CN113285118A - 一种基于mof三维骨架支撑的复合物固态电解质及其制备方法 - Google Patents
一种基于mof三维骨架支撑的复合物固态电解质及其制备方法 Download PDFInfo
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Abstract
本发明属于固态电解质的技术领域,具体涉及一种基于MOF三维骨架支撑的复合物固态电解质及其制备方法,其制备包括如下步骤:将锂盐‑聚合物溶液浇筑到纳米纤维材料中,得到具有三维骨架结构的复合物固态电解质;所述锂盐‑聚合物溶液的制备为锂盐与聚合物混合溶于有机溶剂中;所述纳米纤维材料的制备为将MOF粉体材料与聚合物分别溶解混合,通过静电纺丝得到。所述复合物固态电解质的MOF基三维骨架支撑的构筑不仅能为锂离子提供连续的传输通道,有效地提升了锂离子迁移数,而且其三维骨架与高度连接晶体结构的组合显著增强了复合固态电解质的机械性能,从而从物理上有效地阻碍锂枝晶的生长,能够更好地应用于锂金属负极二次电池。
Description
技术领域
本发明属于固态电解质的技术领域,具体涉及一种基于MOF三维骨架支撑的复合物固态电解质及其制备方法。
背景技术
锂离子电池因其能量密度高、自放电率低及循环寿命长等特点成为便携电子设备、电动汽车和无人机的主要储能装置。然而,锂离子电池的高性能与安全性仍然是一个棘手的问题。同时,对高能量密度锂电池不断增长的需求促使人们使用金属锂阳极,这使得安全性问题更加突出。锂离子电池在电化学锂电镀和剥离过程中形成的锂枝晶可穿透隔膜,内部短路导致强烈的热量释放,并具有潜在的爆炸危险。充放电过程中锂枝晶形成的固有问题以及锂金属低的库伦效率严重阻碍了其在锂金属电池中的应用。
固态电解质因其离子电导率高、机械强度大、非挥发性、不易燃和化学/电化学稳定性好而作为锂金属电池中易燃液体电解质的替代品,并引起了极大的关注。固态电解质可归纳为三类:无机(陶瓷/玻璃)固态电解质、聚合物固态电解质及复合物固体电解质。无机固态电解质离子电导率很高,但是仍然存在致命的缺点,比如质脆且硬,与电极接触存在的界面问题等。聚合物固态电解质的室温离子电导率不高,但聚合物具有较好的柔性和对电极界面稳定性。复合物固体电解质能充分发挥无机固态电解质与聚合物固态电解质两者优点,因此,本发明致力于提供一种性能优异的复合固态电解质。
发明内容
针对上述问题,本发明的目的在于提供一种基于MOF三维骨架支撑的复合物固态电解质及其制备方法,通过静电纺丝,将具有丰富锂离子传导位点的MOF材料均匀分布在聚合物纤维上构筑三维骨架支撑,形成一个三维连续的锂离子快速传输通道,进一步将聚合物/锂盐填充到MOF三维支撑结构中制备出新型离子导电率高、机械性能好、界面阻抗低的复合固态电解质。
本发明的技术内容如下:
本发明提供了一种基于MOF三维骨架支撑的复合物固态电解质的制备方法,包括如下步骤:
将锂盐-聚合物溶液浇筑到纳米纤维材料中,得到具有三维骨架结构的复合物固态电解质;
所述锂盐-聚合物溶液的制备为锂盐与聚合物混合溶于有机溶剂中,锂盐与聚合物的使用比例为(0.1~10):1;
所述纳米纤维材料的制备为将MOF粉体材料与聚合物分别溶解混合,通过静电纺丝得到,MOF粉体材料与聚合物的使用比例为1:(0.2~5);
所述锂盐-聚合物溶液中的聚合物包括聚环氧乙烷(PEO)、聚丙烯腈(PAN)、聚碳酸酯(PC)、聚偏二氟乙烯(PVDF)的一种;
所述锂盐包括双氟磺酰亚胺锂盐(LiFSI)、双三氟甲磺酰亚胺锂盐(LiTFSI)、二氟草酸硼酸锂盐(LiODFB)、六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、三氟甲磺酸锂(LiOTF)、二草酸硼酸锂(LiBOB)、高氯酸锂(LiClO4)、六氟合砷酸锂(LiAsF6)的一种或以上;
所述MOF粉体材料包括UIO-66、UIO-66-NH2、ZIF-8、HKUST、MOF-74、MOF-100、MIL-101的一种;
所述纳米纤维材料的制备所采用的聚合物包括聚丙烯腈(PAN)、聚乙烯醇(PVA)、聚偏二氟乙烯(PVDF)、聚甲基丙烯酸甲酯(PMMA)、聚己内酯(PCL)、聚酰胺-酰亚胺(PAI)的一种。
本发明还提供了一种以上所述制备方法制得的基于MOF三维骨架支撑的复合物固态电解质,所述复合物固态电解质为通过MOF材料与聚合物构筑成三维骨架结构,并在三维骨架结构上填充锂盐-聚合物溶液制备得到;
以上所述基于MOF三维骨架支撑的复合物固态电解质应用于锂金属电池,主要应用于锂金属负极二次电池。
本发明的有益效果如下:
本发明的基于MOF三维骨架支撑的复合物固态电解质的制备方法,通过静电纺丝,将具有丰富锂离子传导位点的MOF材料均匀分布在聚合物纤维上构筑三维骨架支撑,形成一个三维连续的锂离子快速传输通道,进一步将聚合物/锂盐填充到MOF三维支撑结构中制备出新型离子导电率高、机械性能好、界面阻抗低的MOF-聚合物复合固态电解质薄膜;
本发明的基于MOF三维骨架支撑的复合物固态电解质,其MOF基三维骨架支撑的构筑不仅能为锂离子提供连续的传输通道,有效地提升了锂离子迁移数,而且其三维骨架与高度连接晶体结构的组合显著增强了复合固态电解质的机械性能,从而从物理上有效地阻碍锂枝晶的生长。同时,MOFs材料本身具有丰富的有序孔道结构能够促进锂盐的分离,促使锂离子能够沿着MOFs的有序孔道均匀地沉积到锂负极,从而抑制锂枝晶的生长,提高了电池的循环稳定性。
附图说明
图1为实施例1中MOF材料的扫描电镜图;
图2为实施例1中MOF材料的粉末衍射图;
图3为实施例1中纳米纤维材料的扫描电镜图;
图4为实施例1的复合物固态电解质的的扫描电镜图;
图5为本发明的复合物固态电解质的合成示意图;
图6为实施例1的三维骨架支撑的复合物固态电解质的Li|Li对称电池在电流密度为0.3 mA/cm2、60℃下长循环性能图;
图7为各种复合物固态电解质组装的LiFePO4|Li电池在电流密度为0.5 C、60℃下的循环性能对比图;
图8为各种复合物固态电解质组装的LiFePO4|Li电池在电流密度为0.1C-1C、60℃下的倍率性能对比图。
具体实施方式
以下通过具体的实施案例以及附图说明对本发明作进一步详细的描述,应理解这些实施例仅用于说明本发明而不用于限制本发明的保护范围,在阅读了本发明之后,本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定。
若无特殊说明,本发明的所有原料和试剂均为常规市场的原料、试剂。
实施例1
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:将氯化锆,对苯二甲酸在以1:1的摩尔比在N,N-二甲基甲酰胺(DMF)中超声溶解备用,将浓盐酸、苯甲酸以1:10的摩尔比添加到上述溶液中,然后在120℃反应釜中反应24 h。反应停止后,在10000 rpm转速下离心10分钟,得到白色粉末,将其依次用DMF、甲醇(MeOH)洗涤三次后,在100℃真空干燥箱中干燥24 h从而得到UIO-66粉末;
如图1所示,为合成的UIO-66材料的扫描电镜图,可见其呈现为均匀的八面体状;
图2为UIO-66材料的XRD粉末衍射图,可以发现合成的UIO-66粉末特征峰与UIO-66XRD模拟图谱十分吻合,表明UIO-66粉末成功合成;
2)纳米纤维材料:步骤1)合成的UIO-66材料超声溶解于DMF中,将PAN加入DMF中搅拌12 h,UIO-66、PAN与DMF质量比为1:0.5:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料(PAN/UIO-66),其扫描电镜图如图3所示,UIO-66材料均匀分布在PAN中;
3)锂盐-聚合物溶液:将PEO、LiTFSI以1:1的质量比溶解在乙腈中,得到PEO/LiTFSI混合溶液;
4)将PEO/LiTFSI浇筑在PAN/UIO-66上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质(PEO/LiTFSI/PAN/UIO-66),其扫描电镜图如图4所示,三维骨架结构的复合物固态电解质的横截面约为100 μm厚。
实施例2
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:将氯化锆、2-氨基对苯二甲酸在以1:1的摩尔比在去离子水与乙酸混合溶液(体积比3:2)中超声溶解,然后在100℃油浴锅中反应24 h。反应停止后,在10000 rpm转速下离心10分钟,得到淡黄色粉末,将其依次用DMF、MeOH洗涤三次后,在100℃真空干燥箱中干燥24 h从而得到UIO66-NH2粉末;
2)纳米纤维材料:将步骤1)合成的UIO66-NH2材料超声溶解于DMF中,将PAN加入DMF中搅拌12 h,UIO66-NH2、PAN与DMF质量比为1:1:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PEO、LiFSI以1:5的质量比溶解在乙腈中,得到PEO/LiFSI混合溶液;
4)将PEO/LiFSI浇筑在PAN/UIO66-NH2上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质。
实施例3
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:将Zn(NO3)2·6H2O、二甲基咪唑在以1:1的质量比分别溶解在体积比为3:2的甲醇溶液中,然后在55℃油浴锅中反应5分钟,室温静置48 h。反应停止后,在8000 rpm转速下离心8分钟,得到白色粉末,将其用MeOH洗涤三次后,在100℃真空干燥箱中干燥24 h从而得到ZIF-8粉末;
2)纳米纤维材料:将步骤1)合成的ZIF-8材料超声溶解于DMF中,将PCL加入DMF中搅拌12小时,ZIF-8、PCL与DMF质量比为1:2:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PEO、LiODFB以1.84:1的质量比溶解在乙腈中,得到PEO/LiODFB混合溶液;
4)将PEO/LiODFB浇筑在PCL/ZIF-8上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得三维骨架结构的复合物固态电解质。
实施例4
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:称取0.0495g 2,5-二羟基对苯二甲酸溶解于20 mL DMF、MeOH及H2O的混合溶液(体积比1:1:1),超声至配体完全溶解,再称取0.2403 g Co(NO3)2·6H2O完全溶解于上述溶液即得到红棕色合成液,将该合成液转移至含有聚四氟内衬的不锈钢反应釜中,置于100℃鼓风烘箱中晶化24 h。反应停止后,在8000 rpm转速下离心8分钟,得到黄色粉末将,其用DMF、MeOH洗涤三次后,在100℃真空干燥箱中干燥24 h从而得到MOF-74粉末;
2)纳米纤维材料:将步骤1合成的MOF-74材料超声溶解于DMF中,将PVA加入DMF中搅拌12 h,MOF-74、PVA与DMF质量比为1:3:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PAN、LiPF6以5.49:1的质量比溶解在乙腈中,得到PAN/LiPF6混合溶液;
4)将PAN/LiPF6浇筑在PVA/MOF-74上并晾干,100℃真空干燥24 h,放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得三维骨架结构的复合物固态电解质。
实施例5
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:将氯化锆、对苯二甲酸在以1:1的摩尔比在DMF中超声溶解备用,将浓盐酸、苯甲酸以1:10的摩尔比添加到上述溶液中,然后在120℃反应釜中反应24 h。反应停止后,在10000 rpm转速下离心10分钟,得到白色粉末,将其依次用DMF、MeOH洗涤三次后,在100℃真空干燥箱中干燥24 h从而得到UIO-66粉末;
2)纳米纤维材料:将步骤1)合成的UIO-66材料超声溶解于DMF中,将PVDF加入DMF中搅拌12 h,UIO-66、PVDF与DMF质量比为1:1:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PC、LiBF4在以1:10的质量比溶解在乙腈中,得到PC/LiBF4混合溶液;
4)将PC/LiBF4浇筑在PVDF/UIO-66上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质。
实施例6
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:将氯化锆、对苯二甲酸在以1:1的摩尔比在DMF中超声溶解备用,将浓盐酸、苯甲酸以1:10的摩尔比添加到上述溶液中,然后在120℃反应釜中反应24小时。反应停止后,在9000 rpm转速下离心9分钟,得到白色粉末,将其依次用DMF、MeOH洗涤三次后,在100℃真空干燥箱中干燥24 h,得到UIO-66粉末;
2)纳米纤维材料:将步骤1)合成的UIO-66材料超声溶解于DMF中,将聚酰胺-酰亚胺(PAI)加入DMF中搅拌12小时,UIO-66、PAI与DMF质量比为1:4:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝的到三维骨架结构的纳米纤维材料,然后在300℃下热处理得到聚酰亚胺(PI)三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PEO、LiOTF、LiBOB以8.15:1:1的质量比溶解在乙腈中,得到PEO/LiOTF/LiBOB混合溶液;
4)将PEO/LiOTF/LiBOB浇筑在PAI/UIO-66上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质。
实施例7
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:将3.93 g Cu(NO3)2·3H2O和2.00 g聚乙烯吡咯烷酮(PVP,(K30))溶解于250 mL甲醇(溶液A)中,2.15 g 1,3,5-三苯甲酸(H3BTC)溶解于250 mL甲醇(溶液B)中。随后,将溶液B逐滴加入溶液A中,并将所得溶液在室温下保存24小时,将所得的HKUST-1蓝色产品离心收集,用甲醇洗涤三次,然后在60℃下干燥,然后将所得产品放入150℃下的真空烘箱中过夜活化以去除通道中的微量溶剂,从而得到HKUST-1粉末;
2)纳米纤维材料:将步骤1合成的HKUST-1材料超声溶解于DMF中,将PMMA加入DMF中搅拌12 h,HKUST-1、PMMA与DMF质量比为1:1:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PVDF、LiAsF6以3:1的质量比溶于无水N,N-二甲基甲酰胺中,得到PVDF/LiAsF6混合溶液;
4)将PVDF/LiAsF6浇筑在PMMA/HKUST-1上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质。
实施例8
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:称量0.807 g (0.2 mol)九水合硝酸铁(Fe(NO3)3·9H2O)溶解于10 mL超纯水中,将其搅拌均匀后,准确称量0.420 g(0.2 mol)均苯三甲酸(H3BTC)加入其中,使用电动搅拌器将混合物匀速搅拌30 min,此时悬浊液变得均匀,便得到MOF-100(Fe)材料的前驱体物质。将制得的前驱体悬浮液转移至100 mL容量的聚四氟乙烯内衬中,放置反应釜内拧合后将其放入鼓风烘箱中去,并打开鼓风开光,调节温度至200℃,加热反应8 h,得到MOF-100(Fe)粉末;
2)纳米纤维材料:将步骤1合成的MOF-100(Fe)材料超声溶解于DMF中,将PVDF加入DMF中搅拌12 h,MOF-100(Fe)、PVDF与DMF质量比为1:2:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PEO、LiFSI以1:3的质量比溶解在乙腈中,得到PEO/LiFSI混合溶液;
4)将PEO/LiFSI浇筑在PVDF/MOF-100(Fe)上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质。
实施例9
一种基于MOF三维骨架支撑的复合物固态电解质的制备方法:
1)MOF粉体材料制备:取4.0 g Cr(NO3)3·9H2O和1.66 g对苯二甲酸溶于50 mL去离子水中,边搅拌边滴加1 mL 40%的浓盐酸,超声震荡30 min后转移至100 mL的聚四氟乙烯内衬中,置于不锈钢的密封反应釜中,然后200℃下反应12 h。冷却至室温后将产物离心分离,然后用热的DMF和无水乙醇交替洗涤多次,冷却,离心,洗涤。放入干燥箱中100℃下干燥过夜,即得到纯化后的MIL-101(Cr)样品;
2)纳米纤维材料:将步骤1)合成的MIL-101(Cr)材料超声溶解于DMF中,将PVDF加入DMF中搅拌12 h,MIL-101(Cr)、PVDF与DMF质量比为1:5:10;
然后在10 kV高压下,15 cm的接受距离下通过静电纺丝制备的到三维骨架结构的纳米纤维材料;
3)锂盐-聚合物溶液:将PAN、LiClO4在以10:1的质量比溶解在N,N-二甲基甲酰胺中,得到PAN/LiClO4混合溶液;
4)将PAN/LiClO4浇筑在PVDF/MIL-101(Cr)上并晾干,100℃真空干燥24 h。放入手套箱中晾干3天,然后裁剪为16 mm的圆片,即得到三维骨架结构的复合物固态电解质。
如图5所示,为本发明的基于MOF的三维骨架结构的复合物固态电解质的制备流程示意图。可见,通过静电纺丝将具有丰富锂离子传导位点的MOF材料均匀分布在聚合物纤维上构筑三维骨架支撑,形成一个三维连续的锂离子快速传输通道,进一步将聚合物/锂盐填充到MOF三维支撑结构中,制备出离子导电率高、机械性能好、界面阻抗低的MOF-聚合物复合固态电解质薄膜。
将实施例1制得的复合物固态电解质(PEO/LiTFSI/PAN/UIO-66)组装Li|Li对称电池以及Li|LiFePO4电池,并测试其各项电池性能。
锂锂对称电池测试:在手套箱中,以锂片分别作为为正极和负极、PEO/LiTFSI/PAN/UIO-66作为固态电解质膜,组装成锂锂对称电池。运用电化学测试系统在60℃下测试数据。
本发明的复合固态电解质在60℃下的离子电导率达到2.89×10-4 S/m2 。图6为复合物固态电解质(PEO/LiTFSI/PAN/UIO-66)组装Li|Li对称电池,PEO/LiTFSI/PAN/UIO-66可以在0.3 mA/cm2的大电流密度下依然可以稳定的循环700 h,极化稳定在100 mV以下,说明PEO/LiTFSI/PAN/UIO-66三维骨架支撑的复合物固态电解质能够很大程度上提高界面兼容性,并很好地抑制锂枝晶,从而保护锂负极。
磷酸铁锂电池测试:将磷酸铁锂(LiFePO4)和Li400、PVDF粘结剂按照80:12:8的比例利用N-甲基吡咯烷酮(NMP)溶液分散制备成浆料,将其涂覆在铝箔上,在60℃的真空干燥箱中干燥24 h。利用切片机将其切成直径为12 mm的电极圆片,利用不同100 μm厚度的刮刀分制备成载量为2 mg/cm2的极片。在手套箱中,以所制备的极片为正极、锂片为负极、PEO/LiTFSI/PAN/UIO-66固态电解质组装成CR-2032扣式电池。运用电化学测试系统在60℃下测试数据。
图7为复合物固态电解质(PEO/LiTFSI/PAN/UIO-66)组装Li|LiFePO4电池。从图中可以看到本发明基于MOF三维骨架支撑的复合物固态电解质性能远高于纯PEO/LiTFSI、PEO/LiTFSI/PAN及简单混合的PEO/LiTFSI/UIO-66复合物固态电解质,表明利用PEO/LiTFSI/PAN/UIO-66三维骨架支撑的复合物固态电解质的电池具有非常好的循环稳定性,0.5 C电池密度下循环200圈后容量保持率超过90.3%。
图8为各种复合物固态电解质组装的磷酸铁锂电池在电流密度为0.1C-1C、60℃下的倍率性能对比图。表明PEO/LiTFSI/PAN/UIO-66三维骨架支撑的复合物固态电解质的电池具有优异地倍率性能,当速率反转回到0.2 C时,电池比容量几乎可以恢复。
本发明的MOF基三维骨架支撑的构筑不仅能为锂离子提供连续的传输通道,从而有效地提升了锂离子迁移数,而且其三维骨架与高度连接晶体结构的组合显著增强了复合固态电解质的机械性能,从而从物理上有效地阻碍锂枝晶的生长。同时,MOFs材料本身具有丰富的有序孔道结构能够增强锂盐的解离,促使锂离子能够沿着MOFs的有序孔道均匀地沉积到锂负极,从而抑制锂枝晶的生长,提高了电池的循环稳定性。相比现有技术,简单混合的复合物固态电解质无法实现锂枝晶有效均匀的沉积,从而导致锂枝晶快速戳破电解质,导致电池短路,常规的对锂负极保护的措施往往只能在小的电流密度下,如0.1 mA/cm2的电流密度下进行诱导锂枝晶均匀沉积,无法实现大电流密度循环下对锂负极的有效保护。
Claims (9)
1.一种基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,包括如下步骤:
将锂盐-聚合物溶液浇筑到纳米纤维材料中,得到具有三维骨架结构的复合物固态电解质;
所述锂盐-聚合物溶液的制备为锂盐与聚合物混合溶于有机溶剂中;
所述纳米纤维材料的制备为将MOF粉体材料与聚合物分别溶解混合,通过静电纺丝得到。
2.由权利要求1所述的基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,所述锂盐-聚合物溶液的制备中,锂盐与聚合物的使用比例为(0.1~10):1。
3.由权利要求1所述的基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,所述纳米纤维材料的制备中,MOF粉体材料与聚合物的使用比例为1:(0.2~5)。
4.由权利要求1所述的基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,所述锂盐-聚合物溶液中的聚合物包括聚环氧乙烷、聚丙烯腈、聚碳酸酯、聚偏二氟乙烯的一种。
5.由权利要求1所述的基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,所述锂盐包括双氟磺酰亚胺锂盐、双三氟甲磺酰亚胺锂盐、二氟草酸硼酸锂盐、六氟磷酸锂、四氟硼酸锂、三氟甲磺酸锂、二草酸硼酸锂、高氯酸锂、六氟合砷酸锂的一种或以上。
6.由权利要求1所述的基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,所述MOF粉体材料包括UIO-66、UIO-66-NH2、ZIF-8、HKUST、MOF-74、MOF-100、MIL-101的一种。
7.由权利要求1所述的基于MOF三维骨架支撑的复合物固态电解质的制备方法,其特征在于,所述纳米纤维材料的制备所采用的聚合物包括聚丙烯腈、聚乙烯醇、聚偏二氟乙烯、聚甲基丙烯酸甲酯、聚己内酯、聚酰胺-酰亚胺的一种。
8.一种权利要求1~7任一项所述制备方法制得的基于MOF三维骨架支撑的复合物固态电解质。
9.由权利要求8所述的基于MOF三维骨架支撑的复合物固态电解质,其特征在于,所述复合物固态电解质为通过MOF材料与聚合物构筑成三维骨架结构,并在三维骨架结构上填充锂盐-聚合物溶液制备得到。
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