Li5OCl3 and Li3OCl: Two Remarkably Different Lithium Oxide Chlorides

Reckeweg, Olaf; Blaschkowski, Björn; Schleid, Thomas

doi:10.1002/zaac.201200143

Cited by 29 publications

(23 citation statements)

References 30 publications

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“…The changes in chemical composition also show that the sample successively incorporates hydrogen. Also, Reckeweg et al 31 3a (for further details about indexing, symmetry analysis, and structure determination see Figure S2 and Tables S2 and S3). The crystal structure is illustrated in Figure 3c.…”

Section: Chemistry Of Materialsmentioning

confidence: 99%

Untangling the Structure and Dynamics of Lithium-Rich Anti-Perovskites Envisaged as Solid Electrolytes for Batteries

et al. 2018

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Lithium-rich anti-perovskites (LiRAPs) have attracted a great deal of attention as they have been praised as another superior group of solid electrolytes that can be used to realize all-solid-state batteries free of flammable liquids. Despite several studies that have reported on the properties of LiRAPs, many questions remain unanswered. In particular, these include fundamental ones concerning the structure, stability, and Li-ion conductivity and diffusivity. Moreover, it is not clear whether some of the previously reported compounds do really exist. To untangle the current picture of LiRAPs, we synthesized "Li 3 OCl" and Li 2 OHCl polymorphs and applied a wide spectrum of methods, such as powder X-ray diffraction (PXRD), powder neutron diffraction (PND), nuclear magnetic resonance spectroscopy, and impedance spectroscopy to carefully shed some light on LiRAPs. Here we self-critically conclude that the cubic polymorph of the two compounds cannot be easily distinguished by PXRD alone as the lattice metrics and the lattice parameters are very similar. Furthermore, PXRD suffers from the difficulty of detecting H and Li. Even Rietveld refinement of our PND data turned out to be complicated and not easily interpreted in a straightforward way. Nevertheless, here we report the first structural models for the cubic and a new orthorhombic polymorph containing also structural information about the H atoms. In situ PXRD of "Li 3 OCl", intentionally exposed to air, revealed rapid degradation into Li 2 CO 3 and amorphous LiCl•xH 2 O. Most likely, the instability of "Li 3 OCl" explains earlier findings about the unusually high ion conductivities as the decomposition product LiCl•xH 2 O offers an electrical conductivity that is good enough for some applications, excluding, of course, those that need aprotic conditions or electrolytes free of any moisture. Considering "H-free Li 3 OCl" as well as Li 5 (OH) 3 Cl 2 , Li 5 (OH) 2 Cl 3 , Li 3 (OH) 2 Cl, and Li 3 (OH)Cl 2 , we are confident that Li 4 (OH) 3 Cl and variants of Li 3−x (OH x )Cl, where x > 0, are, from a practical point of view, so far the only stable lithium-rich anti-perovskites.

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Section: Chemistry Of Materialsmentioning

confidence: 99%

Untangling the Structure and Dynamics of Lithium-Rich Anti-Perovskites Envisaged as Solid Electrolytes for Batteries

et al. 2018

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“…Recently, lithium-rich compounds with the anti-perovskite structure, Li 3 OX (X = Cl, Br, etc), were synthesized. 13, 14 The Li 3 OX crystal contains Li 6 O +4 octahedral units, which are connected via all six vertices to form a three-dimensional framework with a negative monovalent halogen anion Xsitting at the center. 14 It has been considered a promising alternative SSE, 15,16,17 since it (a) exhibits good thermodynamic and electrochemical stability;…”

mentioning

confidence: 99%

From anti-perovskite to double anti-perovskite: tuning lattice chemistry to achieve super-fast Li⁺ transport in cubic solid lithium halogen–chalcogenides

Wang

Xuan

et al. 2018

J. Mater. Chem. A

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Using a materials genome approach on the basis of the density functional theory, we have formulated a new class of inorganic electrolytes for fast diffusion of Li + ions, through fine-tuning of lattice chemistry of anti-perovskite structures. Systematic modelling has been carried out to elaborate the structural stability and ion transportation characteristics in Li 3 AX based cubic anti-perovskite, through alloying on the chalcogen lattice site (A) and alternative occupancy of the halogen site (X). In addition to identifying effective ways for reduction of diffusion barriers for Li + ions in anti-perovskite phases via suitable designation of lattice occupancy, the current theoretical study leads to discovery and synthesis of a new phase with a double-anti-perovskite structure, Li 6 OSI 2 (or Li 3 O 0.5 S 0.5 I). Such a new compound is of fairly low activation barrier for Li + diffusion, together with a wide energy band gap to hinder conduction of electrons.Keywords: First-principles materials formulation; Superfast solid lithium ion conductor; double anti-perovskite; Li-ion battery Ⅰ. IntroductionSolid-state electrolytes (SSE) for lithium-ion battery (LIB) have attracted enormous attention, owing to their highly superior safety advantage over organic liquid ionic conductors and great potential in offering improved electrochemical capacity with lithium anode. 1-4 Still, extensive substitution of liquid organic electrolytes by SSE is yet desired, unless related technologies are further improved to meet the following key criteria: (a) High Li + ionic conductivity being greater than 1 mScm -1 (current technical request for liquid organic electrolytes); (b) Low electronic conductivity to avoid self-discharging in service; (c) Broad working temperature for stable operation from −100 to 300 °C; (d) being electrochemically compatible to lithium anode, 5 and (e) being light, economical, and environmentally friendly.As a landmark breakthrough, a new family of SSEs based on multi-component sulfides has been shown to provide significantly increased ionic conductivity, making them potential candidates as fast ion conductor for solid lithium-ion batteries. The discovery of Li 10 GeP 2 S 12 (LGPS), 6,7 which had high bulk Li + ions conductivity of over 10 mScm -1 at room temperature, demonstrated for the first time that Li + ionic conductivity in solid electrolytes could be superior to that in organic liquid electrolytes. The efficient conduction pathway for Li + was along the longer c-axis of the tetragonal phase of Li 10 GeP 2 S 12 , with an activation barrier of 0.22-0.25 eV for Li + diffusion. 6,7 The motivation in replacing the expensive Ge content led to discovery of a cheaper candidate Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 , 8,9 which exhibited an even higher ionic conductivity of about 25 mScm -1 at room temperature. However, this latter electrolyte was shown not to be electrochemically stable with the lithium anode, which is considered an issue to hinder the full potential of the lithium metal anode, which has the highe...

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“…This approach was first proposed in 1968 [56] and recently developed into a coherent crystal chemical theory (see [57,58] for reviews and historical remarks). In general, description of certain crystal structures in terms of anion-centered coordination polyhedra became more popular over the years, in part due to the recent reports on interesting structural and physical properties and mineralogical importance of antiperovskites, i.e., materials with structures based upon anion-centered octahedra [59][60][61][62][63][64][65][66].…”

Section: Cu 5 O 2 (Seo 3 ) 2 CL 2 Polymorphsmentioning

confidence: 99%

“…The complex 1-dimensional structural units with the composition {[O 2 Cu 5 ](SeO 3 ) 2 } 2+ shown in Figure 4b are the basic structural modules for both polymorphs and it is the mode of their combination that generates the structural difference. interesting structural and physical properties and mineralogical importance of antiperovskites, i.e., materials with structures based upon anion-centered octahedra [59][60][61][62][63][64][65][66].…”

Section: Cu 5 O 2 (Seo 3 ) 2 CL 2 Polymorphsmentioning

confidence: 99%

Se–Cl Interactions in Selenite Chlorides: A Theoretical Study

Krivovichev

Gorelova

2018

Crystals

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The Se-Cl interactions in five selenite chlorides (α,β-Zn 2 (SeO 3)Cl 2 (sofiite and its polymorph), α,β-Cu 5 O 2 (SeO 3) 2 Cl 2 (georgbokiite and parageorgbokiite), and KCdCu 7 O 2 (SeO 3) 2 Cl 9 (burnsite)) have been investigated by means of the analysis of their theoretical electron density distributions. The analysis reveals the existence in the structures of two basic types of interactions: intermediate interactions with essential covalent contribution and closed-shell interactions. In Zn 2 (SeO 3)Cl 2 polymorphs and burnsite, all metal-oxide and metal-chloride interactions are of the first type, whereas in georgbokiite and parageorgbokiite, the Jahn-Teller distortion results in the elongation of some of the Cu-X bonds and their transition to the closed-shell type. All anion-anion interactions are of the closed-shell type. The energy of the closed-shell Se-Cl interactions can be estimated as 1.4-2.6 kcal. mol −1 , which is comparable to weak hydrogen bonds. Despite their weakness, these interactions provide additional stabilization of structural architectures. The Se 4+-Cl − configurations are localized inside framework channels or cavities, which can be therefore be viewed as regions of weak and soft interactions in the structure.

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Li₅OCl₃ and Li₃OCl: Two Remarkably Different Lithium Oxide Chlorides

Cited by 29 publications

References 30 publications

Untangling the Structure and Dynamics of Lithium-Rich Anti-Perovskites Envisaged as Solid Electrolytes for Batteries

Untangling the Structure and Dynamics of Lithium-Rich Anti-Perovskites Envisaged as Solid Electrolytes for Batteries

From anti-perovskite to double anti-perovskite: tuning lattice chemistry to achieve super-fast Li⁺ transport in cubic solid lithium halogen–chalcogenides

Se–Cl Interactions in Selenite Chlorides: A Theoretical Study

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Li5OCl3 and Li3OCl: Two Remarkably Different Lithium Oxide Chlorides

Cited by 29 publications

References 30 publications

Untangling the Structure and Dynamics of Lithium-Rich Anti-Perovskites Envisaged as Solid Electrolytes for Batteries

Untangling the Structure and Dynamics of Lithium-Rich Anti-Perovskites Envisaged as Solid Electrolytes for Batteries

From anti-perovskite to double anti-perovskite: tuning lattice chemistry to achieve super-fast Li+ transport in cubic solid lithium halogen–chalcogenides

Se–Cl Interactions in Selenite Chlorides: A Theoretical Study

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Product

Resources

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Li₅OCl₃ and Li₃OCl: Two Remarkably Different Lithium Oxide Chlorides

From anti-perovskite to double anti-perovskite: tuning lattice chemistry to achieve super-fast Li⁺ transport in cubic solid lithium halogen–chalcogenides