Structural and electronic characterization of fluorine-doped La0.5Sr0.5CoO3-δ using electron energy-loss spectroscopy.

Perovskite oxides, ABO3, are potential catalysts for the oxygen evolution reaction, which is important in the production of hydrogen as a sustainable energy resource. Optimizing the chemical composition of such oxides by substitution or doping with additional elements is an effective approach to improving the activity of such catalysts. Here, we characterized the crystal and electronic structures of fluorine-doped La0.5Sr0.5CoO3-δ particles using scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS). High-resolution STEM imaging demonstrated the formation of a disordered surface phase caused by fluorine doping. In addition, spatially resolved EELS data showed that fluorine anions were introduced into the interiors of the particles and that Co ions near the surfaces were slightly reduced by fluorine doping in conjunction with the loss of oxygen ions. Peak fitting of energy-loss near-edge structure data demonstrated an unexpected nanostructure in the vicinity of the surface. An EELS characterization comprising elemental mapping together with an energy-loss near-edge structure analysis indicated that this nanostructure could not be assigned to Co-based materials but rather to the solid electrolyte BaF2. Complementary structural and electronic characterizations using STEM and EELS as demonstrated herein evidently have the potential to play an increasingly important role in elucidating the nanostructures of functional materials.

5D Analysis of Capacity Degradation in Battery Electrodes Enabled by Operando CT-XANES.

For devices encountering long-term stability challenges, a precise evaluation of degradation is of paramount importance. However, methods for comprehensively elucidating the degradation mechanisms in devices, particularly those undergoing dynamic chemical and mechanical changes during operation, such as batteries, are limited. Here, a method is presented using operando computed tomography combined with X-ray absorption near-edge structure spectroscopy (CT-XANES) that can directly track the evolution of the 3D distribution of the local capacity loss in battery electrodes during (dis)charge cycles, thereby enabling a five-dimensional (the 3D spatial coordinates, time, and chemical state) analysis of the degradation. This paper demonstrates that the method can quantify the spatiotemporal dynamics of the local capacity degradation within an electrode during cycling, which has been truncated by existing bulk techniques, and correlate it with the overall electrode performance degradation. Furthermore, the method demonstrates its capability to uncover the correlation among observed local capacity degradation within electrodes, reaction history during past (dis)charge cycles, and electrode microstructure. The method thus provides critical insights into the identification of degradation factors that are not available through existing methods, and therefore, will contribute to the development of batteries with long-term stability.

High-temperature ionic logic gates composed of an ionic rectifying solid-electrolyte interface.

Direct data collection from extremely high temperature environments is vitally important for the progress of industrial technologies such as combustion-engines, turbines and furnaces for various purposes. However, present semiconductor-based information devices are not suitable for such high-temperature applications due to thermal excitation of electronic carriers. Herein, we demonstrate high-temperature ionic AND and OR logic gates composed of the oxide-ion-conducting yttria stabilized zirconia (YSZ) and the mixed oxide-ion and electron conducting La2NiO4+δ as an ultra-high temperature information device. The ionic AND and OR gates developed in this work exhibited proper and stable electrical responses at 1073 K. The ionic logic gates shown in this work are promising demonstrations for robust information devices in extreme environments.

Fast fluoride ion conduction of NH4(Mg1-xLix)F3-x and (NH4)2(Mg1-xLix)F4-x assisted by molecular cations.

Aiming development of the fast anion conductors, we proposed a new material design using flexible molecular cation as a host cation, and demonstrated it with fluoride ion conduction in NH4MgF3 and (NH4)2MgF4 based materials. Dominant fluoride ion conduction with relatively high conductivities of 4.8 × 10-5 S cm-1 and 8.4 × 10-6 S cm-1 were achieved at 323 K in (NH4)2(Mg0.85Li0.15)F3.85 and NH4(Mg0.9Li0.1)F2.9, respectively. It is implied that the molecular cation in the host lattice can assist the anion conduction. Our findings suggest molecular cation-containing compounds can be attractive material groups for fast anion conductors.

Rate-Determining Process at Electrode/Electrolyte Interfaces for All-Solid-State Fluoride-Ion Batteries.

Developing high-performance solid electrolytes that are operable at room temperature is one of the toughest challenges related to all-solid-state fluoride-ion batteries (FIBs). In this study, tetragonal ß-Pb0.78Sn1.22F4, a promising solid electrolyte material for mild-temperature applications, was modified through annealing under various atmospheres using thin-film models. The annealed samples exhibited preferential growth and enhanced ionic conductivities. The rate-determining factor for electrode/electrolyte interface reactions in all-solid-state FIBs was also investigated by comparing ß-Pb0.78Sn1.22F4 with representative fluoride-ion- and lithium-ion-conductive materials, namely, LaF3, CeF3, and Li7La3Zr2O12. The overall rate constant of the interfacial reaction, k0, which included both mass and charge transfers, was determined using chronoamperometric measurements and Allen-Hickling simulations. Arrhenius-type correlations between k0 and temperature indicated that activation energies calculated from k0 and ionic conductivities (σion) were highly consistent. The results indicated that the mass transfer (electrolyte-side fluoride-ion conduction) should be the rate-determining process at the electrode/electrolyte interface. ß-Pb0.78Sn1.22F4, with a large σion value, had a larger k0 value than Li7La3Zr2O12. Therefore, it is hoped that the development of high-conductivity solid electrolytes can lead to all-solid-state FIBs with superior rate capabilities similar to those of all-solid-state Li-ion batteries.

Comparison of electrochemical impedance spectra for electrolyte-supported solid oxide fuel cells (SOFCs) and protonic ceramic fuel cells (PCFCs).

Protonic ceramic fuel cells (PCFCs) are expected to achieve high power generation efficiency at intermediate temperature around 400-600 °C. In the present work, the distribution of relaxation times (DRT) analysis was investigated in order to deconvolute the anode and cathode polarization resistances for PCFCs supported on yttria-doped barium cerate (BCY) electrolyte in comparison with solid oxide fuel cells (SOFCs) supported on scandia-stabilized zirconia (ScSZ) electrolyte. Four DRT peaks were detected from the impedance spectra measured at 700 °C excluding the gas diffusion process for ScSZ and BCY. The DRT peaks at 5 × 102-1 × 104 Hz and 1 × 100-2 × 102 Hz were related to the hydrogen oxidation reaction at the anode and the oxygen reduction reaction at the cathode, respectively, for both cells. The DRT peak at 2 × 101-1 × 103 Hz depended on the hydrogen concentration at the anode for ScSZ, while it was dependent on the oxygen concentration at the cathode for BCY. Compared to ScSZ, steam was produced at the opposite electrode in the case of BCY, which enhanced the cathode polarization resistance for PCFCs.

3D Operando Imaging and Quantification of Inhomogeneous Electrochemical Reactions in Composite Battery Electrodes.

The performances of electrochemical systems such as solid-state batteries (SSBs) can be severely hindered by the three-dimensional (3D) and mesoscopically inhomogeneous electrochemical reactions that take place in the electrodes. However, the majority of existing methods for analyzing such inhomogeneous reactions are restricted to one- or two-dimensional observations. Herein, we performed 3D operando imaging of the mesoscopically inhomogeneous electrochemical reaction in a composite SSB electrode using hard X-ray computed-tomography with X-ray absorption near edge structure spectroscopy (CT-XANES). The 3D inhomogeneous reaction evolution during (dis)charge was successfully visualized for the first time. Furthermore, our 3D quantitative analysis unambiguously revealed the origin of the inhomogeneous reaction in the investigated electrode. Our results suggested that slow ion transport through active material particles can considerably restrict SSB performances. Our technique therefore provides new insights into the electrochemical reactions taking place in electrodes and enables us to maximize the performance of electrochemical systems.

Guidelines for All-Solid-State Battery Design and Electrode Buffer Layers Based on Chemical Potential Profile Calculation.

Protective coatings on cathode active materials have become paramount for the implementation of solid-state batteries; however, the development of coatings lacks the understanding of the necessary coating properties. In this study, guidelines for the design of solid electrolytes and electrode coatings in all-solid-state batteries are proposed from the viewpoint of the steady-state Li chemical potential profile across the battery cell. The model calculation of the (electro)chemical potential profile in all-solid-state batteries is established by considering the steady-state mixed ionic and electronic conduction in the solid electrolyte under the assumption of local equilibrium. For quantitative discussion, the potential profiles within oxygen ion conductors are calculated instead of Li/Na ion conductors as their partial electronic conductivities have not been reported so far in sufficient detail. Based on the calculated chemical potential profile, two main conclusions are obtained: (1) the decisive factor for the formation of the chemical potential profile of the neutral mobile component (e.g., oxygen or lithium) in the solid electrolyte is its electronic conductivity (and the activity dependence), and (2) a particularly large potential drop is formed in a region where the electronic conductivity becomes small. While these conclusions are valid and general for any solid electrolyte device, they are particularly important for the design of protective coatings and the understanding of the functionality of self-assembled solid electrolyte interphases in all-solid-state batteries. To protect the solid electrolyte from decomposition by reduction/oxidation at the anode/cathode interfaces, a sufficient chemical potential drop is necessary within the coating layer or directly at the interphase layer. To achieve this situation, the coating/interphase materials need to have a lower electronic conductivity than the solid electrolyte.

Effect of Cation Ordering on the Performance and Chemical Stability of Layered Double Perovskite Cathodes.

The effect of A-site cation ordering on the cathode performance and chemical stability of A-site cation ordered LaBaCo2O5+δ and disordered La0.5Ba0.5CoO3-δ materials are reported. Symmetric half-cells with a proton-conducting BaZr0.9Y0.1O3-δ electrolyte were prepared by ceramic processing, and good chemical compatibility of the materials was demonstrated. Both A-site ordered LaBaCo2O5+δ and A-site disordered La0.5Ba0.5CoO3-δ yield excellent cathode performance with Area Specific Resistances as low as 7.4 and 11.5 Ω·cm² at 400 °C and 0.16 and 0.32 Ω·cm² at 600 °C in 3% humidified synthetic air respectively. The oxygen vacancy concentration, electrical conductivity, basicity of cations and crystal structure were evaluated to rationalize the electrochemical performance of the two materials. The combination of high-basicity elements and high electrical conductivity as well as sufficient oxygen vacancy concentration explains the excellent performance of both LaBaCo2O5+δ and La0.5Ba0.5CoO3-δ materials at high temperatures. At lower temperatures, oxygen-deficiency in both materials is greatly reduced, leading to decreased performance despite the high basicity and electrical conductivity. A-site cation ordering leads to a higher oxygen vacancy concentration, which explains the better performance of LaBaCo2O5+δ. Finally, the more pronounced oxygen deficiency of the cation ordered polymorph and the lower chemical stability at reducing conditions were confirmed by coulometric titration.

Operando Soft X-ray Absorption Spectroscopic Study on a Solid Oxide Fuel Cell Cathode during Electrochemical Oxygen Reduction.

An operando soft X-ray absorption spectroscopic technique, which enabled the analysis of the electronic structures of the electrode materials at elevated temperature in a controlled atmosphere and electrochemical polarization, was established and its availability was demonstrated by investigating the electronic structural changes of an La2 NiO4+δ dense-film electrode during an electrochemical oxygen reduction reaction. Clear O K-edge and Ni L-edge X-ray absorption spectra could be obtained below 773 K under an atmospheric pressure of 100 ppm O2 /He, 0.1 % O2 /He, and 1 % O2 /He gas mixtures. Considerable spectral changes were observed in the O K-edge X-ray absorption spectra upon changing the PO2 and application of electrical potential, whereas only small spectral changes were observed in Ni L-edge X-ray absorption spectra. A pre-edge peak of the O K-edge X-ray absorption spectra, which reflects the unoccupied partial density of states of Ni 3d-O 2p hybridization, increased or decreased with cathodic or anodic polarization, respectively. The electronic structural changes of the outermost orbital of the electrode material due to electrochemical polarization were successfully confirmed by the operando X-ray absorption spectroscopic technique developed in this study.

The determining factor for interstitial oxygen formation in Ruddlesden-Popper type La2NiO4-based oxides.

The interstitial oxygen formation mechanism in La2NiO4-based oxides was studied using soft X-ray absorption spectroscopy. When the interstitial oxygen concentration increased, the pre-edge peak of O K-edge spectra increased while Ni L-edge spectra was almost invariant. These spectral changes strongly suggest the significant contribution of ligand oxygen to interstitial oxygen formation by providing/accepting electronic charge carriers. The variation of the integrated peak intensity of the O K-edge strongly suggests that interstitial oxygen formation is determined by the equilibrium unoccupied pDOS of ligand oxygen. From this hypothesis, we propose that modulating the electronic structure is the key to control the capability of interstitial oxygen formation in La2NiO4-based oxides.

Oxygen nonstoichiometry, the defect equilibrium model and thermodynamic quantities of the Ruddlesden-Popper oxide Sr3Fe2O(7-δ).

Oxygen nonstoichiometry of the Ruddlesden-Popper oxide Sr3Fe2O7-δ was measured at intermediate temperatures (773-1073 K) by coulometric titration and high temperature gravimetry. The oxygen nonstoichiometric behavior was analyzed using the defect equilibrium model with localized electrons. From the defect chemical analysis, estimated oxygen vacancy concentration at the O3 sites increases and at the O1 sites decreases with the increasing temperature. This characteristic behavior is considered to be caused by the redistribution of oxygen and vacancies between the O1 and O3 sites. The obtained thermodynamic quantities of the partial molar enthalpy of oxygen, h(O) - h°(O), and the partial molar entropy of oxygen, s(O) - s°(O), calculated from the Gibbs-Helmholtz equation are in good agreement with those from the statistical thermodynamic calculation based on the defect equilibrium model, indicating that the proposed defect equilibrium model is reasonable.

The crystal structure, oxygen nonstoichiometry and chemical stability of Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF).

The oxygen nonstoichiometry and the crystal structure of Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) were investigated by using coulometric titration, high-temperature gravimetry and in situ HT-XRD. The chemical stability diagram of BSCF was established as a function of temperature between room temperature and 1373 K and oxygen partial pressure, p(O2), between 1 and 1 × 10(-21) bar. The results showed that the cubic BSCF had poor chemical stability both under highly oxidative conditions at low temperatures and highly reductive conditions at high temperatures. The phase analysis of the decomposition products showed that the chemical instability of BSCF was mainly owing to the oxidation/reduction of trivalent Co ions.

An X-ray absorption spectroscopic study on mixed conductive La0.6Sr0.4Co0.8Fe0.2O(3-δ) cathodes. I. Electrical conductivity and electronic structure.

The electrical conduction mechanism of mixed conductive perovskite oxides, La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-δ), for cathode materials of solid oxide fuel cells has been investigated from electronic structural changes during oxygen vacancy formation. La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-δ) was annealed under various oxygen partial pressures p(O(2))s at 1073 K and quenched. Iodometric titration indicated that the oxygen nonstoichiometry of La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-δ) depended on the annealing p(O(2)), with more oxygen vacancies introduced at lower than at higher p(O(2))s. X-Ray absorption spectroscopic measurements were performed at the O K-, Co L-, Fe L-, Co K-, and Fe K-edges. The valence states of the Co and Fe ions were investigated by the X-ray absorption near edge structure (XANES) at the Co and Fe L(III)-edges. While the Fe average valence was almost constant, the valence of the Co ions decreased with oxygen vacancy introduction. The O K-edge XANES spectra indicated that electrons were injected into the Co 3d/O 2p hybridization state with oxygen vacancy introduction. Both absorption edges at the Co and Fe K-edge XANES shifted towards lower energies with oxygen vacancy introduction. The shift at the Co K-edge resulted from the decrease in the Co average valence and that at the Fe K-edge appeared to be caused by changes in the coordination environment around the Fe ions. The total conductivity of La(0.6)Sr(0.4)Co(0.8)Fe(0.2)O(3-δ) decreased with decreasing p(O(2)), due to a decreasing hole concentration.