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Title: Lithium nickel borides: evolution of [NiB] layers driven by Li pressure

Abstract

Here we show the effect of Li chemical pressure on the structure of layered polymorphs with LiNiB composition: RT-LiNiB (room temperature polymorph) and HT-LiNiB (high temperature polymorph), resulting in stabilization of the novel RT-Li1+xNiB (x ~ 0.17) and HT-Li1+yNiB (y ~ 0.06) phases. Depending on the synthesis temperature and initial Li content, precisely controlled via hydride route synthesis, [NiB] layers undergo structural deformations, allowing for extra Li atoms to be accommodated between the layers. In situ variable temperature synchrotron and time-dependent laboratory powder X-ray diffraction studies suggest Li step-wise deintercalation processes: RT-Li1+xNiB → RT-LiNiB (high temp.) → LiNi3B1.8 → binary Ni borides and HT-Li1+yNiB → HT-LiNiB (high temp.) → LiNi3B1.8 → binary Ni borides. Quantum chemistry calculations and solid state 7Li and 11B NMR spectroscopy shed light on the complexity of real superstructures of these compounds determined from high resolution synchrotron powder diffraction data.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1];  [4]; ORCiD logo [4];  [3];  [5];  [3]; ORCiD logo [4]; ORCiD logo [3];  [5]; ORCiD logo [1]
  1. Department of Chemistry, Iowa State University, Ames, USA
  2. Department of Applied Physics and Applied Mathematics, Columbia University, New York, USA
  3. Ames Laboratory, US DOE, Iowa State University, Ames, USA
  4. Department of Chemistry, Iowa State University, Ames, USA, Ames Laboratory
  5. Department of Physics and Astronomy, Iowa State University, Ames, USA
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
OSTI Identifier:
1737838
Alternate Identifier(s):
OSTI ID: 1777940
Report Number(s):
IS-J-10,462
Journal ID: ISSN 2052-1553; ICFNAW
Grant/Contract Number:  
AC02-06CH11357; AC02-07CH11358
Resource Type:
Published Article
Journal Name:
Inorganic Chemistry Frontiers (Online)
Additional Journal Information:
Journal Name: Inorganic Chemistry Frontiers (Online) Journal Volume: 8 Journal Issue: 7; Journal ID: ISSN 2052-1553
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gvozdetskyi, Volodymyr, Sun, Yang, Zhao, Xin, Bhaskar, Gourab, Carnahan, Scott L., Harmer, Colin P., Zhang, Feng, Ribeiro, Raquel A., Canfield, Paul C., Rossini, Aaron J., Wang, Cai-Zhuang, Ho, Kai-Ming, and Zaikina, Julia V.. Lithium nickel borides: evolution of [NiB] layers driven by Li pressure. United Kingdom: N. p., 2021. Web. https://doi.org/10.1039/D0QI01150A.
Gvozdetskyi, Volodymyr, Sun, Yang, Zhao, Xin, Bhaskar, Gourab, Carnahan, Scott L., Harmer, Colin P., Zhang, Feng, Ribeiro, Raquel A., Canfield, Paul C., Rossini, Aaron J., Wang, Cai-Zhuang, Ho, Kai-Ming, & Zaikina, Julia V.. Lithium nickel borides: evolution of [NiB] layers driven by Li pressure. United Kingdom. https://doi.org/10.1039/D0QI01150A
Gvozdetskyi, Volodymyr, Sun, Yang, Zhao, Xin, Bhaskar, Gourab, Carnahan, Scott L., Harmer, Colin P., Zhang, Feng, Ribeiro, Raquel A., Canfield, Paul C., Rossini, Aaron J., Wang, Cai-Zhuang, Ho, Kai-Ming, and Zaikina, Julia V.. Tue . "Lithium nickel borides: evolution of [NiB] layers driven by Li pressure". United Kingdom. https://doi.org/10.1039/D0QI01150A.
@article{osti_1737838,
title = {Lithium nickel borides: evolution of [NiB] layers driven by Li pressure},
author = {Gvozdetskyi, Volodymyr and Sun, Yang and Zhao, Xin and Bhaskar, Gourab and Carnahan, Scott L. and Harmer, Colin P. and Zhang, Feng and Ribeiro, Raquel A. and Canfield, Paul C. and Rossini, Aaron J. and Wang, Cai-Zhuang and Ho, Kai-Ming and Zaikina, Julia V.},
abstractNote = {Here we show the effect of Li chemical pressure on the structure of layered polymorphs with LiNiB composition: RT-LiNiB (room temperature polymorph) and HT-LiNiB (high temperature polymorph), resulting in stabilization of the novel RT-Li1+xNiB (x ~ 0.17) and HT-Li1+yNiB (y ~ 0.06) phases. Depending on the synthesis temperature and initial Li content, precisely controlled via hydride route synthesis, [NiB] layers undergo structural deformations, allowing for extra Li atoms to be accommodated between the layers. In situ variable temperature synchrotron and time-dependent laboratory powder X-ray diffraction studies suggest Li step-wise deintercalation processes: RT-Li1+xNiB → RT-LiNiB (high temp.) → LiNi3B1.8 → binary Ni borides and HT-Li1+yNiB → HT-LiNiB (high temp.) → LiNi3B1.8 → binary Ni borides. Quantum chemistry calculations and solid state 7Li and 11B NMR spectroscopy shed light on the complexity of real superstructures of these compounds determined from high resolution synchrotron powder diffraction data.},
doi = {10.1039/D0QI01150A},
journal = {Inorganic Chemistry Frontiers (Online)},
number = 7,
volume = 8,
place = {United Kingdom},
year = {2021},
month = {4}
}

Journal Article:
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https://doi.org/10.1039/D0QI01150A

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