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

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 similar to 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 Li-7 and B-1(1) NMR spectroscopy, combined with X-ray pair distribution function (PDF) analysis and DFT calculations, were utilized to elucidate the novel structures of (Li similar to 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 similar to 0.5NiB is best described as an intergrowth of the ordered single [NiB], double [NiB](2), or triple [NiB](3) layers alternating with singlemore » 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 similar to 0.5NiB counterparts. LiNiB compounds showcase the potential to access a plethora of unique materials, including 2D MBenes (NiB).« less

Authors:

Bhaskar, Gourab ^[1]; Gvozdetskyi, Volodymyr ^[1]; Batuk, Maria  ^[2];

• Search DOE PAGES for author "Batuk, Maria"
• Search DOE PAGES for ORCID "0000-0003-1411-9785"

Wiaderek, Kamila M. ^[3]; Sun, Yang ^[4]; Wang, Renhai  ^[5];

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• Search DOE PAGES for ORCID "0000-0003-4539-9273"

Zhang, Chao  ^[6];

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• Search DOE PAGES for ORCID "0000-0002-5957-2287"

Carnahan, Scott L. ^[7]; Wu, Xun ^[7]; Ribeiro, Raquel A. ^[1]; Bud’ko, Sergey L. ^[7]; Canfield, Paul C. ^[7]; Huang, Wenyu  ^[7];

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• Search DOE PAGES for ORCID "0000-0003-2327-7259"

Rossini, Aaron J.  ^[7];

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• Search DOE PAGES for ORCID "0000-0002-1679-9203"

Wang, Cai-Zhuang  ^[7];

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• Search DOE PAGES for ORCID "0000-0002-0269-4785"

Ho, Kai-Ming ^[1]; Hadermann, Joke  ^[2];

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• Search DOE PAGES for ORCID "0000-0002-1756-2566"

Zaikina, Julia V.  ^[1]

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• Search DOE PAGES for ORCID "0000-0002-8755-1926"

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+ Show Author Affiliations

1. Iowa State Univ., Ames, IA (United States)
2. Univ. of Antwerp (Belgium)
3. Argonne National Lab. (ANL), Lemont, IL (United States)
4. Columbia Univ., New York, NY (United States)
5. Ames Lab., and Iowa State Univ., Ames, IA (United States); Univ. of Science and Technology of China, Hefei (China)
6. Yantai Univ. (China)
7. Ames Lab., and Iowa State Univ., Ames, IA (United States)

Publication Date:

Mon Mar 15 00:00:00 EDT 2021

Research Org.:

Iowa State Univ., Ames, IA (United States); Ames Lab., Ames, IA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:

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

OSTI Identifier:

1772549

Alternate Identifier(s):

OSTI ID: 1774052; OSTI ID: 1839992

Report Number(s):

IS-J 10,448
Journal ID: ISSN 0002-7863

Grant/Contract Number:  

AC02-07CH11358; GBMF4411; AC02-06CH11357; DMR 1944551

Resource Type:

Accepted Manuscript

Journal Name:

Journal of the American Chemical Society

Additional Journal Information:

Journal Volume: 143; Journal Issue: 11; Journal ID: ISSN 0002-7863

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

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