Superionic Fluorinated Halide Solid Electrolytes for Highly Stable Li‐Metal in All‐Solid‐State Li Batteries

Yu, Tianwei; Liang, Jianwen; Luo, Liang; Wang, Limin; Zhao, Feipeng; Xu, Guangyang; Bai, Xiaojun; Yang, Rong; Zhao, Shangqian; Wang, Jiantao; Yu, Jinqiu; Sun, Xueliang

doi:10.1002/aenm.202101915

Cited by 91 publications

(86 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Note that although we noticed that certain specific halide doping procedures for the Li–argyrodite electrolyte were reported recently, , such a quantitative design through precise composition control within our two-parameter phase space and the experimental implementation through the core–shell strategy and related synthesis are proposed and demonstrated for the first time, representing a unique fundamental understanding with significant practical values. More importantly, our approach can be further applied to the design of broad types of electrolyte materials with similar dynamic stabilities to various interfaces, including sulfides, halides, − oxides, , ceramics, glasses, and polymers and their composites.…”

Section: Discussionmentioning

confidence: 99%

A Two-Parameter Space to Tune Solid Electrolytes for Lithium Dendrite Constriction

Wang

Chen

et al. 2022

JACS Au

View full text Add to dashboard Cite

Li dendrite penetration, and associated microcrack propagation, at high current densities is one main challenge to the stable cycling of solid-state batteries. The interfacial decomposition reaction between Li dendrite and a solid electrolyte was recently used to suppress Li dendrite penetration through a novel effect of “dynamic stability”. Here we use a two-parameter space to classify electrolytes and propose that the effect may require the electrolyte to occupy a certain region in the space, with the principle of delicately balancing the two property metrics of a sufficient decomposition energy with the Li metal and a low critical mechanical modulus. Furthermore, in our computational prediction prepared using a combination of high-throughput computation and machine learning, we show that the positions of electrolytes in such a space can be controlled by the chemical composition of the electrolyte; the compositions can also be attained by experimental synthesis using core–shell microstructures. The designed electrolytes following this principle further demonstrate stable long cycling from 10 000 to 20 000 cycles at high current densities of 8.6–30 mA/cm 2 in solid-state batteries, while in contrast the control electrolyte with a nonideal position in the two-parameter space showed a capacity decay that was faster by at least an order of magnitude due to Li dendrite penetration.

show abstract

Section: Discussionmentioning

confidence: 99%

A Two-Parameter Space to Tune Solid Electrolytes for Lithium Dendrite Constriction

Wang

Chen

et al. 2022

JACS Au

View full text Add to dashboard Cite

show abstract

“…The LSV results for Li 3 YBr 5.7 F 0.3 compared to Li 3 YBr 6 showed that the onset voltage for the reduction was shifted in the negative direction and the overall reduction currents were decreased (Figure d). In addition, the XPS depth profiling results revealed the formation of LiF at the Li metal interfaces, which helped the passivation of the interfaces . For Li/SE/Li symmetric cells using Li 3 YBr 6 , a high overpotential of ∼0.25 V occurred initially and continued to increase after 300 h. In contrast, a much lower overpotential was maintained for more than 1000 h for the F-substituted sample (Figure e).…”

Section: Halide Ses For All-solid-state Batteriesmentioning

confidence: 93%

“…9 Indeed, several literature reports on halide SEs have adopted the dual electrolyte configuration for ASSB systems. 22,49,51,72,126,127 ■ INDUSTRIAL PERSPECTIVE OF HALIDE SEs Air/Moisture Stability. Better chemical oxidation stability is a key positive feature of halide SEs compared to sulfide SEs.…”

mentioning

confidence: 99%

Emerging Halide Superionic Conductors for All-Solid-State Batteries: Design, Synthesis, and Practical Applications

et al. 2022

View full text Add to dashboard Cite

Recently, halide superionic conductors have emerged as promising solid electrolyte (SE) materials for all-solid-state batteries (ASSBs), owing to their inherent properties combining high Li + conductivity, good chemical and electrochemical oxidation stabilities, and mechanical deformability, compared to sulfide or oxide SEs. In this Review, recent advances in halide Li + -and Na + -conducting SEs are comprehensively summarized. After introducing the ionic diffusion mechanism and related governing factors of the crystal structures, we discuss the design strategies, such as the substitution and synthesis protocols, of the halide materials for further improving their properties. We review theoretical and experimental results on electrochemical stabilities and compatibilities with electrode materials. Moreover, we offer a critical assessment of the challenges and issues associated with the development of practical ASSB applications, such as cost considerations, stabilities in atmospheric air, aqueous solutions, and slurryprocessing, and the wet-slurry or dry fabrication of sheet-type electrodes (or SE membranes) for large-format ASSBs. Based on these discussions, we provide a perspective on the future research directions of halide SEs, emphasizing the need for expanding the materials space.

show abstract

“…This is remarkably different from most of the previous studies employing elemental doping to stabilize the sulfide solid electrolytes. [61,62]…”

Section: (3 Of 10)mentioning

confidence: 99%

Operating High‐Energy Lithium‐Metal Pouch Cells with Reduced Stack Pressure Through a Rational Lithium‐Host Design

Ren

Shin

Manthiram

2022

Advanced Energy Materials

View full text Add to dashboard Cite

cyclability under low-Li-excess and lean electrolyte conditions. [20][21][22] The formation of a stable, dense, atomically thin solid electrolyte interphase (SEI) is critical to suppress the depletion of metallic Li and liquid electrolytes. However, the relatively thin SEI usually undergoes a repeated fracture and rebuilding process over cycling. [23,24] Transitioning from liquid electrolytes to more stable inorganic solid electrolytes offers a potential pathway to enable highly reversible Li-metal anode. [7,25,26] Careful cell and material design of anode-free Li metal || NMC full cells based on sulfide solid electrolytes has enabled thousands of full cycles without degradation. [27] Though solid electrolytes, such as the sulfide-based electrolytes, are unstable with Li metal, parasitic interfacial reaction ceases when a kinetically stable interphase layer is formed. [27] Moreover, the solid electrolyte usually displays a high stiffness and good ductility than the porous separator in liquid electrolyte cells; therefore, it performs as mechanically strong support to prevent the fracture of the interphase layer. [27,28] Despite these efforts, the interface between the Li-metal anode and solid electrolyte suffers from chemomechanical degradation under practical cycling conditions (e.g., high current density). [29][30][31] First, the Li stripping reaction creates voids at the Li-metal/solid electrolyte interface, inducing a loss of ionic contact (Figure 1a). [32] Moreover, high-rate Li plating induces nonuniformity in the stress and electric fields, leading to heterogeneous Li plating, and further deteriorating the interfacial contacts. [33][34][35][36][37] An impractically high stack pressure (e.g., >1.0 MPa) is constantly required during cell operation to smooth the surface of the planar Li-metal anode. [38] With a stack pressure of above 1.0 MPa, most solid-state cells were tested with pressure jigs and a rigid sleeve to avoid the side effects of Li-metal creep in the radial direction. [39] The complicated cell design increases the manufacturing cost and dilutes the celllevel energy. In contrast, the optimized stack pressure adopted by scalable Li-ion pouch cells is usually within the range of 0.05-0.5 MPa. [40] The design of a 3D Li-metal anode potentially enables a mild stack pressure since the high surface area of the anode scaffold provides more intimate ionic contacts (Figure 1b). In addition, a small local current at the interface benefits the interface stability. [41][42][43][44][45] However, this direction has Transitioning from a liquid electrolyte to an inorganic solid electrolyte offers a potential pathway to enable highly reversible lithium-metal anodes. However, the solid-electrolyte-protected lithium-metal anode suffers from poor interfacial ionic contacts and requires an impractically high stack pressure (>1.0 MPa) to maintain the interfacial contacts. It is demonstrated here that combining a hollow silver/carbon fiber scaffold and an inorganic/ organic composite electrolyte enables a highly revers...

show abstract

Superionic Fluorinated Halide Solid Electrolytes for Highly Stable Li‐Metal in All‐Solid‐State Li Batteries

Cited by 91 publications

References 34 publications

A Two-Parameter Space to Tune Solid Electrolytes for Lithium Dendrite Constriction

A Two-Parameter Space to Tune Solid Electrolytes for Lithium Dendrite Constriction

Emerging Halide Superionic Conductors for All-Solid-State Batteries: Design, Synthesis, and Practical Applications

Operating High‐Energy Lithium‐Metal Pouch Cells with Reduced Stack Pressure Through a Rational Lithium‐Host Design

Contact Info

Product

Resources

About