Supertetrahedral polyanionic network in the first lithium phosphidoindate Li3InP2 – structural similarity to Li2SiP2 and Li2GeP2 and dissimilarity to Li3AlP2 and Li3GaP2

Restle, Tassilo M. F.; Deringer, Volker L.; Meyer, Joseph; Raudaschl‐Sieber, Gabriele; Fässler, Thomas F.

doi:10.1039/d0sc05851c

Cited by 11 publications

(15 citation statements)

References 29 publications

(83 reference statements)

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“…Unfortunately, none of them can conduct lithium. 24,25 These results suggest that the conductivities of SEs are closely related to their structural frame. Despite the high ionic conductivity, most of these phosphides have not been tested in full cell configurations, and their electrochemical stability has rarely been reported.…”

Section: Introductionmentioning

confidence: 75%

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First-Principles Insights into Lithium-Rich Ternary Phosphide Superionic Conductors: Solid Electrolytes or Active Electrodes

Min

Yang

Zhong

et al. 2022

ACS Appl. Mater. Interfaces

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Lithium-rich ternary phosphides are recently found to possess high ionic conductivity and are proposed as promising solid electrolytes (SEs) for solid-state batteries. While lithium ions can facilely transport within these materials, their electrochemical and interfacial stability in complex battery setups remain largely uncharacterized. We study the phase stability and electrochemical stability of phosphide-type SEs via first-principles calculations and thermodynamic analysis. Our results indicate that these SEs have intrinsic electrochemical stability windows narrower than 0.5 V. The SEs exhibit low anodic limits of about 1 V vs Li/Li+ due to the oxidation of the electrolytes to form various P binary compounds, indicating the poor electrochemical stability in contact with the cathode. In particular, we find that the thermodynamic driving force of such electrochemical decomposition is critically dependent on the new phases formed at the interfaces. Therefore, these phosphides might not be suitable as electrolytes. Despite the electrochemical instability, further calculations of Li diffusion kinetics show that the Li conduction is highly efficient through face-sharing octahedral and tetrahedral sites with low energy barriers, in spite of the possible variation of the local environments. In addition, an analysis of the terminal decomposition products shows impressive Li storage capacity as high as 2547 mAh·g–1 based on the conversion mechanism, indicating they are capable as high-rate and energy-dense anode materials for battery applications.

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Section: Introductionmentioning

confidence: 75%

“…Li 3 AlP 2 and the isotypic gallium and indium counterparts have been investigated as well. Unfortunately, none of them can conduct lithium. , These results suggest that the conductivities of SEs are closely related to their structural frame.…”

Section: Introductionmentioning

confidence: 93%

First-Principles Insights into Lithium-Rich Ternary Phosphide Superionic Conductors: Solid Electrolytes or Active Electrodes

Min

Yang

Zhong

et al. 2022

ACS Appl. Mater. Interfaces

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“…[30,36] Moreover, supertetrahedral polyanionic networks have been reported in phosphide-type Li/Na ion conductors. [37][38][39][40][41] Such large 3D diffusion channels will also be beneficial for diffusion of the larger Na cation. These findings inspired us to explore sodium thioborates with a similar motif.…”

Section: Introductionmentioning

confidence: 99%

A New Sodium Thioborate Fast Ion Conductor: Na₃B₅S₉

et al. 2023

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We report a new sodium fast-ion conductor, Na 3 B 5 S 9 , that exhibits a high Na ion total conductivity of 0.80 mS cm À 1 (sintered pellet; cold-pressed pellet = 0.21 mS cm À 1 ). The structure consists of corner-sharing B 10 S 20 supertetrahedral clusters, which create a framework that supports 3D Na ion diffusion channels. The Na ions are well-distributed in the channels and form a disordered sublattice spanning five Na crystallographic sites. The combination of structural elucidation via single crystal X-ray diffraction and powder synchrotron X-ray diffraction at variable temperatures, solid-state nuclear magnetic resonance spectra and ab initio molecular dynamics simulations reveal high Na-ion mobility (predicted conductivity: 0.96 mS cm À 1 ) and the nature of the 3D diffusion pathways. Notably, the Na ion sublattice orders at low temperatures, resulting in isolated Na polyhedra and thus much lower ionic conductivity. This highlights the importance of a disordered Na ion sublattice-and existence of well-connected Na ion migration pathways formed via face-sharing polyhedra -in dictating Na ion diffusion.

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“…The phosphidotrielates Li 3 TrP 2 (Tr = Al, Ga, In) were reinvestigated recently, but there is a lack of information concerning the corresponding arsenides. [8,9,10] We synthesized Li 3 AlAs 2 , reinvestigated the crystal structure and propose a new structure model isotypic to Li 3 AlP 2 . The heavier homologues Li 3 GaAs 2 and Li 3 InAs 2 were also synthesized, they are new members to this class of compounds.…”

Section: Introductionmentioning

confidence: 99%

Li₃TrAs₂ (Tr=Al, Ga, In) – Derivatives of the antifluorite type structure, conductivities and electronic structures

Wegner¹,

Kamm²,

Pielnhofer³

et al. 2022

Zeitschrift anorg allge chemie

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Dedicated to Prof. Wolfgang Schnick on the occasion of his 65 th birthday. Li 3 AlAs 2 , Li 3 GaAs 2 and Li 3 InAs 2 were obtained from the elements via high temperature synthesis. Li 3 AlAs 2 and Li 3 GaAs 2 crystallize in a distorted 2 • 2 • 1 superstructure of the antifluorite structure type. The orthorhombic crystal structure is isotypic to Li 3 AlP 2 and Li 3 GaP 2 , space group Cmce (No. 64) showing layers of condensed TrAs 4 -tetrahedra (Tr = Al, Ga). Li 3 InAs 2 crystallizes isotypic to Li 3 InP 2 in a distorted 2 • 2 • 4 antifluorite type super-structure. The crystal structure is tetragonal, space group I4 1 / acd (No. 142), showing a 3D-network of In 4 As 10 -supertetrahedra. Structural characterization by powder X-ray diffraction, thermal analysis, conductivity measurements and band structure calculations show ion conductivity for Li 3 InAs 2 and electronic charge transport for Li 3 AlAs 2 and Li 3 GaAs 2 .

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Supertetrahedral polyanionic network in the first lithium phosphidoindate Li₃InP₂ – structural similarity to Li₂SiP₂ and Li₂GeP₂ and dissimilarity to Li₃AlP₂ and Li₃GaP₂

Abstract: Phosphide-based materials have been investigated as promising candidates for solid electrolytes, among which the recently reported Li9AlP4 displays an ionic conductivity of 3 mS∙cm−1. While the phases Li-Al-P and Li-Ga-P...

Cited by 11 publications

References 29 publications

First-Principles Insights into Lithium-Rich Ternary Phosphide Superionic Conductors: Solid Electrolytes or Active Electrodes

First-Principles Insights into Lithium-Rich Ternary Phosphide Superionic Conductors: Solid Electrolytes or Active Electrodes

A New Sodium Thioborate Fast Ion Conductor: Na₃B₅S₉

Li₃TrAs₂ (Tr=Al, Ga, In) – Derivatives of the antifluorite type structure, conductivities and electronic structures

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Supertetrahedral polyanionic network in the first lithium phosphidoindate Li3InP2 – structural similarity to Li2SiP2 and Li2GeP2 and dissimilarity to Li3AlP2 and Li3GaP2

Abstract: Phosphide-based materials have been investigated as promising candidates for solid electrolytes, among which the recently reported Li9AlP4 displays an ionic conductivity of 3 mS∙cm−1. While the phases Li-Al-P and Li-Ga-P...

Cited by 11 publications

References 29 publications

First-Principles Insights into Lithium-Rich Ternary Phosphide Superionic Conductors: Solid Electrolytes or Active Electrodes

First-Principles Insights into Lithium-Rich Ternary Phosphide Superionic Conductors: Solid Electrolytes or Active Electrodes

A New Sodium Thioborate Fast Ion Conductor: Na3B5S9

Li3TrAs2 (Tr=Al, Ga, In) – Derivatives of the antifluorite type structure, conductivities and electronic structures

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Supertetrahedral polyanionic network in the first lithium phosphidoindate Li₃InP₂ – structural similarity to Li₂SiP₂ and Li₂GeP₂ and dissimilarity to Li₃AlP₂ and Li₃GaP₂

A New Sodium Thioborate Fast Ion Conductor: Na₃B₅S₉

Li₃TrAs₂ (Tr=Al, Ga, In) – Derivatives of the antifluorite type structure, conductivities and electronic structures