Li Cells Research Articles

Multilayer asymmetric solid polymer electrolyte with modified interface for high-voltage solid-state Li metal batteries

Solid polymer electrolytes (SPEs) are promising for achieving safe solid-state Li metal batteries (SSLMBs). However, unstable electrode/electrolyte interface contact of SPEs limits their application at high voltage. To address this issue, we designed a multi-layer asymmetric SPE with a sandwich structure based on the hydroxyapatite (HAP) enhanced PVDF-HFP matrix. Two different interfacial modification layers were introduced on the anode and cathode sides. Methyl (2,2,2-trifluoromethyl) carbonate (FEMC) and tetramethylene sulfone (TMS) were selected as plasticizers in the layers, respectively, contacting the anode and cathode to reduce the reactivity of the anode interface and enhance the high-voltage compatibility of the cathode interface. Unlike usual designs, each layer of the asymmetric SPE has essentially the same composition except the plasticizers, effectively eliminating interface resistance and promoting Li+ fast migration. Consequently, the asymmetric SPE exhibits excellent ionic conductivity at room temperature (8.8 × 10−4 S cm−1), superior interfacial stability, and Li dendrite inhibition ability. In addition, LiFePO4||SPE||Li cell demonstrates a stable retention rate of over 92 % after 500 cycles at 1 C. These findings provide a new approach for implementing SSLMBs under high voltage.

Toward high-performance ionic liquid-based quasi-solid-state electrolytes: Tunable electrochemical properties by introducing suitable diluents

Superior to conventional liquid electrolytes, incombustible ionic liquids (ILs) with wide electrochemical stability windows show privilege to endow quasi-solid-state electrolyte (QSE) with benign interfacial contact with both metallic Li and high-voltage cathode, which bodes well for implementation of high-performance solid-state Li metal battery. But regardless of its merits, the inherent high-viscosity and frail interphase chemistry of IL towards cathodes still jeopardize ionic conductivity within QSE and even crossing the interface, and should be overcame. Herein, we creatively introduce N, N-Dimethyltrifluoroacetamide (FDMAC) into QSE fabrication, design a quasi-solid-state electrolyte (QSE-EF) by hybridizing FDMAC/EMImFSI-based IL mixture and nano-LLZTO@PVDF-HFP. This FDMAC with well compatibility to IL, significantly decreases the viscosity but without sacrificing noncombustible feature. With the aid of FDMAC, QSE-EF exhibits fast ion-conducting and high Li+ transference number. More importantly, FDMAC also contributes to tuning interphase chemistry, and therefore, the high compatibilities of both QSE-EF|Li and QSE-EF|NCM622 interfaces are fulfilled involving profitable CEI&SEI establishment. Consequently, the assembled NCM622|QSE-EF|Li cell delivers outstanding electrochemical behaviors even at 4.4 V high voltage. 1.0 Ah NCM811ǁLi pouch cell also shows satisfactory energy density (350 Wh·kg−1) with negligible capacity loss. This work provides a feasible strategy to circumvent inherent defect of ionic liquid in QSE, and emphasizes the importance of tuning compatible interfacial chemistry in further QSE design.

A novel hierarchical “ceramic in polymer - polymer in ceramic” structure composite solid-state electrolyte for safer lithium ion batteries

The development of advanced composite solid-state electrolytes (CSSEs) is considered to be one of the most promising solutions for technological breakthroughs in lithium ion batteries (LIBs). However, it is challenging to fabricate satisfied CSSEs that can meet requirements from mechanical, thermal, safety, and electrochemical perspectives at the same time. Herein, a novel CSSE with the “ceramic in polymer - polymer in ceramic (CIP–PIC)” hierarchical structure is introduced, which exhibits enhanced mechanical properties, safer thermal behavior, and better fire resistance compared to conventional Polyethylene oxide (PEO) solid-polymer electrolytes (SPEs). The fabricated PMC10 CSSE shows a crystallinity of 15.2 %, a Young's modulus of 3.1 MPa, and an optimal ionic conductivity of 2.33 × 10−4 S cm−1 at 50 °C. The compatible interface enables assembled symmetrical Li cells stable plating/stripping galvanostatic cycles for 900 h at 0.2 mA cm−2. The LiFePO4|PMC10|Li cell shows an initial capacity density of 158.5 Ah kg−1, and a capacity retention of 80.3 % after 200 cycles. More importantly, compared to PEO SPE, a reduction of 33.4 % of the heat release capacity (HRC) verifies the enhanced fire safety performance of PMC10 CSSE. This work provides an effective approach for the development of CSSEs for the realization of fire-safer LIBs.

Highly concentrated solvation structure for reversible high-voltage lithium-ion battery at low temperature

The commercial electrolytes exhibit subpar performance under low temperature and high voltage, severely limiting the application of lithium-ion batteries (LIBs) for extreme temperature and high energy density. As a groundbreaking advancement, the regulation of Li+ solvation structure was adopted and highly concentrated in this work, obtaining an improved electrolyte with excellent low-temperature and high-voltage performance. The electrolyte exhibited outstanding oxidation potential of 5.25 V and high ionic conductivity, maintaining transparency liquid even at −60 °C. Notably, the NCM811||Li cell exhibited high initial capacity (71.41 % of that at room temperature) at −40 °C 0.2C, with almost no capacity decay after 50 cycles. Impressively, the as-assembled NCM811||Graphite pouch battery (2.5 Ah) showed an initial capacity of 2.07 Ah at 0.1C under −30 °C, with an excellent capacity retention ratio of 84.53 % after 50 cycles. This work points out a promising approach for the practical application of high-voltage LIBs at low temperature.

Ni(OH)2 nanosheets modified Prussian blue tubes to construct buffer layer for lithium dendrite regulation

Although the Li metal anode has a high theoretical capacity and low potential, the uncontrolled growth of Li dendrites and the significant volume variation of the Li anode prevent the practical deployment of lithium metal batteries (LMBs). To effectively control the Li dendrite growth with suppression, in this contribution, the Ni(OH)2 nanosheets modified Prussian blue tubes (PBT/Ni(OH)2) are employed to construct a three-dimensional framework (3D) on the surface of Li. The PBT can homogenize the Li+ flux, while the Ni(OH)2 nanosheets provide sufficient space to accommodate the volume change of Li. Thus, the growth of Li dendrites is largely suppressed compared to pristine Li. In detail, with the introduction of PBT/Ni(OH)2, the Li||Li cells provide 500 h of consistent cycling performance at 1 mA cm−2, while the Li||Li4Ti5O12 (LTO) cells also exhibit superior cycle reversibility over 450 cycles at 175 mAh g−1.

Ionic Liquid Boosting the Electrochemical Stability of a Poly(1,3-dioxolane) Gel Electrolyte for High-voltage Solid-State Lithium Batteries.

Poor interfacial contact between solid-state electrolytes and electrodes limits high-voltage performance of solid-state lithium batteries. A new gel electrolyte is proposed via in-situ polymerization, incorporating fluoroethylene carbonate (FEC) solvent and ionic liquid1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide (PP14 TFSI). This combination synergistically enhances Li ion transport, achieving a transfer number of 0.58 and improved electrochemical performance. FEC protects the Al current collectors from LiPF6 corrosion and promotes a protective interfacial layer formation. PP14 TFSI improves interfacial contact and provides stable components. An interface layer of fluorine and nitrogen composites forms, preventing side reactions. LiCoO2 ||PPE||Li cell exhibits robust cycling stability at 4.45 V, retaining ~80 % capacity after 200 cycles at room temperature with 0.2 C and 1 C rates, showing increased coulombic efficiency. NCM811||PPE||Li cell also displays exceptional cycling. In-situ polymerization and FEC-ionic liquid coordination enable high-voltage solid-state lithium metal batteries for practical use.

Highly conductive and nonflammable boron-based gel type single ion conducting electrolyte membranes toward high-safety and dendrite-free lithium metal batteries

Single-ion conducting polymer electrolytes (SIPEs), having a high Li-ion transference number (tLi+) close to unity, hold great promise for circumventing the lithium dendrite growth of lithium metal batteries (LMBs). However, SIPEs synthesized by a simple method that also simultaneously fulfill the requirements of high ionic conductivity, good thermal stability, and remarkable fire resistance are still quite rare. Herein, a novel single-ion conducting fibrous membrane (es-DDBSB-Li) based on borate anions of single-ion conductors (denoted as DDBSB-Li) and poly(vinylidene fluoride-hexafluoropropylene) P(VDF-HFP) as a binder was prepared via facile electrospinning technology. The introduction of borate anions promotes the homogeneous distribution of highly concentrated Li-ions and accelerates the ionic migration, leading to an enhanced ionic conductivity of 3.75 × 10−4 S cm−1 at 25 °C for DDBSB-Li saturated with organic solvents. Additionally, the thermally stable and nonflammable DDBSB-Li endows the resultant fibrous membranes to possess good high-temperature stability and fire-resistance properties. The Li||Li cell using this electrolyte displays a high tLi+ of 0.91 and effectively mitigates concentration polarization, thereby enabling a remarkably stable cyclic performance over 2000 h at 2.5 mA cm−2 at 25 °C. Also, this gel SIPE-based Li||LiFePO4 battery demonstrates superior rate performances up to 3C and delivers long-term cycling durability over 600 cycles under 1C at 25 °C. We believe this novel gel SIPE-based fibrous membrane has great potential for practical application in high-safety and dendrite-proof LMBs.

A composite solid-state electrolyte of high ionic-conductivity garnet-type Li6.5La3Zr1.5Ta0.1Nb0.4O12 filler in PEO matrix

In this work, highly ionically conductive Li6.5La3Zr1.5Ta0.1Nb0.4O12 (LLZTNO) fillers were blended into a poly(ethylene oxide) matrix to construct a composite solid-state electrolyte (CSSE). The LLZTNO fillers decrease the crystallinity of the PEO and provide extra lithium-ion transport pathways. Additionally, TFSI− anions are immobilized by the LLZTNO ceramic powders, and more Li ions are mobilized, increasing the overall ionic conductivity in CSSE. The PEO-LiTFSI-10% LLZTNO (i.e., PL-LLZTNO10%) CSSE shows the highest conductivity of 0.36 × 10−4 S cm−1 with a broad voltage window of 4.7 V at room temperature. The Li/ PL-LLZTNO10% CSSE/Li symmetric cells could operate for approximately 1200 h at 63 mV polarization voltage. The assembled solid-state LFP/PL-LLZTNO10%/Li cells deliver a 158.3 mAh g−1 capacity at 0.2C and 60 °C. After 300 cycles, its specific discharge capacity remains at 143.5 mAh g−1 with a Coulombic efficiency of 99.54%.

Dual-layer composite solid polymer electrolytes with Janus properties for interface modification of solid state lithium metal batteries

Solid polymer electrolytes are widely applied in lithium metal batteries owing to good flexibility and machinability. However, monolayer polymer electrolyte are difficult to simultaneously satisfy the interfacial contact with the cathode and Li anode. Herein, the dual-layer composite solid polymer electrolyte with polypropylene film (CSPE@PP) are designed to promote the interfacial compatibility between the solid electrolytes and electrodes. The X-ray photoelectron spectroscopy (XPS) results confirm that poly (vinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) can react with Li metal to form LiF layer, restraining the Li dendrite growth. Meanwhile, the polyacrylonitrile (PAN) antioxidant layer strengthens the contact stability between the electrolytes and the cathodes. Moreover, the PP film serves as the electrolyte's skeleton and connecting layer, enhancing the ion diffusion and mechanical strength of the solid electrolytes. As a result, the Li||CSPE@PP||Li cell is able to stably cycle over 400 h at 0.1 mA cm−2. The LFP||CSPE@PP||Li solid-state batteries deliver 141.98 mAh g−1 discharge capacity and high retention rate (91.1%) after 100 cycles at 0.1C. This work provides a viable strategy for expanding the application of composite solid polymer electrolyte (CSPE) in lithium metal batteries.

Nafion-212 Membrane Solvated by Ethylene and Propylene Carbonates as Electrolyte for Lithium Metal Batteries.

The use of cation-exchange membranes as electrolytes for lithium metal batteries can prevent the formation of lithium dendrites during extended cycling and guarantee safe battery operation. In our study, the Nafion-212 membrane in lithium form solvated by a mixture of ethylene carbonate and propylene carbonate (EC-PC) was used as an electrolyte in a lithium metal battery with the LiFePO4 cathode. The Nafion-212-EC-PC electrolyte is electrochemically stable up to 6 V, indicating its suitability for high-energy density batteries. It has an ionic conductivity of 1.9 × 10-4 S/cm at 25 °C and a high lithium transference number. The symmetric Li|Nafion-212-EC-PC|Li cell shows a very low overvoltage of ~0.3 V at a current density of ±0.1 mA/cm2. At 25 °C, the LiFePO4|Nafion-212-EC-PC|Li battery exhibits a capacity of 141, 136, 125, and 100 mAh/g at 0.1, 0.2, 0.5, and 1C rates, respectively. It maintains a capacity of 120 mAh/g at 0 °C and 0.1C with stable performance for 50 charge/discharge cycles. The mechanism of conductivity and capacity retention at low temperatures is discussed.

Reinforcing interfacial compatibility of LLZTO/PVDF-HFP composite electrolytes by chemical interaction for solid-state lithium metal batteries

Composite electrolytes (CEs) have a significant potential for achieving excellent safety and energy density in solid-state lithium metal batteries owing to applicable ionic conductivity, easy fabrication, and good electrochemical properties. However, achieving good interfacial compatibility between inorganic fillers and polymer matrix remains challenging. Herein, we design a Li6.4La3Zr1.4Ta0.6O12 filler modified with isopropyl tri(dioctyl pyrophosphate) titanate for poly (vinylidene fluoride-co-hexafluoropropylene) electrolyte (denoted as Ti@LLZTO/PVDF-HFP). We reveal the enhanced mechanism of a modified interface on the electrochemical performance by combining experimental results and theoretical calculations. The reinforced interface can facilitate the uniform dispersion of filler in the polymer matrix as well as dissociate more lithium salt, which enables enhanced ionic conductivity (6.86 × 10−5 S cm−1 at 30 °C). Besides, the Ti@LLZTO can immobilize the anions in lithium salt via hydrogen bonding interactions and the Ti–O chemical bonding. Consequently, the Li||Ti@LLZTO/PVDF-HFP||Li cell shows great cyclability over 1550 h at 0.1 mA cm−2, 0.1 mAh cm−2. Moreover, the Li||Ti@LLZTO/PVDF-HFP||LFP cell achieves superior cycling stability at 0.5 C with a high Coulombic efficiency of 98.8 %. This work provides an insightful understanding of designing good interfacial compatibility for advanced composite electrolytes.

Self-healing polyurethane-based polymer electrolyte with high strength for all-solid-state lithium metal batteries

Polyethylene oxide, as one of the most common polymers, has been extensively studied for solid-state polymer electrolytes. However, its poor mechanical properties and low ionic conductivity severely limit its application. Herein, a series of double dynamic self-healing polyurethane polymer electrolyte (PUSPE-X) with hydrogen bonds and dynamic urea bonds was prepared by a simple polycondensation reaction. The constructed network exhibits excellent mechanical properties, strong self-healing and good shape memory properties. Benefiting from the oxygens in the PEG segment and the nitrogen atom in the imide (–NH–) group simultaneously act as electron donor to form coordination bonds with lithium ions by coulombic interaction, further promoting the anion and cation of the lithium salt to dissociate, the PUSPE-6000 demonstrates good ion conductivity of 0.127 m S cm−1 and satisfactory lithium-ion transference number (tLi+=0.55) at 60 °C. The Li|PUSPE-6000|Li symmetric cell works stable for 1200 h at 0.1 mA cm−2 and the LFP|PUSPE-6000|Li cell also achieves excellent cycling stability. The flexible battery based on PUSPE-6000 can continue to work under a variety of harsh conditions, which expand the choice for the all solid-state electrolyte in the flexible wearable electronic device.

A magnetic-assisted construction of functional gradient interlayer for dendrite-free solid-state lithium batteries

Garnet-based solid-state Li batteries are considered as important candidates of the next generation batteries due to their potentially high energy density and reliable safety, however the Li dendrite issue is a serious impediment to their further development. Herein, a functional gradient interlayer (FGIL) is introduced at the interface between the garnet and Li anode, which is formed by the in-situ reaction of molten Li with FeF3 assisted by a magnetic force. The FGIL not only reduces the interfacial impedance, evens out the local current distribution, and prevents the growth of Li dendrites on the electrode surface, but also blocks electron transport and prevents the formation of "Li filaments" inside the electrolyte. Consequently, the Li|LLZTO-FGIL|Li cells have a critical current density of up to 2.3 mA cm−2 and exhibit stable cycling for more than 3400 h at 0.3 mA cm−2.

SEI growth on Lithium metal anodes in solid-state batteries quantified with coulometric titration time analysis

Lithium-metal batteries with a solid electrolyte separator are promising for advanced battery applications, however, most electrolytes show parasitic side reactions at the low potential of lithium metal. Therefore, it is essential to understand how much (and how fast) charge is consumed in these parasitic reactions. In this study, a new electrochemical method is presented for the characterization of electrolyte side reactions occurring on active metal electrode surfaces. The viability of this new method is demonstrated in a so-called anode-free stainless steel ∣ Li6PS5Cl ∣ Li cell. The method also holds promise for investigating dendritic lithium growth (and dead lithium formation), as well as for analyzing various electrolytes and current collectors. The experimental setup allows easy electrode removal for post-mortem analysis, and the SEI’s heterogeneous/layered microstructure is revealed through complementary analytical techniques. We expect this method to become a valuable tool in the future for solid-state lithium metal batteries and potentially other cell chemistries.

A Non-Expendable Leveler as Electrolyte Additive Enabling Homogenous Lithium Deposition.

Li metal anodes are extensively studied owing to their unparalleled advantages in achieving high energy density. However, safety issues originating from dendritic Li growth are always a huge hindrance for applications in Li metal batteries (LMBs). In this study, a functional additive, 4,6-dimethyl-2-mercaptopyrimidine (DMP), which is a typical leveler in the copper electroplating industry, is selected to suppress Li dendrite formation. Various Li-metal-based batteries are systematically investigated and they show stable performances, such as excellent cycling stability above 800h at 3mAcm-2 in Li||Li cells and 400 cycles with high coulombic efficiencies (CEs >98%) at 1mAcm-2 in Li||Cu cells. Furthermore, a comprehensive verification of the protective mechanism induced by the DMP leveling agent shows that the leveler updated the Li+ solvation structure and occupied the inner Helmholtz plane of the Li anode. The planar DMP molecular layer absorbed on the surface of the Li metal can suppress side reactions and modify the Li deposition behavior via steric hindrance, inducing homogeneous Li deposition. Interestingly, the DMP leveler does not participate in the formation of the solid electrolyte interphase. This study can stimulate further ideas on non-depleting but effective levelers as electrolyte additives for high-performance LMBs.

In-situ electrochemical optical techniques in the investigation of lithium interfacial phenomena with a liquid and a solid-state electrolyte

An in-situ electrochemical optical diagnosis is the key to the investigation of electrode interface during a redox reaction. Because the morphology changes particularly, dendrite formation, dendrite shapes, solid electrolyte interface formation and gas generation can be revealed visually. The challenge of ensuring uniform current density on a flat Li anode in a liquid electrolyte is addressed and uniform Li plating is demonstrated. The dendrite shape change under different reduction current density is discussed. The Li dendrite shape change and the performance of Li anodes with a surface lamination of graphite and red phosphate are used as examples to demonstrate the capability of the in-situ optical cell. An in-situ electrochemical optical cell used in the investigation of the increasingly popular solid-state Li batteries has its own challenges. Due to the untransparent nature of a solid-state electrolyte, an optical investigation on a solid-state electrolyte Li battery needs to be done by exposing the cross-section of the cell. In addition, it is very difficult to assemble an optical cell with a brittle and fragile solid-state electrolyte in a glove box. A set of formation and transfer dies, and an optical cell are introduced. The Li dendrite growth at the interface can be observed in a solid-state Li cell.

Computational materials discovery and development for Li and non-Li advanced battery chemistries

Since the discovery of batteries in the 1800s, their fascinating physical and chemical pro­perties have led to much research on their synthesis and manufacturing. Though lithium-ion batteries have been crucial for civilization, they can still not meet all the growing demands for energy storage because of the geographical distribution of lithium resources and the intrinsic limitations in the cell energy density, performance, and reliability issues. As a result, non-Li-ion batteries are becoming increasingly popular alternatives. Designing novel materials with desired properties is crucial for a quicker transition to the green energy ecosystem. Na, K, Mg, Zn, Al ion, etc. batteries are considered the most alluring and promising. This article covers all these Li, non-Li, and metal-air cell chemistries. Recently, com­putational screening has proven to be an effective tool to accelerate the discovery of active materials for all these cell types. First-principles methods such as density functional theory, molecular dynamics, and Monte Carlo simulations have become established techni­ques for the preliminary, theoretical analysis of battery systems. These computational methods generate a wealth of data that might be immensely useful in the training and vali­dating of artificial intelligence and machine learning techniques to reduce the time and capital expenditure needed for discovering advanced materials and final product develop­ment. This review aims to summarize the application of these techniques and the recent deve­lopments in computational methods to discover and develop advanced battery chemistries.

Monodispersed Sub-1nm Inorganic Cluster Chains in Polymers for Solid Electrolytes with Enhanced Li-Ion Transport.

The organic-inorganic interfaces can enhance Li+ transport in composite solid-state electrolytes (CSEs) due to the strong interface interactions. However, Li+ non-conductive areas in CSEs with inert fillers will hinder the construction of efficient Li+ transport channels. Herein, CSEs with fully active Li+ conductive networks are proposed to improve Li+ transport by composing sub-1nm inorganic cluster chains and organic polymer chains. The inorganic cluster chains are monodispersed in polymer matrix by a brief mixed-solvent strategy, their sub-1nm diameter and ultrafine dispersion state eliminate Li+ non-conductive areas in the interior of inert fillers and filler-agglomeration, respectively, providing rich surface areas for interface interactions. Therefore, the 3D networks connected by the monodispersed cluster chains finally construct homogeneous, large-scale, continuous Li+ fast transport channels. Furthermore, a conjecture about 1D oriented distribution of organic polymer chains along the inorganic cluster chains is proposed to optimize Li+ pathways. Consequently, the as-obtained CSEs possess high ionic conductivity at room temperature (0.52mScm-1 ), high Li+ transference number (0.62), and more mobile Li+ (50.7%). The assembled LiFePO4 /Li cell delivers excellent stability of 1000 cycles at 0.5C and 700 cycles at 1C. This research provides a new strategy for enhancing Li+ transport by efficient interfaces.

Taming Active‐Ion Crosstalk by Targeted Ion Sifter Toward High‐Voltage Lithium Metal Batteries

AbstractLithium metal batteries (LMBs), based on high‐voltage (HV) LiNixCoyMnzO2 (NCM, x+y+z = 1) materials, exhibit great potential for next‐generation electric vehicle (EV) cells. Nevertheless, the inevitable dissolution and shuttle of transition metal (TM) ions from NCM cathodes poses a threat to the electrochemical sustainability of LMBs, especially at high voltage and high temperatures. Herein, ethylene diamine tetraacetic acid (EDTA)‐grafted MOF‐808 is proposed to serve as a multifunctional ion‐selective separator coating, in which EDTA molecules play a targeted ion sifter role in restricting active‐ion crosstalk. Judicious characterizations and theoretical calculations reveal that the separator coating effectively captures the TM‐ions in the electrolyte and thus ensures stable Li deposition without dendrites. As a result, the 4.5 V NCM622//Li cell with the ion‐selective separator achieves a high‐capacity retention over 1000 cycles with a high Coulombic efficiency of 99.68%, and its cycling stability at 55 °C is also upgraded. This crosstalk‐taming strategy offers fresh insight into constructing long‐life HV‐LMBs.

Stable Harsh-Temperature Lithium Metal Batteries Enabled by Tailoring Solvation Structure in Ether Electrolytes.

For lithium metal batteries (LMBs), the elevated operating temperature results in severe capacity fading and safety issues due to unstable electrode-electrolyte interphases and electrolyte solvation structures. Therefore, it is crucial to construct advanced electrolytes capable of tolerating harsh environments to ensure stable LMBs. Here, we proposed a stable localized high-concentration electrolyte (LHCE) by introducing the highly solvating power solvent diethylene glycol dimethyl ether (DGDME). Computational and experimental evidence discloses that the original DGDME-LHCE shows favorable features for high-temperature LMBs, including high Li+-binding stability, electro-oxidation resistance, thermal stability, and nonflammability. The tailored solvated sheath structure achieves the preferred decomposition of anions, inducing the stable (cathode and Li anode)/interphases simultaneously, which enables a homogeneous Li plating-stripping behavior on the anode side and a high-voltage tolerance on the cathode side. For the Li||Li cells coupled with DGDME-LHCE, they showcase outstanding reversibility (a long lifespan of exceeding 1900 h). We demonstrate exceptional cyclic stability (∼95.59%, 250 cycles), high Coulombic efficiency (>99.88%), and impressive high-voltage (4.5 V) and high-temperature (60 °C) performances in Li||NCM523 cells using DGDME-LHCE. Our advances shed light on an encouraging ether electrolyte tactic for the Li-metal batteries confronted with stringent high-temperature challenges.