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Minimizing the overpotential at the air electrode of solid oxide fuel cells (SOFC) is one of the key challenges regarding a broad applicability of this technology. Next to novel materials and geometry optimization, surface modification is a promising and flexible method to alter the oxygen exchange kinetics at SOFC cathode surfaces. Despite extensive research, the mechanism behind the effect of surface decorations is still under debate. Moreover, for Sr decoration, previous studies yielded conflicting results, reporting either a beneficial or a detrimental impact on the oxygen exchange kinetics. In this contribution, in situ impedance spectroscopy during pulsed laser deposition was used to investigate the effect of Sr containing decorations under different deposition conditions. Depending on deposition temperature and interactions with the gas phase, opposing effects of Sr decoration were found. In combination with near-ambient pressure X-ray photoelectron spectroscopy and non-ambient X-ray diffractometry, it was possible to trace this phenomenon back to different chemical environments of the surface Sr. At high temperatures, Sr is deposited as SrO, which can have a beneficial effect on the oxygen exchange kinetics. At low temperatures, SrCO3 adsorbates are formed from trace amounts of CO2 in the measurement atmosphere, causing a decrease of the oxygen exchange rate. These results are in excellent agreement with the concept of surface acidity as a descriptor for the effect of surface decorations, providing further insight into the oxygen exchange kinetics on SOFC cathode surfaces and its degradation. In addition, this study shows that Sr segregation itself initially does not lead to performance degradation but that segregated SrO readily reacts with acidic compounds, reducing the catalytic capability of mixed conducting oxides. [ABSTRACT FROM AUTHOR]

Cubic Li7La3Zr2O12 (LLZO) garnets are among the most promising solid electrolytes for solid-state batteries with the potential to exceed conventional battery concepts in terms of energy density and safety. The electrochemical stability of LLZO is crucial for its application, however, controversial reports in the literature show that it is still an unsettled matter. Here, we investigate the electrochemical stability of LLZO single crystals by applying electric field stress via macro- and microscopic ionically blocking Au electrodes in ambient air. Induced material changes are subsequently probed using various locally resolved analysis techniques, including microelectrode electrochemical impedance spectroscopy (EIS), laser induced breakdown spectroscopy (LIBS), laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), and microfocus X-ray diffraction (XRD). Our experiments indicate that LLZO decomposes at 4.1–4.3 V vs. Li+/Li, leading to the formation of Li-poor phases like La2Zr2O7 beneath the positively polarized electrode. The reaction is still on-going even after several days of polarization, indicating that no blocking interfacial layer is formed. The decomposition can be observed at elevated as well as room temperature and suggests that LLZO is truly not compatible with high voltage cathode materials. [ABSTRACT FROM AUTHOR]

La0.6Sr0.4CoO3−δ thin films grown on YSZ single crystals were investigated directly in the stage of deposition by means of in situ impedance spectroscopy during pulsed laser deposition (IPLD). This method allows the observation of dense thin films unaltered by degradation and provides information about the oxygen exchange kinetics as well as the defect chemistry of pristine LSC thin films. These measurements revealed remarkably low surface resistance values (1.3 Ω cm2 at 600 °C and 0.04 mbar O2) compared to films measured outside the PLD chamber (∼20 Ω cm2 at 600 °C and 0.04 mbar O2). Also the activation energy of the surface exchange resistance at 0.04 mbar p(O2) is significantly lower than at ambient conditions (∼1 eV vs. ∼1.3 eV) and degradation happens considerably slower. Furthermore, the grain size of the LSC thin film does not affect its initial surface resistance directly after deposition. The chemical capacitance of LSC thin films was linked to the concentration of oxygen vacancies and shows that LSC thin films exhibit lower oxygen vacancy concentrations than the corresponding bulk material. [ABSTRACT FROM AUTHOR]

The attractiveness of cubic Li7La3Zr2O12 (LLZO) based garnets lies in their high ionic conductivity and the combination of thermal and electrochemical stability. However, relationships between the exact chemical composition and ionic conductivity are still not well understood and samples of very similar composition and processing may show very different properties. In this contribution, we investigated Al stabilized LLZO by employing a combination of local conductivity measurements and 3D local chemical analysis using laser ablation inductively coupled plasma optical emission spectroscopy (LA-ICP-OES). These measurements revealed significant conductivity variations across some samples, with variations up to almost one order of magnitude, as well as an inhomogeneous elemental distribution of Al and Li, largely along the samples. Surprisingly, neither the local Al content nor the local Li content showed a clear correlation with the local Li-ion conductivity. Accordingly, an in-depth understanding of the conduction properties of Al stabilized LLZO has to concentrate on aspects beyond the simple chemical composition. Yet unknown factors (e.g. oxygen vacancies or local cation site occupancies) seem to have a much higher impact on the ionic conductivity than the exact stoichiometry. [ABSTRACT FROM AUTHOR]

The surface composition of dense La0.6Sr0.4CoO3−δ (LSC) thin film model electrodes, deposited by pulsed laser deposition at 600 °C on yttria-stabilized zirconia (100) electrolytes, was investigated by low-energy ion scattering (LEIS) and time resolved inductively coupled plasma mass spectrometry (ICP-MS). Results obtained by both methods agree qualitatively and quantitatively and provide a comprehensive picture of the surface composition and cation diffusion kinetics of LSC. The measurements revealed that freshly prepared LSC thin films already show a Sr-rich and Co-poor termination layer (80% Sr surface coverage). This Sr-rich surface layer was proven to be an equilibrium property of LSC as it forms again at elevated temperatures after removal. The kinetics of this surface reconstruction is surprisingly fast (＜1 h at 550 °C) and indicates high Sr mobility in LSC. Electrochemical Impedance Spectroscopy (EIS) measurements at 400 °C revealed the detrimental effect of this surface layer on the oxygen surface exchange and suggest that higher Co concentrations in the termination layer facilitate the oxygen exchange reaction. [ABSTRACT FROM AUTHOR]

Minimizing the overpotential at the air electrode of solid oxide fuel cells (SOFC) is one of the key challenges regarding a broad applicability of this technology. Next to novel materials and geometry optimization, surface modification is a promising and flexible method to alter the oxygen exchange kinetics at SOFC cathode surfaces. Despite extensive research, the mechanism behind the effect of surface decorations is still under debate. Moreover, for Sr decoration, previous studies yielded conflicting results, reporting either a beneficial or a detrimental impact on the oxygen exchange kinetics. In this contribution, in situ impedance spectroscopy during pulsed laser deposition was used to investigate the effect of Sr containing decorations under different deposition conditions. Depending on deposition temperature and interactions with the gas phase, opposing effects of Sr decoration were found. In combination with near-ambient pressure X-ray photoelectron spectroscopy and non-ambient X-ray diffractometry, it was possible to trace this phenomenon back to different chemical environments of the surface Sr. At high temperatures, Sr is deposited as SrO, which can have a beneficial effect on the oxygen exchange kinetics. At low temperatures, SrCO 3 adsorbates are formed from trace amounts of CO 2 in the measurement atmosphere, causing a decrease of the oxygen exchange rate. These results are in excellent agreement with the concept of surface acidity as a descriptor for the effect of surface decorations, providing further insight into the oxygen exchange kinetics on SOFC cathode surfaces and its degradation. In addition, this study shows that Sr segregation itself initially does not lead to performance degradation but that segregated SrO readily reacts with acidic compounds, reducing the catalytic capability of mixed conducting oxides., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The oxygen exchange reaction mechanism on truly pristine surfaces of SOFC cathode materials (La 0.6 Sr 0.4 CoO 3- δ = LSC, La 0.6 Sr 0.4 FeO 3- δ = LSF, (La 0.6 Sr 0.4 ) 0.98 Pt 0.02 FeO 3- δ = Pt:LSF, SrTi 0.3 Fe 0.7 O 3- δ = STF, Pr 0.1 Ce 0.9 O 2- δ = PCO and La 0.6 Sr 0.4 MnO 3- δ = LSM) was investigated employing in situ impedance spectroscopy during pulsed laser deposition (i-PLD) over a wide temperature and p (O 2 ) range. Besides demonstrating the often astonishing catalytic capabilities of the materials, it is possible to discuss the oxygen exchange reaction mechanism based on experiments on clean surfaces unaltered by external degradation processes. All investigated materials with at least moderate ionic conductivity ( i.e. all except LSM) exhibit polarization resistances with very similar p (O 2 )- and T -dependences, mostly differing only in absolute value. In combination with non-equilibrium measurements under polarization and defect chemical model calculations, these results elucidate several aspects of the oxygen exchange reaction mechanism and refine the understanding of the role oxygen vacancies and electronic charge carriers play in the oxygen exchange reaction. It was found that a major part of the effective activation energy of the surface exchange reaction, which is observed during equilibrium measurements, originates from thermally activated charge carrier concentrations. Electrode polarization was therefore used to control defect concentrations and to extract concentration amended activation energies, which prove to be drastically different for oxygen incorporation and evolution (0.26 vs. 2.05 eV for LSF)., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

Cubic Li 7 La 3 Zr 2 O 12 (LLZO) garnets are among the most promising solid electrolytes for solid-state batteries with the potential to exceed conventional battery concepts in terms of energy density and safety. The electrochemical stability of LLZO is crucial for its application, however, controversial reports in the literature show that it is still an unsettled matter. Here, we investigate the electrochemical stability of LLZO single crystals by applying electric field stress via macro- and microscopic ionically blocking Au electrodes in ambient air. Induced material changes are subsequently probed using various locally resolved analysis techniques, including microelectrode electrochemical impedance spectroscopy (EIS), laser induced breakdown spectroscopy (LIBS), laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), and microfocus X-ray diffraction (XRD). Our experiments indicate that LLZO decomposes at 4.1-4.3 V vs. Li + /Li, leading to the formation of Li-poor phases like La 2 Zr 2 O 7 beneath the positively polarized electrode. The reaction is still on-going even after several days of polarization, indicating that no blocking interfacial layer is formed. The decomposition can be observed at elevated as well as room temperature and suggests that LLZO is truly not compatible with high voltage cathode materials., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)