• Energy Research

Spinel LiNi0.5Mn1.5O4 as one of the high-energy positive electrode materials for next generation Li-ion batteries has attracted significant interest due to its economic and environmental advantages. However, the sensitivity of this type of material upon short to long term ambient storage conditions and the impact on the electrochemical performances remains poorly explored. Nevertheless, this remains an important aspect for practical large-scale synthesis, storage and utilization. Herein, we study and compare the evolution of surface chemistry, bulk crystal structure and elemental content evolution and distribution of LiNi0.5Mn1.5O4 using a variety of characterization techniques including XPS and STEM-EDS-EELS, as well as electrochemical analysis. We show that Mn species dominate the outer surface (0–5 nm), while Ni and Li are preferentially located further away and in the bulk. The studied LiNi0.5Mn1.5O4 material is found to be stable, with minor changes in surface or bulk characteristics detected, even after 12 months of storage under ambient air conditions. The low surface reactivity to air also accounts for the minor changes to the electrochemical performance of the air-exposed LiNi0.5Mn1.5O4, compared to the pristine material. This study provides guidance for the appropriate storage, handling and processing of this high-performance cathode material.

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AbstractGood quality contacts between metal and silicon emitter are crucial for high crystalline solar cell efficiencies. We investigate the impact of defects originating from electrically inactive phosphorus on contact formation within silver thick film metallized silicon solar cells. For this purpose, emitters with varying sheet resistance, depth, and dead layer were metallized with silver pastes from different generations. Macroscopic contact resistivity measurements were compared with the microscopic contact configurations studied by scanning electron microscopy. The density of direct contacts between Ag crystallites grown into Si and the Ag finger bulk is essential for low contact resistivity. The presence of glass‐free regions needed for such direct contacts depends on the paste composition and on the surface texture, and does not vary with the Si emitter properties. Indeed, the decrease in contact resistivity correlates with increasing density of Ag crystallites embedded in the Si surface. Furthermore, the density of Si surface‐embedded Ag crystallites scales proportional to the electrically inactive P and is independent of the sheet resistance. Using the newest silver paste, the Ag crystallite density is independent of the emitter doping, but the Ag crystallite size increases as a function of the thickness of the dead layer. Transmission electron microscopy characterization of the excess P‐doped Si crystal lattice shows that significant strain and Si bond weakening may play a major role for both Ag crystallite nucleation and growth. Finally, we studied Si crystal defects by metallizing nanocracks, dislocations, and grain boundaries and found that Ag crystallite nucleation is defect‐property dependent. Copyright © 2013 John Wiley & Sons, Ltd.