CN112615046A - 一种锂电池固态电解质界面层原位调控的方法 - Google Patents
一种锂电池固态电解质界面层原位调控的方法 Download PDFInfo
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Abstract
本发明公开了一种锂电池固态电解质界面层原位调控的方法，该方法包括以下步骤：(1)将有机聚合物、有机单体、锂盐形成的溶液浇铸于聚四氟乙烯模具中，采用分段式真空干燥，获得固态电解质膜；(2)将所述的固态电解质膜按照“正极材料‑电解质膜‑负极材料”的顺序装成电池；(3)将组装的电池在温度50～80℃，电压0～2.5V，4.9～5.1μA的恒电流下，进行电化学聚合，在固体电极电解质界面形成电子/离子混合导体的聚合物导电层。本发明通过在固体电解质膜中生长出导电聚合物，在原子层面上将电极和电解质界面紧密连接起来，可以有效解决电极与电解质膜界面接触不好、阻抗过大的问题，明显改善固态锂离子电池界面稳定性、循环稳定性及倍率性能。
Description
技术领域
本发明属于全固态锂电池技术领域，特别是一种锂电池固态电解质界面层原位调控的方法。
背景技术
全固态锂离子电池被认为是下一代具有高安全性和高能量密度的二次电池，固态电解质代替液态电解质能够有效地解决传统锂离子电池中有机电解液易燃、易爆的缺点，又能与金属锂负极兼容，减缓电解质膜与锂金属电极之间的界面劣化，防止枝晶生长，同时又能够实现高比容量性能。
然而，电极和固态电解质之间的固固接触存在严重的界面接触阻抗，接触不好，导致锂离子在界面迁移受阻；电池在长期循环过程中界面易恶化，抗氧化降解能力差，锂离子电池的容量利用率降低，循环稳定性衰退快，电池的循环寿命短。
发明内容
针对全固态锂离子电池电极和固态电解质界面接触不好，阻抗过大，导致固态锂离子电池在充放电过程中循环稳定性和倍率性能较差的问题，本发明的提供了一种锂电池固态电解质界面层原位调控的方法。本发明通过原位电化学使有机单体在电极/电解质膜界面发生聚合，形成导电聚合物。由于导电聚合物是从在电解质膜中生长出来，能够在原子规模上将电极和电解质界面紧密连接起来，形成的聚合物导电层，其既能够传导电子又不影响锂离子的迁移，从而改善固-固界面接触不好的问题，提高电极/电解质界面稳定性，电池的循环稳定性。
为实现上述目的，本发明采用以下技术方案实现。
在固态电极电解质界面原位制备聚合物导电层，所述的聚合物导电层由有机单体、有机聚合物、锂盐通过电化学原位聚合得到。
所述的有机单体为噻吩、吡咯、苯胺、2,2`-联二噻吩、3-溴噻吩、3-氰基噻吩、N-取代基吡咯、3-十二烷基噻吩中的一种或任意两种的混合物；所述有机单体质量占电解膜质量的7～20％。
所述的有机聚合物为聚氧化乙烯、聚甲基丙烯酸甲酯、聚丙烯腈、聚偏氟乙烯-六氟丙烯共聚物中的一种或多种的混合物，所述的有机聚合物质量为电解膜质量的65～85％。
所述的锂盐为双三氟甲磺酰亚胺基锂、高氯酸锂、草酸锂、二氟草酸硼酸锂中的一种或任意两种的混合物；所述的锂盐质量占电解膜质量的10～40％。
所述的一种锂电池固态电解质界面层原位调控的方法，包括如下技术步骤：
(1)将有机聚合物、有机单体、锂盐形成的溶液浇铸于直径为85～95cm圆形的聚四氟乙烯模具中，采用分段式真空干燥，获得固态电解质膜；
(2)将所述的固态电解质膜按照“正极材料-电解质膜-负极材料”的顺序装成电池；
(3)将组装的电池在温度50～80℃，电压0～2.5V，4.9～5.1μA的恒电流下，进行电化学聚合，在固体电极电解质界面形成电子/离子混合导体的聚合物导电层。
所述分段式真空干燥条件为首先在压力0.03～0.05Mpa，温度35-50℃，干燥23～25h；然后在压力0.05～0.1Mpa，温度35～50℃，干燥23～25h。
所述的正极材料为磷酸铁锂、钴酸锂、三元电极材料及不锈钢片；所述的负极材料为金属锂片、石墨。
对于组装的不对称电池，利用蓝电充放电仪，电压优选1.5～2.0V，电流4.9～5.1μA，恒流充放电290～310次；对于组装的对称电池，在电化学工作站上，电压优选0～1.0V，电流4.9～5.1μA，恒流充放电290～310次。
本发明设计原理是：有机单体噻吩、吡咯、苯胺及其衍生物在一定电压的驱动下，通过电化学催化，会在电极/电解质界面层原位聚合，形成“离子/电子导电聚合物。由于导电聚合物是从电解质膜中生长出来，能够在原子层面上将电极和电解质界面紧密连接起来，形成的聚合物导电层具有较好的稳定性和电子传输能力，可有效消除电极/电解质界面的空间电荷层，促进锂离子的扩散和电子的传输；同时噻吩、吡咯、苯胺及其衍生物等形成的导电聚合物具有较好抗高压分解能力，进一步增强了界面的稳定性，抵抗固态电池长期循环过程中界面的氧化降解。高稳定、致密接触的界面是维持了固态离子电池良好容量性能和长期循环稳定性的重要动力。
与现有技术相比，本发明的有益效果如下：
(1)本发明通过原位电化学催化，将有机单体在电极-电解膜界面聚合成导电聚合物，可增强固态电解质膜-电极间的电子传输能力，降低界面阻抗，提高离子导电率、电池界面稳定性、阻止副反应发生。
(2)本发明可促进锂在负极和金属锂界面的均匀沉积、抑制锂枝晶生长，提高正负两极与电解膜界面层的稳定性、致密性，该方法简单、高效，适合商业化。
附图说明
图1为固态电极电解质界面原位制备聚合物导电层示意图，形成的离子/电子导电聚合物界面层数码图片。
图2为原位电化学形成离子/电子导电聚合物颗粒形貌表征及电解质膜形貌表征，其中，a为离子/电子导电聚合物颗粒光学显微镜图片，b、d为离子/电子导电聚合物颗粒扫描电镜图，c为离子/电子导电聚合物界面层的电解质膜表面原子力显微镜图。
图3为原位电化学形成离子/电子导电聚合物界面层的非对称锂电池切面界面表征。其中，a为正极-电解质膜-负极全截面界面扫描电镜图，b为负极-电解质膜截面界面扫描电镜图，c为正极-电解质膜截面界面扫描电镜图。
图4为电池内部离子/电子导电聚合物界面层形成前后交流阻抗对比图。其中，a为对称电池在电压促使下，离子/电子导电聚合物界面层形成过程中，恒流充放电不同循环圈数交流阻抗对比，b为非对称全电池在电压促使下，离子/电子导电聚合物界面层形成前后交流阻抗对比图。
图5为非对称全电池性能图，其中，a为测试不同倍率下的电压-比容量，b为2C大倍率条件下长循环性能。
具体实施方式
以下将结合具体实例对本发明做进一步阐述。
【实施例1】
所述的一种锂电池固态电解质界面层原位调控的方法，在固态电极电解质界面原位制备聚合物导电层，包括如下技术步骤：
有机单体噻吩、有机聚合物PEO、锂盐双三氟甲磺酰亚胺基锂质量分别占电解膜质量的7.7％、77％和15.3％，得到的1.30g的固态电电解质溶解在20ml乙腈中，其中磁力搅拌溶解18-36h，形成均一、透明的溶液，浇铸于直径为90cm圆形的聚四氟乙烯模具中，采用分段式真空干燥，条件为首先在压力0.03～0.05Mpa，温度35-50，℃干燥23～25h；然后在压力0.05～0.1Mpa，温度35～50℃，干燥23～25h，除去溶剂，获得固态电解质膜。
(2)将所述的固态电解质膜切成厚度为70μm的薄片，按照“正极材料-电解质膜-负极材料”的顺序装成CR2025型对称/非对称电池，见图1。
(3)将组装的电池在温度60℃，电压0～2.5V，5μA的恒电流下，进行电化学聚合，在固体电极电解质界面形成电子/离子混合导体界面层。
对于组装的不对称电池，利用蓝电充放电仪，电压优选1.5～2.0V和电流为5μA，恒流充放电300次；对于组装的对称电池，在电化学工作站上，电压优选0～1.0V和电流为5μA，恒流充放电300次。利用扫描电镜、原子力显微镜等设备对其进行形貌等特性表征，结果见图2-5。
【实施例2】
与实施例1不同的是，实施例2中以2,2`-联二噻吩作为有机单体，添加量与噻吩保持一致，其中PEO含量为77％、2,2`-联二噻吩含量占7.7％及双三氟甲磺酰亚胺基锂含量占15.3％，其余均相同，在此实施例中不再赘述。
【实施例3】
与实施例1不同的是，实施例3中以吡咯作为有机单体，添加量相比施例1增加一倍，其中PEO含量为71.4％、2,2`-联二噻吩含量占14.3％及双三氟甲磺酰亚胺基锂含量占14.3％，其余均相同，组装成CR2025型对称/不对称电池。对于组装的不对称电池，放置于蓝电充放电仪，设置充放电电压区间2～2.5V和电流为5μA，恒流充放电300次；对于组装的对称电池，在电化学工作站上，电压优选0～1.0V和电流为5μA，恒流充放电300次。其余步骤与实施例1相同，在此实施例中不再赘述。
【实施例4】
与实施例1不同的是，实施例4中高氯酸锂为锂盐取代双三氟甲磺酰亚胺基锂，添加质量相同，所用量占固态电电解质总量的15.3％。其余均相同，在此实施例中不再赘述。
以上对本发明实施例做了详细的阐述，需要强调的是，上述的阐述、说明仅为本发明的具体实施例，本发明包括但不局限于上述实施例，该技术领域相关技术人员应该清晰明了，凡在本发明的思想和原则之内所做的任何等效替换、辅助成分的添加、改进等，均应包含在本发明的保护范围和公开范围之内。
Claims (8)
1.一种锂电池固态电解质界面层原位调控的方法，其特征在于，在固态电极电解质界面原位制备聚合物导电层，所述的聚合物导电层由有机单体、有机聚合物、锂盐通过电化学原位聚合得到。
2.根据权利要求1所述的一种锂电池固态电解质界面层原位调控的方法，其特征在于，所述的有机单体为噻吩、吡咯、苯胺、2,2`-联二噻吩、3-溴噻吩、3-氰基噻吩、N-取代基吡咯、3-十二烷基噻吩中的一种或任意两种的混合物；所述有机单体质量占电解膜质量的7～20％。
3.根据权利要求1所述的一种锂电池固态电解质界面层原位调控的方法，其特征在于，所述的有机聚合物为聚氧化乙烯、聚甲基丙烯酸甲酯、聚丙烯腈、聚偏氟乙烯-六氟丙烯共聚物中的一种或多种的混合物，所述的有机聚合物质量为电解膜质量的65～85％。
4.根据权利要求1所述的一种锂电池固态电解质界面层原位调控的方法，其特征在于，所述的锂盐为双三氟甲磺酰亚胺基锂、高氯酸锂、草酸锂、二氟草酸硼酸锂中的一种或任意两种的混合物；所述的锂盐质量占电解膜质量的10～40％。
5.根据权利要求1所述的一种锂电池固态电解质界面层原位调控的方法，其特征在于，该方法包括如下技术步骤：
(1)将有机聚合物、有机单体、锂盐形成的溶液浇铸于直径为85～95cm圆形的聚四氟乙烯模具中，采用分段式真空干燥，获得固态电解质膜；
(2)将所述的固态电解质膜按照“正极材料-电解质膜-负极材料”的顺序装成电池；
(3)将组装的电池在温度50～80℃，电压0～2.5V，4.9～5.1μA的恒电流下，进行电化学聚合，在固体电极电解质界面形成电子/离子混合导体的聚合物导电层。
6.根据权利要求5所述的一种锂电池固态电解质界面层原位调控的方法，其特征在于，所述分段式真空干燥条件为首先在压力0.03～0.05Mpa，温度35-50℃，干燥23～25h；然后在压力0.05～0.1Mpa，温度35～50℃，干燥23～25h。
7.根据权利要求5所述的一种锂电池固态电解质界面层原位调控的方法，其特征在于，所述的正极材料为磷酸铁锂、钴酸锂、三元电极材料及不锈钢片；所述的负极材料为金属锂片、石墨。
8.根据权利要求5所述的一种锂电池固态电解质界面层原位调控的方法，其特征在于，对于组装的不对称电池，利用蓝电充放电仪，电压优选1.5～2.0V，电流4.9～5.1μA，恒流充放电290～310次；对于组装的对称电池，在电化学工作站上，电压优选0～1.0V，电流4.9～5.1μA，恒流充放电290～310次。
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