CN115332624A - 热稳定、超薄轻质、阻燃peo基固态电解质的制备方法 - Google Patents
热稳定、超薄轻质、阻燃peo基固态电解质的制备方法 Download PDFInfo
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Abstract
本发明公开了一种热稳定、超薄轻质、阻燃PEO基固态电解质的制备方法,包括以下步骤:利用静电纺丝制备刚性PAN支撑层‑活化MOF材料,而后去除其微孔内的客体分子‑合成负载阻燃剂的MOF@FR改性填料‑将一定配比的PEO与NaTFSI以及MOF@FR在乙腈中进行混合搅拌,得到PEO基固态电解质的浆料‑将PEO基固态电解质的浆料涂覆在PAN支撑层的两面并烘干,得到PAN支撑膜‑热压。本发明采用上述方法,通过具有多重功能的改性核壳MOF填料来提高PEO基固态聚合物电解质的电化学性能和阻燃性,并以具有优异机械性能和高温热稳定性的静电纺丝PAN膜作为支撑层提高机械韧性,在实现阻燃性能、优异的机械性能和电化学性能的同时,具有超薄的厚度,有利于钠电池高能量密度的实现。
Description
技术领域
本发明涉及一种钠电池固态电解质材料技术,尤其涉及一种热稳定、超薄轻质、阻燃PEO基固态电解质的制备方法。
背景技术
目前,锂电体系已经运用到生活中的各个方面。由于全球锂资源的有限性,且我国目前还没有大规模的锂矿,所以对国内企业来说锂资源算是一种稀缺资源。同时由于钠电池钠储量远过于锂,生产成本低(比锂电池体系成本下降30%-40%左右)以及与锂电池工作原理类似等优点被认为是锂电池体系的替代产品。
为了构建高比能电池体系,我们希望电池正极电位尽可能高,负极电位尽可能低。基于此直接使用钠金属(低还原电位-2.71 V)作为负极的钠金属电池最高理论比容量可达1165 mAh/g。因此钠金属电池是实现高比能电池,解决锂电池资源缺陷和价格上涨的新型策略。
但是目前钠金属电池所面临的挑战主要是金属钠与液态电解液非常容易发生不可逆的化学反应,从而降低电池的循环稳定性,以及有机电解液由于热失控引发的易泄露、易燃、易爆等安全性问题。
目前已有多种钠电池用固态电解质被开发解决此类问题。比如采用固态电解质。与易燃、易挥发的液体电解质相比,固态电解质的安全性得到明显提升,并保护金属阳极组件,从而使电池的更高理论能量密度和运行可靠性朝着更广泛的应用范围发展。其中在所有的固态电解质中,PEO基固态聚合物电解质因其具有的优异的碱金属盐溶解性、易加工和低成本等优点被认为具有很大的发展潜力。
但是固态电解质仍然存在安全隐患,尤其是针对聚合物电解质而言。PEO是一种典型的易燃聚合物,本身极易燃烧,在热失控条件下会释放大量的热量,进一步增加电池爆炸的风险,这使其应用到电池中非常致命。阻燃剂(FR)直接添加是提高合成聚合物防火安全性的常用方法。然而阻燃剂与金属阳极的不相容性,以及对相应复合材料热稳定性和力学性能的恶化。这使得设计防火安全的聚合物电解质仍然是一个挑战。
即如何在不影响电化学性能的同时提升钠电池用PEO基固态电解质的阻燃性能亟待解决。
发明内容
本发明公开了一种含有阻燃剂的核壳结构的MOF颗粒(MOF微孔内灌入阻燃剂DMMP)作为阻燃性无机填料,辅以热稳定性的静电纺丝聚丙烯腈(PAN)膜作为支撑层的超薄、轻质、高机械强度PEO基固态电解质的制备方法。解决了传统固态电解质的安全性虽然得到了提升,但是仍然存在安全隐患,尤其是针对固态聚合物电解质而言,因为聚合物基底(如PEO)是极易燃烧的,在电池热失控时释放出大量的热量同样会剧烈燃烧甚至爆炸的问题。
为实现上述目的,本发明提供了一种热稳定、超薄轻质、阻燃PEO基固态电解质的制备方法,包括以下步骤:
步骤1、利用静电纺丝制备刚性PAN支撑层;
步骤2、活化MOF材料,而后去除其微孔内的客体分子;
步骤3、基于步骤2制备的活化后的MOF材料,合成负载阻燃剂的MOF@FR改性填料;
步骤4、将一定配比的PEO与NaTFSI以及MOF@FR在乙腈中进行混合搅拌,得到PEO基固态电解质的浆料;
步骤5、将PEO基固态电解质的浆料通过涂覆机涂覆在PAN支撑层的两面并烘干,得到PAN支撑膜;
步骤6、将烘干的PEO基固态电解质热压。
优选的,所述步骤1具体包括以下步骤:
步骤1.1、将PAN粉末置于60 ℃真空环境下干燥12 h;
步骤1.2、称取1 g 干燥后的PAN粉末溶于N,N-二甲基甲酰胺中,配制质量分数为10%的溶液;
步骤1.3、在室温环境下搅拌1.5 h后完全溶解,获得静电纺丝前驱液;
步骤1.4、通过控制静电纺丝工艺参数纺出纤维尺寸均一的PAN膜;
步骤1.5、将制备的PAN膜于真空烘箱中并于100 ℃条件下真空干燥24 h,去除残留溶剂及水分。
优选的,所述步骤1.4中的静电纺丝工艺参数为:高压电15 KV,低压电-2 KV,喷头流速0.1 mm/min,接收器的转速600 r/min,喷头与接收器距离15 cm,平移距离200 cm。
优选的,所述步骤2具体包括以下步骤:
通过水热法合成的MOF材料置于真空烘箱中并于170 ℃条件下真空干燥5 h,去除MOF微孔内的客体分子。
优选的,所述客体分子包括残留有机溶剂及空气中的水分。
优选的,所述步骤3具体包括以下步骤:
步骤3.1、将活化后的MOF粉末完全浸入甲基膦酸二甲酯溶剂中3天,在此过程中,每隔12 h更换一次甲基膦酸二甲酯溶剂,确保最大量的甲基膦酸二甲酯填充MOF的孔隙;
步骤3.2、用甲醇快速清洗粉末,去除附着在MOF颗粒表面的甲基膦酸二甲酯;
步骤3.3、在室温下干燥。
优选的,所述步骤4中的MOF@FR的占比为的30%,PEO和NaTFSI的配比为[EO/Na+]=15:1,搅拌时间为10小时。
优选的,所述步骤5中PAN支撑膜的厚度为10-20 μm,PEO基固态电解质的浆料的涂覆刻度为15-35μm。
优选的,所述步骤5中烘干过程为先置于室温下12h,然后置于真空烘箱中并于60℃条件下烘干12h。
优选的,所述步骤6中热压压力为50 MPa, 热压温度为65℃,热压时间为10-30min。
因此,本发明采用上述方法具有以下有益效果:
1、将阻燃剂封装在保护性MOF孔道内,防止了阻燃剂直接溶解在电解质中对电解质电化学性能和机械性能产生负面影响。在电池的热失控过程中,由于温度的升高,填料内部阻燃剂溢出,有效抑制高可燃电解质的燃烧。
2、热稳定性的静电纺丝PAN框架使聚合物电解质薄层的形成在机械强度(MPa)下得到数量级的改善,使得聚合物电解质薄膜表现出出色的抑制钠枝晶生长的能力。
即使用改用核壳结构的MOF@FR填料,并以静电纺丝PAN膜作为支撑层,制备热稳定性、超薄、轻质的阻燃PEO基固态电解质,提升阻燃性的同时避免阻燃剂对电解质机械性能和电化学性能的负面作用,并且使所组装的电池具有高的倍率性能及高的循环性能,有利于钠电池高能量密度的实现。
下面通过附图和实施例,对本发明的技术方案做进一步的详细描述。
附图说明
图1为本发明的实施例1的TEM图;
图2为本发明的实施例1的SEM图;
图3为本发明的实施例1的FTIR图;
图4为本发明的实施例1的TG图;
图5为本发明的实施例1的DTG图;
图6为本发明的实施例1的XRD图;
图7为本发明的实施例1与对比例1和对比例2中制备的 PEO基固态电解质的微型量热仪测试对比图;
图8为本发明实施例1、对比例2中制备的PEO基固态电解质的点燃测试对比图;
图9为本发明实施例1、对比例1、对比例2中制备的PEO基固态电解质的SEM对比图;
图10为本发明实施例1、对比例1、对比例2中制备的PEO基固态电解质的应力应变曲线对比图;
图11为本发明实施例1、对比例1、对比例2中制备的PEO基固态电解质的临界电流密度对比图;
图12为本发明实施例1、对比例1、对比例2中制备的PEO基固态电解质的离子电导率对比图;
图13为本发明实施例1制备的PEO基固态电解质的钠离子迁移数变化图;
图14为本发明对比例1制备的PEO基固态电解质的钠离子迁移数变化图;
图15为本发明实施例1、对比例1和对比例2中制备的 PEO基固态电解质循环曲线对比图;
图16为本发明实施例1、对比例1和对比例2中制备的PEO基固态电解质的倍率性能对比图。
具体实施方式
以下将结合附图对本发明作进一步的描述,需要说明的是,本实施例以本技术方案为前提,给出了详细的实施方式和具体的操作过程,但本发明的保护范围并不限于本实施例。
图1为本发明的实施例一种的结构示意图,如图1所示,本发明包括以下步骤:
步骤1、利用静电纺丝制备刚性PAN支撑层;
优选的,所述步骤1具体包括以下步骤:
步骤1.1、将PAN粉末置于60 ℃真空环境下干燥12 h;
步骤1.2、称取1 g 干燥后的PAN粉末溶于N,N-二甲基甲酰胺中(DMF),配制质量分数为10%的溶液;
步骤1.3、在室温环境下搅拌1.5 h后完全溶解,获得静电纺丝前驱液;
步骤1.4、通过控制静电纺丝工艺参数纺出纤维尺寸均一的PAN膜;
步骤1.5、将制备的PAN膜于真空烘箱中并于100 ℃条件下真空干燥24 h,去除残留溶剂及水分。
优选的,所述步骤1.4中的静电纺丝工艺参数为:高压电15 KV,低压电-2 KV,喷头流速0.1 mm/min,接收器的转速600 r/min,喷头与接收器距离15 cm,平移距离200 cm。
步骤2、活化MOF材料,而后去除其微孔内的客体分子;
优选的,所述步骤2具体包括以下步骤:
通过水热法合成的MOF材料(HKUST-1)置于真空烘箱中并于170 ℃条件下真空干燥5 h,去除MOF微孔内的客体分子。优选的,所述客体分子包括残留有机溶剂及空气中的水分。
步骤3、基于步骤2制备的活化后的MOF材料,合成负载阻燃剂的MOF@FR改性填料;
优选的,所述步骤3具体包括以下步骤:
步骤3.1、将活化后的MOF粉末完全浸入甲基膦酸二甲酯溶剂(DMMP)中3天,在此过程中,每隔12 h更换一次甲基膦酸二甲酯溶剂,确保最大量的甲基膦酸二甲酯填充MOF的孔隙;
步骤3.2、用甲醇快速清洗粉末,去除附着在MOF颗粒表面的甲基膦酸二甲酯;
步骤3.3、在室温下干燥。
步骤4、将一定配比的PEO与NaTFSI以及MOF@FR在乙腈中进行混合搅拌,得到PEO基固态电解质的浆料;
优选的,所述步骤4中的MOF@FR(HKUST-1@DMMP)的占比为的30%,PEO和NaTFSI的配比为[EO/Na+]=15:1,搅拌时间为10小时。
步骤5、将PEO基固态电解质的浆料通过涂覆机涂覆在PAN支撑层的两面并烘干,得到PAN支撑膜;
优选的,所述步骤5中PAN支撑膜的厚度为10-20 μm,PEO基固态电解质的浆料的涂覆刻度为15-35μm。且所述步骤5中烘干过程为先置于室温下12h,然后置于真空烘箱中并于60℃条件下烘干12h。
步骤6、将烘干的PEO基固态电解质热压。
优选的,所述步骤6中热压压力为50 MPa, 热压温度为65℃,热压时间为 10-30min。
为进一步说明提供以下实施例和对比例:
实施例1公开了以下制备方法:
步骤1、将1 g PAN(已真空干燥)溶于N,N-二甲基甲酰胺(DMF)中配制质量分数为10%的溶液,在室温搅拌1.5 h后完全溶解,获得静电纺丝前驱液。通过控制静电纺丝工艺参数(高压电:15 KV,低压电:-2 KV,喷头流速:0.1 mm/min,接收器的转速:600 r/min,喷头与接收器距离15 cm,平移距离:200 cm)纺出纤维尺寸均一的PAN膜。随后,将制备的PAN膜于真空烘箱中100 ℃真空干燥24 h,去除残留溶剂及水分;
步骤2、通过水热法合成的MOF材料(HKUST-1)于真空烘箱中170 ℃ 真空干燥5 h,去除MOF微孔内客体分子(客体分子包括残留有机溶剂及空气中的水分);
步骤3、将活化后的MOF粉末浸入甲基膦酸二甲酯(DMMP)中3天,每隔12 h更换一次DMMP溶剂,确保最大量的DMMP填充MOF的孔隙。然后,用甲醇快速清洗粉末,去除附着在颗粒表面的DMMP,并在室温下干燥;
步骤4、将500 mg PEO与245 mg NaTFSI、214 mg MOF@FR在乙腈中进行混合搅拌,得到PEO基固态电解质的浆料;搅拌时间为10小时;
步骤5、将PEO基固态电解质的浆料通过涂覆机涂敷在静电纺丝PAN框架两面并烘干;PAN支撑膜的厚度为10-20 μm;PEO基固态电解质的浆料的涂覆刻度为15-35μm;烘干过程为先室温12小时,然后真空烘箱60度12小时;
步骤6、将烘干的PEO基固态电解质热压;热压压力为50 MPa, 热压温度为65度,热压时间为 15 min。
对比例1
步骤1、将500 mg PEO与245 mg NaTFSI在乙腈中进行混合搅拌,得到PEO基固态电解质的浆料;搅拌时间为10小时;
步骤2、将得到PEO基固态电解质的浆料浇筑到聚四氟乙烯的模具上,室温烘干12小时,真空60度烘干12小时;
对比例2
步骤1、将1 g PAN(已真空干燥)溶于N,N-二甲基甲酰胺(DMF)中配制质量分数为10%的溶液,在室温搅拌1.5 h后完全溶解,获得静电纺丝前驱液。通过控制静电纺丝工艺参数(高压电:15 KV,低压电:-2 KV,喷头流速:0.1 mm/min,接收器的转速:600 r/min,喷头与接收器距离15 cm,平移距离:200 cm)纺出纤维尺寸均一的PAN膜。随后,将制备的PAN膜于真空烘箱中100 ℃真空干燥24 h,去除残留溶剂及水分;
步骤2、将500 mg PEO与245 mg NaTFSI在乙腈中进行混合搅拌,得到PEO基固态电解质的浆料;搅拌时间为10小时;
步骤3、将PEO基固态电解质的浆料通过涂覆机涂敷在静电纺丝PAN框架两面并烘干;PAN支撑膜的厚度为10-20 μm;PEO基固态电解质的浆料的涂覆刻度为15-35μm;烘干过程为先室温12小时,然后真空烘箱60度12小时;
步骤4、将烘干的PEO基固态电解质热压;热压压力为50 MPa, 热压温度为65度,热压时间为 15 min。
透射电子显微镜(TEM)表征
将本发明实施例1中制备的改性核壳结构MOF@FR进行TEM表征,结果如图1为本发明的实施例1的TEM图;图2为本发明的实施例1的SEM图,如图1和图2,可以看到所制备的改性核壳结构MOF@FR有P元素的存在;
红外光谱(FTIR)表征
图3为本发明的实施例1的FTIR图,将本发明实施例1中制备的改性核壳结构MOF@FR进行FTIR表征,结果如图3所示,可以看到制备的改性核壳结构MOF@FR分别存在MOF, FR的极性基团的非对称振动特征峰;
热重分析仪(TG)测试
图4为本发明的实施例1的TG图;图5为本发明的实施例1的DTG图,将本发明实施例1中制备的改性核壳结构MOF@FR进行TG表征,结果如图4、5所示,可以看到制备的改性核壳结构MOF@FR与FR仅暴露于MOF表面不同,证明FR已被固定在MOF保护性孔道内;
X射线衍射仪(XRD)表征
图6为本发明的实施例1的XRD图,将本发明实施例1中制备的改性核壳结构MOF@FR进行XRD表征,结果如图6所示,可以看到制备的改性核壳结构MOF@FR与MOF具有相同晶体结构,MOF框架未遭到破坏;
微型量热仪(MCC)测试
图7为本发明的实施例1与对比例1和对比例2中制备的 PEO基固态电解质的微型量热仪测试对比图,将本发明实施例1、对比例1、对比例2中制备的PEO基固态电解质进行MCC (微型量热仪)测试,结果如图7所示,以改性核壳结构MOF@FR作为填料制备的PEO基固态电解质,热释放速率峰值(peak Heat Release Rate, pHRR)由629 W g-1和628.2 W g-1降至344.5 W g-1
点燃表征:
图8为本发明实施例1、对比例2中制备的PEO基固态电解质的点燃测试对比图,将本发明实施例1、对比例2中制备的PEO基固态电解质进行点燃测试,结果如图8所示,改性阻燃电解质相较于纯PEO缓解了燃烧情况,具有自熄性;
扫描电子显微镜(SEM)表征:
图9为本发明实施例1、对比例1、对比例2中制备的PEO基固态电解质的SEM对比图,将本发明实施例1中制备的PEO基固态电解质进行SEM表征,结果如图9所示,可以看到所制备的PEO基固态电解质厚度约为25μm;
力学性能测试
图10为本发明实施例1、对比例1、对比例2中制备的PEO基固态电解质的应力应变曲线对比图,将本发明实施例1、对比例1、对比例2中制备的PEO基固态电解质(120μm、25μm、25μm)进行应力应变测试,结果如图10所示,可观察到实施例1中制备的PEO基固态电解质的机械性能得到了很大的提高;
临界电流密度(CCD)测试
图11为本发明实施例1、对比例1、对比例2中制备的PEO基固态电解质的临界电流密度对比图,将本发明实施例1、对比例1、对比例2中制备的PEO基固态电解质(120μm、25μm、25μm)进行临界电流密度测试,结果如图11所示, 可观察到实施例1中制备的PEO基固态电解质相比于对比例1和对比例2具有更高的临界电流密度和更低的过电位,同时综合临界电流密度、过电位以及力学性能测试,实施例1的综合性能最为优异;
离子电导率测试(EIS)
图12为本发明实施例1、对比例1、对比例2中制备的PEO基固态电解质的离子电导率对比图,将本发明实施例1、对比例1、对比例2中制备的PEO基固态电解质进行离子电导率测试,结果如图12所示,可观察到实施例1中制备的PEO基固态电解质具有更高的离子电导率;
钠离子迁移数测试(i-t)
图13为本发明实施例1制备的PEO基固态电解质的钠离子迁移数变化图;图14为本发明对比例1制备的PEO基固态电解质的钠离子迁移数变化图,将本发明实施例1中制备的PEO基固态电解质进行锂离子迁移数测试,结果如图13所示;将对比例1所得的传统PEO基固态电解质进行离子迁移数测试,结果如图14所示;可观察到实施例1中制备的PEO基固态电解质具有更高的的锂离子迁移数(0.76);
电化学性能测试
图15为本发明实施例1、对比例1和对比例2中制备的 PEO基固态电解质循环曲线对比图;图16为本发明实施例1、对比例1和对比例2中制备的PEO基固态电解质的倍率性能对比图,将本发明实施例1、对比例1、对比例2中制备的PEO基固态电解质与Na3V2(PO4)3正极以及钠金属负极组装纽扣电池进行电化学性能测试,结果如图15、16所示,实施例1中制备的PEO基固态电解质具有更好的循环性能和倍率性能。
通过实施例1与对比例1和对比例2可以看出本发明制备的改性核壳结构MOF@FR避免了阻燃剂直接溶解在电解质中所造成的负面影响,并发挥阻燃作用。以此为填料制备的热稳定性、超薄、轻质的阻燃PEO基固态电解质在厚度约为25μm时,其的机械性能、离子电导率以及临界电流密度的综合性能较好,通过实施例1与对比例1可以看出本发明制备的热稳定性、超薄、轻质的阻燃PEO基固态电解质(25μm厚)具有更优异的机械性能、离子电导率、离子迁移数以及临界电流密度,所组装的电池具有更好的循环性能和倍率性能。综合以上优点,该电解质膜有利于实现全固态钠金属电池高能量密度的同时,实现阻燃性和安全性。
因此,本发明采用上述方法,当将具有高孔隙率、良好的热稳定性和超大的比表面积等特点的多孔金属-有机框架(MOF)颗粒,应用于固态聚合物电解质时,超大的比表面积和金属离子(内)-有机配体(外)形成的电荷分布结构可以吸附阴离子,释放更多可自由传导的离子。另一方面,MOF可以提高聚合物的阻燃性。另外,MOF材料的多孔特性在气体分离、过滤和捕捉挥发性有机物已得到广泛应用。因此,利用MOF的多孔特性吸附阻燃剂形成的核壳结构的MOF@FR改性MOF颗粒用于聚合物基的无机填料,一方面可以发挥MOF本身能够提高聚合物离子迁移数的电化学作用,另一方面可以提高聚合物基固态电解质的阻燃性能。同时,为了提高电芯体系的能量密度,采用具有热稳定性且耐氧化的PAN静电纺丝膜作为刚性骨架,用来制备超薄、轻质、高机械强度PEO基阻燃固态电解质。
最后应说明的是:以上实施例仅用以说明本发明的技术方案而非对其进行限制,尽管参照较佳实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对本发明的技术方案进行修改或者等同替换,而这些修改或者等同替换亦不能使修改后的技术方案脱离本发明技术方案的精神和范围。
Claims (10)
1.一种热稳定、超薄轻质、阻燃PEO基固态电解质的制备方法,其特征在于:包括以下步骤:
步骤1、利用静电纺丝制备刚性PAN支撑层;
步骤2、活化MOF材料,而后去除其微孔内的客体分子;
步骤3、基于步骤2制备的活化后的MOF材料,合成负载阻燃剂的MOF@FR改性填料;
步骤4、将一定配比的PEO与NaTFSI以及MOF@FR在乙腈中进行混合搅拌,得到PEO基固态电解质的浆料;
步骤5、将PEO基固态电解质的浆料通过涂覆机涂覆在PAN支撑层的两面并烘干,得到PAN支撑膜;
步骤6、将烘干的PEO基固态电解质热压。
2.根据权利要求1所述的热稳定、超薄轻质、阻燃PEO基固态电解质的制备方法,其特征在于:所述步骤1具体包括以下步骤:
步骤1.1、将PAN粉末置于60 ℃真空环境下干燥12 h;
步骤1.2、称取1 g 干燥后的PAN粉末溶于N,N-二甲基甲酰胺中,配制质量分数为10%的溶液;
步骤1.3、在室温环境下搅拌1.5 h后完全溶解,获得静电纺丝前驱液;
步骤1.4、通过控制静电纺丝工艺参数纺出纤维尺寸均一的PAN膜;
步骤1.5、将制备的PAN膜于真空烘箱中并于100 ℃条件下真空干燥24 h,去除残留溶剂及水分。
3.根据权利要求2所述的热稳定、超薄轻质、阻燃PEO基固态电解质的制备方法,其特征在于:所述步骤1.4中的静电纺丝工艺参数为:高压电15 KV,低压电-2 KV,喷头流速0.1mm/min,接收器的转速600 r/min,喷头与接收器距离15 cm,平移距离200 cm。
4.根据权利要求1所述的热稳定、超薄轻质、阻燃PEO基固态电解质的制备方法,其特征在于:所述步骤2具体包括以下步骤:
通过水热法合成的MOF材料置于真空烘箱中并于170 ℃条件下真空干燥5 h,去除MOF微孔内的客体分子。
5.根据权利要求1或4所述的热稳定、超薄轻质、阻燃PEO基固态电解质的制备方法,其特征在于:所述客体分子包括残留有机溶剂及空气中的水分。
6.根据权利要求1所述的热稳定、超薄轻质、阻燃PEO基固态电解质的制备方法,其特征在于:所述步骤3具体包括以下步骤:
步骤3.1、将活化后的MOF粉末完全浸入甲基膦酸二甲酯溶剂中3天,在此过程中,每隔12 h更换一次甲基膦酸二甲酯溶剂,确保最大量的甲基膦酸二甲酯填充MOF的孔隙;
步骤3.2、用甲醇快速清洗粉末,去除附着在MOF颗粒表面的甲基膦酸二甲酯;
步骤3.3、在室温下干燥。
7.根据权利要求1所述的热稳定、超薄轻质、阻燃PEO基固态电解质的制备方法,其特征在于:所述步骤4中的MOF@FR的占比为的30%,PEO和NaTFSI的配比为[EO/Na+]=15:1,搅拌时间为10小时。
8.根据权利要求1所述的热稳定、超薄轻质、阻燃PEO基固态电解质的制备方法,其特征在于:所述步骤5中PAN支撑膜的厚度为10-20 μm,PEO基固态电解质的浆料的涂覆刻度为15-35μm。
9.根据权利要求1所述的热稳定、超薄轻质、阻燃PEO基固态电解质的制备方法,其特征在于:所述步骤5中烘干过程为先置于室温下12h,然后置于真空烘箱中并于60℃条件下烘干12h。
10.根据权利要求1所述的热稳定、超薄轻质、阻燃PEO基固态电解质的制备方法,其特征在于:所述步骤6中热压压力为50 MPa, 热压温度为65℃,热压时间为10-30 min。
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