Abstract：
:Spinel transition metal oxides (TMOs) have emerged as promising anode materials for lithium-ion batteries. It has been shown that reducing their particle size to nanoscale dimensions benefits overall electrochemical performance. Here, we use in situ transmission electron microscopy to probe the lithiation behavior of spinel ZnFe2O4 as a function of particle size. We have found that ZnFe2O4 undergoes an intercalation-to-conversion reaction sequence, with the initial intercalation process being size dependent. Larger ZnFe2O4 particles (40 nm) follow a two-phase intercalation reaction. In contrast, a solid-solution transformation dominates the early stages of discharge when the particle size is about 6-9 nm. Using a thermodynamic analysis, we find that the size-dependent kinetics originate from the interfacial energy between the two phases. Furthermore, the conversion reaction in both large and small particles favors {111} planes and follows a core-shell reaction mode. These results elucidate the intrinsic mechanism that permits fast reaction kinetics in smaller nanoparticles.
journal_name
Nat Communjournal_title
Nature communicationsauthors
Li J,Meng Q,Zhang Y,Peng L,Yu G,Marschilok AC,Wu L,Su D,Takeuchi KJ,Takeuchi ES,Zhu Y,Stach EAdoi
10.1038/s41467-018-07831-5subject
Has Abstractpub_date
2019-01-09 00:00:00pages
93issue
1issn
2041-1723pii
10.1038/s41467-018-07831-5journal_volume
10pub_type
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