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硬度和尺寸稳定性都高的离子传导膜

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CN1608099A
CN1608099A CN 02820444 CN02820444A CN1608099A CN 1608099 A CN1608099 A CN 1608099A CN 02820444 CN02820444 CN 02820444 CN 02820444 A CN02820444 A CN 02820444A CN 1608099 A CN1608099 A CN 1608099A
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ion
conducting
dimensional
membrane
high
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CN100372883C (zh )
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A·R·赫布森
S·J·麦肯齐
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戈尔企业控股股份有限公司
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Abstract

整体复合膜,由膨胀聚四氟乙烯构成,具有一定形貌结构,是由原纤维交织而成的很长结节,该微结构被离子聚合物所浸渍。该复合膜有很高的硬度,因而减少短路的可能,改善了燃料电池的性能和寿命。

Description

硬度和尺寸稳定性都高的离子传导膜

发明领域本发明涉及离子传导膜(ICM),具体地说是涉及在聚合物电解质膜(PEM)燃料电池中使用的ICM。

发明背景在PEM燃料电池应用中,质子传导膜置于两个电极即阴极与阳极之间,且在有些场合下,该两个电极与传导膜直接相接。质子通过离子传导膜由阳极传导到阴极。该膜的电导会影响燃料电池的性能与功率密度。为了改善燃料电池的性能,离子传导膜的电阻必须降下来。降低电阻的方法之一就是减小ICM的膜厚。然而,对于离子键聚合物挤压或浇注的膜,这层膜的强度随厚度变薄而降低,使得该膜的尺寸稳定性较差,且更难于处理。

授权给Asahi玻璃公司的日本专利JP11067246描述了一种增强型离子交换膜。该发明的ICM是采用碳氟聚合物纤维编织成10-100支经纬织物而得以增强。这种结构可以提高复合膜的强度。

授权给Bahar等人的美国US Pat.No.5,547,551描述了一种ICM复合膜的基质材料以及离子交换树脂。该基质材料是一种厚度小于1密耳(0.025mm),有原纤维交织而成的节结的微结构,或没有结点的原纤维构成的微结构的薄膜。该离子交换树脂浸透薄膜,使该膜基本上不透空气。在整个复合膜中,它的强度由微孔膜而得以增强,薄膜厚度还可以进而降低,使得传导质子的阻力也减小。因此,这种整体复合膜的电阻较小,还能维持高的强度。

然而,PEM燃料电池系统对任何一种膜都是有侵蚀性的环境。为了减小部件之间的接触电阻,电池通常被压缩到约50-400psi的压力。在如此高压力下,薄膜极易引发电极短路。此外,高压下电池的长期机械稳定性对ICM显得越发重要。尽管ICM微孔增强结构能提高薄膜强度,也即降低溶胀性和破损,但现有的强度还不足以抵挡穿过平面引起的穿孔。本专利采用膜面上“(in-plane)”意指平行于材料的平面,而“穿过膜面(through-plane)”意指垂直穿过材料的平面。

ICM的两侧通常有碳粒子,离子键聚合物,以及催化剂组成的电极。电极层的外侧通常为碳纤维组成的扩散层,碳纤维的形式或为编织物或为非织造织物。在有些场合下,有个微结构层被加在气体扩散介质上,它由碳或石墨颗粒、离子聚合物和含氟聚合物构成。大多数气体扩散介质相对于ICM层很显粗糙。此外,气体扩散介质厚度的差异会很大,特别是编织型气体扩散介质。对于编织型气体扩散介质,厚度的差异通常为0.002-0.004”。气体扩散介质厚度的不均匀性可导致系统内高压区域的形成。这些高压区域可造成ICM膜变薄。有时候会引起阳极与阴极的短路。而且,气体扩散介质的硬质碳纤维会刺穿ICM,导致燃料电池组装时或稍后由于纤维持续不断穿透ICM而造成短路。燃料电池正常运行时温度很高,会加速离子键聚合物的机械变形。这种蠕变会使ICM变薄,增加了纤维从气体扩散介质到ICM层的穿透。

ICM薄膜的另一种问题是电极周围厚度不均匀加压缩变形造成的电极周围厚度不均匀。在电极层厚度不均匀情况下,作用在ICM膜上的压力会变化极大。在较厚电极区域,压力较高,很容易出现变形,还会导致ICM膜变薄。实际上,ICM膜的压缩变形会造成阳极与阴极的接触,发生薄膜的电子短路。

ICM膜的电极短路会降低燃料电池的工作效率。薄膜电子短路的电压差应与电池工作电压相同。因此,相应的电流从燃料电池分流,且经过电子短路而流走。短路的电阻值越低,相关的电流值越高。

因此,ICM薄膜必须保持低离子电阻,而有更强的抗击穿能力,以及随之的抗短路能力。此外,还必须减小由于水合作用引起的膜面上尺寸的变化。然而,穿过膜面的水合溶胀是符合理想要求的性质,因为它会进一步降低燃料电池内各部件之间的接触电阻。

发明综述本发明相对于过去已知的离子传导膜的性能有明显的改善,例如提高了其硬度与尺寸稳定性。在本发明的一个实施方式中,整个复合膜是由具有形貌结构的扩展聚四氟乙烯组成,该形貌结构是由原纤维交织而成的异常拉长结节的微结构,此复合膜然后用离子键聚合物浸渍。这种复合膜显示出超强硬度,因而能降低电短路,改善燃料电池的性能与使用寿命。

更具体地说,本发明提供的复合膜是由(a)原纤维交织成结结而形成内部微结构的聚四氟乙烯膜,结节基本上呈平行排列,异常拉长,并且其径宽比大于25∶1;(b)薄膜整体为离子交换材料所浸透,浸渍的扩展聚四氟乙烯膜具有的Gurley数大于10,000秒,其中离子交换材料浸透该薄膜,造成该薄膜的内孔基本上闭塞。

在另一方面,本发明提供的复合膜由具有含有节结微结构的基质材料构成,且由原纤维交织而成通道,其硬度大于1,000MPa,并且离子交换材料浸透整个基质材料。复合膜的Gurley数大于10,000秒,其中离子交换材料浸透该基膜,造成其中通道基本上闭塞。

附图简要说明图1是根据本发明一个示例性实施方式的复合ICM膜的截面面。

图2是根据本发明一个示例性实施方式的基质材料表面的扫描电镜照片。

图3是根据本发明另一个示例性实施方式的基质材料表面的扫描电镜照片。

本发明详细说明正如图1所示,复合膜10包括基质材料11和离子交换材料12,离子交换材料最好为离子交换树脂。基质材料11是一个具有形貌结构的膜,是由有原纤维交织而成空穴或孔隙的网状结构的异常拉长的结点的微结构形态。薄膜整体基本上浸渍有离子交换材料12,造成其内部空穴和孔隙基本上闭塞。如图1所示,基材的单面或双面都可含有离子交换材料12。

本发明的复合膜在膜面方向上具有极好的尺寸稳定性,硬度高并且厚度均匀。这里采用“极好尺寸稳定性”意指根据下面所述的试验方法,计算出该复合膜干燥状态和完全水合状态之间的尺寸变化不超过2%。

“高硬度”即指硬度超过1,000MPa,“产品均匀”是指该复合膜结构内无针眼或断续结构。“基本上闭塞”意指该复合膜内部填满了离子交换材料,使最终形成的复合膜的Gurley数大于10,000秒。为达到本发明的目的,应填满了90%以上膜内部的空穴体积。

根据美国专利US Pat.No.5,814,405所述,基质材料是一种膨胀的聚四氟乙烯(ePTFE),其中节结异常长,其径宽比大于25∶1。其空气渗透性与强度合起来表明该ICM膜的性能有所提高。高强度保证了其尺寸稳定性,高透气性要求其内部有相当多空穴体积,浸渍后具有高离子传导率。该美国专利5,814,405参考引用。

合适的离子交换材料包括(但不限于)全氟硫酸树脂,全氟羧酸树脂,聚乙烯醇,二乙烯基苯、苯乙烯类聚合物,以及含聚合物或不含聚合物的金属盐类。适用于离子交换材料的溶剂包括醇,碳酸盐,四氢呋喃(THF),水,以及它们的混合物。

为了在该基质材料上施加,制备一种溶液,该溶液的溶剂中含有离子交换材料。该溶液通过常规涂覆技术施涂在基质材料上,括前辊涂,逆辊涂,凹面涂或刮辊涂,以及浸涂,刷涂,喷涂等手段,只要该溶液能渗入基质材料的间隙和内部空穴即可。去除膜面上的多余溶液。然后,将处理过的薄膜置于烘箱内干燥。烘箱温度置于60-200℃之间,但较佳在160-180℃之间。可以进行重复施涂及随后的干燥,直至薄膜完全透明,使ICM膜的Gurley数大于10,000秒。通常要求2-6次处理,但实际处理次数取决于膜基的浓度与厚度。如果薄膜无支撑结构,则该膜的两面可以同时处理,进而减少处理次数。

本发明人发现根据授权给Branca等人的美国专利US.Pat.No.5,814,405(下简称“405”)所述制备的薄膜,具有意想不到令人称奇的ICM增强效果。Branca描述的微孔膜为具有原纤维交织而成空穴或孔隙的网状结构,其中有很长的结节。Branca认为,其优点为这种微结构提供了强度与高空气透过率的独特组合。

本领域技术人员并不认为“405”专利所述的ICM薄膜具有可以接受的增强效果,其理由如下:首先,可以认为该高定向结构会导致膜面方向上的强度差异很大。这种差异不宜于ICM的增强,因为它会导致ICM膜水平方向上的非均匀性,会导致沿膜面上的两个方向有性质差异。例如可能导致燃料电池中ICM在热循环期间的不同收缩,而影响薄膜的寿命。

理由之二,采用这些薄膜达不到增强膜的效果,因为存在又长、径宽比很大的节结。这会是有缺点的,因为这样会难以用离子键聚合物填满节结周围的孔隙。长节结可能会阻碍浸渍工艺,导致薄膜中的孔隙不会充分闭塞。Bahar认为薄膜中孔隙的充分闭塞是较佳的。长而径宽比比大的节结的另一后果是因为它们遮盖相对较大的一片面积,会发现这样会降低薄膜浸渍过后质子传递的有效面积。这样就提高电阻,进而降低ICM膜的性能要求。

令人惊奇的是本发明发现,如用“405”专利所述的膜基制成的ICM膜寿命较长,膜面尺寸稳定性好,硬度高,均匀性好。

下述测试步骤用于根据本发明制备的样品。

测试步骤基材的拉伸测试测试采用Instron型号5567的拉伸试验机(Instron公司IX系列自动材料测试系统1.00)。样品宽1”,长为6”。计量长度(夹具之间距离)2”。样品以十字头速率为20”/分钟,温度为20℃,相对湿度为50%下进行拉伸。记录断裂时的伸长与最大负荷。基材拉伸强度的计算是最大负荷被样品的原来横截面积所除,然后被测得的孔隙率所除。孔隙率的获得是先计算样品的密度,即样品重量除以样品的长宽度,然后除以样品的真密度。聚四氟乙烯(PTFE)的真密度取2.19g/cm2(cm3?)。

厚度基材厚度采用卡规测量,卡规为Mitutoyo No.2804F-10型。每个样品取至少四个部位测量,然后再取平均值。采用上述卡规和扫描电子显微镜测量干燥后复合膜的厚度。

尺寸稳定性与穿过膜面水合膨胀率按如下方式测量样品在纵向,横向和Z方向上的水合膨胀率。取3”×3”样品,在室温和相对湿度在40-60%下至少保存一天,然后置于80℃去离子水中长达5分钟,保证该离子传导膜充分进行水合作用。然后取出样品,置于一橡皮垫上。样品呈直角排列,且平铺。用直尺沿样品纵向与横向测量其膨胀,测量精度达0.016”(1/64”)。采用上述厚度测量方法测定厚度方向上的膨胀。尺寸稳定性以每个方向上的变化百分率计,穿过膜面水合膨胀率以厚度增加的百分率计。

硬度ICM样品的硬度由Micro Photonics Inc.,加州的Irvine采用CSEM仪器公司(瑞士)的微硬度测试仪进行。直径为1mm的碳化钨压头以10牛/分速率压在ICM样品上,最大穿透深度设定为15,000nm,硬度计算单位为MPa。选择这个深度可以消除来自放置样品的基片的影响。在所有测试中采用小于原来样品厚度60%的深度。

当达到予置的最大值时,减小标称负载直至发生部分或全部的松弛。重复进行该过程。在实验的每个阶段,压头相对于样品表面的位置采用微分电容传感器精确测量。

采用下列一组测量条件:最大施力:无最大深度:15000nm负载速率:10牛/分钟卸载速率:10牛/分钟停顿时间:15秒标定与    20%/0.010选择:30牛/100μm泊松系数:0.50计算方法:Oliver和Pharr压头类型:碳化钨,直径1mm温度:室温相对湿度:与周围环境同空气流动数据Gurley空气流动测试法测量100cm3的空气在4.88”高水压下流过截面1吋2样品所需的时间,单位为秒。样品在GurleyDeusometer(ASTM 0726-58)中测量。样品置于两个夹板之间。然后柱塞缓缓下降。自动计时器(或秒表)用于记录100cm3空气被柱塞取代所需的时间(秒)。该时间就是Gurley数。

单位面积质量单位面积质量数按测量已知尺寸的样品重量,该重量除以样品的长与宽即得。

引发短路的压力测量引发短路的压力是测定迫使气体扩散介质纤维穿透ICM样品直至出现短路的电阻为<200Ω时所需的力(psi)。本发明的ICM膜样品置于两层CarbelTM气体扩散介质CL(GDM)(日本Gore-Tex公司有售)之间,电极界面层面朝ICM膜。一个手工驱动机械压机上的一块1吋2(5.6cm2)钢质顶板降下来,与置于钢质底板上样品接触。该底板与顶板互相电绝缘。以50psi/分的速率提高压力。用一数字万用表测量顶板与底板之间的电阻。当该电阻降至200Ω以下时,记录当时的压力。

径宽比按照Branca的“405”专利中第八栏的第30-36行所述的测试方法测量。

燃料电池寿命按如下方式测量燃料电池的寿命。采用本发明ICM复合膜制成一MEA此ICM复合膜用作电解质,置于两个PRIMEATM5510电极(由日本Gore-Tex公司制作)之间。阳极与阴极的含铂量0.4mg Pt/cm2。阳极与阴极两侧为CarbelTM气体扩散介质CL(日本Gore-Tex公司有售)。电池尺寸在各种场合下均为25cm2。按如下操作组装电池:a)将所述薄膜置于两个PRIMEATM5510电极(日本Gore-Tex公司有售)之间,压在两个平板之间,顶板加热至180。每个平板与电极之间放置一块厚为0.25”的GR片(马里兰州Elkton的W.L.Gore关联公司有售)。本系统采用15吨压力长达3分钟,将两电极结合到膜上。

b)将25cm2三螺旋通道流场(新墨西哥州Albuquerque的燃料电池技术公司提供)置于工作台上。

c)取一窗形CHR(Furon)粘合弹性的(cohrelastic)硅烷涂覆的织物垫圈(由马里兰州巴尔的摩的Tate工程系统公司提供),其尺寸使得25cm2的GDM能安在里面,将此垫圈置于流场的顶部。

d)将一块Carbel CLGDM置于垫圈内。

e)取另一只窗形聚萘二甲酸乙二醇酯膜垫圈(北卡罗来纳州夏洛特的Tekra公司有售),其尺寸刚好盖过GDM的所有边,将此垫圈置于GDM之上。

f)将a)中制作的阳极/膜/阴极系统置于垫圈之上。

g)按b)-e)步骤反过来的次序制作阴极室。

h)将电池置于台钳上,以45吋-磅的力拧紧八只紧固螺拴。

在燃料电池内测试电池,温度为60℃,阳极阴极上入口气体相对湿度为100%。进入阳极气体为实验室级氢气,流量为维持电池中氢气转换速率(决定于电池中的电流)所需的1.2倍(即化学计量的1.2倍)。进入阴极的压缩空气经过滤,流量二倍于化学计量。

将电池调适14小时,调适过程是将电池在60℃,二极之间电位为600mV循环30分钟,再在300mV循环30分钟,再在950mV循环0.5分钟,总共5小时。然后作极化曲线,控制好施加的电位,从600mV起始,然后每步递减50mV直至400mV,其后再每步递增50mV直至900mV,记录每步的稳态电流值。电位在600mV-650mV之间的记下开路电压。调适结束后,将阴极气体切换成氮气,流通二个小时,并且在0.1V-1.2V区间,以100mV/S速率扫描三次,在扫描期间测量动态电流,绘制出伏安特性曲线。在10mV和600mV之间以2mV/S速率扫描得到在400mV氢气转换值(crossover value)。计算氢气转换曲线的斜率得到电路短路的测量。电阻值(Ω)为该斜率的倒数。

最后,阴极气体切换回到空气,流通10-15分钟,如前所述,得到极化曲线。

将电流设定为0.8A/cm2,电池在90℃,阳极与阴极上的露点为83,阳极与阴极的背压为15psi下工作。每隔168小时(1周)照前所述测量电流与电压值,以及氢转换值mA/cm2。当氢转换值达到或超过10mA/cm2时,进行机械性针眼试验,即在阴极上施压2psi以上,然后在阳极一侧进行气泡计数。如果内径为1/8吋管内气泡数超过10气泡/分钟,该时间(小时)即为燃料电池的寿命。

实施例正如本领域技术人员所熟知,本发明提供的聚合物树脂复合膜具有的硬度明显高于普通膜,且有横向与纵向上很高的尺寸稳定性。因此,本发明提供的薄膜具有较高的抗剌穿阻力,膜的寿命也较长。

如前所述,本发明聚合物树脂复合膜在燃料电池系统中使用很有益。本发明薄膜在给定条件下,由于高的抗剌穿阻力与水合期间能维持其原来尺寸,且工作寿命更长。例如,本发明薄膜硬度大于2,000MPa,纵向尺寸稳定性小于1%。在本发明燃料电池寿命测量操作所述工作条件下,本发明ICM膜可使膜电极组合件工作时间达2,000小时,2.3倍于本发明比较例1中膜制成的膜电极组合件的寿命,而后者的硬度仅为958MPa,纵向尺寸稳定性达7.3%。

并不愿对本发明的范围加以限制,本发明的制造方法及其使用设备可通过下面一些实施例更好地理解。下面实施例中所有ePTFE样品均按US Pat.No.5,814,405所述方法制造。

更具体地说,制造了两类ePTFE材料,具有下列材料性质:

类型1                          类型2

如本领域技术人员所熟知,ePTFE膜厚度<1.5密耳时,它的物理性能范围很宽。物理性能范围远远超出上述两实施例给出的值。图2是1型膜表面的扫描电镜照片,1型膜的径宽比由此照片测得。图3是2型膜的扫描电镜照片,它的径宽比由此照片测得。

实施例11型ePTFE膜的标称厚度为1.38密耳,装在一10”木质装饰环上,制备离子交换材料溶液,它含有100体积%的全氟磺酸/四氟乙烯共聚树脂溶液(以H+形式,其本身由10%全氟磺酸/四氟乙烯共聚树脂,10%水和80%的低分子量市售醇的混合物组成,Asahi玻璃与化学品公司有售,品名为Flemion F950型(950 EW),下文简称“F950”)用4”宽海棉刷将该溶液刷涂到膜的两面上,让其向内浸透。然后将样品用电吹风吹干2分钟,再在180℃烘箱内干燥3分钟。该过程重复二次以上,使膜内空隙充分闭塞。干燥后复合膜的厚度经测量约为原来基材的50%。硬度列于表1,此样品的尺寸稳定性列于表2,强度与基材拉伸强度列于表5。

实施例22型ePTFE膜的标称厚度为0.78密耳,装在一10”木质装饰环上,制备离子交换材料溶液,它含有100体积%的全氟磺酸/四氟乙烯共聚树脂溶液(以H+形式,其本身由10%全氟磺酸/四氟乙烯共聚树脂,10%水和80%的低分子量市售醇的混合物组成,Asahi玻璃与化学品公司有售,品名为Flemion F950型(950EW),下文简称“F950”)用4”宽海棉刷将该溶液刷涂到薄膜的两面上,让其向内浸透。然后将样品用电吹风吹干2分钟,再在180烘箱内干燥3分钟。该过程重复三次以上,使膜内空隙充分闭塞。干燥后复合膜的厚度经测量约为原来基材的18%(18μm)。硬度列于表1,此样品的尺寸稳定性列于表2。

实施例3采用与实施例2相同方法制备样品。测量短路时压力,测量结果列于表3。

实施例4采用与实施例1相同方法制备样品。按照上述方法测量此样品用于燃料电池的寿命。该值列于表4内为1000小时。

实施例5采用与实施例2相同方法制备样品。按照上述方法测量此样品用于燃料电池的寿命。上述薄膜的使用寿命达2000小时。

比较例1FORE-SELECT膜,一种全氟磺酸/四氟乙烯(TFE)共聚阳离子交换膜,经ePTFE增强,其标称厚度为25μm。该样品按授权给Bahar等人的USPat.No.5,814,405所述方法制作。该样品经过如前所述的尺寸稳定性试验,硬度试验,和燃料电池寿命试验,以及强度测试。测试结果列于表1-5。

比较例2Nafion 101(N101),一种1000EW重量的未增强的全氟磺酸/四氟乙烯(TFE)/共聚阳离子交换膜,德拉韦州格拉斯哥的Ion Power公司有售。其标称厚度为1密耳(0.025mm)。如前所述,该样品经过硬度,尺寸稳定性和燃料电池寿命试验。实验结果分别列于表1,2和4。

不愿对本发明的范围加以限制,离子交换膜的测试数据是根据前面实施例方法采集,并列于各表之中。正如本领域技术人员所知,表内这些数据揭示了本发明离子交换膜在水合作用下能维持原有尺寸,与已知的增强膜和未增强的ePTFE离子交换膜相比,硬度高得多。而且,将本发明膜用于燃料电池中,其寿命获得提高。

表1硬度

表2尺寸稳定性和穿透膜面水合膨胀率(尺寸变化百分率%)

表3引发短路的压力

表4燃料电池寿命

表5强度

Claims (21)

1.一种复合膜,包括:(a)膨胀聚四氟乙烯膜,它的内部微结构基本上由原纤维交织的结节组成,所述结节基本上平行排列,结节高度拉伸,其径宽比等于或大于25∶1;(b)浸透该薄膜的离子交换树脂,此浸渍过的膨胀聚四氟乙烯膜的Gurley数大于10,000秒,其中离子交换材料基本上浸透该膜,使膜内空穴基本上闭塞。
2.如权利要求1所述的复合膜,其硬度大于1000MPa。
3.如权利要求1所述的复合膜,其硬度大于1500MPa。
4.如权利要求1所述的复合膜,其硬度大于2000MPa。
5.如权利要求1所述的复合膜,其纵向尺寸稳定性小于6%。
6.如权利要求1所述的复合膜,其纵向尺寸稳定性小于4%。
7.如权利要求1所述的复合膜,其纵向尺寸稳定性小于2%。
8.如权利要求1所述的复合膜,其横向尺寸稳定性小于10%。
9.如权利要求1所述的复合膜,其横向尺寸稳定性小于8%。
10.如权利要求1所述的复合膜,其横向尺寸稳定性小于6%。
11.如权利要求1所述的复合膜,其横向尺寸稳定性小于4%。
12.如权利要求1所述的复合膜,其引发短路时压力大于400psi。
13.如权利要求1所述的复合膜,其引发短路时压力大于200psi。
14.膜电极组合件,包括权利要求1所述的复合膜以及阳极和阴极。
15.燃料电池,含括权利要求12所述的膜电极组合件。
16.电解质电池,包括权利要求1所述的复合膜和至少一个阳极与阴极。
17.权利要求1所述的复合膜,其强度在纵向上大于8,500psi。
18.权利要求1所述的复合膜,其强度在横向上大于8,500psi。
19.权利要求1所述的复合膜,其穿透膜面的水合膨胀率大于30%。
20.权利要求1所述的复合膜,其穿透膜面的水合膨胀率大于40%。
21.复合膜,包含结节和原纤维交织而成的通道的微结构的基质材料,其硬度大于1000MPa,离子交换材料浸透此基质材料,复合膜的Gurley数大于10,000秒,其中离子交换材料完全浸透基膜使所属通道基本上闭塞。
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