Solvent-Free and Long-Cycling Garnet-Based Lithium-Metal Batteries

Abstract

Solid-state batteries using ceramic solid electrolytes promise to deliver enhanced energy density and intrinsic safety. However, the challenge of integrating solid electrolytes with electrode materials limits the electrochemical performance. Herein, we report a solvent-free ceramic-based lithium-metal battery with good cycling stability at a wide temperature range from 45 to 100 °C, enabled by an inorganic ternary salt of low eutectic point. By using a garnet electrolyte with molten salts at the electrolyte|cathode interface, the Li||LiFePO4 cells perform a long cycling with capacity retention of 81.4% after 1000 cycles at 1 C. High-voltage LiFe0.4Mn0.6PO4 cathodes also deliver good electrochemical performance. Specifically, commercial electrode pieces with high area capacities can be adopted directly in the quasi-solid-state lithium-metal batteries. These stable performances are ascribable to the low melting point, high ionic conductivity and good thermal/electrochemical stability of the ternary salt system. Our findings provide an effective method on fabrication of solid-state batteries for practical applications.

Two-dimensional lead-free silver-bismuth double perovskite nanobelts with intrinsic chirality via co-antisolvent modulation strategy

“…This result was fitted using a biexponential function and yielded an average PL lifetime of 1.39 ns, which is close to that of (R-MPA) 4 AgBiI 8 (t ave = 3.36 ns). 15 Differing from the previously reported achiral 3D Cs 2 AgInCl 6 , our 2D material possessed chirality through the introduction of chiral amine cation R-MPEA + . 16,17 Differing from the chiral ammonium (Fig.…”

“…Recent advancements in synthesizing macroscopic single crystals based on chiral silver-bismuth (Ag-Bi) double perovskites had demonstrated immense potential in the field of circularly polarized lightsensitive detection and self-powered X-ray detection. 7,8 Inevitably, the challenges associated with the utilization of corrosive acid solutions and the resulting pollution, as well as the stringent requirements for temperature control and time-consuming processes in single crystal growth, pose significant obstacles to largescale production. 1 Additionally, the resultant single crystals often exceed the nanoscale in size, lacking desirable colloidal dispersity and solution processability, limiting the detailed investigation of size and structure-dependent characteristics of chiral perovskite nanomaterials.…”

Asymmetric Trihalogenated Aromatic Lithium Salt Induced Lithium Halide Rich Interface for Stable Cycling of All-Solid-State Lithium Batteries

“…7,8 To tackle these dilemmas, replacing the flammable organic solvent with an all-solid-state electrolyte is a feasible way. 9,10 Great research efforts have been devoted to exploring solid polymer electrolytes (SPEs) due to their low density, excellent flexibility, and good processing compatibility with the current roll-to-roll technique for all-solid-state lithium metal batteries. 11,12 Up to now, the most widely studied and employed SPE is still the composite of p o l y ( e t h y l e n e o x i d e ) ( P E O ) a n d l i t h i u m b i s -(trifluoromethanesulfonyl) imide (LiTFSI), whose ion transport behavior was found more than 40 years ago though the ionic conductivity was relatively low (∼10 −6 S cm −1 ).…”

“…Lithium (Li) metal with a high theoretical capacity (3860 mAh g –1 ) and the lowest redox potential (−3.04 V vs the standard hydrogen electrode) is one of the most promising anode alternatives for next-generation rechargeable batteries with high energy density. , However, the industrialized carbonate-based liquid electrolytes are incompatible with the Li anode, thus resulting in an unstable solid electrolyte interphase (SEI), , limited cycle life, , and severe safety risks of electrolyte leakage and fires. , To tackle these dilemmas, replacing the flammable organic solvent with an all-solid-state electrolyte is a feasible way. , Great research efforts have been devoted to exploring solid polymer electrolytes (SPEs) due to their low density, excellent flexibility, and good processing compatibility with the current roll-to-roll technique for all-solid-state lithium metal batteries. , Up to now, the most widely studied and employed SPE is still the composite of poly­(ethylene oxide) (PEO) and lithium bis­(trifluoromethanesulfonyl) imide (LiTFSI), whose ion transport behavior was found more than 40 years ago though the ionic conductivity was relatively low (∼10 –6 S cm –1 ). , During the following decades, efforts have been devoted to solve the problem of sluggish Li ion transport in the SPE, and a moderate ionic conductivity (∼10 –4 S cm –1 ) has already been achieved at room temperature by modifying polymer molecules, − optimizing electrolyte physical structures, − introducing organic plasticizers or inorganic fillers, etc. − However, the long-term cycling stability of all-solid-state lithium batteries with the LiTFSI-PEO SPE is still affected by the poor SPE/Li anode interface compatibility . This is mainly attributed to the low lithium ion transference number ( t + < 0.2) and weak film-forming ability on a Li metal anode of the LiTFSI salt. , It is well-known that LiTFSI exhibits high charge delocalization and ionic conductivity in SPEs .…”

Cyclotriphosphonitrile-Based Electroactive Flame-Retardant Polymers for Electrochromic/Supercapacitor Devices

“…Electrochemical energy storage devices, − such as rechargeable batteries, supercapacitors, and electrochromic devices, , have raised an upwell of interest due to their high potentials for providing efficient energy storage and environmental sustainability. However, their safety concern is becoming the spotlight because of numerous reports of battery explosions and fire accidents .…”