Lithium Metal Polymer Batteries: Towards Operation at Ambient Temperature

A canonical electrolyte for lithium metal polymer batteries is PEO (Polyethylene Oxide) doped with lithium salts1. Its ionic conductivity is closely related to the local dynamics (Å, ps) of the polymer chains acting as a solid solvent. For good conductive performances, these batteries must be maintained above the melting point of the bulk PEO (TM =60°C). In order to lower this operating temperature, we propose to use one-dimensional nanoscale confinement to downshift the melting point of the confined electrolyte according to ΔTM ≈ 1/d where d is the pore diameter (Gibbs-Thomson effect)². Porous polymer composite membranes based on vertically aligned Carbon NanoTubes (VA-CNTs)3 ,4 seem to be able to meet this ambitious target. The pores are cylindrical (diameter 4nm, length 100µm) and have the particularity of being all macroscopically oriented and parallel. The effect we are seeking is driven by the curvature of the confining pore. It is then critical to ensure that only the interior of the CNTs is the permeable part of the membrane. We have followed by neutron imaging the time dependence of the penetration of the electrolyte within the membrane. We evidence a critical feature we target: only the interior of the CNTs are the permeable moieties of the membrane. As for the PEO dynamics under confinement, the electrolyte’s multiscale transport properties and ionic conductivity are characterized by PFG-NMR at the micrometer scale and Electrochemical Impedance Spectroscopy (EIS) at the macroscopic scale. We report a conductivity gain of one order of magnitude under VA-CNT confinement. Nevertheless, on a multitude of non-connected CNT pores, conductivity fluctuations are not in phase: by such classical spectroscopic techniques, only an averaged conductivity is measured. To complement the spectroscopic approach, we also probe the system by the Voltage Clamp (also called Single Pore) technique. The analysis of the conductivity noise going through a single CNT pore can indeed reveal whether the conductivity under confinement5 is due to an anomalous mobility and/or charge fluctuations. (1) Xue, Z. et al., Poly(Ethylene Oxide)-Based Electrolytes for Lithium-Ion Batteries. J. Mater. Chem. A 2015, 3 (38), 19218–19253. (2) Alba-Simionesco, C. et al., M. Effects of Confinement on Freezing and Melting. J. Phys.: Condens. Matter 2006, 18 (6), R15–R68. (3) Berrod, Q. et al., Enhanced Ionic Liquid Mobility Induced by Confinement in 1D CNT Membranes. Nanoscale 2016, 8 (15), 7845–7848. (4) Zanotti, J.-M. et al., Nanocomposite membranes for electrochemical devices. Patent WO2016151142 A1.(2016) (5) Tasserit, C. et al., Pink Noise of Ionic Conductance through Single Artificial Nanopores Revisited. Phys. Rev. Lett. 2010, 105 (26), 260602. Figure 1