Hexavalent Ions Insertion in Garnet Li7 La3 Zr2 O12 Toward a Low Temperature Densification Reaction.

Nowadays, solid electrolytes are considered the main alternative to conventional liquid electrolytes in lithium batteries. The fabrication of these materials is however limited by the strict synthesis conditions, requiring high temperatures which can negatively impact the final performances. Here, it is shown that a modification of garnet-based Li7 La3 Zr2 O12 (LLZO) and the incorporation of tellurium can accelerate the synthesis process by lowering the formation temperature of cubic LLZO at temperatures below 700 °C. Optimized synthesis at 750 °C showed a decrease in particle size and cell parameter for samples with higher amounts of Te and the evaluation of electrochemical performances reported for LLZO Te0.25 a value of ionic conductivity of 5,15×10-5  S cm-1 after hot-pressing at 700 °C, two orders of magnitude higher than commercial Al-LLZO undergoing the same working conditions, and the highest value at this densification temperature. Partial segregation of Te-rich phases occurs for high-temperature densification. Our study shows the advantages of Te insertion on the sintering process of LLZO garnet and demonstrates the achievement of highly conductive LLZO with a low-temperature treatment.

Thermal evolution of NASICON type solid-state electrolytes with lithium at high temperature via in situ scanning electron microscopy.

We present the thermal evolution of two NASICON-type ceramics namely LATP (Li1+xAlxTi2-x(PO4)3) and LAGP (Li1+xAlxGe2-x(PO4)3) by monitoring the electrode-electrolyte interfaces (i.e., Li/LATP and Li/LAGP) at temperatures up to 330 °C via in situ scanning electron microscopy, post-mortem energy-dispersive spectroscopy, and X-ray diffraction. Upon melting of Li and contacting electrolytes, LAGP decomposes completely to form Li based alloys, while LATP is partially decomposed without alloying.

On high-temperature evolution of passivation layer in Li-10 wt % Mg alloy via in situ SEM-EBSD.

Li-10 wt % Mg alloy (Li-10 Mg) is used as an anode material for a solid-state battery with excellent electrochemical performance and no evidence of dendrite formation during cycling. Thermal treatment of Li metal during manufacturing improves the interfacial contact between a Li metal electrode and solid electrolyte to achieve an all solid-state battery with increased performance. To understand the properties of the alloy passivation layer, this paper presents the first direct observation of its evolution at elevated temperatures (up to 325°C) by in situ scanning electron microscopy. We found that the morphology of the surface passivation layer was unchanged above the alloy melting point, while the bulk of the material below the surface was melted at the expected melting point, as confirmed by in situ electron backscatter diffraction. In situ heat treatment of Li-based materials could be a key method to improve battery performance.

Behavior of Solid Electrolyte in Li-Polymer Battery with NMC Cathode via in-Situ Scanning Electron Microscopy.

We present the first results of in situ scanning electron microscopy (SEM) of an all-solid Li battery with a nickel-manganese-cobalt-oxide (NMC-622) cathode at 50 °C and an operating voltage of 2.7-4.3 V. Experiments were conducted under a constant current at several C rates (nC rate: cycling in 1/n h): C/12, C/6, and C/3. The microstructure evolution during cycling was monitored by continuous secondary electron imaging. We found that the chemical degradation of the solid polymer electrolyte (SPE) was the main mechanism for battery failure. This degradation was observed in the form of a gradual thinning of the SPE as a function of cycling time, resulting in gas generation from the cell. We also present various dynamic electrochemical and mechanical phenomena, as observed by SEM images, and compare the performance of this battery with that of an all-solid Li battery with a LiFePO4 cathode.

Rotation axes analysis of deformed magnesium based on rotation contour contrast in a scanning electron microscope.

A crystallographic orientation contrast in the form of cross-shaped and intersecting contours was observed in a backscattered electron (BSE) micrograph of deformed magnesium (Mg) grains in a cold field emission scanning electron microscope (CFE-SEM). This contrast was identified as rotation contour contrast (RCC). A model is presented to link the RCC in the BSE micrograph to the channeling contrast in the corresponding channeling pattern. Based on this model, the appearance of the cross-shaped RCC in the BSE micrograph was attributed to the rotation of the crystal about two rotation axes and the RCC was related to a two dimensional angular scan of the corresponding channeling pattern. This model was experimentally validated using the selected area channeling pattern (SACP) technique. The crystallographic directions of the rotation axes were identified using the electron backscatter diffraction (EBSD) technique.

Electron channeling contrast imaging of plastic deformation induced by indentation in polycrystalline nickel.

Vickers microindentation and Berkovich nanoindentation tests were carried out on a polycrystalline nickel (Ni) bulk specimen. Electron channeling contrast imaging (ECCI) in conjunction with electron backscattered diffraction was used to image and characterize plastic deformation inside and around the indents using a field emission scanning electron microscope. The ECCI was performed with a 5 keV beam energy and 0° tilt specimen position. The strain field distribution, slip lines, and Taylor lattices were imaged on an indented surface. Orientation mapping was used to investigate the local crystallographic misorientation and identify specific ⟨110⟩ slip systems. An ion milling surface preparation technique was used to remove materials from the surface which permitted the study of deformed microstructure below the indent. A dislocation density of 1011 cm-2 was calculated based on the curvature of bend contours observed in the ECCI micrographs obtained from the Vickers indents. A yield strength of 500 MPa was calculated based on the size of the strain field measured from the ECCI micrographs of the nanoindents. The combination of ion milling, ECCI, and electron backscattered diffraction was shown to be beneficial to investigate the indentation-induced plastic deformation in a polycrystalline Ni bulk specimen.