W. Andrew MacFarlane

β‑NMR Measurements of Lithium Ion Transport in Thin Films of Pure and Lithium-Salt-Doped Poly(ethylene oxide)

β-Detected nuclear spin relaxation of (8)Li(+) has been used to study the microscopic diffusion of lithium ions in thin films of poly(ethylene oxide) (PEO), where the implanted lithium ions are present in extremely low concentration, and PEO with 30 wt % LiCF3SO3 over a wide range of temperatures both above and below the glass transition temperature. Recent measurements by Do et al. [Phys. Rev. Lett. 2013, 111, 018301] found that the temperature dependence of the Li(+) conductivity was identical to that of the dielectric α relaxation and was well described by the Vogel-Fulcher-Tammann relation, implying the α relaxation dominates the Li(+) transport process. In contrast, we find the hopping of Li(+) in both samples in the high temperature viscoelastic phase follows an Arrhenius law and depends significantly on the salt content. We propose that the hopping of Li(+) between cages involves motion of the polymer but that it is only for long-range diffusion where the α relaxation plays an important role.

β-NMR measurements of molecular-scale lithium-ion dynamics in poly(ethylene oxide)-lithium-salt thin films

β-detected NMR (β-NMR) has been used to study the molecular-scale dynamics of lithium ions in thin films of poly(ethylene oxide) (PEO) containing either lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium trifluoroacetate (LiTFA) salts at monomer-to-salt ratios (EO/Li) of 8.3. The results are compared with previous β-NMR measurements on pure PEO and PEO with lithium triflate (LiOTf) at the same loading [McKenzie et al., J. Am. Chem. Soc. 136, 7833 (2014)]. Activated hopping of 8Li+ was observed in all of the films above ∼250 K, with the hopping parameters strongly correlated with the ionicity of the lithium salt rather than the polymer glass transition temperature. The pre-exponential factor increases exponentially with ionicity, while the activation energy for hopping increases approximately linearly, going from 6.3±0.2 kJ mol-1 in PEO:LiTFA to 17.8±0.2 kJ mol-1 in PEO:LiTFSI. The more rapid increase in the pre-exponential factor outweighs the effect of the larger activation energy and results in 8Li+ hopping being fastest in PEO followed by PEO:LiTFSI, PEO:LiOTf, and PEO:LiTFA.

Microscopic Dynamics of Li+ in Rutile TiO2 Revealed by 8Li β-Detected Nuclear Magnetic Resonance

Ryan M. L. McFadden,1, 2, ∗ Terry J. Buck,3 Aris Chatzichristos,2, 3 Chia-Chin Chen,4 David L. Cortie,1, 2, 3, † Kim H. Chow,5 Martin H. Dehn,2, 3 Victoria L. Karner,1, 2 Dimitrios Koumoulis,6, ‡ C. D. Philip Levy,7 Chilin Li,8 Iain McKenzie,7, 9 Rotraut Merkle,4 Gerald D. Morris,7 Matthew R. Pearson,7 Zaher Salman,10 Dominik Samuelis,4, § Monika Stachura,7 Jiyu Xiao,1 Joachim Maier,4 Robert F. Kiefl,2, 3, 7 and W. Andrew MacFarlane1, 2, 7, ¶ 1Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1, Canada 2Stewart Blusson Quantum Matter Institute, University of British Columbia, 2355 East Mall, Vancouver, BC V6T 1Z4, Canada 3Department of Physics and Astronomy, University of British Columbia, 6224 Agricultural Road, Vancouver, BC V6T 1Z1, Canada 4Max-Planck-Institut für Festkörperforschung, Heisenbergstraße 1, 70569 Stuttgart, Germany 5Department of Physics, University of Alberta, 4-181 CCIS, Edmonton, AB T6G 2E1, Canada 6Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095, USA 7TRIUMF, 4004 Wesbrook Mall, Vancouver, BC V6T 2A3, Canada 8Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai, P.R. China 200050 9Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, BC V5A 1S6, Canada 10Laboratory for Muon Spin Spectroscopy, Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland (Dated: August 11, 2018)