Nonionic Amphiphilic Copolymers of Poly(poly(ethylene Glycol) Methacrylate) Brushes with Methyl Methacrylate Prepared by Atom Transfer Radical Polymerization as Dry Solid Polymer Electrolytes for Next Generation Li-ion Battery Applications

IF 5.4 3区 材料科学 Q2 CHEMISTRY, PHYSICAL
Ákos Szabó, Denis Ershov, Ágnes Ábrahám, Éva Kiss, Györgyi Szarka, Ilona Felhősi, Benjámin Gyarmati, Attila Domján, Béla Iván* and Robert Kun*, 
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引用次数: 0

Abstract

Amphiphilic copolymers of comb-like poly(poly(ethylene glycol) methacrylate) (PPEGMA) with methyl methacrylate (MMA) synthesized by one-pot atom transfer radical polymerization were mixed with lithium bis (trifluoromethanesulfonyl) imide salt to formulate dry solid polymer electrolytes (DSPE) for semisolid-state Li-ion battery applications. The PEO-type side chain length (EO monomer’s number) in the PEGMA macromonomer units was varied, and its influence on the mechanical and electrochemical characteristics was investigated. It was found that the copolymers, due to the presence of PMMA segments, possess viscoelastic behavior and less change in mechanical properties than a PEO homopolymer with 100 kDa molecular weight in the investigated temperature range. In contrast to the PEO homopolymer, it was found that no crystallization of the copolymers occurs in the presence of the Li-salt. Solid-state NMR and cross-polarization NMR studies revealed that no crystallization (i.e., ion-pair formation) of the Li-salt occurs in the case of the copolymer samples at ambient temperatures; thereby, no phase separation takes place, in contrast to the reference PEO homopolymer sample, which resulted in fairly good ionic conductivity of the copolymers at lower temperatures. The temperature-dependent Li-ion conductivity analyses showed that the conductivity of the copolymers falls in the 10–6–10–3 S/cm range, which is typical for polyether-type DSPEs, but the much lower mass fraction of EO monomers in the copolymers provides the same ionic conductivity values than that of the PEO homopolymer. From a large-scale practical point of view, this clearly indicates reduced Li-salt usage if such copolymer matrices are used instead of PEO homopolymer. Moreover, linear sweep voltammetry (LSV) polarization measurements showed that the PPEGMA-MMA copolymer electrolytes can exhibit a 200–300 mV broader electrochemical stability window than the PEO homopolymer, which is crucial in designing high energy density semisolid-state Li-ion batteries.

原子转移自由基聚合法制备的聚(聚乙二醇)甲基丙烯酸甲酯刷与甲基丙烯酸甲酯非离子两亲性共聚物作为干固体聚合物电解质用于下一代锂离子电池
采用一锅原子转移自由基聚合法制备梳状聚(聚(乙二醇)甲基丙烯酸酯)(PPEGMA)与甲基丙烯酸甲酯(MMA)两亲共聚物,与二(三氟甲烷磺酰)亚胺锂盐混合,制备用于半固态锂离子电池的干固体聚合物电解质(DSPE)。研究了聚乙二醇(PEGMA)大单体单元中peo型侧链长度(EO单体数目)的变化,并对其力学和电化学特性的影响进行了研究。结果表明,在研究温度范围内,由于PMMA片段的存在,共聚物具有粘弹性行为,并且力学性能的变化小于分子量为100 kDa的PEO均聚物。与PEO均聚物相比,在锂盐的存在下,共聚物不发生结晶。固体核磁共振和交叉极化核磁共振研究表明,共聚物样品在室温下没有发生锂盐的结晶(即离子对的形成);因此,与参考PEO均聚物样品相反,没有发生相分离,这导致共聚物在较低温度下具有相当好的离子电导率。温度相关的锂离子电导率分析表明,共聚物的电导率在10-6-10-3 S/cm范围内,这是聚醚型dspe的典型特征,但共聚物中EO单体的质量分数远低于PEO均聚物,其离子电导率值与PEO均聚物相同。从大规模实践的角度来看,这清楚地表明,如果使用这种共聚物基质代替PEO均聚物,则锂盐的使用量会减少。线性扫描伏安法(LSV)极化测量结果表明,PPEGMA-MMA共聚物电解质的电化学稳定窗口比PEO均聚物宽200-300 mV,这对设计高能量密度半固态锂离子电池至关重要。
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来源期刊
ACS Applied Energy Materials
ACS Applied Energy Materials Materials Science-Materials Chemistry
CiteScore
10.30
自引率
6.20%
发文量
1368
期刊介绍: ACS Applied Energy Materials is an interdisciplinary journal publishing original research covering all aspects of materials, engineering, chemistry, physics and biology relevant to energy conversion and storage. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important energy applications.
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