7 research outputs found
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Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFe<inf>x</inf>Co<inf>1-x</inf>PO<inf>4</inf>
The delithiation mechanisms occurring within the olivine-type class of cathode materials for Li-ion batteries have received considerable attention owing to the good capacity retention at high rates for LiFePO4. A comprehensive mechanistic study of the (de)lithiation reactions that occur when the substituted olivine-type cathode materials LiFexCo1-xPO4 (x = 0, 0.05, 0.125, 0.25, 0.5, 0.75, 0.875, 0.95 and 1) are electrochemically cycled is reported here, using in situ X-ray diffraction (XRD) data, and supporting ex situ 31P NMR spectra. On the first charge, two intermediate phases are observed and identified: Li1-x(Fe3+)x(Co2+)1-xPO4 for 0 Fe3+) and Li2/3FexCo1-xPO4 for 0 ≤ x ≤ 0.5 (i.e. the Co-majority materials). For the Fe-rich materials, we study how nonequilibrium, single-phase mechanisms that occur discretely in single particles, as observed for LiFePO4 at high rates, are affected by Co substitution. In the Co-majority materials, a two-phase mechanism with a coherent interface is observed, as was seen in LiCoPO4, and we discuss how it is manifested in the XRD patterns. We then compare the nonequilibrium, single-phase mechanism with the bulk single-phase and the coherent interface two-phase mechanisms. Despite the apparent differences between these mechanisms, we discuss how they are related and interconverted as a function of Fe/Co substitution and the potential implications for the electrochemistry of this system.This is the final version of the article. It first appeared from The American Chemical Society via https://doi.org/10.1021/acs.chemmater.6b0031
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Mapping the inhomogeneous electrochemical reaction through porous LiFePO<inf>4</inf>-electrodes in a standard coin cell battery
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Nanosized, carbon-coated LiFePO4 (LFP) is a promising cathode for Li-ion batteries. However, nano-particles are problematic for electrode design, optimized electrodes requiring high tap densities, good electronic wiring, and a low tortuosity for efficient Li diffusion in the electrolyte in between the solid particles, conditions that are difficult to achieve simultaneously. Using in situ energy-dispersive X-ray diffraction, we map the evolution of the inhomogeneous electrochemical reaction in LFP-electrodes. On the first cycle, the dynamics are limited by Li diffusion in the electrolyte at a cycle rate of C/7. On the second cycle, there appear to be two rate-limiting processes: Li diffusion in the electrolyte and electronic conductivity through the electrode. Three-dimensional modeling based on porous electrode theory shows that this change in dynamics can be reproduced by reducing the electronic conductivity of the composite electrode by a factor of 8 compared to the first cycle. The poorer electronic wiring could result from the expansion and contraction of the particles upon cycling and/or the formation of a solid-electrolyte interphase layer. A lag was also observed perpendicular to the direction of the current: the LFP particles at the edges of the cathode reacted preferentially to those in the middle, owing to the closer proximity to the electrolyte source. Simulations show that, at low charge rates, the reaction becomes more uniformly distributed across the electrode as the porosity or the width of the particle-size distribution is increased. However, at higher rates, the reaction becomes less uniform and independent of the particle-size distribution.We acknowledge the Engineering Physical Science Research Council (EPSRC) for a Doctoral Training Account Award (for FCS) and the US Department of Energy (DOE) for support via the NECCES, an Energy Frontier Research Center (DE-SC0001294 and DE-SC0012583). FCS acknowledges the Science and Technology Facilities Council for travel funding through the Global Challenge Network in Batteries and Electrochemical Energy Devices. Synchrotron X-ray beamtime was provided by Diamond Light Source, under experiment number EE8385. We also thank Zlatko Saracevic at the Department of Chemical Engineering at the University of Cambridge for help with the BET experiments and Jon Rickard at the Department of Physics at the University of Cambridge for help with the SEM. Lastly; we thank Charles Monroe and Paul Shearing for discussions on this project.This is the final version of the article. It first appeared from ACS Publications via http://dx.doi.org/10.1021/cm504317
A rational approach to screen for hydrated forms of the pharmaceutical derivative magnesium naproxen using liquid-assisted grinding
Variation of water content in liquid-assisted grinding was utilised to mechanochemically screen for different hydrated forms of magnesium naproxen directly from a mixture of magnesium oxide and naproxen. Structure determination from powder and single crystal X-ray diffraction data, supported by solid-state NMR and synchrotron radiation diffraction experiments, revealed a monohydrate coordination polymer, a discrete tetrahydrate complex, and provided a preliminary structural model for a highly hydrated salt