Focused Ion Beam Scanning Electron Microscopy Research Articles

Local Structural Modifications in Metallic Micropillars Induced by Plasma Focused Ion Beam Processing.

A focused ion beam scanning electron microscope (FIB-SEM) is a powerful tool that is routinely used for scale imaging from the micro- to nanometer scales, micromachining, prototyping, and metrology. In spite of the significant capabilities of a FIB-SEM, there are inherent artefacts (e.g., structural defects, chemical interactions and phase changes, ion implantation, and material redeposition) that are produced due to the interaction of Ga+ or other types of ions (e.g., Xe+, Ar+, O+, etc.) with the sample. In this study, we analyzed lattice distortion and ion implantation and subsequent material redeposition in metallic micropillars which were prepared using plasma focus ion beam (PFIB) milling. We utilized non-destructive synchrotron techniques such as X-ray fluorescence (XRF) and X-ray nanodiffraction to examine the micropillars prepared using Xe+ ion energies of 10 keV and 30 keV. Our results demonstrate that higher Xe ion energy leads to higher density of implanted ions within the redeposited and milled material. The mixing of ions in the redeposited material significantly influences the lattice structure, causing deformation in regions with higher ion concentrations. Through an X-ray nanodiffraction analysis, we obtained numerical measurements of the strain fields induced in the regions, which revealed up to 0.2% lattice distortion in the ion bombardment direction.

The 3D organization of the mineralized scales of the sturgeon has structures reminiscent of dentin and bone: a FIB-SEM study

Scales are structures composed of mineralized collagen fibrils embedded in the skin of fish. Here we investigate structures contributing to the bulk of the scale material of the sturgeon (Acipencer guldenstatii) at the millimeter, micrometer and nanometer length scales. Polished and fracture surfaces were prepared in each of the three anatomic planes for imaging with light and electron microscopy, as well as focused ion beam – scanning electron microscopy (FIB-SEM). The scale is composed of three layers, upper and lower layers forming the bulk of the scale, as well as a thin surface layer. FTIR shows that the scale is composed mainly of collagen and carbonated hydroxyapatite. Lacunae are present throughout the structure. Fracture surfaces of all three layers are characterized by large diameter collagen fibril bundles (CFBs) emanating from a plane comprising smaller diameter CFBs orientated in different directions. Fine lineations seen in polished surfaces of both major layers are used to define planes called here the striation planes. FIB-SEM image stacks of the upper and lower layers acquired in planes aligned with the striation planes, show that CFBs are oriented in various directions within the striation plane, with larger CFBs emanating from the striation plane. Fibril bundles oriented in different directions in the same plane is reminiscent of a similar organization in orthodentin. The large collagen fibril bundles emanating out of this plane are analogous to von Korff fibrils found in developing dentin with respect to size and orientation. Scales of the sturgeon are unusual in that their mineralized collagen fibril organization contains structural elements of both dentin and bone. The sturgeon scale may be an example of an early evolved mineralized material which is neither bone nor dentin but contains characteristics of both materials, however, the fossil data required to confirm this is missing.

Intraoral low-temperature degradation of monolithic zirconia dental prostheses: 5-year results of a prospective clinical study with ex vivo monitoring

ObjectivesTo investigate the 5-year intraoral evolution and kinetics of low-temperature degradation (LTD) of second-generation monolithic prostheses made of 3% molar yttrium-doped tetragonal zirconia polycrystal (3Y-TZP) and the influence of masticatory mechanical stresses and glaze layer on this evolution. MethodsA total of 101 posterior tooth elements were included in this prospective clinical study, which comprised ex vivo LTD monitoring (at baseline, 6 months, 1 year, 2 years, 3 years, and 5 years) using Raman spectroscopy (n = 2640 monoclinic phase measurement points per evaluation time) and scanning electron microscopy (SEM). Four types of areas (1–2 mm2 surface, six on molars, and four on premolars) were analysed on each element surface: occlusal, axial, glazed, or unglazed. Raman mapping, high-resolution SEM, and focused ion beam-SEM were performed on selected samples. ResultsThe dental prostheses developed a tetragonal-to-monoclinic transformation at the extreme surface of the material after six months in a buccal environment, and this process increased significantly over time. Over the five years of monitoring, the transformation developed nonuniformly with the presence of localised clusters of monoclinic grains. Tribological stresses generate grain pull-out from these clusters, which may raise questions regarding the release of 3Y-TZP nanoparticles into the body. The prosthesis fracture rate was 4.5% after 5 years. SignificanceLTD developed in vivo on the surfaces of 3Y-TZP dental prostheses and progressed slowly but significantly over time, up to 5 years investigation. However, the effects of aging on the failure rate recorded and of zirconia nanoparticles released into the body require further investigation.

Three-dimensional architecture of granulosa cell derived from oocyte cumulus complex, revealed by FIB-SEM

The oocyte cumulus complex is mainly composed of an oocyte, the perivitelline space, zona pellucida and numerous granulosa cells. The cumulus granulosa cells (cGCs) provide a particularly important microenvironment for oocyte development, regulating its growth, maturation and meiosis. In this study, we studied the internal structures and cell-to-cell connections of mouse cGCs using focused ion beam scanning electron microscopy (FIB-SEM). We reconstructed three-dimensional models to display characteristic connections between the oocyte and cGCs, and to illustrate various main organelles in cGCs together with their interaction relationship. A special form of cilium identified in granulosa cell was never reported in previous literature.

Bone Hierarchical Structure: Heterogeneity and Uniformity

AbstractBone has a complex hierarchical structure with structural integration from nm to cm. The understanding of bone structure is developing rapidly due to improvements in available methodologies that allow unravelling structures across several length scales. These methods include advances in electron microscopy, in particular, focused ion beam scanning electron microscopy (FIB‐SEM), confocal laser scanning microscopy techniques, X‐ray imaging, X‐ray diffraction tomography (XRD‐CT), and tensor tomography (small angle X‐ray scattering tensor tomgraphy, SAXS‐TT and wide angle X‐ray scattering tensor tomgraphy, WAXS‐TT). Special emphasis is placed on the latter X‐ray techniques that are emerging into powerful tools. Through a review of selected recent results on the structure of the bone matrix as well as the lacuno‐canalicular network housing the osteocyte cells of bone, it is proposed that bone is more heterogeneous than typically described and that local variation in composition and crystallography may play a significant role in bone biology in health and disease.

Use of Heat-killed Aspergillus ochraceus NRRL 3174 Discs as Biosorbent for petroleum Removal

The purpose of this work was to evaluate the petroleum sorption capacity of heat-killed fungal discs obtained from Aspergillus ochraceus strain. Effect of various parameters such as biosorbent dose (0.5g-2.5g/100mL), petroleum concentration (0.5-5%), pH (4.0-8.0), contact time (1-12h) and re-usability of biosorbent (1-6) were investigated. Accordingly, the highest biosorption capacity was obtained with 1% petroleum concentration, 1.5 g/100mL heat-killed fungal discs, 10h contact time at pH: 5.0 and room temperature. Additionally, each disc was able to actively use for at least 6 more cycles in biosorption experiments. The specific removal rate was calculated as 0.114 day−1, the rate constant and half-life period were also 1.609 day-1, t1/2 = 0.431, respectively. The kinetic study was described by the pseudo-second order model and the equilibrium modeling was found to be well fitted with Langmuir isotherm. The biosorbent(s) were characterized by Focused Ion Beam Scanning Electron Microscopy (FIB-SEM). Over 80% removal of long-chain n-alkanes by the heat-killed fungal discs was confirmed by GC-MS analysis. Since there has been no similar study investigating the sorption of petroleum with heat-killed Aspergillus ochraceous discs, this novel bio-based sorbent with its low cost, environmentally friendly and easy-to-apply properties can be used in advanced biosorption studies.

Revealing the aging process of solid electrolyte interphase on SiOx anode

As one of the most promising alternatives to graphite negative electrodes, silicon oxide (SiOx) has been hindered by its fast capacity fading. Solid electrolyte interphase (SEI) aging on silicon SiOx has been recognized as the most critical yet least understood facet. Herein, leveraging 3D focused ion beam-scanning electron microscopy (FIB-SEM) tomographic imaging, we reveal an exceptionally characteristic SEI microstructure with an incompact inner region and a dense outer region, which overturns the prevailing belief that SEIs are homogeneous structure and reveals the SEI evolution process. Through combining nanoprobe and electron energy loss spectroscopy (EELS), it is also discovered that the electronic conductivity of thick SEI relies on the percolation network within composed of conductive agents (e.g., carbon black particles), which are embedded into the SEI upon its growth. Therefore, the free growth of SEI will gradually attenuate this electron percolation network, thereby causing capacity decay of SiOx. Based on these findings, a proof-of-concept strategy is adopted to mechanically restrict the SEI growth via applying a confining layer on top of the electrode. Through shedding light on the fundamental understanding of SEI aging for SiOx anodes, this work could potentially inspire viable improving strategies in the future.

Enhanced mechanical and functional properties of chitosan/polyvinyl alcohol/hydroxypropyl methylcellulose/alizarin composite film by incorporating cinnamon essential oil and tea polyphenols

In this study, cinnamon essential oil and tea polyphenols were added to chitosan/ polyvinyl alcohol/ hydroxypropyl methylcellulose/ alizarin composite films to enhance their mechanical and functional properties. Their addition to the composite films enhanced their antibacterial and antioxidant properties and significantly improved its elongation at break (p < 0.05). Cinnamon essential oil reduced the water vapor permeability, water content, and water solubility of composite films and improved their transparency. The composite films with additive exhibited excellent UV-barrier ability and pH responsivity. Fourier Transform infrared spectroscopy and X-Ray Diffraction analyses confirmed hydrogen bond formation between the polymer molecules and additives. The results of Scanning Electron Microscope-Focused Ion Beam revealed improved surface and cross-section morphology of the films, leading to the generation of a cross-linked structure. Thermogravimetric and differential scanning calorimetry analysis indicated enhanced thermal stability of the composite films upon cinnamon essential oil addition. Analysis of storage quality indicators (TBARS value, TVC, and TVB-N) revealed that the composite films could prolong the freshness of surimi. The incorporation of cinnamon essential oil and tea polyphenols into the composite films has demonstrated significant potential as an effective and natural alternative for active food packaging.

Porosity evolution in proton irradiated microfine-grained POCO graphite

This work investigated the porosity evolution of POCO ZXF-5Q graphite that has been irradiated by 340 kW, 120 GeV protons inside NT02 target system in Fermilab's NuMI beamline. This POCO graphite has undergone direct bulk dimensional swelling at low dose irradiation and its local microstructural change is still not well-understood during this process. In this work, the (sub-) micrometre scale porosity from six locations across proton beam fluence and temperature gradients have been studied using focused ion beam-scanning electron microscopy (FIB-SEM) tomography. A deep learning-based tomographic image segmentation technique has been established and implemented for porosity segmentation and quantification. It has been found that there is a decrease in the total volumetric percentage of the porosity at proton beam centre (∼ 8 – 8.4 vol.%), by comparing to un-irradiated POCO (∼ 12 – 13 vol.%) and to beam 2σ and 5σ radii (∼ 12 vol.%). This decrease in porosity volume percentage was found to be caused by the reduction in pores with volumes > 0.1 μm3 induced by material bulk dimensional swelling at proton beam centre area. The porosity reduction in relation to dimensional change and irradiation creep was discussed among with other contributing factors, and further investigations through well-controlled irradiation experiment are still needed.

Three dimensional microstructures of carbon deposition on Ni-YSZ anodes under polarization

In the present study, two Ni/YSZ anodes with different volume ratios of Ni and YSZ, 30: 70 and 45: 55 vol%, are operated in dry methane under open circuit and polarized conditions. Three-dimensional (3D) Ni/YSZ microstructures after carbon deposition are reconstructed by the focused ion beam-scanning electron microscopy (FIB-SEM) with the help of machine learning segmentation. From the reconstructed mircostructures, volume fraction, connectivity, three phase boundary (TPB) density, and tortuosity are quantified. In addition, local carbon microstructures are quantitatively reconstructed, and the effect of polarization on carbon morphology is investigated. It is demonstrated that Ni surface in the vicinity of active TPB near the electrolyte is free from carbon formation, while remaining Ni surface at some distances from TPB exhibits severe carbon deposition. In average, total amount of carbon deposition is larger near the electrolyte. These observations imply complex interplay between the electrochemical steam generation and methane cracking on Ni surface which take place very locally near the active TPB.

3D relationship between hierarchical canal network and gradient mineralization of shark tooth osteodentin.

Osteodentin is a dominant mineralized collagenous tissue in the teeth of many fishes, with structural and histological characteristics resembling those of bone. Osteodentin, like bone, comprises osteons as basic structural building blocks, however, it lacks the osteocytes and the lacuno-canalicular network (LCN), which are known to play critical roles in controlling the mineralization of the collagenous matrix in bone. Although numerous vascular canals exist in osteodentin, their role in tooth maturation and the matrix mineralization process remain poorly understood. Here, high resolution micro-computed tomography (micro-CT) and focused ion beam-scanning electron microscopy (FIB-SEM) were used to obtain 3D structural information of osteodentin in shark teeth at multiple scales. We observed a complex 3D network of primary canals with a diameter ranging from ∼10 µm to ∼120 µm, where the canals are surrounded by osteon-like concentric layers of lamella, with 'interosteonal' tissue intervening between neighboring osteons. In addition, numerous hierarchically branched secondary canals extended out radially from the primary canals into the interosteonal tissue, with a decreasing diameter from ∼10 µm to hundreds of nanometers. Interestingly, the mineralization degree increases from the periphery of primary canals to the interosteonal tissue, suggesting that mineralization begins in the interosteonal tissue. Correspondingly, the hardness and elastic modulus of the interosteonal tissue is higher than those of the osteonal tissue. These results demonstrate that the 3D hierarchical canal network is positioned to play a critical role in controlling the gradient mineralization of osteodentin, also providing valuable insight into the formation of mineralized collagenous tissue without osteocytes and LCN. STATEMENT OF SIGNIFICANCE: : Bone is a composite material with versatile mechanical properties. Osteocytes and lacuno-canalicular network (LCN) are kown to play critical roles during formation of human bone. However, the skeleton of many fishes, including bone and osteodentin, although lacking osteocytes and LCN, could exhibit similar osteon-like structure and mechanical functions. Here, using various high resolution 3D characterization techniques, we reveal that the 3D network of primary canals and numerous hierarchically branched secondary canals correlate with the mineralization gradient and micromechanical properties of osteonal and interosteonal tissues of shark tooth osteodentin. This work significantly improves our understanding of the construction of bone-like mineralized tissue without osteocytes and LCN, and provides inspirations for the fabrication of functional materials with hierarchical structure.

An interactive deep learning-based approach reveals mitochondrial cristae topologies.

The convolution of membranes called cristae is a critical structural and functional feature of mitochondria. Crista structure is highly diverse between different cell types, reflecting their role in metabolic adaptation. However, their precise three-dimensional (3D) arrangement requires volumetric analysis of serial electron microscopy and has therefore been limiting for unbiased quantitative assessment. Here, we developed a novel, publicly available, deep learning (DL)-based image analysis platform called Python-based human-in-the-loop workflow (PHILOW) implemented with a human-in-the-loop (HITL) algorithm. Analysis of dense, large, and isotropic volumes of focused ion beam-scanning electron microscopy (FIB-SEM) using PHILOW reveals the complex 3D nanostructure of both inner and outer mitochondrial membranes and provides deep, quantitative, structural features of cristae in a large number of individual mitochondria. This nanometer-scale analysis in micrometer-scale cellular contexts uncovers fundamental parameters of cristae, such as total surface area, orientation, tubular/lamellar cristae ratio, and crista junction density in individual mitochondria. Unbiased clustering analysis of our structural data unraveled a new function for the dynamin-related GTPase Optic Atrophy 1 (OPA1) in regulating the balance between lamellar versus tubular cristae subdomains.

The fate of mitochondria during platelet activation

AbstractBlood platelets undergo several successive motor-driven reorganizations of the cytoskeleton when they are recruited to an injured part of a vessel. These reorganizations take place during the platelet activation phase, the spreading process on the injured vessel or between fibrin fibers of the forming clot, and during clot retraction. All these steps require a lot of energy, especially the retraction of the clot when platelets develop strong forces similar to those of muscle cells. Platelets can produce energy through glycolysis and mitochondrial respiration. However, although resting platelets have only 5 to 8 individual mitochondria, they produce adenosine triphosphate predominantly via oxidative phosphorylation. Activated, spread platelets show an increase in size compared with resting platelets, and the question arises as to where the few mitochondria are located in these larger platelets. Using expansion microscopy, we show that the number of mitochondria per platelet is increased in spread platelets. Live imaging and focused ion beam–scanning electron microscopy suggest that a mitochondrial fission event takes place during platelet activation. Fission is Drp1 dependent because Drp1-deficient platelets have fused mitochondria. In nucleated cells, mitochondrial fission is associated with a shift to a glycolytic phenotype, and using clot retraction assays, we show that platelets have a more glycolytic energy production during clot retraction and that Drp1-deficient platelets show a defect in clot retraction.

Fluid Flow in the Gas Diffusion Layer Using Computational Fluid Dynamics and Microscopy Techniques

The utilization of a proton exchange membrane fuel cell (PEMFC) as an energy provider using hydrogen as a fuel has increased drastically. The reasons are the current limitation of fossil fuel-based devices, pollutants-free, high efficiency, and zero-carbon emission. The life-cycle assessment results of this type of fuel cell have also indicated the lowest contribution to global warming, human health, and resource scarcity in comparison to other types of fuel cells. In this regard, improving the performance of PEMFC is of importance.As an important component of the PEMFC, the gas diffusion layer (GDL) transports the gas reactants to the catalyst layer with the least electrical resistance. The GDL is often made of carbon fibers and should have a surface with good electrical contact and hydrophobic properties to facilitate the water removal. Remaining water in the GDL will result in difficulties during the cold-start and enhances the degradation of this layer. It is believed that the water removal of the GDL has a direct relationship with the capillary pressure, which is strongly linked to the GDL’s microstructure and wettability. However, further investigations can be done once a comprehensive simulation model is developed to monitor the changes in the GDL liquid removal by the effective parameters.In this regard, the Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) has been used to perform three-dimensional cross-section imaging of the GDL. The GDL samples are provided by Freudenberg in which the Microporous layer (MPL) is impregnated into the GDL. The average porosity of this sample is in the range of 75% while having the in-plane gas permeability of 2.4 under a compressive stress of 1 MPa. The utilized resin for FIB-SEM imaging is a mixture of Epoxy embedding medium (diglycidyl ether of bisphenol – A) with two different hardeners DDSA (2-Dodecenylsuccinic anhydride) and MNA (Methylnadic anhydride), which will be mixed with DPM – 30 [2,4,6 – Tris(dimethylaminomethyl)phenol] as the accelerator, all provided by Sigma Aldrich. After the preparation of the resin, 0.4 gr of Cobalt (II) acetylacetonate nanoparticles (supported by Sigma Aldrich) were added to 7.14 ml of the resin to improve the contrast of the images. The samples were impregnated with the resin under vacuum to be pressurized (3 MPa) for 20 minutes, and afterward, heated in an oven at 60℃ for 12 hours. The surfaces for analyses were cut by a diamond wire, polished by abrasive plates down to 0.1 and gold coated (20nm).FIB-SEM acquisition consisted of the polishing of cross-sections with a focused ion beam (LMIS Ga+ source) at 30 keV and 1 nA (Zeiss Crossbeam 540), followed by imaging with an electron beam at acceleration voltages of 1.0, 3.0 kV. Milling and imaging were performed at a working distance of 5.2 mm and stage tilt of 54°, i.e., the coincidence point of the electron and ion beams.Once the three-dimensional cross-sections of the GDL are obtained, the segmentation and reconstruction will be made to provide the needed geometry for fluid flow simulation and to calculate the microstructural properties. Fig. 1 shows the generated structure of the GDL after the segmentation and reconstruction of the cross-section images. The geometry will be then used to characterize the effective parameters of the thermal/water management of the PEMFC. This study can also be a valid reference for future computational fluid dynamic analyses in the GDL using the numerical modeling with the conservative equations or the Lattice Boltzmann modeling (LBM) with the kinetic and particle distribution equations. Keywords : Proton exchange membrane fuel cell (PEMFC); Gas Diffusion Layer (GDL); Focused Ion Beam- Scanning Electron Microscopy (FIB-SEM); Three-dimensional simulation; Lattice Boltzmann method (LBM) Figure 1

Synergistic Application of Machine Learning to Microstructural Characterization on Electrode Composites of Solid Oxide Fuel Cells

Solid oxide fuel cells (SOFCs) have been recognized as one of the most potent next-generation energy conversion systems, owing to their higher efficiency, better fuel flexibility, and smaller amount of pollution, unlike their counterpart fuel cells. SOFCs can be analyzed as a highly-complex multi-component materials system consisting of porous electrodes (cathodes and anodes), densified electrolytes, interconnects, and sealing materials, which are sequentially layered and characteristic of heterogeneous and multi-phase materials. The resultant power generation is achieved through the electrochemical reactions involving electronic carriers, ionic carries, and gaseous transports at anodes and cathodes, influencing their electrical, mechanical, and thermal properties. In particular, both cathodes and anodes are typically constructed based on three components: mixed ionic/electronic electrodes, electrolytes, and a porous section. Those three constituents should be optimized at both electrodes with the aim of maximizing the electrochemical reaction sites, i.e., triple-phase boundaries in association with the gaseous transport involved in oxygen reduction reactions at cathodes and hydrogen oxidation reactions at anodes, which leads to high cell performance and guaranteed durability. The electrochemical performances are crucially dependent on their complex microstructures, demanding for highly informative analyses on the electron microscopy images under investigation.This work reports quantitative microstructural analysis methodology incorporating machine learning-assisted microstructural analysis strategy. Quantitative microstructural interpretations were carried out without human involvement through an integrated combination of deep learning and focused ion beam-scanning electron microscopy (FIB-SEM) analytics on Ni/Y2O3-stabilized ZrO2 (Ni/YSZ) cermets. The Ni/YSZ/pore composites were analyzed for the automated extraction of microstructural parameters with the aim to preventing the subjective analysis problems and unavoidable artifacts frequently encountered in lengthy image processing tasks and eliminate biased evaluations. Considering the high volume of image data and future expectations for electron microscopy usage, FIB-SEM was efficiently combined with semantic segmentation targeted at detailed phase recognition on three constituents, i.e, Ni, YSZ, and pores. Traditional image processing analysis tools are in the synergistic manner combined with phase separation predictions by semantic segmentation algorithms, allowing for a quantitative evaluation of microstructural parameters. The combined strategy enables one to significantly enhance poor image quality originating from artifacts in electron microscopy, including charging effects, curtain effects, out-of-focus problems, and unclear phase boundaries encountered in searching for high-efficiency solid oxide fuel cells (SOFCs).

Microstructural Analysis of Solid Oxide Electrochemical Cells via 3D Reconstruction Using a FIB-SEM Dual Beam System

The 3D reconstruction based on tomography technology enables quantitative and qualitative microstructural analysis of complex multiphase oxide structures. This powerful approach is widely investigated in diverse areas, in particular, gaining more importance in solid oxide electrochemical cells (SOCs) fields. SOCs are promising energy conversion devices with high efficiency, however, they have complex and porous/dense multilayered microstructures, which are closely related to the electrochemical reaction in the electrodes, thus, one of the major factors determining overall output performance of SOCs. Therefore, it is necessary to quantify the microstructural parameters of the cell. A focused ion beam-scanning electron microscope (FIB-SEM) dual beam system is one well-established method to obtain tomographic images to reconstruct 3D microstructures. It has an appropriate scale of tenth of nm to μm-level with high spatial resolution to represent the microstructural characteristics of the SOC electrodes. This presentation is intended to introduce our progress on 3D reconstruction techniques to quantitatively analyse SOCs, obtaining microstructural features such as particle size, connectivity, tortuosity, contact area, and triple phase boundary density. These in-depth analyses are helpful in extensively understanding electrochemical behavior in SOC electrodes.

(Digital Presentation) Phase-Field Modeling of the Reduction Process in Solid Oxide Fuel Cell Anode

It is well-known that the reduction process of nickel oxide-yttria-stabilized zirconia (NiO-YSZ) composite anode influences the initial performances and durability of solid oxide fuel cell. In this work, phase field method is used to simulate the reduction process of nickel oxide (NiO) in anode-supporting solid oxide fuel cell (SOFC), which captures the competition effects among diffusion, crystal phase transition of NiO to Ni, and sintering. A real three-dimensional microstructure of NiO-YSZ composite anode reconstructed using focused ion beam-scanning electron microscopy (FIB-SEM) technique is used to initialize the simulation. The simulation results are qualitatively compared to experimental results under different reduction conditions. The results reveal that the stress distribution in SOFC anode can be largely influenced by the interactions between the residual stress in yttria-stabilized zirconia (YSZ) and the reduction process. The results explain the phenomena of mechanical damage formed in SOFC single cell during reduction. Figure 1

Chemical and Mechanical Degradation of the Interface between Li7La3Zr2O12 Electrolyte and LiNi0.6Mn0.2Co0.2O2 Cathode as a Result of Electrochemistry

All solid-state Li-ion cells promises high energy density and high safety standards over conventional Li-ion cells based on liquid electrolytes. The first principle calculations shows that the most of the potential candidates for solid electrolytes for Li-ion cells have small electrochemical stability window. The limited electrochemical stability window leads to electrochemical reactivity with the cathode when cycled beyond the voltage limit. The reactions products are often leads to increased overpotential, hence rapid capacity fade during continuous cell operation. In addition to the electrochemical reactions, mechanical incompatibility further makes the cathode-solid-electrolyte interfaces prone to cracking, as cathodes undergoes structural changes during lithiation/delithiation. Indeed many experimental works have also showed limited cyclability of all-solid-state Li-ion cells owing to interfacial side reactions and mechanical cracking. Therefore, electrochemistry induced mechanical failure and electrochemical side reactions at the interface remains the bottleneck for the development of all-soli-state Li-ion cells. This paramount challenge invites us to systematically investigate the aforementioned problem by probing non-destructively near the cathode-solid-electrolyte interface. We introduce a model system that utilizes very thin layer of LiNi0.6Mn0.2Co0.2O2 (NMC622) cathode (60-600 nm) on top of bulk Al-doped-Li7La3Zr2O12 (Al-LLZO) solid-electrolyte pellet. This unique system allows us to non-destructively probe the electrochemical reaction by combined in-operando and ex-situ X-ray absorption spectroscopy (XAS), with probing depth beyond the cathode-solid-electrolyte interfaces.In this work, we elucidate the mechanism of electrochemical failure of NMC622 cathode and Al-LLZO solid-electrolyte interface at different temperature, through combined ex-situ and in-operando characterization techniques. The study revealed that the electrochemical reactivity is dependent on cell operation temperature. For the ex-situ samples that was cycled at higher temperature (80 ⁰C), the reduction of transition metals in cathode, i.e., nickel and cobalt was evident by soft X-ray absorption spectroscopy (XAS) of their respective L-edges. The results match closely with DFT prediction for the interfaces at high voltage. On the other hand, the in-operando XAS experiment, where characterization was done at room temperature, the reduction of transition metals in cathode, and hence electrochemical reactivity, was not observed. These results remarkably outline that electrochemical reactivity of solid-electrolyte and cathode interfaces at high voltage is kinetically inhibited at low or near room temperature, and hence very sensitive to cell operating condition. Nonetheless, it was found that irrespective of operating conditions i.e., temperature, the cell capacity rapidly decays as number of cycles continue. The focused ion beam scanning electron microscopy (FIB-SEM) revealed that this can be mostly attributed to intergranular cracks in NMC622 cathode films as well as to delamination of the cathode-solid-electrolyte interfaces during cell operation. As these cracks, in cathode films and at the interfaces, grows, the overpotential/impedance increases due to limited contacts for effective Li+ migration.The current work contributes to the field by showcasing interfacial degradation pathways in cell operation by novel design of experiments that allows for both in-operando and non-destructive characterization. The findings of this work will guide towards engineering cells of practical use. Figure 1

Advanced Nanoscale Characterizations of Solid Oxide Cell Electrodes

The growing interest in the transition towards a fossil-free energy system has accelerated research and development on hydrogen-based energy conversion technologies. In this context, solid oxide cells (SOCs) have attracted attention as they can be operated in both electrolysis (SOEC) and fuel cell (SOFC) modes providing a clean and sustainable way of producing both green hydrogen and electricity at high efficiency. Despite their great potential, the current SOC technology faces some challenges due to the significant cell degradation upon operation. The performance loss has been attributed to several factors, such as microstructural evolution in the electrodes [1], and inter-diffusion of elements between the cell layers associated to material decomposition and reactivity [2–4]. Despite several efforts, all these degradation phenomena are still not precisely understood as they involve complex and intricate processes arising at different length scales. To address this issue, durability tests have been performed in representative operating conditions at high current density and humidity at the air side for both SOFC and SOEC modes. In addition, the tested cells were analyzed with advanced characterization techniques to study the material degradation down to the nanometer and the atomic scales.In this work, standard fuel electrode supported cells have been studied. They are composed of a La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) current collecting layer (CCL) and a LSCF/Ce0.8Gd0.2O2-δ (LSCF/GDC) composite functional layer (FL) for the air electrode, GDC for the barrier layer, (Y2O3)0.08(ZrO2)0.92 (YSZ) for the electrolyte and Ni-YSZ for the fuel electrode. The samples were aged for 2000 h in various operating conditions: temperature (750, 800, 850 °C), humidity in the air flow (0%, 3% and 8%) and operating mode (SOEC and SOFC at ±1 A cm-2). The electrochemical behaviour of the cells has been characterized using electrochemical impedance spectroscopy (EIS) and polarization curves. The advanced post-mortem characterizations include techniques such as synchrotron X-ray nano-diffraction and nano-fluorescence (nano-XRD and nano-XRF) spectroscopy performed at the European Synchrotron Radiation Facility (ESRF, ID16B), scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray spectroscopy (EDX), and atom probe tomography (APT). A larger range of information was acquired by using complementary techniques, including focused ion beam scanning electron microscopy (FIB-SEM), X-ray photoelectron spectroscopy (XPS), and high-resolution secondary ion mass spectroscopy (SIMS) imaging.The electrochemical characterizations (Fig. 1a) have shown that the degradation was aggravated by increasing the operating temperature, the presence of humidity at the air side and the operation in electrolysis mode. The impedance spectra have been interpreted using a physically-based multiscale model [5]. The analysis has revealed that the performance loss was mainly due to the fuel electrode degradation, while the air electrode degradation remained limited, except when operated under humid conditions in the SOEC mode. The post-mortem characterizations have shown that such degradation in the SOEC mode was mainly related to a strong Ni depletion, which became more pronounced with increasing operating temperature. For the cell operated under humid air in the SOEC mode, a significant amount of SrCO3 phase was observed on top of the air electrode. On the contrary, the cell operated under humid air in the SOFC mode did not show such phase formation. Advanced characterization techniques (nano-XRD, nano-XRF, STEM-EDX, and APT) put in evidence an intermixing of elements in the air electrode (LSCF/GDC) at the atomic scale (Fig. 1b). Moreover, the presence of an inter-diffusion layer (IDL) between GDC and YSZ phases was observed (Fig. 1c) for all samples, including the freshly prepared sample. Nevertheless, neither the mixing of elements in the air electrode nor the presence of the IDL seem to have a major influence on the cell degradation. It can be speculated that these phenomena make the air electrode more stable against phase decomposition by inhibiting the formation of commonly observed insulating phases such as SrZrO3 and SrO.

Validation of and Simulations using a High-Temperature Electrolysis Model

Efforts for increasing the share of renewable power generation are dramatically boosted since electrical power from fossil fuels has been used as weapon [1]. Therefore, efficient conversion systems are of great importance to conserve most of the delivered power by nature. High-temperature electrolysis is such an efficient type of energy conversion system compared to similar technologies [2-4]. To bridge the gap to an industrial scale application, the electrochemical and chemical processes have to be understood in detail which is enlightened by some publications from our group [5-8]. In this contribution, a multiphysics model for three types of electrolysis processes (steam, CO2 and co-electrolysis) is presented and evaluated. Relevant parameters like the exchange current density or the anodic / cathodic transfer coefficient including parameter variations for the inlet gas stream, flow rate of the gas, temperature and applied current are investigated. For the microscale properties in the functional layer, Focused Ion Beam Scanning Electron Microscopy (FIB-SEM) is used with the “Slice and View” technique [9,10]. Extracting information like the Triple Phase Boundary Length (TPBL), the fraction of electronic and ionic phase in mixed ionic-electronic conducting (MIEC) materials or the porosity and tortuosity of the (La,Sr)CoO3-δ (LSC) air electrode and the Ni / 8 mol% yttria stabilized zirconia (Ni-8YSZ) fuel electrode help in enhancing the modeling quality of high-temperature SOC model. A conversion from the TPBL (s. Figure 1) to an active area to volume ratio for the computation is needed.Calculated iV-characteristics and experimental curves are compared and serve as a validation for (I,V) data points at higher currents. Depending on the degree of agreement, the (missing) main contributions to loss mechanisms can be identified and initiate a feedback loop for material optimization. Sensitivity analyses are carried out for parameters that are difficult to vary in experiments (e.g. porosity). Porosity and tortuosity parametrize the porous structure for a homogeneously distributed property assumption across the material layers. The ratio between electronic and ionic phase fine-tunes the positioning of iV-characteristics within the potential regime of Ohmic and polarization losses. Calculated electrochemical impedance spectra (EIS) enhance the insight into the theoretical system and may be compared to experimental spectroscopy data via Equivalent Circuit Models (ECM). Calculated data from the model are acquired as in the used experimental setup. As an example, calculated EIS data from steam electrolysis show good agreement with a R-(RQ)4 ECM which as well describes most of the corresponding experimental data in our group. Effects of degradation are envisioned to be incorporated into the model as well.[1] Hosp, G.; Höltschi, R.; Keusch, N.; Schürpf, T.: https://www.nzz.ch/wirtschaft/rohstoffe-als-waffen-die-neusten-entwicklungen-ld.1681268 (28th October 2022, 2.13 pm)[2] Foit, S.R.; Dittrich, L.; Duyster, T.; Vinke, I.; Eichel, R.-A.; de Haart, L.G.J. (2020): Direct Solid Oxide Electrolysis of Carbon Dioxide: Analysis of Performance and Processes. In: Processes 8 (11), 1390[3] Foit, S.R.; Vinke, I.C.; de Haart, L.G.J.; Eichel, R.-A. (2017): Power-to-Syngas: An Enabling Technology for the Transition of the Energy System? In: Angew. Chem. Int. Edit. 56 (20), 5402–5411[4] Tanaka, Y.; Hoerlein, M.P.; Schiller, G. (2016): Numerical simulation of steam electrolysis with a solid oxide cell for proper evaluation of cell performances. In: Int. J. Hydrogen Energ. 41, 752–763[5] Wolf, S.E.; Dittrich, L.; Nohl, M.; Duyster, T.; Vinke, I.C.; Eichel, R.-A.; de Haart, L.G.J. (2022): Boundary Investigation of High-Temperature Co-Electrolysis Towards Direct CO2 Electrolysis. In: J. Electrochem. Soc. 169, 034531[6] Unachukwu, I.D.; Vibhu, V.; Vinke, I.C.; Eichel, R.-A.; de Haart, L.G.J. (2022): Sr Substituted La2-xSrxNi0.8Co0.2O4+ d (0 ≤ x ≤ 0.8): Impact on Oxygen Stoichiometry and Electrochemical Properties.In: Energies 15, 2136[7] Mebrahtu, C.+; Nohl, M.+; Dittrich, L.; Foit, S.R.; de Haart, L.G.J.; Eichel, R.-A.; Palkovits, R. (2021): Integrated Co-Electrolysis and Syngas Methanation for the Direct Production of Synthetic Natural Gas from CO2 and H2O. In: ChemSusChem 14, 2295 – 2302[8] Dittrich, L.; Nohl, M.; Jaekel, E.E.; Foit, S.R.; de Haart, L.G.J. (Bert), Eichel, R.-A. (2019): High-Temperature Co-Electrolysis: A Versatile Method to Sustainably Produce Tailored Syngas Compositions. In: J. Electrochem. Soc. 166 (13), F971 – F975[9] Wilson, J.R.; Kobsiriphat, W.; Mendoza, R.; Chen, H.; Hiller, J.M.; Miller, D.J.; Thornton, K.; Voorhees, P.W.; Adler, S.B.; Barnett, S.A. (2006): Three-dimensional reconstruction of a solid-oxide fuel-cell anode. In: Nat. Mater. 5, 541–544[10] Gostovic, D.; Smith, J.R.; Kundinger, D.P.; Jones, K.S.; Wachsman, E.D. (2007): Three-Dimensional Reconstruction of Porous LSCF Cathodes. In: Electrochem. Solid St. 10 (12), B214–B217Figure 1: Histogram of the TPBL from a 400 image sample set of a FIB-SEM cut of a Ni-8YSZ electrode. Figure 1