Heteroanionic Materials by Design: Progress Toward Targeted Properties

Harada, Jaye K.; Charles, Nenian; Poeppelmeier, Kenneth R.; Rondinelli, James M.

doi:10.1002/adma.201805295

Cited by 168 publications

(179 citation statements)

References 242 publications

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“…[LiO 4 ] 7À , [BeO 4 ] 6À ,[ MgO 4 ] 6À ,[ ZnO 4 ] 6À )a st hey often contain metals bondedt om ore than one elemental anion (Table S5). [26] Metalfree anion tetrahedron centers (i.e. [PO 4 ] 3À )d irectly linked two distinct anion groupsi so nly found in this work.…”

mentioning

confidence: 61%

An Uncommon Hypervalent Fluorooxosilicophosphate

Ding

Zhao

Xiao

et al. 2019

Chemistry An Asian Journal

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The species diversity of silicon (including traditional tetrahedral coordinated silicon and hypervalent penta‐ and hexa‐coordinate silicon) gives rise to the structural richness and diverse properties of silicates. Among these silicon species, hypervalent silicon is very rare, not to mention almost unexplored mixed‐anion hypervalent fluoroxosilicate species. In this work, we successfully obtained a mixed‐anion fluorooxosilicophosphate Na4Si2PO4F9 consisting of two uncommon hypervalent fluoroxosilicate species, namely, trans‐SiO2F4 species and SiOF5 species. To the best of our knowledge, such hypervalent silicon species are reported for the first time in inorganic compounds. Remarkably, the coexistence of two distinct hypervalent fluoroxosilicate species in one compound is somewhat conflicted with Pauling's parsimony rule, but it indeed achieves an unlikely connection by PO4 and our phonon dispersion calculation confirms the structure stability of Na4Si2PO4F9. Temperature‐dependent conductivity measurements show that Na4Si2PO4F9 is a promising solid ionic conductor with a high conductivity of 4.0×10−5 S⋅cm−1 at 700 K and a low active energy of about 53.1 KJ⋅mol−1. This work will enrich the structure chemistry of silicates and may provide a new platform for solid ionic batteries.

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mentioning

confidence: 61%

An Uncommon Hypervalent Fluorooxosilicophosphate

Ding

Zhao

Xiao

et al. 2019

Chemistry An Asian Journal

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“…There has been a surge of research activities in the area of heteroanionic materials such as oxychalcogenides, oxynitrides, oxypnictides, and oxyhalides [ 1 ]. By virtue of the difference in charges, electronegativity, and sizes these heteroanions modulate the electronic properties and induce structural complexities in the material [ 2 , 3 , 4 , 5 ].…”

Section: Introductionmentioning

confidence: 99%

Interplay between Oxo and Fluoro in Vanadium Oxyfluorides for Centrosymmetric and Non-Centrosymmetric Structure Formation

et al. 2021

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Herein, we report the syntheses of two lithium-vanadium oxide-fluoride compounds crystallized from the same reaction mixture through a time variation experiment. A low temperature hydrothermal route employing a viscous paste of V2O5, oxalic acid, LiF, and HF allowed the crystallization of one metastable phase initially, Li2VO0.55(H2O)0.45F5⋅2H2O (I), which on prolonged heating transforms to a chemically similar yet structurally different phase, Li3VOF5 (II). Compound I crystallizes in centrosymmetric space group, I2/a with a = 6.052(3), b = 7.928(4), c = 12.461(6) Å, and β = 103.99(2)°, while compound II crystallizes in a non-centrosymmetric (NCS) space group, Pna21 with a = 5.1173(2), b = 8.612(3), c = 9.346(3) Å. Synthesis of NCS crystals are highly sought after in solid-state chemistry for their second-harmonic-generation (SHG) response and compound II exhibits SHG activity albeit non-phase-matchable. In this article, we also describe their magnetic properties which helped in unambiguous assignment of mixed valency of V (+4/+5) for Li2VO0.55(H2O)0.45F5⋅2H2O (I) and +4 valency of V for Li3VOF5 (II).

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“…Research on mixed anion materials is expanding significantly and presents as an original way to modulate structure and properties in many fields of material science. 10,11 While multiple anion chemistry is less understood and explored than multiple cation, single anion chemistry, even this restricted chemistry to date has afforded promising materials offering the stabilization of disordered phases and improved conductivity properties. [12][13][14][15][16][17][18] Examples include the lithium phosphorus oxynitride (LiPON), which is known for its outstanding electrochemical performance 19,20 , and more recently, the lithium argyrodite family has received particular attention.…”

Section: Introductionmentioning

confidence: 99%

Li4.3AlS3.3Cl0.7: A Sulfide-Chloride Lithium Ion Conductor with a Highly Disordered Structure

Gamon¹,

Dyer²,

Duff³

et al. 2021

Preprint

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Mixed anion materials and anion doping are very promising strategies to improve solid-state electrolyte properties by enabling an optimized balance between good electrochemical stability and high ionic conductivity. In this work, we present the discovery of a novel lithium aluminum sulfide-chloride phase. The structure is strongly affected by the presence of chloride anions on the sulfur site, as this stabilizes a higher symmetry phase presenting a large degree of cationic site disorder, as well as disordered octahedral lithium vacancies, in comparison with Li-Al-S ternaries. The effect of disorder on the lithium conductivity properties was assessed by a combined experimental-theoretical approach. In particular, the conductivity is increased by a factor 103 compared to the pure sulfide phases. Although it remains moderate (10−6 S·cm-1), Ab Initio Molecular Dynamics and Maximum Entropy (applied to neutron diffraction data) methods show that disorder leads to a 3D diffusion pathway, where Li atoms move thanks to a concerted mechanism. An understanding of the structure-property relationships is developed to determine the limiting factor governing lithium ion conductivity. This analysis, added to the strong step forward obtained in the determination of the dimensionality of diffusion paves the way for accessing even higher conductivity in materials comprising an hcp anion arrangement.

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Heteroanionic Materials by Design: Progress Toward Targeted Properties

Cited by 168 publications

References 242 publications

An Uncommon Hypervalent Fluorooxosilicophosphate

An Uncommon Hypervalent Fluorooxosilicophosphate

Interplay between Oxo and Fluoro in Vanadium Oxyfluorides for Centrosymmetric and Non-Centrosymmetric Structure Formation

Li4.3AlS3.3Cl0.7: A Sulfide-Chloride Lithium Ion Conductor with a Highly Disordered Structure

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