RESUMO
Electrochemical phase transformation in ion-insertion crystalline electrodes is accompanied by compositional and structural changes, including the microstructural development of oriented phase domains. Previous studies have identified prevailingly transformation heterogeneities associated with diffusion- or reaction-limited mechanisms. In comparison, transformation-induced domains and their microstructure resulting from the loss of symmetry elements remain unexplored, despite their general importance in alloys and ceramics. Here, we map the formation of oriented phase domains and the development of strain gradient quantitatively during the electrochemical ion-insertion process. A collocated four-dimensional scanning transmission electron microscopy and electron energy loss spectroscopy approach, coupled with data mining, enables the study. Results show that in our model system of cubic spinel MnO2 nanoparticles their phase transformation upon Mg2+ insertion leads to the formation of domains of similar chemical identity but different orientations at nanometre length scale, following the nucleation, growth and coalescence process. Electrolytes have a substantial impact on the transformation microstructure ('island' versus 'archipelago'). Further, large strain gradients build up from the development of phase domains across their boundaries with high impact on the chemical diffusion coefficient by a factor of ten or more. Our findings thus provide critical insights into the microstructure formation mechanism and its impact on the ion-insertion process, suggesting new rules of transformation structure control for energy storage materials.
RESUMO
Interfaces have crucial, but still poorly understood, roles in the performance of secondary solid-state batteries. Here, using crystallographically oriented and highly faceted thick cathodes, we directly assess the impact of cathode crystallography and morphology on the long-term performance of solid-state batteries. The controlled interface crystallography, area and microstructure of these cathodes enables an understanding of interface instabilities unknown (hidden) in conventional thin-film and composite solid-state electrodes. A generic and direct correlation between cell performance and interface stability is revealed for a variety of both lithium- and sodium-based cathodes and solid electrolytes. Our findings highlight that minimizing interfacial area, rather than its expansion as is the case in conventional composite cathodes, is key to both understanding the nature of interface instabilities and improving cell performance. Our findings also point to the use of dense and thick cathodes as a way of increasing the energy density and stability of solid-state batteries.
RESUMO
Sn-based compounds are promising candidates for application as anodes in lithium-ion batteries (LIBs) due to the favourable storage capacity of Sn at 993 mAh g-1 compared to carbon at 372 mAh g-1. The use of Sn-based anodes also avoids some of the safety concerns associated with carbon anodes. However, the large volume changes during lithiation and delithiation of pure Sn anodes often results in poor cyclic performance. Alloying Sn with Cu, an element inactive with respect to Li, buffers the expansion stresses and can improve cycling performance. Cu6Sn5 is therefore a promising candidate anode material. In this work, the effects of Sb and Zn additions on the morphology, crystal structure, atomic arrangements and the electrochemical performance of the anodes were evaluated. Characterisation with synchrotron X-ray powder diffraction and Cs-corrected transmission electron microscopy revealed the larger lattice parameters, higher symmetry crystal structures and well-ordered atomic arrangements in the Sb and Zn modified electrodes, which resulted in a more than 50% increase in cycling capacity from 490 mAh g-1 to 760 mAh g-1.
