Joachim Sann

A comprehensive study on the cell chemistry of the sodium superoxide (NaO2) battery

This work reports on the cell chemistry of a room temperature sodium-oxygen battery using an electrolyte of diethylene glycol dimethyl ether (diglyme) and sodium trifluoromethanesulfonate (NaSO3CF3, sodium triflate). Different from lithium-oxygen cells, where lithium peroxide is found as the discharge product, sodium superoxide (NaO2) is formed in the present cell, with overpotentials as low as 100 mV during charging. Several analytical methods are used to follow the cell reaction during discharge and charge. Changes in structure and morphology are studied by SEM and XRD. It is found that NaO2 grows as cubic particles with feed sizes in the range of 10-50 μm; upon recharge the particles consecutively decompose. Pressure monitoring during galvanostatic cycling shows that the coulombic efficiency (e(-)/O2) for discharge and charge is approx. 1.0, the expected value for NaO2 formation. Also optical spectroscopy is identified as a convenient and useful tool to follow the discharge-charge process. The maximum discharge capacity is found to be limited by oxygen transport within the electrolyte soaked carbon fiber cathode and pore blocking near the oxygen interface is observed. Finally electrolyte decomposition and sodium dendrite growth are identified as possible reasons for the limited capacity retention of the cell. The occurrence of undesired side reactions is analyzed by DEMS measurements during cycling as well as by post mortem XPS investigations.

Shallow donors and acceptors in ZnO

In order to realize controlled p-type doping in ZnO the role of extrinsic and intrinsic donors has to be clarified. The extrinsic n-type dopants Al, Ga and In are commonly found in bulk ZnO crystals, but hydrogen also appears in relevant concentrations eventually controlling the residual n-type carrier concentrations in nominally undoped ZnO. The optical properties of excitonic recombinations in bulk, n-type ZnO are investigated by photoluminescence (PL). At liquid helium temperature the neutral donor–bound excitons dominate in the PL spectrum. Two electron satellite (TES) transitions of the donor–bound excitons allow us to determine the donor binding energies ranging from 46 to 73 meV. In the as-grown crystals a shallow donor with an activation energy of 30 meV controls the conductivity. Annealing annihilates this shallow donor which has a bound exciton recombination at 3.3628 eV. Correlated by magnetic resonance experiments we attribute this particular donor to hydrogen. These results are in line with the temperature-dependent Hall-effect measurements. The Al, Ga and In donor–bound exciton recombinations are identified based on doping and diffusion experiments, and using secondary ion mass spectroscopy. We report on the optical properties of the shallow nitrogen acceptor in ZnO incorporated by diffusion, by ion implantation and by in situ doping in epitaxial films.

Defect chemistry of oxide nanomaterials with high surface area: ordered mesoporous thin films of the oxygen storage catalyst CeO2-ZrO2.

Herein we report the electrical transport properties of a series of ordered mesoporous ceria-zirconia (CexZr1-xO2, referred to as mp-CZO) thin films with both a cubic structure of (17±2) nm diameter pores and nanocrystalline walls. Samples over the whole range of composition, including bare CeO2 and ZrO2, were fabricated by templating strategies using the large diblock copolymer KLE as the structure-directing agent. Both the nanoscale structure and the chemical composition of the mesoporous materials were analyzed by a combination of scanning and transmission electron microscopy, grazing incidence small-angle X-ray scattering, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry. The total conductivity as a function of the film composition, temperature, and oxygen partial pressure was measured using impedance spectroscopy. The mesoporous solid solutions of CeO2-ZrO2 prepared in this work showed a higher stability against thermal ripening than both binary oxides, making them ideal model systems to study both the charge transport properties and the oxygen storage at elevated temperatures. We find that the redox properties of nanocrystalline mp-CZO thin films differ significantly from those of bulk CZO materials reported in the literature and, therefore, propose a defect chemical model of surface regions.

Crystalline ZnO with an enhanced surface area obtained by nanocasting

The authors report the synthesis of nanoporous ZnO, which exhibits a periodically ordered, uniform pore system with crystalline pore walls. The crystalline structure is investigated by x-ray diffraction, transmission electron microscopy, and selected area electron diffraction. The large specific surface area and the uniformity of the pore system are confirmed by nitrogen physisorption. Raman spectroscopy along with low-temperature photoluminescence measurements confirms the high degree of crystallinity and gives insight into defects participating in the radiative recombination processes.

Interfacial Reactivity Benchmarking of the Sodium Ion Conductors Na3PS4 and Sodium β-Alumina for Protected Sodium Metal Anodes and Sodium All-Solid-State Batteries

The interfacial stability of solid electrolytes at the electrodes is crucial for an application of all-solid-state batteries and protected electrodes. For instance, undesired reactions between sodium metal electrodes and the solid electrolyte form charge transfer hindering interphases. Due to the resulting large interfacial resistance, the charge transfer kinetics are altered and the overvoltage increases, making the interfacial stability of electrolytes the limiting factor in these systems. Driven by the promising ionic conductivities of Na3PS4, here we explore the stability and viability of Na3PS4 as a solid electrolyte against metallic Na and compare it to that of Na-β″-Al2O3 (sodium β-alumina). As expected, Na-β″-Al2O3 is stable against sodium, whereas Na3PS4 decomposes with an increasing overall resistance, making Na-β″-Al2O3 the electrolyte of choice for protected sodium anodes and all-solid-state batteries.

(Electro)chemical expansion during cycling: monitoring the pressure changes in operating solid-state lithium batteries

Solid-state lithium-ion batteries (SSBs) are a promising concept for future energy storage applications. Interestingly, the mechanical effects during operation of SSBs, and their correlation to the electrochemical performance, have rarely been investigated. In such systems, the rigid mechanical coupling between the active phases and the solid electrolyte will lead to more complex non-local strain effects than in the common liquid electrolyte-based lithium-ion batteries, where the chemical expansion or compression of the active phases is accommodated by the liquid electrolyte, and only local mechanical strain within the electrode particles exists. In this work we report on the pressure and height changes within typical solid-state batteries, which were measured in situ during galvanostatic cycling conditions. The continuous volume changes of both the anode and the cathode during lithiation/delithiation are responsible for a highly reproducible cycle of pressure changes during the operation of the solid-state battery cell. Bending and cracking of the solid-state battery cells are observed with X-ray tomography and provide evidence for the critical role of the macroscopic strain generated during cycling. Furthermore, these pressure and dilatometry measurements as well as X-ray tomography underline the importance of external confinement and pressure control for SSBs.

Redox-active cathode interphases in solid-state batteries

All-solid-state batteries are expected to provide a next-generation solution for energy storage. Employing fast conducting lithium thiophosphates as a replacement for liquid electrolytes in conventional lithium ion batteries has shown great promise, however, capacity fading and the underlying interfacial side reactions of thiophosphates and cathode active materials are not yet understood well. In this study, we charge solid-state batteries to different cut-off potentials and find the formation of a redox-active resistive layer in the solid electrolyte, which impedes the conductivity depending on the state-of-charge of the battery. Using electrochemical impedance spectroscopy as well as depth profiling with X-ray photoelectron spectroscopy we find a thick passivation layer at the current collector and decomposition products within the cathode composite. In addition, an in situ electrochemical experiment during X-ray photoelectron spectroscopy shows that the solid electrolyte is redox active at the cathode/solid electrolyte interface in solid-state batteries. This work highlights the importance of protecting interface layers at the current collector, and the influence of the resulting electric potential drop, as well as provides insight into the redox chemistry of lithium conducting thiophosphates.

Synthesis and Physicochemical Characterization of Ce1−xGdxO2−δ: A Case Study on the Impact of the Oxygen Storage Capacity on the HCl Oxidation Reaction

This study reports the synthesis of high‐surface‐area Ce1−xGdxO2−δ (CGO) fibers that are used as catalysts for the oxidation of HCl. Special emphasis is put on the role of the oxygen storage capacity (OSC) of the CGO fibers on the catalytic performance. An in‐depth physicochemical characterization of high‐surface‐area CGO was achieved by employing a multitude of dedicated spectroscopic techniques. The increasing OSC with Gd content is traced to the development of a space charge region with increased electron concentration as a result of the nano size of the CGO particles. The activity of CGO in the HCl oxidation reaction is shown to decrease with Gd concentration.

Homogeneous Coating with an Anion-Exchange Ionomer Improves the Cycling Stability of Secondary Batteries with Zinc Anodes

Limited cycling stability of secondary cells with zinc anodes arises mainly from the high solubility of oxidized zinc species in the alkaline electrolyte resulting in electrode shape change and loss of active material during repeated discharge and charge. We propose and successfully employ a homogeneous coating with an anion-exchange ionomer (AEI) on model electrodes with electron-conductive host structures to confine the oxidized zinc species. Ideally, the confinement of oxidized zinc species reduces the shape change of the electrode and keeps the active material as close as possible at its place of origin. In this work, the confinement concept for the oxidized zinc species is elucidated by means of electrochemical studies and X-ray photoelectron spectroscopy: as intended, an interlayer of zinc oxide forms between the AEI and the surface of the zinc electrode. This interlayer implies that the hydroxide ions are able to pass and react as intended, whereas the migration of oxidized zinc species into the bulk electrolyte is hindered. The coating with an AEI yields a higher amount of restored zinc during electrodeposition in comparison to an uncoated zinc electrode-applying an AEI coating increases the achievable cycle number by up to six times. We investigate the morphology of the cycled electrodes and derive thereby the needs for further material classes that might be employed in the confinement concept. This approach demonstrates the benefit of ion-selective coatings, allowing for the permeation of hydroxide ions but not of oxidized zinc species, a concept which improves rechargeable batteries with zinc anodes, such as zinc-oxygen batteries.

Photonic properties of ZnO epilayers

The characterization by various experimental techniques of homoepitaxial growth and photonic properties of ZnO epilayers was exhaustively analyzed. The photonic properties of ZnO as promising material for the realization of polariton lasers were investigated by angular dependent reflection spectroscopy. The fitting of the polariton dispersion curve with the experimental results provided us information about the longitudinal-transverse exciton-polariton splitting and damping constants. In addition, the valence band symmetry was examined by angular resolved magneto-optical photoluminescence. From our theoretical and experimental results we extracted evidence that the topmost A valence band possesses Г7 symmetry. Micro-Raman spectroscopy revealed even in homoepitaxially grown samples the existence of compressive or tensile strain which varied not only in the ZnO layers but also in the templates. In contrast, the untreated substrates were uniformly strained. Sporadically crystal perturbations culminating in the formation of separated growth domains were observed. Additionally, resonant Raman scattering was performed, showing a strong enhancement of the 2E1(LO) mode for resonant excitation of the I8 bound exciton complex. We suggest that the resonant Raman scattering led to a longer lifetime of the resonantly excited phonon mode due to a strong exciton-phonon interaction.