Uncoordinated chemistry enables highly conductive and stable electrolyte/filler interfaces for solid-state lithium-sulfur batteries.

Composite-polymer-electrolytes (CPEs) embedded with advanced filler materials offer great promise for fast and preferential Li+ conduction. The filler surface chemistry determines the interaction with electrolyte molecules and thus critically regulates the Li+ behaviors at the interfaces. Herein, we probe into the role of electrolyte/filler interfaces (EFI) in CPEs and promote Li+ conduction by introducing an unsaturated coordination Prussian blue analog (UCPBA) filler. Combining scanning transmission X-ray microscope stack imaging studies and first-principle calculations, fast Li+ conduction is revealed only achievable at a chemically stable EFI, which can be established by the unsaturated Co-O coordination in UCPBA to circumvent the side reactions. Moreover, the as-exposed Lewis-acid metal centers in UCPBA efficiently attract the Lewis-base anions of Li salts, which facilitates the Li+ disassociation and enhances its transference number (tLi+). Attributed to these superiorities, the obtained CPEs realize high room-temperature ionic conductivity up to 0.36 mS cm-1 and tLi+ of 0.6, enabling an excellent cyclability of lithium metal electrodes over 4,000 h as well as remarkable capacity retention of 97.6% over 180 cycles at 0.5 C for solid-state lithium-sulfur batteries. This work highlights the crucial role of EFI chemistry in developing highly conductive CPEs and high-performance solid-state batteries.

Solvent selection criteria for temperature-resilient lithium-sulfur batteries.

All-climate temperature operation capability and increased energy density have been recognized as two crucial targets, but they are rarely achieved together in rechargeable lithium (Li) batteries. Herein, we demonstrate an electrolyte system by using monodentate dibutyl ether with both low melting and high boiling points as the sole solvent. Its weak solvation endows an aggregate solvation structure and low solubility toward polysulfide species in a relatively low electrolyte concentration (2 mol L-1). These features were found to be vital in avoiding dendrite growth and enabling Li metal Coulombic efficiencies of 99.0%, 98.2%, and 98.7% at 23 °C, -40 °C, and 50 °C, respectively. Pouch cells employing thin Li metal (50 µm) and high-loading sulfurized polyacrylonitrile (3.3 mAh cm-2) cathodes (negative-to-positive capacity ratio = 2) output 87.5% and 115.9% of their room temperature capacity at -40 °C and 50 °C, respectively. This work provides solvent-based design criteria for a wide temperature range Li-sulfur pouch cells.

Mussel and Cobweb Inspired High Areal Capacity SPAN Electrode.

Lithium-sulfur batteries (LSBs) with superior energy density are among the most promising candidates for next-generation energy storage techniques. Sulfurized polyacrylonitrile (SPAN) exhibits competitive advantages in terms of cycle stability, rate performance as well as cost. However, the preparation of high-loading SPAN electrodes is still challenging. Herein, inspired by mussel and cobweb, a high-loading SPAN electrode is enabled by the combination of polydopamine (PDA) coating and a bimodal distributed single-wall carbon nanotubes (SWCNT) slurry dispersed in polyvinylpyrrolidone (PVP), their synergistic effect not only constructs effective electron percolating networks within the electrode but also make high active material (AM) ratio possible. High areal capacity PDA@SPAN electrode (18.40 mAh cm-2 in the initial cycle) with negligible specific capacity attenuation as the mass loading increasement is realized through the facile slurry casting process. The dynamic N─H…O hydrogen bond is formed between PDA and PVP and the electrode integrity during charge/discharge is greatly strengthened. The battery with an areal AM loading of 7.16 mg cm-2 (5.16 mAh cm-2) retains 92.0% of capacity in 80 cycles and 87.18% in 160 cycles, and it also shows stable cycle performances even with a high loading of 19.79 mg cm-2 and lean electrolyte (3.28 µL mg-1).

Cobalt Nitride Nanoparticles Encapsulated in N-Doped Carbon Nanotubes Modified Separator of Li-S Battery Achieving the Synergistic Effect of Restriction-Adsorption-Catalysis of Polysulfides.

Although lithium-sulfur (Li-S) batteries have broad market prospects due to their high theoretical energy density and potential cost-effectiveness, the practical applications still face serious shuttle effects of polysulfides (LiPSs) and slow redox reactions. Therefore, in this paper, cobalt nitride nanoparticles encapsulated in nitrogen-doped carbon nanotube (CoN@NCNT) are prepared as a functional layer for the separator of high-performance Li-S batteries. Carbon nanotubes with large specific surface areas not only promote the transport of ions and electrons but also weaken the migration of LiPSs and confine the dissolution of LiPSs in electrolytes. The lithiophilic heteroatom N adsorbs LiPSs by strong chemical adsorption, and the CoN particles with high catalytic activity greatly improve the kinetics of the conversion between LiPSs and Li2S2/Li2S during the charge-discharge process. Due to these advantages, the battery with CoN@NCNT modified separator has superior rate performance (initial discharge capacity of 834.7 mAh g-1 after activation at 1 C) and excellent cycle performance (capacity remains 729.7 mAh g-1 after 200 cycles at 0.2 C). This work proposes a strategy that can give the separator a strong ability to confinement-adsorption-catalysis of LiPSs in order to provide more possibilities for the development of Li-S batteries.

Modulation of Potential-Limiting Steps in Lithium-Sulfur Batteries by Catalyst Synergy.

Electrocatalysis is considered to be an effective method to solve the sluggish kinetics of lithium-sulfur batteries. However, a single catalyst cannot simultaneously catalyze multi-step sulfur reductions. And once the catalyst surface is covered by the initially deposited solid products, the subsequent catalytic activity will significantly deteriorate. Here, microporous ZIF-67 and its derivative nano-metallic Co0 are used as dual-catalyst aiming to address these drawbacks. The dual catalytic center effectively cooperates the adsorption and electron transfer for multi-steps of sulfur reductions, transforming the potential-limited step (Li2S4→Li2S2/Li2S) into a thermodynamic spontaneous reaction. ZIF-67 first adsorbs soluble Li2S4 to form a coordination structure of ZIF-Li2S4. Then nano-metallic Co0 attracts uncoordinated S atoms in ZIF-Li2S4 and facilitates the breaking of S-S bonds to form transient reductive ZIF-Li2S2 and Co-S2 via. spontaneous electron transfer. These intermediates facilitate continuous conversion to Li2S with reduced formation energy, which is beneficial to the regeneration of the catalyst. As a result, the cathode with ZIF@CNTs/Co@CNFs synergetic catalyst achieves initial areal capacity of 4.7 mAh cm-2 and maintains 3.5 mAh cm-2 at low electrolyte/sulfur ratio (E/S) of 5 µL mg-1. This study provides valuable guidance for improving the electrochemical performance of lithium-sulfur batteries through catalyst synergistic strategies for multi-step reactions.

Engineering Oxygen Vacancies in In2O3 with Enhanced Polysulfides Immobilization and Selective Catalytic Capability.

Lithium-sulfur (Li-S) battery is identified as an ideal candidate for next-generation energy storage systems in consideration of its high theoretical energy density and abundant sulfur resources. However, the shuttling behavior of soluble polysulfides (LiPSs) and their sluggish reaction kinetics severely limit the practical application of the current Li-S battery. In this work, a series of In2O3 nanocubes with different oxygen vacancy concentrations are designed and prepared via a facile self-template method. The introduced oxygen vacancy on In2O3 can effectively rearrange the charge distribution and enhance sulfiphilic property. Moreover, the In2O3 with high oxygen vacancy concentration (H-In2O3) can slightly slow down the solid-liquid conversion process and significantly accelerate the liquid-solid conversion process, thus reducing the accumulation of LiPSs in electrolyte and inhibiting the shuttle effect. Contributed by the unique selective catalytic capability, the prepared H-In2O3 exhibits excellent electrochemical performance when used as sulfur host. For instance, a high reversible capacity of 609 mAh g-1 is obtained with only 0.044% capacity decay per cycle over 1000 cycles at 1.0 C. This work presents a typical example for designing advanced sulfur hosts, which is crucial for the commercialization of Li-S battery.

Advanced Polymers in Cathodes and Electrolytes for Lithium-Sulfur Batteries: Progress and Prospects.

Lithium-sulfur (Li-S) batteries, which store energy through reversible redox reactions with multiple electron transfers, are seen as one of the promising energy storage systems of the future due to their outstanding advantages. However, the shuttle effect, volume expansion, low conductivity of sulfur cathodes, and uncontrollable dendrite phenomenon of the lithium anodes have hindered the further application of Li-S batteries. In order to solve the problems and clarify the electrochemical reaction mechanism, various types of materials, such as metal compounds and carbon materials, are used in Li-S batteries. Polymers, as a class of inexpensive, lightweight, and electrochemically stable materials, enable the construction of low-cost, high-specific capacity Li-S batteries. Moreover, polymers can be multifunctionalized by obtaining rich structures through molecular design, allowing them to be applied not only in cathodes, but also in binders and solid-state electrolytes to optimize electrochemical performance from multiple perspectives. The most widely used areas related to polymer applications in Li-S batteries, including cathodes and electrolytes, are selected for a comprehensive overview, and the relevant mechanisms of polymer action in different components are discussed. Finally, the prospects for the practical application of polymers in Li-S batteries are presented in terms of advanced characterization and mechanistic analysis.

Size Effect for Inhibiting Polysulfides Shuttle in Lithium-Sulfur Batteries.

It is undeniable that the dissolution of polysulfides is beneficial in speeding up the conversion rate of sulfur in electrochemical reactions. But it also brings the bothersome "shuttle effect". Therefore, if polysulfides can be retained on the cathode side, the efficient utilization of the polysulfides can be guaranteed to achieve the excellent performance of lithium-sulfur batteries. Based on this idea, considerable methods have been developed to inhibit the shuttling of polysulfides. It is necessary to emphasize that no matter which method is used, the solvation mechanism, and existence forms of polysulfides are essential to analyze. Especially, it is important to clarify the sizes of different forms of polysulfides when using the size effect to inhibit the shuttling of polysulfides. In this review, a comprehensive summary and in-depth discussion of the solvation mechanism, the existing forms of polysulfides, and the influencing factors affecting polysulfides species are presented. Meanwhile, the size of diverse polysulfide species is sorted out for the first time. Depending on the size of polysulfides, tactics of using size effect in cathode, separator, and interlayer parts are elaborated. Finally, a design idea of materials pore size is proposed to satisfy the use of size effect to inhibit polysulfides shuttle.

Mechanism and Solution of Overcharge Effect in Lithium-Sulfur Batteries.

Increasing the sulfur cathode load is an important method for promoting the commercialization of lithium-sulfur batteries. However, there is a common problem of overcharging in high-loading experiments, which is rarely reported. In this work, it is believed that an insulating layer of S8 forms on the current collector surface, hindering electron exchange with polysulfides. Continuous external current input during layer formation can cause irreversible electrode changes and overcharging. The general solution is to provide nucleation centers with adsorption sites to promote the 3D growth of the insulated S8 , thus avoiding overcharging. In this work,  a solution is proposed by providing nucleation centers by gallium nitrate, by regulating the 3D growth of S8 away from the surface of the current collector to avoid overcharging and by improving battery performance.

2D Nano-Channeled Molybdenum Compounds for Accelerating Interfacial Polysulfides Catalysis in Li-S Battery.

The shuttle effect, which causes the loss of active sulfur, passivation of lithium anode, and leads to severe capacity attenuation, is currently the main bottleneck for lithium-sulfur batteries. Recent studies have disclosed that molybdenum compounds possess exceptional advantages as a polar substrate to immobilize and catalyze lithium polysulfide such as high conductivity and strong sulfiphilicity. However, these materials show incomplete contact with sulfur/polysulfides, which causes uneven redox conversion of sulfur and results in poor rate performance. Herein, a new type of 2D nano-channeled molybdenum compounds (2D-MoNx) via the 2D organic-polyoxometalate superstructure for accelerating interfacial polysulfide catalysis toward high-performance lithium-sulfur batteries is reported. The 2D-MoNx shows well-interlinked nano-channels, which increase the reactive interface and contact surface with polysulfides. Therefore, the battery equipped with 2D-MoNx displays a high discharge capacity of 912.7 mAh g-1 at 1 C and the highest capacity retention of 523.7 mAh g-1 after 300 cycles. Even at the rate of 2 C, the capacity retention can be maintained at 526.6 mAh g-1 after 300 cycles. This innovative nano-channel and interfacial design of 2D-MoNx provides new nanostructures to optimize the sulfur redox chemistry and eliminate the shuttle effect of polysulfides.

Hyphae Carbon Coupled with Gel Composite Assembly for Construction of Advanced Carbon/Sulfur Cathodes for Lithium-Sulfur Batteries.

The design and fabrication of novel carbon hosts with high conductivity, accelerated electrochemical catalytic activities, and superior physical/chemical confinement on sulfur and its reaction intermediates polysulfides are essential for the construction of high-performance C/S cathodes for lithium-sulfur batteries (LSBs). In this work, a novel biofermentation coupled gel composite assembly technology is developed to prepare cross-linked carbon composite hosts consisting of conductive Rhizopus hyphae carbon fiber (RHCF) skeleton and lamellar sodium alginate carbon (SAC) uniformly implanted with polarized nanoparticles (V2O3, Ag, Co, etc.) with diameters of several nanometers. Impressively, the RHCF/SAC/V2O3 composites exhibit enhanced physical/chemical adsorption of polysulfides due to the synergistic effect between hierarchical pore structures, heteroatoms (N, P) doping, and polar V2O3 generation. Additionally, the catalytic conversion kinetics of cathodes are effectively improved by regulating the 3D carbon structure and optimizing the V2O3 catalyst. Consequently, the LSBs assembled with RHCF/SAC/V2O3-S cathode show exceptional cycle stability (capacity retention rate of 94.0% after 200 cycles at 0.1 C) and excellent rate performance (specific capacity of 578 mA h g-1 at 5 C). This work opens a new door for the fabrication of hyphae carbon composites via fermentation for electrochemical energy storage.

Interfacial Synergy in Mo2C/MoC Heterostructure Promoting Sequential Polysulfide Conversion in High-Performance Lithium-Sulfur Battery.

A rational design of sulfur host is the key to conquering the"polysulfide shuttle effects" by accelerating the polysulfide conversion. Since the process involves solid-liquid-solid multistep phase transitions, purposely-engineered heterostructure catalysts with various active regions for catalyzing conversion steps correspondingly are beneficial to promote the overall conversion process. However, the functionalities of the materials surface and interface in heterostructure catalysts remain unclear. In this work, an Mo2C/MoC catalyst with abundant Mo2C surface-interface-MoC surface tri-active-region is developed by in situ converting the MoZn-metal organic framework. The experimental and simulation studies demonstrate the interface can catch long-chain polysulfides and promote their conversion. Instead, the Mo2C and MoC tend to accommodate the short-chain polysulfide and accelerate their conversion and the Li2S dissociation. Benefitting from the high catalytic ability, the Li-S battery assembled with the Mo2C/MoC-S cathode shows more discrete redox reactions and delivers a high initial capacity of 1603.6 mAh g-1 at 1 C charging-discharging rate, which is over twofolds of the one assembled using individual hosts, and 80.4% capacity can be maintained after 1000 cycles at 3 C rate. This work has demonstrated a novel synergy between the interface and material surface, which will help the future design of high-performance Li-S batteries.

Boosting Polysulfide Redox Kinetics by Temperature-Induced Metal-Insulator Transition Effect of Tungsten-Doped Vanadium Dioxide for High-Temperature Lithium-Sulfur Batteries.

The practical application of Li-S batteries is still severely restricted by poor cyclic performance caused by the intrinsic polysulfides shuttle effect, which is even more severe under the high-temperature condition owing to the inevitable increase of polysulfides' solubility and diffusion rate. Herein, tungsten-doped vanadium dioxide (W-VO2) micro-flowers are employed with first-order metal-insulator phase transition (MIT) property as a robust and multifunctional modification layer to hamper the shuttle effect and simultaneously improve the thermotolerance of the common separator. Tungsten doping significantly reduces the transition temperature from 68 to 35 °C of vanadium dioxide, which renders the W-VO2 easier to turn from the insulating monoclinic phase into the metallic rutile phase. The systematic experiments and theoretical analysis demonstrate that the temperature-induced in-suit MIT property endows the W-VO2 catalyst with strong chemisorption against polysulfides, low energy barrier for liquid-to-solid conversion, and outstanding diffusion kinetics of Li-ion under high temperatures. Benefiting from these advantages, the Li-S batteries with W-VO2 modified separator exhibit significantly improved rate and long-term cyclic performance under 50 °C. Remarkably, even at an elevated temperature (80 °C), they still exhibit superior electrochemical performance. This work opens a rewarding avenue to use phase-changing materials for high-temperature Li-S batteries.

Porous Organic Framework Materials (MOF, COF, and HOF) as the Multifunctional Separator for Rechargeable Lithium Metal Batteries.

The separator is an important component in batteries, with the primary function of separating the positive and negative electrodes and allowing the free passage of ions. Porous organic framework materials have a stable connection structure, large specific surface area, and ordered pores, which are natural places to store electrolytes. And these materials with specific functions can be designed according to the needs of researchers. The performance of porous organic framework-based separators used in rechargeable lithium metal batteries is much better than that of polyethylene/propylene separators. In this paper, the three most classic organic framework materials (MOF, COF, and HOF) are analyzed and summarized. The applications of MOF, COF, and HOF separators in lithium-sulfur batteries, lithium metal anode, and solid electrolytes are reviewed. Meanwhile, the research progress of these three materials in different fields is discussed based on time. Finally, in the conclusion, the problems encountered by MOF, COF, and HOF in different fields as well as their future research priorities are presented. This review will provide theoretical guidance for the design of porous framework materials with specific functions and further stimulate researchers to conduct research on porous framework materials.

In Situ Growth Strategy to Construct "Four-In-One" Separators with Functionalized Polyphosphazene Coatings for Safe and Stable Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) are facing many challenges, such as the inadequate conductivity of sulfur, the shuttle effect caused by lithium polysulfide (LiPSs), lithium dendrites, and the flammability, which have hindered their commercial applications. Herein, a "four-in-one" functionalized coating is fabricated on the surface of polypropylene (PP) separator by using a novel flame-retardant namely InC-HCTB to meet these challenges. InC-HCTB is obtained by cultivating polyphosphazene on the surface of carbon nanotubes with an in situ growth strategy. First, this unique architecture fosters an enhanced conductive network, bolstering the bidirectional enhancement of both ionic and electronic conductivities. Furthermore, InC-HCTB effectively inhibits the shuttle effect of LiPSs. LSBs exhibit a remarkable capacity of 1170.7 mA h g-1 at 0.2 C, and the capacity degradation is a mere 0.0436% over 800 cycles at 1 C. Third, InC-HCTB coating serves as an ion migration network, hindering the growth of lithium dendrites. More importantly, InC-HCTB exhibits notable flame retardancy. The radical trapping action in the gas phase and the protective effect of the shielded char layer in the condensed phase are simulated and verified. This facile in situ growth strategy constructs a "four-in-one" functional separator coating, rendering InC-HCTB a promising additive for the large-scale production of safe and stable LSBs.

2D Ultrathin Titanium Nitride Nanosheets as Separator Coatings for Li-S Batteries.

Transition metal nitrides (TMNs) are affirmed to be an appealing candidate for boosting the performance of lithium-sulfur (Li-S) batteries due to their excellent conductivity, strong interaction with sulfur species, and the effective catalytic ability for conversion of polysulfides. However, the traditional bulk TMNs are difficult to achieve large active surface area and fast transport channels for electrons/ions simultaneously. Here, a 2D ultrathin geometry of titanium nitride (TiN) is realized by a facile topochemical conversion strategy, which can not only serve as an interconnected conductive platform but also expose abundant catalytic active sites. The ultrathin TiN nanosheets are coated on a commercial separator, serving as a multifunctional interlayer in Li-S batteries for hindering the polysulfide shuttle effect by strong capture and fast conversion of polysulfides, achieving a high initial capacity of 1357 mAh g-1 at 0.1 C and demonstrating a low capacity decay of only 0.046% per cycle over 1000 cycles at 1 C.

Heterostructured WOx/W2C Nanocatalyst for Li2S Oxidation in Lithium-Sulfur Batteries with High-Areal-Capacity.

Lithium-sulfur (Li-S) batteries show extraordinary promise as a next-generation battery technology due to their high theoretical energy density and the cost efficiency of sulfur. However, the sluggish reaction kinetics, uncontrolled growth of lithium sulfide (Li2S), and substantial Li2S oxidation barrier cause low sulfur utilization and limited cycle life. Moreover, these drawbacks get exacerbated at high current densities and high sulfur loadings. Here, a heterostructured WOx/W2C nanocatalyst synthesized via ultrafast Joule heating is reported, and the resulting heterointerfaces contribute to enhance electrocatalytic activity for Li2S oxidation, as well as controlled Li2S deposition. The densely distributed nanoparticles provide abundant binding sites for uniform deposition of Li2S. The continuous heterointerfaces favor efficient adsorption and promote charge transfer, thereby reducing the activation barrier for the delithiation of Li2S. These attributes enable Li-S cells to deliver high-rate performance and high areal capacity. This study provides insights into efficient catalyst design for Li2S oxidation under practical cell conditions.

Multifunctional Heterostructured Fe3O4-FeTe@MCM Electrocatalyst Enabling High-Performance Practical Lithium-Sulfur Batteries Via Built-in Electric Field.

The development of capable of simultaneously modulating the sluggish electrochemical kinetics, shuttle effect, and lithium dendrite growth is a promising strategy for the commercialization of lithium-sulfur batteries. Consequently, an elaborate preparation method is employed to create a host material consisting of multi-channel carbon microspheres (MCM) containing highly dispersed heterostructure Fe3O4-FeTe nanoparticles. The Fe3O4-FeTe@MCM exhibits a spontaneous built-in electric field (BIEF) and possesses both lithophilic and sulfophilic sites, rendering it an appropriate host material for both positive and negative electrodes. Experimental and theoretical results reveal that the existence of spontaneous BIEF leads to interfacial charge redistribution, resulting in moderate polysulfide adsorption which facilitates the transfer of polysulfides and diffusion of electrons at heterogeneous interfaces. Furthermore, the reduced conversion energy barriers enhanced the catalytic activity of Fe3O4-FeTe@MCM for expediting the bidirectional sulfur conversion. Moreover, regulated Li deposition behavior is realized because of its high conductivity and remarkable lithiophilicity. Consequently, the battery exhibited long-term stability for 500 cycles with 0.06% capacity decay per cycle at 5 C, and a large areal capacity of 7.3 mAh cm-2 (sulfur loading: 9.73 mg cm-2) at 0.1 C. This study provides a novel strategy for the rational fabrication of heterostructure hosts for practical Li-S batteries.

Pinpointing the Cl Coordination Effect on Mn-N3-Cl Moiety Toward Boosting Reaction Kinetics and Suppressing Shuttle Effect in Li-S Batteries.

Single atom catalysts (SACs) are highly favored in Li-S batteries due to their excellent performance in promoting the conversion of lithium polysulfides (LiPSs) and inhibiting their shuttling. However, the intricate and interrelated microstructures pose a challenge in deciphering the correlation between the chemical environment surrounding the active site and its catalytic activity. Here, a novel SAC featuring a distinctive Mn-N3-Cl moiety anchored on B, N co-doped carbon nanotubes (MnN3Cl@BNC) is synthesized. Subsequently, the selective removal of the Cl ligands while inheriting other microstructures is performed to elucidate the effect of Cl coordination on catalytic activity. The Cl coordination effectively enhances the electron cloud density of the Mn-N3-Cl moiety, reducing the band gap and increasing the adsorption capacity and redox kinetics of LiPSs. As a modified separator for Li-S batteries, MnN3Cl@BNC exhibits high capacities of 1384.1 and 743 mAh g-1 at 0.1 and 3C, with a decay rate of only 0.06% per cycle over 700 cycles at 1 C, which is much better than that of MnN3OH@BNC. This study reveals that Cl coordination positively contributes to improving the catalytic activity of the Mn-N3-Cl moiety, providing a fresh perspective for the design of high-performance SACs.

High-efficiency Lithium Metal Stabilization and Polysulfide Suppression in Li-S Battery Enabled by Weakly Solvating Solvent.

Lithium-sulfur batteries (LSBs) are considered a highly promising next-generation energy storage technology due to their exceptional energy density and cost-effectiveness. However, the practical use of current LSBs is hindered primarily by issues related to the "shuttle effect" of lithium polysulfide (LiPS) intermediates and the growth of lithium dendrites. In strongly solvating electrolytes, the solvent-derived solid electrolyte interphase (SEI) lacks mechanical strength due to organic components, leading to ineffective lithium dendrite suppression and severe LiPS dissolution and shuttling. In contrast, the weakly solvating electrolyte (WSE) can create an anion-derived SEI layer which can enhance compatibility with lithium metal anode, and restricting LiPS solubility. Herein, a WSE consisting of 0.4 Ð¼ LiTFSI in the mixture of 1,4-dioxane (DX):dimethoxymethane (DMM) is designed to overcome the issues associated with LSB. Surface analyses confirmed the formation of a beneficial SEI layer rich in LiF, enabling homogeneous lithium deposition with an average Coulombic efficiency CE exceeding 99% over 100 cycles. Implementing the low-concentration WSE in Li||SPAN cells yielded an impressive initial specific capacity of 671 mAh g-1. This research highlights the advantages of WSE and offers the pathway for cost-effective electrolyte development, enabling the realization of high-performance LSBs.