Facile synthesis of C-FeF2 nanocomposites from CFx: influence of carbon precursor on reversible lithium storage.

Transition metal fluorides are an important class of cathode materials for lithium batteries owing to their high specific energy and safety. However, metal fluorides are electrical insulators, exhibiting slow reaction kinetics with Li. Consequently, metal fluorides can show poor electrochemical performance. Instead, carbon-metal fluoride nanocomposites (CMNFCs) were suggested to enhance electrochemical activity. Chemical synthesis of CMNFCs poses particular challenges due to the poor chemical stability of metal fluorides. Recently, we reported a facile one-step method to synthesize carbon-FeF2 nanocomposites by reacting fluorinated carbon (CFx) with iron pentacarbonyl (Fe(CO)5) at 250 °C. The method resulted in C-FeF2 nanocomposites with improved electrochemical properties. Here, we have synthesized four different C-FeF2 nanocomposites by reacting four different CFx precursors made of petro-coke, carbon black, graphite, and carbon-fibers with Fe(CO)5. Electrochemical performance of all four C-FeF2 nanocomposites was evaluated at 25 °C and 40 °C. It is shown that the nature of CFx has a critical impact on the electrochemical performance of the corresponding C-FeF2 nanocomposites. The C-FeF2 nanocomposites were characterized by using various experimental techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, resistivity measurement, and 57Fe Mössbauer spectroscopy to shed light on the differences in electrochemical behaviour of different C-FeF2 nanocomposites.

In situ TEM studies of micron-sized all-solid-state fluoride ion batteries: Preparation, prospects, and challenges.

Trustworthy preparation and contacting of micron-sized batteries is an essential task to enable reliable in situ TEM studies during electrochemical biasing. Some of the challenges and solutions for the preparation of all-solid-state batteries for in situ TEM electrochemical studies are discussed using an optimized focused ion beam (FIB) approach. In particular redeposition, resistivity, porosity of the electrodes/electrolyte and leakage current are addressed. Overcoming these challenges, an all-solid-state fluoride ion battery has been prepared as a model system for in situ TEM electrochemical biasing studies and first results on a Bi/La0.9 Ba0.1 F2.9 half-cell are presented. Microsc. Res. Tech. 79:615-624, 2016. © 2016 Wiley Periodicals, Inc.

Electrochemical fluorination of perovskite type BaFeO2.5.

Here we report on the first electrochemical fluorination exemplarily performed on perovskite type BaFeO2.5. A cell setup of the type BaFeO2.5 II La0.9Ba0.1F2.9 II MFx (with MFx being MgF2 and CeF3) was used to perform the reaction, charging the cell up to voltages of about 4 V. Formation of a compound of approximate composition BaFeO2.5F∼0.5 was observed, in agreement with diffraction studies of the independently performed chemically fluorinated compound using F2 gas, and also possessing a capacity which is close to the theoretical capacity of the material. This new method gives an alternative towards the use of highly reactive and toxic F2 gas, and provides potential in adjusting the chemical potential for oxidative chemical fluorinations.

Solid electrolytes for fluoride ion batteries: ionic conductivity in polycrystalline tysonite-type fluorides.

Batteries based on a fluoride shuttle (fluoride ion battery, FIB) can theoretically provide high energy densities and can thus be considered as an interesting alternative to Li-ion batteries. Large improvements are still needed regarding their actual performance, in particular for the ionic conductivity of the solid electrolyte. At the current state of the art, two types of fluoride families can be considered for electrolyte applications: alkaline-earth fluorides having a fluorite-type structure and rare-earth fluorides having a tysonite-type structure. As regard to the latter, high ionic conductivities have been reported for doped LaF3 single crystals. However, polycrystalline materials would be easier to implement in a FIB due to practical reasons in the cell manufacturing. Hence, we have analyzed in detail the ionic conductivity of La(1-y)Ba(y)F(3-y) (0 ≤ y ≤ 0.15) solid solutions prepared by ball milling. The combination of DC and AC conductivity analyses provides a better understanding of the conduction mechanism in tysonite-type fluorides with a blocking effect of the grain boundaries. Heat treatment of the electrolyte material was performed and leads to an improvement of the ionic conductivity. This confirms the detrimental effect of grain boundaries and opens new route for the development of solid electrolytes for FIB with high ionic conductivities.

Synthesis of LiNH2 + LiH by reactive milling of Li3N.

The hydrogen sorption properties of Li3N under reactive milling conditions have been investigated in- and ex-situ as a function of polytype structure (alpha vs. beta), focusing on the influence of the micro-structure and/or the crystal structure upon hydrogen uptake. LiNH2 and LiH were synthesized by reactive milling of Li3N at 20 bar hydrogen pressure for 4 h. Reactive milling represents a quick and effective technique to produce LiNH2 by hydrogenation of Li3N at low hydrogen pressure and without any need for heating. As to our knowledge, we present a full hydrogenation of Li3N under the aforementioned conditions for the first time. The (de)hydrogenation and rehydrogenation behaviour of milled amides was evaluated using a combination of powder X-ray diffraction, differential scanning calorimetry, thermogravimetry and in situ Raman spectroscopy. In situ Raman spectroscopy showed a shift in the lithium amide stretching modes upon hydrogenation supporting a non-stoichiometric storage mechanism consistent with the literature. The microstructure and polytype composition of the Li3N dehydrogenated materials had no effect on the hydrogenation products and only minor effects on the hydrogen uptake profile during milling.

Determination of the heat of hydride formation/decomposition by high-pressure differential scanning calorimetry (HP-DSC).

Among the thermodynamic properties of novel materials for solid-state hydrogen storage, the heat of formation/decomposition of hydrides is the most important parameter to evaluate the stability of the compound and its temperature and pressure of operation. In this work, the desorption and absorption behaviors of three different classes of hydrides are investigated under different hydrogen pressures using high-pressure differential scanning calorimetry (HP-DSC). The HP-DSC technique is used to estimate the equilibrium pressures as a function of temperature, from which the heat of formation is derived. The relevance of this procedure is demonstrated for (i) magnesium-based compounds (Ni-doped MgH2), (ii) Mg-Co-based ternary hydrides (Mg-CoHx) and (iii) Alanate complex hydrides (Ti-doped NaAlH4). From these results, it can be concluded that HP-DSC is a powerful tool to obtain a good approximation of the thermodynamic properties of hydride compounds by a simple and fast study of desorption and absorption properties under different pressures.