Theoretical formulation of Li3a+bNaXb (X = halogen) as a potential artificial solid electrolyte interphase (ASEI) to protect the Li anode

Sang, Junwu; Yu, Yuran; Wang, Zhuo; Shao, Guosheng

doi:10.1039/d0cp00151a

Cited by 18 publications

(16 citation statements)

References 91 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[37][38][39][40] However, there are serious challenges for supercapacitors/ batteries that need to be overcome for their practical application. [41][42][43][44][45] For example, the main obstacle for MISs is the strong electrostatic interaction between Mg 2+ and conventional electrode materials, resulting in extremely slow diffusion of Mg 2+ in these materials, which limits the specific capacitance and cycling stability of MISs. α-MnO 2 , the most commonly used electrode material, possesses spacious cages (about 5 Å) to accommodate ions, but Mg 2+ ions are difficult to transport in α-MnO 2 , 46 because Mg 2+ cannot be continuously inserted into O 2− -rich electrode materials due to the strong electrostatic force between Mg 2+ and O 2− , which is as high as 0.8-1.0 eV.…”

Section: Introductionmentioning

confidence: 99%

MoS₂ nanosheets with expanded interlayer spacing for ultra-stable aqueous Mg-ion hybrid supercapacitor

Pan

Han

et al. 2022

Inorg. Chem. Front.

View full text Add to dashboard Cite

show abstract

Section: Introductionmentioning

confidence: 99%

MoS₂ nanosheets with expanded interlayer spacing for ultra-stable aqueous Mg-ion hybrid supercapacitor

Pan

Han

et al. 2022

Inorg. Chem. Front.

View full text Add to dashboard Cite

show abstract

“…Thereafter, LNCl was not revisited until Galvez-Aranda and Seminario investigated the solid-solid LM/LNCl interface with ab-initio molecular dynamics (AIMD) simulations and confirmed the stability of the interface . Sang and co-workers recently performed an ab-initio high-throughput investigation and identified new lithium nitride halide phases that may potentially be synthesizable, of which some are predicted to be highly Li-ion conducting (>10 –4 S cm –1 ) …”

Section: Introductionmentioning

confidence: 99%

“…20 Sang and co-workers recently performed an ab-initio highthroughput investigation and identified new lithium nitride halide phases that may potentially be synthesizable, of which some are predicted to be highly Li-ion conducting (>10 −4 S cm −1 ). 21 LNCl crystallizes in the antifluorite structure with the Fm3̅ m space group. N/Cl share occupation of the Wyckoff 4a (0,0,0) site with a 1:2 ratio (Figure 1a).…”

Section: ■ Introductionmentioning

confidence: 99%

Li₅NCl₂: A Fully-Reduced, Highly-Disordered Nitride-Halide Electrolyte for Solid-State Batteries with Lithium-Metal Anodes

Landgraf

Famprikis

Leeuw

et al. 2023

ACS Appl. Energy Mater.

View full text Add to dashboard Cite

Most highly Li-conducting solid electrolytes (σRT > 10–3 S cm–1) are unstable against lithium-metal and suffer from detrimental solid-electrolyte decomposition at the lithium-metal/solid-electrolyte interface. Solid electrolytes that are stable against lithium metal thus offer a direct route to stabilize lithium-metal/solid-electrolyte interfaces, which is crucial for realizing all-solid-state batteries that outperform conventional lithium-ion batteries. In this study, we investigate Li5NCl2 (LNCl), a fully-reduced solid electrolyte that is thermodynamically stable against lithium metal. Combining experiments and simulations, we investigate the lithium diffusion mechanism, different synthetic routes, and the electrochemical stability window of LNCl. Li nuclear magnetic resonance (NMR) experiments suggest fast Li motion in LNCl, which is however locally confined and not accessible in macroscopic LNCl pellets via electrochemical impedance spectroscopy (EIS). With ab-initio calculations, we develop an in-depth understanding of Li diffusion in LNCl, which features a disorder-induced variety of different lithium jumps. We identify diffusion-limiting jumps providing an explanation for the high local diffusivity from NMR and the lower macroscopic conductivity from EIS. The fundamental understanding of the diffusion mechanism we develop herein will guide future conductivity optimizations for LNCl and may be applied to other highly-disordered fully-reduced electrolytes. We further show experimentally that the previously reported anodic limit (>2 V vs Li+/Li) is an overestimate and find the true anodic limit at 0.6 V, which is in close agreement with our first-principles calculations. Because of LNCl’s stability against lithium-metal, we identify LNCl as a prospective artificial protection layer between highly-conducting solid electrolytes and strongly-reducing lithium-metal anodes and thus provide a computational investigation of the chemical compatibility of LNCl with common highly-conducting solid electrolytes (Li6PS5Cl, Li3YCl6, ...). Our results set a framework to better understand and improve highly-disordered fully-reduced electrolytes and highlight their potential in enabling lithium-metal solid-state batteries.

show abstract

“…18 Sang and coworkers recently performed an ab-initio high-throughput investigation and identified new lithium nitride halide phases that may potentially be synthesizable and of which some are predicted to be highly Li-ion conducting (>10 -4 S cm -1 ). 19 LNCl crystallizes in the antifluorite structure with the Fm-3m space group. N/Cl partially occupy the (0,0,0) site with a 1:2 ratio (Figure 1a).…”

Section: Introductionmentioning

confidence: 99%

Investigating diffusion pathways, mechanochemical milling and the electrochemical stability window for the Li5NCl2/Li9N2Cl3 solid electrolyte

Landgraf

Famprikis

Ganapathy

et al. 2022

Preprint

View full text Add to dashboard Cite

Solid electrolytes which are thermodynamically stable against lithium metal may be key to stabilizing lithium metal/solid electrolyte interfaces which is crucial for realizing all solid state batteries that outperform conventional lithium ion batteries in terms of energy density. In this study we investigated LNCl (Li5NCl2 also often reported as Li9N2Cl3), a solid electrolyte that is thermodynamically stable against lithium metal and which features a partially occupied lithium sub-lattice. Combining experiments and simulations we investigated the lithium diffusion mechanism, the effects of mechanochemical treatment and the electrochemical stability window of LNCl. We found that a wide spread of different lithium jumps can occur in LNCl with certain jumps being much more diffusion limiting than others. Additionally, Li nuclear magnetic resonance (NMR) experiments show that fast Li motion (σRT > 0.1 mS cm-1) is present in LNCl which is however not accessible in macroscopic LNCl pellets (σRT~1·10-3 mS cm-1). Ball milling LNCl improves the macroscopic conductivity by one order of magnitude (σRT = 0.015 mS cm-1) and we show for the first time that LNCl can be synthesized mechanochemically without any heat treatment step. Previously, the anodic limit of LNCl was reported to be >2V vs Li+/Li but this study shows that the true anodic limit of LNCl is ~0.6 V (vs Li+/Li) which is in close agreement with our first-principles calculations. Based on our results we conclude that the anodic limit of LNCl confines its applicability to an artificial buffer layer between the lithium metal anode and other highly-conducting solid electrolytes and we computationally investigate the chemical compatibility of LNCl with common highly-conducting solid electrolytes.

show abstract

Theoretical formulation of Li_3a+bN_aX_b (X = halogen) as a potential artificial solid electrolyte interphase (ASEI) to protect the Li anode

Abstract: A major problem against the realization of high energy density and safe solid Li-ion batteries lies in detrimental reactions at the interface between the lithium anode and the solid electrolytes.

Cited by 18 publications

References 91 publications

MoS₂ nanosheets with expanded interlayer spacing for ultra-stable aqueous Mg-ion hybrid supercapacitor

MoS₂ nanosheets with expanded interlayer spacing for ultra-stable aqueous Mg-ion hybrid supercapacitor

Li₅NCl₂: A Fully-Reduced, Highly-Disordered Nitride-Halide Electrolyte for Solid-State Batteries with Lithium-Metal Anodes

Investigating diffusion pathways, mechanochemical milling and the electrochemical stability window for the Li5NCl2/Li9N2Cl3 solid electrolyte

Contact Info

Product

Resources

About

Theoretical formulation of Li3a+bNaXb (X = halogen) as a potential artificial solid electrolyte interphase (ASEI) to protect the Li anode

Abstract: A major problem against the realization of high energy density and safe solid Li-ion batteries lies in detrimental reactions at the interface between the lithium anode and the solid electrolytes.

Cited by 18 publications

References 91 publications

MoS2 nanosheets with expanded interlayer spacing for ultra-stable aqueous Mg-ion hybrid supercapacitor

MoS2 nanosheets with expanded interlayer spacing for ultra-stable aqueous Mg-ion hybrid supercapacitor

Li5NCl2: A Fully-Reduced, Highly-Disordered Nitride-Halide Electrolyte for Solid-State Batteries with Lithium-Metal Anodes

Investigating diffusion pathways, mechanochemical milling and the electrochemical stability window for the Li5NCl2/Li9N2Cl3 solid electrolyte

Contact Info

Product

Resources

About

Theoretical formulation of Li_3a+bN_aX_b (X = halogen) as a potential artificial solid electrolyte interphase (ASEI) to protect the Li anode

MoS₂ nanosheets with expanded interlayer spacing for ultra-stable aqueous Mg-ion hybrid supercapacitor

MoS₂ nanosheets with expanded interlayer spacing for ultra-stable aqueous Mg-ion hybrid supercapacitor

Li₅NCl₂: A Fully-Reduced, Highly-Disordered Nitride-Halide Electrolyte for Solid-State Batteries with Lithium-Metal Anodes