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由空间稳定胶体颗粒构建的剪切增稠电解质。

Shear Thickening Electrolyte Built from Sterically Stabilized Colloidal Particles.

机构信息

Department of Chemical Engineering , University of Rochester , Rochester , New York 14627 , United States.

出版信息

ACS Appl Mater Interfaces. 2018 Mar 21;10(11):9424-9434. doi: 10.1021/acsami.7b19441. Epub 2018 Mar 8.

Abstract

We present a method to prepare shear thickening electrolytes consisting of silica nanoparticles in conventional liquid electrolytes with limited flocculation. These electrolytes rapidly and reversibly stiffen to solidlike behaviors in the presence of external shear or high impact, which is promising for improved lithium ion battery safety, especially in electric vehicles. However, in initial chemistries the silica nanoparticles aggregate and/or sediment in solution over time. Here, we demonstrate steric stabilization of silica colloids in conventional liquid electrolyte via surface-tethered PMMA brushes, synthesized via surface-initiated atom transfer radical polymerization. The PMMA increases the magnitude of the shear thickening response, compared to the uncoated particles, from 0.311 to 2.25 Pa s. Ultrasmall-angle neutron scattering revealed a reduction in aggregation of PMMA-coated silica nanoparticles compared to bare silica nanoparticles in solution under shear and at rest, suggesting good stabilization. Conductivity tests of shear thickening electrolytes (30 wt % solids in electrolyte) at rest were performed with interdigitated electrodes positioned near the meniscus of electrolytes over the course of 24 h to track supernatant formation. Conductivity of electrolytes with bare silica increased from 10.1 to 11.6 mS cm over 24 h due to flocculation. In contrast, conductivity of electrolytes with PMMA-coated silica remained stable at 6.1 mS cm over the same time period, suggesting good colloid stability.

摘要

我们提出了一种方法,可在有限絮凝的常规液体电解质中制备由二氧化硅纳米颗粒组成的剪切增稠电解质。这些电解质在外力剪切或高冲击力作用下迅速且可逆地变硬为固态,这对提高锂离子电池的安全性很有前景,尤其是在电动汽车中。但是,在初始化学中,二氧化硅纳米颗粒会随时间在溶液中聚集和/或沉淀。在这里,我们通过表面引发原子转移自由基聚合,展示了通过表面接枝 PMMA 刷对常规液体电解质中的二氧化硅胶体进行空间稳定。与未涂层的颗粒相比,PMMA 增加了剪切增稠响应的幅度,从 0.311 增加到 2.25 Pa s。超小角中子散射表明,在剪切和静止条件下,溶液中 PMMA 涂覆的二氧化硅纳米颗粒的聚集程度低于裸二氧化硅纳米颗粒,这表明稳定性良好。在 24 小时的过程中,用位于电解质弯月面附近的叉指电极对静止的剪切增稠电解质(电解质中 30wt%的固体)进行了电导率测试,以跟踪上清液的形成。由于絮凝作用,裸二氧化硅的电解质电导率在 24 小时内从 10.1 增加到 11.6 mS cm。相比之下,在相同的时间内,PMMA 涂覆的二氧化硅电解质的电导率保持在 6.1 mS cm 不变,这表明胶体稳定性良好。

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