JP2016139622A5 - - Google Patents
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- JP2016139622A5 JP2016139622A5 JP2016086501A JP2016086501A JP2016139622A5 JP 2016139622 A5 JP2016139622 A5 JP 2016139622A5 JP 2016086501 A JP2016086501 A JP 2016086501A JP 2016086501 A JP2016086501 A JP 2016086501A JP 2016139622 A5 JP2016139622 A5 JP 2016139622A5
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- Prior art keywords
- separator
- storage device
- thermoplastic polymer
- glass transition
- electricity storage
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- 229920001169 thermoplastic Polymers 0.000 claims description 26
- 230000005611 electricity Effects 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 15
- 239000011888 foil Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- -1 aromatic vinyl compound Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000002522 swelling Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 2
- 239000000758 substrate Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 1
Description
すなわち、本発明は下記のとおりである。
［１］ポリオレフィン微多孔膜からなる基材と、その基材の少なくとも片面上の少なくとも一部に形成された熱可塑性ポリマーを含有する層と、を備える蓄電デバイス用セパレータであって、
前記熱可塑性ポリマーがガラス転移温度を少なくとも２つ有しており、
前記ガラス転移温度のうち少なくとも１つは２０℃未満の領域に存在し、
前記ガラス転移温度のうち少なくとも１つは２０℃以上の領域に存在し、
前記ガラス転移温度が２０℃以上の領域に存在する熱可塑性ポリマーが、芳香族ビニル化合物単量体と（メタ）アクリル酸エステル単量体とを単量体単位として有する共重合体を含む、蓄電デバイス用セパレータ。
［２］下記（１）及び（２）の少なくとも一方の剥離強度が、４ｍＮ／ｍｍ以上である、上記蓄電デバイス用セパレータ。
（１）アルミニウム箔（冨士加工紙（株）製アルミニウム箔、厚さ：２０μｍ）に、エチレンカーボネートとジエチルカーボネートとを２：３の比率（体積比）にて混合した電解液に濡らした前記蓄電デバイス用セパレータを、前記熱可塑性ポリマーを含有する層の側から重ね合わせ、それらを重ね合わせた方向に８０℃、１０ＭＰａの圧力で２分間加圧した後、前記アルミニウム箔と前記蓄電デバイス用セパレータとの間を引張速度５０ｍｍ／分で剥離した際の９０°剥離強度。
（２）アルミニウム箔（冨士加工紙（株）製アルミニウム箔、厚さ：２０μｍ）に、前記蓄電デバイス用セパレータを、前記熱可塑性ポリマーを含有する層の側から重ね合わせ、それらを重ね合わせた方向に８０℃、１０ＭＰａの圧力で２分間加圧した後、前記アルミニウム箔と前記蓄電デバイス用セパレータとの間を引張速度５０ｍｍ／分で剥離した際の９０°剥離強度。
［３］下記（３）の剥離強度が４０ｍＮ／ｍｍ以下である、上記蓄電デバイス用セパレータ。
（３）重ね合わせた２０ｍｍ×１００ｍｍの前記セパレータ２枚と、それらのセパレターを挟んだ２枚のＰＴＦＥシートとを備えるサンプルを、温度２５℃、圧力１０ＭＰａの条件で２分間加圧した後、前記サンプルにおけるセパレータ同士を引張速度５０ｍｍ／分で剥離した際の９０°剥離強度。
［４］前記（メタ）アクリル酸エステル単量体が、（メタ）アクリル酸の炭化水素エステルを含む、上記蓄電デバイス用セパレータ。
［５］前記共重合体が有する、前記７４０ｃｍ-1〜７７０ｃｍ-1の波長における赤外吸収ピーク強度に対する１７２０ｃｍ-1〜１７５０ｃｍ-1の波長における赤外吸収ピーク強度の比が、１〜１８である、上記蓄電デバイス用セパレータ。
［６］エチレンカーボネートとジエチルカーボネートとの混合溶媒（質量比２：３）に対する前記共重合体の膨潤度が０．５倍〜６．０倍である、上記蓄電デバイス用セパレータ。
［７］前記共重合体は、更に炭素原子数が４以上の鎖状アルキル基を有する単量体及びシクロアルキル基を有する単量体からなる群より選ばれる１種以上の単量体を単量体単位として有する、上記蓄電デバイス用セパレータ。
［８］前記熱可塑性ポリマーは、ガラス転移温度が２０℃未満の領域に存在する熱可塑性ポリマーと、ガラス転移温度が２０℃以上の領域に存在する熱可塑性ポリマーと、を含み、
前記ガラス転移温度が２０℃未満の領域に存在する熱可塑性ポリマーと、前記ガラス転移温度が２０℃以上の領域に存在する熱可塑性ポリマーとの混合比が、質量基準で５０：５０〜５：９５である、上記記載の蓄電デバイス用セパレータ。
［９］前記熱可塑性ポリマーを含有する層に含まれる熱可塑性ポリマーの少なくとも１つのガラス転移温度が、２０℃以上１２０℃以下である、上記蓄電デバイス用セパレータ。
［１０］前記熱可塑性ポリマーを含有する層の担持量は、固形分として０．０５ｇ/ｍ 2 以上１．５０ｇ/ｍ 2 以下である、上記蓄電デバイス用セパレータ。
［１１］上記蓄電デバイス用セパレータを備える蓄電デバイス。
［１２］上記蓄電デバイス用セパレータを備えるリチウムイオン二次電池。
That is, the present invention is as follows.
[1] An electricity storage device separator comprising: a substrate comprising a polyolefin microporous membrane ; and a layer containing a thermoplastic polymer formed on at least a part of at least one surface of the substrate,
The thermoplastic polymer has at least two glass transition temperatures;
At least one of the glass transition temperatures is in a region below 20 ° C .;
At least one of the glass transition temperatures is present in a region of 20 ° C. or higher,
The electrical storage in which the thermoplastic polymer present in the region having a glass transition temperature of 20 ° C. or higher includes a copolymer having an aromatic vinyl compound monomer and a (meth) acrylate monomer as monomer units. Device separator.
[2] The separator for an electricity storage device, wherein the peel strength of at least one of the following (1) and (2) is 4 mN / mm or more.
(1) The above-mentioned electricity storage wetted with an electrolytic solution obtained by mixing ethylene foil and diethyl carbonate at a ratio (volume ratio) of 2: 3 to aluminum foil (aluminum foil manufactured by Fuji Process Paper Co., Ltd., thickness: 20 μm). The device separator is overlapped from the thermoplastic polymer-containing layer side, pressed in the overlapping direction at 80 ° C. and a pressure of 10 MPa for 2 minutes, the aluminum foil and the electricity storage device separator, 90 ° peel strength when peeled at a tensile rate of 50 mm / min.
(2) A direction in which the separator for an electricity storage device is overlapped on an aluminum foil (aluminum foil manufactured by Fuji Processed Paper Co., Ltd., thickness: 20 μm) from the layer containing the thermoplastic polymer, and the layers are overlapped. 90 ° peel strength when the aluminum foil and the electricity storage device separator were peeled at a tensile rate of 50 mm / min after pressing at 80 ° C. and a pressure of 10 MPa for 2 minutes.
[3] The above separator for an electricity storage device, wherein the peel strength of (3) below is 40 mN / mm or less.
(3) After pressurizing a sample comprising two stacked 20 mm × 100 mm separators and two PTFE sheets sandwiching the separators at a temperature of 25 ° C. and a pressure of 10 MPa for 2 minutes, 90 ° peel strength when the separators in the sample are peeled at a tensile speed of 50 mm / min.
[ 4 ] The above separator for an electricity storage device, wherein the (meth) acrylic acid ester monomer contains a hydrocarbon ester of (meth) acrylic acid.
[5] The copolymer has a ratio of the infrared absorption peak intensity at a wavelength of 1720cm -1 ~1750cm -1 for infrared absorption peak intensity at a wavelength of the 740cm -1 ~770cm -1 is in 1 to 18 The said separator for electrical storage devices.
[ 6 ] The above separator for an electricity storage device, wherein the degree of swelling of the copolymer with respect to a mixed solvent of ethylene carbonate and diethyl carbonate (mass ratio 2: 3) is 0.5 times to 6.0 times.
[ 7 ] The copolymer further comprises at least one monomer selected from the group consisting of a monomer having a chain alkyl group having 4 or more carbon atoms and a monomer having a cycloalkyl group. The said separator for electrical storage devices which has as a monomer unit.
[8] The thermoplastic polymer includes a thermoplastic polymer present in a region where the glass transition temperature is less than 20 ° C, and a thermoplastic polymer present in a region where the glass transition temperature is 20 ° C or higher.
The mixing ratio of the thermoplastic polymer present in the region where the glass transition temperature is less than 20 ° C. and the thermoplastic polymer present in the region where the glass transition temperature is 20 ° C. or higher is 50:50 to 5:95 on a mass basis. The separator for an electricity storage device as described above.
[9] The above separator for an electricity storage device, wherein at least one glass transition temperature of the thermoplastic polymer contained in the layer containing the thermoplastic polymer is 20 ° C. or higher and 120 ° C. or lower.
[10] supported amount of the layer containing said thermoplastic polymer is 0.05 g / m 2 or more 1.50 g / m 2 or less as a solid, separator the electric storage device.
[11 ] An electricity storage device comprising the above electricity storage device separator.
[ 12 ] A lithium ion secondary battery provided with the separator for an electricity storage device.
Claims (12)
前記熱可塑性ポリマーがガラス転移温度を少なくとも２つ有しており、
前記ガラス転移温度のうち少なくとも１つは２０℃未満の領域に存在し、
前記ガラス転移温度のうち少なくとも１つは２０℃以上の領域に存在し、
前記ガラス転移温度が２０℃以上の領域に存在する熱可塑性ポリマーが、芳香族ビニル化合物単量体と（メタ）アクリル酸エステル単量体とを単量体単位として有する共重合体を含む、蓄電デバイス用セパレータ。 A separator for an electricity storage device comprising: a base material comprising a polyolefin microporous film ; and a layer containing a thermoplastic polymer formed on at least a part of at least one side of the base material,
The thermoplastic polymer has at least two glass transition temperatures;
At least one of the glass transition temperatures is in a region below 20 ° C .;
At least one of the glass transition temperatures is present in a region of 20 ° C. or higher,
The electrical storage in which the thermoplastic polymer present in the region having a glass transition temperature of 20 ° C. or higher includes a copolymer having an aromatic vinyl compound monomer and a (meth) acrylate monomer as monomer units. Device separator.
（１）アルミニウム箔（冨士加工紙（株）製アルミニウム箔、厚さ：２０μｍ）に、エチレンカーボネートとジエチルカーボネートとを２：３の比率（体積比）にて混合した電解液に濡らした前記蓄電デバイス用セパレータを、前記熱可塑性ポリマーを含有する層の側から重ね合わせ、それらを重ね合わせた方向に８０℃、１０ＭＰａの圧力で２分間加圧した後、前記アルミニウム箔と前記蓄電デバイス用セパレータとの間を引張速度５０ｍｍ／分で剥離した際の９０°剥離強度。(1) The above-mentioned electricity storage wetted with an electrolytic solution obtained by mixing ethylene foil and diethyl carbonate at a ratio (volume ratio) of 2: 3 to aluminum foil (aluminum foil manufactured by Fuji Process Paper Co., Ltd., thickness: 20 μm). The device separator is overlapped from the thermoplastic polymer-containing layer side, pressed in the overlapping direction at 80 ° C. and a pressure of 10 MPa for 2 minutes, the aluminum foil and the electricity storage device separator, 90 ° peel strength when peeled at a tensile rate of 50 mm / min.
（２）アルミニウム箔（冨士加工紙（株）製アルミニウム箔、厚さ：２０μｍ）に、前記蓄電デバイス用セパレータを、前記熱可塑性ポリマーを含有する層の側から重ね合わせ、それらを重ね合わせた方向に８０℃、１０ＭＰａの圧力で２分間加圧した後、前記アルミニウム箔と前記蓄電デバイス用セパレータとの間を引張速度５０ｍｍ／分で剥離した際の９０°剥離強度。(2) A direction in which the separator for an electricity storage device is overlapped on an aluminum foil (aluminum foil manufactured by Fuji Processed Paper Co., Ltd., thickness: 20 μm) from the layer containing the thermoplastic polymer, and the layers are overlapped. 90 ° peel strength when the aluminum foil and the electricity storage device separator were peeled at a tensile rate of 50 mm / min after pressing at 80 ° C. and a pressure of 10 MPa for 2 minutes.
（３）重ね合わせた２０ｍｍ×１００ｍｍの前記セパレータ２枚と、それらのセパレターを挟んだ２枚のＰＴＦＥシートとを備えるサンプルを、温度２５℃、圧力１０ＭＰａの条件で２分間加圧した後、前記サンプルにおけるセパレータ同士を引張速度５０ｍｍ／分で剥離した際の９０°剥離強度。(3) After pressurizing a sample comprising two stacked 20 mm × 100 mm separators and two PTFE sheets sandwiching the separators at a temperature of 25 ° C. and a pressure of 10 MPa for 2 minutes, 90 ° peel strength when the separators in the sample are peeled at a tensile speed of 50 mm / min.
前記ガラス転移温度が２０℃未満の領域に存在する熱可塑性ポリマーと、前記ガラス転移温度が２０℃以上の領域に存在する熱可塑性ポリマーとの混合比が、質量基準で５０：５０〜５：９５である、請求項１〜７のいずれか１項に記載の蓄電デバイス用セパレータ。The mixing ratio of the thermoplastic polymer present in the region where the glass transition temperature is less than 20 ° C. and the thermoplastic polymer present in the region where the glass transition temperature is 20 ° C. or higher is 50:50 to 5:95 on a mass basis. The electrical storage device separator according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016086501A JP6630620B2 (en) | 2016-04-22 | 2016-04-22 | Power storage device separator, power storage device, and lithium ion secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016086501A JP6630620B2 (en) | 2016-04-22 | 2016-04-22 | Power storage device separator, power storage device, and lithium ion secondary battery |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014014829A Division JP2015141840A (en) | 2014-01-29 | 2014-01-29 | Separator for power storage device, power storage device, and lithium ion secondary battery |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018105149A Division JP2018170281A (en) | 2018-05-31 | 2018-05-31 | Separator for power storage device, power storage device, and lithium ion secondary battery |
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| Publication Number | Publication Date |
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| JP2016139622A JP2016139622A (en) | 2016-08-04 |
| JP2016139622A5 true JP2016139622A5 (en) | 2017-02-23 |
| JP6630620B2 JP6630620B2 (en) | 2020-01-15 |
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| JP2024006988A (en) | 2022-06-30 | 2024-01-17 | 住友化学株式会社 | Laminate separator for non-aqueous electrolyte secondary battery |
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| EP2485295B1 (en) * | 2009-09-30 | 2019-03-20 | Zeon Corporation | Porous membrane for secondary battery, and secondary battery |
| WO2013047853A1 (en) * | 2011-09-26 | 2013-04-04 | 住友化学株式会社 | Adhesive resin composition for secondary battery |
| EP2835844B1 (en) * | 2012-04-05 | 2018-11-14 | Zeon Corporation | Separator for secondary cell |
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