CN113088059A - 不含离型剂的特种离型膜 - Google Patents
不含离型剂的特种离型膜 Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/00—Fuel cells; Manufacture thereof
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Abstract
本发明公开一种不含离型剂的特种离型膜，该不含离型剂的特种离型膜应用于流延法制备电池隔膜；所述不含离型剂的特种离型膜的成分选用含双酚A为主成分的工程塑料或含六氟二甲基双酚A为主成份的工程塑料；其中所述含双酚A为主成分的工程塑料为双酚A聚合或共聚而得的聚合物，且其重量比大于50％；所述含六氟二甲基双酚A为主成份的工程塑料为与含六氟二甲基双酚A聚合或共聚而得的聚合物，且其重量比大于50％。
Description
技术领域
本发明涉及一种不含离型剂的特种离型膜。
背景技术
质子交换膜燃料电池(PEMFC)作为一种可以直接将燃料和化学能转换为电能的高效发电装置，因其相较于传统的电池具有能量转换率高、环境友好、低温启动、低噪音等优点而受到各行业的广泛关注。其核心部件为质子交换膜，处于燃料电池最中心的位置，是为阴极产生的质子传输到阳极提供通道。目前市面使用最多的质子交换膜仍为最早商业化的美国杜邦公司的全氟磺酸Nafion系列膜 (>25微米厚)主要是采熔融挤出压延拉伸所得。近来美国戈尔公司的 Gore-Select膜系列以超薄(<25微米厚)单层微孔PTFE增强型膜，主要是以流延涂覆单层微孔PTFE增强型膜而得(参见美国专利号5547551，5599614)，国内有少数企业在仿制。
含氟磺酸树脂分子结构是由碳氟主链以及末端带有磺酸基的支链构成，碳氟键的主链可极化度小，支链上的亲水性磺酸或羧酸基团能够吸附水分子，由于疏水主链和亲水支链强烈的极性差异，膜内部形成微观相分离结构，这种结构对于它的机械性能和传输性能有着重要的作用。因此，全氟磺酸树脂膜具有优异的质子传导能力，低的气体渗透率，良好的机械性能和尺寸稳定性以及与催化层之间较小的接触电阻等基本性能，满足了作为质子交换膜应用的条件。采用磺酸树脂溶液制备质子交换膜的方法较多，例如：流延浇铸法，浸渍法，喷涂法等。目前，质子交换膜及各种增强复合质子交换膜的制备工艺复杂，而且较难实现连续化生产。
专利ZL201010104002.7，公开了一种质子交换膜的制备方法，该方法采用磺化聚醚醚酮与磺化聚醚砜共混形成膜溶液，将膜溶液倒入模具中蒸发溶剂成膜，然后经真空干燥和酸处理得到质子交换膜，其成品膜的制备是一个单元、一个单元进行，生产效率低，生产成本高。
专利ZL200710011141.3，公开了一种新型质子交换膜成型工艺，该方法采用单层膨体聚四氟乙烯微孔薄膜作为基膜，先浸入到低浓度的树脂溶液中，再反复多次浸入高浓度的树脂溶液直至达到合适的膜厚度，该方法生产工艺复杂，效率低，燃料电池的生产和使用成本高，限制了燃料电池的商业化。
专利ZL201710251603.2，公开了一种含氟含氯导电高分子双面填充复合薄膜，然所用制作薄膜方法采用离型纸，在生产高质量薄膜时容易产生因离型纸质带来的毛屑污染。
离型膜是指表面具有分离性的薄膜，离型膜与特定的材料在有限的条件下接触后不具有粘性，或轻微的粘性。通常情况下为了增加塑料薄膜的离型力，会将塑料薄膜做电晕、或等离子处理，接着或做涂离型剂表面改性处理，最常见的是做涂含硅离型剂、或含氟离型剂等于薄膜材质的表层上，让它对于各种不同的有机胶水可以表现出极轻且稳定的离型力。目前，市场上常见的是有机硅离型纸 (膜)，都是采用有机硅作为隔离剂，最大缺点是剥离时存在有机硅残留在产品表面的情况。
聚碳酸酯绝缘离型膜也是离型膜中常见的一种,其成分为2,2＇-双(4-羟基苯基)丙烷聚碳酸酯，俗称聚碳酸脂，是分子链中含有双酚A缩聚的碳酸酯基的高分子聚合物。它是一种无定型、无臭、无毒、高度透明的无色或微黄色热塑性工程塑料，具有优良的物理机械性能，尤其是耐冲击性优异，拉伸强度、弯曲强度、压缩强度高；蠕变性小，尺寸稳定。因此被广泛的应用于各种领域。但聚碳酸酯绝缘离型膜需要添加其他助剂或涂覆离型剂才能工作。
CN105440641A公开一种聚碳酸酯绝缘离型膜，需要添加其他助剂，这些添加剂容易造成在流延过程中释出造成膜面污染。
CN1840324A公开一种离型膜的制作方法，工艺复杂且需要涂覆离型剂易在流延过程释出造成膜面污染。
另如专利CN200710013624.7、US7259208、CN101350415B、CN101780376B、CN104018181A、CN101320818B、CN201546122U、CN103187549A、CN1298890C等公开技术，所述含氟聚合物微纤并非连续相，无法连接成膜。
随着低碳、绿色经济的发展，对含氟质子交换膜或离子交换膜以及其配套的离型膜的要求或用途也越来越高，离型膜在实际使用中，不仅仅要求具有隔离、填充的作用，同时还要求具有保护作用，离型剂不污染流延涂料，散热等方面的作用；对含氟质子交换膜或离子交换膜的洁净度及机械强度及使用寿命要求越趋重要。
发明内容
由于现有技术中存在着传统离型膜含有微量游离的离型剂继而污染最终产品的问题，本申请提出一种不含离型剂的特种离型膜，以克服现有技术中存在的问题。
为达到上述技术问题，本申请采用下述技术方案：
一种不含离型剂的特种离型膜，该不含离型剂的特种离型膜应用于流延法制备电池隔膜；所述不含离型剂的特种离型膜的成分选用含双酚A为主成分的工程塑料或含六氟二甲基双酚A为主成份的工程塑料；其中所述含双酚A为主成分的工程塑料为双酚A聚合或共聚而得的聚合物，且其重量比大于50％；所述含六氟二甲基双酚A为主成份的工程塑料为与含六氟二甲基双酚A聚合或共聚而得的聚合物，且其重量比大于50％。
较佳的是，所述双酚A聚合或共聚而得的聚合物为聚碳酸酯、聚苯醚、聚砜树脂、聚环氧树脂或其混合共聚物之一；所述六氟二甲基双酚A聚合或共聚而得的聚合物为聚碳酸酯、聚苯醚、聚砜树脂、聚环氧树脂或其混合共聚物之一。
较佳的是，所述不含离型剂的特种离型膜的厚度为10～500微米，宽度至少 100毫米，耐热100℃不变形。
较佳的是，所述不含离型剂的特种离型膜的厚度为25～300微米。
此外，上述不含离型剂的特种离型膜应用于流延法制备电池隔膜。
本申请的不含离型剂的特种离型膜无需做电晕或涂覆离型剂即可具备离型功能，可用于连续化生产，生产步骤简化且可降低生产成本。
具体实施方式
下面通过实施例,对本发明的技术方案作进一步具体的说明。
本发明的目的是针对现有生产工艺的不足，因传统离型膜含有微量游离的离型剂、尤其是含硅离型剂，容易被流延涂料吸附而造成最终产品被污染，不易清洗，对生产高质量、洁净度高的质子交换膜极为不利。本发明提供一类不含离型剂的离型膜(即膜本身物性含离型功能，无需再做电晕或涂覆离型剂)，可用于连续化生产、将含氟质子交换树脂溶液或离子交换树脂溶液流延法涂覆在此类不含离型剂的离型膜上，并可至少100℃烘干不变形，可用于制备高质量含氟质子交换膜或含氟离子交换膜。且可不止一次流延涂布、在此种不含离型剂改性的薄膜做表面涂覆，还可在涂覆溶液上再覆盖微孔增强膜，所涂含氟磺酸或羧酸树脂溶液，经烘干及反复加工、实现含氟质子交换膜的规模生产更便捷，进一步降低生产成本。
本发明公开了一类特种离型膜，不含任何涂覆离型剂，无需电晕，厚度可选在10～500微米，优选的在25～300微米厚，宽度至少100毫米，至少能耐热100℃不变形，优选的能耐热120℃不变形，可用于制备含氟质子交换膜或含氟离子交换膜等，可应用于电池隔膜。电池隔膜的生产工艺采用成膜性好的含氟质子交换树脂溶液或含氟离子交换树脂溶液，流延平铺到此特种离型膜烘干成膜定型收卷。
其中离型膜成份可选于：(1)含双酚A为主成分(重量比>50％)的工程塑料：选自与双酚A聚合或共聚而得的聚合物，比如聚碳酸酯、聚苯醚、聚砜树脂、聚环氧树脂、或其混合共聚物；或者(2)含六氟二甲基双酚A(重量比>50％)为主成份的工程塑料：选自含六氟二甲基双酚A聚合或共聚而得的聚合物，比如聚碳酸酯、聚苯醚、聚砜树脂、聚环氧树脂、或其混合共聚物。
膜面不含任何外加涂覆离型剂，无需电晕，可单次或多次流延涂覆膜，并可在流延过程中覆盖微孔增强膜以增强复合膜强度，流延后经烘干后意外发现可形成易剥离且无残留溶剂或离型剂污染的质子交换膜或离子交换膜。本发明的材料的优点是该类离型膜因不含任何涂覆离形剂，可免去离形剂污染产品膜的风险，多次流延涂覆多层微孔增强膜，可掩盖并大大降低因单次涂覆膜可能形成的气泡缺失，得率可大大提高，可实现连续化生产，满足商业大规模批量生产的要求，制得的产品膜洁净度和稳定性高，及方便废料回收。
实施例：(不含离型剂的离型膜)
(1A)将由双酚A缩聚而得的碳酸脂树脂(不添加任何助剂或离型剂)熔融挤出、双向拉伸、得到约300微米厚、150微米厚、25微米厚的透明膜(可直接使用、没有电晕)；
(1B)将由六氟二甲基双酚A缩聚而得的碳酸脂树脂(不添加任何助剂或离型剂)熔融挤出、双向拉伸、得到约300微米厚、150微米厚、25微米厚的透明膜(可直接使用、没有电晕)；
(1C)制备类似上述厚度的离型膜，用的是聚苯醚对双酚A型环氧树脂(EHPPO 型，不添加任何助剂或离型剂，可直接使用、没有电晕)。
上述三个实施例制备所得膜在没有电晕以及涂布离型剂的操作下，均具备较好的离型效果，且不会出现残留。
不含离型剂的特种离型膜应用于流延法制备电池隔膜时，其制作工艺为1. 将所述特种离型膜上单面被含氟质子交换树脂溶液或含氟离子交换树脂溶液涂覆亲润，随后在所涂覆的树脂溶液上覆上微孔增强薄膜，使在特种离型膜上已涂覆的树脂溶液与已覆上的微孔增强膜充分亲润，随后可先烘干；2.将步骤1所得的复合膜(依托在所述特种工程塑料膜上)，再进行第二次树脂溶液流延涂覆在已覆的第一层微孔增强膜上，随后在第二次所流延涂覆的树脂溶液上覆上第二层微孔增强薄膜，使在特种离型膜上已涂覆的树脂溶液与已覆上的微孔增强膜充分亲润，再烘干，烘干后所述每层微孔增强膜的双面的孔隙体积超过60％被含氟质子交换树脂所填充，优选的超过80％被填充，最优的超过90％被填充；3.把步骤2 至少再重复0～48次，优选的再重复0～28次，然后再进行最后一次树脂溶液涂覆在最后已覆的那层微孔增强膜上，再烘干，即得至少含两层(2～50层，优选的2～ 30层)微孔增强膜的高增强型质子交换膜或离子交换膜或膜电极。
以上所述的实施方式仅用于说明本发明而不用于限制本发明的范围。本领域技术人员对本发明所做的均等变化与修饰，皆应属于本发明所附的权利要求书的涵盖范围。
Claims (5)
1.一种不含离型剂的特种离型膜，其特征在于，该不含离型剂的特种离型膜的成分选用含双酚A为主成分的工程塑料或含六氟二甲基双酚A为主成份的工程塑料；其中所述含双酚A为主成分的工程塑料为双酚A聚合或共聚而得的聚合物，且其重量比大于50％；所述含六氟二甲基双酚A为主成份的工程塑料为与含六氟二甲基双酚A聚合或共聚而得的聚合物，且其重量比大于50％。
2.根据权利要求1所述的不含离型剂的特种离型膜，其特征在于，所述双酚A聚合或共聚而得的聚合物为聚碳酸酯、聚苯醚、聚砜树脂、聚环氧树脂或其混合共聚物之一；所述六氟二甲基双酚A聚合或共聚而得的聚合物为聚碳酸酯、聚苯醚、聚砜树脂、聚环氧树脂或其混合共聚物之一。
3.根据权利要求1所述的不含离型剂的特种离型膜，其特征在于，所述不含离型剂的特种离型膜的厚度为10～500微米，宽度至少100毫米，耐热100℃不变形。
4.根据权利要求3所述的不含离型剂的特种离型膜，其特征在于，所述不含离型剂的特种离型膜的厚度为25～300微米。
5.如权要求1至4中任一所述的不含离型剂的特种离型膜应用于流延法制备电池隔膜。
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| EP21934675.6A EP4318693A1 (en) | 2021-03-29 | 2021-12-16 | Composite membrane of special highly-enhanced fluorine-containing proton or ion exchange membrane, composite membrane electrode, special highly-enhanced fluorine-containing chlor-alkali battery membrane, special release membrane, and preparation method therefor |
| BR112023019970A BR112023019970A2 (pt) | 2021-03-29 | 2021-12-16 | Membrana composta, eletrodo de membrana composta de membrana de troca iônica ou de prótons contendo flúor altamente aprimorada especial, membrana de bateria de cloro e álcalis contendo flúor altamente aprimorada especial, membrana de liberação especial e método de preparação da mesma |
| PCT/CN2021/138855 WO2022206039A1 (zh) | 2021-03-29 | 2021-12-16 | 特种高增强型含氟质子或离子交换膜的复合膜、复合膜电极、特种高增强型含氟氯碱电池膜、特种离型膜及其制备方法 |
| CN202180096477.2A CN117242608A (zh) | 2021-03-29 | 2021-12-16 | 特种高增强型含氟质子或离子交换膜的复合膜、复合膜电极、特种高增强型含氟氯碱电池膜、特种离型膜及其制备方法 |
| JP2023559744A JP2024515480A (ja) | 2021-03-29 | 2021-12-16 | 特殊高補強型フッ素含有プロトン又はイオン交換膜の複合膜、複合膜電極、特殊高補強型フッ素塩素含有アルカリ電池膜、特殊離型膜及びそれらの製造方法 |
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| KR1020237033275A KR20230152725A (ko) | 2021-03-29 | 2021-12-16 | 특수 고강화 불소 함유 양성자 또는 이온 교환막의 복합막, 복합막 전극, 특수 고강화 불소 함유 클로르-알칼리 전지막, 특수 이형막 및 이의 제조 방법 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1840324A (zh) * | 2005-03-30 | 2006-10-04 | 林启祥 | 离型膜的制作方法 |
| CN104945875A (zh) * | 2015-05-29 | 2015-09-30 | 吉翔宝（太仓）离型材料科技发展有限公司 | 一种聚碳酸酯离型膜 |
| CN105440641A (zh) * | 2015-12-30 | 2016-03-30 | 太仓卡斯特姆新材料有限公司 | 一种聚碳酸酯绝缘离型膜 |
| CN106273937A (zh) * | 2016-07-29 | 2017-01-04 | 苏州睿利斯电子材料科技有限公司 | 一种用于镀铝基材的pet离型膜 |
| CN109897162A (zh) * | 2019-02-18 | 2019-06-18 | 江苏澳盛复合材料科技有限公司 | 具有离型功能的环氧树脂、固化物及其碳纤维复合材料 |
-
2021
- 2021-03-29 CN CN202110337061.7A patent/CN113088059A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1840324A (zh) * | 2005-03-30 | 2006-10-04 | 林启祥 | 离型膜的制作方法 |
| CN104945875A (zh) * | 2015-05-29 | 2015-09-30 | 吉翔宝（太仓）离型材料科技发展有限公司 | 一种聚碳酸酯离型膜 |
| CN105440641A (zh) * | 2015-12-30 | 2016-03-30 | 太仓卡斯特姆新材料有限公司 | 一种聚碳酸酯绝缘离型膜 |
| CN106273937A (zh) * | 2016-07-29 | 2017-01-04 | 苏州睿利斯电子材料科技有限公司 | 一种用于镀铝基材的pet离型膜 |
| CN109897162A (zh) * | 2019-02-18 | 2019-06-18 | 江苏澳盛复合材料科技有限公司 | 具有离型功能的环氧树脂、固化物及其碳纤维复合材料 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022206039A1 (zh) * | 2021-03-29 | 2022-10-06 | 浙江汉丞新能源有限公司 | 特种高增强型含氟质子或离子交换膜的复合膜、复合膜电极、特种高增强型含氟氯碱电池膜、特种离型膜及其制备方法 |
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