Active Interphase Enables Stable Performance for an All-Phosphate-Based Composite Cathode in an All-Solid-State Battery.

High interfacial resistance and unstable interphase between cathode active materials (CAMs) and solid-state electrolytes (SSEs) in the composite cathode are two of the main challenges in current all-solid-state batteries (ASSBs). In this work, the all-phosphate-based LiFePO4 (LFP) and Li1.3 Al0.3 Ti1.7 (PO4 )3 (LATP) composite cathode is obtained by a co-firing technique. Benefiting from the densified structure and the formed redox-active Li3- x Fe2- x - y Tix Aly (PO4 )3 (LFTAP) interphase, the mixed ion- and electron-conductive LFP/LATP composite cathode facilitates the stable operation of bulk-type ASSBs in different voltage ranges with almost no capacity degradation upon cycling. Particularly, both the LFTAP interphase and LATP electrolyte can be activated. The cell cycled between 4.1 and 2.2 V achieves a high reversible capacity of 2.8 mAh cm-2 (36 µA cm-2 , 60 °C). Furthermore, it is demonstrated that the asymmetric charge/discharge behaviors of the cells are attributed to the existence of the electrochemically active LFTAP interphase, which results in more sluggish Li+ kinetics and more expansive LFTAP plateaus during discharge compared with that of charge. This work demonstrates a simple but effective strategy to stabilize the CAM/SSE interface in high mass loading ASSBs.

Chemical Prelithiated 3D Lithiophilic/-Phobic Interlayer Enables Long-Term Li Plating/Stripping.

The up-to-date lifespan of zero-excess lithium (Li) metal batteries is limited to a few dozen cycles due to irreversible Li-ion loss caused by interfacial reactions during cycling. Herein, a chemical prelithiated composite interlayer, made of lithiophilic silver (Ag) and lithiophobic copper (Cu) in a 3D porous carbon fiber matrix, is applied on a planar Cu current collector to regulate Li plating and stripping and prevent undesired reactions. The Li-rich surface coating of lithium oxide (Li2O), lithium carboxylate (RCO2Li), lithium carbonates (ROCO2Li), and lithium hydride (LiH) is formed by soaking and directly heating the interlayer in n-butyllithium hexane solution. Although only a thin coating of ∼10 nm is created, it effectively regulates the ionic and electronic conductivity of the interlayer via these surface compounds and reduces defect sites by reactions of n-butyllithium with heteroatoms in the carbon fibers during formation. The spontaneously formed lithiophilic-lithiophobic gradient across individual carbon fiber provides homogeneous Li-ion deposition, preventing concentrated Li deposition. The porous structure of the composite interlayer eliminates the built-in stress upon Li deposition, and the anisotropically distributed carbon fibers enable uniform charge compensation. These features synergistically minimize the side reactions and compensate for Li-ion loss while cycling. The prepared zero-excess Li metal batteries could be cycled 300 times at 1.17 C with negligible capacity fading.

Toward Quantitative Electrodeposition via In Situ Liquid Phase Transmission Electron Microscopy: Studying Electroplated Zinc Using Basic Image Processing and 4D STEM.

High energy density electrochemical systems such as metal batteries suffer from uncontrollable dendrite growth on cycling, which can severely compromise battery safety and longevity. This originates from the thermodynamic preference of metal nucleation on electrode surfaces, where obtaining the crucial information on metal deposits in terms of crystal orientation, plated volume, and growth rate is very challenging. In situ liquid phase transmission electron microscopy (LPTEM) is a promising technique to visualize and understand electrodeposition processes, however a detailed quantification of which presents significant difficulties. Here by performing Zn electroplating and analyzing the data via basic image processing, this work not only sheds new light on the dendrite growth mechanism but also demonstrates a workflow showcasing how dendritic deposition can be visualized with volumetric and growth rate information. These results along with additionally corroborated 4D STEM analysis take steps to access information on the crystallographic orientation of the grown Zn nucleates and toward live quantification of in situ electrodeposition processes.

Laboratory X-ray computed tomography imaging protocol allowing the operando investigation of electrode material evolution in various environments.

A robust imaging protocol utilizing laboratory XCT is presented. Hybrid 2D/3D imaging at different scales with real-time monitoring allowed to assess, in operation, the evolution of zinc electrodes within three environments, namely alkaline, near-neutral, and mildly acidic. Different combinations of currents were used to demonstrate various scenarios exhibiting both dendritic and smooth deposition of active material. Directly from radiograms, the volume of the electrode and therefore its growth/dissolution rate was estimated and compared against tomographic reconstructions and theoretical values. The protocol combines simplistic cell design with multiple three-dimensional and two-dimensional acquisitions at different magnifications, providing a unique insight into electrode's morphology evolution within various environments.

Effect of Low Environmental Pressure on Sintering Behavior of NASICON-Type Li1.3Al0.3Ti1.7(PO4)3 Solid Electrolytes: An In Situ ESEM Study.

Solid-state sintering at high temperatures is commonly used to densify solid electrolytes. Yet, optimizing phase purity, structure, and grain sizes of solid electrolytes is challenging due to the lack of understanding of relevant processes during sintering. Here, we use an in situ environmental scanning electron microscopy (ESEM) to monitor the sintering behavior of NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP) at low environmental pressures. Our results show that while no major morphological changes are observed at 10-2 Pa and only coarsening is induced at 10 Pa, environmental pressures of 300 and 750 Pa lead to the formation of typically sintered LATP electrolytes. Furthermore, the use of pressure as an additional parameter in sintering allows the grain size and shape of electrolyte particles to be controlled.

Operando transmission electron microscopy of battery cycling: thickness dependent breaking of TiO2 coating on Si/SiO2 nanoparticles.

Conformal coating of silicon (Si) anode particles is a common strategy for improving their mechanical integrity, to mitigate battery capacity fading due to particle volume expansion, which can result in particle crumbling due to lithiation induced strain and excessive solid-electrolyte interface formation. Here, we use operando transmission electron microscopy in an open cell to show that TiO2 coatings on Si/SiO2 particles undergo thickness dependent rupture on battery cycling where thicker coatings crumble more readily than thinner (∼5 nm) coatings, which corroborates the difference in their capacities.

Microstructural details of spindle-like lithium titanium phosphate revealed in three dimensions.

Lithium titanium phosphate LiTi2(PO4)3 is an electrode material for lithium-ion batteries with a specific capacity of 138 mA h g-1. Owing to its potential of 2.5 V vs. Li/Li+ it provides an electrochemically stable interface when used as an anode in all-solid state batteries with NASICON type lithium aluminium titanium phosphate electrolyte. High performance has been identified for in situ carbon coated LiTi2(PO4)3 synthesized via a hydrothermal route, resulting in micro-scaled spindle shaped particles consisting of nano-scaled sub-particles. To elucidate the internal microstructure of these spindle-like particles in three dimensions we applied tomographic Focused Ion Beam - Scanning Electron Microscopy. For more detailed chemical analysis we performed electron-energy loss spectroscopy and energy dispersive X-ray spectroscopy in the scanning electron microscope as well as high resolution (scanning) transmission electron microscopy for structural insight. It could be clearly shown that the spindle-like particles mainly are made up of LiTi2(PO4)3 sub-particles in the 100 to 400 nm range. Additionally, two types of secondary phase materials were identified. LiTiOPO4, which shows different surface morphology, as a volume component of the spindles and TiO2 nanoparticles (anatase), which are not only present at the particle surface but also inside the spindle, were detected. Reconstruction from tomography reveals the nanoparticles form a three-dimensionally interconnected network even though their phase fraction is low.

A robust method for the detection of small changes in relaxation parameters and free water content in the vicinity of the substantia nigra in Parkinson's disease patients.

Alterations in the substantia nigra are strongly associated with Parkinson's disease. However, due to low contrast and partial volume effects present in typical MRI images, the substantia nigra is not of sufficient size to obtain a reliable segmentation for region-of-interest based analysis. To combat this problem, the approach proposed here offers a method to investigate and reveal changes in quantitative MRI parameters in the vicinity of substantia nigra without any a priori delineation. This approach uses an alternative method of statistical, voxel-based analysis of quantitative maps and was tested on 18 patients and 15 healthy controls using a well-established, quantitative free water mapping protocol. It was possible to reveal the topology and the location of pathological changes in the substantia nigra and its vicinity. Moreover, a decrease in free water content, T1 and T2* in the vicinity of substantia nigra was indicated in the Parkinson's disease patients compared to the healthy controls. These findings reflect a disruption of grey matter and iron accumulation, which is known to lead to neurodegeneration. Consequently, the proposed method demonstrates an increased sensitivity for the detection of pathological changes-even in small regions-and can facilitate disease monitoring via quantitative MR parameters.

Accelerated Parameter Mapping of Multiple-Echo Gradient-Echo Data Using Model-Based Iterative Reconstruction.

A new reconstruction method, coined MIRAGE, is presented for accurate, fast, and robust parameter mapping of multiple-echo gradient-echo (MEGE) imaging, the basis sequence of novel quantitative magnetic resonance imaging techniques such as water content and susceptibility mapping. Assuming that the temporal signal can be modeled as a sum of damped complex exponentials, MIRAGE performs model-based reconstruction of undersampled data by minimizing the rank of local Hankel matrices. It further incorporates multi-channel information and spatial prior knowledge. Finally, the parameter maps are estimated using nonlinear regression. Simulations and retrospective undersampling of phantom and in vivo data affirm robustness, e.g., to strong inhomogeneity of the static magnetic field and partial volume effects. MIRAGE is compared with a state-of-the-art compressed sensing method, -ESPIRiT. Parameter maps estimated from reconstructed data using MIRAGE are shown to be accurate, with the mean absolute error reduced by up to 50% for in vivo results. The proposed method has the potential to improve the diagnostic utility of quantitative imaging techniques that rely on MEGE data.

A method for accurate localisation of EBSD pattern centres.

The moving screen technique for pattern centre localisation is revisited. A cross-correlation based iterative procedure is developed to find both the zoom factor and the zoom centre (which is also the pattern centre) between two EBSD diffraction patterns acquired at two camera positions. The procedure involves two steps: first, a rough estimate of the pattern centre position and zoom factor (the ratio of the two detector distances) is obtained by cross-correlating the entire images. Then, based on this first estimate, cross-correlation of smaller regions of interest (ROIs) gives the displacement field which is interpreted as a zoom factor misfit coupled with a zoom centre position misfit. These misfits are iteratively decreased until the displacement field is reduced to the noise level. The procedure is first applied to simulated patterns and it is shown that the iterative procedure converges very rapidly to the exact solution with an accuracy better than 1/100th of pixel. The potential of this technique for experimental patterns is discussed and recommendations for new EBSD detectors are proposed.