Visualizing Crystallization Dynamics and Transformation Pathways of Disordered Rocksalt Oxides During Thermally Activated Sol-Gel Synthesis

TL;DR

This study visualizes and analyzes the nanoscale crystallization pathways of disordered rocksalt oxides during sol-gel synthesis, revealing diverse transformation mechanisms and informing better control of material properties.

Contribution

It provides multiscale characterization of crystallization pathways in DRX oxides, combining in situ TEM, FTIR, and SXRD to uncover local and macroscopic transformation mechanisms.

Findings

Nanoscale TEM visualizes diverse local transformation pathways.

FTIR links chemical environments to transformation mechanisms.

Macroscopic SXRD shows predominant pathways through spinel and titanite intermediates.

Abstract

Sol-gel synthesis is a wet-chemical processing route for the fabrication of functional materials offering control over composition, morphology, and microstructure at relatively low processing temperatures compared to conventional solid-state synthesis methods. While the sol-gel process initiates with intermixed molecular precursors, the transformation pathways at the early nucleation stage are insufficiently understood. Here, the chemical and structural transformation of disordered rocksalt (DRX) Li1.2Mn0.4Ti0.4O2 (LMTO), a promising cathode material for lithium batteries, is studied by multiscale characterization tools. In situ heating transmission electron microscopy (TEM) using a liquid cell visualizes and identifies crystallization pathways at nanoscale. While some regions follow a classical multi-step transition through thermodynamically stable intermediates, others exhibit a kinetic shortcut in which intermediate nanocrystals dissolve into a localized amorphous matrix that directly precipitates the DRX structure. Macroscale FTIR corroborates the findings to be related to chemically distinct microenvironments in the gel precursor, with transition metal ions more strongly incorporated into the acetate-coordinated network than lithium. Although in situ heating TEM captures diverse local transformation pathways, in situ SXRD indicates that the macroscopic transformation proceeds predominantly through spinel LMTO and lithium titanite intermediates toward DRX-LMTO. The findings shed light on the spatiotemporal chemical and structural transformations in sol-gel derived DRX-LMTO materials, and call for fine tuning of such sol-gel chemistries to manipulate the crystallization pathways and achieve target material homogeneity more efficiently.