Abstract
The formation of a solid–electrolyte interphase (SEI) on the surface of Li4Ti5O12 (LTO) has become a highly controversial topic, with arguments for it and against it. However, prior studies supporting the formation of an SEI layer have typically suggested that a layer forms upon cycling of a cell, although the layer is probed after disassembling. In this study, cubic mesostructured LTO is synthesized with crystallite domain sizes between 3 and 4 nm and uniform pores with diameters ≤8 nm. The mean pore size is controlled between 4–8 nm through the use of a triblock amphipathic copolymer with a tunable hydrophobic block as template and by thermal treatment. The LTO morphology obtained is spherical and evolves upon heat treatment. These materials show excellent electrochemical performance, including high rate capability and capacity retention. The LTO material is subjected to operando small‐angle neutron scattering and X‐ray photoelectron spectroscopy experiments, which reveal that the highly debated SEI forms at potentials as high as 2.2 V, first as a LiF‐rich layer and subsequently by the growth of a carbonaceous layer. These SEI products form first on the smaller pores before forming on the mesopores.
