Li-Ga Alloy-Contained Hybrid Solid Electrolyte Interphase Induced by In Situ Polymerization for High-Performance Lithium Metal Batteries.

Construction of quasi-solid-state lithium metal batteries (LMBs) by in situ polymerization is considered a key strategy for the next generation of energy storage systems with high specific energy and safety. Poly(1,3-dioxolane) (PDOL)-based electrolytes have attracted wide attention among researchers, benefiting from the low cost and high ionic conductivity. However, interfacial deterioration and uncontrollable growth of lithium dendrites easily appeared in LMBs due to the high reactivity of lithium metal, resulting in the failure of LMBs. In this work, a strategy is developed of using Ga(OTF)3 as the initiator to obtain a PDOL-based gel electrolyte (GaPD). In addition, a hybrid stable solid electrolyte interphase (SEI) of lithium fluoride/Li2O/Li-Ga alloys is observed on the surface of lithium metal. Combined with density functional theory calculations, the hybrid SEI shows high affinity toward Li+, indicating that a uniform deposition of Li+ could be achieved. Therefore, the Li/GaPD/Li cell operates stably for 1600 h at room temperature. In addition, the LiFePO4/GaPD/Li cell retains a capacity retention rate of 90.2% over 200 cycles at 1 C. This work provides a reference for the practical application of in situ polymerization technology in high-performance and safe LMBs.

Dual-Interphase-Stabilizing Sulfolane-Based Electrolytes for High-Voltage and High-Safety Lithium Metal Batteries.

High-voltage Li metal battery (HV-LMB) is one of the most promising energy storage technologies to achieve ultrahigh energy density. Nevertheless, electrolytes reported to date are difficult to simultaneously stabilize the Li metal anode and high-voltage cathode, especially without the assistance of expensive and corrosive high-concentration Li salts. Herein, a dual-interphase-stabilizing (DIS) and safe electrolyte that bypasses the high-concentration Li salt is reported. The electrolyte consists of high-flash-point sulfolane as solvent, molecular-orbital-engineered additives that enable stable B-F rich cathodic interphase, and unique C-F rich organic anodic interphase. The stable cycling of both Li metal anode and 4.75 V-LiCoO2 cathode in the DIS electrolyte (> 500 cycles) is demonstrated. HV-LMB pouch cells of a high energy density (435 Wh kg-1) can sustainably operate for more than 100 cycles. Moreover, the low cost and high thermal stability of the DIS electrolyte offer superior cost-effectiveness and safety for large-scale applications of HV-LMBs in the future.

Regulating Non-Equilibrium Solvation Structure in Locally Concentrated Ionic Liquid Electrolytes for Wide-Temperature and High-Voltage Lithium Metal Batteries.

The development of high-voltage lithium metal batteries (LMBs) encounters significant challenges due to aggressive electrode chemistry. Recently, locally concentrated ionic liquid electrolytes (LCILEs) have garnered attention for their exceptional stability with both Li anodes and high-voltage cathodes. However, there remains a limited understanding of how diluents in LCILEs affect the thermodynamic stability of the solvation structure and transportation dynamics of Li+ ions. Herein, we propose a wide-temperature LCILEs with 1,3-dichloropropane (DCP13) diluent to construct a non-equilibrium solvation structure under external electric field, wherein the DCP13 diluent enters the Li+ ion solvation sheath to enhance Li+ ion transport and suppress oxidative side reactions at high-nickel cathode (LiNi0.9Co0.05Mn0.05O2, NCM90).Consequently, a Li/NCM90 cell utilizing this LCILE achieves a high capacity retention of 94% after 240 cycles at 4.3 V, also operates stably at high cut-off voltages from 4.4 to 4.6 V and over a wide temperature range from -20 to 60 °C. Additionally, an Ah-level pouch cell with this LCILE simultaneously achieves high-energy-density and stable cycling, manifesting the practical feasibility. This work redefines the role of diluents in LCILEs, providing inspiration for electrolyte design in developing high-energy-density batteries.

Surface Coordination of Garnet Fillers Improves the Organic-Inorganic Interfacial Compatibility of Composite Solid Electrolyte.

Composite solid electrolytes (CSEs) have become one of the most promising solid-state electrolytes due to their favorable safety and flexibility. However, the weak interaction between inorganic fillers and polymer matrix leads to poor organic-inorganic interfacial compatibility, which degrades the electrochemical performance of CSEs. Herein, it is demonstrated that Li6.4La3Zr1.4Ta0.6O12 (LLZTO) can be chemically bonded to the polymer matrix by surface coordination of the 1,2-dithiolane group of lipoic acid (LA) with metal atoms on the surface of LLZTO through a combination of experimental investigations and theoretical calculations. The surface coordination not only enhances the interfacial compatibility between LLZTO and the polymer matrix, but also facilitates rapid Li+ transport, which leads to the ionic conductivity of the prepared CSE (P-V-M@LLZTO) as high as 6.1 × 10-4 S cm-1 at 30 °C. The excellent interface compatibility ensures a stable cycle of Li/P-V-M@LLZTO/Li symmetrical cell for more than 3500 h. As a result, LiFePO4/P-V-M@LLZTO/Li cell delivers the discharge capacity of 161 mAh g-1 after 5 cycles with a capacity retention of 81% after 500 cycles at 0.5C under 30 °C. This work demonstrates that surface coordination is an effective strategy to solve the inherent interfacial incompatibility problem in CSEs.

Exploring Chemical and Electrochemical Limitations in Sulfide Solid State Electrolytes: A Critical Review on Current Status and Manufacturing Scope.

Lithium-ion batteries (LIBs) have gained recognition for their high energy density and cost-effectiveness. However, issues such as safety concerns, dendrite formation, and limited operational temperatures necessitate alternative solutions. A promising approach involves replacing flammable liquid electrolytes with non-flammable solid electrolytes (SEs). SEs represent a transformative shift in battery technology, offering stability, safety, and expanded temperature ranges. They effectively mitigate dendrite growth, enhancing battery reliability and lifespan. SEs also improve energy density, making them crucial for applications like portable gadgets, electric vehicles, and renewable energy storage. However, challenges such as ionic conductivity, chemical and thermal stability, mechanical strength, and manufacturability must be addressed. This review paper briefly identifies SE types, discusses their advantages and disadvantages, and explores ion transport fundamentals and all-solid-state batteries (ASSBs) production challenges. It comprehensively analyzes sulfide SEs (SSEs), focusing on recent advancements, chemical and electrochemical challenges, and potential future improvements. Electrochemical reactions, electrolyte materials, compositions, and cell designs are critically assessed for their impact on battery performance. The review also addresses challenges in ASSB production. The objective is to provide a comprehensive understanding of SSEs, laying the groundwork for advancing sustainable and efficient energy storage systems.

Trace Dual-Salt Electrolyte Additive Enabling a LiF-Rich Solid Electrolyte Interphase for High-Performance Lithium Metal Batteries.

The composition and physiochemical properties of the solid electrolyte interphase (SEI) significantly impact the electrochemical cyclability of the Li metal. Here, we introduce a trace dual-salt electrolyte additive (TDEA) that accelerates LiF production from FEC decomposition and improves the LiF distribution, resulting in earlier LiF precipitation and the formation of a LiF-rich SEI on the Li anode. TDEA at a millimolar-level concentration was found to alter the morphology of deposited Li, suppress Li dendrite formation, and increase the cycling time and operating current density for Li anodes. Li∥NCM811 full cells using TDEA-based electrolytes exhibited approximately two times longer lifespan than those without additives. Additionally, the TDEA-based electrolytes enabled a high energy density of 347 Wh kg-1 for 500-mAh pouch cells, maintaining stable cycling over 180 cycles under stringent conditions (N/P = 1.26 and E/C = 2.2 g A h-1). Our findings suggest that the proposed TDEA strategy offers a promising path to achieving high-performance Li metal batteries.

Modulating the Inner Helmholtz Plane towards Stable Solid Electrolyte Interphase by Anion-π Interactions for High-Performance Anode-Free Lithium Metal Batteries.

Anode-free lithium (Li) metal batteries (AFLBs) featured high energy density are viewed as the viable future energy storage technology. However, the irregular Li deposition and unstable solid electrolyte interphase (SEI) on anode current collectors reduce their cycling performance. Here, we propose a concept of anion-recognition electrodes enabled by anion-π interactions to regulate the inner Helmholtz plane (IHP) and electrolyte solvation chemistry for high-performance AFLBs. By engineering the electrodes with electron-deficient aromatic-π systems that possess high permanent quadrupole moment (Qzz ), the anion-π interactions can be generated to concentrate the anions on the electrode surface and tune the IHP structure to construct a stable anion-derived SEI layer, thus achieving highly reversible Li plating/stripping process. Through designing various current collectors with different Qzz values, the intimate correlations among the surface charge of the electrode, competitive adsorption of the IHP, and SEI structures are demonstrated. Particularly, the modified carbon cloth current collector with a high Qzz value (+35.1) delivers a high average Li stripping/plating Coulombic efficiency of 99.1% over 230 cycles in the carbonated electrolyte, enabling a long lifespan and high capacity retention of LiNi0.8Co0.1Mn0.1O2-based AFLBs with a commercial-level areal capacity (4.1 mA h cm-2).

Toward High-Energy-Density Initial-Anode-Free Lithium-Metal Batteries via Ultra-Thin Protective Ion-Transport-Promoting Interface Modification and Surface Prelithiation.

Anode-free lithium-metal batteries (AFLMBs) are desirable candidates for achieving high-energy-density batteries, while severe active Li+ loss and uneven Li plating/stripping behavior impede their practical application. Herein, a trilaminar LS-Cu (LiCPON + Si/C-Cu) current collector is fabricated by radio frequency magnetron sputtering, including a Si/C hybrid lithiophilic layer and a supernatant carbon-incorporated lithium phosphorus oxynitride (LiCPON) solid-state electrolyte layer. Joint experimental and computational characterizations and simulations reveal that the LiCPON solid-state electrolyte layer can decompose into an in situ stout ion-transport-promoting protective layer, which can not only regulate homogeneous Li plating/stripping behavior but also inhibit the pulverization and deactivation of Si/C hybrid lithiophilic layer. When combined with surface prelithiated Li1.2Ni0.13Co0.13Mn0.54O2 (Preli-LRM) cathode, the Preli-LRM||LS-Cu full cell delivers 896.1 Wh kg-1 initially and retains 354.1 Wh kg-1 after 50 cycles. This strategy offers an innovative design of compensating for active Li+ loss and inducing uniform Li plating/stripping behavior simultaneously for the development of AFLMBs.

Advances in Functional Organosulfur-Based Mediators for Regulating Performance of Lithium Metal Batteries.

Rechargeable lithium metal batteries (LMBs) are promising next-generation energy storage systems due to their high theoretical energy density. However, their practical applications are hindered by lithium dendrite growth and various intricate issues associated with the cathodes. These challenges can be mitigated by using organosulfur-based mediators (OSMs), which offer the advantages of abundance, tailorable structures, and unique functional adaptability. These features enable the rational design of targeted functionalities, enhance the interfacial stability of the lithium anode and cathode, and accelerate the redox kinetics of electrodes via alternative reaction pathways, thereby effectively improving the performance of LMBs. Unlike the extensively explored field of organosulfur cathode materials, OSMs have garnered little attention. This review systematically summarizes recent advancements in OSMs for various LMB systems, including lithium-sulfur, lithium-selenium, lithium-oxygen, lithium-intercalation cathode batteries, and other LMB systems. It briefly elucidates the operating principles of these LMB systems, the regulatory mechanisms of the corresponding OSMs, and the fundamentals of OSMs activity. Ultimately, strategic optimizations are proposed for designing novel OSMs, advanced mechanism investigation, expanded applications, and the development of safe battery systems, thereby providing directions to narrow the gap between rational modulation of organosulfur compounds and their practical implementation in batteries.

Designing a Refined Multi-Structural Polymer Electrolyte Framework for Highly Stable Lithium-Metal Batteries.

Rational structural designs of solid polymer electrolytes featuring rich interface-phase morphologies can improve electrolyte connection and rapid ion transport. However, these rigid interfacial structures commonly result in diminished or entirely inert ionic conductivity within their bulk phase, compromising overall electrolyte performance. Herein, a multi-component ion-conductive electrolyte was successfully designed based on a refined multi-structural polymer electrolyte (RMSPE) framework with uniform Li+ solvation chemistry and rapid Li+ transporting kinetics. The RMSPE is constructed via polymerization-induced phase separation based on a rational combination of lithiophilic components and rigid/flexible chain units with significant hydrophobic/hydrophilic contrasts. Further refined by coating a robust polymer network, this all-organic design endows a homogenous micro-nano porous structure, providing a novel framework favorable for rapid ion transport in both its soft interfacial and bulk phases. The RMSPE exhibited excellent ion conductivity of 1.91 mS cm-1 at room temperature and a high Li+ transference number of 0.7. Assembled symmetrical Li cells realized stable cycling for over 2400 h at 3.0 mA cm-2. LiFePO4 full batteries demonstrated a long lifespan of 3300 cycles with a capacity retention of 93.5% and stable cycling performance at -35 °C. This innovative design concept offers a promising perspective for achieving high-performance polymer-based Li metal batteries.

A Review of Carbon Nanofiber Materials for Dendrite-Free Lithium-Metal Anodes.

Lithium metal is regarded as ideal anode material due to its high theoretical specific capacity and low electrode potential. However, the uncontrollable growth of lithium dendrites seriously hinders the practical application of lithium-metal batteries (LMBs). Among various strategies, carbon nanofiber materials have shown great potential in stabilizing the lithium-metal anode (LMA) due to their unique functional and structural characteristics. Here, the latest research progress on carbon nanofibers (CNFs) for LMA is systematically reviewed. Firstly, several common preparation techniques for CNFs are summarized. Then, the development prospects, strategies and the latest research progress on CNFs for dendrite-free LMA are emphatically introduced from the perspectives of neat CNFs and CNF-based composites. Finally, the current challenges and prospects of CNFs for stabilizing LMA are summarized and discussed. These discussions and proposed strategies provide new ideas for the development of high-performance LMBs.

H3PO4-Impregnated Covalent Organic Framework Membrane on Separators to Prevent Lithium Metal Anode Dendrite Growth.

Inhibiting the growth of lithium dendrites is crucial for battery safety. For separators, their favorable electrolyte wettability, uniform current density, and high ionic conductivity are beneficial for avoiding Li dendrite growth. In this work, we propose a separator (PA@COF/PP) by modifying a polypropylene separator with H3PO4-functionalized covalent organic frameworks. The uniform channels of the covalent organic frameworks and H3PO4 can homogenize the current and act as ionic conductors for efficient Li+ migration. The synthesized separator effectively suppresses the growth of lithium dendrites and improves the stability of the batteries. A symmetric cell with the PA@COF/PP separator exhibits a stable life span over 4000 hours at a high current density of 5 mA cm-2, compared to the commercial PP separator, which lasts only 159 hours. This work provides an efficient method and novel inspiration for the construction of dendrite-free lithium metal batteries.

Bimetal Fluorides with Adjustable Vacancy Concentration Reinforcing Ion Transport in Poly(ethylene oxide) Electrolyte.

The poor ambient ionic transport properties of poly(ethylene oxide) (PEO)-based SPEs can be greatly improved through filler introduction. Metal fluorides are effective in promoting the dissociation of lithium salts via the establishment of the Li-F bond. However, too strong Li-F interaction would impair the fast migration of lithium ions. Herein, magnesium aluminum fluoride (MAF) fillers are developed. Experimental and simulation results reveal that the Li-F bond strength could be readily altered by changing fluorine vacancy (VF) concentration in the MAF, and lithium salt anions can also be well immobilized, which realizes a balance between the dissociation degree of lithium salts and fast transport of lithium ions. Consequently, the Li symmetric cells cycle stably for more than 1400 h at 0.1 mA cm-2 with a LiF/Li3N-rich solid electrolyte interphase (SEI). The SPE exhibits a high ionic conductivity (0.5 mS cm-1) and large lithium-ion transference number (0.4), as well as high mechanical strength owing to the hydrogen bonding between MAF and PEO. The corresponding Li//LiFePO4 cells deliver a high discharge capacity of 160.1 mAh g-1 at 1 C and excellent cycling stability with 100.2 mAh g-1 retaining after 1000 cycles. The as-assembled pouch cells show excellent electrochemical stability even at rigorous conditions, demonstrating high safety and practicability.

Tailoring the Electrode-Electrolyte Interface for Reliable Operation of All-Climate 4.8†V Li||NCM811 Batteries.

Combining high-voltage nickel-rich cathodes with lithium metal anodes is among the most promising approaches for achieving high-energy-density lithium batteries. However, most current electrolytes fail to simultaneously satisfy the compatibility requirements for the lithium metal anode and the tolerance for the ultra-high voltage NCM811 cathode. Here, we have designed an ultra-oxidation-resistant electrolyte by meticulously adjusting the composition of fluorinated carbonates. Our study reveals that a solid-electrolyte interphase (SEI) rich in LiF and Li2O is constructed on the lithium anode through the synergistic decomposition of the fluorinated solvents and PF6 - anion, facilitating smooth lithium metal deposition. The superior oxidation resistance of our electrolyte enables the Li||NCM811 cell to deliver a capacity retention of 80 % after 300 cycles at an ultrahigh cut-off voltage of 4.8 V. Additionally, a pioneering 4.8 V-class lithium metal pouch cell with an energy density of 462.2 Wh kg-1 stably cycles for 110 cycles under harsh conditions of high cathode loading (30 mg cm-2), low N/P ratio (1.18), and lean electrolytes (2.3 g Ah-1).

Ionic Covalent Organic Framework Solid-State Electrolytes.

Rechargeable secondary batteries, widely used in modern technology, are essential for mobile and consumer electronic devices and energy storage applications. Lithium (Li)-ion batteries are currently the most popular choice due to their decent energy density. However, the increasing demand for higher energy density has led to the development of Li metal batteries (LMBs). Despite their potential, the commonly used liquid electrolyte-based LMBs present serious safety concerns, such as dendrite growth and the risk of fire and explosion. To address these issues, using solid-state electrolytes in batteries has emerged as a promising solution. In this Perspective, recent advancements are discussed in ionic covalent organic framework (ICOFs)-based solid-state electrolytes, identify current challenges in the field, and propose future research directions. Highly crystalline ion conductors with polymeric versatility show promise as the next-generation solid-state electrolytes. Specifically, the use of anionic or cationic COFs is examined for Li-based batteries, highlight the high interfacial resistance caused by the intrinsic brittleness of crystalline ICOFs as the main limitation, and presents innovative ideas for developing all- and quasi-solid-state batteries using ICOF-based solid-state electrolytes. With these considerations and further developments, the potential for ICOFs is optimistic about enabling the realization of high-energy-density all-solid-state LMBs.

Organic Cationic-Coordinated Perfluoropolymer Electrolytes with Strong Li+-Solvent Interaction for Solid State Li-Metal Batteries.

The practical application of solid-state polymer lithium-metal batteries (LMBs) is plagued by the inferior ionic conductivity of the applied polymer electrolytes (PEs), which is caused by the coupling of ion transport with the motion of polymer segments. Here, solvated molecules based on ionic liquid and lithium salt with strong Li+-solvent interaction are inserted into an elaborately engineered perfluoropolymer electrolyte via ionic dipole interaction, extensively facilitating Li+ transport and improving mechanical properties. The intensified formation of solvation structures of contact ion pairs and ionic aggregates, as well as the strong electron-withdrawal properties of the F atoms in perfluoropolymers, give the PE high electrochemical stability and excellent interfacial stability. As a result, Li||Li symmetric cells demonstrate a lifetime of 2500 h and an exceptionally high critical current density above 2.3 mA cm-2, Li||LiFePO4 batteries exhibit consistent cycling for 550 cycles at 10 C, and Li||uncoated LiNi0.8Co0.1Mn0.1O2 cells achieve 1000 cycles at 0.5 C with an average Coulombic efficiency of 98.45%, one of the best results reported to date based on PEs. Our discovery sheds fresh light on the targeted synergistic regulation of the electro-chemo-mechanical properties of PEs to extend the cycle life of LMBs.

Non-Fluorinated Cyclic Ether-Based Electrolyte with Quasi-Conjugate Effect for High-Performance Lithium Metal Batteries.

Fluorinated ether-based electrolytes are commonly employed in lithium metal batteries (LMBs) to attenuate the coordination ability of ether solvents with Li+ and induce inorganic-rich interphase, whereas fluorination inevitably introduces exorbitant production expenses and environmental anxieties. Herein, a non-fluorinated molecular design strategy has been conceptualized by incorporating methoxy as an electron-donating group to generate a quasi-conjugate effect for tuning the affinity of Li+-solvent, thereby enabling the cyclic ether solvent 2-methoxy-1,3-dioxolane with weak solvation ability and exceptional Li metal-compatibility. Accordingly, the optimized electrolyte exhibits anion-dominant solvation structure for inorganic-rich interphase and fulfills an impressive Li plating/stripping Coulombic efficiency of 99.6%. As-fabricated Li||LiFePO4 full cells with limited Li (N/P = 2.5) showcase a high capacity retention of 83% after 150 cycles, indicating excellent cycling stability. Moreover, the full LMBs demonstrate exceptional tolerance towards a wide temperature range from -20 oC to 60 oC, displaying a remarkable capacity retention of 90% after 110 cycles at -20 oC. Such a molecular design strategy offers a promising avenue for electrolyte engineering beyond fluorination in order to cultivate high-performance LMBs.

Conducting Composite Polymer-Based Solid-State Electrolyte with High Ion Conductivity via Amorphous Condensed Structure and Multiple Li+ Transport Channels.

Traditional PEO electrolyte has high crystallinity which hinders the transmission of Li+, resulting in poor ion conductivity and complicated processing technology. Herein, a polymer electrolyte (p-electrolyte) with a wide electrochemical window and high ionic conductivity is designed, which possesses an amorphous condensed structure. The amorphous structure provides fast transport channels for Li+, so the p-electrolyte possesses an electrochemical window of 4.2 V, and high ionic conductivity of 1.58 × 10-5 S cm-1 at room temperature, which is 1-2 orders of magnitude higher than that of traditional PEO electrolyte. By using the designed polymer electrolyte as the foundation, an in situ curable composite polymer electrolyte (CPE-L) with multiple Li+ transport channels is elaborately constructed. The Cu-BTC MOF stores abundant Li+, which is introduced into the p-electrolyte. The rich unsaturated Cu2+ coordination sites of Cu-BTC can anchor TFSI- to release Li+, and the pore structure of Cu-BTC MOF cooperates with LLZTO nanoparticles to provide multiple fast transport channel for Li+, resulting in remarkable ionic conductivity (1.02 × 10-3 S cm-1) and Li+ transference number (0.58). The Li||CPE-L||Li symmetric battery cycles stably for more than 700 h at 0.1 mA cm-2, while the specific capacity of full battery is ≈153 mAh g-1 (RT, 0.2 C).

Magnetic field-assisted vertically aligned NiFe2O4 nanosheets in composite solid polymer electrolytes for advanced all solid-state lithium metal batteries.

Two-dimensional materials (2D Ms) as fillers have been applied in polyethylene oxide (PEO)-based electrolyte to enhance the low ionic conductivity and poor interface compatibility. However, the randomly dispersed fillers in PEO matrix result in anisotropy of Li+ transportation and insufficent ionic conductivity. Herein, NiFe2O4 (NFO) nanosheets are firstly introduced in polymer matrix to form vertically aligned NFO-PEO (ANFO-PEO) composite solid-state electrolytes (CSEs) through magnetic field-assisted alignment strategy. The vertically aligned NFO/PEO interface in CSEs can construct oriented Li+ transport channels and maximize the utilization of high in-plane conductivity. Meanwhile, the NFO nanosheets with abundant oxygen vacancies could effectively anchor TFSI- to promote the dissociation of Li salts. Furthermore, the optimized Li+ transport flux in CSEs enables homogeneous Li deposition and effectively mitigates the growth of dendrites. Owing to the synergistic effects, the ANFO-PEO CSEs exhibit high ionic conductivity (9.16 × 10-4 S cm-1 at 60 °C) and stable potential window up to 5.0 V vs Li/Li+. Therefore, LiFePO4 in the full cell and pouch cell with ANFO-PEO CSEs could deliver excellent cycling performance (92.78 % capacity retention after 1000 cycles at 0.5C; 96.88 % capacity retention after 105 cycles at 0.1C).

Aluminum Corrosion Chemistry in High-Voltage Lithium Metal Batteries with LiFSI-Based Ether Electrolytes.

High-voltage Li metal batteries (LMBs) based on ether electrolytes hold potential for achieving high energy densities exceeding 500 Wh kg-1, but face challenges with electrolyte oxidative stability, particularly concerning aluminum (Al) current collector corrosion. However, the specific chemistry behind Al corrosion and its effect on electrolyte components remains unexplored. Here, our study delves into Al corrosion in the representative LiFSI-DME electrolyte system, revealing that low-concentration electrolytes exacerbate Al current collector corrosion and solvent decomposition. In contrast, high-concentration electrolytes mitigate these issues, enhancing long-term stability. Remarkably, LiFSI-0.7DME electrolyte demonstrates exceptional stability with up to 1000 cycles at high voltage without significant capacity decay. These findings offer crucial insights into Al corrosion mechanisms in ether-based electrolytes, advancing our comprehension of high-voltage LMBs and facilitating their development for practical applications.