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The implementation of high potential materials as positive electrodes in high energy Li-ion batteries requires to develop scalable and smart synthetic routes. In the case of the LiNi0.5Mn1.5O4 (LNMO) spinel material, a successful preparation strategy must drive the phase formation in order to obtain structural, morphological and surface properties capable to boost performances in lithium cells and minimize the electrolyte degradation. Here we discuss a novel simple and easily scalable mechanochemical synthetic route, followed by a high temperature annealing in air, to prepare LMNO materials starting from oxides. A synergic doping with chromium and iron has been incorporated, resulting in the spontaneous segregation of a CrOx-rich surface layer. The effect of the annealing temperature on the physico-chemical properties of the LMNO material has been investigated as well as the effect on the performances in Li-cells. © 2017 Elsevier Ltd

Ionic liquid (IL) and hybrid IL/organic electrolytes with pyrrolidinium cation based ILs have been investigated for application in high temperature lithium-ion batteries (HT-LIBs). The IL based electrolytes show high thermal stabilities, up to 340 degrees C, ionic conductivities of > 5 x 10(-3) S cm(-1) at 80 degrees C, and broad electrochemical stability windows: 0-5 V vs. Li+/Li degrees. The performance of LiFePO4 based half-cells at 80 degrees C is promising, delivering ca. 160 mAh g(-1) at 1C, with a rate capability up to 4C and ca. 98% coulombic efficiency. The creation of hybrid IL/organic electrolytes by adding different organic cyclic carbonate solvents reduces viscosity of the electrolytes by 28% at 80 degrees C, thereby improving the ion transport, and further improves the electrochemical performance; higher stability, better rate capability, and >= 99% coulombic efficiency. Overall, the electrolytes proposed have a potential to be applied in HT-LIBs, a concept with large advantages at the vehicle system level. (C) 2016 Elsevier Ltd. All rights reserved.

In this work we demonstrate the application of a highly concentrated aqueous electrolyte to a hybrid supercapacitor cell. We combine an 8 m Sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) aqueous electrolyte with a nanostructured VO2-cathode to enhance the voltage widow up to 2.4 V in a full cell. With the enhanced potential window, we are able to exploit the full contribution of the VO2 material, where a part is outside the stability window of standard alkaline aqueous electrolytes. We show that the VO2 material in the highly concentrated electrolyte provides a faradaic contribution even at the highest current density (25 A/g) and in this way increases the energy content also in high power conditions. The full cell shows a good efficiency but also a capacity fade over 500 cycles (39%) which is most likely related to dissolution of VO2.

We have investigated new poly-vinylidene fluoride/poly-acrylonitrile (PVdF/PAN) based proton conducting membranes by means of vibrational spectroscopy. We find that a complete phase inversion occurs during the preparation procedure, when the gelling solvents are replaced by an acidic solution, providing the proton conducting property. The uptake of acid is promoted both by the presence of PAN and the ceramic filler, Al 2 O 3 . No particular interaction between the polymer matrix and the acidic solution could be detected, supporting the picture of an inert matrix entrapping a liquid component. However, the dissociation degree of the acid is decreased due to the spatial confinement in the membrane. By comparing the dissociation degree and the actual amount of acid in the membrane to the conductivity, we conclude that the limiting factor for the conductivity is the long-range mobility of the protons, which is governed by the morphology of the membrane.