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

Date
2021-03-15
Authors
Rossini, Aaron
Huang, Wenyu
Bhaskar, Gourab
Gvozdetskyi, Volodymyr
Batuk, Maria
Wiaderek, Kamila
Sun, Yang
Wang, Renhai
Canfield, Paul
Zhang, Chao
Carnahan, Scott
Wu, Xun
Ribeiro, Raquel
Bud’ko, Sergey
Canfield, Paul
Huang, Wenyu
Rossini, Aaron
Wang, Cai-Zhuang
Ho, Kai-Ming
Hadermann, Joke
Zaikina, Julia
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Ames LaboratoryPhysics and AstronomyChemistry
Abstract

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∼0.5NiB) with unique crystal structures. Partial removal of Li is accomplished by exposing the parent phases to air, water, or dilute HCl under ambient conditions. Scanning transmission electron microscopy and solid-state 7Li and 11B NMR spectroscopy, combined with X-ray pair distribution function (PDF) analysis and DFT calculations, were utilized to elucidate the novel structures of Li∼0.5NiB 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∼0.5NiB 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∼0.5NiB counterparts. LiNiB compounds showcase the potential to access a plethora of unique materials, including 2D MBenes (NiB).

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