Toluene Tolerated Li9.88GeP1.96Sb0.04S11.88Cl0.12 Solid Electrolyte toward Ultrathin Membranes for All-Solid-State Lithium Batteries.

Sulfide solid electrolyte membranes employed in all-solid-state lithium batteries generally show high thickness and poor chemical stability, which limit the cell-level energy density and cycle life. In this work, Li9.88GeP1.96Sb0.04S11.88Cl0.12 solid electrolyte is synthesized with Sb, Cl partial substitution of P, S, possessing excellent toluene tolerance and stability to lithium. The formed SbS43- group in Li9.88GeP1.96Sb0.04S11.88Cl0.12 exhibits low adsorption energy and reactivity for toluene molecules, confirmed by first-principles density functional theory calculation. Using toluene as the solvent, ultrathin Li9.88GeP1.96Sb0.04S11.88Cl0.12 membranes with adjustable thicknesses can be well prepared by the wet coating method, and an 8 µm thick membrane exhibits an ionic conductivity of 1.9 mS cm-1 with ultrahigh ionic conductance of 1860 mS and ultralow areal resistance of 0.68 Ω cm-2 at 25 °C. The obtained LiCoO2|Li9.88GeP1.96Sb0.04S11.88Cl0.12 membrane|Li all-solid-state lithium battery shows an initial reversible capacity of 125.6 mAh g-1 with a capacity retention of 86.3% after 250 cycles at 0.1 C under 60 °C.

Large Organic Polar Molecules Tailored Electrode Interfaces for Stable Lithium Metal Battery.

Lithium (Li) metal batteries (LMBs) are deemed as ones of the most promising energy storage devices for next electrification applications. However, the uneven Li electroplating process caused by the diffusion-limited Li+ transportation at the Li metal surface inherently promotes the formation of dendritic morphology and instable Li interphase, while the sluggish Li+ transfer kinetic can also cause lithiation-induced stress on the cathode materials suffering from serious structural stability. Herein, a novel electrolyte designing strategy is proposed to accelerate the Li+ transfer by introducing a trace of large organic polar molecules of lithium phytate (LP) without significantly altering the electrolyte structure. The LP molecules can afford a competitive solvent attraction mechanism against the solvated Li+, enhancing both the bulk and interfacial Li+ transfer kinetic, and creating better anode/cathode interfaces to suppress the side reactions, resulting in much improved cycling efficiency of LMBs. Using LP-based electrolyte, the performance of LMB pouch cell with a practical capacity of ~1.5 Ah can be improved greatly. This strategy opens up a novel electrolyte designing route for reliable LMBs.

Flexible Sulfide Electrolyte Thin Membrane with Ultrahigh Ionic Conductivity for All-Solid-State Lithium Batteries.

All-solid-state lithium batteries (ASSLBs) employing Li-metal anode, sulfide solid electrolyte (SE) can deliver high energy density with high safety. The thick SE separator and its low ionic conductivity are two major challenges. Herein, a 30 µm sulfide SE membrane with ultrahigh room temperature conductivity of 8.4 mS cm-1 is realized by mechanized manufacturing technologies using highly conductive Li5.4PS4.4Cl1.6 SE powder. Moreover, a 400 nm magnetron sputtered Al2O3 interlayer is introduced into the SE/Li interface to improve the anodic stability, which suppresses the short circuit in Li/Li symmetric cells. Combining these merits, ASSLBs with LiNi0.5Co0.2Mn0.3O2 as the cathode exhibit a stable cyclic performance, delivering a discharge specific capacity of 135.3 mAh g-1 (1.4 mAh cm-2) with a retention of 80.2% after 150 cycles and an average Coulombic efficiency over 99.5%. The high ionic conductivity SE membrane and interface design principle show promising feasible strategies for practical high performance ASSLBs.

Understanding LiI-LiBr Catalyst Activity for Solid State Li2S/S Reactions in an All-Solid-State Lithium Battery.

Li||MoS2 solid-state batteries have higher volumetric energy density and power density than Li||Li2S batteries. However, they suffer from energy and power decay due to the formation of lithium sulfide that has low ionic/electronic conductivity and a strong Li-S bond. Herein, we overcome these challenges by incorporating the catalytic LiI-LiBr compound and carbon black into MoS2. The comprehensive simulations, characterizations, and electrochemical evaluations demonstrated that LiI-LiBr significantly reduces Li+/S2- interaction and increases the ionic conductivity of Li2S, thus enhancing the reaction kinetics and Li2S/S redox reversibility. MoS2@LiI-LiBr@C||Li cells with an areal capacity of 0.87 mAh cm-2 provide a reversible capacity of 816.2 mAh g-1 at 200 mA g-1 and maintain 604.8 mAh g-1 (based on the mass of MoS2) for 100 cycles. At a high areal capacity of 2 mAh cm-2, the battery still delivers reversible capacity of 498 mAh g-1. LiI-LiBr-carbon additive can be broadly applied for all transition-metal sulfide cathodes to enhance the cyclic and rate performance.

Densified Li6PS5Cl Nanorods with High Ionic Conductivity and Improved Critical Current Density for All-Solid-State Lithium Batteries.

Solid electrolytes are receiving great interest owing to their good mechanical properties and high lithium-ion transference number, which could potentially suppress lithium dendrites. However, lithium dendrites can still penetrate solid electrolytes even at low current densities. In this work, a flat-surface Li6PS5Cl nanorod pellet with high density is achieved, which exhibits an ionic conductivity as high as 6.11 mS cm-1 at 25 °C. The flat surface of the pellet is beneficial for the homogeneous lithium deposition, and the dense pellet microstructure can suppress the growth of lithium dendrites along the grain boundaries, leading to a significantly improved critical current density of 1.05 mA cm-2 at 25 °C. The resultant dense Li6PS5Cl pellet is further employed in a LiCoO2/Li6PS5Cl/Li all-solid-state lithium battery, showing an initial discharge capacity of 115.3 mAh g-1 at 1C (0.35 mA cm-2, 25 °C) with a capacity retention of 80.3% after 100 cycles.

Self-Formed Electronic/Ionic Conductive Fe3 S4  @ S @ 0.9Na3 SbS4 ⋠0.1NaI Composite for High-Performance Room-Temperature All-Solid-State Sodium-Sulfur Battery.

Fe3 S4  @ S @ 0.9Na3 SbS4 ⋅0.1NaI composite cathode is prepared through one-step wet-mechanochemical milling procedure. During milling process, ionic conduction pathway is self-formed in the composite due to the formation of 0.9Na3 SbS4 ⋅0.1NaI electrolyte without further annealing treatment. Meanwhile, the introduction of Fe3 S4 can increase the electronic conductivity of the composite cathode by one order of magnitude and nearly double enhance the ionic conductivities. Besides, the aggregation of sulfur is effectively suppressed in the obtained Fe3 S4  @ S @ 0.9Na3 SbS4 ⋅0.1NaI composite, which will enhance the contact between sulfur and 0.9Na3 SbS4 ⋅0.1NaI electrolyte, leading to a decreased interfacial resistance and improving the electrochemical kinetics of sulfur. Therefore, the resultant all-solid-state sodium-sulfur battery employing Fe3 S4  @ S @ 0.9Na3 SbS4 ⋅0.1NaI composite cathode shows discharge capacity of 808.7 mAh g-1 based on Fe3 S4 @S and a normalized discharge capacity of 1040.5 mAh g-1 for element S at 100 mA g-1 for 30 cycles at room temperature. Moreover, the battery also exhibits excellent cycling stability with a reversible capacity of 410 mAh g-1 at 500 mA g-1 for 50 cycles, and superior rate capability with capacities of 952.4, 796.7, 513.7, and 445.6 mAh g-1 at 50, 100, 200, and 500 mA g-1 , respectively. This facile strategy for sulfur-based composite cathode is attractive for achieving room-temperature sodium-sulfur batteries with superior electrochemical performance.

Construction of 3D Electronic/Ionic Conduction Networks for All-Solid-State Lithium Batteries.

High and balanced electronic and ionic transportation networks with nanoscale distribution in solid-state cathodes are crucial to realize high-performance all-solid-state lithium batteries. Using Cu2 SnS3 as a model active material, such a kind of solid-state Cu2 SnS3 @graphene-Li7 P3 S11 nanocomposite cathodes are synthesized, where 5-10 nm Cu2 SnS3 nanoparticles homogenously anchor on the graphene nanosheets, while the Li7 P3 S11 electrolytes uniformly coat on the surface of Cu2 SnS3 @graphene composite forming nanoscaled electron/ion transportation networks. The large amount of nanoscaled triple-phase boundary in cathode ensures high power density due to high ionic/electronic conductions and long cycle life due to uniform and reduced volume change of nano-Cu2 SnS3. The Cu2 SnS3 @graphene-Li7 P3 S11 cathode layer with 2.0 mg cm-2 loading in all-solid-state lithium batteries demonstrates a high reversible discharge specific capacity of 813.2 mAh g-1 at 100 mA g-1 and retains 732.0 mAh g-1 after 60 cycles, corresponding to a high energy density of 410.4 Wh kg-1 based on the total mass of Cu2 SnS3 @graphene-Li7 P3 S11 composite based cathode. Moreover, it exhibits excellent rate capability and high-rate cycling stability, showing reversible capacity of 363.5 mAh g-1 at 500 mA g-1 after 200 cycles. The study provides a new insight into constructing both electronic and ionic conduction networks for all-solid-state lithium batteries.

High-Energy All-Solid-State Lithium Batteries with Ultralong Cycle Life.

High energy and power densities are the greatest challenge for all-solid-state lithium batteries due to the poor interfacial compatibility between electrodes and electrolytes as well as low lithium ion transfer kinetics in solid materials. Intimate contact at the cathode-solid electrolyte interface and high ionic conductivity of solid electrolyte are crucial to realizing high-performance all-solid-state lithium batteries. Here, we report a general interfacial architecture, i.e., Li7P3S11 electrolyte particles anchored on cobalt sulfide nanosheets, by an in situ liquid-phase approach. The anchored Li7P3S11 electrolyte particle size is around 10 nm, which is the smallest sulfide electrolyte particles reported to date, leading to an increased contact area and intimate contact interface between electrolyte and active materials. The neat Li7P3S11 electrolyte synthesized by the same liquid-phase approach exhibits a very high ionic conductivity of 1.5 × 10-3 S cm-1 with a particle size of 0.4-1.0 µm. All-solid-state lithium batteries employing cobalt sulfide-Li7P3S11 nanocomposites in combination with the neat Li7P3S11 electrolyte and Super P as the cathode and lithium metal as the anode exhibit excellent rate capability and cycling stability, showing reversible discharge capacity of 421 mAh g-1 at 1.27 mA cm-2 after 1000 cycles. Moreover, the obtained all-solid-state lithium batteries possesses very high energy and power densities, exhibiting 360 Wh kg-1 and 3823 W kg-1 at current densities of 0.13 and 12.73 mA cm-2, respectively. This contribution demonstrates a new interfacial design for all-solid-state battery with high performance.

Tungsten and Boron Codoping toward High Ionic Conductivity and Stable Sodium Solid Electrolyte for All-Solid-State Sodium Batteries.

Sodium solid electrolytes with high ionic conductivity and good interfacial stability with sodium metal are crucial to realize high-performance all-solid-state sodium batteries. In this work, W and B-codoped Na3Sb1-xWxS4-xBx solid electrolytes are prepared by melt-quenching with further annealing. The synthesized Na3Sb0.95W0.05S3.95B0.05 solid electrolyte possesses a high ionic conductivity of 11.06 mS cm-1 under 25 °C and shows significantly improved interface compatibility with metal sodium. Specifically, Na/Na3Sb0.95W0.05S3.95B0.05/Na symmetric cell can stable cycle for 500 h under a current density of 0.05 mA cm-2. In addition, the resultant TiS2/Na3Sb0.95W0.05S3.95B0.05/Na battery exhibits an initial charge capacity of 164.1 mAh g-1 at 0.1 C with a capacity retention of 76.4% after 100 cycles. This work provides a new strategy to realize the high ionic conductivity of sodium solid electrolytes with improved interfacial stability with sodium anode.

Inorganic Sodium Solid Electrolytes: Structure Design, Interface Engineering and Application.

All-solid-state sodium batteries (ASSSBs) are particularly attractive for large-scale energy storage and electric vehicles due to their exceptional safety, abundant resource availability, and cost-effectiveness. The growing demand for ASSSBs underscores the significance of sodium solid electrolytes; However, the existed challenges of sodium solid electrolytes hinder their practical application despite continuous research efforts. Herein, recent advancements and the challenges for sodium solid electrolytes from material to battery level are reviewed. The in-depth understanding of their fundamental properties, synthesis techniques, crystal structures and recent breakthroughs is presented. Moreover, critical challenges on inorganic sodium solid electrolytes are emphasized, including the imperative need to enhance ionic conductivity, fortifying interfacial compatibility with anode/cathode materials, and addressing dendrite formation issues. Finally, potential applications of these inorganic sodium solid electrolytes are explored in ASSSBs and emerging battery systems, offering insights into future research directions.

Deeply Lithiated Carbonaceous Materials for Great Lithium Metal Protection in All-Solid-State Batteries.

Protection of lithium (Li) metal electrode is a core challenge for all-solid-state Li metal batteries (ASSLMBs). Carbon materials with variant structures have shown great effect of Li protection in liquid electrolytes, however, can accelerate the solid-state electrolyte (SE) decomposition owing to the high electronic conductivity, seriously limiting their application in ASSLMBs. Here, a novel strategy is proposed to tailor the carbon materials for efficient Li protection in ASSLMBs, by in situ forming a rational niobium-based Li-rich disordered rock salt (DRS) shell on the carbon materials, providing a favorable percolating Li+ diffusion network for speeding the carbon lithiation, and enabling simultaneously improved lithiophilicity and reduced electronic conductivity of the carbon structure at deep lithiation state. Using the proposed strategy, different carbon materials, such as graphitic carbon paper and carbon nanotubes, are tailored with great ability to speed the interfacial kinetics, homogenize the Li plating/stripping processes, and suppress the SE decompositions, enabling much improved performances of ASSLMBs under various conditions approaching the practical application. This strategy is expected to create a novel roadmap of Li protection for developing reliable high-energy-density ASSLMBs.

Calcium Doped NASICON Electrolyte with Graphite Coating for Stable All-solid-state Sodium Metal Batteries.

All-solid-state sodium metal batteries face the challenges of low ionic conductivity of solid electrolytes and poor wettability towards metallic Na anode. Herein, Na3Zr2Si2PO12 solid electrolyte is doped with Ca2+, obtaining a high ionic conductivity of 2.09×10-3 S cm-1 with low electronic conductivity of 1.43×10-8 S cm-1 at room temperature, which could accelerate Na+ transportation and suppress sodium dendrite growth. Meanwhile, a graphite-based interface layer is coated on Na3.4Zr1.8Ca0.2Si2PO12 (Na3.4Zr1.8Ca0.2Si2PO12-G) in order to improve the solid-solid contact between solid electrolyte and Na anode, realizing a uniform current distribution and smooth Na metal plating/stripping, and thus achieving a triple higher critical current density of 3.5 mA cm-2 compared with that of Na3.4Zr1.8Ca0.2Si2PO12. In addition, the assembled Na3V2(PO4)3/Na3.4Zr1.8Ca0.2Si2PO12-G/Na all-solid-state battery exhibits excellent electrochemical performances with a reversible capacity of 81.47 mAh g-1 at 1 C and capacity retention of 97.75 % after 500 cycles.

Niobium sulfide nanocomposites as cathode materials for all-solid-state lithium batteries with enhanced electrochemical performance.

All-solid-state lithium batteries coupled with transition metal sulfide cathodes have gained significant attention due to their high energy density and exceptional safety. However, there are still critical challenges impeding their practical application, such as limited capacity delivery, weak ionic reaction kinetics and volume expansion. Herein, an a-NbS4/20%VGCF@15%Li7P3S11 nanocomposite cathode material is employed in all-solid-state batteries. A certain proportion of VGCF is introduced into crystalline NbS4 in order to mitigate the volume expansion and improve electronic conductivity. At the same time, a-NbS4/20%VGCF is in situ coated with a Li7P3S11 solid electrolyte layer to achieve an intimate interfacial contact. The obtained a-NbS4/20%VGCF@15%Li7P3S11 nanocomposite exhibits a remarkable electronic conductivity (1.0 × 10-1 S cm-1) and ionic conductivity (5.5 × 10-4 S cm-1), which are improved by five and two orders of magnitude compared to those of NbS4, respectively. The Li/Li6PS5Cl/a-NbS4/20%VGCF@15%Li7P3S11 battery exhibits a high initial discharge capacity of 1043.25 mA h g-1 at 0.1 A g-1. Even at 0.5 A g-1, it could provide a reversible capacity of 403.2 mA h g-1 after 500 cycles. This work provides a promising cathode material for all-solid-state lithium batteries with improved ionic/electronic conductivity, high reversible capacity and superior cycling stability.

Embedding alloying sites in a lithiated polymer matrix as a stable interphase of lithium electrodes.

Designing a stable interphase with lithium (Li) dendrite suppressing ability is a surging demand for high-energy-density Li metal batteries (LMBs). Here, a hybrid inorganic-organic interphase is achieved on a Li anode, on which the nanoscale phase separation between antimony nucleation sites and an interconnected Li+ conducting polymer matrix endows the Li growing behavior with high uniformity and stability, resulting in a long lifespan of LMB over 500 cycles with a practical capacity of ∼2.5 mA h cm-2.

Polyimide-Based Solid-State Gel Polymer Electrolyte for Lithium-Oxygen Batteries with a Long-Cycling Life.

Metal-air batteries have attracted wide interest owing to their ultrahigh theoretical energy densities, particularly for lithium-oxygen batteries. One of the challenges inhibiting the practical application of lithium-oxygen batteries is the unavoidable liquid electrolyte evaporation accompanying oxygen fluxion in the semi-open system, which leads to safety issues and poor cyclic performance. To address these issues, we propose a solid-state polyimide based gel polymer electrolyte (PI@GPE), immobilizing and reserving a liquid electrolyte in the gelled polymer substrate. The liquid electrolyte uptake of PI@GPE is measured to be 842%, 6 times higher than that of the commercial glass fiber separator, contributing to a high ionic conductivity of 0.44 mS cm-1. Additionally, PI@GPE possesses an enhanced lithium transference number of 0.596 as well as superior interfacial compatibility with lithium metals. Under 0.1 mA cm-2 and 0.25 mA h cm-2, PI@GPE-based lithium-oxygen batteries demonstrate distinguished long-cycling stability of 366 cycles, 4 times more than that with a glass fiber separator and liquid electrolyte. Our work provides a unique solid-state gel polymer electrolyte to mitigate liquid electrolyte leakage, exhibiting promising potential application in highly safe lithium-oxygen batteries with a long-cycling life.

LiAlO2-Modified Li Negative Electrode with Li10GeP2S12 Electrolytes for Stable All-Solid-State Lithium Batteries.

Lithium (Li) metal has an ultrahigh specific capacity in theory with an extremely negative potential (versus hydrogen), receiving extensive attention as a negative electrode material in batteries. However, the formation of Li dendrites and unstable interfaces due to the direct Li metal reaction with solid sulfide-based electrolytes hinders the application of lithium metal in all-solid-state batteries. In this work, we report the successful fabrication of a LiAlO2 interfacial layer on a Li/Li10GeP2S12 interface through magnetic sputtering. As LiAlO2 can be a good Li+ ion conductor but an electronic insulator, the LiAlO2 interface layer can effectively suppress Li dendrite growth and the severe interface reaction between Li and Li10GeP2S12. The Li@LiAlO2 200 nm/Li10GeP2S12/Li@LiAlO2 200 nm symmetric cell can remain stable for 3000 h at 0.1 mA cm-2 under 0.1 mAh cm-2. Moreover, unlike the rapid capacity decay of a cell with a pristine lithium negative electrode, the Li@LiAlO2 200 nm/Li10GeP2S12/LiCoO2@LiNbO3 cell delivers a reversible capacity of 118 mAh g-1 and a high energy efficiency of 96.6% after 50 cycles. Even at 1.0 C, the cell with the Li@LiAlO2 200 nm electrode can retain 95% of its initial capacity after 800 cycles.

Zn-Alloying Sites with Self-Adsorbed Molecular Crowding Layer as a Stable Interfacial Structure of Zn Electrodes.

Rechargeable aqueous zinc (Zn) metal batteries (ZMBs) have gained tremendous attention because of their intrinsic safety and low cost. However, the lifespan of ZMBs is seriously limited by severe Zn dendritic growth in aqueous electrolytes. Despite the feasibility of Zn deposition regulation by introducing Zn-alloying sites at the Zn plating surface, the activity of the Zn-alloying sites can be seriously reduced by side reactions in the aqueous environment. Here, we propose a facile but efficacious strategy to reinforce the activity of the Zn-alloying sites by introducing a low quantity of polar organic additive in the electrolyte that can be self-adsorbed on the Zn-alloying sites to form a molecular crowding layer against the parasitic water reduction during Zn deposition. As a consequence, stable cycling of the Zn anode can be maintained at such a multifunctional interfacial structure, arising from the synergism between the seeded low-overpotential Zn deposition on the stabilized Zn-alloying sites and a Zn2+ redistributing feature of the self-adsorbed molecular crowding layer. The interfacial design principle here can be widely employed due to the great variety of Zn-alloy and polar organic materials and potentially be applied to improve the performance of other aqueous metal batteries.

Fluorinated Li10 GeP2 S12 Enables Stable All-Solid-State Lithium Batteries.

The instability of Li10 GeP2 S12 toward moisture and that toward lithium metal are two challenges for the application in all-solid-state lithium batteries. In this work, Li10 GeP2 S12 is fluorinated to form a LiF-coated core-shell solid electrolyte LiF@Li10 GeP2 S12 . Density-functional theory calculations confirm the hydrolysis mechanism of Li10 GeP2 S12 solid electrolyte, including H2 O adsorption on Li atoms of Li10 GeP2 S12 and the subsequent PS4 3- dissociation affected by hydrogen bond. The hydrophobic LiF shell can reduce the adsorption site, thus resulting in superior moisture stability when exposing in 30% relative humidity air. Moreover, with LiF shell, Li10 GeP2 S12 shows one order lower electronic conductivity, which can significantly suppress lithium dendrite growth and reduce the side reaction between Li10 GeP2 S12 and lithium, realizing three times higher critical current density to 3 mA cm-2 . The assembled LiNbO3 @LiCoO2 /LiF@Li10 GeP2 S12 /Li battery exhibits an initial discharge capacity of 101.0 mAh g-1 with a capacity retention of 94.8% after 1000 cycles at 1 C.

NaF-Rich Multifunctional Layers toward Stable All-Solid-State Sodium Batteries.

NASICON oxide solid electrolytes are considered promising candidates for all-solid-state sodium batteries due to their extremely high ionic conductivity and favorable electrochemical stability. However, the practical application of NASICON electrolytes is greatly impeded by poor electrolyte-electrode interfacial contact and continuous sodium dendrite propagation. Herein, a NaF-rich multifunctional interface layer on the surface of a Na anode (Na@NaF-rich), containing NaF, amorphous carbon, and an unreacted C-F bond species, is developed in situ by the reaction between Na and commercial poly(tetrafluoroethylene). This NaF-rich interface layer is proven to reduce the diffusion barriers at the Na/NASICON electrolyte interface and homogenize Na deposition as well as suppress Na dendrite growth, thus achieving a high critical current density of 4 mA cm-2. The resultant Na3V2(PO4)3@C/Na@NaF-rich all-solid-state cell showed a high initial specific capacity of 117.6 mAh g-1 at 0.1 C with a Coulombic efficiency of 94.8%. Even at 0.5 and 1 C, it still exhibited high capacity retentions of 83.3% and 80.4%, respectively, after 750 cycles.

Achieving Practical High-Energy-Density Lithium-Metal Batteries by a Dual-Anion Regulated Electrolyte.

Lithium-metal batteries (LMBs) using lithium-metal anodes and high-voltage cathodes have been deemed as one of the most promising high-energy-density battery technology. However, its practical application is largely hindered by the notorious dendrite growth of lithium-metal anodes, the fast structure degradation of the cathode, and insufficient electrode-electrolyte interphase kinetics. Here, a dual-anion regulated electrolyte is developed for LMBs using lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and lithium difluoro(bisoxalato)phosphate (LiDFBOP) as anion regulators. The incorporation of TFSI- in the solvation sheath reduces the desolvation energy of Li+ , and DFBOP- promotes the formation of highly ion-conductive and sustainable inorganic-rich interphases on the electrodes. Significantly enhanced performance is demonstrated on Li||LiNi0.83 Co0.11 Mn0.06 O2 pouch cells, with 84.6% capacity retention after 150 cycles in 6.0 Ah pouch cells and an ultrahigh rate capability up to 5 C in 2.0 Ah pouch cells. Furthermore, a pouch cell with an ultralarge capacity of 39.0 Ah is fabricated and achieves an ultrahigh energy density of 521.3 Wh kg-1 . The findings provide a facile electrolyte design strategy for promoting the practical utilization of high-energy-density LMBs.