Abstract

Composite polymer electrolytes provide an emerging solution for new battery development by replacing liquid electrolytes, which are commonly complexes of polyethylene oxide (PEO) with ceramic fillers. However, the agglomeration of fillers and weak interaction restrict their conductivities. By contrast with the prevailing methods of blending preformed ceramic fillers within the polymer matrix, here we proposed an in situ synthesis method of SiO2 nanoparticles in the PEO matrix. In this case, robust chemical interactions between SiO2 nanoparticles, lithium salt and PEO chains were induced by the in situ non-hydrolytic sol gel process. The in situ synthesized nanocomposite polymer electrolyte delivered an impressive ionic conductivity of ~1.1 × 10−4 S cm−1 at 30 °C, which is two orders of magnitude higher than that of the preformed synthesized composite polymer electrolyte. In addition, an extended electrochemical window of up to 5 V vs. Li/Li+ was achieved. The Li/nanocomposite polymer electrolyte/Li symmetric cell demonstrated a stable long-term cycling performance of over 700 h at 0.01–0.1 mA cm−2 without short circuiting. The all-solid-state battery consisting of the nanocomposite polymer electrolyte, Li metal and LiFePO4 provides a discharge capacity of 123.5 mAh g−1, a Coulombic efficiency above 99% and a good capacity retention of 70% after 100 cycles.

Highlights

  • The first application of solid polymer electrolytes in lithium-based batteries was pioneered by Armand and co-workers [1], which has inspired a series of studies in this field

  • Solid polymer electrolytes consisting of lithium salts and poly (PEO) represent a unique category of lithium solid electrolytes, which are compatible with Li metal [9,10] and suitable for building cells and strongly relaxed lithium dendrites [11,12]

  • The ionic conductivities of the membranes were determined via electrochemical impedance spectroscopy (EIS) on an Autolab PGSTAT302N (Metrohm, Herisau, Switzerland) under frequencies from 1 MHz to 0.1 Hz and amplitude of 10 mV at room temperature in a CR2025 coin cell consisting of the given membrane and stainless steel blocking electrodes

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Summary

Introduction

The first application of solid polymer electrolytes in lithium-based batteries was pioneered by Armand and co-workers [1], which has inspired a series of studies in this field. Solid polymer electrolytes consisting of lithium salts and poly (ethylene oxide) (PEO) represent a unique category of lithium solid electrolytes, which are compatible with Li metal [9,10] and suitable for building cells and strongly relaxed lithium dendrites [11,12] These materials enable the construction of flexible, stretchable, compact and laminated batteries [13,14,15]. An extended electrochemical stability voltage window of up to 5 V vs Li/Li+ is achieved By using this reliable nanocomposite polymer electrolyte membrane, the Li/nanocomposite polymer electrolyte/Li symmetric cell demonstrated a stable long-term cycling performance of over 700 h at 0.01–0.1 mA cm−2 without short circuiting, and the high-energy solid lithium cell with Li metal paired with LiFePO4 cathode exhibited a reversible capacity of 123.5 mAh g−1 at 0.1 C and 55 ◦C

Chemical Reagents and Materials
Preparation of Electrolyte Membranes
Characterizations of Electrolyte Membranes
Physicochemical Properties of the Nanocomposite Polymer Electrolyte Membranes
Ionic Conductivity and Electrochemical Stability Window
Interactions Between Polymer and Nanofiller
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