Optimising organic ionic plastic crystal electrolyte for all solid-state and higher than ambient temperature lithium batteries

Organic ionic plastic crystal (OIPC) electrolytes are among the key enabling materials for solid-state and higher than ambient temperature lithium batteries. This work overviews some of the parameter studies on the Li|OIPC interface using lithium symmetrical cells as well as the optimisation and performance of Li|OIPC|LiFePO₄ cells. The effects of temperature and electrolyte thickness on the cycle performance of the lithium symmetrical cell, particularly with respect to the interfacial and bulk resistances, are demonstrated. Whilst temperature change substantially alters both the interfacial and bulk resistance, changing the electrolyte thickness predominantly changes the bulk resistance only. In addition, an upper limit of the current density is demonstrated, above which irreversible processes related to electrolyte decomposition take place. Here, we demonstrate an excellent discharge capacity attained on LiFePO₄|10 mol% LiNTf₂-doped [C₂mpyr][NTf₂]|Li cell, reaching 126 mAh g^-1 at 50 °C (when the electrolyte is in its solid form) and 153 mAh g^-1 at 80 °C (when the electrolyte is in its liquid form). Most remarkably, at high temperature operation, the capacity retention at long cycles and high current is excellent with only a slight (3%) drop in discharge capacity upon increasing the current from 0.2 C to 0.5 C. These results highlight the real prospects for developing a lithium battery with high temperature performance that easily surpasses that achievable with even the best contemporary lithium-ion technology.     

Proximal magnetometry in thin films using betaNMR

Low energy ion implantation of hyperpolarized radioactive magnetic resonance probes allows the NMR study of thin film heterostructures by enabling depth-resolved measurements on a nanometer lengthscale. By stopping the probe ions in a layer adjacent to a layer of interest, it is possible to study magnetic fields proximally. Here we show that, in the simplest case of a uniformly magnetized layer, this yields an unperturbed in situ frequency reference. We also discuss demagnetization contributions to measured shifts for this case. With a simple illustrative calculation, we show how a nonuniformly magnetized layer causes a strongly depth-dependent line broadening in an adjacent layer. We then give some experimental examples of resonance line broadening in heterostructures.     

Photonic electric field sensor based on polymeric microspheres

The detection of electric field by monitoring the optical whispering gallery mode shifts of polymeric microspheres is demonstrated. Two types of spheres are considered; (i) a polydimethylsiloxane (PDMS) sphere with 60 parts base silicon elastomer-to-1 part polymer curing agent by volume and; (ii) a silica sphere coated with a PDMS (uncured) base. The optical mode shifts are caused by perturbations to the resonator morphology induced by electrostriction effect in the presence of an external electric field. Preliminary experiments show that the latter microsphere yields higher sensitivity (0.027 pm/V m⁻¹) with a measurement precision of ∼1.8 V/m. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 276–279     

Zero-field μSR in crystalline C60

The C_o60Mu radical in polycrystalline C₆₀ has been studied in zero magnetic field between 9 K and 200 K, and at room temperature. At low temperatures, we observe three low-frequency oscillations which correspond to the intra-triplet transitions of a completely anisotropic muon-electron hyperfine interaction. These signals exhibit a strongly temperature-dependent T₁, attributed to thermally-activated jump rotational diffusion of the C₆₀Mu radical. A fit to an Arhenius law yields an activation energy of 200(20) meV for temperatures below the fcc-sc structural phase transition. At room temperature only the motionally-narrowed 325 MHz singlet-triplet transition is observed.     

Characterization of Five-Coordinate Ruthenium(II) Phosphine Complexes by X-ray Diffraction and Solid-State (31)P CP/MAS NMR Studies and Their Reactivity with Sulfoxides and Thioethers

31P CP/MAS NMR spectroscopy is examined as a method of characterization for ruthenium(II) phosphine complexes in the solid state, and the results are compared with X-ray crystallographic data determined for RuCl(2)(dppb)(PPh(3)) (dppb = Ph(2)P(CH(2))(4)PPh(2)), RuBr(2)(PPh(3))(3), and the previously determined RuCl(2)(PPh(3))(3). Crystals of RuBr(2)(PPh(3))(3) (C(54)H(45)Br(2)P(3)Ru) are monoclinic, space group P2(1)/a, with a = 12.482(4) ?, b = 20.206(6) ?, c = 17.956(3) ?, beta = 90.40(2) degrees, and Z = 4, and those of RuCl(2)(dppb)(PPh(3)) (C(46)H(43)Cl(2)P(3)Ru) are also monoclinic, space group P2(1)/n, with a = 10.885(2) ?, b = 20.477(1) ?, c = 18.292(2) ?, beta = 99.979(9) degrees, and Z = 4. The structure of RuBr(2)(PPh(3))(3) was solved by direct methods, and that of RuCl(2)(dppb)(PPh(3)) was solved by the Patterson method. The structures were refined by full-matrix least-squares procedures to R = 0.048 and 0.031 (R(w) = 0.046 and 0.032) for 5069 and 5925 reflections with I >/= 3sigma(I), respectively. Synthetic routes to RuBr(2)(dppb)(PPh(3)) and [RuBr(dppb)](2)(&mgr;(2)-dppb) are reported. The reactivity of RuCl(2)(dppb)(PPh(3)) with the neutral two-electron donor ligands (L) dimethyl sulfoxide, tetramethylene sulfoxide, tetrahydrothiophene, and dimethyl sulfide to give [(L)(dppb)Ru(&mgr;-Cl)(3)RuCl(dppb)] is discussed.