WO2020075866A1 - 架橋セパレータを用いたリチウムイオン電池 - Google Patents

架橋セパレータを用いたリチウムイオン電池 Download PDF

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Publication number
WO2020075866A1
WO2020075866A1 PCT/JP2019/040343 JP2019040343W WO2020075866A1 WO 2020075866 A1 WO2020075866 A1 WO 2020075866A1 JP 2019040343 W JP2019040343 W JP 2019040343W WO 2020075866 A1 WO2020075866 A1 WO 2020075866A1
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WO
WIPO (PCT)
Prior art keywords
storage device
separator
electricity storage
elastic modulus
silane
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
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PCT/JP2019/040343
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English (en)
French (fr)
Japanese (ja)
Inventor
シュン 張
諒 黒木
悠希 福永
小林　博実
三都子 齋藤
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.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Kasei Corp
Asahi Chemical Industry Co 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 to KR1020247011220A priority Critical patent/KR102834252B1/ko
Priority to CN202211419385.6A priority patent/CN115642366A/zh
Priority to KR1020227039349A priority patent/KR102601002B1/ko
Priority to EP23176183.4A priority patent/EP4235940A3/en
Priority to KR1020207012551A priority patent/KR102435806B1/ko
Priority to CN202210749649.8A priority patent/CN114976483A/zh
Priority to EP22169052.2A priority patent/EP4064443B1/en
Priority to EP23176153.7A priority patent/EP4235939A3/en
Priority to KR1020217034635A priority patent/KR102467607B1/ko
Priority to CN202210750993.9A priority patent/CN115051117B/zh
Priority to EP23176156.0A priority patent/EP4235934A3/en
Priority to JP2020507143A priority patent/JP6898512B2/ja
Priority to EP23157951.7A priority patent/EP4220844A3/en
Priority to CN202210752468.0A priority patent/CN115036645B/zh
Priority to KR1020227015370A priority patent/KR102611025B1/ko
Priority to EP23176142.0A priority patent/EP4235933A3/en
Priority to KR1020237021105A priority patent/KR102632166B1/ko
Priority to EP24174823.5A priority patent/EP4425682A1/en
Priority to KR1020217034639A priority patent/KR102466829B1/ko
Priority to EP22169029.0A priority patent/EP4068488A1/en
Priority to EP23166690.0A priority patent/EP4224613A3/en
Priority to KR1020237021108A priority patent/KR102655732B1/ko
Application filed by Asahi Kasei Corp, Asahi Chemical Industry Co Ltd filed Critical Asahi Kasei Corp
Priority to CN202211426208.0A priority patent/CN115799602A/zh
Priority to CN201980007742.8A priority patent/CN111630687B/zh
Priority to KR1020217034641A priority patent/KR102384050B1/ko
Priority to EP19870116.1A priority patent/EP3866219B1/en
Priority to CN202410842338.5A priority patent/CN118630423A/zh
Priority to US16/957,421 priority patent/US11588208B2/en
Priority to KR1020237004268A priority patent/KR102609222B1/ko
Priority to EP22169036.5A priority patent/EP4053986B1/en
Priority to CN202211425326.XA priority patent/CN115810870A/zh
Priority to CN202210751481.4A priority patent/CN115051106B/zh
Priority to KR1020217034638A priority patent/KR102466827B1/ko
Priority to KR1020237004271A priority patent/KR102609224B1/ko
Publication of WO2020075866A1 publication Critical patent/WO2020075866A1/ja
Anticipated expiration legal-status Critical
Priority to US17/967,002 priority patent/US12407068B2/en
Priority to US17/967,012 priority patent/US20230111013A1/en
Priority to US17/966,990 priority patent/US11837750B2/en
Ceased legal-status Critical Current

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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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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Definitions

  • the present invention relates to an electricity storage device separator and a method for crosslinking the same, an electricity storage device assembly kit, an electricity storage device manufacturing method, and the like.
  • Microporous membranes are widely used as separation or selective permeation separation membranes for various substances, and separators.
  • Examples of their applications include microfiltration membranes, fuel cell separators, condenser separators, or functional materials. Examples thereof include a base material of a functional film for filling the inside of the resin to exhibit a new function, a separator for an electricity storage device, and the like.
  • the polyolefin microporous film is preferably used as a lithium ion battery separator that is widely used in notebook personal computers, mobile phones, digital cameras and the like.
  • Patent Document 1 describes that the higher-order physical properties of a polyolefin resin, which is an essential component of a lithium ion battery separator, are adjusted. Further, as shown in Patent Document 2, in a specific crystallinity and gel fraction region, heat generation due to a short circuit inside the battery is suppressed by a shutdown function, and even if a high temperature portion is partially generated in the battery cell. It is known that the safety of the battery can be ensured by having the property of not rupturing the membrane (breakdown at 170 ° C. or higher). Regarding Patent Documents 1 and 2, more specifically, it has been experimentally found that high-temperature film rupture properties can be exhibited by constructing a silane cross-linked portion (gelation structure) in a polyolefin separator.
  • Patent Documents 1 to 6 describe a silane crosslinked structure formed by contact between a silane-modified polyolefin-containing separator and water.
  • Patent Document 8 describes a crosslinked structure formed by ring-opening of norbornene by irradiation with ultraviolet rays, electron beams or the like.
  • Patent Document 9 describes that the insulating layer of the separator has a (meth) acrylic acid copolymer having a crosslinked structure, a styrene-butadiene rubber binder, and the like.
  • a separator has been proposed in which the thickness ratio of the A layer having the shutdown characteristic and the B layer containing the aramid resin and the inorganic material is adjusted within a predetermined range (see Patent Document 11).
  • the material for the electricity storage device separator has a chemical structure that is inert to electrochemical reactions or other chemical reactions, so the development and practical application of the microporous polyolefin membrane is widely expanded. Has been done.
  • polyolefin is used as the resin, there is a limit to the performance improvement even if the mechanical microporous structure of the separator is improved.
  • the separator's heat resistance stability above the melting point of the polyolefin or the electronegativity of the olefin unit the affinity or liquid retention with the electrolyte is insufficient, resulting in the formation of Li ions or solvated ion clusters thereof.
  • the transparency in the separator cannot be satisfied.
  • JP, 9-216964 A International Publication No. 97/44839 JP-A-11-144700 JP, 11-172036, A JP 2001-176484 A JP-A-2000-319441 JP, 2017-203145, A JP, 2011-071128, A JP, 2014-056843, A Japanese Patent Laid-Open No. 10-261435 JP, 2007-299612, A International Publication No. 2010/134585 JP, 2016-072150, A
  • Patent Document 3 a crosslinking catalyst masterbatch is used during the extrusion step to promote the crosslinking reaction of the silane-modified polyethylene in the extruder, but resin agglomerates are also observed and the physical properties of the separator are uniform. Reduce sex.
  • the methods described in Patent Documents 4, 5, and 6 are provided with a plasticizer extraction step or a silane gel crosslinking step, control the gel fraction of the resin film, and convert the uncrosslinked resin into hot water. Measures are taken by passing through molding and then dehydrating. Further, in Patent Document 7, the gel fraction of the microporous polyolefin membrane, the storage elastic modulus at a temperature of 40 ° C. to 250 ° C.
  • At least one surface of a microporous polyolefin film is provided with calcined kaolin, boehmite, etc. It has been proposed to dispose an inorganic porous layer containing the above inorganic particles and a resin binder (Patent Documents 12 and 13).
  • Patent Document 4 cannot sufficiently advance the silane cross-linking reaction, and it is difficult to obtain high temperature film-rupture resistance.
  • the plasticizer extraction step described in Patent Documents 3 and 4 since the tin (II) -based crosslinking catalyst is used, the crosslinking reaction can proceed, but there is a concern that the crosslinking catalyst may remain afterwards.
  • the heat-resistant resin microporous film described in Patent Document 7 is merely obtained by applying a photopolymerizable coating liquid to a dry and porous film. Further, in Example 5 of Patent Document 7, a low-molecular weight silane coupling agent such as ⁇ -methacryloxypropyltrimethoxysilane is added to the porous membrane, but if the low-molecular weight silane coupling agent is used in the wet porosification method. Since the low molecular weight silane coupling agent easily reacts with or binds to the plasticizer for porosity, it is expected that it does not bind to the resin of the porous membrane. Furthermore, a battery including a heat-resistant resin microporous film as a separator as described in Patent Document 7 has poor cycle characteristics, and induces an unexpected side reaction in the battery during long-term use, resulting in reduced battery safety. Is concerned.
  • the coating layer described in Patent Document 7 is formed by a cross-linking reaction after applying a compound having a polymerizable functional group to the resin porous membrane, so that the resin porous membrane is applied simultaneously with the coating of the coating layer. It is expected that a part of the liquid will be infiltrated, and after the cross-linking reaction has progressed, a mixed region of them is also formed near the interface between the film layer and the resin porous film. As a result, good TMA heat shrinkage performance can be obtained, but a decrease in battery cycle characteristics due to clogging of the resin porous membrane or a decrease in Fuse (shutdown) performance due to melting phenomenon of the resin porous membrane is expected.
  • the multilayer porous membranes described in Patent Documents 12 and 13 are provided with a polyolefin microporous membrane and an inorganic porous layer, but have a low temperature shutdown function as a separator for an electricity storage device and a high temperature membrane rupture property, or an electricity storage device There is room for consideration on improving cycle characteristics and battery nail penetration safety.
  • the batteries using the separators described in Patent Documents 3 to 7 have poor cycle characteristics, and when they are used for a long period of time, unexpected side reactions are induced in the batteries, which may reduce the battery safety. .
  • a tin (Sn) -based catalyst is put into the extruder during the extrusion process.
  • the wet manufacturing process of a separator for an electricity storage device usually includes steps such as extrusion / sheet molding, stretching, plasticizer extraction (poration), heat treatment, and winding, so that silane crosslinking occurs in the extruder during the sheet molding process. If accelerated, the gelled part causes production failure, and it becomes difficult to stretch the silane-crosslinked polyolefin in the subsequent stretching step. Therefore, there is still room for study on a new separator for an electricity storage device that is suitable for the manufacturing process.
  • the cross-linking methods described in Patent Documents 1 to 6, 8 and 9 are all performed in-process of separator film formation or in a batch immediately after separator film formation. Therefore, after forming the cross-linked structure described in Patent Documents 1 to 6, 8 and 9, coating and slitting of the separator must be performed, and internal stress is not generated in the subsequent lamination / winding process with the electrode. Due to the increase, the manufactured battery may be deformed. For example, if a crosslinked structure is formed by heating, the internal stress of the separator having the crosslinked structure may increase at room temperature or room temperature.
  • the crosslinked structure is formed by irradiation with light such as ultraviolet rays or electron beams
  • the irradiation of light becomes non-uniform and the cross-linked structure may become non-uniform. It is considered that this is because the periphery of the crystal part of the resin forming the separator is easily cross-linked by the electron beam.
  • Patent Document 10 describes a technique for improving cycle characteristics of a lithium ion secondary battery by adding succinimides or the like to an electrolytic solution.
  • the technique described in Patent Document 10 does not attempt to improve the cycle characteristics by specifying the structure of the separator.
  • the present invention is compatible with a shutdown function and a high-temperature puncture resistance, and an electric storage device separator capable of ensuring safety, output and / or cycle stability of an electric storage device, and a manufacturing process thereof. It is an object of the present invention to provide a novel crosslinking method, an assembling kit for an electricity storage device, or a manufacturing method.
  • An electricity storage device separator comprising a silane-modified polyolefin, wherein the silane crosslinking reaction of the silane-modified polyolefin starts when the electricity storage device separator comes into contact with an electrolytic solution.
  • the separator for an electricity storage device according to item 1 wherein the silane-modified polyolefin is not a masterbatch resin containing a dehydration condensation catalyst that crosslinks the silane-modified polyolefin.
  • the separator for an electricity storage device according to item 1 or 2 wherein the electricity storage device separator contains polyethylene in addition to the silane-modified polyolefin.
  • E ′ S Is a storage elastic modulus of the electricity storage device separator measured at 160 ° C. to 220 ° C. after the silane-modified polyolefin is cross-linked, and E ′ j Or E ’ S
  • the conditions for measuring the storage elastic modulus E ′ are defined by the following configurations (i) to (iv).
  • the static tensile load refers to an intermediate value between the maximum stress and the minimum stress in each cyclic motion
  • the sine wave load refers to the vibration stress centered on the static tensile load.
  • the sine wave tension mode refers to measuring the vibration stress while performing periodic motion with a fixed amplitude of 0.2%. In the sine wave tension mode, the static tension load and the sine wave load are used. When the sine wave load is 0.02N or less by varying the gap distance and the static tensile load so that the difference is within 20%, the sine wave load is 5N or less. The vibration stress is measured by amplifying the amplitude value so that the increase amount of the amplitude value is within 25%.
  • E ′′ j Or E ′′ S The condition for measuring the loss elastic modulus E ′′ is defined by the following configurations (i) to (iv).
  • the static tensile load refers to an intermediate value between the maximum stress and the minimum stress in each cyclic motion
  • the sine wave load refers to the vibration stress centered on the static tensile load.
  • the sine wave tension mode refers to measuring the vibration stress while performing periodic motion with a fixed amplitude of 0.2%. In the sine wave tension mode, the static tension load and the sine wave load are used. When the sine wave load is 0.02N or less by varying the gap distance and the static tensile load so that the difference is within 20%, the sine wave load is 5N or less. The amplitude value is amplified so that the increase amount of the amplitude value is within 25%, and the vibration stress is measured.
  • a separator for an electricity storage device characterized in that a silane cross-linking reaction of a silane-modified polyolefin occurs when the separator for an electricity storage device comes into contact with an electrolytic solution.
  • E ′ 0 Is a storage elastic modulus of the electricity storage device separator not containing the silane-modified polyolefin, measured at 160 ° C. to 220 ° C., and E ′. a Or E ’ 0
  • the conditions for measuring the storage elastic modulus E ′ are defined by the following configurations (i) to (iv).
  • the static tensile load refers to an intermediate value between the maximum stress and the minimum stress in each cyclic motion
  • the sine wave load refers to the vibration stress centered on the static tensile load.
  • the sine wave tension mode refers to measuring the vibration stress while performing periodic motion with a fixed amplitude of 0.2%. In the sine wave tension mode, the static tension load and the sine wave load are used. When the sine wave load is 0.02N or less by varying the gap distance and the static tensile load so that the difference is within 20%, the sine wave load is 5N or less. The vibration stress is measured by amplifying the amplitude value so that the increase amount of the amplitude value is within 25%.
  • a separator for an electricity storage device containing 5 to 40% by mass of a silane-modified polyolefin and 60 to 95% by mass of a polyolefin other than the silane-modified polyolefin represented by the following formula (4):
  • R E '' mix E ′′ a / E ′′ 0 (4) ⁇ In the formula, E ′′ a Is the loss elastic modulus of the electricity storage device separator measured at 160 ° C. to 220 ° C., and E ′′ 0 Is the loss modulus of the electricity storage device separator not containing the silane-modified polyolefin, measured at 160 ° C.
  • E ′′ The condition for measuring the loss elastic modulus E ′′ is defined by the following configurations (i) to (iv).
  • the static tensile load refers to an intermediate value between the maximum stress and the minimum stress in each cyclic motion
  • the sine wave load refers to the vibration stress centered on the static tensile load.
  • the sine wave tension mode refers to measuring the vibration stress while performing periodic motion with a fixed amplitude of 0.2%. In the sine wave tension mode, the static tension load and the sine wave load are used. When the sine wave load is 0.02N or less by varying the gap distance and the static tensile load so that the difference is within 20%, the sine wave load is 5N or less. The amplitude value is amplified so that the increase amount of the amplitude value is within 25%, and the vibration stress is measured.
  • the electricity storage device separator not containing the silane-modified polyolefin is a silane-unmodified polyolefin microporous film having a gelation degree of 0% or more and 10% or less.
  • What is claimed is: 1. A separator for an electricity storage device comprising 5 to 40% by mass of a silane-modified polyolefin and 60 to 95% by mass of a polyolefin other than the silane-modified polyolefin, wherein the rubber-like flat region is obtained when the storage elastic modulus of the separator for the electricity storage device changes with temperature. And an electric storage device separator having a transition temperature of 135 ° C.
  • a separator for an electricity storage device comprising a polyolefin microporous film, In the solid viscoelasticity measurement of the electricity storage device separator at a temperature of ⁇ 50 ° C.
  • the conditions of the solid viscoelasticity measurement for measuring the storage elastic modulus and the loss elastic modulus are as follows (i) to (iv): (I) Dynamic viscoelasticity measurement under the following conditions: ⁇ Measuring device used: RSA-G2 (manufactured by TA Instruments) -Sample film thickness: 200 ⁇ m to 400 ⁇ m (However, when the film thickness of the sample alone is less than 200 ⁇ m, measure the dynamic viscoelasticity so that the total thickness falls within the range of 200 ⁇ m to 400 ⁇ m by stacking multiple samples.
  • a power storage device separator comprising a polyolefin microporous film, wherein the storage viscoelasticity of the power storage device separator from the film softening transition temperature to the film rupture temperature has an average storage elastic modulus of 1.0 MPa to 12 MPa, A separator for an electricity storage device having an average loss elastic modulus of 0.5 MPa to 10 MPa.
  • the electricity storage device separator according to any one of Items 12 to 14, which includes a silane-modified polyolefin and a polyolefin other than the silane-modified polyolefin.
  • Items 12 to 14 which includes a silane-modified polyolefin and a polyolefin other than the silane-modified polyolefin.
  • Item 16 The electricity storage device separator according to Item 15, which contains 5% to 40% by mass of the silane-modified polyolefin and 60% to 95% by mass of the polyolefin other than the silane-modified polyolefin.
  • a separator for a power storage device containing polyolefin has one or more functional groups, and After storage in an electricity storage device, (1) the functional groups undergo a condensation reaction with each other, (2) the functional group reacts with a chemical substance inside the electricity storage device, or (3) the functional group has another type.
  • a separator for an electricity storage device characterized in that a crosslinked structure is formed by reacting with the functional group of.
  • Item 18 The electricity storage device separator according to Item 17, wherein the chemical substance is any of an electrolyte, an electrolytic solution, an electrode active material, an additive, or a decomposition product thereof contained in the electricity storage device.
  • a separator for an electricity storage device containing a polyolefin the separator for an electricity storage device having an amorphous part crosslinked structure in which an amorphous part of the polyolefin is crosslinked.
  • R E''x ⁇ Mixed loss elastic modulus ratio (R E''x ) Is 1.5 to 20 times, and the separator for an electricity storage device according to Item 19 or 20.
  • R E '' mix 24 The separator for an electricity storage device according to any one of Items 17 to 23, wherein) is 1.5 times to 20 times.
  • the separator for an electricity storage device according to any one of Items 17 to 26, wherein the crosslinked structure is formed by a reaction via any of a covalent bond, a hydrogen bond and a coordinate bond.
  • the reactions via the covalent bond are the following reactions (I) to (IV): (I) Condensation reaction of multiple identical functional groups; (II) Reaction between multiple different functional groups; (III) Chain condensation reaction between functional group and electrolyte; and (IV) Reaction between functional group and additive; Item 28.
  • the electricity storage device separator according to Item 27 which is at least one selected from the group consisting of: [29]
  • the reaction via the coordination bond is the following reaction (V): (V) A reaction in which a plurality of identical functional groups are crosslinked via a coordinate bond with a metal ion; Item 27.
  • Item 29. The electricity storage device separator according to Item 28, wherein the reaction (I) and / or (II) is catalytically promoted by a chemical substance inside the electricity storage device.
  • Item 29 The electricity storage device separator according to Item 28, wherein the reaction (I) is a condensation reaction of a plurality of silanol groups.
  • the reaction (IV) is a nucleophilic substitution reaction, a nucleophilic addition reaction, or a ring-opening reaction of a compound Rx forming the electricity storage device separator and a compound Ry forming the additive, and the compound Rx is a functional group.
  • the compound Ry has a group x and is a ligation reaction unit y 1 Item 28.
  • the above reaction (IV) is a nucleophilic substitution reaction
  • the functional group x of the compound Rx is —OH, —NH 2 At least one selected from the group consisting of, --NH--, --COOH, and --SH, and Connection reaction unit y of the compound Ry 1 But CH 3 SO 2 -, CF 3 SO 2 -, ArSO 2 -, CH 3 SO 3 -, CF 3 SO 3 -, ArSO 3 -, And the following formula (y 1 -1) to (y 1 -6): ⁇ In the formula, X is a hydrogen atom or a monovalent substituent. ⁇ ⁇ In the formula, X is a hydrogen atom or a monovalent substituent.
  • X is a hydrogen atom or a monovalent substituent.
  • X is a hydrogen atom or a monovalent substituent.
  • X is a hydrogen atom or a monovalent substituent.
  • X is a hydrogen atom or a monovalent substituent.
  • the electricity storage device separator which is at least two selected from the group consisting of monovalent groups represented by: [34]
  • the above reaction (IV) is a nucleophilic substitution reaction
  • the compound Ry is the ligation reaction unit y 1 In addition to chain unit y 2 And The chain unit y 2
  • ⁇ ⁇ In the formula, n is an integer of 1 to 20.
  • ⁇ ⁇ In the formula, n is an integer of 1 to 20.
  • ⁇ ⁇ In the formula, n is an integer of 1 to 20.
  • ⁇ ⁇ In the formula, n is an integer of 1 to 20.
  • X is an alkylene group having 1 to 20 carbon atoms or an arylene group, and n is an integer of 1 to 20.
  • X is an alkylene group having 1 to 20 carbon atoms or an arylene group, and n is an integer of 1 to 20.
  • Item 34 The electricity storage device separator according to Item 32 or 33, which is at least one selected from the group consisting of divalent groups represented by.
  • the above reaction (IV) is a nucleophilic addition reaction
  • the functional group x of the compound Rx is —OH, —NH 2 At least one selected from the group consisting of, --NH--, --COOH, and --SH, and Connection reaction unit y of the compound Ry 1
  • the electricity storage device separator according to item 32 which is at least one selected from the group consisting of groups represented by: [36]
  • the above reaction (IV) is a ring opening reaction
  • the functional group x of the compound Rx is —OH, —NH 2 At least one selected from the group consisting of, --NH--, --COOH, and --SH, and Connection reaction unit y of the compound Ry 1
  • the following formula (ROy 1 -1) ⁇ In the formula, plural Xs are each independently a hydrogen atom or a monovalent substituent.
  • the electricity storage device separator according to item 32 which is at least two groups represented by.
  • the electricity storage device separator according to Item 29 which is at least one selected from the group consisting of: [38] A separator for an electricity storage device, comprising a first porous layer (A layer) containing a silane-modified polyolefin and capable of forming a crosslinked structure, and a second porous layer (B layer) containing inorganic particles, the crosslinked structure being The separator for an electricity storage device having a heat shrinkage rate at 150 ° C. after formation of 0.02 to 0.91 times the heat shrinkage rate at 150 ° C. before formation of the crosslinked structure.
  • a separator for an electricity storage device comprising a first porous layer (A layer) containing a silane-modified polyolefin and capable of forming a crosslinked structure, and a second porous layer (B layer) containing inorganic particles, the crosslinked structure being The separator for an electricity storage device having a heat shrinkage rate at 150 ° C. after formation of 0.02 to 0.91 times the heat shrinkage rate at 150 °
  • the separator for an electricity storage device according to item 40 or 41, wherein the content of the silane-modified polyolefin in the microporous film is 0.5% by weight to 40% by weight.
  • the inorganic particles are alumina (Al 2 O 3 ), Silica, titania, zirconia, magnesia, ceria, yttria, zinc oxide, iron oxide, silicon nitride, titanium nitride, boron nitride, silicon carbide, aluminum hydroxide oxide (AlO (OH)), talc, kaolinite, dickite, Item 40 to at least one selected from the group consisting of nacrite, halloysite, pyrophyllite, montmorillonite, sericite, mica, amethite, bentonite, asbestos, zeolite, diatomaceous earth, silica sand, and glass fiber.
  • R ⁇ E ' Storage elastic modulus change ratio (R ⁇ E ' ) Is 1.5 to 20 times, and / or the following formula (1B):
  • R ⁇ E '' E ′′ S / E ′′ j (1B) ⁇ In the formula, E ′′ j Is a loss elastic modulus measured at 160 ° C. to 220 ° C. of the electricity storage device separator before the silane-modified polyolefin is cross-linked, and E ′′ S Is a loss elastic modulus measured at 160 ° C. to 220 ° C. of the electricity storage device separator after the silane-modified polyolefin has undergone a crosslinking reaction.
  • the electricity storage device separator according to any one of Items 40 to 45, wherein ′′) is 1.5 times to 20 times.
  • R E'mix Is 1.5 to 20 times and / or the following formula (2B):
  • R E '' mix E ′′ / E ′′ 0 (2B) ⁇
  • E ′′ is the loss elastic modulus of the electricity storage device separator measured at 160 ° C. to 220 ° C.
  • E ′′ is 0 Is the loss elastic modulus measured at 160 ° C. to 220 ° C. of the electricity storage device separator not containing the silane-modified polyolefin.
  • R E '' mix 47 The separator for an electricity storage device according to any one of items 40 to 46, wherein the ratio is 1.5 times to 20 times. [48] 48.
  • the electricity storage device according to any one of items 40 to 47, wherein a transition temperature between a rubber-like flat region and a crystal melt flow region is 135 ° C. to 150 ° C. when the storage elastic modulus of the electricity storage device separator changes with temperature.
  • An electricity storage device including an electrode, the electricity storage device separator according to any one of items 1 to 48, and a non-aqueous electrolyte.
  • a sheet forming step in which a mixture of silane-modified polyolefin, polyethylene and a plasticizer is extruded, solidified by cooling, and formed into a sheet to obtain a sheet; (2) a stretching step of stretching the sheet in at least one axial direction to obtain a stretched product; (3) a porous body forming step of extracting the plasticizer from the stretched product in the presence of an extraction solvent to make the stretched product porous to form a porous body; and (4) Heat treatment step of subjecting the porous body to heat treatment; 51.
  • the method for producing a separator for an electricity storage device including: [52] The following steps: (1) A sheet forming step in which a silane-modified polyolefin, polyethylene and a plasticizer are extruded into a sheet with an extruder, cooled and solidified, and processed into a sheet-shaped molded body; (2) A stretching step of forming the stretched product by biaxially stretching the sheet-shaped molded product at an area ratio of 20 times or more and 250 times or less; (3) Porous body forming step of forming a porous body by extracting the plasticizer from the stretched product; (4) A heat treatment step of subjecting the porous body to a heat treatment, stretching and relaxation in the width direction to obtain a heat treated porous body; (8B) a coating step of forming an inorganic porous layer containing inorganic particles and a resin binder on at least one surface of the heat-treated porous body to form a silane crosslinking precursor; (9) An assembling step in which a
  • the electric storage device assembly kit according to item 53 wherein the non-aqueous electrolyte contains a fluorine (F) -containing lithium salt.
  • the non-aqueous electrolyte is lithium hexafluorophosphate (LiPF 6 57.
  • a step of preparing an electricity storage device assembly kit according to any one of items 53 to 56 A step of initiating a silane crosslinking reaction of the silane-modified polyolefin by contacting the electricity storage device separator in the element (1) of the electricity storage device assembly kit with the non-aqueous electrolyte solution in the element (2)
  • a method of manufacturing an electricity storage device including: [58] Further steps below: And a step of connecting a lead terminal to the electrode of the element (1), And a process of charging and discharging at least one cycle Item 57.
  • the method for manufacturing an electricity storage device including: [59] A method of manufacturing an electricity storage device using a separator containing polyolefin, comprising: The polyolefin contains one or more functional groups, and the following steps: (1) by subjecting the functional groups to a condensation reaction, (2) reacting the functional group with a chemical substance inside the electricity storage device, or (3) reacting the functional group with another type of functional group. , Cross-linking step to form cross-linked structure A method of manufacturing an electricity storage device including: [60] The method for manufacturing an electricity storage device according to item 59, wherein the crosslinking step is performed at a temperature of 5 ° C to 90 ° C.
  • both the low-temperature shutdown function and the high-temperature puncture resistance of the electricity storage device separator can be made compatible, and the generation of unmelted resin aggregates can also be suppressed in the manufacturing process to contribute to productivity and economic efficiency. It is possible to provide an electricity storage device having better cycle characteristics and higher safety, and an assembly kit for the same.
  • a cross-linking structure can be imparted to the separator to reduce cross-linking unevenness.
  • a cross-linking structure is formed not only inside the separator but also between the separator and the electrode or between the separator and the solid electrolyte interface (SEI) to improve the strength between the plurality of members of the electricity storage device.
  • FIG. 1 is an example of a graph for explaining the relationship between the temperature and the storage elastic modulus.
  • the storage elastic moduli of the reference film and the post-crosslinking film in the temperature range of ⁇ 50 ° C. to 225 ° C. are compared to show the rubber-like property.
  • the transition temperatures of the flat region and the crystal melt flow region are shown.
  • FIG. 2 is an example of a graph for explaining the relationship between temperature and loss elastic modulus.
  • the loss elastic moduli of the reference film and the post-crosslinking film in the temperature range of ⁇ 50 ° C. to 225 ° C. are compared and the rubber-like property is compared.
  • the transition temperatures of the flat region and the crystal melt flow region are shown.
  • FIG. 3 is a graph showing a relationship between temperature and resistance of an electricity storage device including the separator obtained in Example I-1.
  • FIG. 4 is a graph for explaining the relationship between the temperature, the gap distance, the storage elastic modulus, and the loss elastic modulus in the viscoelasticity measurement of the electricity storage device separator, and is compared with the graph (a) of Example II-1. 7 illustrates graph (b) of Example II-1.
  • FIG. 5 is a graph for determining the film softening transition temperature based on the temperature, the gap distance, and the first derivative value of the gap displacement in the viscoelasticity measurement of the electricity storage device separator, and the graph of Example II-1 ( The graph (a) and the graph (b) of Comparative Example II-1 are illustrated.
  • FIG. 4 is a graph for explaining the relationship between the temperature, the gap distance, the storage elastic modulus, and the loss elastic modulus in the viscoelasticity measurement of the electricity storage device separator, and is compared with the graph (a) of Example II-1. 7 illustrates graph (b) of
  • FIG. 6 is a schematic diagram for explaining a crystalline polymer having a higher-order structure divided into a lamella (crystal part) having a crystal structure, an amorphous part, and an intermediate layer part between them.
  • FIG. 7 is a schematic diagram for explaining crystal growth of polyolefin molecules.
  • FIG. 8 is a strain amount-crystal fragmentation rate graph for showing a change in X-ray crystal structure at the time of tensile rupture fracture test for the film according to one embodiment of the present invention.
  • FIG. 9 is an example of a graph for explaining the relationship between the temperature and the storage elastic modulus, and compares the storage elastic moduli of the reference membrane and the crosslinked membrane in the temperature range of ⁇ 50 ° C.
  • FIG. 10 is an example of a graph for explaining the relationship between the temperature and the loss elastic modulus, and compares the loss elastic moduli of the reference film and the post-crosslinking film in the temperature range of ⁇ 50 ° C. to 310 ° C. with a rubber-like shape.
  • the transition temperatures of the flat region and the crystal melt flow region are shown.
  • FIG. 11 is a 1 H-NMR chart (a) and a 13 C-NMR chart (b) of a silane-modified polyolefin raw material 1 obtained by using a polyolefin.
  • FIG. 10 is an example of a graph for explaining the relationship between the temperature and the loss elastic modulus, and compares the loss elastic moduli of the reference film and the post-crosslinking film in the temperature range of ⁇ 50 ° C. to 310 ° C. with a rubber-like shape.
  • the transition temperatures of the flat region and the crystal melt flow region are shown.
  • FIG. 11 is a 1 H-NMR chart (a) and
  • FIG. 12 is a 1 H-NMR chart (a) and a 13 C-NMR chart (b) of a silane-modified polyolefin raw material 2 obtained by using polyolefin.
  • FIG. 13 is a 1 H-NMR chart (a) and a 13 C-NMR chart (b) of the separator obtained in Example I-1 in a state before crosslinking.
  • the upper limit value and the lower limit value of the numerical range can be arbitrarily combined.
  • the upper limit of the preferable numerical range and the lower limit of the more preferable numerical range may be combined, and conversely, the upper limit of the more preferable numerical range and the lower limit of the preferable numerical range may be combined.
  • the terms “above” and “formed on the surface” do not mean that the positional relationship of each member is “directly above”.
  • the expressions "layer B formed on layer A” and “layer B formed on the surface of layer A” mean any layer between layer A and layer B that does not fall under any of them. Does not exclude aspects including.
  • the characteristics of only the microporous film described below can be measured after removing the layers other than the microporous film (for example, the inorganic porous layer) from the electricity storage device separator.
  • One embodiment of the present invention is a power storage device separator (hereinafter, also simply referred to as a “separator”). Since the separator needs to have insulating properties and ion permeability, it generally includes paper, a polyolefin nonwoven fabric, a resin microporous film, or the like, which is an insulating material having a porous structure. Particularly, in a lithium ion battery, a polyolefin microporous film that is capable of constructing a dense and uniform porous body structure by oxidation-reduction resistance deterioration of a separator is excellent.
  • the microporous film means a film (film) made of a porous body, and its average pore diameter is preferably 10 nm or more and 500 nm or less, more preferably 30 nm or more and 100 nm or less.
  • the separator can be taken out from the electricity storage device.
  • the separator according to the first embodiment contains a silane-modified polyolefin, and may also contain other polyolefins if desired.
  • the separator according to the first embodiment is brought into contact with the electrolytic solution, the silane crosslinking reaction of the silane-modified polyolefin contained in the separator is started. Since the separator according to the first embodiment can perform crosslinking of the silane-modified polyolefin at the time of contact with the electrolytic solution, it is possible to control the timing of crosslinking, and thereby the crosslinking reaction in the manufacturing process of the separator. Instead, the crosslinking reaction can be performed in the manufacturing process of the electricity storage device.
  • the separator according to the second embodiment is characterized in that a silane cross-linking reaction of a silane-modified polyolefin occurs when it comes into contact with an electrolytic solution.
  • a silane cross-linking reaction of a silane-modified polyolefin occurs when it comes into contact with an electrolytic solution.
  • silane cross-linking reaction of the silane-modified polyolefin that occurs when the separator according to the second embodiment contacts the electrolytic solution, it is possible to achieve control of the cross-linking timing without being affected by the manufacturing or use process of the separator.
  • the separators according to the first and second embodiments can accelerate the crosslinking reaction when pouring the electrolytic solution into the exterior body that houses the separator, so that production defects can be avoided in the manufacturing process, and the storage device can be manufactured. In the process, it is possible to achieve safety and high output of the electricity storage device. From the viewpoint of the content of the separator and the timing of the crosslinking reaction, it is preferable that the silane crosslinking reaction of the silane-modified polyolefin is started at the time of mixing or contacting the separator and the electrolytic solution.
  • the separator according to the third embodiment contains 5 to 40% by mass of a silane-modified polyolefin and 60 to 95% by mass of a polyolefin other than the silane-modified polyolefin, and relates to the viscoelasticity measurement (version 1) described in Examples.
  • the following formula (1): R ⁇ E ' E' S / E 'j (1) ⁇ In the formula, E ′ j is the storage elastic modulus of the electricity storage device separator at 160 ° C. to 220 ° C. before the silane-modified polyolefin cross-links, and E ′ S is the silane-modified polyolefin cross-linking reaction. It is a storage elastic modulus measured at 160 ° C.
  • the loss elastic modulus change ratio (R ⁇ E ′′ ) defined by is 1.5 to 20 times.
  • the storage elastic modulus change ratio (R ⁇ E ′ ) and / or the loss elastic modulus change ratio (R ⁇ E ′′ ) is within the range of 1.5 to 20 times, the shutdown function is realized. It is possible to achieve both high temperature film rupture resistance.
  • the storage elastic modulus change ratio (R ⁇ E ′ ) and / or the loss elastic modulus change ratio (R ⁇ E ′′ ) is preferably 2 to 18 times.
  • E ′ j and E ′ S and E ′′ j and E ′′ S are storage elastic moduli measured within the set temperature range of the measuring device when 160 to 220 ° C.
  • the separator is in the form of a laminated film, only the silane-modified polyolefin-containing porous film is removed from the laminated film to obtain the storage elastic moduli E ′ j and E ′ S and the loss elastic moduli E ′′ j and E ′′ S. Shall be measured.
  • the separator according to the fourth embodiment contains 5 to 40% by mass of a silane-modified polyolefin and 60 to 95% by mass of a polyolefin other than the silane-modified polyolefin, and relates to the viscoelasticity measurement (version 1) described in the examples.
  • the following formula (2): R E'mix E ' a / E' 0 (2) ⁇ Wherein E ′ a is the storage elastic modulus of the electricity storage device separator measured at 160 ° C. to 220 ° C., and E ′ 0 is the electricity storage device separator that does not contain a silane-modified polyolefin. Storage elastic modulus measured at ° C.
  • the mixed loss elastic modulus ratio (R E ′′ mix ) defined by is 1.5 times to 20.0 times.
  • the mixed storage elastic modulus ratio (R E′mix ) and / or the mixed loss elastic modulus ratio (R E ′′ mix ) is in the range of 1.5 times to 20.0 times. It is possible to achieve both the shutdown function and the high temperature film breakage resistance.
  • the mixed storage elastic modulus ratio (R E′mix ) and / or the mixed loss elastic modulus ratio (R E ′′ mix ) is preferably 2 to 18 times.
  • E ′ a and E ′ 0 and E ′′ a and E ′′ 0 are the storage elastic moduli measured within the set temperature range of the measuring device when 160 to 220 ° C. is the widest temperature range. Or, it is the average value of the loss elastic modulus.
  • the separator When the separator is in the form of a laminated film, only the silane-modified polyolefin-containing porous film is removed from the laminated film so that the storage elastic moduli E ′ a and E ′ 0 and the loss elastic moduli E ′′ a and E ′′ 0 Shall be measured.
  • the separator according to the fifth embodiment contains 5 to 40% by mass of a silane-modified polyolefin and 60 to 95% by mass of a polyolefin other than the silane-modified polyolefin, and relates to the viscoelasticity measurement (version 1) described in the examples.
  • the transition temperature between the rubber-like flat region and the crystal melt flow region is 135 ° C. to 150 ° C. when the storage elastic modulus or loss elastic modulus changes with temperature.
  • the transition temperature between the rubber-like flat region and the crystal melt flow region is in the range of 135 ° C. to 150 ° C., so that both the shutdown function and the high temperature film breakage resistance can be achieved.
  • the transition temperature between the rubbery flat region and the crystal melt flow region is preferably 137 ° C to 147 ° C, more preferably 140 ° C to 145 ° C, and further preferably 140 ° C to 143 ° C.
  • the separator is in the form of a laminated film, only the silane-modified polyolefin-containing porous film is removed from the laminated body, and the transition temperatures of the rubber-like flat region and the crystal melt flow region are measured.
  • the separator according to the sixth embodiment includes a polyolefin having one or more kinds of functional groups, and after being stored in an electricity storage device, (1) the functional groups of the polyolefins undergo a condensation reaction or (2) ) A functional group of polyolefin reacts with a chemical substance inside the electricity storage device, or (3) a functional group of polyolefin reacts with another type of functional group to form a crosslinked structure.
  • the functional group contained in the polyolefin constituting the separator is considered not to be taken into the crystalline part of the polyolefin and to be crosslinked in the amorphous part, so the separator according to the sixth embodiment is stored in the electricity storage device,
  • the surrounding environment or chemical substances inside the electricity storage device can be used to form a crosslinked structure, thereby suppressing increase in internal stress or deformation of the produced electricity storage device.
  • a crosslinking reaction is performed before being stored in the electricity storage device and a step such as winding and slit is performed, the influence of stress such as tension generated during the step remains. At this time, if the stress is released after assembling the electricity storage device, it may cause damage to the electrode winding or the like due to deformation or stress concentration, which is not preferable.
  • the condensation reaction between the functional groups of the polyolefin can be, for example, a reaction via a covalent bond between two or more functional groups A contained in the polyolefin.
  • the reaction between the functional group of the polyolefin and another type of functional group can be, for example, a reaction via a covalent bond between the functional group A and the functional group B contained in the polyolefin.
  • the functional group A contained in the polyolefin is an electrolyte, an electrolytic solution, an electrode active material, an additive or the like contained in the electricity storage device.
  • a cross-linking structure is formed not only inside the separator but also between the separator and the electrode or between the separator and the solid electrolyte interface (SEI), and the strength between the plurality of members of the electricity storage device is increased. Can be improved.
  • the separator according to the seventh embodiment includes a polyolefin and has an amorphous part crosslinked structure in which the amorphous part of the polyolefin is crosslinked.
  • the functional group contained in the polyolefin constituting the separator is considered not to be taken into the crystalline part of the polyolefin and to be crosslinked in the amorphous part, so the separator according to the seventh embodiment, the crystalline part and its periphery are crosslinked.
  • the amorphous part of the polyolefin contained in the separator according to the seventh embodiment is preferably selectively crosslinked, and more preferably significantly crosslinked than the crystalline part.
  • cross-linking reaction mechanism and cross-linking structure of the seventh embodiment are not clear, but the present inventors consider as follows.
  • a polyolefin resin represented by high density polyethylene is generally a crystalline polymer, and has a lamella (crystal part) having a crystal structure and an amorphous structure. It has a higher-order structure divided into a quality part and an intermediate layer part between them. In the crystal part and in the intermediate layer part between the crystal part and the amorphous part, the mobility of the polymer chains is low and it cannot be separated, but a relaxation phenomenon can be observed in the 0 to 120 ° C. region by solid viscoelasticity measurement.
  • the amorphous part has very high polymer chain mobility, and is observed in the range of ⁇ 150 to ⁇ 100 ° C. in solid viscoelasticity measurement. This is deeply related to radical relaxation, radical transfer reaction, crosslinking reaction, and the like, which will be described later.
  • the polyolefin molecules that compose the crystal are not single, and as shown in FIG. 7, after a plurality of polymer chains form a small lamella, the lamella aggregates to become a crystal. It is difficult to directly observe such a phenomenon. In recent years, simulations have made it clear that academic research has advanced.
  • the crystal is a unit of the smallest crystal measured by X-ray structural analysis, and is a unit that can be calculated as a crystallite size. As described above, even in the crystal part (inside the lamella), it is predicted that there is a part having slightly high mobility without being partly constrained in the crystal.
  • the reaction mechanism of electron beam crosslinking (hereinafter abbreviated to EB crosslinking) to the polymer is as follows. (I) irradiation with electron beam of several tens kGy to several hundreds kGy, (ii) transmission of electron beam to reaction object (polymer) and generation of secondary electron, (iii) secondary electron in polymer chain Hydrogen abstraction reaction and radical generation, (iv) Radical abstraction of adjacent hydrogen and movement of active site, (v) Cross-linking reaction by recombination of radicals or polyene formation.
  • EB crosslinking electron beam crosslinking
  • the radicals generated in the crystal part have poor motion, and therefore exist for a long period of time, and impurities and the like cannot enter the crystal, so that the probability of reaction / quenching is low.
  • a radical species is called Stable Radical, and remains for a long period of several months, and its lifetime was clarified by ESR measurement.
  • the crosslinking reaction within the crystal is considered to be poor.
  • the generated radical has a slightly long life.
  • a radical species is called Persistent Radical, and it is considered that a cross-linking reaction between molecular chains proceeds with a high probability in a mobile environment.
  • the generated radical species has a short life, and it is considered that not only the cross-linking reaction between molecular chains but also the polyene reaction within one molecular chain proceeds with high probability. .
  • the crosslinking reaction by EB crosslinking is localized inside or around the crystal.
  • the functional group in the polyolefin resin and the chemical substance contained in the electricity storage device, or the chemical substance contained in the electricity storage device is used as a catalyst.
  • the polyolefin resin has a crystalline part and an amorphous part.
  • the above-mentioned functional group does not exist inside the crystal due to steric hindrance and is localized in the amorphous part.
  • Non-Patent Document 2 a unit such as a methyl group, which is slightly contained in a polyethylene chain, may be incorporated into a crystal, but a graft which is more bulky than an ethyl group is not incorporated. Therefore, the cross-linking point due to a reaction different from the electron beam cross-linking is localized only in the amorphous part.
  • the EB cross-linked film shows that the fragmentation of the crystal part is suppressed as the strain amount increases. Do you get it. This is because the inside or periphery of the crystal part was selectively crosslinked. Along with that, the Young's modulus and the breaking strength were remarkably improved, and high mechanical strength could be expressed.
  • the chemically crosslinked film there is no difference in the crystal fragmentation before and after the crosslinking reaction, which suggests that the amorphous part was selectively crosslinked. In addition, there was no change in mechanical strength before and after the crosslinking reaction.
  • the separator according to the seventh embodiment has the following formula with respect to the viscoelasticity measurement (version 2) described in the examples, from the viewpoints of formation of an amorphous part crosslinked structure, compatibility of shutdown function and high temperature film rupture resistance, and the like.
  • R E'X E ' Z / E' z0
  • E ′ Z is a storage elastic modulus measured in a temperature range of 160 ° C. to 300 ° C. after the crosslinking reaction of the electricity storage device separator proceeds in the electricity storage device
  • E ′ z0 is It is a storage elastic modulus measured in a temperature range of 160 ° C. to 300 ° C. before the electricity storage device separator is incorporated into the electricity storage device.
  • R E'x Mixed storage elastic modulus ratio (R E'x ) and / or the following formula (3):
  • R E " X E" Z / E " Z0 (3)
  • E ′′ Z is a loss elastic modulus measured in a temperature range of 160 ° C. to 300 ° C. after the crosslinking reaction of the electricity storage device separator proceeds in the electricity storage device
  • E ′′ Z0 Is a loss elastic modulus measured in a temperature range of 160 ° C. to 300 ° C. before the electricity storage device separator is incorporated into the electricity storage device.
  • the mixing loss elastic modulus ratio (R E ′′ x ) defined by is preferably 1.5 to 20 times, more preferably 3 to 18 times.
  • E ′ Z and E ′ z0 and E ′′ Z and E ′′ z0 are storage measured within the set temperature range of the measuring device when 160 ° C. to 300 ° C. is set as the widest temperature region. It is an average value of elastic modulus or loss elastic modulus.
  • the separator is in the form of a laminated film, only the polyolefin porous film is removed from the laminated film to measure the storage elastic moduli E ′ Z and E ′ z0 and the loss elastic moduli E ′′ Z and E ′′ z0 . It shall be.
  • R E'mix Mixed storage elastic modulus ratio (R E'mix ), and / or the following formula (4):
  • R E ′′ mix E ′′ / E ′′ 0 (4)
  • E ′′ is a loss elastic modulus measured at 160 ° C. to 300 ° C. when the electricity storage device separator has an amorphous part crosslinked structure
  • E ′′ 0 is an amorphous part crosslinked structure. It is a loss elastic modulus measured at 160 ° C. to 300 ° C. of the electricity storage device separator having no structure.
  • the mixing loss elastic modulus ratio (R E ′′ mix ) defined by is preferably 1.5 times to 20 times, more preferably 3 times to 19 times, and further preferably 5 times to 18 times.
  • E ′ and E ′ 0 and E ′′ and E ′′ 0 are the storage elastic moduli measured within the set temperature range of the measuring device, respectively, when 160 ° C. to 300 ° C. is the widest temperature range. It is the average value of the loss elastic modulus.
  • the storage elastic modulus E ′ and E ′ 0 and the loss elastic moduli E ′′ and E ′′ 0 are measured by removing only the polyolefin porous film from the laminated film.
  • the separator according to the eighth embodiment is composed of a polyolefin microporous membrane, and stored in a solid viscoelasticity measurement at a temperature of ⁇ 50 ° C. to 250 ° C. for the viscoelasticity measurement (version 3) described in the example.
  • the minimum value (E ′ min ) of the elastic modulus (E ′) is 1.0 MPa to 10 MPa
  • the maximum value (E ′ max ) of E ′ is 100 MPa to 10,000 MPa
  • / or the loss elastic modulus (E ′′) Has a minimum value (E ′′ min ) of 0.1 MPa to 10 MPa and a maximum value of E ′′ (E ′′ max ) of 10 MPa to 10,000 MPa.
  • 1.1 MPa ⁇ E ′ min ⁇ 9.0 MPa and / or 150 MPa ⁇ E ′ max ⁇ 9,500 MPa is preferable, and 1.2 MPa ⁇ E ′ min ⁇ 8.0 MPa and / or 233 MPa ⁇ E ′ max. ⁇ 9000 MPa is more preferable.
  • 0.2 MPa ⁇ E ′′ min ⁇ 9.0 MPa and / or 56 MPa ⁇ E ′′ max ⁇ 9000 MPa is preferable, and 0.4 MPa ⁇ E ′′ min ⁇ 8.0 MPa and / or 74 MPa ⁇ E ′′. More preferably max ⁇ 8,000 MPa.
  • the average E '(E' ave ) is preferably 1.0 MPa to 12 MPa at a temperature from the film softening transition temperature to the film rupture temperature of the separator made of a polyolefin microporous film. It is preferably 1.2 MPa to 10 MPa, more preferably 1.8 MPa to 8.2 MPa, and / or the average E ′′ (E ′′ ave ) is preferably 0.5 MPa to 10 MPa, more preferably 0.8 MPa. ⁇ 8.2 MPa or 0.9 MPa ⁇ 3.2 MPa.
  • E ′ and / or E ′′ is within the above numerical range at a temperature from the film softening transition temperature to the film rupture temperature, cycle stability and safety of the electricity storage device including the separator tend to be improved.
  • the membrane softening transition temperature of the polyolefin microporous membrane separator is preferably 140 ° C to 150 ° C, more preferably 141 ° C.
  • the film rupture temperature is preferably 180 ° C or higher, more preferably 190 ° C or higher, 200 ° C or higher, 210 ° C or higher, 220 ° C or higher, 230 ° C or higher, or The temperature is 240 ° C or higher, more preferably 250 ° C or higher.
  • the upper limit of the film rupture temperature is not limited and it is understood in the art that the film rupture phenomenon can occur even at temperatures above 250 ° C.
  • the separators according to the first to eighth embodiments are fine in view of achieving both a shutdown function at a relatively low temperature and a film rupture property at a relatively high temperature, and improving cycle characteristics and safety of an electricity storage device. It may include a porous film; and an inorganic porous layer including inorganic particles and a resin binder, which is disposed on at least one surface of the microporous film.
  • the separator can be in a state in which the microporous membrane is used as a base material and the base material and the inorganic coating layer are combined.
  • the separator according to the ninth embodiment is: A microporous membrane containing a silane-modified polyolefin; An inorganic porous layer including inorganic particles and a resin binder, which is disposed on at least one surface of the microporous membrane; including.
  • the separator according to the ninth embodiment may include a layer other than the microporous membrane and the inorganic porous layer, if desired.
  • a combination of a microporous film containing a silane-modified polyolefin and an inorganic porous layer has both a shutdown function at a temperature lower than 150 ° C. and a film rupture property at a relatively high temperature, and an electric storage device It tends to improve cycle characteristics and battery nail penetration safety. Since the silane-modified polyolefin in the microporous film is silane-crosslinkable, the viscosity of the resin in the microporous film may be increased when silane crosslinking occurs, so that an abnormality in an electricity storage device including the separator according to the ninth embodiment is abnormal.
  • the cross-linked high-viscosity resin does not easily flow into the inorganic layer (that is, it is difficult to integrate), the clearance between the electrodes can be sufficiently secured, and the battery short circuit can be suppressed. Guessed.
  • the silane crosslinking reaction of the silane-modified polyolefin is started when the separator according to the ninth embodiment comes into contact with the electrolytic solution. More preferably, the silane cross-linking reaction upon contact with the electrolyte, whether initiated first, sequentially, or continuously, observed silane cross-linking reaction upon contact of the separator and the electrolyte. To be done.
  • the silane cross-linking reaction of the silane-modified polyolefin that occurs when the separator comes into contact with the electrolytic solution controls the cross-linking timing of the separator, avoids production defects in the separator manufacturing process, and increases safety and high output in the storage device manufacturing process. Can also be achieved. Further, by bringing the separator into contact with the electrolytic solution, a crosslinking reaction other than the silane crosslinking reaction can occur.
  • the storage elastic modulus change ratio (R ⁇ E ′ ) defined by is preferably 1.5 times to 20 times, and / or the following formula (1B):
  • R ⁇ E ′′ E ′′ S / E ′′ j (1B) ⁇
  • E ′′ j is a loss elastic modulus measured at 160 ° C. to 220 ° C. of the electricity storage device separator before the silane-modified polyolefin is crosslinked
  • E ′′ S is a silane-modified polyolefin. It is a loss elastic modulus measured at 160 ° C. to 220 ° C. of the electricity storage device separator after the crosslinking reaction.
  • the loss elastic modulus change ratio (R ⁇ E ′′) defined by is preferably 1.5 to 20 times.
  • the storage elastic modulus change ratio (R ⁇ E ′ ) and / or the loss elastic modulus change ratio (R ⁇ E ′′ ) is more preferably 2 to 18 times.
  • E ′ j and E ′ S and E ′′ j and E ′′ S are storage elastic moduli measured within the set temperature range of the measuring device when 160 to 220 ° C. is the widest temperature range.
  • the separator is in the form of a laminated film or a composite film of a microporous film and an inorganic porous layer, only the silane-modified polyolefin-containing microporous film is removed from the laminated film or the composite film, and the silane-modified polyolefin-containing film is contained. and measures the microporous film storage modulus E of 'j and E' S and loss modulus E '' j and E '' S.
  • the separator according to the ninth embodiment has the following formula (2A) when measured by removing the inorganic porous layer from the separator:
  • R E'mix E '/ E' 0 (2A) ⁇
  • E ′ is the storage elastic modulus of the electricity storage device separator measured at 160 ° C. to 220 ° C.
  • E ′ 0 is 160 ° C. to 220 ° C. of the electricity storage device separator containing no silane-modified polyolefin. Is the storage elastic modulus measured in.
  • E ′′ is the loss modulus measured at 160 ° C. to 220 ° C. of the electricity storage device separator
  • E ′′ 0 is from 160 ° C. of the electricity storage device separator containing no silane-modified polyolefin. It is the loss modulus measured at 220 ° C.
  • the mixing loss elastic modulus ratio (R E ′′ mix ) defined by is 1.5 times to 20 times.
  • the mixed storage elastic modulus ratio (R E'mix ) and / or the mixed loss elastic modulus ratio (R E ′′ mix ) being within a range of 1.5 to 20 times, the shutdown function and the high temperature membrane rupture resistance It is easy to achieve both.
  • the mixed storage elastic modulus ratio (R E′mix ) and / or the mixed loss elastic modulus ratio (R E ′′ mix ) is more preferably 2 to 18 times.
  • E ′ and E ′ 0 and E ′′ and E ′′ 0 are the storage elastic modulus or loss measured within the set temperature range of the measuring device when 160 to 220 ° C. is the widest temperature range. This is the average value of the elastic modulus.
  • the separator when the separator is in the form of a laminated film or a composite film of a microporous film and an inorganic porous layer, only the silane-modified polyolefin-containing microporous film is removed from the laminated film or the composite film, and the silane-modified polyolefin-containing film is contained. and measures the storage modulus E 'and E' 0 and the loss modulus E '' and E '' 0 of the microporous membrane.
  • the electricity storage device separator containing no silane-modified polyolefin will be described in detail in the section of Examples.
  • the separator according to the ninth embodiment has a transition temperature between the rubber-like flat region and the crystal melting flow region of 135 ° C. or higher when the storage elastic modulus changes with temperature from the viewpoint of achieving both the shutdown function and the high temperature film rupture resistance. It is preferably 150 ° C.
  • the transition temperature between the rubbery flat region and the crystal melt flow region is preferably 137 ° C to 147 ° C, more preferably 140 ° C to 145 ° C, and further preferably 140 ° C to 143 ° C.
  • the separator When the separator is in the form of a laminated film or a composite film of a microporous film and an inorganic porous layer, only the silane-modified polyolefin-containing microporous film is removed from the laminate or the composite film, and the silane-modified polyolefin-containing film is contained.
  • the transition temperature of the microporous membrane shall be measured.
  • the electricity storage device separator according to the tenth embodiment includes a silane-modified polyolefin, and a first porous layer (A layer) capable of forming a crosslinked structure, and inorganic particles. And a second porous layer (B layer) containing the same.
  • the A layer and the B layer are each a single layer or a plurality of layers.
  • the B layer is formed on only one side or both sides of the A layer.
  • LIB which is a typical example of an electricity storage device, lithium (Li) ions make a round trip between positive and negative electrodes. Therefore, by disposing the separator including the A layer and the B layer between the positive and negative electrodes, it is possible to move Li ions between the positive and negative electrodes at a relatively high speed, while avoiding contact between the positive and negative electrodes.
  • the layer A functions as a microporous film having crosslinkability
  • the layer B functions as an inorganic porous layer formed on the microporous film.
  • the ratio (TA / TB) of the thickness (TA) of the A layer to the thickness (TB) of the B layer is preferably 0.22 or more and 14 or less.
  • the ratio (TA / TB) is 0.22 or more, the existence ratio of the A layer in the separator can be sufficiently secured and the function of the A layer can be exhibited.
  • the ratio (TA / TB) is 14 or less, the existence ratio of the B layer in the separator can be sufficiently secured and the function of the B layer can be exhibited.
  • the A layer and the B layer each have a specific structure and further setting the ratio (TA / TB) in the above range.
  • a separator can be suitably used, for example, as a constituent material of LIB for mobile device mounting or vehicle mounting.
  • the ratio (TA / TB) is preferably 0.8 or more, more preferably 1.0 or more.
  • the ratio (TA / TB) is preferably 5.5 or less, more preferably 3.2 or less.
  • the ratio (TA / TB) may be set to, for example, less than 2.5, 2.0 or less, or 1.0 or less.
  • the thickness (TA) of the A layer is less than 2.5 times the thickness (TB) of the B layer, and is smaller than the thickness (TB) of the B layer, so that the thickness of the A layer is reduced, and It becomes easier to reduce the thickness of the separator.
  • the total thickness (TA + TB) of the A layer and the B layer is preferably 3.0 ⁇ m or more and 22 ⁇ m or less.
  • the total thickness (TA + TB) is 3.0 ⁇ m or more, the film strength of the separator tends to be improved.
  • the total thickness (TA + TB) is 22 ⁇ m or less, the ion permeability of the separator tends to be improved.
  • the total thickness (TA + TB) is more preferably 3.5 ⁇ m or more, and further preferably 4.0 ⁇ m or more.
  • the total thickness (TA + TB) is more preferably 20 ⁇ m or less, still more preferably 18 ⁇ m or less.
  • the total thickness (TA + TB) may be set to less than 11 ⁇ m, 10 ⁇ m or less, or 8 ⁇ m or less, for example. Even in the case of such a thinned separator, the cycle characteristics and safety of the electricity storage device can be improved within the scope of the present invention.
  • Each of the ratio (TA / TB) and the total thickness (TA + TB) can be measured by the method described in the Example section, and can be controlled by adjusting the thickness (TA) and / or the thickness (TB).
  • the layers A and B will be described later.
  • the shutdown temperature (sometimes referred to as fuse temperature) measured from the electric resistance under pressure of 0.1 Mpa or more and 10.0 Mpa or less (preferably under 10 Mpa pressure) is 130 ° C to 160 ° C. Further, it is preferable that the meltdown temperature (sometimes referred to as the film rupture temperature) is 200 ° C. or higher.
  • the shutdown temperature is 130 ° C. or higher, it is possible to prevent the shutdown function from being unnecessarily exhibited during the normal reaction of the electricity storage device, and it is possible to secure sufficient output characteristics of the electricity storage device.
  • the shutdown temperature is 160 ° C. or lower, the shutdown function can be suitably exerted during abnormal reaction of the electricity storage device.
  • the shutdown temperature is 200 ° C. or higher, the abnormal reaction can be stopped before reaching the ultra-high temperature region during the abnormal reaction of the electricity storage device, and the melt-disrupted film of the separator during the abnormal reaction of the electricity storage device. Can be prevented.
  • the shutdown temperature and the meltdown temperature satisfy the above conditions, it is possible to realize a separator that can provide an electricity storage device having excellent heat resistance, pore blocking characteristics (shutdown function), and melt rupture property (meltdown function). In addition, mechanical characteristics, ion permeability and the like can be secured in the separator itself. Therefore, by including a separator whose shutdown temperature and meltdown temperature satisfy the above conditions, the electricity storage device can improve cycle characteristics and safety.
  • the shutdown temperature is preferably higher than 130 ° C, more preferably 135 ° C or higher, still more preferably 136 ° C or higher.
  • the shutdown temperature is preferably 150 ° C. or lower, more preferably 148 ° C.
  • the meltdown temperature is preferably 175 ° C. or higher, more preferably 178 ° C. or higher, still more preferably 180 ° C. or higher.
  • the meltdown temperature is preferably 230 ° C. or lower, more preferably 225 ° C. or lower, still more preferably 220 ° C. or lower.
  • shutdown temperature and the “meltdown temperature” mean the values obtained when measured based on the electric resistance under the above pressure. That is, while the above pressure is applied to the laminated body including the positive electrode, the separator, and the negative electrode, the temperature of the laminated body is increased, and the shutdown is performed based on the AC resistance (AC resistance between the electrodes) that rises accordingly.
  • the temperature and meltdown temperature are derived.
  • the temperature when the AC resistance exceeds a predetermined reference value (for example, 1000 ⁇ ) for the first time is set as the shutdown temperature, and then the heating is further continued and the AC resistance that exceeds the reference value is the above-mentioned.
  • the temperature at which the temperature falls below the reference value (for example, 1000 ⁇ ) is set as the meltdown temperature.
  • a hydraulic jack can be used to press the laminated body, but the present invention is not limited to this, and a known pressurizing means other than the hydraulic jack may be used.
  • An aluminum heater can be used to heat the laminate, but the present invention is not limited to this, and known heating means other than the aluminum heater may be used.
  • the shutdown temperature and the meltdown temperature can be measured by the method described in the Example section, and can be controlled by adjusting the constitution or the manufacturing method in the A layer.
  • the heat shrinkage rate (T2) at 150 ° C. after the formation of the crosslinked structure is 0.02 times or more and 0.91 times or less the heat shrinkage rate (T1) at 150 ° C. before the formation of the crosslinked structure.
  • the ratio (T2 / T1) of the heat shrinkage rate (T2) at 150 ° C. after the formation of the crosslinked structure to the heat shrinkage rate (T1) at 150 ° C. before the formation of the crosslinked structure is 0.02 or more. It is 0.91 or less.
  • the larger value of the heat shrinkage of the A layer in the machine direction (MD) and the heat shrinkage of the A layer in the width direction (TD) is used. Since the layer A can form a crosslinked structure of the silane-modified polyolefin, it becomes possible to pay attention to the change in the heat shrinkage rate before and after the crosslinking.
  • the ratio (T2 / T1) is 0.02 or more, it is possible to effectively suppress the occurrence of a short circuit, and thereby reliably prevent the temperature increase of the entire power storage device, smoke that may occur with it, and further ignition.
  • the ratio (T2 / T1) is 0.91 or less, it can be judged that the crosslinking reaction in the A layer could be sufficiently advanced. That is, when the ratio (T2 / T1) is within the above range, it is possible to provide a separator for an electricity storage device, which can improve cycle characteristics and safety in the electricity storage device. Therefore, from the viewpoint of the above effects, the ratio (T2 / T1) is preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.07 or more. On the other hand, the ratio (T2 / T1) is preferably 0.7 or less, more preferably 0.5 or less, still more preferably 0.4 or less.
  • the heat shrinkage rate (T1) at 150 ° C. before forming the crosslinked structure is preferably 70% or less, more preferably 60% or less.
  • the heat shrinkage ratio (T2) at 150 ° C. after forming the crosslinked structure is preferably 60% or less, more preferably 50% or less.
  • the heat shrinkage ratio (T2) is generally smaller than the heat shrinkage ratio (T1). is there.
  • the heat shrinkage rate at 150 ° C. can be measured by the method described in the Example section, and can be controlled by adjusting the constitution or manufacturing method in the A layer.
  • the separators according to the embodiments described above can be interchangeable or can be combined with each other.
  • the separator according to the ninth or tenth embodiment described above may optionally include a layer other than the microporous membrane and the inorganic porous layer.
  • the components of the separator according to the first to tenth embodiments will be described below.
  • the microporous membrane can be formed of polyolefin or modified polyolefin.
  • the microporous membrane contains a silane-modified polyolefin, and may optionally contain other polyolefins.
  • the silane-crosslinking property of the silane-modified polyolefin enables the microporous membrane to perform a crosslinking reaction in the separator manufacturing process.
  • the polyolefin contained in the microporous membrane is not particularly limited, but for example, a homopolymer of ethylene or propylene, or ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, And a copolymer formed from at least two monomers selected from the group consisting of norbornene.
  • high-density polyethylene (homopolymer) or low-density polyethylene is preferable from the viewpoint that heat fixation (sometimes abbreviated as “HS”) can be performed at a higher temperature without blocking pores, and high density Polyethylene (homopolymer) is more preferred.
  • the polyolefins may be used alone or in combination of two or more.
  • the microporous membrane is preferably manufactured by using both silane-modified polyolefin and ultra-high molecular weight polyethylene (UHMWPE) as raw materials from the viewpoints of oxidation-reduction resistance deterioration and a dense and uniform porous body structure.
  • UHMWPE ultra-high molecular weight polyethylene
  • the ultrahigh molecular weight polyethylene (UHMWPE) has a weight average molecular weight of 1,000,000 or more. More preferably, in the production of the microporous membrane or the separator, the weight ratio of silane-modified polyolefin and UHMWPE (silane-modified polyolefin weight / UHMWPE weight) is 0.05 / 0.95 to 0.40 / 0.60.
  • the content of the polyolefin contained in the microporous membrane is preferably 50% by weight or more and 100% by weight or less, preferably 70% by weight or more and 100% by weight or less, and preferably 80% by weight or more and 100% by weight or less.
  • the microporous membrane contains a polyolefin having a weight average molecular weight of 100,000 or more and less than 1,000,000 (preferably 40% by weight or more, more preferably 80% by weight or more based on the total weight of the polyolefin). ) Is preferred.
  • the weight average molecular weight of the polyolefin is more preferably 120,000 or more and less than 950,000, further preferably 130,000 or more and less than 930,000.
  • a polyolefin having a weight average molecular weight of 100,000 or more and less than 1,000,000 relaxation of polymer shrinkage occurs early in a heat test of an electricity storage device, and it is easy to maintain safety particularly in a heat safety test. There is a tendency.
  • the weight average molecular weight of the microporous film By adjusting the weight average molecular weight of the microporous film to be less than 1,000,000, it is possible to suppress molding defects (film pattern) called extrusion called melt fracture at the time of extrusion.
  • the weight average molecular weight of the microporous film to 100,000 or more, it is possible to suppress the transfer of the depression when the microporous film is wound around the core (winding core).
  • the viscosity average molecular weight of the microporous membrane at the time of removing the inorganic porous layer and at the time of non-crosslinking treatment is preferably 100,000 or more from the viewpoint that polymer powder due to friction shear does not occur during roll transportation of the separator. It is 1,200,000 or less, more preferably 150,000 or more and 800,000 or less.
  • the film thickness of the microporous film is preferably 1.0 ⁇ m or more, more preferably 2.0 ⁇ m or more, further preferably 3.0 ⁇ m or more, 4.0 ⁇ m or more, or 4.5 ⁇ m or more.
  • the film thickness of the microporous film is preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, and further preferably 80 ⁇ m or less, 22 ⁇ m or less or 19 ⁇ m or less.
  • the film thickness of the microporous film is 500 ⁇ m or less, the ion permeability tends to be further improved.
  • the film thickness of the microporous film can be measured by the method described in the examples.
  • the film thickness of the microporous film is preferably 25 ⁇ m or less, more preferably 22 ⁇ m or less or 20 ⁇ m or less. , More preferably 18 ⁇ m or less, particularly preferably 16 ⁇ m or less. In this case, when the thickness of the microporous film is 25 ⁇ m or less, the permeability tends to be further improved.
  • the lower limit of the film thickness of the microporous film may be 1.0 ⁇ m or more, 3.0 ⁇ m or more, 4.0 ⁇ m or more, 6.0 ⁇ m or more, or 7.5 ⁇ m or more.
  • the microporous membrane as the separator has a melting rupture temperature of preferably 180 ° C. to 220 ° C. during thermomechanical analysis (TMA) measurement. C., and more preferably 180 to 200.degree.
  • TMA thermomechanical analysis
  • the poofin-made electricity storage device separator fuses at a low temperature (for example, 150 ° C. or lower), and Li ions move early, and the electricity storage device Alternatively, the discharge outside the power storage device is stopped.
  • the entire power storage device is cooled by cooling the power storage device with outside air or a refrigerant, and it is expected that the ignition of the electrolytic solution or the decomposition and exothermic reaction of the electrolyte can be prevented and the safety can be ensured.
  • the runaway reaction that has occurred in the electricity storage device continues to generate heat without being stopped by the fuse of the separator, and the separator melts and ruptures, making it impossible to ensure the safety of the device. Therefore, it is important that the separator does not melt and rupture until the entire electricity storage device is sufficiently cooled. Further, when the temperature is raised to an extremely high temperature region of 220 ° C.
  • the decomposition reaction of the electrolytic solution or the electrolyte rapidly progresses, a corrosion reaction occurs on the electrode due to the decomposition product, further heat generation, and an explosion occurs.
  • the separator is melted and ruptured, and the electrodes are coated with the active material to prevent corrosion reaction.
  • the layer A contains a silane-modified polyolefin and can form a crosslinked structure. From the viewpoint of ensuring deterioration resistance to redox and ensuring a dense and uniform porous body structure, the layer A preferably further contains polyethylene as a polyolefin different from the silane-modified polyolefin.
  • the A layer may contain components other than the silane-modified polyolefin and polyethylene.
  • the polyolefin constituting the silane-modified polyolefin in the layer A is a homopolymer of ethylene or propylene; selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and norbornene. Examples thereof include a copolymer formed from at least two kinds of selected monomers.
  • the polyolefin is preferably a homopolymer of ethylene (polyethylene), more preferably high-density polyethylene and / or low-density polyethylene, from the viewpoint of enabling heat setting at a higher temperature while avoiding clogging of pores. Density polyethylene is more preferred.
  • the polyolefin may be used alone or in combination of two or more.
  • the layer A may contain a polymer (other polymer) that does not correspond to any of the silane-modified polyolefin and polyethylene, within a range where the effect of the present invention is not excessively impaired.
  • the weight average molecular weight of the entire A layer is preferably 100,000 or more and 1,200,000 or less, more preferably 150,000 or more and 800,000 or less.
  • the thickness (TA) of the layer A is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, still more preferably 3 ⁇ m or more. When the thickness (TA) is 1 ⁇ m or more, the film strength tends to be further improved. On the other hand, the thickness (TA) is preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 80 ⁇ m or less. When the thickness (TA) is 500 ⁇ m or less, ion permeability tends to be further improved.
  • the thickness (TA) may be set to, for example, 1.00 ⁇ m or more, 2.00 ⁇ m or more, or 3.00 ⁇ m or more.
  • the thickness (TA) is preferably less than 22 ⁇ m, more preferably 21 ⁇ m or less, still more preferably 20.5 ⁇ m or less.
  • the upper limit of the thickness (TA) may be set to less than 13 ⁇ m or 8.5 ⁇ m or less.
  • the thickness (TA) is 25 ⁇ m or less, the transparency tends to be further improved.
  • the thickness (TA) may be set to, for example, less than 22.00 ⁇ m, 21.00 ⁇ m or less, 20.00 ⁇ m or less, 13.00 ⁇ m or less, or 8.50 or less.
  • the lower limit of the thickness (TA) may be the same as above.
  • the thickness (TA) can be measured by the method described in the Example section, and can be controlled by changing the stretching ratio of the A layer.
  • the thickness of the A layer is treated as the thickness (TA).
  • the total thickness of the A layers of the plurality of layers is treated as the thickness (TA).
  • the film rupture temperature of the layer A measured by thermomechanical analysis (TMA) is preferably 180 ° C or higher and 220 ° C or lower. Even if the power storage device abnormally generates heat due to an unexpected runaway reaction, it is expected that the shutdown function of the separator will stop the movement of Li ions and the accompanying discharge inside or outside the power storage device. After that, it is expected that the refrigerant will cool the entire power storage device and ensure safety. On the other hand, when the membrane rupture temperature is within the above range, even if the entire electricity storage device is not sufficiently cooled, or even if it reaches the ultra-high temperature region, the separator melts and ruptures and penetrates into both electrodes. As a result, the active material can be coated, which makes it easier to suppress further heat generation.
  • the film rupture temperature can be measured by the method described in the Example section, and can be controlled by changing the stretching temperature and / or the stretching ratio in the manufacturing process.
  • the porosity of the microporous membrane or the layer A is preferably 20% or more, more preferably 25% or more, still more preferably 28% or more, 30% or more, 32% or more or 35% or more.
  • the porosity is 20% or more, the followability to the rapid movement of Li ions tends to be further improved.
  • the porosity is preferably 90% or less, more preferably 80% or less, still more preferably 60% or less.
  • the porosity can be measured by the method described in the Example section, and can be controlled by changing the stretching temperature and / or the stretching ratio in the manufacturing process.
  • the air permeability of the microporous film or layer A preferably from 1 sec / 100 cm 3 or more, more preferably 50 sec / 100 cm 3 or more, more preferably 55 sec / 100 cm 3 or more, still more preferably 70 seconds or more, It is 90 seconds or longer, or 110 seconds or longer.
  • the air permeability is 1 second / 100 cm 3 or more, the balance among the film thickness, the porosity and the average pore diameter tends to be further improved.
  • the air permeability is preferably 400 seconds / 100 cm 3 or less, more preferably 300 seconds or less / 100 cm 3 , and further preferably 270 seconds / 100 cm 3 or less.
  • the air permeability is 400 seconds / 100 cm 3 or less, the ion permeability tends to be further improved.
  • the air permeability can be measured by the method described in the Example section, and can be controlled by changing the stretching temperature and / or the stretching ratio in the manufacturing process.
  • the puncture strength of the microporous membrane or layer A is preferably 200 gf / 20 ⁇ m or more, more preferably 300 gf / 20 ⁇ m or more.
  • the puncture strength is 200 gf / 20 ⁇ m or more, even when the active material or the like is dropped off when the laminated body of the separator and the electrode is wound, it is easy to suppress film breakage due to the dropped active material or the like. In addition, it is easy to reduce the possibility of short circuit due to expansion and contraction of the electrodes due to charge and discharge.
  • the puncture strength is preferably 4000 gf / 20 ⁇ m or less, more preferably 3800 gf / 20 ⁇ m or less.
  • the puncture strength is 3500 gf / 20 ⁇ m or less, it is easy to reduce heat shrinkage during heating.
  • the puncture strength can be measured by the method described in the Example section, and can be controlled by changing the stretching temperature and / or the stretching ratio in the manufacturing process.
  • the tensile strength of the microporous membrane or A layer is respectively in both MD (longitudinal direction of the membrane or A layer, machine direction or flow direction) and TD (direction orthogonal to MD, width direction of the membrane or A layer), respectively. It is preferably 1000 kgf / cm 2 or more, more preferably 1050 kgf / cm 2 or more, and further preferably 1100 kgf / cm 2 or more. When the tensile strength is 1000 kgf / cm 2 or more, breakage during slitting or winding of the power storage device is more suppressed, or short circuit due to foreign matter in the power storage device tends to be further suppressed.
  • the tensile strength is preferably 5000 kgf / cm 2 or less, more preferably 4500 kgf / cm 2 or less, and further preferably 4000 kgf / cm 2 or less.
  • the tensile strength is 5000 kgf / cm 2 or less, the microporous membrane or the A layer is relaxed early in the heating test, the contraction force is weakened, and as a result, the safety tends to be improved.
  • the tensile modulus of elasticity of the microporous membrane or A layer is preferably 120 N / cm or less, more preferably 100 N / cm or less, and further preferably 90 N / cm or less in both MD and TD directions.
  • a tensile modulus of 120 N / cm or less indicates that the lithium ion secondary battery separator is not extremely oriented, and in a heating test or the like, for example, when a blocking agent such as polyethylene melts and shrinks, Polyethylene or the like causes stress relaxation at an early stage, which suppresses contraction of the separator in the battery and tends to prevent short circuit between electrodes (that is, the safety of the separator during heating may be improved).
  • Such a low tensile elastic modulus is easily achieved by including polyethylene having a weight average molecular weight of 500,000 or less in the polyolefin forming the microporous membrane or the A layer.
  • the lower limit of the tensile elastic modulus is not particularly limited, but is preferably 10 N / cm or more, more preferably 30 N / cm or more, and further preferably 50 N / cm or more.
  • the tensile modulus can be appropriately adjusted by adjusting the degree of stretching in the manufacturing process, and if necessary, relaxing after stretching.
  • the polyolefin is not particularly limited, but is, for example, a homopolymer of ethylene or propylene, or a group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and norbornene. Examples thereof include a copolymer formed from at least two selected monomers. Among these, high-density polyethylene or low-density polyethylene is preferable, and high-density polyethylene is more preferable, from the viewpoint that heat fixation (which may be abbreviated as “HS”) can be performed at a higher temperature without blocking the pores.
  • the polyolefins may be used alone or in combination of two or more.
  • the separator preferably contains a polyolefin having a weight average molecular weight (Mw) of less than 2,000,000, and more preferably 40% by mass of the polyolefin having Mw of less than 2,000,000 with respect to the entire polyolefin.
  • Mw weight average molecular weight
  • the above content is more preferably 80% by mass or more.
  • the elastic modulus in the thickness direction of the obtained microporous membrane tends to be smaller when the polyolefin having Mw of less than 2,000,000 is used as compared with the case of using the polyolefin having 1,000,000 or more.
  • a microporous film is obtained in which the irregularities of the core are relatively easily transferred.
  • the weight average molecular weight of the entire polyolefin microporous membrane that constitutes the separator is preferably 100,000 or more and 2,000,000 or less, and more preferably 150,000 or more and 1,500,000 or less.
  • the separator is a functional group-modified polyolefin, or a unit amount having a functional group, as a polyolefin having one or more functional groups, from the viewpoint of formation of a crosslinked structure, redox resistance, and a dense and uniform porous body structure. It is preferred that the body comprises a copolymerized polyolefin.
  • a functional group-modified polyolefin refers to a product to which a functional group is bound after the production of the polyolefin.
  • the functional group is one that can be bonded to the polyolefin skeleton or introduced into a comonomer, and is preferably one that participates in the selective crosslinking of the amorphous portion of the polyolefin, for example, a carboxyl group, a hydroxy group, a carbonyl group.
  • Polymerizable unsaturated hydrocarbon group isocyanate group, epoxy group, silanol group, hydrazide group, carbodiimide group, oxazoline group, acetoacetyl group, aziridine group, ester group, active ester group, carbonate group, azido group, chain or It can be at least one selected from the group consisting of cyclic heteroatom-containing hydrocarbon groups, amino groups, sulfhydryl groups, metal chelate groups, and halogen-containing groups.
  • the separator contains both a polyolefin having one or more functional groups and a silane-unmodified polyethylene. Is preferred.
  • the mass ratio of the polyolefin having one or more functional groups and the silane unmodified polyethylene (1 The mass of the polyolefin having one kind or two or more kinds of functional groups / the mass of the silane-unmodified polyethylene) is 0.05 / 0.95 to 0.80 / 0.20.
  • the crosslinked structure of the separator contributes to both the shutdown function of the separator and the high temperature puncture resistance and the safety of the electricity storage resistant device, and is preferably formed in the amorphous portion of the polyolefin contained in the separator.
  • the crosslinked structure can be formed, for example, by a reaction via either a covalent bond, a hydrogen bond or a coordinate bond.
  • the reaction via the covalent bond includes the following reactions (I) to (IV): (I) Condensation reaction of a plurality of identical functional groups (II) Reaction between a plurality of different functional groups (III) Chain condensation reaction of functional group and electrolyte (IV) Chain condensation reaction of functional group and additive At least one selected is preferable.
  • the reaction via the coordinate bond is the following reaction (V): (V) A plurality of the same functional groups are preferably a reaction of crosslinking with the eluting metal ion via a coordinate bond.
  • reaction (I) A schematic scheme and specific examples of the reaction (I) are shown below, where A is the first functional group of the separator.
  • R is an alkyl group having 1 to 20 carbon atoms or a heteroalkyl group which may have a substituent.
  • the polyolefin contained in the separator is preferably silane graft modified.
  • the silane-grafted modified polyolefin has a main chain of polyolefin and has a structure having alkoxysilyl as a graft on the main chain.
  • examples of the alkoxide substituted with the alkoxysilyl include methoxide, ethoxide, and butoxide.
  • R may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, or the like.
  • the main chain and the graft are linked by a covalent bond, and examples thereof include structures such as alkyl, ether, glycol or ester.
  • the ratio of silicon to carbon Si / C is 0.2 to 1.8% before the crosslinking treatment step. It is preferably 0.5 to 1.7%, and more preferably 0.5 to 1.7%.
  • the preferred silane-grafted modified polyolefin has a density of 0.90 to 0.96 g / cm 3 and a melt flow rate (MFR) at 190 ° C. of 0.2 to 5 g / min.
  • the silane-grafted modified polyolefin is not a masterbatch resin containing a dehydration condensation catalyst from the viewpoint of suppressing the generation of resin aggregates in the manufacturing process of the separator and maintaining the silane crosslinkability until it comes into contact with the electrolytic solution. Is preferred. It is known that the dehydration condensation catalyst also functions as a catalyst for the siloxane bond forming reaction of the alkoxysilyl group-containing resin.
  • a compound obtained by previously adding a dehydration condensation catalyst for example, an organometallic catalyst
  • a dehydration condensation catalyst for example, an organometallic catalyst
  • Reaction (II) A schematic scheme and a specific example of the reaction (II) are shown below, where the first functional group of the separator is A and the second functional group is B.
  • the reaction (I) and the reaction (II) can be catalyzed, and for example, can be catalytically promoted by a chemical substance inside the electricity storage device in which the separator is incorporated.
  • the chemical substance can be, for example, any of an electrolyte, an electrolytic solution, an electrode active material, an additive, or a decomposed product thereof contained in an electricity storage device.
  • Reaction (III) A schematic scheme and a specific example of the reaction (III) are shown below, where the first functional group of the separator is A and the electrolytic solution is Sol.
  • Reaction (IV) A schematic scheme of the reaction (IV) is shown below, where the first functional group of the separator is A, the second functional group optionally incorporated is B, and the additive is Add.
  • the reaction (IV) is a nucleophilic substitution reaction or a nucleophilic addition reaction between the compound Rx forming the separator and the compound Ry forming the additive (Add) from the viewpoint of forming a covalent bond represented by a dotted line in the above scheme. Alternatively, it is preferably a ring-opening reaction.
  • the compound Rx may be a polyolefin contained in the separator, such as polyethylene or polypropylene, preferably the polyolefin is, depending on the functional group x, for example -OH, -NH 2 , -NH-, -COOH and -SH. Is modified by at least one selected from
  • the compound Ry preferably has two or more ligation reaction units y 1 .
  • the plurality of ligation reaction units y 1 may have any structures or groups, and may be substituted or unsubstituted, as long as they can cause a nucleophilic substitution reaction, a nucleophilic addition reaction or a ring opening reaction with the functional group x of the compound Rx. , Heteroatoms or inorganic substances, which may be the same or different from each other.
  • the plurality of ligation reaction units y 1 can independently be a terminal group, incorporated into the main chain, or a side chain or a pendant.
  • the reaction (IV) is a nucleophilic substitution reaction
  • the functional group x of the compound Rx is regarded as a nucleophilic group
  • the ligation reaction unit y 1 of the compound Ry is regarded as a leaving group, which will be described below as an example.
  • both the functional group x and the ligation reaction unit y 1 can be a leaving group depending on the nucleophilicity.
  • the functional group x of the compound Rx is preferably an oxygen nucleophilic group, a nitrogen nucleophilic group, or a sulfur nucleophilic group.
  • the oxygen-based nucleophilic group include a hydroxyl group, an alkoxy group, an ether group, a carboxyl group and the like, among which —OH and —COOH are preferable.
  • the nitrogen-based nucleophilic group include an ammonium group, a primary amino group, a secondary amino group and the like, among which —NH 2 and —NH— are preferable.
  • the sulfur-based nucleophilic group include —SH and thioether group, with —SH being preferred.
  • the coupling reaction unit y 1 of the compound Ry may be an alkylsulfonyl group such as CH 3 SO 2 — and CH 3 CH 2 SO 2 — from the viewpoint of a leaving group.
  • an arylsulfonyl group (-ArSO 2 -); CF 3 SO 2 -, CCl 3 SO 2 - haloalkylsulfonyl group such as; CH 3 SO 3 - -, CH 3 CH 2 SO 3 - - alkylsulfonate group and the like;
  • Aryl sulfonate group (ArSO 3 ⁇ ⁇ ); haloalkyl sulfonate group such as CF 3 SO 3 ⁇ ⁇ , CCl 3 SO 3 ⁇ ⁇ , and heterocyclic group are preferable, and these are used alone or in combination of two or more kinds.
  • hetero atom contained in the heterocycle examples include a nitrogen atom, an oxygen atom and a sulfur atom, and among them, a nitrogen atom is preferable from the viewpoint of elimination.
  • the leaving group containing a nitrogen atom in the heterocycle include the following formulas (y 1 -1) to (y 1 -6): ⁇ In the formula, X is a hydrogen atom or a monovalent substituent. ⁇ ⁇ In the formula, X is a hydrogen atom or a monovalent substituent. ⁇ ⁇ In the formula, X is a hydrogen atom or a monovalent substituent. ⁇ ⁇ In the formula, X is a hydrogen atom or a monovalent substituent. ⁇ ⁇ In the formula, X is a hydrogen atom or a monovalent substituent. ⁇ ⁇ In the formula, X is a hydrogen atom or a monovalent substituent. ⁇ ⁇ In the formula, X is a hydrogen atom or a monovalent substituent. ⁇ A monovalent group represented by
  • X is a hydrogen atom or a monovalent substituent.
  • the monovalent substituent include an alkyl group, a haloalkyl group, an alkoxyl group, and a halogen atom.
  • the compound Ry is represented by the following formula (y 2) as a chain unit y 2 in addition to the linking reaction unit y 1. -1) to (y 2 -6): ⁇ In the formula, m is an integer of 0 to 20 and n is an integer of 1 to 20. ⁇ ⁇ In the formula, n is an integer of 1 to 20. ⁇ ⁇ In the formula, n is an integer of 1 to 20. ⁇ ⁇ In the formula, n is an integer of 1 to 20. ⁇ ⁇ In the formula, n is an integer of 1 to 20. ⁇ ⁇ In the formula, n is an integer of 1 to 20. ⁇ ⁇ In the formula, X is an alkylene group having 1 to 20 carbon atoms or an arylene group, and n is an integer of 1 to 20.
  • X is an alkylene group having 1 to 20 carbon atoms or an arylene group
  • n is an integer of 1 to 20.
  • X is an alkylene group having 1 to 20 carbon atoms or an arylene group
  • n is an integer of 1 to 20.
  • the compound Ry contains a plurality of chain units y 2 , they may be the same or different from each other, and their sequences may be block or random.
  • m is an integer of 0 to 20, and preferably 1 to 18 from the viewpoint of the crosslinked network.
  • n is an integer of 1 to 20 and is preferably 2 to 19 or 3 to 16 from the viewpoint of the crosslinked network.
  • X is an alkylene group having 1 to 20 carbon atoms or an arylene group, and from the viewpoint of stability of the chain structure, preferably a methylene group, Ethylene group, n-propylene group, n-butylene group, n-hexylene group, n-heptylene group, n-octylene group, n-dodecylene group, o-phenylene group, m-phenylene group, or p-phenylene group .
  • reaction (IV) is a nucleophilic substitution reaction
  • preferred combinations of the functional group x of the compound Rx and the ligation reaction unit y 1 and the chain unit y 2 of the compound Ry are shown in Tables 2 to 4 below.
  • the functional group x of the polyolefin is —NH 2
  • the ligation reaction unit y 1 of the additive is a succinimide-derived skeleton
  • a chain unit y 2 The reaction scheme in the case where is — (O—C 2 H 5 ) n — is shown below.
  • the functional group x of the polyolefin is —SH and —NH 2
  • the coupling reaction unit y 1 of the additive is a nitrogen-containing cyclic skeleton, and a chain unit.
  • the reaction scheme in which y 2 is o-phenylene is shown below.
  • the functional group x of the compound Rx and the ligation reaction unit y 1 of the compound Ry can cause an addition reaction.
  • the functional group x of the compound Rx is preferably an oxygen nucleophilic group, a nitrogen nucleophilic group, or a sulfur nucleophilic group.
  • the oxygen-based nucleophilic group include a hydroxyl group, an alkoxy group, an ether group, a carboxyl group and the like, among which —OH and —COOH are preferable.
  • nitrogen-based nucleophilic group examples include an ammonium group, a primary amino group, a secondary amino group and the like, among which —NH 2 and —NH— are preferable.
  • sulfur-based nucleophilic group examples include —SH and thioether group, with —SH being preferred.
  • the ligation reaction unit y 1 of the compound Ry has the following formulas (Ay 1 -1) to (Ay 1 -6): ⁇ In the formula, R is a hydrogen atom or a monovalent organic group. ⁇ It is preferably at least one selected from the group consisting of groups represented by
  • R is a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, C 1 ⁇ 20 alkyl group, an alicyclic group, or aromatic group, more preferably Is a hydrogen atom, a methyl group, an ethyl group, a cyclohexyl group or a phenyl group.
  • reaction (IV) is a nucleophilic addition reaction
  • preferable combinations of the functional group x of the compound Rx and the ligation reaction unit y 1 of the compound Ry are shown in Tables 5 and 6 below.
  • the functional group x of the compound Rx and the ligation reaction unit y 1 of the compound Ry can cause a ring-opening reaction, and the ligation reaction unit can be easily obtained from the viewpoint of availability of raw materials.
  • the cyclic structure on the y 1 side is preferably opened.
  • the ligation reaction unit y 1 is more preferably an epoxy group
  • the compound Ry is further preferably at least two epoxy groups, and even more preferably a diepoxy compound.
  • the functional group x of the compound Rx is at least one selected from the group consisting of —OH, —NH 2 , —NH—, —COOH and —SH.
  • the ligation reaction unit y 1 of the compound Ry has the following formula (ROy 1 -1): ⁇ In the formula, plural Xs are each independently a hydrogen atom or a monovalent substituent.
  • a plurality of X's each independently represent a hydrogen atom or a monovalent substituent, preferably a hydrogen atom, a C 1-20 alkyl group, an alicyclic group, or an aromatic group.
  • a group more preferably a hydrogen atom, a methyl group, an ethyl group, a cyclohexyl group or a phenyl group.
  • Table 7 shows preferred combinations of the functional group x of the compound Rx and the ligation reaction unit y 1 of the compound Ry.
  • Reaction (V) A schematic scheme of the reaction (V) and an example of the functional group A are shown below, where A is the first functional group of the separator and M n + is the metal ion.
  • the metal ions M n + are preferably those eluted from the electricity storage device (hereinafter, also referred to as eluted metal ions), for example, Zn 2+ , Mn 2+ , Co 3+ , Ni 2+ and Li +. It can be at least one selected from the group.
  • the coordination bond in the case where the functional group A is —COO ⁇ is exemplified below.
  • hydrofluoric acid is, for example, one of an electrolyte, an electrolytic solution, an electrode active material, an additive, or a decomposed product or a water-absorbed product thereof, which is included in an electricity storage device, depending on a charge / discharge cycle of the electricity storage device. Can be derived from.
  • the silane-modified polyolefin has a main chain of polyolefin, and has a structure in which an alkoxysilyl group is grafted to the main chain.
  • the silane-modified polyolefin can be obtained by grafting an alkoxysilyl group on the main chain of the silane-unmodified polyolefin. It is presumed that an alkoxysilyl group is converted into a silanol group through a hydrolysis reaction with water and undergoes a cross-linking reaction to form a siloxane bond (see the following formula; the ratio of T1 structure, T2 structure, and T3 structure is arbitrary. Is).
  • alkoxide substituted with the alkoxysilyl group examples include methoxide, ethoxide, butoxide and the like.
  • examples of R include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the like.
  • the main chain and the graft are connected by a covalent bond.
  • Examples of the structure that forms such a covalent bond include alkyl, ether, glycol, and ester.
  • the silanol unit has a modification amount of 2% or less with respect to the main chain ethylene unit before the crosslinking reaction.
  • the preferred silane-grafted modified polyolefin has a density of 0.90 to 0.96 g / cm 3 and a melt flow rate (MFR) at 190 ° C. of 0.2 to 5 g / min.
  • the amount of the silane-modified polyolefin is preferably 0.5% by mass or more or 3% by mass or more, and more preferably 4%, based on the total amount of the microporous membrane or the A layer, from the viewpoint that the effect of the present invention is favorably exhibited. It is at least mass%, more preferably at least 5 mass% or at least 6 mass%. From the viewpoint of cycleability and safety of the electricity storage device, the amount of the silane-modified polyolefin is preferably 40% by mass or less, more preferably 38% by mass or less, based on the total amount of the microporous membrane. The amount of the silane-modified polyolefin may be 30% by mass or more, 50% by mass or more, and further 100% by mass, based on the total amount of the layer A.
  • the crosslinked structure in the microporous film or the A layer is preferably formed by a compound generated in the electricity storage device. That is, in the manufacturing process of the electricity storage device, when the separator is brought into contact with the non-aqueous electrolyte, swelling of the microporous membrane or the A layer and / or a compound generated in the electricity storage device is used to form an oligosiloxane bond. It is also preferable that the crosslinked structure is a crosslinked structure in the microporous membrane or the A layer.
  • the crosslinked structure in this case is a crosslinked structure obtained by positively promoting the crosslinking reaction in the manufacturing process of the electricity storage device without actively promoting the crosslinking reaction in the manufacturing process of the separator. The self-crosslinking property of the separator can be maintained until it is stored.
  • the silane-modified polyolefin is not a masterbatch resin containing a dehydration condensation catalyst from the viewpoint of suppressing the generation of resin aggregates in the manufacturing process of the separator, and maintaining the silane crosslinkability until it comes into contact with the electrolytic solution.
  • the dehydration condensation catalyst also functions as a catalyst for the siloxane bond formation reaction of the alkoxysilyl group-containing resin.
  • a compound obtained by previously adding a dehydration condensation catalyst for example, an organometal-containing catalyst
  • a dehydration condensation catalyst for example, an organometal-containing catalyst
  • polyethylene in the present specification, polyethylene that can be further contained in addition to the silane-modified polyolefin (polyethylene further included as a polyolefin different from the silane-modified polyolefin in the microporous membrane or the layer A) has a weight average molecular weight of 100,000 or more. It means polyethylene, which is a homo-ethylene polymerized polymer having a molecular weight of less than or equal to 2,000,000, and a copolymer copolymerized polymer containing an alkane unit.
  • the content thereof is preferably 20% by mass or more, more preferably 40% by mass, based on the total amount of the silane-modified polyolefin and polyethylene. It is at least mass%, more preferably at least 50 mass%.
  • the content of polyethylene is 20% by mass or more, deterioration resistance to redox tends to be easily secured, and a dense and uniform porous body structure tends to be secured.
  • the content of polyethylene is preferably 97% by mass or less, more preferably 96% by mass or less, and further preferably 95% by mass or less. When the content of polyethylene is 97% by mass or less, the content of silane-modified polyolefin in the microporous membrane or A layer can be secured.
  • the identification of 1 H or 13 C NMR of silane-modified polyolefin as a raw material used for manufacturing a separator can be utilized in a method for detecting a silane-modified polyolefin contained in a separator.
  • An example of 1 H and 13 C NMR measurement techniques will be described below.
  • 11 and 12 are 1 H and 13 C-NMR charts of silane-modified polyolefin raw materials 1 and 2 using two kinds of polyolefins, and raw materials 1 and 2 are melt index (MI) and C 3 grafts, respectively. Amount, C 4 graft amount, and / or silanol modification amount are different.
  • the 1 H and 13 C-NMR measurement conditions in FIG. 11 are as follows.
  • the 1 H and 13 C-NMR measurement conditions in FIG. 12 are as follows.
  • FIG. 13 is a 1 H- and 13 C-NMR chart in a pre-crosslinking state of a separator produced using the silane-modified polyolefin raw material 1 shown in FIG. 11 in Example I-1 described later.
  • the 1 H and 13 C-NMR measurement conditions in FIG. 13 are as follows.
  • crosslinked separator can be measured by the same NMR as in FIG. 13 after the pretreatment described above (not shown).
  • a combination of a microporous membrane containing a silane-modified polyolefin and an inorganic porous layer has both a shutdown function at a temperature lower than 150 ° C and a film rupture property at a relatively high temperature, and has cycle characteristics of an electricity storage device and battery nail penetration safety. Tend to improve the sex. Since the silane-modified polyolefin in the microporous film is silane-crosslinkable, it may increase the viscosity of the resin in the microporous film when silane cross-linking occurs.
  • the crosslinked high-viscosity resin does not easily flow into the inorganic layer (that is, it is difficult to integrate), the clearance between the electrodes can be sufficiently secured, and the battery short circuit can be suppressed.
  • the inorganic porous layer is a layer containing inorganic particles and a resin binder, and may optionally further contain a dispersant for dispersing the inorganic particles in the binder resin.
  • the thickness of the inorganic porous layer is 0.5 ⁇ m to 10 ⁇ m, 0.5 ⁇ m to 7 ⁇ m, 0.5 ⁇ m to 5 ⁇ m, or 0. 0, from the viewpoint of ion permeability of the separator and charge / discharge capacity or cycle stability of the electricity storage device. It is preferably 5 ⁇ m to 4 ⁇ m.
  • the thickness of the inorganic porous layer can be determined by the method described in the examples.
  • the B layer contains inorganic particles.
  • the B layer may further include a resin binder.
  • the B layer can be the inorganic porous layer described above.
  • the B layer may include components other than the inorganic particles and the resin binder.
  • the thickness (TB) of the B layer is preferably 0.2 ⁇ m or more, more preferably 0.5 ⁇ m or more. If the thickness (TB) is 0.5 ⁇ m or more, the mechanical strength tends to be further improved. On the other hand, the thickness (TB) is preferably less than 22 ⁇ m, more preferably 20 ⁇ m or less, still more preferably 15 ⁇ m or less. When the thickness (TB) is 30 ⁇ m or less, the volume occupied by the separator in the electricity storage device decreases, which tends to be advantageous in terms of increasing the capacity of the electricity storage device. It is also preferable from the viewpoint of preventing an excessive increase in air permeability of the separator.
  • the thickness (TB) may be set to, for example, 0.50 ⁇ m or more, 0.80 ⁇ m or more, or 1.00 ⁇ m or more, and less than 22.00 ⁇ m, 20.00 ⁇ m or less, or 15.00 ⁇ m or less. Good.
  • the thickness (TB) can be measured by the method described in the Example section, and can be controlled by changing the coating amount of the coating liquid (slurry) for forming the B layer.
  • the thickness of the B layer is treated as the above “thickness (TB)”.
  • the total thickness of the plurality of B layers is treated as the above-mentioned “thickness (TB)”.
  • the total thickness of the B layer arranged on the one side and the B layer arranged on the other side is the above-mentioned "thickness”. (TB) ”.
  • inorganic particles examples include alumina (Al 2 O 3 ), silica, titania, zirconia, magnesia, ceria, yttria, zinc oxide, iron oxide, and other inorganic oxides (oxide-based ceramics); silicon nitride, titanium nitride. , And inorganic nitrides (nitride-based ceramics) such as boron nitride; silicon carbide, calcium carbonate, magnesium sulfate, aluminum sulfate, aluminum hydroxide, aluminum hydroxide oxide (AlO (OH)), potassium titanate, talc, kaori.
  • Ceramics such as knight, dikite, nacrite, halloysite, pyrophyllite, montmorillonite, sericite, mica, amesite, bentonite, asbestos, zeolite, calcium silicate, magnesium silicate, diatomaceous earth and silica sand; and glass fiber Is You can These may be used alone or in combination of two or more.
  • the amount of the inorganic particles is preferably 5% by mass or more or 20% by mass or more, more preferably 30% by mass or more, from the viewpoint of ensuring heat resistance, based on the total amount of the inorganic porous layer or the B layer.
  • the amount of the inorganic particles may be set to 50% by mass or more, more than 80% by mass, or 85% by mass or more based on the total amount of the inorganic porous layer or the B layer.
  • the amount of the inorganic particles is preferably 99.9% by mass or less, more preferably 99.5% by mass or less or 99% by mass or less.
  • the amount of the inorganic particles may be set to, for example, 20.00 mass% or more, 30.00 mass% or more, 50.00 mass% or more, 80.00 mass% or more, or 85.00 mass% or more, On the other hand, it may be set to 99.90% by mass or less or 99.50% by mass.
  • the shape of the inorganic particles includes a plate shape, a scale shape, a needle shape, a column shape, a spherical shape, a polyhedral shape, a spindle shape, and a lump shape (block shape).
  • a plurality of inorganic particles having these shapes may be used in combination.
  • the number average particle diameter of the inorganic particles is, for example, 0.01 ⁇ m or more, 0.1 ⁇ m or more, or 0.3 ⁇ m or more, and preferably 0.5 ⁇ m or more.
  • the number average particle diameter is, for example, 10.0 ⁇ m or less, 9.0 ⁇ m or less, or 6.0 ⁇ m or less, preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less. More preferably, it is 0.5 ⁇ m or less. It is preferable to adjust the number average particle diameter of the inorganic particles within the above range from the viewpoint of improving safety during short circuit.
  • Examples of the method for adjusting the number average particle diameter of the inorganic particles include a method of pulverizing the inorganic particles by using an appropriate pulverizing device such as a ball mill, a bead mill, a jet mill.
  • the minimum particle size is preferably 0.02 ⁇ m or more, more preferably 0.05 ⁇ m or more, still more preferably 0.1 ⁇ m or more.
  • the maximum particle size is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 7 ⁇ m or less.
  • the ratio of maximum particle diameter / average particle diameter is preferably 50 or less, more preferably 30 or less, and further preferably 20 or less. It is preferable to adjust the particle size distribution of the inorganic particles within the above range from the viewpoint of suppressing heat shrinkage at high temperature. Further, it may have a plurality of particle size peaks between the maximum particle size and the minimum particle size.
  • a method for adjusting the particle size distribution of the inorganic particles for example, a method of crushing the inorganic filler using a ball mill, a bead mill, a jet mill or the like to adjust to a desired particle size distribution, a plurality of particles having a plurality of particle size distributions After the filler is prepared, a method of blending them may be mentioned.
  • the resin binder contains a resin that binds the inorganic particles to each other.
  • the glass transition temperature (Tg) of the resin binder is said to ensure the binding property with the inorganic particles and the stability of the inorganic porous layer or the B layer in the manufacturing process of the separator, the manufacturing process of the electricity storage device, or the charging / discharging process. From the viewpoint, the temperature is preferably ⁇ 50 ° C. to 100 ° C., more preferably ⁇ 35 ° C. to 95 ° C.
  • the glass transition temperature is determined from the DSC curve obtained by differential scanning calorimetry (DSC). Specifically, the temperature at the intersection of the straight line obtained by extending the low temperature side baseline in the DSC curve to the high temperature side and the tangent line at the inflection point of the stepwise change portion of the glass transition may be adopted as the glass transition temperature. it can. More specifically, it may be determined according to the method described in the examples. Further, “glass transition” refers to a change in the amount of heat caused by a change in the state of a polymer as a test piece on the endothermic side in DSC. Such a change in the amount of heat is observed as a step-like change shape in the DSC curve.
  • stepwise change refers to a part of the DSC curve from the baseline on the low temperature side until the curve moves to a new baseline on the high temperature side. Note that a combination of a step change and a peak is also included in the step change. Furthermore, the “inflection point” refers to a point at which the slope of the DSC curve in the stepwise change portion becomes maximum. Further, in the stepwise change portion, when the upper side is the heat generating side, it can be expressed as a point where the upward convex curve changes to the downward convex curve. “Peak” refers to a portion of the DSC curve from the time when the curve leaves the baseline on the low temperature side until it returns to the same baseline again. The “baseline” refers to a DSC curve in a temperature range in which the test piece does not undergo transition and reaction.
  • Examples of the resin binder include the following 1) to 7). These may be used alone or in combination of two or more.
  • 1) Polyolefin For example, polyethylene, polypropylene, ethylene propylene rubber, and modified products thereof; 2) Conjugated diene-based polymer: For example, styrene-butadiene copolymer, its hydride, acrylonitrile-butadiene copolymer, its hydride, acrylonitrile-butadiene-styrene copolymer, and its hydride; 3) Acrylic polymer: For example, methacrylic acid ester-acrylic acid ester copolymer, styrene-acrylic acid ester copolymer, and acrylonitrile-acrylic acid ester copolymer; 4) Polyvinyl alcohol resin: for example, polyvinyl alcohol and polyvinyl acetate; 5) Fluorine-containing resin: for example, PVdF, polytetrafluoroethylene, vinyl
  • polysulfone polysulfone
  • polyether sulfone polyphenylene sulfide
  • polyetherimide 1, polyamideimide, polyamide, and polyester.
  • resin binders can be obtained from a desired monomer as a raw material according to a known production method such as emulsion polymerization or solution polymerization.
  • a known production method such as emulsion polymerization or solution polymerization.
  • the polymerization temperature, the pressure during the polymerization, the method of adding the monomer, and the additives (polymerization initiator, molecular weight adjusting agent, pH adjusting agent, etc.) used are not limited.
  • the amount of the resin binder is, for example, 0.5% by mass or more or 1.0% by mass or more based on the total amount of the inorganic porous layer or the B layer, while, for example, 50% by mass or less or 30% by mass or less. Is. Further, as described above, since the resin binder is an optional component in the B layer, the amount of the resin binder contained in the B layer is less than 20% by mass, 15% by mass or less, or 0% by mass, based on the total amount of the B layer. You can If the amount of the resin binder contained in the B layer is reduced, the room for containing the inorganic particles in the B layer can be increased accordingly.
  • the dispersant is one that is adsorbed on the surface of the inorganic particles in the slurry for forming the inorganic porous layer or the B layer and stabilizes the inorganic particles by electrostatic repulsion or the like. Salts, polyoxyethers, surfactants and the like may be used.
  • the inorganic porous layer or the B layer may further contain other components which are usually added and blended with an aqueous paint or the like within the range of its effect.
  • Such other components are not particularly limited and include, for example, thickeners, film forming aids, plasticizers, cross-linking agents, antifreezing agents, defoamers, dyes, preservatives, ultraviolet absorbers, and light stabilizers. Agents and the like. These other components may be used alone or in combination of two or more.
  • the microporous membrane, the inorganic porous layer, the A layer, and / or the B layer can optionally contain known additives.
  • additives include organic metal-containing catalysts (dehydration condensation catalysts); plasticizers; antioxidants such as phenol-based, phosphorus-based, and sulfur-based; metal soaps such as calcium stearate and zinc stearate; thickeners A film forming aid; a cross-linking agent; an antifreezing agent; an antifoaming agent; an antiseptic; an ultraviolet absorber; a light stabilizer; an antistatic agent; an antifogging agent; a dye; and a coloring pigment.
  • the B layer may contain a crosslinking agent.
  • Such a cross-linking agent may contain a functional group having reactivity with the above-mentioned inorganic particles.
  • the thickness of the entire separator is preferably 25 ⁇ m or less, more preferably 22 ⁇ m or less or 20 ⁇ m or less, and further preferably 18 ⁇ m or less. , Particularly preferably 16 ⁇ m or less.
  • the lower limit of the thickness of the entire separator may be, for example, 1.0 ⁇ m or more, 3.0 ⁇ m or more, 4.0 ⁇ m or more, 6.0 ⁇ m or more, or 7.5 ⁇ m or more.
  • the air permeability of the separator is preferably 50 seconds / 100 cm 3 to 400 seconds / 100 cm 3 , more preferably 75 seconds / 100 cm 3 to 275 seconds / 100 cm 3 , and further preferably 100 seconds / 100 cm 3 to 200 seconds. / 100 cm 3 .
  • the separator has suitable mechanical strength if it has an air permeability of 50 seconds / 100 cm 3 or more, and preferably has an air permeability of 400 seconds / 100 cm 3 because the battery characteristics are improved from the viewpoint of permeability.
  • an electricity storage device assembly kit including the electricity storage device separator described above.
  • the storage device assembly kit has the following two components: (A) An exterior body that houses a laminate or a wound body of the electrode and the electricity storage device separator according to each embodiment described above; and (B) a container that stores a non-aqueous electrolyte. Is provided.
  • the separator in the element (A) and the nonaqueous electrolytic solution in the element (B) are brought into contact with each other to bring the electrolytic solution into contact with the laminated body or the wound body, And / or by continuing the charge / discharge cycle of the assembled electric storage device, a crosslinked structure can be formed in the separator to form an electric storage device having both safety and output.
  • the substance or cross-linked structure that catalyzes the cross-linking reaction when the electrolyte or electrolyte contacts the electrodes and / or when charging and discharging the electricity storage device.
  • the substance having a functional group is present in the electrolytic solution, on the inner surface of the exterior body or on the electrode surface, and they are dissolved in the electrolytic solution, and are uniformly swollen and diffused into the amorphous part in the polyolefin, whereby the separator-containing laminate or It is considered to uniformly promote the crosslinking reaction of the wound body.
  • the substance which catalyzes the cross-linking reaction may be in the form of an acid solution or a film, and when the electrolyte contains lithium hexafluorophosphate (LiPF 6 ), hydrogen fluoride (HF) or hydrogen fluoride (HF) It can be a fluorine-containing organic substance derived from.
  • the substance having a functional group which becomes a part of the crosslinked structure can be, for example, the compound having the functional group A and / or B described above, the electrolytic solution itself, various additives, and the like.
  • the electrolyte contained in the element (2) is a fluorine (F) -containing lithium salt such as LiPF 6 or LiN (SO 2 CF 3 ) 2 which produces HF.
  • F fluorine
  • LiPF 6 LiN
  • SO 2 CF 3 LiN
  • LiSO 3 CF 3 or the like having an unshared electron pair is preferable, and LiBF 4 , LiBC 4 O 8 (LiBOB) or the like is also preferable.
  • the electricity storage device assembly kit includes, as an accessory (or element (C)), a catalyst for accelerating the crosslinking reaction, for example, a mixture of an organic metal-containing catalyst and water, an acid solution, Another container may be provided to store the base solution and the like.
  • a catalyst for accelerating the crosslinking reaction for example, a mixture of an organic metal-containing catalyst and water, an acid solution
  • Another container may be provided to store the base solution and the like.
  • the separator described above can be used in an electricity storage device.
  • the electricity storage device includes a positive electrode, a negative electrode, the separator according to the present embodiment arranged between the positive and negative electrodes, an electrolytic solution, and optionally an additive.
  • the separator When the separator is housed in the device exterior body, the functional group-modified polyethylene or the functional group graft copolymerized polyethylene and the chemical substance contained in the electrolytic solution or the additive react with each other to form a crosslinked structure.
  • the power storage device has a crosslinked structure.
  • the functional group-modified polyethylene or the functional group graft copolymerized polyethylene may be, but is not limited to, derived from a polyolefin raw material of the microporous membrane or derived from a polyolefin modified during the manufacturing process of the microporous membrane. it can.
  • a lithium battery As the electricity storage device, specifically, a lithium battery, a lithium secondary battery, a lithium ion secondary battery, a sodium secondary battery, a sodium ion secondary battery, a magnesium secondary battery, a magnesium ion secondary battery, a calcium secondary battery.
  • Calcium ion secondary battery aluminum secondary battery, aluminum ion secondary battery, nickel hydrogen battery, nickel cadmium battery, electric double layer capacitor, lithium ion capacitor, redox flow battery, lithium sulfur battery, lithium air battery, zinc air battery And so on.
  • a lithium battery, a lithium secondary battery, a lithium ion secondary battery, a nickel hydrogen battery, or a lithium ion capacitor is preferable, and a lithium battery or a lithium ion secondary battery is more preferable.
  • the additive may be, for example, a dehydration condensation catalyst, metal soap such as calcium stearate or zinc stearate, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antifogging agent, a color pigment and the like.
  • the lithium ion secondary battery contains a lithium transition metal oxide such as lithium cobalt oxide or lithium cobalt composite oxide as a positive electrode, a carbon material such as graphite or graphite as a negative electrode, and a lithium salt such as LiPF 6 as an electrolytic solution. It is a storage battery using an organic solvent.
  • the electrolytes described above for the electricity storage device assembly kit may also be used for lithium ion secondary batteries.
  • ionized lithium reciprocates between the electrodes. Further, since the ionized lithium needs to move between the electrodes at a relatively high speed while suppressing contact between the electrodes, a separator is arranged between the electrodes.
  • Another aspect of the present invention is a method for manufacturing a separator for an electricity storage device.
  • the method for producing the separator may include, for example, a step of producing a microporous membrane or an A layer, and, if desired, a step of producing an inorganic porous layer into the microporous membrane, or a step of producing a B layer into the A layer. it can.
  • the materials used in the method for manufacturing the separator may be those described in the first to tenth embodiments, unless otherwise specified.
  • the manufacturing method of the microporous membrane according to the eleventh embodiment includes the following steps: (1) Sheet forming step; (2) Stretching step; (3) Porous body forming step; and (4) Heat treatment step; including. By performing steps (1) to (4), the A layer described above can also be formed.
  • the separator manufacturing method according to the eleventh embodiment may include the following steps in addition to the steps (1) to (4): (8B) A coating step of forming an inorganic porous layer containing inorganic particles and a resin binder on at least one surface of the heat-treated porous body to form a silane crosslinking precursor. (9) An assembling step in which a laminate of the electrode and the silane cross-linking precursor or a wound body thereof, and a non-aqueous electrolytic solution are housed in an outer package and the silane cross-linking precursor and the non-aqueous electrolytic solution are brought into contact with each other; Can be included.
  • the inorganic porous layer is applied in the step (8B) to the microporous film maintaining the silane crosslinkability, and then the separator in the electricity storage device is applied in the step (9). Since the electrolytic solution is brought into contact with the storage device, the stress resistance of the power storage device and the separator in the power storage device is improved, and thus cycle stability and safety of the power storage device can be achieved.
  • the method for producing a microporous membrane according to the eleventh embodiment may optionally include a kneading step before the sheet forming step (1) and / or a winding / slit step after the heat treatment step (3).
  • the silane crosslinking treatment step it is preferable not to include the silane crosslinking treatment step from the viewpoint of maintaining the silane crosslinking property until it comes into contact with the electrolyte.
  • the silane cross-linking treatment step generally, an object to be treated containing a silane-modified polyolefin is brought into contact with a mixture of an organic metal-containing catalyst and water, or is immersed in a base solution or an acid solution, and a silane dehydration condensation reaction is performed to perform oligosiloxane. This is a step of forming a bond.
  • the metal of the organometallic-containing catalyst may be, for example, at least one selected from the group consisting of sgandium, titanium, vanadium, copper, zinc, aluminum, zirconium, palladium, gallium, tin and lead.
  • Organometallic-containing catalysts include di-butyltin-di-laurate, di-butyltin-di-acetate, di-butyltin-di-octoate and the like, and Weij et al. (FW van. Der. Weij: Macromol. Chem). , 181, 2541, 1980.) is known to be able to overwhelmingly accelerate the reaction rate by the reaction mechanism proposed by the authors.
  • the base solution has a pH of more than 7, and may contain, for example, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal phosphates, ammonia, amine compounds and the like.
  • alkali metal hydroxides or alkaline earth metal hydroxides are preferable, alkali metal hydroxides are more preferable, and sodium hydroxide is further preferable, from the viewpoint of safety of the electricity storage device and silane cross-linking property.
  • the acid solution has a pH of less than 7 and may contain, for example, an inorganic acid or an organic acid.
  • Preferred acids are hydrochloric acid, sulfuric acid, carboxylic acids, or phosphoric acids.
  • a silane-modified polyolefin and, if desired, a plasticizer or an inorganic material and other polyolefin can be kneaded by using a kneader. It is preferable not to add the masterbatch resin containing the dehydration condensation catalyst to the kneaded product from the viewpoints of suppressing the generation of resin aggregates in the production process and maintaining the silane crosslinkability until it comes into contact with the electrolytic solution.
  • the plasticizer is not particularly limited, and examples thereof include an organic compound capable of forming a uniform solution with the polyolefin at a temperature equal to or lower than the boiling point. More specific examples include decalin, xylene, dioctyl phthalate, dibutyl phthalate, stearyl alcohol, oleyl alcohol, decyl alcohol, nonyl alcohol, diphenyl ether, n-decane, n-dodecane and paraffin oil. Among these, paraffin oil and dioctyl phthalate are preferable.
  • the plasticizers may be used alone or in combination of two or more.
  • the proportion of the plasticizer is not particularly limited, but from the viewpoint of the porosity of the obtained microporous film, the polyolefin and the silane-modified polyolefin are, if necessary, preferably 20% by mass or more with respect to the total mass, and at the time of melt kneading. From the viewpoint of viscosity, 90% by mass or less is preferable.
  • the sheet forming step is a step of extruding the obtained kneaded product or a mixture of a silane-modified polyolefin, polyethylene and a plasticizer, cooling and solidifying, and forming into a sheet to obtain a sheet.
  • the sheet forming method is not particularly limited, and examples thereof include a method in which the melt-kneaded and extruded melt is solidified by compression cooling.
  • Examples of the cooling method include cold air, a method of directly contacting a cooling medium such as cooling water, and a method of contacting with a roll cooled with a refrigerant and / or a press machine, but with a roll cooled with a refrigerant and / or a press machine.
  • the contacting method is preferable because the film thickness controllability is excellent.
  • the mass ratio of the silane-modified polyolefin and polyethylene is 0.05 / 0.95 to 0. It is preferably 4 / 0.6, and more preferably 0.06 / 0.94 to 0.38 / 0.62.
  • Silane modification is used in the sheet molding process from the viewpoint of suppressing the thermal runaway at the time of destruction of the electricity storage device and improving safety while having a low temperature shutdown property of 150 ° C. or less and a film rupture resistance at a high temperature of 180 to 220 ° C. It is preferable that the polyolefin is not a masterbatch resin containing a dehydration condensation catalyst for crosslinking the silane-modified polyolefin before the sheet forming step.
  • the stretching step is a step of extracting a plasticizer and / or an inorganic material from the obtained sheet, if necessary, and further stretching the sheet in a uniaxial or more direction.
  • a stretching method of the sheet MD uniaxial stretching by a roll stretching machine, TD uniaxial stretching by a tenter, sequential biaxial stretching by a roll stretching machine and a tenter, or a combination of a tenter and a tenter, simultaneous biaxial tenter or simultaneous biaxial stretching by inflation molding.
  • Axial stretching and the like can be mentioned. From the viewpoint of obtaining a more uniform film, simultaneous biaxial stretching is preferable.
  • the total areal magnification is preferably 8 times or more, more preferably 15 times or more, and further preferably 20 times or more, from the viewpoint of uniformity of film thickness, balance of tensile elongation, porosity and average pore diameter. Or 30 times or more.
  • the total surface magnification is 8 times or more, it tends to be easy to obtain a product having high strength and good thickness distribution. Further, this surface magnification may be 250 times or less from the viewpoint of prevention of breakage and the like.
  • the porous body forming step is a step of extracting the plasticizer from the stretched material after the stretching step to make the stretched material porous.
  • the method of extracting the plasticizer is not particularly limited, and examples thereof include a method of immersing the stretched product in an extraction solvent and a method of showering the stretched product with the extraction solvent.
  • the extraction solvent is not particularly limited, but for example, a poor solvent for polyolefin, and a good solvent for plasticizer and / or inorganic material, and one having a boiling point lower than the melting point of polyolefin are preferable. .
  • the extraction solvent is not particularly limited, but examples thereof include hydrocarbons such as n-hexane and cyclohexane; halogenated hydrocarbons such as methylene chloride, 1,1,1-trichloroethane, and fluorocarbons; ethanol, isopropanol, etc. Alcohols; acetone, 2-butanone and other ketones; alkaline water and the like.
  • the extraction solvent may be used alone or in combination of two or more.
  • the heat treatment step is a step in which after the stretching step, a plasticizer is further extracted from the sheet, if necessary, and further heat treated to obtain a microporous membrane.
  • the heat treatment method is not particularly limited, and examples thereof include a heat setting method of performing stretching and relaxation operations using a tenter and / or a roll stretching machine.
  • the relaxation operation refers to a reduction operation performed in the machine direction (MD) and / or the width direction (TD) of the film at a predetermined temperature and relaxation rate.
  • the relaxation rate is a value obtained by dividing the MD dimension of the membrane after the relaxation operation by the MD dimension of the membrane before the operation, or the value obtained by dividing the TD dimension after the relaxation operation by the TD dimension of the membrane before the operation, or MD and TD. When both are relaxed, it is a value obtained by multiplying the MD relaxation rate and the TD relaxation rate.
  • the inorganic porous layer coating step (8B) is a step of forming an inorganic porous layer containing inorganic particles and a resin binder on at least one surface of the microporous film obtained above.
  • the coating step (8B) can be performed while maintaining the silane crosslinkability of the silane-modified polyolefin.
  • the B layer described above can also be formed.
  • a known manufacturing method can be adopted.
  • a method of producing a laminate including the A layer and the B layer for example, a method of applying a slurry containing inorganic particles to the A layer, a raw material of the B layer, and a raw material of the A layer are coextruded. Examples thereof include a method of laminating and extruding, a method of individually manufacturing the A layer and the B layer, and then laminating them.
  • the inorganic porous layer is, for example, a slurry containing inorganic particles, a resin binder, water or an aqueous solvent (for example, a mixture of water and alcohol), and optionally a dispersant, at least one of the microporous membrane. It can be formed by coating the surface.
  • the inorganic particles, the resin binder and the dispersant may be as described in the first to tenth embodiments.
  • the solvent contained in the slurry is preferably one that can uniformly or stably disperse or dissolve the inorganic particles.
  • a solvent include N-methylpyrrolidone (NMP), N, N-dimethylformamide, N, N-dimethylacetamide, water, ethanol, toluene, hot xylene, methylene chloride, and hexane.
  • the inorganic particle-containing slurry for example, ball mill, bead mill, planetary ball mill, vibrating ball mill, sand mill, colloid mill, attritor, roll mill, high speed impeller dispersion, disperser, homogenizer, high speed impact mill, ultrasonic dispersion, stirring.
  • a mechanical stirring method using blades and the like can be mentioned.
  • the coating method of the inorganic particle-containing slurry for example, gravure coater method, small diameter gravure coater method, reverse roll coater method, transfer roll coater method, kiss coater method, dip coater method, knife coater method, air doctor coater method, blade coater Method, rod coater method, squeeze coater method, cast coater method, die coater method, screen printing method, spray coating method and the like.
  • the solvent As a method of removing the solvent from the coating film, there are a method of drying at a temperature below the melting point of the material forming the microporous film, a method of drying under reduced pressure at a low temperature, and the like.
  • the solvent may be partially left as long as it does not significantly affect the device characteristics.
  • the winding step is a step of slitting the obtained microporous film or the microporous film coated with the inorganic porous layer, if necessary, and winding it into a predetermined core.
  • a separator precursor (hereinafter also referred to as a silane crosslinking precursor) that maintains silane crosslinkability and an electrode are laminated to form a laminated body, and the laminated body is further wound if desired. Is formed, and the laminated body or wound body and the non-aqueous electrolytic solution are housed in an exterior body, and the silane crosslinking precursor and the non-aqueous electrolytic solution are brought into contact with each other.
  • the film loss of the microporous membrane is suppressed and the morphology is maintained, the permeation of the polyolefin resin from the microporous membrane to the inorganic porous layer can be suppressed, and the stress of the electricity storage device or the separator can be suppressed. Tolerance is improved.
  • the silane cross-linking reaction of the separator may occur after the electricity storage device is manufactured to cause a silane cross-linking reaction of the separator after the electricity storage device is manufactured.
  • the safety can be improved.
  • the laminate or the wound body is housed in the outer package and then the non-aqueous electrolytic solution is poured into the outer package, or the electrolytic solution is poured into the outer package. It is preferable to store the laminated body or the wound body in the exterior body.
  • the electrolyte of the non-aqueous electrolyte solution is a fluorine (F) -containing lithium salt such as LiPF 6 that generates hydrogen fluoride (HF), LiN (SO 2 CF 3 ) 2 or LiSO 3.
  • F fluorine
  • LiPF 6 that generates hydrogen fluoride
  • LiN LiN (SO 2 CF 3 ) 2 or LiSO 3.
  • An electrolyte having an unshared electron pair such as CF 3 may be used, and LiBF 4 , LiBC 4 O 8 (LiBOB), or the like may be used.
  • the methoxysilane graft part is converted to silanol by a small amount of water contained in the electricity storage device (water contained in members such as electrodes, separators and electrolytes), and a crosslinking reaction occurs. , It is estimated that the siloxane bond is changed. Further, when the electrolyte or the electrolytic solution is brought into contact with the electrode, a substance which catalyzes the silane cross-linking reaction is generated in the electrolytic solution or on the surface of the electrode, and they are dissolved in the electrolytic solution. It is considered that the cross-linking reaction of the separator-containing laminate or wound body is uniformly promoted by uniformly swelling and diffusing into the amorphous part.
  • the substance which catalyzes the silane crosslinking reaction may be in the form of an acid solution or a film, and when the electrolyte contains lithium hexafluorophosphate (LiPF 6 ), LiPF 6 reacts with water to generate HF, or It can be a fluorine-containing organic substance derived from HF.
  • LiPF 6 lithium hexafluorophosphate
  • the lead terminals are connected to the electrodes to carry out charge / discharge for at least one cycle. It is preferable to carry out. It is conceivable that a substance that catalyzes the silane cross-linking reaction is generated in the electrolytic solution or on the electrode surface by the charge / discharge cycle, and thereby the silane cross-linking reaction is achieved.
  • the cycle charge / discharge can be performed by a known method and device, and specifically, the method described in the examples is possible.
  • Another aspect of the present invention is a method for manufacturing an electricity storage device.
  • the method of manufacturing an electricity storage device includes the following steps; (A) a step of preparing the electricity storage device assembly kit described above, (A) a step of initiating a silane crosslinking reaction of the silane-modified polyolefin by bringing the separator in the element (1) of the electricity storage device assembly kit into contact with the nonaqueous electrolytic solution in the element (2); (C) optionally connecting a lead terminal to the electrode of the element (1), (D) If desired, a step of performing charge / discharge for at least one cycle, including.
  • the steps (a) to (d) can be performed by a method known in the technical field except that the separator for an electricity storage device according to the present embodiment is used, and the steps (a) to (d).
  • a positive electrode, a negative electrode, an electrolytic solution, an outer package, and a charging / discharging device known in the technical field can be used.
  • a vertically long separator having a width of 10 to 500 mm (preferably 80 to 500 mm) and a length of 200 to 4000 m (preferably 1000 to 4000 m) can be manufactured.
  • the positive electrode-separator-negative electrode-separator or the negative electrode-separator-positive electrode-separator may be laminated in this order and wound in a circular or flat spiral shape to obtain a wound body.
  • the wound body is housed in a device can (for example, a battery can), and a nonaqueous electrolytic solution is further injected, whereby a power storage device can be manufactured.
  • the electricity storage device can be manufactured by a method in which the electrode and the separator are folded to form a wound body, which is placed in a device container (for example, an aluminum film) and a nonaqueous electrolytic solution is injected.
  • the wound body can be pressed.
  • the separator, the current collector, and the electrode having the active material layer formed on at least one surface of the current collector can be stacked and pressed.
  • the pressing temperature is preferably, for example, 20 ° C. or higher as a temperature at which adhesiveness can be effectively exhibited. Further, from the viewpoint of suppressing clogging of pores or heat shrinkage in the separator due to hot pressing, the pressing temperature is preferably lower than the melting point of the material contained in the microporous membrane, and more preferably 120 ° C. or lower.
  • the pressing pressure is preferably 20 MPa or less from the viewpoint of suppressing clogging of holes in the separator.
  • the pressing time may be 1 second or less when a roll press is used, or a surface press for several hours, but is preferably 2 hours or less from the viewpoint of productivity.
  • the method for manufacturing the separator when the method for manufacturing the A layer described above does not include the silane crosslinking treatment step, it is possible to positively promote the crosslinking reaction by bringing the separator into contact with the non-aqueous electrolytic solution. it can.
  • the silane-modified graft part is converted to silanol by a small amount of water contained in the electricity storage device (a small amount of water contained in the electrode, separator, non-aqueous electrolyte solution, etc.) and crosslinked. It is presumed that it reacts and changes into a siloxane bond.
  • a substance that catalyzes the silane crosslinking reaction may be generated in the non-aqueous electrolytic solution or on the electrode surface.
  • a substance that exerts a catalytic action on the silane crosslinking reaction is dissolved in the non-aqueous electrolytic solution and uniformly swells and diffuses into the amorphous portion in the polyolefin where the silane-modified graft portion is present, whereby the separator-containing laminate Alternatively, it is considered to uniformly promote the crosslinking reaction of the wound body.
  • the substance that catalyzes the silane crosslinking reaction may be in the form of an acid solution or a film.
  • the electrolyte contains lithium hexafluorophosphate (LiPF 6 )
  • LiPF 6 reacts with water, and hydrogen fluoride (HF) generated by this reaction or a fluorine-containing organic substance derived from hydrogen fluoride (HF) is generated. It is treated as a substance that exerts a catalytic action on a silane cross-linking reaction (a compound generated in an electricity storage device).
  • the thirteenth embodiment is a method of manufacturing an electricity storage device using a separator containing a polyolefin having one or more kinds of functional groups, and the following steps: (1) A functional group is subjected to a condensation reaction, (2) a functional group is reacted with a chemical substance inside an electricity storage device, or (3) a functional group of a polyolefin is reacted with another type of functional group to crosslink. It includes a cross-linking step to form a structure.
  • the crosslinking step can be performed in the same manner as the reaction for forming the crosslinked structure of the separator described above.
  • the crosslinking step can be performed using the compound in the electricity storage device and the environment around the device, it does not require excessive conditions such as an electron beam and a high temperature of 100 ° C. or higher, and the temperature is 5 ° C. Mild conditions such as temperatures up to 90 ° C. and / or under ambient atmosphere can be employed.
  • cross-linking structure By performing the cross-linking step in the manufacturing process of the electricity storage device, formation of the cross-linking structure can be omitted during or immediately after the film forming process of the separator, and the stress strain after production of the electricity storage device is relaxed or eliminated, and / or Alternatively, a cross-linking structure can be imparted to the separator without using relatively high energy such as light irradiation or heating to reduce cross-linking unevenness, generation of unmelted resin aggregates, and environmental burden.
  • cross-linking step by reacting (2) the functional group with a chemical substance inside the electricity storage device or (3) reacting the functional group of the polyolefin with another type of functional group, not only inside the separator but also
  • a crosslinked structure can be formed between the separator and the electrode or between the separator and the solid electrolyte interface (SEI) to improve the strength between the plurality of members of the electricity storage device.
  • SEI solid electrolyte interface
  • the silane crosslinking reaction occurs after the storage of the electricity storage device to improve the safety of the electricity storage device while being compatible with the conventional production process of the electricity storage device. Can be made.
  • MFR Melt index F-F01
  • Second stage cooling program 110 ° C to 40 ° C / min. Hold for 5 minutes after reaching -50 ° C.
  • 3rd stage heating program Temperature rising from -50 ° C to 130 ° C at a rate of 15 ° C per minute. Data of DSC and DDSC were acquired during the temperature rise of the third stage. The intersection of the baseline (a straight line obtained by extending the baseline in the obtained DSC curve to the high temperature side) and the tangent at the inflection point (the point where the upward convex curve changes to the downward convex curve) is the glass transition temperature ( Tg).
  • ⁇ Film thickness ( ⁇ m)> The film thickness of the microporous film or the separator was measured at a room temperature of 23 ⁇ 2 ° C. and a relative humidity of 60% by using KBM (trademark), a micro thickness gauge manufactured by Toyo Seiki. Specifically, the film thickness at 5 points was measured at substantially equal intervals over the entire width in the TD direction, and the average value thereof was obtained.
  • the thickness of the inorganic porous layer can be calculated by subtracting the thickness of the microporous film from the thickness of the separator including the microporous film and the inorganic porous layer.
  • ⁇ Thickness of layer A (TA) and thickness of layer B (TB)> The thickness (TA) of the A layer was measured at a room temperature of 23 ⁇ 2 ° C. and a relative humidity of 60% by using KBM (trademark), a micro thickness gauge manufactured by Toyo Seiki. Specifically, the film thickness at 5 points was measured at substantially equal intervals over the entire width of the TD, and the average value thereof was obtained. Moreover, the thickness of the laminated body including the A layer and the B layer was obtained by the same method. Then, by subtracting the thickness (TA) of the A layer from the thickness of the obtained laminated body, the thickness (TB) of the B layer was obtained. The thickness of the obtained laminate was treated as the total thickness (TA + TB) of the A layer and the B layer. Further, the thickness ratio (TA / TB) was obtained by dividing the thickness (TA) by the thickness (TB).
  • the porosity of the microporous membrane is calculated from the following equation from the volume, mass and membrane density (g / cm 3 ).
  • Porosity (%) (volume-mass / film density) / volume ⁇ 100
  • the film density means a value measured according to the D) density gradient tube method described in JIS K7112 (1999).
  • Air permeability (sec / 100 cm 3 )> According to JIS P-8117 (2009), the air permeability of the sample or the A layer was measured by G-B2 (trademark), a Gurley type air permeability meter manufactured by Toyo Seiki Co., Ltd.
  • ⁇ Puncture strength of layer A> The layer A was fixed with a sample holder having a diameter of 11.3 mm at the opening using a handy compression tester KES-G5 (model name) manufactured by Kato Tech. Next, a maximum puncture load was obtained by performing a puncture test in a 25 ° C. atmosphere at a puncture speed of 2 mm / sec using a needle with a tip radius of curvature of 0.5 mm on the center of the fixed A layer. was measured. The value obtained by converting the maximum puncture load per thickness of 20 ⁇ m was defined as the puncture strength (gf / 20 ⁇ m). If the thermoplastic polymer is present on only one side of the substrate, the needle can be pierced from the side on which the thermoplastic polymer is present.
  • the resin aggregate in the separator has an area of 100 ⁇ m in length ⁇ 100 ⁇ m in width and more than 100 ⁇ m in width when observing the separator obtained through the film forming steps of Examples and Comparative Examples described later with a transmission optical microscope. Is defined as a region that does not penetrate. In observation with a transmission optical microscope, the number of resin aggregates per 1000 m 2 of separator area was measured.
  • ⁇ Storage modulus, loss modulus and transition temperature (version 1)>
  • the dynamic viscoelasticity of the separator is measured using a dynamic viscoelasticity measuring device, and the storage elastic modulus (E ′), loss elastic modulus (E ′′), and the transition temperature of the rubber-like flat region and the crystal melt flow region are measured. It can be calculated.
  • the storage elastic modulus change ratio (R ⁇ E ′ ) is in accordance with the following formula (1)
  • the mixed storage elastic modulus ratio (R E ′ mix ) is in accordance with the following formula (2)
  • the loss elastic modulus change ratio (R ⁇ E ′′ ) is in the following formula.
  • the mixing loss elastic modulus ratio (R E ′′ mix ) was calculated according to the following equation (4).
  • the static tensile load refers to an intermediate value between the maximum stress and the minimum stress in each periodic motion
  • the sinusoidal load refers to the vibration stress centered on the static tensile load.
  • Sinusoidal tension mode refers to measuring vibrational stress while performing periodic motion with a fixed amplitude of 0.2%, in which case the difference between the static tension load and the sine wave load is within 20%. The vibration stress was measured by changing the gap distance and the static tensile load so that When the sine wave load was 0.02 N or less, the amplitude value was amplified so that the sine wave load was within 5 N and the increase amount of the amplitude value was within 25%, and the vibration stress was measured.
  • E ′ S and E ′ j and E ′′ S and E ′′ j were the average values of storage elastic moduli or loss elastic moduli at 160 ° C. to 220 ° C. in the dynamic viscoelasticity measurement data.
  • E ′ a and E ′ 0 and E ′′ a and E ′′ 0 are the average value of each storage elastic modulus or each loss elastic modulus at 160 ° C. to 220 ° C. in the dynamic viscoelasticity measurement data.
  • FIG. 1 An example of a graph for explaining the relationship between temperature and storage elastic modulus is shown in FIG.
  • the storage elastic moduli of the reference film a separator for an electricity storage device that does not contain silane-modified polyolefin
  • the post-crosslinking film in the temperature range of ⁇ 50 ° C. to 225 ° C. are compared, and in FIG.
  • the transition temperature between the region and the crystal melt flow region can be confirmed.
  • the transition temperature is the temperature at the intersection of the straight line extending the high temperature side baseline to the low temperature side and the tangent line drawn at the inflection point of the curve of the crystal melting change portion.
  • FIG. 2 shows an example of a graph for explaining the relationship between temperature and loss elastic modulus.
  • the loss elastic moduli of the reference film (a separator for a power storage device that does not contain silane-modified polyolefin) and the post-crosslinking film in the temperature range of ⁇ 50 ° C. to 220 ° C. are compared, and are determined by the same method as in FIG. The transition temperature given is indicated.
  • ⁇ Storage modulus, loss modulus and transition temperature (version 2)>
  • the dynamic viscoelasticity of the separator is measured using a dynamic viscoelasticity measuring device, and the storage elastic modulus (E ′), loss elastic modulus (E ′′), and the transition temperature of the rubber-like flat region and the crystal melt flow region are measured. It can be calculated.
  • the storage elastic modulus change ratio (R ⁇ E′X ) is in accordance with the following formula (1)
  • the mixed storage elastic modulus ratio (R E′mix ) is in accordance with the following formula (2)
  • the mixing loss elastic modulus ratio (R E ′′ x ) is The mixing loss elastic modulus ratio (R E ′′ mix ) was calculated according to the following formula (3) according to the following formula (4).
  • the measurement conditions were as follows: using an RSA-G2 dynamic viscoelasticity measuring device manufactured by TA Instruments Co., Ltd., measuring frequency was 1 Hz, strain was 0.2%, and the temperature range was ⁇ 50 ° C. to 310 ° C. in a nitrogen atmosphere.
  • the storage elastic modulus and loss elastic modulus were measured according to version 1 above.
  • E ′ Z and E ′ Z0 and E ′′ Z and E ′′ Z0 are the average value of each storage elastic modulus or each loss elastic modulus at 160 ° C. to 300 ° C. in the dynamic viscoelasticity measurement data.
  • E ′ and E ′ 0 and E ′′ and E ′′ 0 are average values of storage elastic modulus or loss elastic modulus at 160 ° C.
  • Fig. 9 shows an example of a graph for explaining the relationship between temperature and storage elastic modulus.
  • the storage elastic moduli of the reference film a separator for an electricity storage device having no crosslinked amorphous structure
  • the post-crosslinking film in the temperature range of ⁇ 50 ° C. to 310 ° C. are compared, and the rubber in FIG. 9 is compared. It is possible to confirm the transition temperatures of the flat region and the crystal melt flow region.
  • the transition temperature is the temperature at the intersection of the straight line extending the high temperature side baseline to the low temperature side and the tangent line drawn at the inflection point of the curve of the crystal melting change portion.
  • FIG. 10 shows an example of a graph for explaining the relationship between temperature and loss elastic modulus.
  • the loss elastic moduli of the reference film (electric storage device separator not containing silane-modified polyolefin) and the post-crosslinking film in the temperature range of ⁇ 50 ° C. to 310 ° C. are compared, and are determined by the same method as in FIG. The transition temperature given is indicated.
  • a separator for an electricity storage device having no amorphous part cross-linking structure includes polyethylene: X (viscosity average molecular weight of 100,000 to 400,000), PE: Y (viscosity average molecular weight of 400,000 to 800,000) and PE: Z. (A viscosity average molecular weight of 800,000 to 9,000,000) Any one kind selected from the group consisting of, or two kinds or three kinds selected from the group consisting of X, Y and Z was mixed at an arbitrary ratio. It can be a separator made of a composition.
  • the polyolefin comprised only with hydrocarbon skeletons such as low-density polyethylene: LDPE, linear low-density polyethylene: LLDPE, polypropylene: PP, olefin system thermoplastic elastomer, to a mixed composition.
  • the rate of change in solid content in a decalin solution before and after heating at 160 ° C. (hereinafter referred to as “gelation degree”) is 10% or less. It can mean a polyolefin microporous membrane.
  • the degree of gelation of the polyolefin microporous film having an amorphous part crosslinked structure such as a silane crosslinked structure is preferably 30% or more, more preferably 70% or more.
  • Measurement temperature range -50 °C to 250 °C
  • Raising rate 10 ° C / min
  • Measurement frequency 1 Hz
  • Deformation mode Sine wave tension mode (Linear tension)
  • Initial value of static tensile load 0.2N ⁇ Gap distance at the initial stage (at 25 ° C): 10 mm -Automatic distortion adjustment (Auto strain adjustment): Disabled (Disabled) Do with.
  • the static tensile load refers to an intermediate value between the maximum stress and the minimum stress in each periodic motion, and the sinusoidal load refers to the vibration stress centered on the static tensile load;
  • the sine wave tension mode refers to measuring vibration stress while performing periodic motion with a fixed amplitude of 0.1%, and in the sine wave tension mode, the difference between the static tension load and the sine wave load is 5%. The vibration stress is measured by changing the gap distance and the static tensile load so that it is within the range, and when the sine wave load is 0.1N or less, the static tensile load is fixed to 0.1N and vibration is performed. Measure stress.
  • the average value of the maximum and minimum values of E' is calculated as the average E '(E' ave ), and the average value of the maximum and minimum values of E '' is average E '' (E '' ave ).
  • E ′ and E ′′ the maximum value and the minimum value of each storage elastic modulus or each loss elastic modulus at ⁇ 50 ° C. to 250 ° C. in the dynamic viscoelasticity measurement data were calculated. More specifically, in the case where breakage of the sample (rapid decrease in elastic modulus) is not observed at -50 ° C to 250 ° C, the maximum and minimum values of -50 ° C to 250 ° C are calculated, The value at the temperature at which breakage of the sample was observed at ⁇ 250 ° C. was defined as the minimum value.
  • the film softening transition temperature is the minimum temperature obtained by first-order differentiating the curve of the gap distance of the sample in the dynamic viscoelasticity measurement data.
  • the film rupture temperature is the temperature at which the sample rupture (rapid decrease in elastic modulus) is observed in the dynamic viscoelasticity measurement data, and the measurement limit temperature is the viewpoint that the thermal decomposition reaction of the polyolefin resin proceeds. Therefore, it may be specified as 250 ° C. However, since the phenomenon can be similarly understood even when the measurement is performed at a temperature higher than 250 ° C., a separator for an electricity storage device having a film rupture temperature of 180 ° C. or higher can be implemented in this embodiment.
  • TMA film rupture temperature TMA film rupture temperature (trademark) manufactured by Shimadzu Corporation
  • TMA film rupture temperature TMA film rupture temperature
  • TD 3 mm and MD 14 mm were sampled from the A layer, and this was used as a sample piece (a sample piece in which MD is the long side). Both ends of the MD of the sample piece were set on a dedicated probe so that the chuck distance was 10 mm, and a load of 1.0 g was applied to the sample piece.
  • the temperature of the furnace equipped with the test piece was raised, and the temperature at which the load was 0 g was taken as the film rupture temperature (° C).
  • the layer A was sampled in TD 14 mm and MD 3 mm, and this was used as a sample piece.
  • the both ends of the TD were chucked with a dedicated probe, and the chuck distance was set to 10 mm. Then, 1.0 g of initial load is applied, and the same operation as above is performed.
  • ⁇ Heat shrinkage at 150 ° C> TD100mm and MD100mm were sampled from the laminated body (laminated body including the A layer and the B layer) before the formation of the crosslinked structure, and this was used as a sample piece. Then, the sample piece was allowed to stand in an oven at 150 ° C. for 1 hour. At this time, the sample piece was sandwiched between two sheets of paper so that the warm air did not directly hit the sample piece. After the sample piece was taken out of the oven and cooled, the area of the sample piece was measured, and the heat shrinkage rate (T1) at 150 ° C. before the formation of the crosslinked structure was calculated by the following formula. Thermal contraction rate (%) at 150 ° C.
  • Battery breakage safety test 1 is a test in which an iron nail is driven into a battery charged to 4.5 V at a speed of 20 mm / sec and penetrated to cause an internal short circuit.
  • the phenomenon at the time of internal short circuit can be clarified by measuring the time change behavior of the voltage drop of the battery due to the internal short circuit and the temperature rise behavior of the battery surface due to the internal short circuit.
  • due to insufficient shutdown function of the separator or film rupture at low temperature during internal short circuit abrupt heat generation of the battery may occur. is there.
  • Negative Electrode 96.9% by mass of artificial graphite as an anode active material, 1.4% by mass of ammonium salt of carboxymethyl cellulose as a resin binder and 1.7% by mass of styrene-butadiene copolymer latex were dispersed in purified water to form a slurry.
  • This slurry was applied on one surface of a copper foil having a thickness of 12 ⁇ m to be a negative electrode current collector by a die coater, dried at 120 ° C. for 3 minutes, and compression-molded by a roll press. At this time, the amount of active material applied to the negative electrode was adjusted to 106 g / m 2 , and the active material bulk density was adjusted to 1.35 g / cm 3 .
  • Battery assembly A separator is cut out in a width (TD) direction of 60 mm and a length (MD) direction of 1000 mm, and the separator is folded in 99 times, and the positive electrode and the negative electrode are alternately stacked between the separators (12 positive electrodes and 13 negative electrodes). .
  • the positive electrode had an area of 30 mm ⁇ 50 mm, and the negative electrode had an area of 32 mm ⁇ 52 mm.
  • the charging and discharging of the obtained battery was performed 100 cycles in an atmosphere of 60 ° C. Charging is performed by charging the battery with a current value of 6.0 mA (1.0 C) to a battery voltage of 4.2 V, and then holding the battery voltage at 4.2 V and starting to squeeze the current value from 6.0 mA for a total of 3 hours. Charged The battery was discharged to a battery voltage of 3.0 V at a current value of 6.0 mA (1.0 C).
  • the resistance ( ⁇ ) between the electrodes is measured while heating the laminate with an aluminum heater at a heating rate of 2 ° C./min.
  • the resistance between the electrodes of both fuses of the separator increases, and the temperature when the resistance exceeds 1000 ⁇ for the first time is defined as the fuse temperature (shutdown temperature). Further, the temperature when the resistance is lowered to 1000 ⁇ or less is further defined as the meltdown temperature (film rupture temperature).
  • a conductive silver paste was applied to the back of the aluminum foil of the positive electrode prepared by "1a.
  • Preparation of positive electrode in the above item ⁇ Battery destruction safety test 1>.
  • the electric wire for resistance measurement was adhered by.
  • an electric wire for resistance measurement was adhered to the back of the copper foil of the negative electrode prepared by “1b.
  • Preparation of non-aqueous electrolytic solution in the above item ⁇ Battery destruction safety test 1> was also used for the F / MD characteristic test.
  • This slurry was applied to one surface of an aluminum foil having a thickness of 20 ⁇ m to be a positive electrode current collector by using a die coater, dried at 130 ° C. for 3 minutes, and then compression-molded by using a roll press machine to obtain a positive electrode.
  • the coating amount of the positive electrode active material was 109 g / m 2 .
  • Graphite powder A as prepared negative active material of the negative electrode (density 2.23 g / cm 3, number average particle diameter 12.7 [mu] m) 87.6 wt%, and graphite powder B (density 2.27 g / cm 3, number average particle diameter 6.5 ⁇ m) 9.7% by mass, and 1.4% by mass of ammonium salt of carboxymethyl cellulose as a resin binder (solid content conversion) (solid content concentration 1.83% by mass aqueous solution) and diene rubber latex 1.7% by mass. (Solid content conversion) (solid content concentration 40 mass% aqueous solution) was dispersed in purified water to prepare a slurry.
  • This slurry was applied to one surface of a copper foil having a thickness of 12 ⁇ m, which was a negative electrode current collector, by a die coater, dried at 120 ° C. for 3 minutes, and then compression-molded with a roll press machine to prepare a negative electrode. At this time, the coating amount of the negative electrode active material was 52 g / m 2 .
  • the raw material polyolefin used for the silane-grafted modified polyolefin has a viscosity average molecular weight (Mv) of 100,000 or more and 1 million or less, a weight average molecular weight (Mw) of 30,000 or more and 920,000 or less, and a number average molecular weight of 10,000 or more. It may be 150,000 or less, and propylene or butene copolymerized ⁇ -olefin may be used.
  • the residual concentration of unreacted trimethoxyalkoxide-substituted vinylsilane in the pellet is about 10 to 1500 ppm.
  • the silane-grafted modified polyolefin obtained by the above production method is used as "silane-modified polyolefin (B)" in Table 8.
  • Example I-1 MFR (190 ° C) obtained by a modification reaction of a homopolymer polyethylene (A) having a weight average molecular weight of 500,000 with 79.2% by mass of a polyolefin having a viscosity average molecular weight of 20,000, and a trimethoxyalkoxide-substituted vinylsilane.
  • silane-grafted polyethylene silane-modified polyethylene (B)) 19.8% by mass (the resin compositions of (A) and (B) are 0.8 and 0.2, respectively), an antioxidant 1% by mass of pentaerythrityl-tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was added as a mixture, and dry blended using a tumbler blender to obtain a mixture. . The obtained mixture was fed to a twin-screw extruder under a nitrogen atmosphere by a feeder. Liquid paraffin (kinematic viscosity at 37.78 ° C.
  • the sheet-shaped molded product was introduced into a simultaneous biaxial tenter stretching machine and biaxially stretched to obtain a stretched product.
  • the set stretching conditions were an MD magnification of 7.0 times, a TD magnification of 6.0 times (that is, 7 ⁇ 6 times), and a biaxial stretching temperature of 125 ° C.
  • the stretched gel sheet was introduced into a methylethylketone tank and sufficiently immersed in methylethylketone to extract and remove liquid paraffin, and then the methylethylketone was dried and removed to obtain a porous body.
  • the porous body is introduced into a TD tenter to perform heat setting (HS), and HS is performed at a heat setting temperature of 125 ° C. and a draw ratio of 1.8 times, and then a relaxation operation of 0.5 times in the TD direction (ie, The HS relaxation rate was 0.5 times) to obtain a microporous membrane.
  • the obtained microporous membrane was cut at its end and wound as a mother roll having a width of 1,100 mm and a length of 5,000 m.
  • the microporous film unwound from the mother roll was slit as needed and used as an evaluation separator.
  • Examples I-2 to I-6 As described in Table 8, the same operation as in Example I-1 was performed, except that the ratio of the amounts of the components A and B and the crosslinking method / conditions were changed, and the microporous membrane shown in Table 8 was obtained.
  • silane-grafted polyethylene silane-modified polyethylene (B)) 19.8% by mass (the resin compositions of (A) and (B) are 0.8 and 0.2, respectively), an antioxidant 1% by mass of pentaerythrityl-tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was added as a mixture, and dry blended using a tumbler blender to obtain a mixture. . The obtained mixture was fed to a twin-screw extruder under a nitrogen atmosphere by a feeder. Liquid paraffin (kinematic viscosity at 37.78 ° C.
  • the sheet-shaped molded product was introduced into a simultaneous biaxial tenter stretching machine and biaxially stretched to obtain a stretched product.
  • the set stretching conditions were an MD magnification of 7.0 times, a TD magnification of 6.0 times (that is, 7 ⁇ 6 times), and a biaxial stretching temperature of 125 ° C.
  • the stretched gel sheet was introduced into a methylethylketone tank and sufficiently immersed in methylethylketone to extract and remove liquid paraffin, and then the methylethylketone was dried and removed to obtain a porous body.
  • the porous body was introduced into a TD tenter to perform heat setting (HS), and HS was performed at a heat setting temperature of 125 ° C. and a draw ratio of 1.8 times, and thereafter, a relaxation operation of 0.5 times in the TD direction (that is, The HS relaxation rate was 0.5 times). Furthermore, it was introduced into an ethanol bath (affinity treatment tank), dipped for 60 seconds and retained, and the affinity treatment of the heat-treated porous body was performed to obtain an affinity-treated porous body.
  • HS heat setting
  • Comparative Example I-1 25% caustic soda aqueous solution (temperature 80 ° C., pH 8.5-14), in Comparative Example I-2 10% hydrochloric acid aqueous solution (temperature 60 ° C., pH 1-6.5),
  • Each of the affinity-treated porous bodies was guided and stayed for 60 seconds while dwelling, and the affinity-treated porous body was subjected to a crosslinking treatment to obtain a crosslinked-treated porous body.
  • the crosslinked porous body was introduced into water (water washing treatment tank), dipped for 60 seconds and retained therein, and the crosslinked porous body was washed with water. This was introduced into a conveyor dryer and dried at 120 ° C. for 60 seconds to obtain a microporous membrane.
  • the obtained microporous membrane was cut at its end and wound as a mother roll having a width of 1,100 mm and a length of 5,000 m.
  • the microporous film unwound from the mother roll was slit as needed and used as an evaluation separator.
  • FIG. 3 shows the relationship between the temperature and the resistance of the battery provided with the microporous membrane obtained in Example I-1 as a separator. From FIG. 3 and Table 8, it can be seen that the shutdown temperature of the separator obtained in Example I-1 is 143 ° C. and the film rupture temperature is 200 ° C. or higher. Further, FIG. 13 shows the 1 H- and 13 C-NMR charts (b) of the separator obtained in Example I-1 in a state before crosslinking.
  • the “silane-modified polyethylene (B)” in Table 8 is obtained by a modification reaction with a trimethoxyalkoxide-substituted vinylsilane using a polyolefin having a viscosity average molecular weight of 20,000 as a raw material and has a density of 0.95 g / cm 3. And a melt flow rate (MFR) at 190 ° C. of 0.4 g / min.
  • MFR melt flow rate
  • the raw material polyolefin used for the silane-grafted modified polyolefin has a viscosity average molecular weight (Mv) of 100,000 or more and 1 million or less, a weight average molecular weight (Mw) of 30,000 or more and 920,000 or less, and a number average molecular weight of 10,000 or more. It may be 150,000 or less, an ethylene homopolymer, or a copolymerized ⁇ -olefin of ethylene with propylene or butene.
  • the residual concentration of unreacted trimethoxyalkoxide-substituted vinylsilane in the pellet is about 1500 ppm or less.
  • the silane-grafted modified polyethylene obtained by the above production method is used as “silane-modified polyethylene (B)” in Table 9.
  • Silane-modified polyethylene (B) 80% by weight of homopolymer polyethylene (polyethylene (A)) having a weight-average molecular weight of 700,000 and a polyolefin having a viscosity-average molecular weight of 10,000 as a raw material, MFR obtained by a modification reaction with trimethoxyalkoxide-substituted vinylsilane (190 ° C.
  • 1 mass% of lytyl-tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was added and dry blended using a tumbler blender to obtain a mixture. The obtained mixture was fed to a twin-screw extruder under a nitrogen atmosphere by a feeder.
  • Liquid paraffin (kinematic viscosity at 37.78 ° C.
  • the sheet-shaped molded product was introduced into a simultaneous biaxial tenter stretching machine and biaxially stretched to obtain a stretched product.
  • the set stretching conditions were MD magnification of 7.0 times, TD magnification of 6.2 times, and biaxial stretching temperature of 120 ° C.
  • the stretched gel sheet was introduced into a dichloromethane tank and sufficiently immersed in dichloromethane to extract and remove liquid paraffin, and then dichloromethane was dried and removed to obtain a porous body.
  • the porous body was introduced into a TD tenter to carry out heat setting (HS), and HS was carried out at a heat setting temperature of 133 ° C. and a draw ratio of 2.1 times, and thereafter, a relaxation operation was performed up to 2.0 times in the TD direction. It was After that, the obtained microporous membrane was cut at its end and wound as a mother roll having a width of 1,100 mm and a length of 5,000 m. At the time of the above evaluation, the microporous film unwound from the mother roll was slit as needed and used as an evaluation separator.
  • HS heat setting
  • Example II-1 As described in Table 9, Example II-1 except that the ratio of the amounts of components A and B, the presence or absence of (C) other resin as an additional component, the film physical properties, and the crosslinking method / conditions were changed. The same operation as above was performed to obtain the microporous membrane shown in Table 9.
  • component “PP” in Table 9 silane having a MFR of 2.5 g / 10 min or less and a density of 0.89 g / cm 3 or more measured under conditions of a temperature of 230 ° C. and a mass of 2.16 kg is used. Modified polypropylene was used.
  • the crosslinking method “alkali treatment crosslinking” in Table 9 the sample is treated with a 25% caustic soda aqueous solution (temperature 80 ° C., pH 8.5 to 14).
  • Example II-1 to II-8 and Comparative Example II-3 no film breakage was observed at the measurement limit temperature of 250 ° C.
  • Example II-1 and Comparative Example II-1 26 sheets having a thickness of 8 ⁇ m were stacked, and the storage elastic modulus, the loss elastic modulus, the film softening transition temperature, and the film rupture temperature under the condition of the total sample film thickness of 208 ⁇ m. was measured.
  • a separator for an electricity storage device that does not contain a silane-grafted modified polyolefin is polyethylene (PE): X (viscosity average molecular weight 100,000 to 400,000), PE: Y (viscosity average molecular weight 400,000 to 800,000). And PE: Z (viscosity average molecular weight 800,000 to 9,000,000), or any two kinds or three kinds selected from the group consisting of X, Y and Z. It can be manufactured in a composition mixed in proportion.
  • polyolefin comprised only with hydrocarbon skeletons, such as low-density polyethylene: LDPE, linear low-density polyethylene: LLDPE, polypropylene: PP, olefin system thermoplastic elastomer, to a mixed composition.
  • hydrocarbon skeletons such as low-density polyethylene: LDPE, linear low-density polyethylene: LLDPE, polypropylene: PP, olefin system thermoplastic elastomer
  • Crosslinking film As a separator for an electricity storage device after a silane crosslinking reaction (hereinafter referred to as “crosslinking film”), from the polyolefin microporous film of Example II-1 after contacting with the electrolytic solution described above, or from the cell after initial charge / discharge. The taken out polyolefin microporous membrane of Example II-1 was dried and used. The degree of gelation of the crosslinked film was 30% or more or 70% or more.
  • the raw material polyolefin used for the silane-grafted modified polyolefin has a viscosity average molecular weight (Mv) of 100,000 or more and 1,000,000 or less, a weight average molecular weight (Mw) of 30,000 or more and 920,000 or less, and a number average molecular weight of 10,000 or more and 15 or more. It may be 10,000 or less, and may be propylene or butene copolymerized ⁇ -olefin.
  • organic peroxide (di-t-butyl peroxide) was added to generate radicals in the ⁇ -olefin polymer chain, and then trimethoxyalkoxide-substituted vinylsilane was injected.
  • An alkoxysilyl group is introduced into the ⁇ -olefin polymer by an addition reaction to form a silane graft structure.
  • the residual concentration of unreacted trimethoxyalkoxide-substituted vinylsilane in the pellet is about 1000 to 1500 ppm.
  • the silane-grafted modified polyolefin obtained by the above production method is shown as "silane-modified polyethylene" in Tables 11 and 12.
  • Modified PEs and copolymers having various functional groups other than silane-modified PEs were produced by the following methods. The molecular weight of each raw material was adjusted so that MI was in the range of 0.5 to 10. The modified PE having a hydroxyl group was produced by saponifying and neutralizing the EVA copolymer. A modified resin such as amine-modified or oxazoline-modified causes the terminal vinyl group of PE polymerized using a chromium catalyst to act on a tungsten-based catalyst under hydrogen peroxide conditions to convert the vinyl group into an epoxy group.
  • a modified resin such as amine-modified or oxazoline-modified causes the terminal vinyl group of PE polymerized using a chromium catalyst to act on a tungsten-based catalyst under hydrogen peroxide conditions to convert the vinyl group into an epoxy group.
  • the target reaction site was converted into the target functional group by using the already known functional group-converting organic reaction to obtain various modified PEs.
  • modified PEs For example, in the case of amine-modified PE, primary or secondary amines are injected as a liquid while the modified PE having an epoxy group is melt-kneaded at 200 ° C. in an extruder to cause a reaction. Then, unreacted amines are removed from the pressure reducing valve, and the obtained amine-modified resin is extruded into a strand and cut into pellets.
  • the modified PE obtained by the above production method is shown in Tables 11 and 12 as one type of "modified PE or copolymer (B)".
  • Homopolymer polyethylene (A) having a weight average molecular weight of 500,000, 79.2% by weight, and polyolefin having a viscosity average molecular weight of 20,000 as a raw material, and MFR obtained by a modification reaction with trimethoxyalkoxide-substituted vinylsilane are 0.4 g. / Min of silane-grafted polyethylene (PE (B)) 19.8% by mass (the resin compositions of (A) and (B) are 0.8 and 0.2 respectively, and pentaerythrityl-tetrakis as an antioxidant.
  • the mixture and the liquid paraffin are melt-kneaded in the extruder, and the feeder and the pump are adjusted so that the ratio of the amount of the liquid paraffin in the extruded polyolefin composition is 70% (that is, the polymer concentration is 30% by mass).
  • the melt-kneading conditions were set temperature 220 ° C., screw rotation speed 240 rpm, and discharge rate 18 kg / h.
  • the melt-kneaded product was extruded through a T-die onto a cooling roll whose surface temperature was controlled at 25 ° C. and cast to obtain a gel sheet (sheet-shaped molded product) having an original film thickness of 1400 ⁇ m.
  • the sheet-shaped molded product was introduced into a simultaneous biaxial tenter stretching machine and biaxially stretched to obtain a stretched product.
  • the set stretching conditions were an MD magnification of 7.0 times, a TD magnification of 6.0 times (that is, 7 ⁇ 6 times), and a biaxial stretching temperature of 125 ° C.
  • the stretched gel sheet was introduced into a methylethylketone tank and sufficiently immersed in methylethylketone to extract and remove liquid paraffin, and then the methylethylketone was dried and removed to obtain a porous body.
  • the porous body is introduced into a TD tenter to perform heat setting (HS), and HS is performed at a heat setting temperature of 125 ° C.
  • the obtained microporous membrane was cut at its end and wound as a mother roll having a width of 1,100 mm and a length of 5,000 m.
  • the microporous film unwound from the mother roll was slit as needed and used as an evaluation separator.
  • Various evaluations were performed on the evaluation separator and the battery according to the above evaluation methods, and the evaluation results are shown in Table 11.
  • Examples III-2 to III-18 As described in Table 11 or Table 12, the same operations as in Example III-1 were performed except that the types, the ratio of the amounts of the resins A and B, and the crosslinking method / conditions were changed. The microporous membrane and battery shown in 12 were obtained. Various evaluations were performed on the obtained microporous membrane and battery according to the above evaluation methods, and the evaluation results are also shown in Table 11 or Table 12. In addition, in Examples III-8 to III-10 and III-15 to III-18, when the electrolytic solution was injected, the additives shown in Table 11 or Table 12 were dissolved in an appropriate amount in the electrolytic solution in advance. .
  • Example III-1 the microporous membrane shown in Table 12 was prepared in the same manner as in Example III-1, except that the types and ratios of resins A and B, and the crosslinking method and conditions were changed. Got Using the obtained microporous film, irradiation with a predetermined dose was carried out to carry out electron beam crosslinking. Various evaluations were performed on the obtained electron beam crosslinked microporous membrane and battery according to the above evaluation methods, and the evaluation results are also shown in Table 12.
  • Example III-2 For Comparative Example III-2 and Example III-1, a strain amount-crystal subdivision ratio graph is shown in FIG. 8 to observe changes in X-ray crystal structure during a tensile fracture test.
  • the microporous membrane of Comparative Example III-2 is represented by a dotted line “EB crosslink”
  • the microporous membrane of Example III-1 is represented by a solid line “before chemical crosslink” and a broken line “after chemical crosslink”. .
  • Silane-modified polyethylene is obtained by a modification reaction with trimethoxyalkoxide-substituted vinylsilane using polyolefin having a viscosity average molecular weight of 20,000 as a raw material, and has a density of 0.95 g / cm 3 and at 190 ° C. It is a silane-modified polyethylene having a melt flow rate (MFR) of 0.4 g / min.
  • MFR melt flow rate
  • Example IV-1 ⁇ Production of layer A> (Production of silane-grafted modified polyolefin) Polyethylene having a viscosity average molecular weight of 120,000 is used as a raw material polyethylene, and while the raw material polyethylene is melt-kneaded with an extruder, an organic peroxide (di-t-butyl peroxide) is added to generate radicals in the ⁇ -olefin polymer chain. After the generation, trimethoxyalkoxide-substituted vinylsilane was poured and an alkoxysilyl group was introduced into the ⁇ -olefin polymer by an addition reaction to form a silane graft structure.
  • an organic peroxide di-t-butyl peroxide
  • the residual concentration of unreacted trimethoxyalkoxide-substituted vinylsilane in the pellet was about 1500 ppm or less.
  • a silane-modified polyethylene having an MFR (190 ° C.) of 0.4 g / min was obtained by a modification reaction using trimethoxyalkoxide-substituted vinylsilane as described above.
  • the mixture and the liquid paraffin are melt-kneaded in the extruder, and the feeder and the pump are adjusted so that the ratio of the amount of the liquid paraffin in the extruded polyolefin composition is 70% (that is, the polymer concentration is 30% by mass).
  • the melt-kneading conditions were set temperature 220 ° C., screw rotation speed 240 rpm, and discharge rate 18 kg / hour.
  • the melt-kneaded product was extruded through a T-die onto a cooling roll whose surface temperature was controlled at 25 ° C. and cast to obtain a gel sheet (sheet-shaped molded product) having an original film thickness of 1400 ⁇ m.
  • the sheet-shaped molded product was introduced into a simultaneous biaxial tenter stretching machine and biaxially stretched to obtain a stretched product.
  • the set stretching conditions were an MD magnification of 7.0 times, a TD magnification of 6.3 times (that is, 7 ⁇ 6.3 times), and a biaxial stretching temperature of 122 ° C.
  • the stretched gel sheet was introduced into a dichloromethane tank and sufficiently immersed in dichloromethane to extract and remove liquid paraffin, and then dichloromethane was dried and removed to obtain a porous body.
  • the porous body was introduced into a TD tenter to perform heat setting (HS), and HS was performed at a heat setting temperature of 133 ° C.
  • microporous membrane was cut at its end and wound as a mother roll having a width of 1,100 mm and a length of 5,000 m.
  • the microporous film unwound from the mother roll was slit as needed and used as the A layer for evaluation.
  • the film thickness, air permeability, porosity and the like of the obtained evaluation A layer were measured and are shown in Table 13.
  • ⁇ Preparation of layer B> 95 parts by mass of aluminum hydroxide oxide (average particle size 1.4 ⁇ m) as inorganic particles, and 0.4 parts by mass (solid content) of ammonium polycarboxylate aqueous solution (SN Dispersant 5468 manufactured by San Nopco Ltd.) as an ionic dispersant. And a solid content concentration of 40%) were uniformly dispersed in 100 parts by mass of water to prepare a dispersion liquid. The obtained dispersion was crushed with a bead mill (cell volume 200 cc, zirconia beads diameter 0.1 mm, filling amount 80%), and the particle size distribution of inorganic particles was adjusted to D50 1.0 ⁇ m. A particle-containing slurry was prepared.
  • the microporous film is continuously fed from the microporous film mother roll, the inorganic particle-containing slurry is applied to one surface of the microporous film by a gravure reverse coater, and then dried by a dryer at 60 ° C. Was removed and wound to obtain a mother roll of a separator.
  • the separator unwound from the mother roll was slit as required and used as an evaluation separator.
  • Examples IV-2 to IV-5 and Comparative Examples IV-1 to IV-2 Aiming at the physical property values shown in Table 13, at least one of the weight average molecular weight of polyethylene, which is a homopolymer, set stretching conditions, heat setting conditions, and relaxation operation conditions was changed. In addition, the configuration in layer B was changed as described in Table 13. Except for these changes, a separator was produced in the same manner as in Example IV-1, and the obtained separator was used for the above evaluation. The evaluation results are shown in Table 13.
  • the raw material polyolefin used for the silane-grafted modified polyolefin has a viscosity average molecular weight (Mv) of 100,000 or more and 1 million or less, a weight average molecular weight (Mw) of 30,000 or more and 920,000 or less, and a number average molecular weight of 10,000 or more. It may be 150,000 or less, and propylene or butene copolymerized ⁇ -olefin may be used.
  • the residual concentration of unreacted trimethoxyalkoxide-substituted vinylsilane in the pellet is about 10 to 1500 ppm.
  • the silane-grafted modified polyolefin obtained by the above production method is used as “silane-modified polyethylene (B)” in Tables 14 to 16.
  • the silane-grafted modified polyolefin used this time has a density of 0.94 g / cm 3 and an MFR of 0.65 g / min.
  • Example V-1 (Formation of microporous membrane) MFR (190 ° C) obtained by a modification reaction of a homopolymer polyethylene (A) having a weight average molecular weight of 500,000 with 79.2% by weight of a polyolefin having a viscosity average molecular weight of 20,000 as a raw material and a trimethoxyalkoxide-substituted vinylsilane.
  • A homopolymer polyethylene
  • a polyolefin having a viscosity average molecular weight of 20,000 as a raw material and a trimethoxyalkoxide-substituted vinylsilane.
  • the mixture and the liquid paraffin are melt-kneaded in an extruder, and a feeder and a pump are used so that the ratio of the liquid paraffin in the extruded polyolefin composition is 70% by weight (that is, the polymer concentration is 30% by weight).
  • the melt-kneading conditions were set temperature 220 ° C., screw rotation speed 240 rpm, and discharge rate 18 kg / h.
  • the melt-kneaded product was extruded through a T-die onto a cooling roll whose surface temperature was controlled at 25 ° C. and cast to obtain a gel sheet (sheet-shaped molded product) having an original film thickness of 1400 ⁇ m.
  • the sheet-shaped molded product was introduced into a simultaneous biaxial tenter stretching machine and biaxially stretched to obtain a stretched product.
  • the set stretching conditions were an MD magnification of 7.0 times, a TD magnification of 6.0 times (that is, 7 ⁇ 6 times), and a biaxial stretching temperature of 125 ° C.
  • the stretched gel sheet was introduced into a methylethylketone tank and sufficiently immersed in methylethylketone to extract and remove liquid paraffin, and then the methylethylketone was dried and removed to obtain a porous body.
  • the porous body is introduced into a TD tenter to perform heat setting (HS), and HS is performed at a heat setting temperature of 125 ° C.
  • microporous membrane mother roll having a width of 1,100 mm and a length of 5,000 m.
  • the acrylic latex used as the resin binder is manufactured by the following method.
  • a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer 70.4 parts by mass of ion-exchanged water and "Aqualon KH1025" as an emulsifier (registered trademark, 25% aqueous solution manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by mass and 0.5 parts by mass of "Adecaria Soap SR1025" (registered trademark, 25% aqueous solution manufactured by ADEKA CORPORATION) were added.
  • the temperature inside the reaction vessel was raised to 80 ° C., and while maintaining the temperature at 80 ° C., 7.5 parts by mass of a 2% aqueous solution of ammonium persulfate was added to obtain an initial mixture.
  • a 2% aqueous solution of ammonium persulfate was added to obtain an initial mixture.
  • the emulsion was: 70 parts by mass of butyl acrylate; 29 parts by mass of methyl methacrylate; 1 part by mass of methacrylic acid; 3 parts by mass of "Aqualon KH1025" (registered trademark, 25% aqueous solution manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifier. And 5 parts by mass of "ADEKA REASOAP SR1025" (registered trademark, 25% aqueous solution manufactured by ADEKA Co., Ltd.); 2% aqueous solution of ammonium persulfate, 7.5 parts by mass; Prepared by mixing for minutes. After the dropping of the emulsion, the temperature inside the reaction vessel was maintained at 80 ° C.
  • the obtained acrylic latex had a number average particle diameter of 145 nm and a glass transition temperature of -23 ° C.
  • Examples V-2 to V-12, Comparative Example V-2 As described in Tables 14 to 16, the same operation as in Example V-1 was carried out except that the amount ratio of the components A and B, the presence or absence or composition of the inorganic layer, and the crosslinking method / conditions were changed. The microporous membranes shown in Tables 14 to 16 were obtained.
  • erythrityl-tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was added and dry blended using a tumbler blender to obtain a mixture.
  • the obtained mixture was fed to a twin-screw extruder under a nitrogen atmosphere by a feeder.
  • Liquid paraffin (kinematic viscosity at 37.78 ° C. 7.59 ⁇ 10 ⁇ 5 m 2 / s) was injected into the extruder cylinder by a plunger pump.
  • the mixture and the liquid paraffin are melt-kneaded in an extruder, and a feeder and a pump are used so that the ratio of the liquid paraffin in the extruded polyolefin composition is 70% by weight (that is, the polymer concentration is 30% by weight).
  • the melt-kneading conditions were set temperature 220 ° C., screw rotation speed 240 rpm, and discharge rate 18 kg / h.
  • the melt-kneaded product was extruded through a T-die onto a cooling roll whose surface temperature was controlled at 25 ° C. and cast to obtain a gel sheet (sheet-shaped molded product) having an original film thickness of 1400 ⁇ m.
  • the sheet-shaped molded product was introduced into a simultaneous biaxial tenter stretching machine and biaxially stretched to obtain a stretched product.
  • the set stretching conditions were an MD magnification of 7.0 times, a TD magnification of 6.0 times (that is, 7 ⁇ 6 times), and a biaxial stretching temperature of 125 ° C.
  • the stretched gel sheet was introduced into a methylethylketone tank and sufficiently immersed in methylethylketone to extract and remove liquid paraffin, and then the methylethylketone was dried and removed to obtain a porous body.
  • the porous body was introduced into a TD tenter to perform heat setting (HS), and HS was performed at a heat setting temperature of 125 ° C.
  • Comparative Example V-1 in order to use the heat-treated porous body as a separator, the end portion of the obtained porous body was cut and wound as a mother roll having a width of 1,100 mm and a length of 5,000 m. Regarding Comparative Example V-1, during the above evaluation, the microporous film unwound from the mother roll was slit as required and used as an evaluation separator.
  • Porous membranes were formed in the same manner as in Examples 1 to 3 and Comparative Examples 2 to 3 shown in Patent Document 5 (Japanese Patent Laid-Open No. 2001-176484) and labeled as porous membranes V-1 to V-5, respectively.
  • the gel fraction (%), the heat resistant temperature (° C) and the needle penetration strength (gf / 25 ⁇ m) were evaluated according to the method described in Patent Document 5, and further described in the above specification.
  • the separator according to the seventh embodiment of the present invention described above is valuable in selectively chemically crosslinking the amorphous zone between the crystal and the crystal part.
  • the silane-unmodified polyolefin and the silane-modified polyolefin form a mixed crystal, the modified units are repelled in the non-crystalline part and randomly dispersed. ..
  • the plurality of crosslinking units are far from each other, even if the crosslinking units are present, they cannot contribute to the crosslinking reaction.
  • the separator according to the seventh embodiment of the present invention the molecular weight of the raw material resin, the copolymer concentration, the blending ratio, etc. are adjusted, and further combined with the stretching film-forming step, the crosslinking reaction of the crosslinking unit is highly likely.

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PCT/JP2019/040343 2018-10-11 2019-10-11 架橋セパレータを用いたリチウムイオン電池 Ceased WO2020075866A1 (ja)

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EP23166690.0A EP4224613A3 (en) 2018-10-11 2019-10-11 Lithium ion battery using crosslinked separator
KR1020227039349A KR102601002B1 (ko) 2018-10-11 2019-10-11 가교 세퍼레이터를 사용한 리튬 이온 전지
EP23176183.4A EP4235940A3 (en) 2018-10-11 2019-10-11 Lithium ion battery using crosslinkable separator
KR1020207012551A KR102435806B1 (ko) 2018-10-11 2019-10-11 가교 세퍼레이터를 사용한 리튬 이온 전지
CN202210749649.8A CN114976483A (zh) 2018-10-11 2019-10-11 使用交联分隔件的锂离子电池
EP22169052.2A EP4064443B1 (en) 2018-10-11 2019-10-11 Lithium ion battery using crosslinkable separator
EP23176153.7A EP4235939A3 (en) 2018-10-11 2019-10-11 Lithium ion battery using crosslinkable separator
KR1020217034635A KR102467607B1 (ko) 2018-10-11 2019-10-11 가교 세퍼레이터를 사용한 리튬 이온 전지
CN202210750993.9A CN115051117B (zh) 2018-10-11 2019-10-11 使用交联分隔件的锂离子电池
EP23176156.0A EP4235934A3 (en) 2018-10-11 2019-10-11 Lithium ion battery using crosslinkable separator
JP2020507143A JP6898512B2 (ja) 2018-10-11 2019-10-11 架橋セパレータを用いたリチウムイオン電池
EP23157951.7A EP4220844A3 (en) 2018-10-11 2019-10-11 Lithium ion battery using crosslinked separator
CN202210752468.0A CN115036645B (zh) 2018-10-11 2019-10-11 使用交联分隔件的锂离子电池
KR1020227015370A KR102611025B1 (ko) 2018-10-11 2019-10-11 가교 세퍼레이터를 사용한 리튬 이온 전지
EP23176142.0A EP4235933A3 (en) 2018-10-11 2019-10-11 Lithium ion battery using crosslinkable separator
KR1020237021105A KR102632166B1 (ko) 2018-10-11 2019-10-11 가교 세퍼레이터를 사용한 리튬 이온 전지
EP24174823.5A EP4425682A1 (en) 2018-10-11 2019-10-11 Lithium ion battery using crosslinked separator
KR1020217034639A KR102466829B1 (ko) 2018-10-11 2019-10-11 가교 세퍼레이터를 사용한 리튬 이온 전지
EP22169029.0A EP4068488A1 (en) 2018-10-11 2019-10-11 Lithium ion battery using crosslinkable separator
KR1020247011220A KR102834252B1 (ko) 2018-10-11 2019-10-11 가교 세퍼레이터를 사용한 리튬 이온 전지
CN202211419385.6A CN115642366A (zh) 2018-10-11 2019-10-11 使用交联分隔件的锂离子电池
KR1020237021108A KR102655732B1 (ko) 2018-10-11 2019-10-11 가교 세퍼레이터를 사용한 리튬 이온 전지
CN202211426208.0A CN115799602A (zh) 2018-10-11 2019-10-11 使用交联分隔件的锂离子电池
CN201980007742.8A CN111630687B (zh) 2018-10-11 2019-10-11 使用交联分隔件的锂离子电池
KR1020217034641A KR102384050B1 (ko) 2018-10-11 2019-10-11 가교 세퍼레이터를 사용한 리튬 이온 전지
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CN202410842338.5A CN118630423A (zh) 2018-10-11 2019-10-11 使用交联分隔件的锂离子电池
US16/957,421 US11588208B2 (en) 2018-10-11 2019-10-11 Lithium ion battery using crosslinkable separator
KR1020237004268A KR102609222B1 (ko) 2018-10-11 2019-10-11 가교 세퍼레이터를 사용한 리튬 이온 전지
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CN202211425326.XA CN115810870A (zh) 2018-10-11 2019-10-11 使用交联分隔件的锂离子电池
CN202210751481.4A CN115051106B (zh) 2018-10-11 2019-10-11 使用交联分隔件的锂离子电池
KR1020217034638A KR102466827B1 (ko) 2018-10-11 2019-10-11 가교 세퍼레이터를 사용한 리튬 이온 전지
KR1020237004271A KR102609224B1 (ko) 2018-10-11 2019-10-11 가교 세퍼레이터를 사용한 리튬 이온 전지
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