CN115513520A - 一种基于原位固化的快离子导体的制备方法及应用 - Google Patents
一种基于原位固化的快离子导体的制备方法及应用 Download PDFInfo
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- CN115513520A CN115513520A CN202211159701.0A CN202211159701A CN115513520A CN 115513520 A CN115513520 A CN 115513520A CN 202211159701 A CN202211159701 A CN 202211159701A CN 115513520 A CN115513520 A CN 115513520A
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Abstract
一种基于原位固化的快离子导体的制备方法,涉及固态电解质制备技术领域。包括:1)将高空间位阻单体和交联剂混合,经分子筛除水后,再加入锂盐,混合均匀,得到的混合液A在2~8℃下存放;2)将引发剂和增塑剂混合,搅拌混合均匀,得到混合液B;3)混合液A和混合液B混合,得到固化前驱液;4)在带多孔骨架膜的电芯中注入固化前驱液,原位固化,得到固态聚合物快离子导体。本发明通过将高空间位阻单体与高活性交联剂共聚,利用空间位阻体积效应拓宽离子迁移通道,使得原位固态聚合物电解质的离子输运路径变短,离子电导率大幅度提高;高空间位阻单体与高活性交联剂协同构建的三维网络结构具有高的机械强度和稳定的电极电解质界面性质。
Description
技术领域
本发明涉及固态电解质制备技术领域,具体涉及一种基于原位固化的快离子导体的制备方法及应用。
背景技术
随着一次能源逐渐面临枯竭以及日益严重的环境危机,发展太阳能、风能、潮汐能等可再生清洁能源显得尤为必要。然而上述能源大多属于间歇性能源,需要高能量密度、低损耗的新型储能系统进行能源调度。锂二次电池凭借其丰富的锂矿资源和高效的储能与释放能力而受到广泛地应用,但目前已成功商业化的锂离子液态电池存在漏液和爆炸等严重安全问题,同时也不足以满足目前产品对储能系统的需求。因此发展高能量密度、高安全性和高效率的固态电解质电池成为锂二次电池的未来发展方向。
固态电解质电池分为无机固态电池和聚合物固态电池。无机固态电解质尽管具有高的离子电导率和优异的锂枝晶抑制能力,但因其脆性大、不易大规模生产、界面相容性差等问题制约了其大规模商业化应用。聚合物固态电解质又分为原位和非原位,其中原位固态聚合物电解质(ISPE)凭借简单的生产工艺、环境友好的制备过程、超低的界面阻抗、优异的界面相容性和长的循环能力而具有更优于非原位固态聚合物电解质(ESPE)的应用前景。
尽管目前原位固态聚合物电解质技术已发展到一定水平,但仍然存在难以兼顾高离子电导率、机械强度和电极电解质界面性能。固态聚合物电解质通过高分子链段运动进行离子输运,高柔性的固态聚合物电解质,玻璃化转变温度低,离子电导率高,但其机械强度低,刚性不足,同时电极电解质界面不稳定,导致其固态电池循环库伦效率低、循环寿命短。而结晶程度高的固态聚合物电解质,其高分子规整程度高,因而机械强度高,界面性质稳定,但是其高分子链段运动弱,并且离子迁移通道窄,离子电导率相当低(10-5~10-7S/cm),难以实现商业化应用。因此,兼具高离子电导率、高机械强度和界面性质稳定是原位固态聚合物电解质的一大挑战。
发明内容
本发明的目的在于,针对背景技术存在的目前原位固态聚合物电解质存在难以兼顾离子电导率、机械强度和界面稳定性的问题,提出了一种基于原位固化的快离子导体的制备方法及应用。
为实现上述目的,本发明采用的技术方案如下:
一种基于原位固化的快离子导体的制备方法,包括以下步骤:
步骤1.将15~30份(质量)的高空间位阻单体和5~10份(质量)的交联剂混合,经分子筛除水后,向其中加入5~10份(质量)锂盐,混合均匀,得到的混合液A在2~8℃条件下存放;
步骤2.将0.04~0.12份(质量)的引发剂和49.96~79.88份(质量)的增塑剂混合,搅拌30~120min混合均匀,得到混合液B;
步骤3.将步骤1的混合液A和步骤2的混合液B混合,搅拌均匀,得到固化前驱液;
步骤4.在带多孔骨架膜的电芯中注入步骤3配制的固化前驱液,每1cm2中加入10~35μL,在30~80℃温度下原位固化0.5h~48h,得到固态聚合物快离子导体。
进一步的,所述高空间位阻单体为如下结构式中的一种或几种:
其中,R1为H或者-CH3,R2为碳原子个数小于4的碳链,X为F、Cl、Br或I。
优选地,所述高空间位阻单体为马来酸酐、碳酸亚乙烯酯、碳酸二氯维酮、4,5-二甲基-1,3-二氧杂环戊烯-2-酮、4-氯甲基-5-甲基-1,3-二氧杂环戊烯-2-酮、4-甲酰基-5-甲基-1,3-间二氧杂环戊烯-2-酮、奥美沙坦酯杂质83、4-溴代甲烷-1,3-二氧戊环-2酮、4-叔丁基-5-甲基-1,3-二氧戊环-2-酮中的一种或几种。
进一步的,所述交联剂为丙烯酸类或甲基丙烯酸类交联剂,优选为2-甲基-丙烯酸-2-环氧乙烷-乙基酯、聚(乙二醇)二丙烯酸酯、聚(乙二醇)二甲基丙烯酸酯、双酚A乙氧基化物二甲基丙烯酸酯、2-甲基-丙烯酸-2-环氧乙烷-乙基、三羟甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、氟化磷基交联剂中的一种或几种。
进一步的,所述锂盐为六氟磷酸锂、双三氟甲基磺酰亚胺锂、高氯酸锂、双氟磺酰亚胺锂、二草酸硼酸锂、二氟草酸硼酸锂、四氟硼酸锂、聚硼酸酯锂中的一种或几种。
进一步的,所述引发剂为偶氮二异丁腈、偶氮二异戊腈、偶氮二异庚腈、过氧化苯甲酰、Al(OTf)3、碘化锂、六氟磷酸锂中的一种或几种。
进一步的,所述增塑剂为0.8~2mol/L的锂盐溶液,锂盐溶液的溶质为六氟磷酸锂、双三氟甲基磺酰亚胺锂、高氯酸锂、双氟磺酰亚胺锂、二草酸硼酸锂、二氟草酸硼酸锂、四氟硼酸锂、聚硼酸酯锂中的一种或几种,溶剂为碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、1,3-二氧戊烷(DOL)中的一种或几种。
进一步的,步骤4所述带多孔骨架膜的电芯是通过将正极极片、多孔骨架膜和负极极片依次层叠后,铝塑膜封装得到的。其中,正极极片的活性物质为磷酸铁锂、镍酸锂、钴酸锂、磷酸锰铁锂、锰酸锂、镍锰酸锂、镍钴锰三元正极、硫正极中的一种;负极极片的活性物质为金属锂片、金属锂合金、石墨、硬碳、二硫化钼、钛酸锂、石墨烯、硅碳负极中的一种;多孔骨架膜为聚乙烯膜、聚丙烯膜、木质纤维素膜、玻璃纤维膜、聚酰亚胺电纺膜、聚偏氟乙烯电纺膜、聚丙烯腈电纺膜中的一种。
本发明提供的一种基于原位固化的快离子导体的制备方法,得到的固态聚合物快离子导体的结构特征和锂离子输运机理如下:
锂离子在COO-和X-基团位点上进行跳跃传输,连续的COO-和X-基团位点使得锂离子路径连贯。
与现有技术相比,本发明的有益效果为:
本发明提供的一种基于原位固化的快离子导体的制备方法,通过将高空间位阻单体与高活性交联剂共聚,利用空间位阻体积效应拓宽离子迁移通道,使得原位固态聚合物电解质的离子输运路径变短,离子电导率大幅度提高;同时,高空间位阻单体与高活性交联剂协同构建的三维网络结构具有高的机械强度和稳定的电极电解质界面性质,有效解决了目前原位固态聚合物电解质难以兼顾离子电导率、机械强度和界面稳定性的问题;制备得到的快离子导体应用于锂二次电池中,能够有效提升锂二次电池的能量密度、库伦效率和循环稳定性,拓宽了锂二次电池的应用领域。
附图说明
图1为实施例1和对比例1得到的固态聚合物快离子导体的交流阻抗曲线;
图2为实施例2和对比例2得到的固态聚合物快离子导体的线性扫描伏安曲线;
图3为实施例2得到的固态聚合物快离子导体组装的锂二次电池的倍率性能测试结果;
图4为实施例2得到的固态聚合物快离子导体组装的锂二次电池的循环性能测试结果。
具体实施方式
以下结合部分对比例和实施例,对本发明进行进一步阐述。值得说明的是,此处所描述的具体实施例仅用于解释本发明,并不用于限定本发明。
一种基于原位固化的快离子导体制备锂二次电池的方法,具体包括以下步骤:
步骤1、正极的制备:
1.1将相比于正极材料质量5wt.%的聚偏氟乙烯(PVDF)溶解在相比于总浆料质量32wt.%的氮甲基吡咯烷酮(NMP)中,搅拌1h,得到PVDF溶液,搅拌速率为2000r/min;
1.2向步骤1.1得到的PVDF溶液中加入相比于正极材料质量5wt.%的导电炭黑,继续以2000r/min的转速搅拌1h;然后,向得到的混合液中加入相比于正极材料质量的90wt.%的正极活性物质,继续以2000r/min的转速搅拌2h,得到浆料;
1.3将步骤1.2得到的浆料抽真空除泡、过滤后,涂布于铝箔上,在120℃下烘干,辊压,然后在真空烘箱中80℃存放,使用时进行裁片,得到正极;
步骤2、负极的制备:
2.1将质量比为1:1:1:1的负极活性物质、粘结剂、导电炭黑、去离子水混合,得到的浆料抽真空除泡、过滤后,涂布于铜箔上,在120℃下烘干,辊压,然后在真空烘箱中80℃存放,使用时进行裁片,得到负极;其中,所述粘结剂为羧甲基纤维素钠(CMC)、丁苯橡胶(SBR)、聚丙烯酸(PAA)、LA132/LA133中的一种,负极材料容量为正极材料容量的1.01~1.05倍;
步骤3、制备固态聚合物快离子导体的固化前驱液;
步骤4、按照负极、多孔骨架膜、正极的顺序进行叠片,铝塑膜封装,得到带多孔骨架膜的电芯;在带多孔骨架膜的电芯中注入步骤3配制的固化前驱液,每1cm2中加入10~35μL,在30~80℃温度下原位固化0.5h~48h,在室温下静置12h,得到锂二次电池。
采用LAND电池充放电测试仪对得到的锂二次电池进行测试。
其中,步骤3中固态聚合物快离子导体的固化前驱液的制备及应用的实施例如下:
实施例1
在充满氩气的干燥的手套箱中(O2<0.1ppm,H2O<0.1ppm),将20质量份的高空间位阻单体马来酸酐与5质量份的高活性交联剂聚乙二醇二甲基丙烯酸酯(PEGDMA)搅拌混合,经分子筛除水后,再加入5质量份的双氟磺酰亚胺锂搅拌30min使锂盐完全溶解,得到的混合液A在2~8℃条件下存放;将0.04质量份的偶氮二异丁腈AIBN引发剂和69.96质量份的增塑剂(1mol/L的锂盐溶液,溶质为双氟磺酰亚胺锂,溶剂为体积比为1:1的1,3-二氧戊烷(DOL)和碳酸二甲酯(DMC)的混合溶剂)混合,搅拌40min混合均匀,得到混合液B;混合液A和混合液B混合,搅拌均匀,得到固化前驱液。
将干燥好的钴酸锂正极和石墨负极裁片,按照负极、多孔骨架膜、正极的顺序进行叠片,再使用铝塑膜进行封装,得到带多孔骨架膜的电芯,多孔骨架膜采用100um厚的木质纤维素膜;然后,带多孔骨架膜的电芯中注入固化前驱液,每1cm2中加入35μL,在60℃温度下原位固化1h,在室温下静置12h,得到锂二次电池。
实施例1得到的锂二次电池的首次放电比容量(1C)为125mAh/g,有效循环圈数为265。
实施例2
在充满氩气的干燥的手套箱中(O2<0.1ppm,H2O<0.1ppm),将20质量份的高空间位阻单体碳酸亚乙烯酯与5质量份的高活性交联剂季戊四醇四丙烯酸酯搅拌混合,经分子筛除水后,再加入5质量份的双三氟甲基磺酰亚胺锂盐(LITFSI)搅拌30min使锂盐完全溶解,得到的混合液A在2~8℃条件下存放;将0.04质量份的偶氮二异丁腈AIBN引发剂和69.96质量份的增塑剂(1mol/L的锂盐溶液,溶质为双三氟甲基磺酰亚胺,溶剂为体积比为1:1的1,3-二氧戊烷(DOL)和碳酸二甲酯(DMC)的混合溶剂)混合,搅拌40min混合均匀,得到混合液B;混合液A和混合液B混合,搅拌均匀,得到固化前驱液。
将干燥好的磷酸铁锂正极和锂箔负极裁片,按照负极、多孔骨架膜、正极的顺序进行叠片,再使用铝塑膜进行封装,得到带多孔骨架膜的电芯,多孔骨架膜采用22um厚的聚酰亚胺电纺膜;然后,带多孔骨架膜的电芯中注入固化前驱液,每1cm2中加入35μL,在70℃温度下原位固化0.5h,在室温下静置12h,得到锂二次电池。
实施例2得到的锂二次电池的首次放电比容量(1C)为150mAh/g,有效循环圈数为320。
实施例3
在充满氩气的干燥的手套箱中(O2<0.1ppm,H2O<0.1ppm),将15质量份的高空间位阻单体奥美沙坦酯杂质83与5质量份的高活性交联剂氟化磷基交联剂(FTGA)搅拌混合,经分子筛除水后,再加入5质量份的六氟磷酸锂(LiPF6)搅拌30min使锂盐完全溶解,得到的混合液A在2~8℃条件下存放;将0.1质量份的偶氮二异丁腈AIBN引发剂和74.9质量份的增塑剂(1mol/L的锂盐溶液,溶质为六氟磷酸锂,溶剂为体积比为1:1的碳酸乙烯酯(EC)和碳酸二乙酯(DEC)的混合溶剂)混合,搅拌40min混合均匀,得到混合液B;混合液A和混合液B混合,搅拌均匀,得到固化前驱液。
将干燥好的三元正极NCM811和石墨负极裁片,按照负极、多孔骨架膜、正极的顺序进行叠片,再使用铝塑膜进行封装,得到带多孔骨架膜的电芯,多孔骨架膜采用180um厚的玻璃纤维膜;然后,带多孔骨架膜的电芯中注入固化前驱液,每1cm2中加入35μL,在70℃温度下原位固化2h,在室温下静置12h,得到锂二次电池。
实施例3得到的锂二次电池的首次放电比容量(1C)为165mAh/g,有效循环圈数为180。
实施例4
在充满氩气的干燥的手套箱中(O2<0.1ppm,H2O<0.1ppm),将25质量份的高空间位阻单体4-溴代甲烷-1,3-二氧戊环-2酮与5质量份的高活性交联剂三羟甲基丙烷三丙烯酸酯搅拌混合,经分子筛除水后,再加入5质量份的二氟草酸硼酸锂(LIDFOB)搅拌30min使锂盐完全溶解,得到的混合液A在2~8℃条件下存放;将0.09质量份的过氧化苯甲酰引发剂和64.91质量份的增塑剂(1mol/L的锂盐溶液,溶质为二氟草酸硼酸锂,溶剂为体积比为1:1:1的碳酸丙烯酯(PC)、碳酸乙烯酯(EC)和碳酸二乙酯(DEC)的混合溶剂)混合,搅拌40min混合均匀,得到混合液B;混合液A和混合液B混合,搅拌均匀,得到固化前驱液。
将干燥好的硫正极和锂箔负极裁片,按照负极、多孔骨架膜、正极的顺序进行叠片,再使用铝塑膜进行封装,得到带多孔骨架膜的电芯,多孔骨架膜采用20um厚的多孔聚丙烯膜;然后,带多孔骨架膜的电芯中注入固化前驱液,每1cm2中加入35μL,在80℃温度下原位固化1h,在室温下静置12h,得到锂二次电池。
实施例4得到的锂二次电池的首次放电比容量(1C)为850mAh/g,有效循环圈数为150。
对比例1
在充满氩气的干燥的手套箱中(O2<0.1ppm,H2O<0.1ppm),将25质量份的高活性低聚物聚乙二醇二甲基丙烯酸酯(PEGDMA)与5质量份的双氟磺酰亚胺锂搅拌30min使锂盐完全溶解,得到的混合液A在2~8℃条件下存放;将0.04质量份的偶氮二异丁腈AIBN引发剂和69.96质量份的增塑剂(1mol/L的锂盐溶液,溶质为双氟磺酰亚胺锂,溶剂为体积比为1:1的1,3-二氧戊烷(DOL)和碳酸二甲酯(DMC)的混合溶剂)混合,搅拌40min混合均匀,得到混合液B;混合液A和混合液B混合,搅拌均匀,得到固化前驱液。
将干燥好的钴酸锂正极和石墨负极裁片,按照负极、多孔骨架膜、正极的顺序进行叠片,再使用铝塑膜进行封装,得到带多孔骨架膜的电芯,多孔骨架膜采用100um厚的木质纤维素膜;然后,带多孔骨架膜的电芯中注入固化前驱液,每1cm2中加入35μL,在60℃温度下原位固化1h,在室温下静置12h,得到锂二次电池。
对比例1得到的锂二次电池的首次放电比容量(1C)为92mAh/g,有效循环圈数为143。
对比例2
在充满氩气的干燥的手套箱中(O2<0.1ppm,H2O<0.1ppm),将25质量份的季戊四醇四丙烯酸酯与5质量份的双三氟甲基磺酰亚胺锂盐(LITFSI)搅拌30min使锂盐完全溶解,得到的混合液A在2~8℃条件下存放;将0.04质量份的偶氮二异丁腈AIBN引发剂和69.96质量份的增塑剂(1mol/L的锂盐溶液,溶质为双氟磺酰亚胺锂,溶剂为体积比为1:1的1,3-二氧戊烷(DOL)和碳酸二甲酯(DMC)的混合溶剂)混合,搅拌40min混合均匀,得到混合液B;混合液A和混合液B混合,搅拌均匀,得到固化前驱液。
将干燥好的磷酸铁锂正极和锂箔负极裁片,按照负极、多孔骨架膜、正极的顺序进行叠片,再使用铝塑膜进行封装,得到带多孔骨架膜的电芯,多孔骨架膜采用22um厚的聚酰亚胺电纺膜;然后,带多孔骨架膜的电芯中注入固化前驱液,每1cm2中加入35μL,在70℃温度下原位固化0.5h,在室温下静置12h,得到锂二次电池。
对比例2得到的锂二次电池的首次放电比容量(1C)为120mAh/g,有效循环圈数为146。
图1为实施例1和对比例1得到的固态聚合物快离子导体的交流阻抗曲线;由图1可知,实施例固态快离子导体具有成倍离子电导率的提高,表明本发明提出的固态快离子导体有效。图2为实施例2和对比例2得到的固态聚合物快离子导体的线性扫描伏安曲线;由图2可知,相比于对比例,实施例中固态快离子导体的电化学稳定窗口拓宽,表明本发明高空间位阻单体使得原位固态快离子导体体系更加稳定。图3和图4显示,本发明实施例得到的锂二次电池具有更优异的倍率性能和长循环能力。
以上所述实施例与对比例仅是对本发明的优选方式进行描述,并不是对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域可在本发明范围内进行改进与优化,这些改进与优化也应视为本发明的保护范围。
Claims (10)
1.一种基于原位固化的快离子导体的制备方法,其特征在于,包括以下步骤:
步骤1.将15~30质量份的高空间位阻单体和5~10质量份的交联剂混合,经分子筛除水后,加入5~10质量份锂盐,混合均匀,得到的混合液A在2~8℃条件下存放;
步骤2.将0.04~0.12质量份的引发剂和49.96~79.88质量份的增塑剂混合,搅拌30~120min混合均匀,得到混合液B;
步骤3.将步骤1的混合液A和步骤2的混合液B混合,搅拌均匀,得到固化前驱液;
步骤4.在带多孔骨架膜的电芯中注入步骤3配制的固化前驱液,每1cm2中加入10~35μL,在30~80℃温度下原位固化0.5h~48h,得到固态聚合物快离子导体。
3.根据权利要求1所述的基于原位固化的快离子导体的制备方法,其特征在于,所述高空间位阻单体为马来酸酐、碳酸亚乙烯酯、碳酸二氯维酮、4,5-二甲基-1,3-二氧杂环戊烯-2-酮、4-氯甲基-5-甲基-1,3-二氧杂环戊烯-2-酮、4-甲酰基-5-甲基-1,3-间二氧杂环戊烯-2-酮、奥美沙坦酯杂质83、4-溴代甲烷-1,3-二氧戊环-2酮、4-叔丁基-5-甲基-1,3-二氧戊环-2-酮中的一种或几种。
4.根据权利要求1所述的基于原位固化的快离子导体的制备方法,其特征在于,所述交联剂为丙烯酸类或甲基丙烯酸类交联剂。
5.根据权利要求1所述的基于原位固化的快离子导体的制备方法,其特征在于,所述锂盐为六氟磷酸锂、双三氟甲基磺酰亚胺锂、高氯酸锂、双氟磺酰亚胺锂、二草酸硼酸锂、二氟草酸硼酸锂、四氟硼酸锂、聚硼酸酯锂中的一种或几种。
6.根据权利要求1所述的基于原位固化的快离子导体的制备方法,其特征在于,所述引发剂为偶氮二异丁腈、偶氮二异戊腈、偶氮二异庚腈、过氧化苯甲酰、Al(OTf)3、碘化锂、六氟磷酸锂中的一种或几种。
7.根据权利要求1所述的基于原位固化的快离子导体的制备方法,其特征在于,所述增塑剂为0.8~2mol/L的锂盐溶液,锂盐溶液的溶质为六氟磷酸锂、双三氟甲基磺酰亚胺锂、高氯酸锂、双氟磺酰亚胺锂、二草酸硼酸锂、二氟草酸硼酸锂、四氟硼酸锂、聚硼酸酯锂中的一种或几种,溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、1,3-二氧戊烷中的一种或几种。
8.根据权利要求1所述的基于原位固化的快离子导体的制备方法,其特征在于,步骤4所述带多孔骨架膜的电芯是通过将正极极片、多孔骨架膜和负极极片依次层叠后,铝塑膜封装得到的。
9.根据权利要求8所述的基于原位固化的快离子导体的制备方法,其特征在于,所述正极极片的活性物质为磷酸铁锂、镍酸锂、钴酸锂、磷酸锰铁锂、锰酸锂、镍锰酸锂、镍钴锰三元正极、硫正极中的一种;负极极片的活性物质为金属锂片、金属锂合金、石墨、硬碳、二硫化钼、钛酸锂、石墨烯、硅碳负极中的一种;多孔骨架膜为聚乙烯膜、聚丙烯膜、木质纤维素膜、玻璃纤维膜、聚酰亚胺电纺膜、聚偏氟乙烯电纺膜、聚丙烯腈电纺膜中的一种。
10.权利要求1-9任一项方法得到的快离子导体在锂二次电池中的应用。
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