Producing High Concentrations of Hydrogen in Palladium via Electrochemical Insertion from Aqueous and Solid Electrolytes

Metal hydrides are critical materials in numerous technologies including hydrogen storage, gas separation, and electrocatalysis. Here, using Pd-H as a model metal hydride, we perform electrochemical insertion studies of hydrogen via liquid and solid state electrolytes at 1 atm ambient pressure, and achieve H:Pd ratios near unity, the theoretical solubility limit. We show that the compositions achieved result from a dynamic balance between the rate of hydrogen insertion and evolution from the Pd lattice, the combined kinetics of which are sufficiently rapid that operando experiments are necessary to characterize instantaneous PdHx composition. We use simultaneous electrochemical insertion and X-ray diffraction measurements, combined with a new calibration of lattice parameter versus hydrogen concentration, to enable accurate quantification of the composition of electrochemically synthesized PdHx. Furthermore, we show that the achievable hydrogen concentration is severely limited by electrochemomechanical damage to the palladium and/or substrate. The understanding embodied in these results helps to establish new design rules for achieving high hydrogen concentrations in metal hydrides.Comment: 38 page

Li+/H+ exchange of Li7La3Zr2O12 single and polycrystals investigated by quantitative LIBS depth profiling

Li7La3Zr2O12 (LLZO) garnets are highly attractive to be used as solid electrolyte in solid-state Li batteries. However, LLZO suffers from chemical interaction with air and humidity, causing Li+/H+ exchange with detrimental implication on its performance, processing and scalability. To better understand the kinetics of the detrimental Li+/H+ exchange and its dependence on microstructural features, accelerated Li+/H+ exchange experiments were performed on single crystalline and polycrystalline LLZO, exposed for 80 minutes to 80 °C hot water. The resulting chemical changes were quantified by analytical methods, i.e. inductively coupled plasma optical emission spectroscopy (ICP-OES) and laser induced breakdown spectroscopy (LIBS). From the time dependence of the Li+ enrichment in the water, measured by ICP-OES, a bulk interdiffusion coefficient of Li+/H+ could be determined (7 × 10−17 m2 s−1 at 80 °C). Depth dependent concentrations were obtained from the LIBS data for both ions after establishing a calibration method enabling not only Li+ but also H+ quantification in the solid electrolyte. Short interdiffusion lengths in the 1 μm range are found for the single crystalline Ga:LLZO, in accordance with the measured bulk diffusion coefficient. In polycrystalline Ta:LLZO, however, very long diffusion tails in the 20 μm range and ion exchange fractions up to about 70% are observed. Those are attributed to fast ion interdiffusion along grain boundaries. The severe compositional changes also strongly affect the electrical properties measured by impedance spectroscopy. This study highlights that microstructural effects may be decisive for the Li+/H+ ion exchange kinetics of LLZO

Dislocations in ceramic electrolytes for solid-state Li batteries

High power solid-state Li batteries (SSLB) are hindered by the formation of dendrite-like structures at high current rates. Hence, new design principles are needed to overcome this limitation. By introducing dislocations, we aim to tailor mechanical properties in order to withstand the mechanical stress leading to Li penetration and resulting in a short circuit by a crack-opening mechanism. Such defect engineering, furthermore, appears to enable whisker-like Li metal electrodes for high-rate Li plating. To reach these goals, the challenge of introducing dislocations into ceramic electrolytes needs to be addressed which requires to establish fundamental understanding of the mechanics of dislocations in the particular ceramics. Here we evaluate uniaxial deformation at elevated temperatures as one possible approach to introduce dislocations. By using hot-pressed pellets and single crystals grown by Czochralski method of Li6.4La3Zr1.4Ta0.6O12 garnets as a model system the plastic deformation by more than 10% is demonstrated. While conclusions on the predominating deformation mechanism remain challenging, analysis of activation energy, activation volume, diffusion creep, and the defect structure potentially point to a deformation mechanism involving dislocations. These parameters allow identification of a process window and are a key step on the road of making dislocations available as a design element for SSLB

Lithium metal penetration induced by electrodeposition through solid electrolytes: Example in single-crystal Li6La3ZrTaO12 garnet

Solid electrolytes potentially enable rechargeable batteries with lithium metal anodes possessing higher energy densities than today’s lithium ion batteries. To do so the solid electrolyte must suppress instabilities that lead to poor coulombic efficiency and short circuits. In this work, lithium electrodeposition was performed on single-crystal Li6La3ZrTaO12 garnets to investigate factors governing lithium penetration through brittle electrolytes. In single crystals, grain boundaries are excluded as paths for lithium metal propagation. Vickers microindentation was used to introduce surface flaws of known size. However, operando optical microscopy revealed that lithium metal penetration propagates preferentially from a different, second class of flaws. At the perimeter of surface current collectors smaller in size than the lithium source electrode, an enhanced electrodeposition current density causes lithium filled cracks to initiate and grow to penetration, even when large Vickers defects are in proximity. Modeling the electric field distribution in the experimental cell revealed that a 5-fold enhancement in field occurs within 10 micrometers of the electrode edge and generates high local electrochemomechanical stress. This may determine the initiation sites for lithium propagation, overriding the presence of larger defects elsewhere

Ion dynamics in Al-Stabilized Li7La3Zr2O12 single crystals – Macroscopic transport and the elementary steps of ion hopping

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