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

Bhaskar, Gourab; Gvozdetskyi, Volodymyr; Batuk, Maria; Wiaderek, Kamila M.; Sun, Yang; Wang, Renhai; Zhang, Chao; Carnahan, Scott L.; Wu, Xun; Ribeiro, Raquel A.; Bud’ko, Sergey L.; Canfield, Paul C.; Huang, Wenyu; Rossini, Aaron J.; Wang, Cai-Zhuang; Ho, Kai-Ming; Hadermann, Joke; Zaikina, Julia V.

doi:10.1021/jacs.0c11397

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

Journal Article · Mon Mar 15 00:00:00 EDT 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c11397· OSTI ID:1772549

Bhaskar, Gourab ^[1]; Gvozdetskyi, Volodymyr ^[2]; ^[3]; Wiaderek, Kamila M. ^[4]; Sun, Yang ^[5]; ^[6]; ^[7]; Carnahan, Scott L. ^[8]; Wu, Xun ^[8]; Ribeiro, Raquel A. ^[2]; Bud’ko, Sergey L. ^[8]; Canfield, Paul C. ^[8]; ^[8]; ^[8]; ^[8]; Ho, Kai-Ming ^[2]; ^[3]; ^[2]

Iowa State Univ., Ames, IA (United States); Iowa State University
Iowa State Univ., Ames, IA (United States)
Univ. of Antwerp (Belgium)
Argonne National Lab. (ANL), Lemont, IL (United States)
Columbia Univ., New York, NY (United States)
Ames Lab., and Iowa State Univ., Ames, IA (United States); Univ. of Science and Technology of China, Hefei (China)
Yantai Univ. (China)
Ames Lab., and Iowa State Univ., Ames, IA (United States)

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. Here, the formation of double or triple [NiB] layers induces a change in the magnetic behavior from temperatureindependent 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).

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); Iowa State Univ., Ames, IA (United States)

Sponsoring Organization:: Gordon and Betty Moore Foundation; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-06CH11357; AC02-07CH11358

OSTI ID:: 1772549

Alternate ID(s):: OSTI ID: 1839992
OSTI ID: 1774052

Report Number(s):: IS-J 10,448

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 11 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical structure
Crystal structure
Layers
Scanning transmission electron microscopy
X-rays

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

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