of the embodiments of embodiments 1-20: wherein the first layer has a melt flow rate of 2 to 20 g/10 min.
  • Embodiment 22 An embodiment of any one of the embodiments of embodiments 1-21: wherein the second layer has a melt flow rate of 2 to 20 g/10 min.
  • Embodiment 23 An embodiment of any one of the embodiments of embodiments 1-22: wherein the third layer has a melt flow rate of 2 to 20 g/10 min.
  • Embodiment 24 An embodiment of any one of the embodiments of embodiments 1-23: wherein the first layer further comprises an additive.
  • a tab sealant was prepared having the following composition:
  • First layer Polypropylene was grafted with maleic anhydride and styrene to form a polymer comprising 1-10 wt. %monomer and 2-5 wt. %comonomer.
  • the polymer was cast and had a thickness of 10-20 microns, a melting point of 135°C and a melt flow rate of 5-6 g/10 minutes.
  • Second layer Polypropylene having a melting point of 165°C and a melt flow rate of 8 g/10 minutes was cast to a thickness from 60 to 80 microns.
  • Third layer Identical to the first layer.
  • a tab sealant was prepared as in Example 1, except that the comonomer was allylbenzene.
  • a tab sealant was prepared as in Example 1, except that no comonomer was included in either the first or third layer.
  • a tab sealant was prepared as in Example 1, except that glycidyl acrylate, which lacks a benzene ring, was used as a comonomer.
  • a tab sealant was prepared as in Example 1, except that the comonomer was present in an amount of less than 1 wt. %.
  • the tab sealant was high frequency welded to the tab lead. Then the welded tab sealant and tab lead were immersed in an electrolyte solution for 72 hours at 85°C to test the peeling of the tab sealant from the tab lead.
  • the corrosion resistance and adhesive strength were rated as follows:
  • a score of 1 represented bad adhesion and the surface of the tab sealant was clear, indicating poor corrosion resistance.
  • a score of 2 represented medium adhesion and the surface of the tab sealant was partially white, indicating that the tab lead and tab sealant had good adhesion strength and that the tab sealant had good corrosion resistance, and partially clear.
  • a score of 3 represented strong adhesion and the surface of the tab sealant was completely white.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

L'invention concerne des agents d'étanchéité de languette. Les agents d'étanchéité de languette peuvent comprendre trois couches. La première et la troisième couche comprennent chacune un polymère de base greffé avec un monomère. La première couche et/ou la troisième couche est greffée avec un monomère et un comonomère comprenant un cycle benzénique. La seconde couche comprend un polymère de polyoléfine. Les agents d'étanchéité de languette présentent une adhérence, une résistance à la corrosion et une isolation améliorées par comparaison avec des agents d'étanchéité de languette classiques.
PCT/CN2017/071918 2017-01-20 2017-01-20 Agent d'étanchéité de languette WO2018133030A1 (fr)

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WO2021006351A1 (fr) * 2019-07-10 2021-01-14 大日本印刷株式会社 Film adhésif pour bornes métalliques, borne métallique avec film adhésif pour bornes métalliques, dispositif de stockage d'électricité utilisant ledit film adhésif pour bornes métalliques et procédé de production de dispositif de stockage d'électricité
JPWO2021006351A1 (ja) * 2019-07-10 2021-12-02 大日本印刷株式会社 金属端子用接着性フィルム、金属端子用接着性フィルム付き金属端子、当該金属端子用接着性フィルムを用いた蓄電デバイス、及び蓄電デバイスの製造方法
CN114097130A (zh) * 2019-07-10 2022-02-25 大日本印刷株式会社 金属端子用粘接性膜、带有金属端子用粘接性膜的金属端子、使用该金属端子用粘接性膜的蓄电器件和蓄电器件的制造方法
EP3998650A4 (fr) * 2019-07-10 2023-07-19 Dai Nippon Printing Co., Ltd. Film adhésif pour bornes métalliques, borne métallique avec film adhésif pour bornes métalliques, dispositif de stockage d'électricité utilisant ledit film adhésif pour bornes métalliques et procédé de production de dispositif de stockage d'électricité
WO2021246472A1 (fr) * 2020-06-03 2021-12-09 藤森工業株式会社 Film d'étanchéité, élément de fil conducteur d'électrode et batterie

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