JP6334568B2 - 分離膜の製造方法とその分離膜及びこれを用いた電池 - Google Patents
分離膜の製造方法とその分離膜及びこれを用いた電池 Download PDFInfo
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- JP6334568B2 JP6334568B2 JP2015555912A JP2015555912A JP6334568B2 JP 6334568 B2 JP6334568 B2 JP 6334568B2 JP 2015555912 A JP2015555912 A JP 2015555912A JP 2015555912 A JP2015555912 A JP 2015555912A JP 6334568 B2 JP6334568 B2 JP 6334568B2
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- Prior art keywords
- separation membrane
- stretching
- transverse
- polyolefin
- shrinkage
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
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Description
ポリオレフィン系樹脂及びダイリュエントを含む組成物を溶融・混練して押出し、冷却・固形化されたシートを形成する。ポリオレフィン系樹脂及びダイリュエントを含む組成物の溶融・混練は、当業者に知られている方法を用いて行ってもよい。
続いて、前記の固形化されたシートを延伸する工程を行う。本発明の一例にかかる分離膜の製造方法は、ダイリュエント抽出前に延伸工程を行うことによって、ダイリュエントによるポリオレフィンの柔軟化によって延伸作業がより容易になり、その結果、生産安定性を高めることができる。また、延伸によってシートの厚さが薄くなった結果、延伸後、抽出過程でシートからダイリュエントをより容易に除去することができる。
続いて、ダイリュエントを抽出して乾燥することができる。具体的に、MD延伸及び1次TD延伸されたフィルムを有機溶媒に浸漬してダイリュエントを抽出した後、エアナイフ(air knife)を通じて乾燥することができる。前記有機溶媒は、メチレンクロライド、1,1,1―トリクロロエタン、フルオロカーボン系などのハロゲン化炭化水素類、n―へキサン、シクロヘキサンなどの炭化水素類、エタノール、イソプロパノールなどのアルコール類、アセトン、メチルエチルケトン、2―ブタノンなどのケトン類であってもよいが、これに制限されることはない。ダイリュエントとして流動パラフィンを使用する場合は、メチレンクロライドを有機溶媒として使用してもよい。可塑剤を抽出する工程で使用する有機溶媒は、揮発性が高く、有毒なものがほとんどであるので、必要に応じて、有機溶媒の揮発を抑制するために水を使用してもよい。
前記2次横延伸を行うとき、分離膜を横方向に延伸する延伸倍率は、1次横延伸された分離膜の横方向の幅をLとしたとき、前記分離膜の横方向幅が1.1L以上になるように延伸してもよく、具体的には、1.1L〜1.8L、より具体的には、1.1L〜1.5Lになるように延伸してもよい。
重量平均分子量が600000g/molである高密度ポリエチレン(High―density polyethylene、HDPE;Mitsui chemical社製品)25.5重量%、及び重量平均分子量が2,400,000g/molである超高分子量ポリエチレン(Ultra High Molecular Weight Polyethylene、UHMWPE;Mitsui chemical社製)4.5重量%を混合した混合樹脂、及び液体パラフィン(LP)(極東油化製)70重量%を二軸押出器に注入して押出した。
前記実施例1において、前記2次横延伸工程で、乾燥されたフィルムを横方向に延伸倍率が1.4Lになるように横延伸した後、これを横方向に延伸倍率が1.2Lになるように横収縮することを除いては、前記実施例1と同一の方法で分離膜を製造した。
前記実施例1において、前記2次横延伸工程で、乾燥されたフィルムを横方向に延伸倍率が1.2Lになるように横延伸した後、これを横方向に延伸倍率が1.0Lになるように横収縮することを除いては、前記実施例1と同一の方法で分離膜を製造した。
前記実施例1において、前記2次横延伸工程で、乾燥されたフィルムを横方向に延伸倍率が1.1Lになるように横延伸した後、これを横方向に延伸倍率が1.0Lになるように横収縮することを除いては、前記実施例1と同一の方法で分離膜を製造した。
前記実施例1において、前記2次横延伸工程で、乾燥されたフィルムを横方向に延伸倍率が1.2Lになるように横延伸した後、これを横方向に延伸倍率が1.1Lになるように横収縮することを除いては、前記実施例1と同一の方法で分離膜を製造した。
前記実施例1において、前記2次横延伸工程で、乾燥されたフィルムを横方向に延伸倍率が1.1Lになるように横延伸した後、これを横方向に延伸倍率が0.9Lになるように横収縮することを除いては、前記実施例1と同一の方法で分離膜を製造した。
前記実施例1において、前記2次横延伸工程で、乾燥されたフィルムを横方向に延伸倍率が1.1Lになるように横延伸を行い、別途の横収縮を行わないことを除いては、前記実施例1と同一の方法で分離膜を製造した。
分離膜の通気度測定
前記実施例1〜6及び比較例1で製造された各分離膜の通気度を測定するために、次のような実験を行った。
分離膜の突き強度測定
前記実施例1〜6及び比較例1で製造された分離膜の突き強度を測定するために、次のような実験を行った。
分離膜の引張強度測定
前記実施例1〜6及び比較例1で製造された分離膜の引張強度を測定するために、次のような実験を行った。
分離膜の熱収縮率測定
前記実施例1〜6及び比較例1で製造された分離膜の熱収縮率を測定するために、次のような実験を行った。
分離膜の溶融収縮率測定
前記実施例1〜6及び比較例1で製造された分離膜の溶融収縮率を測定するために、次のような実験を行った。
Claims (12)
- TMAによる分離膜の縦方向溶融収縮率(a)に対する横方向溶融収縮率(b)の比(b/a)が1.2以下であり、
前記縦方向溶融収縮率が25%以上28%以下であり、
前記横方向溶融収縮率が18%以上33%以下であり、
縦方向引張強度(x)が2004kgf/cm 2 以上2440kgf/cm 2 以下であり、
横方向引張強度(y)が1570kgf/cm 2 以上2200kgf/cm 2 以下である、ポリオレフィン系分離膜。 - 前記縦方向引張強度(x)に対する前記横方向引張強度(y)の比(y/x)が0.7〜1である、請求項1に記載のポリオレフィン系分離膜。
- 前記分離膜の通気度が350sec/100cc以下である、請求項1または2に記載のポリオレフィン系分離膜。
- 前記分離膜の突き強度が700gf以上である、請求項1から3のいずれか1項に記載のポリオレフィン系分離膜。
- 前記分離膜の105℃で1時間放置した後の熱収縮率が縦方向及び横方向にそれぞれ4%未満である、請求項1から4のいずれか1項に記載のポリオレフィン系分離膜。
- 分離膜を縦延伸及び横延伸し、
前記横延伸された分離膜から応力を除去するために横収縮させることを含み、
横延伸は、1次横延伸及び2次横延伸を含み
前記の1次横延伸された分離膜の横方向幅をLとしたとき、
前記2次横延伸は、前記分離膜の横方向幅が1.1L以上になるように横延伸し、
前記横収縮は、分離膜の横方向幅が0.9L以上1.3L未満になるように横収縮させることを含むポリオレフィン系分離膜の製造方法。 - 縦延伸倍率(L1)に対する1次横延伸倍率(L2)の比は1.1〜1.8である、請求項6に記載のポリオレフィン系分離膜の製造方法。
- 前記縦延伸及び横延伸される分離膜は、
ポリオレフィン系樹脂及びダイリュエントを含む組成物を押出器に注入して押出し、
前記押出後に得られたゲル相をキャスティングしてシートに製造されたものである、請求項6または7に記載のポリオレフィン系分離膜の製造方法。 - 前記縦延伸及び横延伸は、分離膜を縦延伸及び1次横延伸し、延伸された分離膜からダイリュエントを抽出及び乾燥し、前記の乾燥された分離膜を2次横延伸することを含む、請求項8に記載のポリオレフィン系分離膜の製造方法。
- 前記2次横延伸は110℃〜140℃の温度で行われる、請求項6から9のいずれか1項に記載のポリオレフィン系分離膜の製造方法。
- 正極、負極、分離膜及び電解質を含み、
前記分離膜は、請求項1から5のいずれか1項のポリオレフィン系分離膜である電気化学電池。 - 前記電気化学電池はリチウム二次電池である、請求項11に記載の電気化学電池。
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US20150380705A1 (en) | 2015-12-31 |
KR20140098349A (ko) | 2014-08-08 |
CN111668428A (zh) | 2020-09-15 |
KR101611229B1 (ko) | 2016-04-11 |
US10340491B2 (en) | 2019-07-02 |
CN111668428B (zh) | 2023-04-07 |
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