Size effects in the Li(4+x)Ti(5)O(12) spinel

Journal of the American Chemical Society
W J H BorgholsF M Mulder

Abstract

The nanosized Li(4+x)Ti(5)O(12) spinel is investigated by electrochemical (dis)charging and neutron diffraction. The near-surface environment of the nanosized particles allows higher Li ion occupancies, leading to a larger storage capacity. However, too high surface lithium storage leads to irreversible capacity loss, most likely due to surface reconstruction or mechanical failure. A mechanism where the large near-surface capacity ultimately leads to surface reconstruction rationalizes the existence of an optimal particle size. Recent literature attributes the curved voltage profiles, leading to a reduced length of the voltage plateau, of nanosized electrode particles to strain and interface energy from the coexisting end members. However, the unique zero-strain property of the Li(4+x)Ti(5)O(12) spinel implies a different origin of the curved voltage profiles observed for its nanosized crystallites. It is proposed to be the consequence of different structural environments in the near-surface region, depending on the distance from the surface and surface orientation, leading to a distribution of redox potentials in the near-surface area. This phenomenon may be expected to play a significant role in all nanoinsertion materials di...Continue Reading

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Citations

Apr 13, 2012·ACS Applied Materials & Interfaces·Ryan P MaloneyJeffrey S Sakamoto
May 29, 2012·ACS Applied Materials & Interfaces·Laifa ShenGuozhong Cao
Aug 10, 2013·ACS Applied Materials & Interfaces·Rui MaJie Shu
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Apr 4, 2013·Chemical Reviews·M V ReddyB V R Chowdari
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