Defect chemistry of disordered solid-state electrolyte Li10GeP2S12

Gorai, Prashun; Long, Hai; Jones, Eric B.; Santhanagopalan, Shriram; Stevanović, Vladan

doi:10.1039/c9ta10964a

Cited by 40 publications

(45 citation statements)

References 52 publications

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“…Previous investigations of native defects in SEs have put emphasis on strategies to improve ionic conductivity. [54][55][56]68,69 In this study, we focus on all native defects that may alter the concentration of charge carriers (electrons, holes), in addition to ionic carriers i.e., Li + and Na + ions. In a previous study, 55 we found V Na +Li +…”

Section: Discussionmentioning

confidence: 99%

“…Importantly, here, we treat SEs as materials with finite band gaps. 54,55 As such, the defect theory developed for semiconductors can be applied to calculate the defect energetics in SEs. 55,56…”

Section: Point Defects and Electronic Conductivitymentioning

confidence: 99%

“…For example, simply pressing Li-metal against Li 6 PS 5 X (with X=Cl, Br and I), Wenzel et al could verify the formation of Li 2 S, LiX and Li 3 P via X-ray photo-emission spectroscopy. 62 Aware of the important role the structural disorder can play in influencing the electronic structure and defects properties of Li 6 PS 5 I and Li 6 PS 5 Cl, 55,74 here, we have undertaken a statistical ensemble approach 75 to create representative "ordered" structures. Through a sampling of 831 and 1847 structures of Li 6 PS 5 I and Li 6 PS 5 Cl, respectively, which were then relaxed with DFT and their ensemble probabilities calculated (see Section 6), we identified the representative structure that were then utilized for calculating the electronic structure and defect formation energetics.…”

Section: Influence Of Synthesis and Electrochemical Conditions On Natmentioning

confidence: 99%

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The Devil is in the Defects: Electronic Conductivity in Solid Electrolytes

Gorai¹,

Famprikis²,

Singh³

et al. 2020

Preprint

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Rechargeable solid-state batteries continue to gain prominence due to their increased safety. However, a number of outstanding challenges have prevented their adoption in mainstream technology. In this study, we reveal the origins of electronic conductivity (se) in solid electrolytes (SEs), which is deemed responsible for solid-state battery degradation, as well as more drastic short-circuit and failure. Using first-principles defect calculations and physics-based models, we predict se in three topical SEs: Li6PS5Cl and Li6PS5I argyrodites, and Na3PS4 for post-Li batteries. We treat SEs as materials with finite band gaps and apply the defect theory of semiconductors to calculate the native defect concentrations and associated electronic conductivities. Our experimental measurements of the band gap of tetragonal Na3PS4 confirm our predictions. The quantitative agreement of the predicted se in these three materials and those measured experimentally strongly suggests that self-doping via native defects is the primary source of electronic conductivity in SEs. In particular, we find that Li6PS5X are n-type (electrons are majority carriers), while Na3PS4 is p-type (holes). Importantly, the predicted values set the lower bound for se in SEs. We suggest general defect engineering strategies pertaining to synthesis protocols to reduce se in SEs, and thereby, curtailing the degradation of solid-state batteries. The methodology presented here can be extended to investigate se in secondary phases that typically form at electrode-electrolyte interfaces, as well as to complex oxide-based SEs.

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Section: Discussionmentioning

confidence: 99%

Section: Point Defects and Electronic Conductivitymentioning

confidence: 99%

Section: Influence Of Synthesis and Electrochemical Conditions On Natmentioning

confidence: 99%

See 1 more Smart Citation

The Devil is in the Defects: Electronic Conductivity in Solid Electrolytes

Gorai¹,

Famprikis²,

Singh³

et al. 2020

Preprint

Self Cite

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“…Their computational studies were very useful for researchers studying sulfide electrolytes and led to better understanding of the stability of the electrolyte and electrode materials. In addition, Hu et al [274] and Du et al [275] performed computational analysis on LGPS-type structures, Binninger et al [276] investigated the electrochemical stability window of LGPS-type structures, and Gorai et al [277] performed electronic structure and defect chemistry calculations for LGPS-type structures.…”

Section: Li7p2s8imentioning

confidence: 99%

“…Li 11−x M 2−x P 1+x S 12 (M = Ge, Sn, Si) (LGPS)-Type StructuresIn 2011, Kamaya et al[266] synthesized the Li 10 GeP 2 S 12 (LGPS) solid electrolyte and reported a conductivity of 9 × 10 -3 S cm −1(Table 1)and electrochemical properties of a LiCoO 2 -LGPS|LGPS|In cell. Moreover, other researchers have extensively analyzed this system[267][268][269][270][271][272][273][274][275][276][277].LGPS presented tetragonal crystal structure with the lattice parameters a = 8.708 Å and c = 12.605 Å and consisted of negatively charged PS4 3− and GeS 4 4− tetrahedra surrounded by (mobile) Li + ions for charge compensation as shown inFigure 17a,and X-ray powder diffraction patterns and Rietveld refinements of Li 11 Si 2 PS 12 and Li 10 SnP 2 S 12 are compared with those previously reported for Li 10 GeP 2 S 12 and Li 7 GePS 8 in…”

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confidence: 99%

Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review

et al. 2020

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Energy storage materials are finding increasing applications in our daily lives, for devices such as mobile phones and electric vehicles. Current commercial batteries use flammable liquid electrolytes, which are unsafe, toxic, and environmentally unfriendly with low chemical stability. Recently, solid electrolytes have been extensively studied as alternative electrolytes to address these shortcomings. Herein, we report the early history, synthesis and characterization, mechanical properties, and Li+ ion transport mechanisms of inorganic sulfide and oxide electrolytes. Furthermore, we highlight the importance of the fabrication technology and experimental conditions, such as the effects of pressure and operating parameters, on the electrochemical performance of all-solid-state Li batteries. In particular, we emphasize promising electrolyte systems based on sulfides and argyrodites, such as LiPS5Cl and β-Li3PS4, oxide electrolytes, bare and doped Li7La3Zr2O12 garnet, NASICON-type structures, and perovskite electrolyte materials. Moreover, we discuss the present and future challenges that all-solid-state batteries face for large-scale industrial applications.

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Inorganic All‐Solid‐State Sodium Batteries: Electrolyte Designing and Interface Engineering

Yang,

Xue

et al. 2023

Advanced Materials

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Inorganic all‐solid‐state sodium batteries (IASSSBs) are emerged as promising candidates to replace commercial lithium‐ion batteries in large‐scale energy storage systems due to their potential advantages, such as abundant raw materials, robust safety, low price, high‐energy density, favorable reliability and stability. Inorganic sodium solid electrolytes (ISSEs) are an indispensable component of IASSSBs, gaining significant attention. Herein, this review begins by discussing the fundamentals of ISSEs, including their ionic conductivity, mechanical property, chemical and electrochemical stabilities. It then presents the crystal structures of advanced ISSEs (e.g., β/β′′‐alumina, NASICON, sulfides, complex hydride and halide electrolytes) and the related issues, along with corresponding modification strategies. The review also outlines effective approaches for forming intimate interfaces between ISSEs and working electrodes. Finally, current challenges and critical perspectives for the potential developments and possible directions to improve interfacial contacts for future practical applications of ISSEs are highlighted. This comprehensive review aims to advance the understanding and development of next‐generation rechargeable IASSSBs.This article is protected by copyright. All rights reserved

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Defect chemistry of disordered solid-state electrolyte Li₁₀GeP₂S₁₂

Abstract: Most solid-state electrolytes exhibit significant structural disorder, which requires careful consideration when modeling the defect energetics. Here, we model the native defect chemistry of a disordered solid electrolyte, Li10GeP2S12.

Cited by 40 publications

References 52 publications

The Devil is in the Defects: Electronic Conductivity in Solid Electrolytes

The Devil is in the Defects: Electronic Conductivity in Solid Electrolytes

Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review

Inorganic All‐Solid‐State Sodium Batteries: Electrolyte Designing and Interface Engineering

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