CN111082134B - 原位开环聚合制备的聚甲醛类全固态聚合物电解质及应用 - Google Patents
原位开环聚合制备的聚甲醛类全固态聚合物电解质及应用 Download PDFInfo
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- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
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Abstract
本发明涉及全固态聚合物电解质,具体的说是一种原位开环聚合制备的聚甲醛类全固态聚合物电解质及其在构成全固态二次锂电池中的应用。全固态聚合物电解质为三聚甲醛类单体、添加剂和锂盐通过催化剂引发原位开环聚合于多孔支撑材料;其厚度为10μm‑800μm;室温离子电导率为4×10‑5S/cm‑8×10‑3S/cm,电化学窗口不低于4.2V。本发明的全固态聚合物电解质制备容易,成型简单;机械性能优良;室温离子电导率高;与此同时该全固态聚合物电解质能够有效抑制锂枝晶的生长和匹配较高电压正极材料,有效提高了界面稳定性能、长循环性能和能量密度。
Description
技术领域
本发明涉及全固态聚合物电解质,具体的说是一种原位开环聚合制备的聚甲醛类全固态聚合物电解质及其在构成全固态二次锂电池中的应用。
背景技术
电动汽车用动力锂离子电池,除需要满足长续航里程和大功率充放电的要求外,安全性能尤为重要。目前基于液态电解质的商用锂离子电池,在滥用、短路、或极端情况使用时,电池内部会释放大量热量,会引燃有机电解液,产生起火爆炸等安全隐患,极大威胁用于安全和幸福体验,显然难以广泛使用。即使是目前被认为最安全的美国特斯拉汽车,使用了复杂的电池管理系统和防护措施,仍在问世短短的几年内发生多次着火爆炸事故。此外,有机电解液还存在的问题包括:电化学窗口有限,难以兼容金属锂负极和新研发的高电势正极材料;锂离子并非唯一的载流子,在大电流通过时,电池内阻会因离子浓度梯度的出现而增加(浓差极化),电池性能下降;工作温度有限(安工作温度0℃-40℃);与负极材料发生反应,生成solid electrolyte interphase(SEI)层,造成活性锂的持续消耗,使电池容量不断下降。用固态电解质代替有机电解液,有望从根本上解决上述问题,这样形成的锂电池称为固态锂电池。
对于固态二次锂电池的研究,按电解质区分主要包括两大类:一类是以有机聚合物电解质组成的锂离子电池,也称为聚合物固态锂电池;另一类是以无机固体电解质组成的锂离子电池,又称为无机固态锂电池。在聚合物电解质中,形成聚合物的基体的有用聚合物包括聚氧化乙烯、聚偏氟乙烯、聚丙烯腈、聚甲基丙烯酸甲酯和聚偏氯乙烯。公开的聚合物电解质实例如下:US4792504描述了一种聚合物电解质,它含有聚二甲基丙烯酸乙二醇/聚环氧乙烷,但其机械性能不高。CN200710144760描述了一种添加超细粉填料于聚环氧乙烷的电解质,机械性能良好,但其离子电导率不是很高。CN1428363A描述了一种纳米孔聚合物电解质膜,有较优良的充放电性能和循环性能,这两种膜性质较为不错,但都是凝胶聚合物电解质。CN 105826603 A描述了一种原位聚合的碳酸亚乙烯酯基的固态电解质体系及其应用,具有优良的机械性能,但该固态电解质室温离子电导率偏低,不能室温运行。
聚氧化乙烯(PEO)/锂盐型电解质在固态锂聚合物电池中已有应用,但从实用化角度来看仍然有些问题需要解决:线形和接枝聚合物机械性能较差,不易制得独立支撑的聚合物薄膜,而网状聚合物电导率又太小。因此这类电解质体系只适合在高温或小电流条件下工作,而难于在常温下工作的锂电池中得到实际应用。
发明内容
本发明的目的在于提供一种原位开环聚合制备的聚甲醛类全固态聚合物电解质及其在构成全固态二次锂电池中的应用。
为实现上述目的,本发明采用的技术方案为:
一种原位开环聚合制备的聚甲醛类全固态聚合物电解质,全固态聚合物电解质为三聚甲醛类单体、添加剂和锂盐通过催化剂引发原位开环聚合于多孔支撑材料;其厚度为10μm-800μm;室温离子电导率为4×10-5S/cm-8×10-3S/cm,电化学窗口不低于4.2V。
所述聚甲醛类聚合物在电解质中的质量分数为20%-40%;锂盐在聚合物电解质中的质量分数为5%-20%;添加剂在聚合物电解质中的质量分数为5-25%;多孔支撑材料在聚合物电解质中的质量分数为50%-60%。
所述催化剂在聚合物电解质中的质量分数为0%-5%。
所述聚甲醛类聚合物中三聚甲醛类单体如通式1所示的结构:
其中R1、R2、R3可相同或不同的选自-H,-F,-Cl,-Br,-I或-CxH2x+1,其中,x的取值范围为1-5;
所述锂盐为二草酸硼酸锂、四氟硼酸锂、六氟磷酸锂、二氧二氟磷酸锂、高氯酸锂、六氟砷酸锂、三氟甲基磺酸锂、双氟甲烷磺酰亚胺锂、双氟磺酰亚胺锂、二氟草酸硼酸锂的一种或多种;
所述添加剂的通式为NC-(CH2)y-CN,其中,y的取值范围为1-16;
所述的催化剂为二氟草酸硼酸锂、四氟硼酸锂、六氟磷酸锂、二氧二氟磷酸锂、氯化铝、氯化铁、三氟化硼、三氟化硼乙醚、五氟化磷、五氯化铌、四氯化钛、氯化锌、三氟甲磺酸铝、氯化铋、高氯酸、路氨酸、硼酸、乙酸中的一种或多种;
所述多孔支撑材料为聚乙烯隔膜、聚丙烯隔膜、尼龙无纺膜、海藻纤维无纺膜、纤维素无纺膜、细菌纤维素、玻璃纤维、聚对苯二甲酸乙二醇酯薄膜、聚酰亚胺无纺膜、聚酰胺膜,氨纶膜、芳纶膜中的一种或多种。
所述锂盐为二氟草酸硼酸锂、四氟硼酸锂、六氟磷酸锂、二氧二氟磷酸锂中的一种或多种时,催化剂用量为0%。
一种原位开环聚合制备的聚甲醛类全固态聚合物电解质的制备方法,
a)按上述比例将三聚甲醛类单体和添加剂混合均匀,而后加入锂盐和催化剂搅拌混匀;
b)将上述均匀混合的混合物滴加在多孔支撑材料上,使之完全浸润;
c)将上述浸润混合物的多孔支撑材料于40℃-110℃,加热0.05h-100h使混合物原位开环聚合得到聚甲醛类全固态聚合物电解质。
所述步骤a)40-110℃加热条件下,将三聚甲醛类单体和添加剂搅拌0.1h-10h混合混匀,而后加入锂盐和催化剂在40-100℃条件下搅拌0.01h-10h混匀,得混合物待用。
一种原位开环聚合制备的聚甲醛类全固态聚合物电解质的应用,所述全固态聚合物电解质在全固态二次锂电池(全固态锂离子电池、全固态锂金属电池、全固态锂硫电池)中的应用。
一种全固态二次锂电池,包括正极和负极,介于正负极之间为所述的全固态聚合物电解质。
将浸润混合物的多孔支撑材料置于正负极之间,于40℃-110℃,加热0.05h-100h使混合物原位开环聚合得到聚甲醛类全固态聚合物电解质;所述混合物为三聚甲醛类单体和添加剂混合均匀,而后加入锂盐和催化剂搅拌混匀,待用。
本发明所具有的优点:
本发明的固态聚合物电解质采用三聚甲醛基单体,其对于锂盐有良好的溶解性,并且通过原位开环聚合制备的聚三聚甲醛基全固态聚合物电解质无需外加引发剂,锂盐直接作为引发聚合的催化剂制备简单,耗时短,并且具有优良的室温离子电导率。
本发明的固态聚合物电解质制备容易,成型简单,其厚度为10μm-800μm;室温离子电导率为4×10-5S/cm–8×10-3S/cm,电化学窗口不低于4.2V。与此同时该固态电解质有效抑制负极锂枝晶的生长,提高了界面稳定性能和长循环性能;本发明全固态聚合物电解质机械性能优良;室温离子电导率高;且其和匹配较高电压正极材料,有效提高了界面稳定性能、长循环性能和能量密度。
附图说明
图1是附有本发明实施例1提供的原位开环聚合制备的聚三聚甲醛基全固态聚合物电解质的纤维素无纺布
图2是本发明实施例2提供的原位开环聚合制备的聚三聚甲醛基全固态聚合物电解质聚合前后的数码照片。
图3是本发明实施例2提供的聚三聚甲醛基全固态聚合物电解质组装的磷酸铁锂/锂金属电池的长循环曲线。
图4是本发明实施例3提供的聚三聚甲醛基全固态聚合物电解质组装的三元材料/锂金属电池的放电曲线。
图5是本发明实施例8提供的聚三聚甲醛基全固态聚合物电解质组装的钴酸锂/锂金属电池的长循环曲线。
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。
为了解决现有液态锂离子电池存在的电解液易泄露、易挥发、易燃烧爆炸等诸多安全隐患问题,同时为了解决凝胶聚合物电解质成型工艺复杂的问题。本发明提供了一种原位开环聚合制备的聚甲醛类全固态聚合物电解质,来提高现有全固态聚合物二次锂电池的综合性能。
实施例1
在充满氩气的手套箱中在60℃热台上将4g三聚乙醛、1.5g丁二腈搅拌5分钟混匀,而后加入0.375g LiDFOB继续搅拌10分钟混合均匀,将上述混合液取0.15mL滴加入以纤维素作为支撑材料;而后以LiCoO2作为正极,锂作为负极,将上述浸润混合物的多孔支撑材料置于正负极之间,将组装完成的电池在60℃加热2小时,混合物在电池内部多孔支撑材料上实现原位聚合得到全固态聚合物电解质(参见图1),进而得到全固态聚合物锂电池。
由图1可见,形成的全固态电解质均匀附着于纤维素无纺布隔膜上。
实施例2
在充满氩气的手套箱中在80℃热台上将2.5g 1,3,5-三氧六环(TXE)、1.5g丁二腈搅拌5分钟混匀,而后加入0.375g g LiDFOB继续搅拌5分钟混合均匀,将上述混合液取0.15mL滴加入以纤维素作为支撑材料;而后以LiFeO4作为正极,锂作为负极,将上述浸润混合物的多孔支撑材料置于正负极之间,将组装完成的电池在80℃加热5小时,混合物在电池内部多孔支撑材料上实现原位聚合得到全固态聚合物电解质.
利用上述全固态聚合物锂电池进行电池循环测试,电池充放电区间为2.75V-4V,充放电倍率为0.3C,测试温度为室温(参见图3)。。
由图3可知,该全固态电解质在匹配磷酸铁锂正极以及锂负极时展现出了优异的循环稳定性,循环100圈之后仍有97%的容量保持率。
实施例3
在充满氩气的手套箱中在80℃热台上将2.5g 1,3,5-三氧六环(TXE)、2.5g丁二腈搅拌10分钟混匀,而后加入0.375g LiDFOB继续搅拌5分钟混合均匀,将上述混合液取0.15mL滴加入以纤维素作为支撑材料;而后以三元材料作为正极,锂作为负极,将上述浸润混合物的多孔支撑材料置于正负极之间,将组装完成的电池在80℃加热5小时,混合物在电池内部多孔支撑材料上实现原位聚合得到全固态聚合物电解质。
利用上述全固态聚合物锂电池进行电池循环测试,电池充放电区间为2.75V-4.3V,充放电倍率为0.2C,测试温度为室温(参见图4)。
由图4可知,该全固态电解质在匹配三元材料(NCM22)以及锂负极在室温条件下放电比容量为162mAh/g,证明其与三元材料和锂均具有良好的界面相容性以及较高的室温离子电导率。
实施例4
在充满氩气的手套箱中在40℃热台上将4g 1,3,5-三氧六环(TXE)、1.5g丙二腈搅拌20分钟混匀,而后加入0.4g LiPF6继续搅拌2分钟混合均匀,将上述混合液取0.15mL滴加入以纤维素作为支撑材料;而后以LiFeO4作为正极,石墨作为负极,将上述浸润混合物的多孔支撑材料置于正负极之间,将组装完成的电池在40℃加热24小时,混合物在电池内部多孔支撑材料上实现原位聚合得到全固态聚合物电解质,进而得到全固态聚合物锂电池。
实施例5
在充满氩气的手套箱中在50℃热台上将2.5g 1,3,5-三氧六环(TXE)、2.4g丁二腈搅拌40分钟混匀,而后加入0.375g LiDFOB继续搅拌5分钟混合均匀,将上述混合液取0.4mL滴加入以玻璃纤维为支撑材料;而后以三元正极材料作为正极,石墨作为负极,将上述浸润混合物的多孔支撑材料置于正负极之间,将组装完成的电池在50℃加热10小时,混合物在电池内部多孔支撑材料上实现原位聚合得到全固态聚合物电解质,进而得到全固态聚合物锂电池。
实施例6
在充满氩气的手套箱中在60℃热台上将4g 1,3,5-三氧六环(TXE)、1.5g丁二腈搅拌15分钟混匀,而后加入0.7g四氟硼酸锂继续搅拌6分钟混合均匀,将上述混合液取0.4mL滴加入以聚对苯二甲酸乙二醇酯薄膜作为支撑材料;而后以LiFeO4作为正极,锂作为负极,将上述浸润混合物的多孔支撑材料置于正负极之间,将组装完成的电池在60℃加热0.5小时,混合物在电池内部多孔支撑材料上实现原位聚合得到全固态聚合物电解质,进而得到全固态聚合物锂电池。
实施例7
在充满氩气的手套箱中在40℃热台上将4g 1,3,5-三氧六环(TXE)、1.5g戊二腈搅拌25分钟混匀,而后加入0.375g LiDFOB继续搅拌10分钟混合均匀,将上述混合液取0.2mL滴加入以纤维素作为支撑材料;而后以硫作为正极,锂作为负极,将上述浸润混合物的多孔支撑材料置于正负极之间,将组装完成的电池在40℃加热1小时,混合物在电池内部多孔支撑材料上实现原位聚合得到全固态聚合物电解质,进而得到全固态聚合物锂电池。
实施例8
在充满氩气的手套箱中在80℃热台上将2.5g 1,3,5-三氧六环(TXE)、2.5g丁二腈搅拌5分钟混匀,而后加入0.735g LiDFOB继续搅拌10分钟混合均匀,将上述混合液取0.10mL滴加入以纤维素作为支撑材料;而后以LiCoO2作为正极,锂作为负极,将上述浸润混合物的多孔支撑材料置于正负极之间,将组装完成的电池在80℃加热2小时,混合物在电池内部多孔支撑材料上实现原位聚合得到全固态聚合物电解质,进而得到全固态聚合物锂电池。
利用上述全固态聚合物锂电池进行电池循环测试,电池充放电区间为3V-4.3V,充放电倍率为0.3C,测试温度为室温(参见图5)。
由图5可知,该全固态电解质在匹配4.3V钴酸锂正极以及锂负极时展现出了良好的循环稳定性以及耐高电压的性能,循环100圈之后仍有93%的容量保持率。
实施例9
在充满氩气的手套箱中在40℃热台上将1g 1,3,5-三氧六环(TXE)、2g丁二腈搅拌15分钟混匀,而后加入1.5g丁二腈、0.1g LiPF6、0.4g LiBOB继续搅拌10分钟混合均匀,将上述混合液取0.15mL滴加入以纤维素作为支撑材料;而后LiCoO2作为正极,石墨作为负极,将上述浸润混合物的多孔支撑材料置于正负极之间,将组装完成的电池在80℃加热1小时,混合物在电池内部多孔支撑材料上实现原位聚合得到全固态聚合物电解质,进而得到全固态聚合物锂电池。
实施例10
在充满氩气的手套箱中在110℃热台上将2.5g 1,3,5-三氧六环(TXE)、1.5g丁二腈搅拌5分钟混匀,而后加入0.1g LiPF6、0.4g LiBOB继续搅拌10分钟混合均匀,将上述混合液取0.15mL滴加入以纤维素作为支撑材料;而后以LiCoO2作为正极,石墨为负极,将上述浸润混合物的多孔支撑材料置于正负极之间,将组装完成的电池在100℃加热0.5小时,混合物在电池内部多孔支撑材料上实现原位聚合得到全固态聚合物电解质,进而得到全固态聚合物锂电池。
Claims (6)
1.一种原位开环聚合制备的聚甲醛类全固态聚合物电解质,其特征在于:全固态聚合物电解质为三聚甲醛类单体、添加剂和锂盐引发原位开环聚合于多孔支撑材料;其厚度为10 μm - 800 μm;室温离子电导率为4 × 10-5 S/cm - 8 × 10-3 S/cm,电化学窗口不低于4.2 V;
所述聚甲醛类聚合物中三聚甲醛类单体如通式1所示的结构:
其中R1、R2、R3可相同或不同的选自-H,-F,-Cl,-Br,-I或-CxH2x+2,其中,x的取值范围为1- 5;
所述添加剂的通式为 NC-(CH2)y-CN, 其中,y的取值范围为1- 16;
所述聚甲醛类聚合物在电解质中的质量分数为20 % - 40 %;锂盐在聚合物电解质中的质量分数为5 % - 20 %;添加剂在聚合物电解质中的质量分数为5-25%;多孔支撑材料在聚合物电解质中的质量分数为50 % - 60 %;
所述多孔支撑材料为聚乙烯隔膜、聚丙烯隔膜、纤维素无纺膜、玻璃纤维、聚对苯二甲酸乙二醇酯薄膜、聚酰亚胺无纺膜、聚酰胺膜,氨纶膜中的一种或多种;
所述锂盐为二氟草酸硼酸锂、四氟硼酸锂、六氟磷酸锂、二氧二氟磷酸锂中的一种或多种。
2.一种权利要求1所述的原位开环聚合制备的聚甲醛类全固态聚合物电解质的制备方法,其特征在于:
a)按比例将三聚甲醛类单体和添加剂混合均匀,而后加入锂盐搅拌混匀;
b)将均匀混合的混合物滴加在多孔支撑材料上,使之完全浸润;
c)将浸润混合物的多孔支撑材料于40 ℃ - 110 ℃,加热 0.05 h - 100 h使混合物原位开环聚合得到聚甲醛类全固态聚合物电解质。
3.按权利要求2所述的原位开环聚合制备的聚甲醛类全固态聚合物电解质的制备方法,其特征在于:所述步骤a)40-110℃加热条件下,将三聚甲醛类单体和添加剂搅拌0.1 h- 10 h混合混匀,而后加入锂盐在40-100℃条件下搅拌0.01 h - 10 h混匀,得混合物待用。
4.一种权利要求1所述的原位开环聚合制备的聚甲醛类全固态聚合物电解质的应用,其特征在于:所述全固态聚合物电解质在全固态二次锂电池中的应用。
5.一种全固态二次锂电池,包括正极和负极,其特征在于;介于正负极之间为权利要求1所述的全固态聚合物电解质。
6.按权利要求5所述的全固态二次锂电池,其特征在于:将浸润混合物的多孔支撑材料置于正负极之间,于40 - 110 ℃,加热0.05 h - 100 h使混合物原位开环聚合得到聚甲醛类全固态聚合物电解质;所述混合物为三聚甲醛类单体和添加剂混合均匀,而后加入锂盐搅拌混匀,待用。
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