Ionic Conductivity of a Lithium-Doped Deep Eutectic Solvent: Glass Formation and Rotation–Translation Coupling

Deep eutectic solvents with admixed lithium salts are considered as electrolytes in electrochemical devices, such as batteries or supercapacitors. Compared to eutectic mixtures of hydrogen-bond donors and lithium salts, their raw-material costs are significantly lower. Not much is known about glassy freezing and rotational–translation coupling of such systems. Here, we investigate these phenomena by applying dielectric spectroscopy to the widely studied deep eutectic solvent glyceline, to which 1 and 5 mol % LiCl were added. Our study covers a wide temperature range, including a deeply supercooled state. The temperature dependences of the detected dipolar reorientation dynamics and ionic direct current (dc) conductivity reveal the signatures of glassy freezing. In comparison to pure glyceline, the lithium admixture leads to a reduction of ionic conductivity, which is accompanied by a reduction of the rotational dipolar mobility. However, this reduction is much smaller than that for deep eutectic solvents (DESs), where one main component is lithium salt, which we trace back to the lower glass-transition temperatures of lithium-doped DESs. In contrast to pure glyceline, the ionic and dipolar dynamics become increasingly decoupled at low temperatures and obey a fractional Debye–Stokes–Einstein relation, as previously found in other glass-forming liquids. The obtained results demonstrate the relevance of decoupling effects and glass transition to the enhancement of the technically relevant ionic conductivity in such lithium-doped DESs

Discovery of extended VHE gamma-ray emission from the vicinity of the young massive stellar cluster Westerlund 1

11 pages, 6 figuresResults obtained in very-high-energy (VHE; E > 100 GeV) \gamma-ray observations performed with the H.E.S.S. telescope array are used to investigate particle acceleration processes in the vicinity of the young massive stellar cluster Westerlund 1 (Wd 1). Imaging of Cherenkov light from \gamma-ray induced particle cascades in the Earth's atmosphere is used to search for VHE \gamma\ rays from the region around Wd 1. Possible catalogued counterparts are searched for and discussed in terms of morphology and energetics of the H.E.S.S. source. The detection of the degree-scale extended VHE \gamma-ray source HESS J1646-458 is reported based on 45 hours of H.E.S.S. observations performed between 2004 and 2008. The VHE \gamma-ray source is centred on the nominal position of Wd 1 and detected with a total statistical significance of ~20\sigma. The emission region clearly extends beyond the H.E.S.S. point-spread function (PSF). The differential energy spectrum follows a power law in energy with an index of \Gamma=2.19 \pm 0.08_{stat} \pm 0.20_{sys} and a flux normalisation at 1 TeV of \Phi_0 = (9.0 \pm 1.4_{stat} \pm 1.8_{sys}) x 10^{-12} TeV^{-1} cm^{-2} s^{-1}. The integral flux above 0.2 TeV amounts to (5.2 \pm 0.9) x 10^{-11} cm^{-2} s^{-1}. Four objects coincident with HESS J1646-458 are discussed in the search of a counterpart, namely the magnetar CXOU J164710.2-455216, the X-ray binary 4U 1642-45, the pulsar PSR J1648-4611 and the massive stellar cluster Wd 1. In a single-source scenario, Wd 1 is favoured as site of VHE particle acceleration. Here, a hadronic parent population would be accelerated within the stellar cluster. Beside this, there is evidence for a multi-source origin, where a scenario involving PSR J1648-4611 could be viable to explain parts of the VHE \gamma-ray emission of HESS J1646-458