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High rate capabilities Fe3O4-based Cu nano-architectured electrodes for lithium-ion battery applications

Abstract

All battery technologies are known to suffer from kinetic problems linked to the solid-state diffusion of Li in intercalation electrodes, the conductivity of the electrolyte in some cases and the quality of interfaces. For Li-ion technology the latter effect is especially acute when conversion rather than intercalation electrodes are used. Nano-architectured electrodes are usually suggested to enhance kinetics, although their realization is cumbersome. To tackle this issue for the conversion electrode material Fe3O4, we have used a two-step electrode design consisting of the electrochemically assisted template growth of Cu nanorods onto a current collector followed by electrochemical plating of Fe3O4. Using such electrodes, we demonstrate a factor of six improvement in power density over planar electrodes while maintaining the same total discharge time. The capacity at the 8C rate was 80% of the total capacity and was sustained over 100 cycles. The origin of the large hysteresis between charge and discharge, intrinsic to conversion reactions, is discussed and approaches to reduce it are proposed. We hope that such findings will help pave the way for the use of conversion reaction electrodes in future-generation Li-ion batteries.

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Figure 1: The electrochemical cell and the nanostructured current collector.
Figure 2: XRD patterns and scanning electron micrographs of as-prepared copper nanopillar Fe3O4 assemblies.
Figure 3: Potential-capacity profiles for the as-prepared copper-supported Fe3O4 deposits galvanostatically cycled at a rate of 1 Li+/2 h versus Li.
Figure 4: Capacity retention.
Figure 5: Rate capability.
Figure 6: ln(Iapplied) versus ΔE and Iapplied versus ΔE.

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Acknowledgements

The authors express their sincere gratitude to D. Murphy for helpful comments and discussions on this manuscript and the European Network of Excellence 'ALISTORE' for providing the ground scientific discussions to ignite such a study. The authors are deeply grateful to the EU for co-financing ALISTORE.

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Taberna, P., Mitra, S., Poizot, P. et al. High rate capabilities Fe3O4-based Cu nano-architectured electrodes for lithium-ion battery applications. Nature Mater 5, 567–573 (2006). https://doi.org/10.1038/nmat1672

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