High pressure-high temperature synthesis of lithium-rich Li3O(Cl, Br) and Li3−xCax/2OCl anti-perovskite halides

Zhang, Jianzhong; Han, Jiantao; Zhu, Jinlong; Lin, Zhijun; Braga, Maria Helena; Daemen, Luke L.; Wang, L.; Zhao, Yusheng

doi:10.1016/j.inoche.2014.08.036

Cited by 32 publications

(28 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…38 Previous studies have been conducted to explain the mechanism behind lithium superionic conductivity in LiRAP. [13][14][15][16][17][40][41][42][43] Ab initio molecular dynamics simulations showed that pristine antiperovskites are not intrinsically superionic conductors; their dense crystal structures do not provide paths for fast ion diffusion. 44 The ionic conductivity of these materials therefore depends on defect density.…”

Section: Resultsmentioning

confidence: 99%

“…10 Since then, interest in the LiRAP has grown and it has been the subject of many electrochemical experiments and theoretical studies to determine its suitability as a solid electrolyte. [11][12][13][14][15][16][17] Whenever a new lithium compound is discovered, a common trend in the battery community is to investigate the sodium analog. 18 Antiperovskites are not an exception: shortly after the conductivity of the LiRAP was reported, so was the ionic conductivity of the NaRAP analog.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Experimental and Computational Evaluation of a Sodium-Rich Anti-Perovskite for Solid State Electrolytes

Nguyen

et al. 2016

J. Electrochem. Soc.

View full text Add to dashboard Cite

In this study we experimentally investigated the effects of two processing techniques on the sodium-rich anti-perovskite, Na 3 OBr; namely, conventional cold pressing (CP) and spark plasma sintering (SPS). We demonstrated that the electrolyte can be synthesized via a single-step solid state reaction. We compared the CP and SPS processed samples using XRD, SEM, and EIS. From these analyses it was found that SPS reduced Na 3 OBr's interfacial impedance by three orders of magnitude, which translated into an increase in the overall ionic conductivity and a reduction in the activation energy, from 1.142 eV to 0.837 eV. DFT was used to probe the mechanisms for ionic transport in Na-rich Na 3 OBr. The formation energies of ion diffusion-facilitating defects in Na 3 OBr were found to be much higher compared to the lithium-rich anti-perovskites (LiRAP), which can explain the difference in overall ionic conductivity between the two.

show abstract

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

Experimental and Computational Evaluation of a Sodium-Rich Anti-Perovskite for Solid State Electrolytes

Nguyen

et al. 2016

J. Electrochem. Soc.

View full text Add to dashboard Cite

show abstract

“…[20] Recently, Li 3 OCl solid electrolyte films were fabricated via pulsed laser deposition (PLD) using a Li 3 OCl compound target. [24] LiRAPs were also synthesized via a high-pressure high-temperature method [25], a quaternary ammonium salt method, and a wet chemistry method. [26] However, none of these methods can meet the criteria for both phase purity and large scale manufacture.…”

Section: Introductionmentioning

confidence: 99%

Reaction mechanism studies towards effective fabrication of lithium-rich anti-perovskites Li3OX (X= Cl, Br)

Zhu

Wang

et al. 2016

Solid State Ionics

Self Cite

View full text Add to dashboard Cite

Lithium-rich Anti-perovskites (LiRAPs), with general formula Li 3 OX (X = Cl, Br), recently reported as superionic conductors with 3-dimensional Li + migrating channels, are emerging as promising candidates for solid electrolytes in all-solid-state lithium-ion batteries (LIBs). However, great challenges remain in the fabrication of pure LiRAPs due to difficulties such as low yield, impurity phases, thermodynamic instabilities, and moisture-sensitivity. In this work, we thoroughly studied the formation mechanism of Li 3 OCl and Li 3 OBr using various solid state reaction routes. Different experimental strategies were developed to improve the syntheses, namely for the purposes of phase stability, phase purity, and large-scale production. One feasible method is to use the strong reducing agents Li metal or LiH to eliminate the OH species. The results show that LiH is more effective than Li metal, mainly due to negatively charged Hand reaction uniformity. The other successful method employs a solid diffusion approach using Li 2 O and LiX as the starting reagents, thereby avoiding OH entirely; ball milling of reagents under Ar atmosphere was utilized to decrease initial grain size and increase the reaction rate. Fourier transform infrared spectroscopy (FTIR), thermal analyses and first-principles calculations were performed to give indications on the reaction pathway.

show abstract

“…Moreover, the experimentally synthesized antiperovskite Li 3 OCl and Li 3 OBr were predicted to be thermodynamically metastable at low temperature, and tend to decompose into a LiCl-Li 2 O or LiBr-Li 2 O twophase mixture. 55 Li 3 OCl and Li 3 OBr were predicted to be stable with an assumptive kinetic suppression on Li 2 O formation, such as high-pressure (P) and high-temperature (T) condition, 58 which has been experimentally confirmed by Zhang et al 71 Moreover, the cubic antiperovskite Li 3 OCl was also predicted to be dynamically unstable in respect to the negative frequencies of phonon modes at R and M, as shown in Figure 5B. 69 However, the lattice energy of the antiperovskite can be lowered by octahedral tilts, as shown in Figure 5C.…”

Section: Phase Stabilitymentioning

confidence: 76%

Anti‐perovskite materials for energy storage batteries

Deng

Chen

et al. 2021

InfoMat

Self Cite

View full text Add to dashboard Cite

Anti-perovskites X 3 BA, as the electrically inverted derivatives of perovskites ABX 3 , have attracted tremendous attention for their good performances in multiple disciplines, especially in energy storage batteries. The Li/Na-rich antiperovskite (LiRAP/NaRAP) solid-state electrolytes (SSEs) typically show high ionic conductivities and high chemical/electrochemical stability toward the Li-metal anode, illustrating their great potential for applications in the Limetal batteries (LMBs) using nonaqueous liquid electrolyte or all-solid-state electrolyte. The antiperovskites have been studied as artificial solid electrolyte interphase for Li-metal anode protection, film SSEs for thin-film batteries, and low melting temperature solid electrolyte enabling melt-infiltration for the manufacture of all-solid-state lithium batteries. Transition metal-doped LiRAPs as cathodes have demonstrated a high discharge specific capacity and good rate capability in the Li-ion batteries (LIBs). Additionally, the underlying scientific principles in antiperovskites with flexible structural features have also been extensively studied. In this review, we comprehensively summarize the development, structural design, ionic conductivity and ion transportation mechanism, chemical/electrochemical stability, and applications of some antiperovskite materials in energy storage batteries. The perspective for enhancing the performance of the antiperovskites is also provided as a guide for future development and applications in energy storage. K E Y W O R D S antiperovskite, chemical and electrochemical stability, energy storage, solid-state electrolyte Zhi Deng and Dixing Ni contributed equally to this work.

show abstract

High pressure-high temperature synthesis of lithium-rich Li3O(Cl, Br) and Li3−xCax/2OCl anti-perovskite halides

Cited by 32 publications

References 15 publications

Experimental and Computational Evaluation of a Sodium-Rich Anti-Perovskite for Solid State Electrolytes

Experimental and Computational Evaluation of a Sodium-Rich Anti-Perovskite for Solid State Electrolytes

Reaction mechanism studies towards effective fabrication of lithium-rich anti-perovskites Li3OX (X= Cl, Br)

Anti‐perovskite materials for energy storage batteries

Contact Info

Product

Resources

About