NANOSTRUCTURED THIN FILM POLYMER ELECTROLYTES FOR FLEXIBLE BATTERY APPLICATIONS

Abstract

In recent years, the interest in polymeric batteries has increased dramatically. With the advent of lithium ion batteries being used in cell phones and laptop computers, the search for an all solid state battery has continued. Current configurations have a liquid or gel electrolyte along with a separator between the anode and cathode. This leads to problems with electrolyte loss and decreased performance over time. The highly reactive nature of these electrolytes necessitates the use of protective enclosures which add to the size and bulk of the battery. Polymer electrolytes are more compliant than conventional inorganic glass or ceramic electrolytes. The goal of this work was to design and investigate novel nanoscale polymer electrolyte flexible thin films based on the self-assembly of block copolymers.

Block copolymers were synthesized, consisting of a larger PEO block and a smaller block consisting of random copolymer of methyl methacrylate (MMA) and the lithium salt of methacrylic acid (MAALi). The diblock copolymer [PEO-b-(PMMA-ran-PMAALi)] with added lithium bis(oxalato)borate, LiBC₄O₈ (LiBOB) salt (in the molar ratio ethylene oxide:LiBOB = 3:1) was used to form flexible translucent films which exhibited nearly two orders of magnitude greater conductivity than that shown by traditional high molecular weight PEO homopolymer electrolytes, in the absence of ceramic fillers and similar additives. The presence of the smaller second block and the plasticizing effect of the bulky lithium salt were shown to effectively reduce the crystallinity of the solid electrolyte, resulting in improved ion transporting behavior. The tailored solid self-assembled diblock copolymer electrolyte matrix also exhibits an exceptionally high lithium-ion transference number of 0.9, compared to a value between 0.2 and 0.5, shown by typical polymer-lithium salt materials. The electrolyte material also has a wide electrochemical stability window and excellent interfacial behavior with lithium metal electrode. The combination of these properties make electrolyte membranes composed of the diblock copolymer PEO-b-(PMMA-ran-PMAALi) and LiBOB salt, viable electrolyte candidates for flexible lithium ion based energy conversion/storage devices.