Poster (Scientific congresses and symposiums)Electrochemical mechanism and effect of carbon addition during hydrothermal synthesis to improve the electrochemical performance of Fe1.19(PO4)(OH)0.57(H2O)0.43 cathode material for Li-ion batteries
Mahmoud, Abdelfattah; karegeya, Claude; Sougrati, Moulay Tahar et al.
2018 • 2018 MRS Fall Meeting
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Abstract :
[en] Since the introduction of lithium-ion batteries (LIBs) to market in 1991, their performance has improved significantly, which has been achievable through development in materials technologies. However, further breakthroughs are still needed to ameliorate cycle-life, safety and energy density of LIBs. This requires new electrode materials and a detailed understanding of the electrochemical mechanisms during cycling. Transition metal phosphates are interesting candidates as cathode materials for LIBs [1]. In this work, we report the electrochemical performance of FPHH/C and FPHH/CNT composites where FPHH represents Fe1.19(PO4)(OH)0.57(H2O)0.43 while carbon black and carbon nanotubes (CNT) were used as precursors in the one-pot hydrothermal synthesis, respectively. We show that the addition of conducting carbon black into the solution has a strong influence on reducing the particle size and tailoring their morphology, but does not interfere with the formation of the FPHH phase. Thanks to its favorable microstructural characteristics, the FPHH-10 wt% C and FPHH-20 wt% C materials exhibited good performance [2]. The CNT also improve the performance of FPHH such as capacity retention (500 cycles at 1 C).
The mechanisms of lithiation-delithiation were investigated by combining operando X-ray diffraction and 57Fe Mössbauer spectroscopy. FPHH undergoes a monophasic reaction based on Fe3+/Fe2+ redox process. However, the variations of the lattice parameters and 57Fe quadrupole splitting indicate a more complex mechanism than a random occupation of the vacant sites within FPHH. This can be related to the peculiar structure of FPHH formed by chains of face sharing (Fe0.6•0.4)O6 octahedra connected by PO4 tetrahedra and by channels for Li diffusion along [100] and [010] directions. The existence of Fe vacancies provide interconnections between the one-dimensional channels, improving lithium diffusion within FPHH. This mechanism, combined with the addition carbon black or nanotubes in the solution prior to hydrothermal treatment as a simple and effective way to reduce particle size and improve electronic conductivity, provides good cycle life and rate capability for FPHH.
Acknowledgements
A. Mahmoud is grateful to University of Liege and FRS-FNRS for the grants and thanks to the Walloon region for a Beware Fellowship Academia 2015-1, RESIBAT n° 1510399. Part of this work was supported by the Walloon Region under the “PE PlanMarshall2.vert” program (BATWAL – 1318146).
References
1. C. Karegeya, A. Mahmoud, F. Hatert, B. Vertruyen, R. Cloots, P.E. Lippens, F. Boschini, Journal of Power Sources 388 (2018) 57-64.
2. C. Karegeya, A. Mahmoud, R. Cloots, B. Vertruyen, F. Boschini, Electrochim. Acta 250 (2017) 49-58.