TW589757B - Multilayer battery separators - Google Patents

Multilayer battery separators Download PDF

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Publication number
TW589757B
TW589757B TW92103675A TW92103675A TW589757B TW 589757 B TW589757 B TW 589757B TW 92103675 A TW92103675 A TW 92103675A TW 92103675 A TW92103675 A TW 92103675A TW 589757 B TW589757 B TW 589757B
Authority
TW
Taiwan
Prior art keywords
battery separator
layers
layer
film
patent application
Prior art date
Application number
TW92103675A
Other languages
English (en)
Other versions
TW200306030A (en
Inventor
Ronald W Call
Donald K Simmons
Ta-Hua Yu
Original Assignee
Celgard Inc
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Publication date
Application filed by Celgard Inc filed Critical Celgard Inc
Publication of TW200306030A publication Critical patent/TW200306030A/zh
Application granted granted Critical
Publication of TW589757B publication Critical patent/TW589757B/zh

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/28—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving assembly of non-flat intermediate products which are flattened at a later step, e.g. tubes
    • 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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/185—Articles comprising two or more components, e.g. co-extruded layers the components being layers comprising six or more components, i.e. each component being counted once for each time it is present, e.g. in a layer
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • 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
    • H01M50/406—Moulding; Embossing; Cutting
    • H—ELECTRICITY
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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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/80—General aspects of machine operations or constructions and parts thereof
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    • B29C66/834—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools moving with the parts to be joined
    • B29C66/8341—Roller, cylinder or drum types; Band or belt types; Ball types
    • B29C66/83411—Roller, cylinder or drum types
    • B29C66/83413—Roller, cylinder or drum types cooperating rollers, cylinders or drums
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    • B29C66/90—Measuring or controlling the joining process
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    • B29C66/914—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9141—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C66/9141—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
    • B29C66/91421—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature of the joining tools
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/90—Measuring or controlling the joining process
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    • B29C66/9161—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the heat or the thermal flux, i.e. the heat flux
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    • B29C66/91643—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the heat or the thermal flux, i.e. the heat flux the heat or the thermal flux being non-constant over time following a heat-time profile
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
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    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/00—Stock material or miscellaneous articles
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Description

589757 ⑴ 玖、發明說明 (發明說明應敘明··發明所屬之技術領域、先前技術、内容、實施方式及圖式簡單說用) 相關前案 本發明係於2 0 0 〇年1月1 8日申請之共同審查中之申請序 號第〇9M84，184號的接續案。 技術領域
本發明係關於一種電池分隔器，更明確地說，係關於一 種具有改良的強度特性之電池分隔器以及其製備方法。 微孔型薄膜電池分隔器係使用於多種電池中，特別是可 充電電池，例如鋰電池。這樣的電池分隔器容許電解質跨 越該電池分隔器，但同時避免相反極性的電極之間發生接 觸。通常，該微孔型薄膜含有一或多個微孔型薄膜層。
在鋰電池中，特別是二次鋰電池（可充電鋰電池），會發 生過熱的問題並導致電池產生熱失控（thermal runaway) 現象。因此，關閉分隔器（shutdown separators)係經發展 以避免產生熱失控現象。參見例如美國專利第4，6 5 0，7 3 0 號以及美國專利第4，7 3 1，3 0 4號。一關閉電池分隔器具有 一微孔型薄膜，其可在實質上比能夠導致該鋰電池產生熱 失控現象的溫度低的溫度下關閉其微孔型。 一些多層關閉分隔器係此技藝中已知。例如，美國專利 第4,6 50，730號揭示一種具有一未填充的微孔型薄片以及 一填充的微孔型薄片之雙層電池分隔器。每一個薄片分別 藉由使用適合的溶劑之萃取法（extraction process)來形成 。該兩個微孔型薄片然後被層積在一起以形成該關閉分隔 (2)
器。
Celgard®電池分隔器，其已商品化許多年，通常係由二 拉伸法（stretch method)來形成。例如，一無孔的管狀聚丙 烯薄膜先利用p入膜擦製法（bl〇wn film extrusion)形成。該 管狀薄膜係陷落於自身中，以形成一具有兩個聚丙晞層之 播孔平板。選擇性地，該沖模組合體（die asseinbiy)被緩 慢旋轉’稍微擠製該管狀薄膜以避免並去除縐折和不平均 分佈’因此該薄膜的表面在實質上是平·整的。該平板然後 被回火並拉伸以在其内產生微孔型性。該兩個微孔型平板 然後被去膠合（de-plied)成為兩層微孔型電池分隔器。通 常’該平板内兩個層之間的附著力必須夠低以使該兩個層 可以被分開而不損害到該等層。但是，當預期的是一具有 兩層微孔型聚丙晞薄膜的分隔器時，該附著力可以更高， 例如，5公克/英吋（grams/inch)至約35公克/英对，其可以 利用，例如，在陷落該管狀薄膜之後接合該等層來產生。 美國專利第5,691，077號揭示一三層電池分隔器β在其 中揭示的一較佳實施例内，該分離器具有一聚丙晞-聚丙 晞-聚丙烯結構，並且係由層積並接合微孔型層製得。每 一個微孔型層係由一如上所述牵涉一去膠合步驟的 Celgard⑧製程形成。 美國專利弟5,691，047號也揭tjt 一微孔型三層電池分隔 器，其具有一聚丙烯-聚乙埽-聚丙烯結構。複數個無孔 單層前驅物先利用铸模擠製法（cast extrusion)來擠製成 形。該等無孔單層被層積並接合在一起成為一聚丙埽—聚 589757
(3) 乙晞-聚丙埽結構的前驅物。該前驅物然後被回火並拉伸 以形成一微孔型三層電池分隔器。 一 一些製造多層電池分隔器的共擠製製程也被提出。例如 ，英國專利公開案第GB 2,29 8,8 1 7號描述一微孔型三層電 · 池分隔器，其係利用一 T型模（T _ die)來共擠製一具有一 - 無孔聚丙缔〜聚乙埽-聚丙埽結構的三層薄膜前驅物、回 火該三層前驅物、然後拉伸該回火的三層前驅物以形成該 多孔三層電池分隔器來製出。 · ^孔一層分隔器也在由吳羽（Kureha)化學工業有限 公司提出申請的日本專利公開案第5 63 2〇/ 1 995號 (JP8-2 5 0097 A)中提出。該吳羽分隔器係由一製程來製備 ，其包含共燒含有一輔助微孔型形成之溶劑可萃取材料的 三層前驅物的步驟，以及利用在該前驅物中之該可萃取材 料的溶劑萃取來在該前驅物中形成微孔型。 美國專利弟6’346,350就揭利用一吹膜製程中的我擠 製技術來製造一多層電池分隔器。該共擠製融熔膜被快速 Φ 冷卻，因此其處於實質上固化的狀態下。該共擠製膜然後 被回火並拉伸以在其内產生微孔型性。 一多層微孔型關閉分隔器應該要盡可能薄以最小化其 在一電池中佔據的空間並且降低電阻（ER)。但是該關閉分 隔器也必須有足夠的強度以抵抗穿孔。穿孔的電池分隔器 在防止相反極性的電極之間發生接觸上是沒有效果的。在 過熱的情況下，一穿孔的電池分隔器無法有效地關閉以防 止電解質通過該電池分隔器，因此在避免熱失控方面是沒 589757
(4) 有效果的。具有低的抗穿孔強度的電池分隔器是很難處理 的，特別是在電池分隔器製造過程中。一旦穿孔了，電池 分隔器會有分裂的傾向，也就是撕裂。 因此，在技藝中之一目標是進一步發展有效的方法來製 造相對薄的具有改良的穿孔強度之電池分隔器。 發明内容 發明簡述
一種電池分隔器，其係一微孔型薄膜。該薄膜具有一第 一共擠製多層部分以及一第二共擠製多層部分。該第一部 份和該第二部分係實質上相同者。該第一部份和該第二部 分係面對面地接合。該薄膜可以藉由使一管狀薄膜陷落於 自身中而形成。
該分隔器較佳者係由先擠製一管狀多層薄膜來製造。該 管狀薄膜在其自身上陷落以形成一具有兩個該多層薄膜 堆疊的多層電池分隔器前驅物。該前驅物被接合並回火。 然後，該前驅物被拉伸以形成一微孔型的多層電池分隔器。 發明之詳細敘述 本發明提供一具有兩個接合在一起的部分之微孔型電 池分隔器。每一個部分含有兩層或多層共燒的薄膜層。為 了要得到比先前技藝好的抗穿孔強度（puncture strength) ，也就是說，固定厚度之一單一的多層分隔器，本發明接 合至少兩個在結合時被製作成為與先前技藝之分隔器有 相同厚度的多層前驅物。 該電池分隔器的厚度可以有一寬廣的範圍。較佳者該電 589757 (5) 發明辣明續買: 池分隔器的厚度低於5密爾，通常不比2密爾大，並且最佳 者不比1 · 5密爾大。該電池分隔器的抗穿孔強度係約400 克，較佳者至少約4 5 0克。通常，該抗穿孔強度至少約5 0 0 克，並且有利地係大於約5 5 0克。
根據本發明，該等薄膜層可以由任何適於製造電池分隔 器的形成薄膜的聚合物之組合物來擠製，較佳者是聚蹄烴 。單聚物、異聚物，例如嵌段共聚物，任意共聚物以及三 聚物都可以被使用。聚合物可以被選擇以使從其製得之該 電池分隔器展現出低程度的電阻並且在該電池環境下是 穩定的。該聚合物樹脂也可以包含添加劑，例如抗氧化劑 、穩定劑、界面活性劑、以及其他在技藝中已知的處理輔 助劑。
較佳者，聚合物被選擇以使該電池分隔器展現出關閉特 性。也就是說，該分隔器通常在比能夠在一鋰電池中導致 熱失控的溫度低的溫度下關閉其微孔型。較佳者，聚締烴 被使用，包含但不限於聚乙烯、聚丙晞、聚丁晞、乙晞-丁晞共聚物、乙烯-己烯共聚物、乙烯-甲基丙晞酸酯共 聚物、以及其混合物。聚乙烯，例如低密度聚乙晞（LDPE) 、線性低密度聚乙烯（LLDPE)、以及高密度聚乙烯（HDPE) 都可以使用。通常，適用之聚晞烴的平均分子量係從約 100,000至約5,000,000。一般來說，本發明的電池分隔器 展現出關閉特性，也就是說，該分隔器的微孔型通常在比 能夠在一鋰電池内導致熱失控的溫度低的溫度下關閉。通 常，本發明之電池分隔器之關閉溫度，也就是說，該電池 -10- 589757 (6) 發明說明續頁* :纖.2靡逛齡.匕，..心： 分隔器關閉其微孔型的溫度，係從約80 °C至約140°C，較 佳者從約10(TC至約135°C。
如在此所使用者，『微孔型』一詞表示本發明之電池分 隔器通常具有平均孔洞尺寸約0 · 0 0 5至約1 〇微米的微孔蜇 ’較佳者從約〇 · 〇 1至約5微米。有利地，平均孔洞尺寸從 約〇 · 〇 5至約2微米。本發明之電池分隔器通常具有從約5 秒至約1 00秒的Gurley值，較佳者從約1 0秒至約60秒，依 照美國材料暨測試協會ASTM - D726(B)之方法所測試者。
本發明之電池分隔為之兩個部分的每一個都有雨個層 或多個層在製造該電池分隔器的製程期間被共擠製。如在 技藝中已知者，共擠製必須利用一單一模頭，例如一多岐 管内結合模頭（multimanifold internal combining die)，同 時擠製兩個或多個聚合組合物來使該兩個或多個層結合 在一起。通常，該兩個或多個聚合組合物分別進入該模頭 中並且剛好在它們通過最後的模口之前結合、。經由擠製， 該多個聚合組合物形成多個不連續的層積層並且彼此緊 密接觸。通常，該等共擠製層在不經歷一接合步驟下變得 彼此不可分離。也就是說，在正常情況下無法將一個層剝 離其鄰接的層而仍然維持該等層的完整性。 任何習知的共擠製技術可以為本發明的目的所利用。例 如’共擠製可以藉由在技藝中已知的利用一 T型模之融溶 表I技術來完成。或者，共擠製可由一吹膜製程來執行， 也稱為吹膜擠製。在『吹膜擠製』中，聚合組合物從兩個 或多個具有一環狀模頭的擠製器（extruder)擦製以形成一 589757
⑺ 具有兩個或多個層的管狀薄膜（或型坯（par is on))。該管狀 薄膜或型坯然後從該模頭拉離並且利用一陷落I (collapsingframe)、夾輕（niproll)或諸如此類來者陷落或 攤平。通常，當該管狀薄膜形成時，一例如空氣的流體從 該型坯内持續地吹送在該管狀薄膜上。因此，一氣泡被困 在該管狀薄膜内以及該模頭和該陷落裝置之間。此外，當 該管狀薄膜從該模頭拉離時，空氣也環繞該薄膜的外表面 吹送以從外部穩定並冷卻該管狀薄膜。因此，該擠製薄膜 在其陷落之前被冷卻至一實質上結晶的固化狀態。許多習 知的吹膜製程在技藝中是已知的並且都可以在本發明中 使用。 較佳者，接合在該兩個部分的每一個都被擠製之後並且 在它們被製作微孔型之前執行。通常，兩個多層的無孔平 板（例如，該陷落的膜泡）被接合以形成一電池分隔器前驅 物。該前驅物可以被接合，然後利用一在技藝中已知之習 知方法來製造微孔型以形成一多層電池分隔器。 接合是被用來使該兩個多層部分黏結在一起（因為附著 力），因此該兩個部分不容易分開並且不容易去膠合 (de-plied)。因此，本發明之電池分隔器必須有一最小附 著力，其可以作為剝離強度來測量。如在此所使用者，『 剝離強度』係利用一張力及壓縮力測試儀來測量以測定在 每分鐘10英吋的剝離速率下需要用來分離兩個一英吋寬 的接合之薄膜部分的以公克計的力量。該剝離強度應該至 少要約5公克/英吋，較佳者至少約8公克/英吋，並且有 -12- 589757
⑻ 利地應該至少約1 〇公克/英吋。層積和接合兩個薄膜的方 法是一般在技藝中已知的方法，並且在，例如，美國專ij 第5,565,281號中被揭示，其在此經引用而併入。適合用 在本發明中的接合方法包含壓延（calendaring)、利用膠黏 劑黏著、以及焊接。膠黏劑的應用法可以包含空氣霧化 (air atomizing)、凹版印刷/網印、液壓噴塗（hydraulic spraying)、、以及超音波噴塗。膠黏劑和膠黏劑的應用速 率必須被選擇以使形成的該電池分隔器的特性不會被不 g 利地影響。焊接技術包含熱洋接（t h e r m 〇 w e 1 d i n g)以及超音 波焊接。兩個焊接方法的能量值以及焊接圖形應該被選擇 以使該分隔器的孔隙度不會被不利地影響。較佳者，本發 明的接合利用熱壓接合（thermocompression bonding)來執 ·· 行）例如，接合可以利用壓延，在夾輥關閉的狀態下，於 比孩多層部分内的聚合物熔點低至少1 cC的溫度下來完成 ’較佳者在比該多層部分的熔點低至少5 t的溫度下、。通 常’由聚丙烯和聚乙烯所組成的前驅物，該接合溫度範圍 從約1 0 0 °C至約1 5 0 °C，較佳者從約1 2 5 °C至約1 3 5 °C。停留 ® 在該接合溫度的時間可以多至約3 〇分鐘。由其他聚合物所 組成的前驅物之接合條件對於被告知本揭示的熟知技藝 者來說是顯而易見的。 忒多層部分，分開的或接合在一起的，可以利用在技蓺 · 中已知的製造微孔型薄膜之習知方法來製造微孔型，包含 但不限於一拉伸法、一萃取（或相轉化）法、以及一粒子抵 伸法。 -13- 589757
(9) 簡單的說，在一相轉化法中，一微孔型薄膜可以從一含 有一聚合物以及一可萃取材料的組合物來形成。該可萃牙又 材料被選擇以使其至少在該聚合物的熔點下可以與該聚 合物溶混。因此，在此製程中，該組合物被加熱至該聚合 物的熔點以形成一同質相。一薄膜然後從該同質的液態組 合物被擠製成形。該聚合物和該可萃取材料之間的相分離 發生在該薄膜被擠製成形之後溫度被降低時。該可萃取材 料可以從該薄膜中被萃取出來，利用一能夠溶解該可萃取 材料但不會溶解該聚合物的適合溶劑，因此在該薄膜中形 成一微孔型結構。選擇性地，在去除該可萃取材料之前或 之後，該相轉化法中之該擠製成形的薄膜可以被定位或拉 伸超過其彈性限度以產生一内連線微孔型網路之永久結 構。任何在技藝中已知的拉伸方法都可能適用在本發明中 。拉伸可以在一單軸或橫軸方向，參見，例如，美國專利 第5，281，491號和日本專利申請案第56320-1995號，由吳 羽（Kureha)化學工業有限公司於1 995年3月15日申請，雨 者在此皆經引用而併入。 要藉由『粒子拉伸法』表達的意思是一種利用拉伸一由 一填充了在其内分散之固態填充物的聚合物矩陣所組成 之前驅物薄膜來形成一微孔型薄膜的方法。該拉伸會因為 應力集中（stress concentration)而導致微孔型的形成，其 中該薄膜被判定為微孔型的。任何在技藝中已知的粒子拉 伸法可以被使用來製造本發明。這樣的方法的範例可以在 ，例如，美國專利第 3,870,593; 4,350,655; 4,698,372; -14- 589757
(ίο) 以及4，7 7 7，0 7 3號中找到，所有都在此經引用而併入。
較佳者，本發明之電池分隔器的微孔型性係利用一拉知 法來產生，其包含使預形成的無孔平板經受單軸或雙軸拉 伸以使其產生微孔型。廣義地說，該較佳的拉伸法包含回 火該多層無孔平板（分開或接合在一起的），之後拉伸該回 火的平板。藉由無限制的範例，適用於此目的的方法在美 國專利第 5,565,28卜5,691，047、5,691，077、以及5,824,430 號中揭示，每一個都在此經引用而併入。
較佳者，在擠製成形之後，該無孔平板在進一步的拉伸 之前回火。如在技藝中廣泛知道的，回火係一加熱製程， 其改進該前驅物内的結晶結構並促進該拉伸步驟期間微 孔型的形成。回火可以由任何習知方法來執行。例如，該 薄膜前驅物可以與一加熱的滾軸或一加熱的金屬板接觸 ，或可以在空氣中或一惰性氣體中被加熱。或者，該薄膜 前驅物可以沿著一軸心彎折，並以一卷狀物的形式在一氣 相下加熱。一塗覆有，例如，碎樹脂的例如聚乙晞對g太酸 酯膜、氟樹脂膜（fluorine resin film)、和紙或塑膠膜的釋 放板可以被用來避免該捲狀物形式内的薄膜阻塞。通常， 回火可以在從約90 °C至約150°C的溫度下執行，持續一段 從約5分鐘至約3 0分鐘的時間。 該回火的薄膜前驅物然後可以被拉伸（或『定位』）以使 微孔型在該薄膜前驅物的結構内形成。通常，該回火的薄 膜前驅物是在機器方向上單軸地拉伸，並且選擇性地也在 橫軸方向上拉伸。拉伸可以包含幾個步驟，例如，一冷拖 -15- 589757
⑼ 伸步驟（cold drawing step)、一熱拖伸步驟（hot drawing step)、以及一放鬆或熱處理步驟。該放鬆或熱處理步；^ 是為了要降低該分隔器的内部應力，並且可以利用在各種 熱量變下的負拖伸比或實質上沒有拖伸張力來完成。拉伸 可以是在一含有一拖伸架（draw frame)的烤箱内執行的連 續製程。該溫度和拖伸比可以由熟知技藝者在不需過分實 驗的情況下來設定。 在一較佳實施例中，每一個在本發明之電池分隔器内的 共擠製多層部分具有至少一個強化層以及至少一個關閉 層。如在此所使用者，『關閉層』一詞意味著一微孔型薄 膜層會在該電池分隔！§的關閉溫度下關閉其微孔型，也就 是說，一相對低的從約8(TC至約135t的溫度。相反的，『 強化層』一詞係一具有一實質上較高的溶點之微孔型薄膜 層，例如，高於145 °C，較佳者約160 °C。該強化層通常可 以將該電池分隔器的融熔完整性維持在一相對高的溫度 下。較佳者，本發明之電池分隔器的關閉層係由聚乙缔、 乙埽-丁晞共聚物、乙烯-丙晞共聚物、乙埽-己缔共聚 物、或其混合物組成。較佳者高密度聚乙烯（H D P E )被利 用。更佳者，該HDPE具有從0.959 - 〇·964克/分鐘 (g/min)(ASTM D7 9 2)的密度範圍以及從 〇·42 — 〇 33 dg/分 鐘@190\：/2.16公斤（八3丁]^〇 1 23 8)的熔融指數（1^1)範 圍。本發明的電池分隔器内之強化層通常是由聚丙缔或_ 聚丙晞共聚物組成。較佳者，一密度約〇 . 9 〇5克/立方公 分（g/cc)(ASTM D 1 5 05)並且熔融指數約i 5克/ 1〇分鐘 -16- 589757
(12) @23 0 °C / 2.1 6公斤的聚丙晞單聚物。
在本發明之較佳實施例中，該電池分隔器之兩個多層如 分實質上是相同的並且面對面地接合在一起。利用『實質 上相同』，其意思是指兩個接合的多層部分在其物理結構 和化學成分上是彼此相像的。如在此所使用者，『面對面 』一詞表示該兩個實質上相同的部分被接合在一起的方式 為使該兩個部分實質上對稱地排列為如在下面關於圖1 -8所示的組合結構。
圖1 - 8係說明本發明之電池分隔器的一些較佳實施例 之剖面的簡要示圖。每一個實施例都有兩個具有兩個或多 個共擠製層的層積部分。如在圖1中所示者，電池分隔器 10具有兩個實質上相同的部分12和12’。該部分12具有一 共燒的雙層結構，包含一聚丙晞層1 4和一聚乙烯層1 6。該 部分12’具有一共燒的雙層結構，包含一聚丙烯層IV和一 聚乙烯層1 6 1。該部分1 2和1 2 ’以面對面的方式接合在一起 ，因此該兩個聚乙烯層1 6和1 6 ’與彼此接觸。
在圖2中，該電池分隔器20具有兩個部分22和22’，其與 圖1中的兩個部分12和12’是相同的。但是，電池分隔器20 的該兩個部分係以該兩個聚丙烯層彼此接觸來面對面接 合0 現在參見圖3，電池30之該兩個部分32和32*的每一個都 有一三層結構，其具有將一聚乙烯層3 6(3 6〇夾在中間的 兩層聚丙晞3 4 ( 3 4')和3 8 (3 8 ’）。該兩個部分面對面接合以 使該聚丙烯層3 8和3 8'彼此接觸。 -17- 589757
(13) 圖4係本發明之該電池分隔器的另一個示範實施例。電 池分隔器40包含兩個接合在一起的相同部分42和42’。^ 一個部分都具有一共燒的三層結構，其包含一被夾在兩個 聚乙烯層46和48，或46’和48’之間的聚丙晞層44或44%該 兩個部分被面對面接合的方式使聚乙烯層4 8和4 8 f彼此接 觸。
現在參見圖5，該電池分隔器50具有兩個部分52和52’ 。每一個部分都具有一聚乙烯層（5 4或5 4 f)以及兩個鄰接 的聚丙烯層（5 6和5 8或5 6 1和5 8 ’）。該兩個部分藉由連接該 兩個聚丙婦層58和58’來面對面接合在一起。 圖6所示之該電池分隔器60的兩個部分62和62’與圖5所 示的電池分隔器5 0的兩個部分相同。但是，該兩個部分6 2 和62’係利用將該兩個聚乙烯層64和64'接合在一起的方 式來接合在一起。因此，在電池分隔器60中，該第一、第 二、第五和第六層是聚丙晞層，而該第三和第四層是聚乙
晞層。 圖7示出具有一六層結構的電池分隔器7 0，該六層結構 具有兩個接合在一起的部分72和72’。每一個部分都具有 兩個聚乙晞層74和76或74’和76’以及一個聚丙晞層78、7V 。該兩個部分係利用將該兩個聚乙晞層7 6和7 6'接合在一 起來接合在一起。 在圖8中，該電池分隔器80的該兩個部分82和82’與圖7 的兩個部分7 2和7 21相同，除了該兩個部分8 2和8 2 ’係利用 將該兩個聚丙晞層8 8和8 8 ·接合在一起來面對面接合之外 -18 - 589757 (14) 。因此，該電池分隔器80具有一兩個位在内部的聚丙晞層 被夾在四個聚乙晞層之間的六層結構。
較佳者，本發明之電池分隔器内的該兩個多層部分係以 一交叉堆疊（cross-plied)的方式來配置，也就是說，一個 部分的單軸方向相對於另一個部分的單軸方向是傾斜的 。該角度可以在從約0 °至約9 0 °的範圍内。交叉堆疊可 以利用接合該兩個多層部分的時候交叉層積該兩個多層 部分來完成。
該電池分隔器前驅物然後被接合並回火。接合是為了使 該電池分隔器前驅物的兩個層積部分結合在一起。接合可 以利用使該前驅物在一由該兩個合上的夾輥所施加的壓 力下通過該加熱的夾輥之間來執行。較佳者，'接合係在一 範圍從約1 0 0 °C至約1 5 0 °C，約1 2 5 °C至約1 3 5 °C内的溫度下 執行。:;該接合溫度被選擇以使該兩個層被接合並黏結在一 起，而使一完成的電池分隔器在不影響該前驅物内的分子 相位下具有足夠的附著力。由該等夾輥所施加的壓力可以 比每線性英吋（pii)l磅高，或從約1至約3 pli，或較佳者， 約1.2至約2.5 pli。目標附著力是至少約5公克/英吋，較 佳者至少約1 0公克/英吋。該電池分隔器前驅物1 1 0的回 火可以在範圍從1 0 5 - 1 5 0 °C的溫度下執行，較佳者從約 1 1 0至約1 3 0 °C，若聚乙晞-聚丙晞被運用的話，運用其他 聚合物時應該使用其他回火溫度。 該管狀薄膜扭轉所造成的結果，當該管狀薄膜在其自身 上陷落以形成一電池前驅物時，一個部分的單軸方向相對 -19-、 589757 (15)
於另一個部分的單軸方向會有角度偏斜，因此交又堆疊層 積可以完成。一交又堆疊電池分隔器可以在上述之接合一、 回火、以及拉伸步驟之後得到、;。 本發明進一步參考下面提出的實例來說明。在下面的實 例中，Gurley係利用ASTM 一 D726(B)方法來測量。如在此 所使用者，Gurley是利用Gurley透氣度計（GurUy Densometer)(例如型號421〇)所測量到的對氣流的阻力。 在此所提到的Gurley值表示使1〇立方公分（cc)的空氣在 1 2 · 2英吋的水壓下通過一平方英吋的產品所需的以秒計 的時間。 利用張力及壓縮力測試儀來測試剝離強度（附著力）以 測疋扁要用來分離兩個一英忖寬的接合之薄膜部分的以 公克4的力Έ：。剝離速率是1 〇公克/分鐘。從組成中取三 個測量值並將其平均。 該電池分隔器的厚度係利用紙漿工業技術協會贊助開 發的Τ4 1 1 om - 83法來測量。厚度係利用一精密測定儀之 直徑1/2英忖、環狀的金屬箍（circuiair shoe)在7镑/平方 英吋（psi)下接觸該樣本來測量。橫越樣本的寬度多至3〇 個取自測定儀的讀數被平均。 如下為抗穿孔強度（p u n c t u r e s 11* e n g t h)的測量：遍及該 拉伸產品的寬度做多至3 0次的測量並且將其平均。一 Mitech Stevens的LFRA結構分析儀被使用。該刺針具有範 圍為0.5毫米之1.65毫米（mm)的直徑。下降速率是2毫米/ 秒並且偏斜量是6毫米。該薄膜以中心孔1 1 · 3毫米的夾钳 -20- 589757
(16) 設備緊緊钳拉住。被該刺針刺穿的該薄膜的位移（毫米） 相對於該被測試的薄膜所展現出的抗力（以克計的抗力） 來記錄。最大抗力就是該抗穿孔強度。 實施方式
CE1和CE2是拿來做比較的實例^ CE1係一具有聚乙晞 -聚丙晞-聚乙晞（PE/PP/PE)結構的習知三層電池分隔 器並且係利用一吹膜擠製製程之習知方法來製備。CE2係 一具有聚丙烯-聚乙烯-聚丙烯（PP/PE/PP)結構的習知 三層電池分隔器並且係利用一吹膜擦製製程之習知方法 來製備。C E 1和C E 2不是由創新的技術來製造。
El、E1A、E2、E3、以及E3A是本發明的實例。E1和E1A 從一三層型胚，PE/PP/PE，開始，並且產生一六層的產品 ，PE/PP/PE/PE/PP/PE ° E2從一三層型胚，PP/PE/PP，開 始，並且產生一六層的產品，PP/PE/PP/PP/PE/PP。E3和 E3A從一兩層型胚，PP/PE，開始，並且產生一四層的產 品，PP/PE/PE/PP 〇 所有實例係利用習知材料以一習知方法製成：pE〜 HDPE，密度=0.959克/立方公分（ASTM D792)，熔融# 數（MF 1)=0.42 dg / 分鐘 @190 °C / 2.16 公斤（ASTM d 1238);以及PP-同排PP(isotacticPP)，密度=〇.9〇5 克 / 立方公分（ASTMD 1505)，熔融指數（MFI)=1.5克/1〇八 鐘@2 3 0°C / 2· 16公斤。產品結果紀錄在表i中。 -21- 589757 (17)
表1 CE1 E1 E1A CE2 E2 E3 E3A 厚度 (密爾） 1 1.2 1.1 0.83-1.05 1.1-1.2 1.1 1.1 Gurley( 秒） 26 32 ' 27-28 25-33 34-44 30-31 35-36 抗穿孔強 度(克） 354 445-455 400-495 400-495 580-620 544-566 561-562 附著力* (克/英 吋） NA NR 27 NA 10-18 32-40 NR ΝΑ -無實施；NR _無記錄；* _附著力係介於接合層之 間，個別的共擠製層是不可分離的。 CE1和El、E1A的比較顯示出在相同的厚度和Gurley值 下利用創新技術會產生強度大許多的分隔器。同樣地， CE2和E2 ' E3、E3A的比較顯示出在相同的厚度和Guriey 值下大許多的強度。 本發月可以在不背離其精神和基本特性下以其他形式 來實施目il匕相關的裁定應該針對如下表明的本發明之 範圍的申請專利範圍，而非針對上述的說明書。 圖式簡蕈說明_ 為了說明本發明，固-士 -山PI ^ 圖不中7F出目則偏好的形式；但可以 被暸解的疋’本發明並不限於所示之明確的配置和機構。 圖μ ’肩下出本發明之具有四個層的電池分隔器的剖 面簡要示圖；
圖2說明本日日、„ &月< 具有四個層之電池分 施例的剖面圖； 圖3係一顯示出本發明之具有六個層 隔器的另一個實 之電池分隔器之 -22- 589757
(18) 實施例的簡要TF圖； 圖4示出本發明之具有六個層之電池分隔器的不同的i 構之剖面圖； 圖5示出本發明之具有六個層的另一個電池分隔器的結 構， 圖6係一本發明之具有四個外部的聚丙烯層和兩個内部 的聚乙婦層之電池分隔器的剖面圖，
圖7係一本發明之具有四個内部的聚乙晞層和兩個外部 的聚丙烯層之電池分隔器的剖面圖；以及 圖8說明本發明之具有四個外部的聚乙烯層和兩個内部 的聚丙晞層之電池分隔器的剖面圖。 圖式代表符號說明 10、20、30、40、50、60、70、80 電池分隔器 12、12’、22、22,、32、32’、42、42’、52、52’、62、62,、部分 72、72丨、82、82丨
14、14,、34、34,、38、38,、44、44,、56、56,、58、58,、聚丙烯層 66、66丨、68、68丨、78、78丨、88、88丨 16、16’、36、36,、46、46,、48、48,、54、54’、64、641、聚乙烯層 74、74’、76、76’、84、84’、86、86， -23-

Claims (1)

  1. 589757 第092103675號專利申請案 中文申請專利範圍替換本(9^ Γ 補无 拾、申請專利範圍 1 . 一種電池分隔器，包含： 一具有一第一共擠製多層部分以及一第二共擠製多 層部分之微孔型薄膜，該第一部份和該第二部份係實 質上相同，並且面對面地接合。
    2.如申請專利範圍第1項之電池分隔器，其中該薄膜係藉 由使一管狀薄膜陷落於自身中而形成。 3 .如申請專利範圍第1項之電池分隔器，其中該共擠製多 層邵分進一步包含至少一強化層以及至少一關閉層。 4. 如申請專利範圍第1項之電池分隔器，其中該第一部份 之單軸方向相對於該第二部份的單軸方向是傾斜的。 5. 如申請專利範圍第1項之電池分隔器，其中該薄膜進一 步包含四個層，該第一和第四層基本上係由聚丙烯所 構成，該第二和第三層被接合在一起並且基本上係由 聚乙歸所構成。
    6. 如申請專利範圍第1項之電池分隔器，其中該薄膜進一 步包含六個層，該第二和第五層基本上係由聚乙烯所 構成，該第一、第三、第四和第六層基本上係由聚丙 烯所構成，該第三和第四層被接合在一起。 7. 如申請專利範圍第1項之電池分隔器，其中該薄膜具有 從約0 · 5密爾至約1 .5密爾的厚度。 8. 如申請專利範圍第1項之電池分隔器，其中該薄膜具有 至少約5克/英吋的剥離強度。 9 ·如申請專利範圍第1項之電池分隔器，其中該電池分隔 589757 器具有從約〇 . 5密爾至約1 . 5密爾的厚度以及至少約 5 0 0克的抗穿孔強度。
    1 0.如申請專利範圍第3項之電池分隔器，其中每一個該多 層部分都具有一層該強化層以及一層該關閉層，其中 該多層部分被接合在一起的方式使每一個部分的單軸 方向相對於另一個是傾斜的，並且該薄膜具有兩層將 兩層接合在一起之關閉層夾在中間的強化層，該薄膜 具有從約0.5密爾至約1 .5密爾的厚度以及至少約5 0 0 克的抗穿孔強度。
    1 1 .如申請專利範圍第3項之電池分隔器，其中每一個該多 層部分都具有兩層將一層該關閉層夾在中間的該強化 層，該等強化層和該關閉層，其中該兩個多層部分被 接合在一起的方式使每一個部分的單軸方向相對於另 一個是傾斜的，並且該薄膜具有六層結構，該第一、 第三、第四、和第六層是強化層，而該第二和第五層 是關閉層，該薄膜具有從約0.5密爾至約1 .5密爾的厚 度以及至少約5 0 0克的抗穿孔強度。 1 2 · —種製造多層電池分隔器的方法，包含如下步騾： 擠製一管狀多層薄膜； 使該多層薄膜陷落於自身中，以形成一具有兩個該 多層薄膜堆叠之多層電池分隔器前驅物； 接合並回火該前驅物；以及 拉伸該已接合以及回火的前驅物以形成一微孔型多 層電池分隔器。 589757 申讀:蓴利範圍續頁 1 3 .如申請專利範圍第1 2項之方法，其中該前驅物係藉由 熱壓接合法（thermocompression bonding)來接合。 1 4.如申請專利範圍第1 2項之方法，其中該管狀多層薄膜 具有包含一關閉層和一強化層的兩個層。 1 5 .如申請專利範圍第1 4項之方法，其中該強化層基本上 係由聚丙晞所構成，而該關閉層基本上係由聚乙烯所 構成。
    1 6 .如申請專利範圍第1 2項之方法，其中該管狀多層薄膜 具有三層，包含兩層將一關閉層夾在中間的強化層。 1 7.如申請專利範圍第1 6項之方法，其中該強化層基本上 係由聚丙烯所構成，而該關閉層基本上係由聚乙烯所 構成。 18.—種製造多層電池分隔器的方法，包含如下步驟： 共擠製一第一多層平板； 共擠製一第二多層平板；
    層積該第一和第二平板以形成一電池分隔器前驅物； 接合並回火該前驅物；以及 拉伸該已接合以及回火的前驅物以形成一微孔型電 池分隔器。 1 9 ·如申請專利範圍第1 8項之方法，進一步包含從該前驅 物中萃取一可萃取材料。 589757 ，知夂曰修至 補无 第 0921036fT^liTffy 中文圖式替換頁(93年4月） •50 圖式績頁: -54 r56 r5Q 52 尽驚333·wmSSA (54，飞56. 〔58厂圖5 ， 52, /68 /-66 r64 /60 rnwii丨丨 1丨丨丨丨丨丨丨 mj· 62 62· 70 L68· l66e ^64' 圖6 ^ 厂 7Ό
    Μ·Μν ---- mm m mmm L78f v.74t l76.圖7 厂86 厂84 .80 88
    ^8* ^84^86'圖8 82
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CN1300862C (zh) 2007-02-14
CN1447460A (zh) 2003-10-08
US20070207376A1 (en) 2007-09-06
US9908317B2 (en) 2018-03-06
KR20030077998A (ko) 2003-10-04
JP2003297330A (ja) 2003-10-17
CA2418600A1 (en) 2003-09-27
KR100554637B1 (ko) 2006-02-24
US20180134024A1 (en) 2018-05-17
US20020136945A1 (en) 2002-09-26
TW200306030A (en) 2003-11-01

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