Elucidation of the Transport Properties of Calcium-Doped High Entropy Rare Earth Aluminates for Solid Oxide Fuel Cell Applications.

Solid oxide fuel cells (SOFCs) are paving the way to clean energy conversion, relying on efficient oxygen-ion conductors with high ionic conductivity coupled with a negligible electronic contribution. Doped rare earth aluminates are promising candidates for SOFC electrolytes due to their high ionic conductivity. However, they often suffer from p-type electronic conductivity at operating temperatures above 500 °C under oxidizing conditions caused by the incorporation of oxygen into the lattice. High entropy materials are a new class of materials conceptualized to be stable at higher temperatures due to their high configurational entropy. Introducing this concept to rare earth aluminates can be a promising approach to stabilize the lattice by shifting the stoichiometric point of the oxides to higher oxygen activities, and thereby, reducing the p-type electronic conductivity in the relevant oxygen partial pressure range. In this study, the high entropy oxide (Gd,La,Nd,Pr,Sm)AlO3 is synthesized and doped with Ca. The Ca-doped (Gd,La,Nd,Pr,Sm)AlO3 compounds exhibit a higher ionic conductivity than most of the corresponding Ca-doped rare earth aluminates accompanied by a reduction of the p-type electronic conductivity contribution typically observed under oxidizing conditions. In light of these findings, this study introduces high entropy aluminates as a promising candidate for SOFC electrolytes.

State of Charge-Dependent Impedance Spectroscopy as a Helpful Tool to Identify Reasons for Fast Capacity Fading in All-Solid-State Batteries.

Thiophosphate-based all-solid-state batteries (ASSBs) are considered the most promising candidate for the next generation of energy storage systems. However, thiophosphate-based ASSBs suffer from fast capacity fading with nickel-rich cathode materials. In many reports, this capacity fading is attributed to an increase of the charge transfer resistance of the composite cathode caused by interface degradation and/or chemo-mechanical failure. The change in the charge transfer resistance is typically determined using impedance spectroscopy after charging the cells. In this work, we demonstrate that large differences in the long-term cycling performance also arise in cells, which exhibit a comparable charge transfer resistance at the cathode side. Our results confirm that the charge transfer resistance of the cathode is not necessarily responsible for capacity fading. Other processes, such as resistive processes on the anode side, can also play a major role. Since these processes usually depend on the state of charge, they may not appear in the impedance spectra of fully charged cells; i.e., analyzing the impedance spectra of charged cells alone is insufficient for the identification of major resistive processes. Thus, we recommend measuring the impedance at different potentials to get a complete understanding of the reasons for capacity fading in ASSBs.

Contribution of Electrolyte Decomposition Products and the Effect of Temperature on the Dissolution of Transition Metals from Cathode Materials.

A fundamental understanding of aging processes in lithium-ion batteries (LIBs) is imperative in the development of future battery architectures for widespread electrification. Herein, dissolution of transition metals from cathode active materials of LIBs is among the most important degradation processes. Research has demonstrated that elevated operating temperatures accelerate battery degradation. However, the exact mechanism of transition-metal dissolution at elevated temperatures has still to be clarified. Current literature suggests that the reaction rate of dissolution increases with increasing temperature; moreover, the decomposition of electrolytes results in products that also accelerate dissolution processes. Most studies focus on ex situ analyses of thermally treated full cells. This approach is not appropriate to get detailed insights and to distinguish between different contributions. In this work, with the help of real-time dissolution analysis using an electroanalytical flow cell (EFC) coupled to an inductively coupled plasma mass spectrometer (ICP-MS), we present novel details of the temperature effects on in situ dissolution at the cathode electrolyte interface. With fresh electrolytes, we find increased Mn dissolution even at open-circuit conditions as well as with constant voltage polarization when the electrode sample is heated at constant temperatures between 50 and 80 °C. The release of transition metals also responds in a nuanced manner when applying temperature transients. Utilizing electrolytes preheated at 60 and 100 °C, we demonstrate that decomposition products in the bulk electrolyte have no influence on transition-metal (TM) dissolution when constantly flushing the cell with the thermally aged electrolyte samples. Only when keeping the cathode temperature at 60 °C, the dissolution increases by a factor of 2-3. Our findings highlight the interplay between the cathode and electrolyte and provide new insights into the dissolution mechanism of cathode materials.

Influence of Microstructure on the Material Properties of LLZO Ceramics Derived by Impedance Spectroscopy and Brick Layer Model Analysis.

Variants of garnet-type Li7La3Zr2O12 are being intensively studied as separator materials in solid-state battery research. The material-specific transport properties, such as bulk and grain boundary conductivity, are of prime interest and are mostly investigated by impedance spectroscopy. Data evaluation is usually based on the one-dimensional (1D) brick layer model, which assumes a homogeneous microstructure of identical grains. Real samples show microstructural inhomogeneities in grain size and porosity due to the complex behavior of grain growth in garnets that is very sensitive to the sintering protocol. However, the true microstructure is often omitted in impedance data analysis, hindering the interlaboratory reproducibility and comparability of results reported in the literature. Here, we use a combinatorial approach of structural analysis and three-dimensional (3D) transport modeling to explore the effects of microstructure on the derived material-specific properties of garnet-type ceramics. For this purpose, Al-doped Li7La3Zr2O12 pellets with different microstructures are fabricated and electrochemically characterized. A machine learning-assisted image segmentation approach is used for statistical analysis and quantification of the microstructural changes during sintering. A detailed analysis of transport through statistically modeled twin microstructures demonstrates that the transport parameters derived from a 1D brick layer model approach show uncertainties up to 150%, only due to variations in grain size. These uncertainties can be even larger in the presence of porosity. This study helps to better understand the role of the microstructure of polycrystalline electroceramics and its influence on experimental results.

Understanding the Impedance of Mesoporous Oxides: Reliable Determination of the Material-Specific Conductivity.

The unique architecture of ordered mesoporous oxides makes them a promising class of materials for various electrochemical applications, such as gas sensing or energy storage and conversion. The high accessibility of the internal surface allows tailoring of their electrochemical properties, e.g., by adjusting the pore size or surface functionalization, resulting in superior device performance compared to nanoparticles or disordered mesoporous counterparts. However, optimization of the mesoporous architecture requires reliable electrochemical characterization of the system. Unfortunately, the interplay between nanocrystalline grains, grain boundaries, and the open pore framework hinders a simple estimation of material-specific transport quantities by using impedance spectroscopy. Here, we use a 3D electric network model to elucidate the impact of the pore structure on the electrical transport properties of mesoporous thin films. It is demonstrated that the impedance response is dominated only by the geometric current constriction effect arising from the regular pore network. Estimating the effective conductivity from the total resistance and the electrode geometry, thus, differs by more than 1 order of magnitude from the material-specific conductivity of the solid mesoporous framework. A detailed analysis of computed impedances for varying pore size allows for the correlation of the effective conductivity with the material-specific conductivity. We derive an empirical expression that accounts for the porous structure of the thin films and allows a reliable determination of the material-specific conductivity with an error of less than 8%.

Reproducible long-term cycling data of Al2O3 coated LiNi0.70Co0.15Mn0.15O2 cathodes for lithium-ion batteries.

LiNixCoyMn1-x-yO2 (NCM) based cathodes for Li-ion batteries (LIBs) are of great interest due to their higher energy density and lower costs compared to conventional LiCoO2 based cathodes. However, NCM based cathodes suffer from instabilities of the cathode-electrolyte interface resulting in faster capacity fading during long-term cycling. Different NCM compositions along with different coatings have been developed to protect the interface. However, a detailed understanding why and how coatings work is still missing. Up to now, no state-of-the-art NCM or coating material have been agreed upon yet, making it difficult to benchmark the performance of the coating material. Undefined standards complicate the use of experimentally produced data for model-based studies, which are a key element in assessing the beneficial effect of coatings. In this work, we therefore describe reproducible long-term cycling data of NCM based cathodes with and without an Al2O3 based coating. The data set is provided to be used for parameter fitting and/or as training data to encourage the simulation of the performance of LIBs in model-based approaches.

Design of Ordered Mesoporous CeO2-YSZ Nanocomposite Thin Films with Mixed Ionic/Electronic Conductivity via Surface Engineering.

Mixed ionic and electronic conductors represent a technologically relevant materials system for electrochemical device applications in the field of energy storage and conversion. Here, we report about the design of mixed-conducting nanocomposites by facile surface modification using atomic layer deposition (ALD). ALD is the method of choice, as it allows coating of even complex surfaces. Thermally stable mesoporous thin films of 8 mol-% yttria-stabilized zirconia (YSZ) with different pore sizes of 17, 24, and 40 nm were prepared through an evaporation-induced self-assembly process. The free surface of the YSZ films was uniformly coated via ALD with a ceria layer of either 3 or 7 nm thickness. Electrochemical impedance spectroscopy was utilized to probe the influence of the coating on the charge-transport properties. Interestingly, the porosity is found to have no effect at all. In contrast, the thickness of the ceria surface layer plays an important role. While the nanocomposites with a 7 nm coating only show ionic conductivity, those with a 3 nm coating exhibit mixed conductivity. The results highlight the possibility of tailoring the electrical transport properties by varying the coating thickness, thereby providing innovative design principles for the next-generation electrochemical devices.

Ordered mesoporous metal oxides for electrochemical applications: correlation between structure, electrical properties and device performance.

Ordered mesoporous metal oxides with a high specific surface area, tailored porosity and engineered interfaces are promising materials for electrochemical applications. In particular, the method of evaporation-induced self-assembly allows the formation of nanocrystalline films of controlled thickness on polar substrates. In general, mesoporous materials have the advantage of benefiting from a unique combination of structural, chemical and physical properties. This Perspective article addresses the structural characteristics and the electrical (charge-transport) properties of mesoporous metal oxides and how these affect their application in energy storage, catalysis and gas sensing.

Surface Diffusion Control Enables Tailored-Aspect-Ratio Nanostructures in Area-Selective Atomic Layer Deposition.

Area-selective atomic layer deposition is a key technology for modern microelectronics as it eliminates alignment errors inherent to conventional approaches by enabling material deposition only in specific areas. Typically, the selectivity originates from surface modifications of the substrate that allow or block precursor adsorption. The control of the deposition process currently remains a major challenge as the selectivity of the no-growth areas is lost quickly. Here, we show that surface modifications of the substrate strongly manipulate surface diffusion. The selective deposition of TiO2 on poly(methyl methacrylate) and SiO2 yields localized nanostructures with tailored aspect ratios. Controlling the surface diffusion allows tuning such nanostructures as it boosts the growth rate at the interface of the growth and no-growth areas. Kinetic Monte-Carlo calculations reveal that species move from high to low diffusion areas. Further, we identify the catalytic activity of TiCl4 during the formation of carboxylic acid on poly(methyl methacrylate) as the reaction mechanism responsible for the loss of selectivity and show that process optimization leads to higher selectivity. Our work enables the precise control of area-selective atomic layer deposition on the nanoscale and offers new strategies in area-selective deposition processes by exploiting surface diffusion effects.

Optimized atomic layer deposition of homogeneous, conductive Al2O3 coatings for high-nickel NCM containing ready-to-use electrodes.

Atomic layer deposition (ALD) derived ultrathin conformal Al2O3 coating has been identified as an effective strategy for enhancing the electrochemical performance of Ni-rich LiNixCoyMnzO2 (NCM; 0 ≤x, y, z < 1) based cathode active materials (CAM) in Li-ion batteries. However, there is still a need to better understand the beneficial effect of ALD derived surface coatings on the performance of NCM based composite cathodes. In this work, we applied and optimized a low-temperature ALD derived Al2O3 coating on a series of Ni-rich NCM-based (NCM622, NCM71.51.5 and NCM811) ready-to-use composite cathodes and investigated the effect of coating on the surface conductivity of the electrode as well as its electrochemical performance. A highly uniform and conformal coating was successfully achieved on all three different cathode compositions under the same ALD deposition conditions. All the coated cathodes were found to exhibit an improved electrochemical performance during long-term cycling under moderate cycling conditions. The improvement in the electrochemical performance after Al2O3 coating is attributed to the suppression of parasitic side reactions between the electrode and the electrolyte during cycling. Furthermore, conductive atomic force microscopy (C-AFM) was performed on the electrode surface as a non-destructive technique to determine the difference in surface morphology and conductivity between uncoated and coated electrodes before and after cycling. C-AFM measurements on pristine cathodes before cycling allow clear separation between the conductive carbon additives and the embedded NCM secondary particles, which show an electrically insulating behavior. More importantly, the measurements reveal that the ALD-derived Al2O3 coating with an optimized thickness is thin enough to retain the original conduction properties of the coated electrodes, while thicker coating layers are insulating resulting in a worse cycling performance. After cycling, the surface conductivity of the coated electrodes is maintained, while in the case of uncoated electrodes the surface conductivity is completely suppressed confirming the formation of an insulating cathode electrolyte interface due to the parasitic side reactions. The results not only show the possibilities of C-AFM as a non-destructive evaluation of the surface properties, but also reveal that an optimized coating, which preserves the conductive properties of the electrode surface, is a crucial factor for stabilising the long-term battery performance.

Polarization-dependence of the Raman response of free-standing strained Ce0.8Gd0.2O2 membranes.

Square-shaped Ce0.8Gd0.2O2 (GDC) membranes are prepared by microstructuring techniques from (111)-oriented, polycrystalline GDC thin films. The strain state of the membranes is investigated by micro-Raman mapping using polarized excitation light. Using circularly polarized excitation, the maps of the Raman shifts reveal circular contour lines in concordance with the quadratic shape of the membrane and with optical investigations of the residual strain distribution. In contrast, asymmetric contours of the maps of the Raman shifts exhibiting a two-fold symmetry are found when using linearly polarized excitation. The contour plots for a linear polarization perpendicular or parallel to the local curvature are rotated by 90°. This behavior is caused by the polarization dependence of three overlapping Raman modes arising from the splitting of the triply degenerate F2g mode due to strain. The contribution of their Raman intensity to the overall Raman signal depends on the measurement geometry and the polarization of the incoming and scattered light. Varying the polarization of the incoming excitation light results in different averaging of the Raman-active modes contributing to the broad Raman signal observed. These results clearly demonstrate that polarization-dependent Raman measurements have the potential to yield additional insight into the local strain distribution in free-standing oxide membranes.

Enhancing the Electrochemical Performance of LiNi0.70Co0.15Mn0.15O2 Cathodes Using a Practical Solution-Based Al2O3 Coating.

Ni-rich Li[NixCoyMn1-x-y]O2 (NCM) cathode materials have attracted great research interest owing to their high energy density and relatively low cost. However, capacity fading because of parasitic side reactions, mainly occurring at the interface with the electrolyte, still hinders widespread application in advanced Li-ion batteries (LIBs). Surface modification via coating is a feasible approach to tackle this issue. Nevertheless, achieving uniform coatings is challenging, especially when using wet chemistry methods. In this work, a protective alumina shell on NCM701515 (70% Ni) was prepared through the reaction of surface-active -OH groups with trimethylaluminum as the precursor. The coated NCM701515 shows significantly improved capacity retention over uncoated (pristine) NCM701515. Part of the reason is the lower impedance buildup during cycling due to the effective suppression of adverse side reactions and secondary particle fracture. Taken together, the solution-based coating strategy described herein offers an easy way to apply surface treatment to stabilize Ni-rich NCM cathode materials in next-generation LIBs.

Tailoring the protonic conductivity of porous yttria-stabilized zirconia thin films by surface modification.

Porous yttria-stabilized zirconia (YSZ) thin films were prepared by pulsed laser deposition to investigate the influence of specific surface area on the electronic, oxygen ion, and protonic transport properties. Electrochemical impedance spectroscopy was carried out as a function of temperature, oxygen activity and humidity of the surrounding atmosphere. At high humidity, protons on the surface of the porous YSZ thin films lead to increased conductivity, even for temperatures up to 700 °C. With increasing relative humidity, the activation energy of proton transport decreases because of changes in the transport mechanism from Grotthuss-type to vehicle-type transport. By coating the porous YSZ films with an amorphous titania (TiO2) layer of only a few nanometer thickness using atomic layer deposition, the protonic contribution to conductivity is significantly reduced. Depositing an 18 nm-thick anatase TiO2 surface layer, the protonic conductivity contribution increases again, which can be attributed to enhanced capillary condensation because of the lower pore size. Interestingly, the filling of pores is accompanied by a decrease in proton mobility. Theses results demonstrate the significant effect that the porosity and the surface properties have on the protonic transport and further provide new design principles for developing nanostructured proton-conducting oxides.

Anomalous Angle-Dependent Magnetotransport Properties of Single InAs Nanowires.

We study the magnetotransport properties of single InAs nanowires grown by selective-area metal-organic vapor-phase epitaxy. The semiconducting InAs nanowires exhibit a large positive ordinary magnetoresistance effect. However, a deviation from the corresponding quadratic behavior is observed for an orientation of the applied magnetic field perpendicular to the nanowire axis. This additional contribution to the magnetoresistance can be explained by diffuse boundary scattering of free carriers in the InAs nanowire and results in a reduction of the charge carrier mobility. As a consequence, angle-dependent magnetotransport measurements reveal a highly anomalous behavior. Numerical simulations have been conducted to further investigate the effect of classical boundary scattering in the nanowires. On the basis of the numerical simulations, an empirical description is derived, which yields excellent agreement with the experimental data and allows one to quantify the contribution of boundary scattering to the magnetoresistance effect.

Thermal stability, electrochemical and structural characterization of hydrothermally synthesised cobalt ferrite (CoFe2O4).

Monophasic nano-crystalline CoFe2O4 (CFO) nanoparticles of high purity have been synthesised through a low temperature hydrothermal route, which does not involve hazardous chemicals, or conditions. The easy, green procedure involves a hydrothermal treatment at 135 °C of an aqueous suspension of the oxalate salts of the precursors. No further purification or annealing procedure was necessary to obtain the crystalline nano-structured oxide. The nanoparticles were characterized structurally and chemically by powder X-ray diffraction (PXRD), Inductively Coupled Plasma Spectrometry (ICP-MS) and Scanning Electron Microscopy (SEM), thus confirming the successful synthesis of the CoFe2O4 particles with the expected crystal phase and stoichiometry and an almost complete inverse spinel structure. From the nanoparticles pellets were pressed to investigate the electronic conduction properties using electrochemical impedance spectroscopy (EIS). At low temperatures, the conductivity measurements reveal a semiconducting behavior originating from hopping between Co sites and a total conductivity dominated by the grain boundary contribution. At higher temperatures (T > 400 °C) a metallic-insulator transition occurs, which is attributed to additional hopping of electrons between the Fe sites.

Platinum microelectrodes on gadolinia doped ceria single crystals - bulk properties and electrode kinetics.

To better understand the electrode kinetics of oxygen reduction and oxidation of gadolinia doped ceria (GDC), the electrochemical properties of platinum electrodes on GDC single crystals and polycrystalline samples were investigated with geometrically well-defined microelectrodes. For comparison measurements were also performed on polycrystalline samples using platinum interdigital electrodes in order to access the effect of the electrode geometry on the electrochemical properties. The transport properties were characterised using impedance spectroscopy, allowing to separate the transport processes of the electrode and the electrolyte. Evaluation of the temperature dependence shows activation energies of 0.77 eV for bulk transport and 1.03 eV for the electrode exchange. Oxygen partial pressure dependent measurements in a reducing atmosphere reveal a strong increase in activation energy due to electronic defect formation. A distinct chemical capacitance is observed in the electrode impedance for all sample types independent of the electrode geometry. While this chemical capacitance is only visible in the electrolyte contribution for the samples measured with interdigital electrodes, for the samples investigated with microelectrodes no chemical capacitance is observed in the electrolyte contribution of the impedance. As the chemical capacitance is related to stoichiometry changes in the electrolyte materials, the results confirm the non-uniform potential distribution occurring at a microelectrode, which results in a vanishing lateral potential gradient and therefore in a negligible stoichiometry gradient inside the electrolyte at a distance from the microelectrode.

Nanostructured Composites of Bi1-xSbx Nanoparticles and Carbon Nanotubes and the Characterization of Their Thermoelectric Properties.

The impact of inclusions of carbon nanotubes (CNT) on the thermoelectric properties of nanostructured Bi1-xSbx alloys with an Sb content between 10 and 20% was investigated for varying amounts of CNT. Three series of Bi1-xSbx pellets with 0, 0.3, and 0.5 wt % CNT were synthesized by mechanical alloying followed by uniaxial pressing. The resistivity was investigated in the temperature range from 30 to 500 K, revealing an enlargement of the band gap due to nanostructuring of the Bi1-xSbx alloy, which is even more pronounced for alloys including CNT. This enlargement is attributed to a modification of the interface between the Bi1-xSbx nanoparticles by a graphene-like coating, which is formed during the fabrication process due to the addition of CNT. Measurements of the Seebeck coefficient and the thermal conductivity were also performed to determine the thermoelectric properties. In total, the CNT-containing samples show a significant improvement of the figure of merit up to 250% for the Bi0.88Sb0.12 composition with 0.3 wt % CNT due to the interface modification between the nanoparticles, demonstrating the beneficial effect of CNT on the thermoelectric properties.

Combining two redox active rare earth elements for oxygen storage - electrical properties and defect chemistry of ceria-praseodymia single crystals.

Solid solutions of ceria and praseodymia are highly relevant for electrochemical applications as the incorporation of praseodymium into the ceria lattice shifts the range of mixed ionic electronic conductivity to higher oxygen partial pressures. To better understand the influence of praseodymium substitution on the transport processes and oxygen storage capacity in ceria, single crystals of ceria substituted with 14 mol% praseodymium have been investigated, obtaining the bulk properties without the influence of grain boundaries. Beside the characterization of structural changes caused by the substitution using XRD and Raman spectroscopy, the electrochemical transport properties of ceria-praseodymia single crystals are reported. Measurements of the total electrical conductivity, the ionic transference number and the non-stoichiometry of Ce0.85Pr0.14Zr0.01O2-δ were performed in an oxygen partial pressure range of -25 < lg[p(O2)/bar] < 0 at 700 °C. With praseodymium being redox active itself, higher values of oxygen deficiency and electrical conductivity than in pure ceria have been observed in the high oxygen partial pressure region, while no significant structural changes occur due to the similar ionic radii of both cations. From measurements of the impedance at different temperatures, the migration enthalpy for the electronic charge carriers has been determined. By analysing the non-stoichiometry at 700 °C using a defect chemical model it was also possible to determine the equilibrium constants of Pr and Ce reduction in Ce0.85Pr0.14Zr0.01O2-δ single crystals.

Doping-Induced Universal Conductance Fluctuations in GaN Nanowires.

The transport properties of Ge-doped single GaN nanowires are investigated, which exhibit a weak localization effect as well as universal conductance fluctuations at low temperatures. By analyzing these quantum interference effects, the electron phase coherence length was determined. Its temperature dependence indicates that in the case of highly doped nanowires electron-electron scattering is the dominant dephasing mechanism, while for the slightly doped nanowires dephasing originates from Nyquist-scattering. The change of the dominant scattering mechanism is attributed to a modification of the carrier confinement caused by the Ge-doping. The results demonstrate that the phase coherence length can be tuned by the donor concentration making Ge-doped GaN nanowires an ideal model system for studying the influence of impurities on quantum-interference effects in mesoscopic and nanoscale systems.