Synergistic Effect of CO2 in Accelerating the Galvanic Corrosion of Lithium/Sodium Anodes in Alkali Metal-Carbon Dioxide Batteries.

Rechargeable alkali metal-CO2 batteries, which combine high theoretical energy density and environmentally friendly CO2 fixation ability, have attracted worldwide attention. Unfortunately, their electrochemical performances are usually inferior for practical applications. Aiming to reveal the underlying causes, a combinatorial usage of advanced nondestructive and postmortem characterization tools is used to intensively study the failure mechanisms of Li/Na-CO2 batteries. It is found that a porous interphase layer is formed between the separator and the Li/Na anode during the overvoltage rising and battery performance decaying process. A series of control experiments are designed to identify the underlying mechanisms dictating the observed morphological evolution of Li/Na anodes, and it is found that the CO2 synergist facilitates Li/Na chemical corrosion, the process of which is further promoted by the unwanted galvanic corrosion and the electrochemical cycling conditions. A detailed compositional analysis reveals that the as-formed interphase layers under different conditions are similar in species, with the main differences being their inconsistent quantity. Theoretical calculation results not only suggest an inherent intermolecular affinity between the CO2 and the electrolyte solvent but also provide the most thermodynamically favored CO2 reaction pathways. Based on these results, important implications for the further development of rechargeable alkali metal-CO2 batteries are discussed. The current discoveries not only fundamentally enrich our knowledge of the failure mechanisms of rechargeable alkali metal-CO2 batteries but also provide mechanistic directions for protecting metal anodes to build high-reversible alkali metal-CO2 batteries.

Designing Solvated Double-Layer Polymer Electrolytes with Molecular Interactions Mediated Stable Interfaces for Sodium Ion Batteries.

Unstable cathode-electrolyte and/or anode-electrolyte interface in polymer-based sodium-ion batteries (SIBs) will deteriorate their cycle performance. Herein, a unique solvated double-layer quasi-solid polymer electrolyte (SDL-QSPE) with high Na+ ion conductivity is designed to simultaneously improve stability on both cathode and anode sides. Different functional fillers are solvated with plasticizers to improve Na+ conductivity and thermal stability. The SDL-QSPE is laminated by cathode- and anode-facing polymer electrolyte to meet the independent interfacial requirements of the two electrodes. The interfacial evolution is elucidated by theoretical calculations and 3D X-ray microtomography analysis. The Na0.67 Mn2/3 Ni1/3 O2 |SDL-QSPE|Na batteries exhibit 80.4 mAh g-1 after 400 cycles at 1 C with the Coulombic efficiency close to 100 %, which significantly outperforms those batteries using the monolayer-structured QSPE.

Codependent failure mechanisms between cathode and anode in solid state lithium metal batteries: mediated by uneven ion flux.

An in-depth understanding of the degradation mechanisms is a prerequisite for developing the next-generation all solid-state lithium metal battery (ASSLMB) technology. Herein, synchrotron X-ray computed tomography (SXCT) together with other probing tools and simulation method were employed to rediscover the decaying mechanisms of LiNi0.8Co0.1Mn0.1O2 (NCM)|Li6PS5Cl (LPSCl)|Li ASSLMB. It reveals that the detachment and isolation of NCM particles cause the current focusing on the remaining active regions of cathode. The extent of Li stripping and the likelihood of Li+ plating into LPSCl facing the active NCM particles becomes higher. Besides, the homogeneity of Li stripping/plating is improved by homogenizing the electrochemical reactions at the cathode side by LiZr2(PO4)3 (LZP) coating. These results suggest a codependent failure mechanism between cathode and anode that is mediated by uneven Li ion flux. This work contributes to a holistic understanding of the degradation mechanisms in ASSLMBs and opens new opportunities for their further optimization and development.

Synchrotron X-Ray Tomography for Rechargeable Battery Research: Fundamentals, Setups and Applications.

Understanding the complicated interplay of the continuously evolving electrode materials in their inherent 3D states during the battery operating condition is of great importance for advancing rechargeable battery research. In this regard, the synchrotron X-ray tomography technique, which enables non-destructive, multi-scale, and 3D imaging of a variety of electrode components before/during/after battery operation, becomes an essential tool to deepen this understanding. The past few years have witnessed an increasingly growing interest in applying this technique in battery research. Hence, it is time to not only summarize the already obtained battery-related knowledge by using this technique, but also to present a fundamental elucidation of this technique to boost future studies in battery research. To this end, this review firstly introduces the fundamental principles and experimental setups of the synchrotron X-ray tomography technique. After that, a user guide to its application in battery research and examples of its applications in research of various types of batteries are presented. The current review ends with a discussion of the future opportunities of this technique for next-generation rechargeable batteries research. It is expected that this review can enhance the reader's understanding of the synchrotron X-ray tomography technique and stimulate new ideas and opportunities in battery research.

Bone metabolism and evolutionary origin of osteocytes: Novel application of FIB-SEM tomography.

Lacunae and canaliculi spaces of osteocytes are remarkably well preserved in fossilized bone and serve as an established proxy for bone cells. The earliest bone in the fossil record is acellular (anosteocytic), followed by cellular (osteocytic) bone in the jawless relatives of jawed vertebrates, the osteostracans, about 400 million years ago. Virtually nothing is known about the physiological pressures that would have initially favored osteocytic over anosteocytic bone. We apply focused ion beam-scanning electron microscopy tomography combined with machine learning for cell detection and segmentation to image fossil cell spaces. Novel three-dimensional high-resolution images reveal areas of low density around osteocyte lacunae and their canaliculi in osteostracan bone. This provides evidence for demineralization that would have occurred in vivo as part of osteocytic osteolysis, a mechanism of mineral homeostasis, supporting the hypothesis that a physiological demand for phosphorus was the principal driver in the initial evolution of osteocytic bone.

Operando Laboratory X-Ray Imaging of Silver-Based Gas Diffusion Electrodes during Oxygen Reduction Reaction in Highly Alkaline Media.

Operando laboratory X-ray radiographies were carried out for imaging of two different silver-based gas diffusion electrodes containing an electroconductive Ni mesh structure, one gas diffusion electrode composed of 95 wt.% Ag and 5 wt.% polytetrafluoroethylene and one composed of 97 wt.% Ag and 3 wt.% polytetrafluoroethylene, under different operating parameters. Thereby, correlations of their electrochemical behavior and the transport of the 30 wt.% NaOH electrolyte through the gas diffusion electrodes were revealed. The work was divided into two parts. In the first step, the microstructure of the gas diffusion electrodes was analyzed ex situ by a combination of focused ion beam technology and synchrotron as well as laboratory X-ray tomography and radiography. In the second step, operando laboratory X-ray radiographies were performed during chronoamperometric measurements at different potentials. The combination of the ex situ microstructural analyses and the operando measurements reveals the impact of the microstructure on the electrolyte transport through the gas diffusion electrodes. Hence, an impact of the Ni mesh structure within the gas diffusion electrode on the droplet formation could be shown. Moreover, it could be observed that increasing overpotentials cause increasing electrolyte transport velocities and faster droplet formation due to electrowetting. In general, higher electrolyte transport velocities were found for the gas diffusion electrode with 97 wt.% Ag in contrast to that with 95 wt.% Ag.

Quantitative synchrotron X-ray tomography of the material-tissue interface in rat cortex implanted with neural probes.

Neural probes provide many options for neuroscientific research and medical purposes. However, these implantable micro devices are not functionally stable over time due to host-probe interactions. Thus, reliable high-resolution characterization methods are required to understand local tissue changes upon implantation. In this work, synchrotron X-ray tomography is employed for the first time to image the interface between brain tissue and an implanted neural probe, showing that this 3D imaging method is capable of resolving probe and surrounding tissue at a resolution of about 1 micrometer. Unstained tissue provides sufficient contrast to identify electrode sites on the probe, cells, and blood vessels within tomograms. Exemplarily, we show that it is possible to quantify characteristics of the interaction region between probe and tissue, like the blood supply system. Our first-time study demonstrates a way for simultaneous 3D investigation of brain tissue with implanted probe, providing information beyond what was hitherto possible.

Characterization of the 3D microstructure of Ibuprofen tablets by means of synchrotron tomography.

A new methodology to segment the three-dimensional (3D) internal structure of Ibuprofen tablets from synchrotron tomography is presented, introducing a physically coherent trinarization for greyscale images of Ibuprofen tablets consisting of three phases: microcrystalline cellulose, Ibuprofen and pores. For this purpose, a hybrid approach is developed combining a trinarization by means of statistical learning with a trinarization based on a watershed algorithm. This hybrid approach allows us to compute microstructure characteristics of tablets using methods of statistical image analysis. A comparison with experimental results shows that there is a significant amount of pores which is below the resolution limit. At the same time, results from image analysis let us conjecture that these pores constitute the great majority of the surface between pores and solid. Furthermore, we compute microstructure characteristics, which are experimentally not accessible such as local percolation probabilities and chord length distribution functions. Both characteristics are meaningful in order to quantify the influence of tablet compaction on its microstructure. The presented approach can be used to get better insight into the relationship between production parameters and microstructure characteristics based on 3D image data of Ibuprofen tablets manufactured under different conditions and elucidate key effects on the strength and solubility kinetics of the final  formulation. LAY DESCRIPTION: A typical formulation of uniaxial compacted Ibuprofen tablets consist of a mixture of an excipient (microcrystalline cellulose) with an active ingredient (a ground fraction of Ibuprofen). The final mechanical strength of the tablet as well as the release kinetics are strongly influenced by the underlying microstructure, i.e. the spatial arrangement of the microcrystalline cellulose and Ibuprofen within the tablet. In order to optimize the performance of the tablet, it is important to investigate the relationship between its microstructure and the corresponding production parameters. For this purpose, 3D imaging is a powerful tool as it allows computing microstructural properties such as the internal arrangement, interconnectivity and pore location and distribution, characteristics that cannot be computed by experimental characterization techniques. In the present study, a new algorithm for an accurate trinarization of 3D image data obtained by synchrotron tomography is presented. Trinarization means that we reconstruct microcrystalline cellulose, Ibuprofen and pores on the basis of the 3D images, where one can only observe different greyscale values, but not the different constituents themselves. For this purpose, a hybrid approach combining a trinarization by means of artificial intelligence with a trinarization based on a geometrically motivated algorithm is developed. This hybrid approach allows to compute microstructure characteristics of tablets using image analysis. A comparison with experimental results shows that there is a significant amount of pores below the resolution limit. At the same time results from image analysis lead to the conjecture that these pores constitute the major part of the surface between pores and solid. Moreover, characteristics are computed by image analysis, which are meaningful in order to quantify the influence of tablet compaction parameters on its microstructure. The presented novel approach can be used to elucidate the relationship between production parameters and microstructure characteristics based on 3D image data of Ibuprofen tablets manufactured under different mixing, loading and processing conditions.

An X-ray Tomographic Study of Rechargeable Zn/MnO2 Batteries.

We present non-destructive and non-invasive in operando X-ray tomographic investigations of the charge and discharge behavior of rechargeable alkaline-manganese (RAM) batteries (Zn-MnO2 batteries). Changes in the three-dimensional structure of the zinc anode and the MnO2 cathode material after several charge/discharge cycles were analyzed. Battery discharge leads to a decrease in the zinc particle sizes, revealing a layer-by-layer dissolving behavior. During charging, the particles grow again to almost their initial size and shape. After several cycles, the particles sizes slowly decrease until most of the particles become smaller than the spatial resolution of the tomography. Furthermore, the number of cracks in the MnO2 bulk continuously increases and the separator changes its shape. The results are compared to the behavior of a conventional primary cell that was also charged and discharged several times.

Visualizing Current-Dependent Morphology and Distribution of Discharge Products in Sodium-Oxygen Battery Cathodes.

Synchrotron X-ray tomography and scanning electron microscopy were applied to elucidate the spatial distribution of discharge product (NaO2) in the carbon cathode of sodium-oxygen batteries. Various batteries were discharged galvanostatically and their cathodes were analyzed. We observe a particle density gradient along the cathode that scales with the current density applied. Besides, we show that the particle size and shape of discharge product strongly depend on current density, and on whether the particles are deposited close to the oxygen reservoir or near the separator. We correlate our findings to transport limitations for the supplied oxygen and gain crucial information for optimal operation of sodium-oxygen batteries. Our findings imply that for low current densities pore clogging might occur, and that for elevated current densities small high surface area particles with limited electric conductivity form; both phenomena can decrease the available discharge and charge capacity significantly.