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

Gvozdetskyi, Volodymyr; Sun, Yang; Zhao, Xin; Bhaskar, Gourab; Carnahan, Scott L.; Harmer, Colin P.; Zhang, Feng; Ribeiro, R. A.; Canfield, Paul C.; Rossini, Aaron J.; Wang, Cai‐Zhuang; Ho, Kai‐Ming; Zaikina, Julia V.

doi:10.1039/d0qi01150a

Cited by 8 publications

(31 citation statements)

References 52 publications

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“…There are four different types of B atoms present in the crystal structure: B1 atoms in the 16 n position are coordinated by eight Ni atoms in a square antiprismatic environment; B2 atoms occupy the 16 n site that has seven nearest Ni atoms forming a capped trigonal prism; B3 atoms occupy 8 h sites with six nearest Ni atoms in a trigonal prism, and B4 atoms at 8 i sites are coordinated by eight Ni atoms forming a square antiprism (Figure a–e). The Ni–B bond distances are in the range of 2.04–2.26 Å and are comparable to the Ni–B distances found in binary nickel borides − and ternary Li–Ni–B borides. ,, The crystal structure of the LiNi 12 B 8 compound can be represented as a framework of B-centered 6-, 7-, and 8-vertex polyhedra of Ni atoms, as shown in Figure a–e. Here, the B4-centered polyhedra are linked together by two Ni–Ni bridges (Figure g).…”

Section: Crystal Structuresupporting

confidence: 69%

“…In addition to five Ni/Li mixed occupied sites, there are two fully occupied Li sites (Figure ), Li1 at the 4 c position and Li2 at the 2 b position, each inside cuboctahedra of 12 Ni atoms. The Li–Ni bond distances are in the range of 2.50–2.66 Å, comparable to Li–Ni distances in the known Li–Ni–B compounds. ,, The Li-centered nickel polyhedra are connected by corner sharing; however, Li2-centered polyhedra are separated from each other by two face-shared Ni-centered rectangular prisms (Figure d).…”

Section: Crystal Structuresupporting

confidence: 58%

“…The layered lithium nickel borides RT -LiNiB, HT -LiNiB, RT -Li 1+ x NiB, and HT -Li 1+ y NiB , represent a family of layered compounds whose crystal structures are built up of alternating [NiB] and Li layers (Figure ). These compounds feature different topologies of individual M Bene (NiB) and Li layers depending on the temperature and Li “chemical” pressure.…”

Section: Resultsmentioning

confidence: 99%

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Path Less Traveled: A Contemporary Twist on Synthesis and Traditional Structure Solution of Metastable LiNi₁₂B₈

et al. 2022

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Achieving kinetic control to synthesize metastable compounds is a challenging task, especially in solid-state reactions where the diffusion is slow. Another challenge is the unambiguous crystal structure determination for metastable compounds when high-quality single crystals suitable for single-crystal X-ray diffraction are inaccessible. In this work, we report an unconventional means of synthesis and an effective strategy to solve the crystal structure of an unprecedented metastable compound LiNi12B8. This compound can only be produced upon heating a metastable layered boride, HT-Li0.4NiB (HT: high temperature), in a sealed niobium container. A conventional heating and annealing of elements do not yield the title compound, which is consistent with the metastable nature of LiNi12B8. The process to crystallize this compound is sensitive to the annealing temperature and dwelling time, a testament to the complex kinetics involved in the formation of the product. The unavailability of crystals suitable for single-crystal X-ray diffraction experiments prompted solving the crystal structure from high-resolution synchrotron powder X-ray diffraction data. This compound crystallizes in a new structure type with space group I4/mmm (a = 10.55673(9) Å, c = 10.00982(8) Å, V = 1115.54(3) Å3, Z = 6). The resulting complex crystal structure of LiNi12B8 is confirmed by scanning transmission electron microscopy and solid-state 11B and 7Li NMR spectroscopy analyses. The extended Ni framework with Li/Ni disorder in its crystal structure resulted in the spin-glass or cluster glass type magnetic ordering below 24 K. This report illustrates a “contemporary twist” to traditional methodologies toward synthesizing a metastable compound and provides a recipe for solving structures by combining the complementary characterization techniques in the cases where the traditionally used single-crystal X-ray diffraction method is nonapplicable.

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Section: Crystal Structuresupporting

confidence: 69%

Section: Crystal Structuresupporting

confidence: 58%

Section: Resultsmentioning

confidence: 99%

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Path Less Traveled: A Contemporary Twist on Synthesis and Traditional Structure Solution of Metastable LiNi₁₂B₈

et al. 2022

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“…Previously, it was shown that the hydride route is advantageous for the synthesis of different complex antimonides, arsenides, borides, germanides, and silicides. − Unlike ductile alkali and alkaline-earth metals, a salt-like nature of their hydrides allows for the implementation of a ball-milling technique in synthesis. Due to the thorough mixing of precursors in the hydride route, the sample compositions can be precisely controlled, yielding high purity materials.…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, it is often limited to the scarce number of thermodynamically stable phases. In contrast, a recently developed hydride synthetic route − is considerably faster, aided by the salt-like nature of metal hydrides, which allows for a thorough mixing of precursors and the elemental homogeneity of the starting mixture; this leads to a lower synthetic temperature and provids access to hindered metastable phases.…”

Section: Introductionmentioning

confidence: 99%

Ternary Zinc Antimonides Unlocked Using Hydride Synthesis

et al. 2021

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were synthesized utilizing sodium hydride NaH as a reactive sodium source. In comparison to the synthesis using sodium metal, salt-like NaH can be ball-milled, leading to the easy and uniform mixing of precursors in the desired stoichiometric ratios. Such comprehensive compositional control enables a fast screening of the Na− Zn−Sb system and identification of new compounds, followed by their preparation in bulk with high purity. Na 11 Zn 2 Sb 5 crystallizes in the triclinic P1 space group (No. 2, Z = 2, a = 8.8739( 6) Å, b = 10.6407(7) Å, c = 11.4282(8) Å, α = 103.453(2)°, β = 96.997(2)°, γ = 107.517(2)°) and features polyanionic [Zn 2 Sb 5 ] 11clusters with unusual 3-coordinated Zn atoms. Both Na 4 Zn 9 Sb 9 (Z = 4, a = 28.4794(4) Å, b = 4.47189(5) Å, c = 17.2704(2) Å, β = 98.3363(6)°) and NaZn 3 Sb 3 (Z = 8, a = 32.1790(1) Å, b = 4.51549(1) Å, c = 9.64569(2) Å, β = 98.4618( 1)°) crystallize in the monoclinic C2/m space group (No. 12) and have complex new structure types. For both compounds, their frameworks are built from ZnSb 4 distorted tetrahedra, which are linked via edge-, vertex-sharing, or both, while Na cations fill in the framework channels. Due to the complex structures, Na 4 Zn 9 Sb 9 and NaZn 3 Sb 3 compounds exhibit low thermal conductivities (0.97−1.26 W•m −1 K −1 ) at room temperature, positive Seebeck coefficients (19−32 μV/K) suggestive of holes as charge carriers, and semimetallic electrical resistivities (∼1.0−2.3 × 10 −4 Ω•m). Na 4 Zn 9 Sb 9 and NaZn 3 Sb 3 decompose into the equiatomic NaZnSb above ∼800 K, as determined by in situ synchrotron powder Xray diffraction. The discovery of multiple ternary compounds highlights the importance of judicious choice of the synthetic method.

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Hydride precursors in materials synthesis

Adeyemi

Bhaskar²,

Cox³

et al. 2023

Comprehensive Inorganic Chemistry III

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

Abstract: Here we show the effect of Li chemical pressure to the structure of layered polymorphs RT-LiNiB and HT-LiNiB, resulting in stabilization of the novel RT-Li1+xNiB (x ~ 0.17) and HT-Li1+yNiB...

Cited by 8 publications

References 52 publications

Path Less Traveled: A Contemporary Twist on Synthesis and Traditional Structure Solution of Metastable LiNi₁₂B₈

Path Less Traveled: A Contemporary Twist on Synthesis and Traditional Structure Solution of Metastable LiNi₁₂B₈

Ternary Zinc Antimonides Unlocked Using Hydride Synthesis

Hydride precursors in materials synthesis

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

Abstract: Here we show the effect of Li chemical pressure to the structure of layered polymorphs RT-LiNiB and HT-LiNiB, resulting in stabilization of the novel RT-Li1+xNiB (x ~ 0.17) and HT-Li1+yNiB...

Cited by 8 publications

References 52 publications

Path Less Traveled: A Contemporary Twist on Synthesis and Traditional Structure Solution of Metastable LiNi12B8

Path Less Traveled: A Contemporary Twist on Synthesis and Traditional Structure Solution of Metastable LiNi12B8

Ternary Zinc Antimonides Unlocked Using Hydride Synthesis

Hydride precursors in materials synthesis

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Product

Resources

About

Path Less Traveled: A Contemporary Twist on Synthesis and Traditional Structure Solution of Metastable LiNi₁₂B₈

Path Less Traveled: A Contemporary Twist on Synthesis and Traditional Structure Solution of Metastable LiNi₁₂B₈