Microporous gel electrolytes based on amphiphilic poly(vinylidene fluoride-co-hexafluoropropylene) for lithium batteries

• Published in: Applied surface science 2012-03, Vol.258 (11), p.4983-4989
• Main Authors: Yu, Shicheng, Chen, Lie, Chen, Yiwang, Tong, Yongfen
• Format: Article
• Language: English
• Subjects: Atom transfer radical polymerization; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Ionic conductivity; Physics; Polyelectrolytes
• ISSN: 0169-4332; 1873-5584
• DOI: 10.1016/j.apsusc.2012.01.146

[Display omitted] ► Amphiphilic poly(vinylidene fluoride-co-hexafluoropropylene) grafted poly(poly(ethylene glycol) methyl ether methacrylate) are simply prepared directly via atom transfer radical polymerization. ► The strong affinity of PPEGMA segments dramatically improves the electrolyte uptakes and ion conductivities of the graft copolymer membranes. ► The highest ion conductivity at room temperature is 2.01×10−3Scm−1. Poly(vinylidene fluoride-co-hexafluoropropylene) grafted poly(poly(ethylene glycol) methyl ether methacrylate) (PVDF-HFP-g-PPEGMA) is simply prepared by single-step synthesis directly via atom transfer radical polymerization (ATRP) of poly(ethylene glycol) methyl ether methacrylate (PEGMA) from poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP). Thermal, mechanical, swelling and electrochemical properties, as well as microstructures of the prepared polymer electrolytes, are evaluated and the effects of the various contents and average molecular weights of PEGMA on those properties are also been investigated. By phase inversion technique, the copolymer membranes tend to form well-defined microporous morphology with the increase of content and average molecular weight of PEGMA, due to the competition and cooperation between the hydrophilic PEGMA segments and hydrophobic PVDF-HFP. When these membranes are gelled with 1M LiCF3SO3 in ethylene carbonate (EC)/propylene carbonate (PC) (1:1, v/v), their saturated electrolyte uptakes (up to 323.5%) and ion conductivities (up to 2.01×10−3Scm−1) are dramatically improved with respect to the pristine PVDF-HFP, ascribing to the strong affinity of the hydrophilic PEGMA segments with the electrolytes. All the polymer electrolytes are electrochemically stable up to 4.7V versus Li/Li+, and show good mechanical properties. Coin cells based on the polymer electrolytes show stable charge–discharge cycles and deliver discharge capacities to LiFePO4 is up to 156mAhg−1.