Structural and electrochemical investigation of crystallite size controlled zinc ferrite (ZnFe 2 O 4 ).

Autor:	Tallman KR; Institute for Electrochemically Stored Energy, Stony Brook University, Stony Brook, NY 11794, United States of America.; Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, United States of America., West PJ; Institute for Electrochemically Stored Energy, Stony Brook University, Stony Brook, NY 11794, United States of America.; Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, NY 11794, United States of America., Yan S; Institute for Electrochemically Stored Energy, Stony Brook University, Stony Brook, NY 11794, United States of America.; Interdisciplinary Science Department, Brookhaven National Laboratory, Upton, NY 11973, United States of America., Yao S; Interdisciplinary Science Department, Brookhaven National Laboratory, Upton, NY 11973, United States of America., Quilty CD; Institute for Electrochemically Stored Energy, Stony Brook University, Stony Brook, NY 11794, United States of America.; Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, United States of America., Wang F; Interdisciplinary Science Department, Brookhaven National Laboratory, Upton, NY 11973, United States of America., Marschilok AC; Institute for Electrochemically Stored Energy, Stony Brook University, Stony Brook, NY 11794, United States of America.; Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, United States of America.; Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, NY 11794, United States of America.; Interdisciplinary Science Department, Brookhaven National Laboratory, Upton, NY 11973, United States of America., Bock DC; Institute for Electrochemically Stored Energy, Stony Brook University, Stony Brook, NY 11794, United States of America.; Interdisciplinary Science Department, Brookhaven National Laboratory, Upton, NY 11973, United States of America., Takeuchi KJ; Institute for Electrochemically Stored Energy, Stony Brook University, Stony Brook, NY 11794, United States of America.; Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, United States of America.; Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, NY 11794, United States of America.; Interdisciplinary Science Department, Brookhaven National Laboratory, Upton, NY 11973, United States of America., Takeuchi ES; Institute for Electrochemically Stored Energy, Stony Brook University, Stony Brook, NY 11794, United States of America.; Department of Chemistry, Stony Brook University, Stony Brook, NY 11794, United States of America.; Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, NY 11794, United States of America.; Interdisciplinary Science Department, Brookhaven National Laboratory, Upton, NY 11973, United States of America.
Jazyk:	angličtina
Zdroj:	Nanotechnology [Nanotechnology] 2021 Jun 25; Vol. 32 (37). Date of Electronic Publication: 2021 Jun 25.
DOI:	10.1088/1361-6528/ac09a9
Abstrakt:	Zinc ferrite, ZnFe 2 O 4 (ZFO), is a promising electrode material for next generation Li-ion batteries because of its high theoretical capacity and low environmental impact. In this report, synthetic control of crystallite size from the nanometer to submicron scale enabled probing of the relationships between ZFO size and electrochemical behavior. A facile two-step coprecipitation and annealing preparation method was used to prepare ZFO with controlled sizes ranging ∼9 to >200 nm. Complementary synchrotron and electron microscopy techniques were used to characterize the series of materials. Increasing the annealing temperature increased crystallinity and decreased microstrain, while local structural ordering was maintained independent of crystallite size. Electrochemical characterization revealed that the smaller sized materials delivered higher capacities during initial lithiation. Larger sized particles exhibited a lack of distinct electrochemical signatures above 1.0 V, suggesting that the longer diffusion length associated with greater crystallite size causes the lithiation process to proceed via non discrete lithium insertion, cation migration, and conversion processes. Notably, larger particles exhibited enhanced electrochemical reversibility over 50 cycles, with capacity retention improving from <20% to >40% at C/2 cycling rate. This intriguing result was probed through x-ray absorption spectroscopy (XAS) and x-ray photoelectron spectroscopy (XPS) measurements of the cycled electrodes. XAS revealed that the larger crystallite size materials do not completely convert to Fe 0 during the first lithiation and that independent of size, delithiation results in the formation of nanocrystalline FeO and ZnO phases rather than ZnFe 2 O 4 . After 20 cycles, the larger crystallites showed reversibility between partially oxidized FeO in the charged state and Fe 0 in the discharged state, while the smaller crystallite size material was electrochemically inactive as Fe 0 . XPS analysis revealed more significant solid electrolyte interphase (SEI) formation on the cycled electrodes utilizing ZFO with smaller crystallite size. This finding suggests that excessive SEI buildup on the smaller sized, higher surface area ZFO particles contributes to their reduced electrochemical reversibility relative to the larger crystallite size materials. (© 2021 IOP Publishing Ltd.)
Databáze:	MEDLINE
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