CN112271326B - 一种具有水清除功能的聚合物电解质及其应用 - Google Patents
一种具有水清除功能的聚合物电解质及其应用 Download PDFInfo
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- CN112271326B CN112271326B CN202011071670.4A CN202011071670A CN112271326B CN 112271326 B CN112271326 B CN 112271326B CN 202011071670 A CN202011071670 A CN 202011071670A CN 112271326 B CN112271326 B CN 112271326B
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- water
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- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
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- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- IKULXUCKGDPJMZ-UHFFFAOYSA-N sodium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Na+] IKULXUCKGDPJMZ-UHFFFAOYSA-N 0.000 description 1
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- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
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- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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Abstract
本发明涉及聚合物电解质领域，具体的说是一种具有水清除功能的聚合物电解质及其在锂/钠电池中的应用。电解质中含聚异氰酸酯，其添加量占电解质中的质量分数为10～70％。且该聚合物电解质具有氧化分解电压>5.0V，室温离子电导率为0.9～5×10‑3S/cm，拉伸强度为5～80MPa，与高电压正极和锂/钠负极具有较高的相容性，适合应用于锂/钠电池。本发明也提供了上述聚合物电解质在锂/钠电池中的应用实例。
Description
技术领域
本发明涉及聚合物电解质领域，具体的说是一种具有水清除功能的聚合物电解质及其在锂/钠电池中的应用。
背景技术
二次锂离子电池具有高能量密度、长循环寿命、无记忆效应等优点，目前已经广泛应用于小型储能设备、电动汽车等领域。然而，目前商业化的锂离子电池常用有机碳酸酯类液态电解液，存在着漏液、起火、爆炸等安全隐患。此外，这类锂离子电池也存在不均匀的锂沉积和溶解现象导致锂枝晶的生成，诱发电池容量的快速衰减、胀气甚至短路。为了提高循环稳定性和安全性能，学者们提出了一系列改进方法，其中使用聚合物电解质代替液态电解液是一种有效的方法。
相对于液态有机电解质，聚合物电解质具有以下诸多优势：1.有较高的机械强度，能一定程度上抑制锂/钠枝晶的生成；2.聚合物往往参与电极/电解质界面的形成，构筑高相容性的固态电解质界面，因此不存在持续的界面反应，循环稳定性优异；3.电化学窗口较宽，可以匹配高电压正极，有利于提高电池的能量密度；4.没有易燃液体泄漏，因此不易燃烧、爆炸，安全性能好。
目前已报道许多聚合物电解质体系，例如聚氧化乙烯(PEO)、聚甲基丙烯酸酯，聚碳酸亚乙烯酯以及聚离子液体等电解质体系，虽然都展现了一定的应用潜力，但是电池的循环性能亟待提高。众所周知，锂电池中的水含量是影响电池性能的关键参数。在锂电池运行过程中，水会加速锂/钠盐的分解(例如，水与六氟磷酸锂会生成HF、PF5、HPO2F2，H2PO3F和H3PO4)，导致严重的电解液分解、界面阻抗增大以及正极材料的破坏，伴随严重的过渡金属离子溶出，最终导致电池的快速老化和失效。由于电池所用材料的痕量水含量很难达到理想的水平，因此为了进一步提高电池的循环性能，开发具有水清除功能的聚合物电解质是一种有效的途径。
目前，虽然多篇专利公开了具有水清除功能的电解液体系，但尚未有水清除功能的聚合物电解质的专利报道。例如，CN111430781A公开了一种含氟膦酸添加剂的电解液，其中氟膦酸添加剂具有除水功能，可以提高电池性能；CN111244550A公开了一种用于高镍体系的锂离子电池电解液添加剂，具有一定除水抑酸功能，可有效抑制正极与电解液之间的副反应和电池内阻的增加；CN109301309A公开了一种高电压镍钴锰三元正极材料的电解液体系，该电解液体系含有除水功能的1,1,1-三甲基-N-(三苯基正膦亚基)硅烷胺添加剂，可以提高电池循环性能。以上公开的电解液体系由于含有水清除功能的添加剂，因此可以减少因水导致的锂/钠盐分解等不利因素，从而提高电池性能。然而，这些公开的电解液体系含有的添加剂含量较少导致除水能力有限，而且都含有易泄露的可燃有机溶剂，存在重大安全隐患。因此，发展具有水清除功能的聚合物电解质具有重要的应用价值。
发明内容
本发明的目的在于提供一种具有水清除功能的聚合物电解质及其应用，进一步优化锂/钠电池的循环性能，推动其商业化应用进程。
为实现上述目的，本发明采用的技术方案为：
一种具有水清除功能的聚合物电解质，电解质中含所述聚异氰酸酯，其添加量占电解质中的质量分数为10～70％。所述聚合物电解质的氧化分解电压>5.0V，室温离子电导率为0.9～5×10-3S/cm，拉伸强度为5～80MPa。
所述聚异氰酸酯由含有异氰酸酯结构的单体自聚或与其他单体共聚所得；其中异氰酸酯结构的单体占聚合物组分的5～100％；其他单体占聚合物组分的0～95％。
上述水清除功能源于异氰酸酯基团的缩合反应。
所述异氰酸酯结构的单体结构如通式1所示：
通式1
其中，A选自H，甲基，F，CN或CF3；B选自O或NH；C-选自PF6 -，BF4 -，TFSI-或FSI-；x取值为0或1；y的取值为0～3的自然数。
优选A的取值为甲基；B的取值为O；C-的取值为PF6 -或FSI-；x取值为1；y的取值为1或2。
所述其他单体为聚乙二醇单甲醚甲基丙烯酸酯、聚乙二醇二丙烯酸酯、甲基丙烯酸甲酯、丙烯腈、聚四氢呋喃二甲基丙烯酸酯、马来酸酐(MAH)、醋酸乙烯酯(VA)、丙烯腈(AN)、丙烯酰胺(AM)、氰基丙烯酸酯(ECA)、
(v的取值为1-4)、
中的一种或多种的混合物，或四氢呋喃及取代四氢呋喃、1,3-二氧戊烷，
取代环氧乙烷类单体的一种或多种的混合物；
其中，上述各结构式中B选自O或NH；D选自H，甲基；C-选自PF6 -，BF4 -，TFSI-或FSI-；v的取值为1-4的正整数。
优选其他单体为聚乙二醇单甲醚甲基丙烯酸酯、甲基丙烯酸甲酯或
所述电解质为聚异氰酸酯，金属盐，添加剂，引发剂(或催化剂)和多孔支撑材料；其中，聚异氰酸酯在电解质中的质量分数为10～70％；金属盐在电解质中的质量分数为0～29.9％；添加剂在电解质中的质量分数为0～80％；引发剂(或催化剂)在聚合物电解质中的质量分数为0.5％～1％；多孔支撑材料在电解质中的质量分数为0～35％。
所述金属盐为锂或钠盐；其中，锂或钠盐为六氟磷酸锂(LiPF6)、高氯酸锂(LiClO4)、双草酸硼酸锂(LiBOB)、二氟草酸硼酸锂(LiDFOB)、三氟甲磺酸锂(CF3SO3Li)、双三氟甲基磺酰亚胺锂(LiTFSI)、双氟磺酰亚胺锂，或高氯酸钠、磷酸钒钠、三氟甲磺酸钠、六氟磷酸钠、双草酸硼酸钠、二氟草酸硼酸钠、三氟甲磺酰亚胺钠、四氟硼酸盐钠中的一种或者几种；
所述添加剂为二氧化硅，二氧化锆，二氧化钛，三氧化二铝，无机锂盐、无机钠盐、碳酸乙烯酯、碳酸二甲酯、碳酸甲乙酯、碳酸丙烯酯、碳酸二乙酯、丁二腈、戊二腈、氟代碳酸乙烯酯、四乙二醇二甲醚、环丁砜、磷酸三甲酯、磷酸三乙酯、磷酸三(2,2,2-三氟乙基)酯、磷酸三异丙酯、磷酸三(六氟异丙基)酯的一种或几种的混合物；
其中，无机锂盐为Li3aLa(2/3)-aTiO3(0.04<a<0.14)、Li3+bXaY1-bO4(X＝Si、Sc、Ge、Ti；Y＝P、As、V、Cr，0<b<1)、LiZr2(PO4)3、Li7La3Zr2O12、Li1+cAlcTi2-c(PO4)3(0<c<2)、Li1+dAldGe2-d(PO4)3(0<d<2)、Li3OCl、Li3OCl0.5Br0.5、Li10GeP2S12、Li14Zn(GeO4)4、Li5La3Z2O12(Z＝Ta、Nb)、Li5.5La3Nb1.75In0.25O12、Li3N-LiU(U＝Cl、Br、I)、Li9-neVeN2Cl3(V＝Na、K、Rb、Cs、Mg、Al，0<e<9，0<n<4)、3Li3N-JI(J＝Li、Na、K)、LiPON、Li2S-LfSg(L＝Al、Si、P，0<f<3，0<g<6)、Li6PS5I(I＝F，Cl，Br，I)；无机钠盐为前述无机锂盐中锂替换成钠，即得相应的无机钠盐。
所述多孔支撑材料为纤维素无纺膜、海藻纤维无纺膜、芳纶无纺膜、聚芳砜酰胺无纺膜、聚丙烯无纺膜、玻璃纤维、聚对苯二甲酸乙二醇酯薄膜或聚酰亚胺无纺膜；所述引发剂(或催化剂)为偶氮二异丁腈(AIBN)、偶氮二异庚腈(ABVN)、偶氮二异丁酸二甲酯(AIBME)、过氧化苯甲酰(BPO)、过氧化苯甲酰叔丁酯(TBPB)、过氧化甲乙酮(MEKPO)、三氟化硼乙醚或三氟甲磺酸盐。
优选，所述金属盐为六氟磷酸锂或三氟甲磺酰亚胺钠；添加剂为二氧化硅或磷酸三甲酯；多孔支撑材料为纤维素或芳纶无纺膜；引发剂(或催化剂)为AIBN或三氟化硼乙醚。
一种电解质的应用，所述电解质在作为在锂/钠电池中的应用。
所述电解质为由异氰酸酯结构的单体或异氰酸酯结构的单体/共聚单体在引发剂(或催化剂)的作用下，在电池内部原位聚合作为锂/钠电池的水清除功能电解质。
一种锂/钠电池，包括正极、负极、介于正负极之间电解质，电解质为所述的具有水清除功能的聚合物电解质。
所述正极的活性材料为钴酸锂、磷酸铁锂、磷酸锰铁锂、锰酸锂、镍锰酸锂、富锂锰基、三元材料、锂离子氟磷酸盐、锂钒氟磷酸盐、锂铁氟磷酸盐、锂锰氧化物，或NaxPR(CN)6(P,R为Fe,Co,Ni,Mn)、磷酸钒钠，硫酸铁钠，钠离子氟磷酸盐，钠钒氟磷酸盐，钠铁氟磷酸盐，钠锰氧化物或钠钴氧化物中的一种。所述负极的活性材料为金属锂、金属锂合金、金属钠、金属钠合金、钛酸钠、硬碳、石墨、二硫化钼、钛酸锂、石墨烯、氧化锑、硅单体和硅薄膜中的一种
一种锂/钠电池的制备，将所述具有水清除功能的聚合物电解质将正负极极片分隔开，密封，在40～80℃条件下原位聚合得到高电压锂/钠电池。一种锂/钠电池的制备方法：由异氰酸酯结构的单体或异氰酸酯结构的单体/共聚单体在引发剂的作用下，在电池内部原位聚合得到聚合物电解质，主要步骤如下：
(1)将锂/钠盐以一定的比例溶于添加剂中，混合均匀，得到混合物；
(2)加入异氰酸酯结构的单体或异氰酸酯结构的单体/共聚单体以及引发剂(或催化剂)得到均一的前驱体溶液；
(3)将上述溶液注入含有正负极的锂/钠电池中，放在40℃～80℃条件下，使异氰酸酯结构的单体或异氰酸酯结构的单体/其他单体原位聚合，得到具有水清除功能的聚合物电解质。
本发明水清除原理，将电解质注入含有正负极的锂/钠电池中，在一定温度下，使电解质中异氰酸酯结构的单体或异氰酸酯结构的单体/其他单体在引发剂或催化剂的作用下异氰酸酯基团原位聚合，得到具有水清除功能的聚合物电解质。
本发所具体优点为：
本发明聚合物电解质具有清除水的功能，因此能够抑制因水导致的电池性能的衰退；具有宽的电化学窗口，能匹配高电压正极，提高电池的能量密度；机械性能较好，提高了整体聚合物电解质的机械强度；制备的聚合物电解质锂离子电导率高(0.9～5×10-3S/cm)，室温下充放电长循环性能稳定；机械性能好，拉伸强度可达5～80MPa，可以抑制锂/钠枝晶。
本发明获得的固态聚合物电解质制备简单，能够有效提高电池的安全性能和循环稳定性。所述电解质可应用到高能量密度的锂金属电池、锂合金负极电池、固态锂电池、钠金属电池以及其他二次电池(钾金属电池、非水系镁电池)中。
附图说明
图1为本发明实施例1组装的含300和1100ppm水的电池在室温时的长循环性能
图2为本发明实施例2组装的含100和600ppm水的电池在室温时的长循环性能
图3为本发明实施例3组装的含有1000ppm水的电池在室温时的长循环性能
图4为本发明实施例4组装的含有1000ppm水的电池在室温时的长循环性能
具体实施方式
以下结合实例对本发明的具体实施方式做进一步说明，应当指出的是，此处所描述的具体实施方式只是为了说明和解释本发明，并不局限于本发明。
实施例1
用于制备该固态电解质的原料配比如表1所示，在充满氩气的手套箱中配置LiTFSI/DMC溶液。将
和丙烯腈加入上述溶液中，并加入引发剂AIBN，完全溶解后，将溶液注入含有正、负极材料的锂离子电池中，放置在60℃条件下使其原位聚合，8h后得到所需要的原位聚合固态电解质。
表1：
由上述实施例所得电解质具有高离子电导率、宽电化学窗口以及高的拉伸强度(表1)。利用上述电解质组装锂电池，将上述获得电解质与水分别获得含水在300或1100ppm水的电解质组装NCM622/Li金属电池，在运行电压2.5～4.4V和0.1C下循环100圈后容量保持率分别为90％和88％(图1)，而以含有1100ppm液态电解液(1M LiPF6-EC/DMC)作为对照，与上述相同的条件进行组装电池，并运行下电池循环20圈后容量保持率为10％，可见所得聚合物电解质具有优异的水清除能力。
实施例2
用于制备该固态电解质的原料配比如表2所示，在充满氩气的手套箱中将LiPF6溶解在EC中，待其搅拌均匀备用。将
和甲基丙烯酸甲酯溶解在上述溶液中，加入引发剂，完全溶解后，将溶液注入含有正、负极材料的锂离子电池中，放置在70℃条件下使其原位聚合，8h后得到所需要的原位聚合固态电解质。
表2：
由上述实施例所得电解质具有高离子电导率、宽电化学窗口以及高的拉伸强度(表2)。将分别含有100和600ppm水的上述电解质组装NCM811/锂金属电池，在运行电压2.3～4.4V和0.5C下循环100圈后容量保持率分别为86％和84％(图2)；而以含有600ppm液态电解液作为对照电池，与上述相同的条件进行组装电池，并运行下循环50圈后容量保持率仅为20％，可见所得聚合物电解质具有优异的水清除能力。
实施例3
用于制备该固态电解质的原料配比如表3所示，在充满氩气的手套箱中,将
碳酸亚乙烯酯和LiDFOB共同混合配成溶液，并加入引发剂过氧化苯甲酰，完全溶解后，将溶液注入含有正负极材料的锂离子电池中，放置在80℃条件下使其原位聚合，6h后得到所需要的原位聚合固态电解质。
表3：
由上述实施例所得电解质具有高离子电导率、宽电化学窗口以及高的拉伸强度(表3)。将含有200和1000ppm水的上述电解质组装NCM622/Li金属电池，在工作电压2.0～4.4V和0.5C下循环100圈后容量保持率分别为92％和84％(图3)，可见所得聚合物电解质具有优异的水清除能力。
实施例4
用于制备该固态电解质的原料配比如表4所示，在充满氩气的手套箱中配置LiPF6/SN溶液，搅拌均匀备用。将
和四氢呋喃加入到上述溶液中，再加入催化剂三氟化硼乙醚，完全溶解后，将溶液注入含有正、负极材料的锂离子电池中，放置在70℃条件下使其原位聚合，8h后得到所需要的原位聚合固态电解质。
表4：
由上述实施例所得电解质具有高离子电导率、宽电化学窗口以及高的拉伸强度(表4)。利用上述电解质组装锂电池，将上述获得电解质与水分别得含有100和1000ppm水的电解质组装NCM811/Si-C600全电池，在工作电压2.0～4.5V和0.1C下循环400圈后容量保持率分别为88％和82％(图4)，可见所得聚合物电解质具有优异的水清除能力。
实施例5
用于制备该固态电解质的原料配比如表5所示，在充满氩气的手套箱中，将
和1,3-二氧戊烷以及Li7La3Zr2O12混合均匀中，再加入催化剂三氟甲磺酸钪，完全溶解后，将溶液注入含有正负极材料的锂离子电池中，放置在40℃条件下使其原位聚合，10h后得到所需要的原位聚合固态电解质。
表5：
由上述实施例所得电解质具有高离子电导率、宽电化学窗口以及高的拉伸强度(表5)。将分别含有100和800ppm水的上述电解质组装硫/Li电池，在工作电压1.0～3.0V和0.5C下循环300圈后剩余容量分别为1000和950mAh/g，可见所得聚合物电解质具有优异的水清除能力。
实施例6
用于制备该固态电解质的原料配比如表6所示，在充满氩气的手套箱中配置LiTFSI/四氢呋喃溶液，待其搅拌均匀备用。将
和
溶解在上述溶液中，再加入引发剂AIBN，完全溶解后，将溶液注入含有正负极材料的锂离子电池中，放置在60℃条件下使其原位聚合，8h后得到所需要的原位聚合固态电解质。
表6：
由上述实施例所得电解质具有高离子电导率、宽电化学窗口以及高的拉伸强度(表6)。将分别含有150和800ppm水的上述电解质组装钴酸锂/Si-C400全电池，在工作电压2.0～4.55V和0.1C下循环400圈后容量保持率分别为92％和85％，可见所得聚合物电解质具有优异的水清除能力。
实施例7
用于制备该固态电解质的原料配比如表7所示，在充满氩气的手套箱中配置LiPF6/DEC溶液，待其搅拌均匀备用。将
和聚四氢呋喃二甲基丙烯酸酯加入上述溶液中，并加入TBPB，完全溶解后，将溶液注入含有正、负极材料的锂离子电池中，放置在60℃条件下使其原位聚合，8h后得到所需要的原位聚合固态电解质。
上述制备所得的固态电解质经测试室温锂离子电导率为1.2×10-3S cm-1，氧化分解电压为5.25V。
表7：
由上述实施例所得电解质具有高离子电导率、宽电化学窗口以及高的拉伸强度(表7)。将分别得含有150和1500ppm水的上述电解质组装Li1.2Ni0.15Co0.1Mn0.55O2/Si全电池，在运行电压2.0～4.4V和0.1C下循环200圈后容量保持率分别为91％和82％。，可见所得聚合物电解质具有优异的水清除能力。
实施例8
用于制备该固态电解质的原料配比如表8所示，在充满氩气的手套箱中配置LiTFSI/SN溶液，然后加入
和
以及引发剂TPO，完全溶解后，将溶液注入含有正、负极材料的锂离子电池中，放置在60℃条件下使其原位聚合，12h后得到所需要的原位聚合固态电解质。
表8：
由上述实施例所得电解质具有高离子电导率、宽电化学窗口以及高的拉伸强度(表8)。将分别含有100和100ppm水的电解质组装镍锰酸锂/Si全电池，在工作电压2.0～5.0V和0.1C下循环120圈后容量保持率分别为94％和92％，可见所得聚合物电解质具有优异的水清除能力。
实施例9
用于制备该电解质的原料配比如表9所示，在充满氩气的手套箱中配置NaTFSI/SN溶液，然后加入
和
以及引发剂BPO，完全溶解后，将溶液注入含有正、负极材料的钠电池中，放置在60℃条件下使其原位聚合，12h后得到所需要的原位聚合固态电解质。
表9
由上述实施例所得电解质具有高离子电导率、宽电化学窗口以及高的拉伸强度(表9)。利用上述电解质组装锂电池，将上述获得电解质与水分别得含有200和1000ppm水的电解质组装NaFeMn(CN)6/Na电池，在工作电压2.0～4.0V和0.1C下循环200圈后容量保持率分别为91％和87％。，可见所得聚合物电解质具有优异的水清除能力。
Claims (10)
1.一种具有水清除功能的聚合物电解质，其特征在于：电解质中含聚异氰酸酯，其添加量占电解质中的质量分数为10~70%；
所述聚异氰酸酯由含有异氰酸酯结构的单体与其他单体共聚所得；其中异氰酸酯结构的单体占聚合物组分的5~100%；其他单体占聚合物组分的0~95%；
所述异氰酸酯结构的单体结构如通式1所示：
通式1
其中，A选自H，甲基，F，CN或CF3；B选自O或NH；C−选自PF6ˉ，BF4ˉ，TFSIˉ或FSIˉ；x取值为0或1；y的取值为0~3的自然数；
所述其他单体为聚乙二醇单甲醚甲基丙烯酸酯、聚乙二醇二丙烯酸酯、甲基丙烯酸甲
酯、丙烯腈、聚四氢呋喃二甲基丙烯酸酯、马来酸酐（MAH）、醋酸乙烯酯（VA）、丙烯酰胺（AM）、
氰基丙烯酸酯（ECA）、
、
、
、
、
中的一种或多种的混合物，或四
氢呋喃及取代四氢呋喃、1,3-二氧戊烷、
、取代环氧乙烷单体的一种或多种的混合
物；
其中，上述各结构式中B选自O或NH；D选自H，甲基； C−选自PF6ˉ，BF4ˉ，TFSIˉ或FSIˉ； v的取值为1-4的正整数。
2.按权利要求1所述的具有水清除功能的聚合物电解质，其特征在于：
所述聚合物电解质的氧化分解电压>5.0 V，室温离子电导率为0.9~5 ×10−3 S/cm，拉伸强度为5~80 MPa。
3.按权利要求1-2任意一项所述具有水清除功能的聚合物电解质，其特征在于：所述电解质为聚异氰酸酯，金属盐，添加剂，引发剂和多孔支撑材料；其中，聚异氰酸酯在电解质中的质量分数为10~70%；金属盐在电解质中的质量分数为0~29.9%；添加剂在电解质中的质量分数为0~80%；引发剂在聚合物电解质中的质量分数为0.5%~1%；多孔支撑材料在电解质中的质量分数为0~35%。
4.按权利要求3所述具有水清除功能的聚合物电解质，其特征在于：所述金属盐为锂或钠盐；所述添加剂为二氧化硅，二氧化锆，二氧化钛，三氧化二铝，无机锂盐、无机钠盐、碳酸乙烯酯、碳酸二甲酯、碳酸甲乙酯、碳酸丙烯酯、碳酸二乙酯、丁二腈、戊二腈、氟代碳酸乙烯酯、四乙二醇二甲醚、环丁砜、磷酸三甲酯、磷酸三乙酯、磷酸三（2,2,2-三氟乙基）酯、磷酸三异丙酯、磷酸三（六氟异丙基）酯的一种或几种的混合物；所述多孔支撑材料为纤维素无纺膜、海藻纤维无纺膜、芳纶无纺膜、聚芳砜酰胺无纺膜、聚丙烯无纺膜、玻璃纤维、聚对苯二甲酸乙二醇酯薄膜或聚酰亚胺无纺膜；所述引发剂为偶氮二异丁腈（AIBN）、偶氮二异庚腈（ABVN）、偶氮二异丁酸二甲酯（AIBME）、过氧化苯甲酰（BPO）、过氧化苯甲酰叔丁酯（TBPB）、过氧化甲乙酮（MEKPO）、三氟化硼乙醚或三氟甲磺酸盐。
5.一种权利要求1所述的电解质的应用，其特征在于：所述电解质在作为锂或钠电池中的应用。
6.按权利要求5所述的电解质的应用，其特征在于：所述电解质为由异氰酸酯结构的单体和其他单体在引发剂的作用下，在电池内部原位聚合作为锂或钠电池的水清除功能电解质。
7.一种锂电池，包括正极、负极、介于正负极之间电解质，其特征在于：电解质为权利要求1所述的具有水清除功能的聚合物电解质。
8.一种钠电池，包括正极、负极、介于正负极之间电解质，其特征在于：电解质为权利要求1所述的具有水清除功能的聚合物电解质。
9.一种锂电池的制备，其特征在于：将权利要求1所述具有水清除功能的聚合物电解质将正负极极片分隔开，密封，在40 ~ 80 ℃条件下原位聚合得到高电压锂电池。
10.一种钠电池的制备，其特征在于：将权利要求1所述具有水清除功能的聚合物电解质将正负极极片分隔开，密封，在40 ~ 80 ℃条件下原位聚合得到高电压钠电池。
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| CN114388886B (zh) * | 2021-12-28 | 2022-09-27 | 广东马车动力科技有限公司 | 一种聚合物电解质及其制备方法、二次电池 |
| CN115842165A (zh) * | 2022-11-18 | 2023-03-24 | 广州天赐高新材料股份有限公司 | 一种电解液添加剂、电解液、锂二次电池 |
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