Topochemical Deintercalation of Li from Layered LiNiB: toward 2D MBene

摘要

The pursuit of two-dimensional (2D) borides, MBenes, has proven to be challenging, not the least because of the lack of a suitable precursor prone to the deintercalation. Here, we studied room-temperature topochemical deintercalation of lithium from the layered polymorphs of the LiNiB compound with a considerable amount of Li stored in between [NiB] layers (33 at. % Li). Deintercalation of Li leads to novel metastable borides (Li_(～0.5)NiB) with unique crystal structures. Partial removal of Li is accomplished by exposing the parent phases to air, water, or dilute HC1 under ambient conditions. Scanning transmission electron microscopy and solid-state ~7Li and ~(11)B NMR spectroscopy, combined with X-ray pair distribution function (PDF) analysis and DFT calculations, were utilized to elucidate the novel structures of Li_(～0.5)NiB and the mechanism of Li-deintercalation. We have shown that the deintercalation of Li proceeds via a "zip-lock" mechanism, leading to the condensation of single [NiB] layers into double or triple layers bound via covalent bonds, resulting in structural fragments with Li[NiB]_2 and Li[NiB]_3 compositions. The crystal structure of Li_(～0.5)NiB is best described as an intergrowth of the ordered single [NiB], double [NiB]_2, or triple [NiB]_3 layers alternating with single Li layers; this explains its structural complexity. The formation of double or triple [NiB] layers induces a change in the magnetic behavior from temperature-independent paramagnets in the parent LiNiB compounds to the spin-glassiness in the deintercalated Li_(～0.5)NiB counterparts. LiNiB compounds showcase the potential to access a plethora of unique materials, including 2D MBenes (NiB).