Solid Electrolyte Interface Formation Research Articles

A Large-Scale Fabrication of Flexible, Ultrathin, and Robust solid Electrolyte for Solid-State Lithium-Sulfur Batteries.

solid-state electrolytes, 3D supporting skeleton, mechanical strength, uniform Li deposition, F-enriched SEIAll-solid-state lithium metal batteries (ASSLMBs) are considered as the most promising candidates for the next-generation high-safety batteries. To achieve high energy density in ASSLMBs, it is essential that the solid-state electrolytes (SSEs) are lightweight, thin, and possess superior electrochemical stability. In this study, we propose a feasible and scalable fabrication approach to construct 3D supporting skeleton using an electro-blown spinning technique. This skeleton not only enhances the mechanical strength, but also hinders the migration of Li-salt anions, improving the lithium-ion transference number of the SSE. This provides a homogeneous distribution of Li-ion flux and local current density, promoting uniform Li deposition. As a result, based on the mechanically robust and thin SSEs, the Li symmetric cells show outstanding Li plating/stripping reversibility. Besides, a stableinterfacecontact between SSE and Li anode has been established with the formation of a F-enriched solid electrolyte interface (SEI) layer. The solid-state Li|sulfurized polyacrylonitrile (Li|SPAN) cell achieves a capacity retention ratio of 94.0% after 350 cycles at 0.5 C. Also, the high-voltage Li|LCO cell shows a capacity retention of 92.4% at 0.5 C after 500 cycles. This fabrication approach for SSEs is applicable for commercially large-scale production and application in high-energy-density and high-safety ASSLMBs. This article is protected by copyright. All rights reserved.

Reconstructing Solvation Structure by Steric Hindrance-Coordination Push-Pull of Dipolymer-H2O-Zn2+ toward Long-life Aqueous Zinc-Metal Batteries.

Aqueous zinc-metal batteries are prospective energy storge devices due to their intrinsically high safety and cost effectiveness. Yet, uneven deposition of zinc ions in electrochemical reduction and side reactions at the anode interface significantly hinder their development and application. Here, we propose a solvation-interface attenuation strategy enabled by a frustrated tertiary amine amphiphilic dipolymer electrolyte additive. The configuration of superhydrophilic segments with covalently bonded lipophilic spacers enables coupled steric hindrance/coordination, which establishes a balanced push-pull dynamic of dipolymer-H2O-Zn2+. Such interplay reconstructs the solvation structure of Zn2+ and allows the formation of a stable dipolymer-inorganic hybrid solid electrolyte interface (SEI) layer. This SEI layer effectively shields the zinc-metal anode from water and anions, significantly reducing side reactions. In addition, the dipolymer adsorbed at the zinc-metal anode interface regulates the interfacial electrochemical reduction kinetics and ensures uniform zinc deposition. As a result, the Zn-Zn symmetric cells with dipolymer-containing electrolyte exhibit remarkable cycling stability exceeding 5800 h (242 days). The Zn-NVO batteries and Zn-AC hybrid ion supercapacitors also deliver stable cycling for up to 1440 h (60 days) with high-capacity retention over 80%. This research demonstrates the potential to facilitate the development and commercialization of zinc-based energy storage devices.

SEI/dead Li-turning capacity loss for high-performance anode-free solid-state lithium batteries

Anode-free solid-state lithium metal batteries (AF-SSLBs) have the potential to deliver higher energy density and improved safety beyond lithium-metal batteries. However, the unclear mechanism for the fast capacity decay in AF-SSLBs, either determined by dead Li or solid electrolyte interface (SEI), limits the proposal of effective strategies to prolong cycling life. To clarify the underlying mechanism, herein, the evolution of SEI and dead Li is quantitatively analyzed by a solid-state nuclear magnetic resonance (ss-NMR) technology in a typical LiPF6-based polymer electrolyte. The results show that the initial capacity loss is attributed to the formation of SEI, while the dead Li dominates the following capacity loss and the growth rate is 0.141 mA h cm−2 cycle−1. To reduce the active Li loss, the combination of inorganic-rich SEI and self-healing electrostatic shield effect is proposed to improve the reversibility of Li deposition/dissolution behavior, which reduces the capacity loss rate for the initial SEI and following dead Li generation by 2.3 and 20.1 folds, respectively. As a result, the initial Coulombic efficiency (ICE) and stable CE increase by 15.1% and 15.3% in Li-Cu cells, which guides the rational design of high-performance AF-SSLBs.

Enhanced Silicon Anodes with Robust SEI Formation Enabled by Functional Conductive Binder

AbstractThe application of silicon (Si) anode is limited by the drastic volume change of silicon in the lithiation/delithiation process, the repeated formation of the solid electrolyte interface (SEI), and the low intrinsic conductivity. In this work, a small amount of poly (3,4‐ethylenedioxythiophene):poly (styrene sulfonic acid) (PEDOT:PSS) (PP), citric acid (CA), isopropyl alcohol (IPA), and silicon nanoparticles (SiNPs) are mixed and vacuum treated at a specific temperature to obtain silicon‐based anode electrode composite Si@PP@CA. The interphase forms a robust elastic network with hydrogen and chemical bonds, which have good mechanical properties and self‐repairing characteristics. The modified PEDOT:PSS as the conductive medium significantly improves the charge transfer rate. Moreover, the rapid formation of SEI by CA on the surface of SiNPs enhances the structural stability of the material. The electrochemical results show that the capacity of Si@PP@CA composite electrode canretain more than 2200 mAh g−1 after 200 cycles at 0.2 A g−1. It still shows a high capacity retention of 89% even at the current density of 1.0 A g−1 after 2000 cycles. More importantly, such excellent performance can be obtained using an electrode with an active material content of up to 90 wt%, which is essential for practical applications.

Thermodynamic Understanding of Formation and Evolution of Solid Electrolyte Interface in Li‐ion Batteries

AbstractFormation is an essential process in the manufacturing of lithium‐ion batteries and determines the performance of batteries, including life time, rate capability and so forth. The core of formation is to form a stable solid electrolyte interphase (SEI), which profoundly influences interfacial reactions and ion transport within Li‐ion batteries, on the surface of electrode. It is crucial to fully and deeply understand the intricate structure and evolution of SEI, which remains largely uncharted. This paper aims to systematically analyze SEI thermodynamics, encompassing energy distribution, entropy dynamics during SEI formation, and enthalpy changes. SEI evolves towards an equilibrium state, maximizing entropy. The intricate relationship between SEI thermodynamics and battery performance is established by dissecting the impacts of temperature and current density on SEI thermodynamic parameters and battery characteristics. Elevated temperatures and higher current densities foster the development of a more porous and high‐entropy outer SEI layer, rendering organic SEI constituents prone to decompose into high‐energy gases and low‐energy inorganic compounds. Notably, a fast formation strategy within a high state‐of‐charge range offers a potential solution to high quality SEI. This review strives to bridge the divide between fundamental thermodynamics and practical battery performance, ultimately contributing to the advancement of battery manufacturing.

Water/DMSO-Based Hybrid Electrolyte and Urea Additive Engineering for Performance Regulation in Aqueous Sodium Batteries

Electrochemical energy storage devices are of interest, especially aqueous sodium ion batteries (ASIBs), due to their safety, low-cost, and environmental friendliness. However, ASIBs suffer from poor cyclic stability and a narrow electrochemical window, which hinders their large-scale application. Compared to the traditional dilute saline electrolytes, high concentration electrolytes show a wider potential window. In this study, we designed a novel NaClO4-H2O/DMSO-Urea hybrid electrolyte to suppress these problems, in which DMSO and Urea create a synergistic effect. The formation of hydrogen bonds between DMSO and H2O reduced water activity, thereby suppressing the hydrogen evolution reaction. The addition of DMSO resulted in the reduction from −1.2 to −1.6 V for the hydrogen evolution potential. Therefore, we were able to expand the electrochemical window on the basis of reducing the concentration of sodium salts. Moreover, the addition of Urea facilitated formation of a stable solid electrolyte interface on the electrode surface, which improved the cycling stability of NVP/C (Na3V2(PO3)4/C) symmetric cell which exhibited a specific capacity of 59.7 mAh g−1 with the retention capacity of 80.1% after 200 cycles at 1 C. This work points out a promising strategy for developing stable and wide voltage aqueous electrolyte.

On the Practicability of the Solid‐State Electrochemical Pre‐Sodiation Technique on Hard Carbon Anodes for Sodium‐Ion Batteries

AbstractHard carbon (HC) with low cost and high specific capacity is considered the appropriate anode material for sodium‐ion batteries (SIBs), but the low initial coulombic efficiency (ICE) caused by solid electrolyte interface (SEI) formation and inherent active defects impede its practical battery application. Here, the practicability of solid‐state electrochemical (SSE) pre‐sodiation technique for hard carbon anode is assessed to conquer such challenges. The uniformly pre‐sodiated HC (Pre‐HC) can be fabricated through the SSE reaction between the HC and preloaded sodium metal film without introducing a liquid electrolyte. After being immerged in the electrolyte, a thin artificial SEI with abundant inorganic species is formed on the surface of Pre‐HC due to the spontaneous chemical reaction, and the ICE of HC is improved from 76.0% to 107.9%. Full cell paired with Na3V2(PO4)3 cathode exhibits a high ICE of 94.0% with 70% of energy density augment (from 126.5 to 214.4 Wh kg−1) after anode pre‐sodiation. Pre‐HC anode still retains the pre‐sodiation capacity of 671.1 mAh gNa−1 after being stored in the dry air for 2 h. This work demonstrates the practical applicability of this SSE pre‐sodiation strategy to enhance the energy density of SIBs.

Synergistically enhanced LiF–rich protective layer for highly stable silicon anodes

Silicon (Si) is considered as one of the most promising anode materials with an extremely high specific capacity (3579 mAh/g), which is beyond the limit of conventional graphite anodes in lithium (Li) ion batteries (LIBs). However, large volume changes during the lithiation/delithiation process and formation of an unstable solid electrolyte interface (SEI) layer hinder the practical application of Si anodes. To address these issues, constructing a stable protective layer at the interface between anode and electrolyte is a desirable strategy. In this study, a LiF-rich SEI inducing protective layer (LPL) comprising aluminum fluoride (AlF3) and poly(acrylic acid) (PAA) is introduced onto Si anode to construct a stable LiF–rich SEI layer and mitigate the volume changes of the Si anodes during cycling. Owing to the synergetic effects of AlF3 and PAA, a LiF-rich SEI layer with robust physicochemical properties is uniformly formed on the Si anode. As a result, the LPL coated Si (LPL@Si) anodes exhibit outstanding electrochemical properties in Li metal cell tests. In addition, a full-cell prepared with the LPL@Si anode and LiNi0.8Co0.1Mn0.1O2 as a cathode exhibits an excellent cycling performance and mitigated volume changes, demonstrating the potential of this strategy to protect the Si anodes for the development of high-energy–density LIBs.

Stabilizing Solid Electrolyte Interphase on Liquid Metal Via Dynamic Hydrogel-Derived Carbon Framework Encapsulation.

Eutectic gallium-indium liquid metal (EGaIn-LM), with a considerable capacity and unique self-healing properties derived from its intrinsic liquid nature, gains tremendous attention for lithium-ion batteries (LIBs) anode. However, the fluidity of the LM can trigger continuous consumption of the electrolyte, and its liquid-solid transition during the lithiation/de-lithiation process may result in the rupture of the solid electrolyte interface (SEI). Herein, LM is employed as an initiator to in situ assemble the 3D hydrogel for dynamically encapsulating itself; the LM nanoparticles can be homogeneously confined within the hydrogel-derived carbon framework (HDC) after calcination. Such design effectively alleviates the volume expansion of LM and facilitates electron transportation, resulting in a superior rate capability and long-term cyclability. Further, the "dual-layer" SEI structure and its key components, including the robust LiF outer layer and corrosion-resistant and ionic conductive LiGaOx inner layer are revealed, confirming the involvement of LM in the formation of SEI, as well as the important role of carbon framework in reducing interfacial side reactions and SEI decomposition. This work provides a distinct perspective for the formation, structural evolution, and composition of SEI at the liquid/solid interface, and demonstrates an effective strategy to construct a reliable matrix for stabilizing the SEI.

Regulating the inner Helmholtz plane structure at the electrolyte-electrode interface for highly reversible aqueous Zn batteries

The development of aqueous Zn batteries is limited by parasitic water reactions, corrosion, and dendrite growth. To address these challenges, an inner Helmholtz plane (IHP) regulation method is proposed by employing low-cost, non-toxic maltitol as the electrolyte additive. The preferential adsorption behavior of maltitol can expel the water from the inner Helmholtz plane, and thus hinder the immediate contact between Zn metal and H2O. Meanwhile, strong interaction between maltitol and H2O molecules can restrain the activity of H2O. Besides, the “IHP adsorption effect” along with the low LUMO energy level of maltitol-CF3SO3- can promote the in-situ formation of an organic–inorganic complex solid electrolyte interface (SEI) layer. As a result, the hydrogen/oxygen evolution side reaction, corrosion, and dendrites issues are effectively suppressed, thereby leading to highly reversible and dendrite-free Zn plating/stripping. The Zn||I2 battery with hybrid electrolytes also demonstrates high electrochemical performance and ultralong cycling stability, showing a capacity retention of 75% over 20000 charge-discharge cycles at a large current density of 5 A g−1. In addition, the capacity of the device has almost no obvious decay over 20000 cycles even at −30 °C. This work offers a successful electrolyte regulation strategy via the IHP adsorption effect to design electrolytes for high-performance rechargeable Zn-ion batteries.

Recent progress about transmission electron microscopy characterizations on lithium-ion batteries

With the rapid development of portable electronics, new energy vehicles, and smart grids, ion batteries are becoming one of the most widely used energy storage devices, while the safety concern of ion batteries has always been an urgent problem to be solved. To develop a safety-guaranteed battery, the characterization of the internal structure is indispensable, where electron microscopy plays a crucial role. Based on this, this paper summarizes the application of transmission electron microscopy (TEM) in battery safety, further concludes and analyzes the aspects of dendrite growth and solid electrolyte interface (SEI) formation that affect the safety of ion batteries, and emphasizes the importance of electron microscopy in battery safety research and the potential of these techniques to promote the future development of this field. These advanced electron microscopy techniques and their prospects are also discussed.

Understanding solid electrolyte interface formation on graphite and silicon anodes in lithium-ion batteries: Exploring the role of fluoroethylene carbonate

This study explores how fluoroethylene carbonate (FEC) influences the solid electrolyte interface (SEI) layer formation during battery cycling process. FEC improves SEI properties, producing a uniform, chemically stable layer enriched with lithium fluoride. This enhances mechanical resilience and electrochemical stability. FEC also suppresses electrolyte deformation and decomposition, maintaining its initial state. The findings highlight the significance and comprehension of electrolyte additives, offering an electrolyte research pathway for improving Li-ion battery performance and durability.

Selective construction of amorphous/crystalline heterostructure high entropy oxide for Li-ion batteries

High entropy oxides (HEO) are widely used as anode for lithium-ion batteries due to their exceptional chemical stability and mechanical strength. However, HEO encounters challenges such as low initial coulomb efficiency (ICE) and poor capacity. To address these issues, a simple mechanochemical method is employed to selectively amorphized and densely embed LiF within the HEO matrix. Taking advantage of the differing chemical properties of LiF and HEO, the transformation of LiF’s crystal structure not only overcomes its poor ionic conductivity but also successfully constructs an amorphous LiF/crystalline HEO heterostructure, which also improves the transport capacity of lithium ions. Additionally, the presence of abundant defects (e.g., oxygen vacancies, dislocations, and stacking faults) boosts the material's lithium transport and storage capacity. Furthermore, LiF facilitates the formation of a stable solid electrolyte interface (SEI) film on the HEO surface, preventing the corrosion of active materials and minimizing side reactions, effectively improving the ICE. The as-prepared LiF/HEO-48 demonstrates a superior initial capacity of 1632.9/1158.5 mAh g−1, along with an ICE of 70.9%. It maintains a high reversible capacity of 552.2 mAh g−1 after 1000 cycles at 0.5 A g−1, and even after 400 cycles at 2 A g−1, it retains 99.4% of its capacity. This study may open up new ways to selectively construct amorphous/heterostructures to improve the ICE and capacity of lithium-ion anodes.

In Situ Plasma Polymerization of Self-Stabilized Polythiophene Enables Dendrite-Free Lithium Metal Anodes with Ultra-Long Cycle Life.

Constructing a flexible and chemically stable multifunctional layer for the lithium (Li) metal anodes is a highly effective approach to improve the uneven deposition of Li+ and suppress the dendrite growth. Herein, an organic protecting layer of polythiophene is in situ polymerized on the Li metal via plasma polymerization. Compared with the chemically polymerized thiophene (C-PTh), the plasma polymerized thiophene layer (P-PTh), with a higher Young's modulus of 8.1GPa, shows strong structural stability due to the chemical binding of the polythiophene and Li. Moreover, the nucleophilic C─S bond of polythiophene facilitates the decomposition of Li salts in the electrolytes, promoting the formation of LiF-rich solid electrolyte interface (SEI) layers. The synergetic effect of the rigid LiF as well as the flexible PTh-Li can effectively regulate the uniform Li deposition and suppress the growth of Li dendrites during the repeated stripping-plating, enabling the Li anodes with long-cycling lifespan over 8000h (1mAcm-2 , 1 mAhcm-2) and 2500h (10mAcm-2 , 10 mAhcm-2 ). Since the plasma polymerization is facile (5-20min) and environmentally friendly (solvent-free), this work offers a novel and promising strategy for the construction of the forthcoming generation of high-energy-density batteries.

Regulating Electron Filling and Orbital Occupancy of Anti-Bonding States of Transition Metal Nitride Heterojunction for High Areal Capacity Lithium-Sulfur Full Batteries.

The commercialization of lithium-sulfur (Li-S) battery is seriously hindered by the shuttle behavior of lithium (Li) polysulfide, slow conversion kinetics, and Li dendrite growth. Herein, a novel hierarchical p-type iron nitride and n-type vanadium nitride (p-Fe2 N/n-VN) heterostructure with optimal electronic structure, confined in vesicle-like N-doped nanofibers (p-Fe2 N/n-VN⊂PNCF), is meticulously constructed to work as "one stone two birds" dual-functional hosts for both the sulfur cathode and Li anode. As demonstrated, the d-band center of high-spin Fe atom captures more electrons from V atom to realize more π* and moderate σ* bond electron filling and orbital occupation; thus, allowing moderate adsorption intensity for polysulfides and more effective d-p orbital hybridization to improve reaction kinetics. Meanwhile, this unique structure can dynamically balance the deposition and transport of Li on the anode; thereby, more effectively inhibiting Li dendrite growth and promoting the formation of a uniform solid electrolyte interface. The as-assembled Li-S full batteries exhibit the conspicuous capacities and ultralong cycling lifespan over 2000 cycles at 5.0 C. Even at a higher S loading (20mg cm-2 ) and lean electrolyte (2.5µL mg-1 ), the full cells can still achieve an ultrahigh areal capacity of 16.1 mAh cm-2 after 500 cycles at 0.1 C.

Interface engineering with fluorine-doped amorphous carbon thin film coating on graphite anodes compatible with non-flammable sulfone-based electrolyte

To achieve full commercialization of Li-ion batteries, fire safety issues, which primarily start and accelerate from the electrode/electrolyte interface, should be resolved. Therefore, ionic liquids containing sulfone-based Li salts and solvents have been demonstrated to exhibit higher flame-retardancy than carbonate-based electrolytes. However, these sulfone-based electrolytes (sulfone EL) still face the challenges of sluggish Li-ion diffusivity of the electrolyte itself and poor compatibility especially with graphite anodes, lowering the specific capacity and high rate capability of the anodes. Herein, interface engineering was achieved by introducing a fluorine-doped amorphous carbon thin film coating (sub-20 nm) between graphite and sulfone EL, thereby simultaneously enhancing the ultrafast rate capability and flame-retardancy. The semi-ionic C–F abundant surface chemistry of graphite (F–C/Gra) not only induces robust solid electrolyte interface (SEI) formation with a LiF-rich composition and moderate thickness, but it also promotes fast-rated electron transfer into the graphite interior, which differs from bare graphite in sulfone EL. Surprisingly, this robust SEI formation on F–C/Gra was achieved at an elevated temperature (60 °C), enhancing Li-ion transport kinetics and allowing graphite-based anodes to achieve ultrafast longevity (discharge capacity of 152.6 mAh/g after 300 cycles at 1000 mA/g, 60 °C) even under harsh conditions.

Artificial LiF-Rich Interface Enabled by In situ Electrochemical Fluorination for Stable Lithium-Metal Batteries.

Lithium (Li)-metal batteries are promising next-generation energy storage systems. One drawback of uncontrollable electrolyte degradation is the ability to form a fragile and nonuniform solid electrolyte interface (SEI). In this study, we propose the use of a fluorinated carbon nanotube (CNT) macrofilm (CMF) on Li metal as a hybrid anode, which can regulate the redox state at the anode/electrolyte interface. Due to the favorable reaction energy between the plated Li and fluorinated CNTs, the metal can be fluorinated directly to a LiF-rich SEI during the charging process, leading to a high Young's modulus (~2.0 GPa) and fast ionic transfer (~2.59×10-7 S cm-1 ). The obtained SEI can guide the homogeneous plating/stripping of Li during electrochemical processes while suppressing dendrite growth. In particular, the hybrid of endowed full cells with substantially enhanced cyclability allows for high capacity retention (~99.3 %) and remarkable rate capacity. This work can extend fluorination technology into a platform to control artificial SEI formation in Li-metal batteries, increasing the stability and long-term performance of the resulting material.

Artificial LiF‐Rich Interface Enabled by In situ Electrochemical Fluorination for Stable Lithium‐Metal Batteries

AbstractLithium (Li)‐metal batteries are promising next‐generation energy storage systems. One drawback of uncontrollable electrolyte degradation is the ability to form a fragile and nonuniform solid electrolyte interface (SEI). In this study, we propose the use of a fluorinated carbon nanotube (CNT) macrofilm (CMF) on Li metal as a hybrid anode, which can regulate the redox state at the anode/electrolyte interface. Due to the favorable reaction energy between the plated Li and fluorinated CNTs, the metal can be fluorinated directly to a LiF‐rich SEI during the charging process, leading to a high Young's modulus (~2.0 GPa) and fast ionic transfer (~2.59×10−7 S cm−1). The obtained SEI can guide the homogeneous plating/stripping of Li during electrochemical processes while suppressing dendrite growth. In particular, the hybrid of endowed full cells with substantially enhanced cyclability allows for high capacity retention (~99.3 %) and remarkable rate capacity. This work can extend fluorination technology into a platform to control artificial SEI formation in Li‐metal batteries, increasing the stability and long‐term performance of the resulting material.

Regenerated Graphite Electrodes with Reconstructed Solid Electrolyte Interface and Enclosed Active Lithium Toward >100% Initial Coulombic Efficiency.

Solid electrolyte interface (SEI) is arguably the most important concern in graphite anodes, which determines their achievable Coulombic efficiency (CE) and cycling stability. In spent graphite anodes, there are already-formed (yet loose and/or broken) SEIs and some residual active lithium, which, if can be inherited in the regenerated electrodes, are highly desired to compensate for the lithium loss due to SEI formation. However, current graphite regenerated approaches easily destroy the thin SEIs and residue active lithium, making their reuse impossible. Herein, this work reports a fast-heating strategy (e.g., 1900 K for ≈150ms) to upcycle degraded graphite via instantly converting the loose original SEI layer (≈100nm thick) to a compact and mostly inorganic one (≈10-30nm thick with a 26X higher Young's Modulus) and still retaining the activity of residual lithium. Thanks to the robust SEI and enclosed active lithium, the regenerated graphite exhibited 104.7% initial CE for half-cell and gifted the full cells with LiFePO4 significantly improved initial CE (98.8%versus 83.2%) and energy density (309.4versus 281.4Wh kg-1), as compared with commercial graphite. The as-proposed upcycling strategy turns the "waste" graphite into high-value prelithiated ones, along with significant economic and environmental benefits.

Enhancing Li-S Battery Performance with Limiting Li[N(SO2F)2] Content in a Sulfolane-Based Sparingly Solvating Electrolyte.

By enhancing the stability of the lithium metal anode and mitigating the formation of lithium dendrites through electrolyte design, it becomes feasible to extend the lifespan of lithium-sulfur (Li-S) batteries. One widely accepted approach involves the utilization of Li[N(SO2F)2] (Li[FSA]), which holds promise in stabilizing the lithium anode by facilitating the formation of an inorganic-dominant solid electrolyte interface (SEI) film. However, the use of Li[FSA] encounters limitations due to inevitable side reactions between lithium polysulfides (LiPSs) and [FSA] anions. In this study, our focus lies in precisely controlling the composition of the SEI film and the morphology of the deposited lithium, as these two critical factors profoundly influence lithium reversibility. Specifically, by subjecting an initial charging process to an elevated temperature, we have achieved a significant enhancement in lithium reversibility. This improvement is accomplished through the employment of a LiPS sparingly solvating electrolyte with a restricted Li[FSA] content. Notably, these optimized conditions have resulted in an enhanced cycling performance in practical Li-S pouch cells. Our findings underscore the potential for improving the cycling performance of Li-S batteries, even when confronted with challenging constraints in electrolyte design.