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    Lifetime vs. rate capability: Understanding the role of FEC and VC in high-energy Li-ion batteries with nano-silicon anodes
    (Amsterdam : Elsevier, 2016) Jaumann, Tony; Balach, Juan; Langklotz, Ulrike; Sauchuk, Viktar; Fritsch, Marco; Michaelis, Alexander; Teltevskij, Valerij; Mikhailova, Daria; Oswald, Steffen; Klose, Markus; Stephani, Guenter; Hauser, Ralf; Eckert, Jürgen; Giebeler, Lars
    Fluoroethylene carbonate (FEC) and vinylene carbonate (VC) are the most frequently used electrolyte components to enhance the lifetime of anode materials in Li-ion batteries, but for silicon it is still ambiguous when FEC or VC is more beneficial. Herein, a nanostructured silicon/carbon anode derived from low-cost HSiCl3 is tailored by the rational choice of the electrolyte component, to obtain an anode material outperforming current complex silicon structures. We demonstrate highly reversible areal capacities of up to 5 mA h/cm2 at 4.4 mg/cm2 mass loading, a specific capacity of 1280 mA h/gElectrode, a capacity retention of 81% after 500 deep-discharge cycles versus lithium metal and successful full-cell tests with high-voltage cathodes meeting the requirements for real application. Electrochemical impedance spectroscopy and post-mortem investigation provide new insights in tailoring the interfacial properties of silicon-based anodes for high performance anode materials based on an alloying mechanism with large volume changes. The role of fluorine in the FEC-derived interfacial layer is discussed in comparison with the VC-derived layer and possible degradation mechanisms are proposed. We believe that this study gives a valuable understanding and provides new strategies on the facile use of additives for highly reversible silicon anodes in Li-ion batteries.
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    Ion dynamics in Al-Stabilized Li7La3Zr2O12 single crystals – Macroscopic transport and the elementary steps of ion hopping
    (Amsterdam : Elsevier, 2020) Posch, Patrick; Lunghammer, Sarah; Berendts, Stefan; Ganschow, Steffen; Redhammer, Günther J.; Wilkening, Alexandra; Lerch, Martin; Gadermaier, Bernhard; Rettenwander, Daniel; Wilkening, H. Martin R.
    Li7La3Zr2O12 (LLZO) garnet-type ceramics are considered as very promising candidates for solid electrolytes and have been extensively studied in the past few years. Several studies report on an increase in ionic conductivity by doping with ions, such as Al3+ and Ga3+, to stabilize the cubic modification of LLZO. Unfortunately, so far ion dynamics have mainly been studied using powdered samples. Such studies may suffer from chemical heterogeneities concerning Al distribution. Here, we took advantage of Al-stabilized LLZO single crystals to throw light on the elementary steps of ion hopping. We used 7Li nuclear magnetic resonance (NMR) spin-lattice relaxation measurements and conductivity spectroscopy to probe dynamic parameters from both a microscopic and macroscopic point of view. At 293 K the total conductivity turned out to be 0.082 mS cm−1, which is remarkably good for LLZO exhibiting an Al-content of only 0.37 wt%. Most importantly, 7Li NMR spin-lock transients revealed two overlapping diffusion-induced processes. Overall, activation energies from spin-lock NMR excellently agree with that from conductivity measurements; both techniques yield values around 0.36 eV. The corresponding diffusion coefficients deduced from NMR and conductivity measurements almost coincide. The magnetic spin fluctuations sensed by NMR provide an in-depth look at the elementary jump processes, which can barely be revealed by macroscopic impedance spectroscopy providing average values. In particular, we were able to precisely measure the local hopping barrier (0.20 eV) characterizing forward-backward jumps between the sites 24d and 96h. © 2019 The Author(s)
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    Energy system changes in 1.5 °C, well below 2 °C and 2 °C scenarios
    (Amsterdam : Elsevier, 2019) Gambhir, Ajay; Rogelj, Joeri; Luderer, Gunnar; Few, Sheridan; Napp, Tamaryn
    Meeting the Paris Agreement's goal to limit global warming to well below 2 °C and pursuing efforts towards 1.5 °C is likely to require more rapid and fundamental energy system changes than the previously-agreed 2 °C target. Here we assess over 200 integrated assessment model scenarios which achieve 2 °C and well-below 2 °C targets, drawn from the IPCC's fifth assessment report database combined with a set of 1.5 °C scenarios produced in recent years. We specifically assess differences in a range of near-term indicators describing CO2 emissions reductions pathways, changes in primary energy and final energy across the economy's major sectors, in addition to more detailed metrics around the use of carbon capture and storage (CCS), negative emissions, low-carbon electricity and hydrogen. © 2018 The Authors