Role of the Electrolyte Concentration in Polysulfide Shuttle and Electrochemical Performance of Lithium–Sulfur Batteries
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Role of the Electrolyte Concentration in Polysulfide Shuttle and Electrochemical Performance of Lithium–Sulfur Batteries
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ACS Energy Letters

Cite this: ACS Energy Lett. 2026, XXXX, XXX, XXX-XXX
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https://doi.org/10.1021/acsenergylett.6c00391
Published April 9, 2026

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Abstract

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Lithium–sulfur (Li–S) batteries promise high energy density, yet their operation is constrained by a complex interplay of electrolyte, electrode, and interfacial processes. The electrolyte governs dissolution, redox kinetics, and ionic transport, serving as both the enabler and the bottleneck of cell performance. In this work, we develop a microstructure-coupled mechanistic framework to examine how the electrolyte concentration, volume, and solvation strength jointly regulate charge-carrier availability, ionic mobility, and shuttle reactions. The analysis reveals distinct regimes defined by the competition among dissolution, transport, and conversion processes. The electrolyte-to-sulfur ratio and cathode porosity further modulate this balance, delineating a narrow, conductivity-optimal window where kinetics and transport remain coupled. Solvent solubility shifts this window: weak solvation impedes conversion, whereas excessive solvation accelerates shuttle losses. These insights establish a comprehensive conductivity-based design framework linking electrolyte chemistry, solvent properties, and cathode architecture for achieving high-efficiency and durable liquid Li–S batteries.

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Lithium–sulfur (Li–S) batteries offer a theoretical specific energy of 2600 Wh kg–1 and rely on sulfur, an abundant and low-cost material, making them strong candidates for next-generation electrochemical storage. (1−9) In a Li–S cell, the sulfur cathode operates through a multi-step conversion mechanism in which the electrolyte acts as both a transport medium and reactive reservoir (Figure 1a). During discharge, solid sulfur [S8(s)] dissolves into the electrolyte and is electrochemically reduced to soluble polysulfides (PSs) (S82–, S62–, and S42–) that eventually precipitate as insoluble Li2S within the porous cathode matrix. A major barrier to commercialization is the “shuttle effect”, the migration of soluble PSs from the cathode to the lithium anode. (10−17) At the anode, these species undergo parasitic reduction to Li2S, leading to active-material loss, low coulombic efficiency, and rapid capacity decay. (18,19) The continual transformation from dissolved to precipitated sulfur couples phase-change reactions with ionic transport, making the electrolyte composition and cathode microstructure central to performance. (20−22)

Figure 1

Figure 1. (a) During the Li–S discharge process, species evolution occurs within both the cathode microstructure and the electrolyte. S8(s) first dissolves into the electrolyte, followed by a multi-step electrochemical reduction at the cathode, ultimately leading to the precipitation of solid Li2S. (b) Electrolyte properties influence reaction kinetics, dissolution–precipitation behavior, and species transport in Li–S batteries. Variations in the electrolyte-to-sulfur (E/S) ratio, solvation strength, and LiTFSI concentration modify ion transport and electrochemical reaction pathways, collectively defining the electrolyte signatures governing Li–S performance. Solvation free energies are adapted from Kim et al. (37)

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Recent efforts have been made to produce high-energy-density Li–S batteries. Catalytic interfaces and polar host materials have been shown to enhance sulfur redox kinetics, promote controlled Li2S nucleation and growth, and suppress polysulfide migration through adsorption and electrocatalytic conversion pathways. (23−29) While these advances emphasize material-level regulation of reaction pathways and interfacial chemistry, the electrolyte transport environment governs ionic conductivity, species distribution, and shuttle flux within porous electrodes. The evolution of sulfur species is intricately linked to the physicochemical properties of the electrolyte, as depicted in Figure 1b. (30) Variations in the solvent composition and salt concentration alter the coordination environment, polysulfide solubility, and ionic conductivity. (31−36) Traditional ether-based systems, particularly, 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) mixtures with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), have been extensively used in Li–S cells. (38−40) While these ether-based electrolytes are favorable for their ability to dissolve PSs and facilitate sulfur utilization, their inherently high solubility exacerbates the shuttle phenomenon. (26,38,39,41−43)
Specifically, solvation is strongly influenced by the electrolyte’s solvating power, which governs the interaction strength between PSs, solvent molecules, and lithium ions. (44−47) Strongly solvating electrolytes accelerate cathode kinetics but intensify shuttle and anode-side side reactions, whereas weakly solvating systems suppress shuttling at the expense of sulfur conversion and increased polarization. (48,49) An optimal electrolyte therefore requires medium solvating power that sustains polysulfide dissolution and transport without excessive migration. (50)
The electrolyte-to-sulfur (E/S) ratio and LiTFSI concentration further modulate viscosity, coordination environments, and ionic diffusivity, collectively determining active-species distribution and the onset of transport limitations (Figure 1b). (51−55) Elevated E/S ratios enhance sulfur dissolution but intensify shuttling and reduce volumetric energy density, whereas lean electrolyte conditions increase viscosity and internal resistance, limiting sulfur conversion. (56−58) The salt concentration, especially LiTFSI, exerts a similar dual influence by controlling ionic conductivity, polysulfide solubility, viscosity, and interfacial stability. (59−61) At low salt concentrations, enhanced sulfur dissolution and mobility enable rapid cathode reactions but promote shuttle-driven parasitic losses at the anode. Increasing the salt concentration suppresses dissolution and shuttling but raises viscosity, thereby lowering ionic conductivity and hindering transport. Furthermore, sulfur solubility exhibits a nonlinear dependence on the salt concentration and solvent coordination structure, leading to abrupt shifts in reaction pathways and performance. (37,62) These nonlinearities highlight the need for a mechanistic understanding of how electrolyte formulation governs redox continuity, mass transport, and stability. While qualitative trends associated with electrolyte parameters, such as the salt concentration and electrolyte-to-sulfur (E/S) ratio, have been widely reported in Li–S batteries, the coupled influence of the electrolyte composition and cathode microstructure on ion transport and overall reaction progression remain insufficiently quantified. How variations in electrolyte composition interact with sulfur loading and pore structure to control ionic transport and determine the dominant limiting mechanisms governing cell operation is not yet well-understood.
In this work, we develop a microstructure-resolved modeling framework that couples multi-step electrochemical kinetics with composition-dependent ion transport and resolves electrolyte-mediated interspecies interactions and polysulfide shuttle reactions within the electrode microstructure. Using this framework, we identify the dominant limiting mechanisms governing Li–S performance and map how electrolyte composition and cathode structure jointly influence cell behavior across the operating space. The framework captures the coupled evolution of sulfur speciation and transport limitations within the porous cathode, with mass and charge conservation, including multi-step sulfur redox and anode-side shuttle reactions, implemented using a finite-volume formulation (section S1 of the Supporting Information). We examine how electrolyte descriptors, such as the E/S ratio, solubility, and LiTFSI concentration, individually and collectively dictate performance trade-offs in Li–S cells. We further quantify polysulfide flux and consumption at the anode–separator interface to identify conditions that minimize shuttle activity and distinguish reversible from irreversible pathways. Quantitative metrics, such as discharge capacity and cumulative shuttle loss, are used to relate the initial discharge performance to long-term stability. Systematic variation of the salt concentration, pristine porosity, and sulfur loading enables conversion of local transport and speciation behavior into design maps connecting the electrolyte formulation and cathode architecture to operating regimes that enable efficient sulfur utilization and extended cycle life.
The electrolyte concentration dictates the competition between the charge-carrier availability and ion mobility. Moderate salt concentrations provide sufficient Li+ ions to sustain redox reactions, whereas concentrated electrolytes impose viscous and clustering-related transport losses. Our analysis reveals that discharge capacity decreases steadily with an increasing salt concentration, as the normalized discharge capacity drops from approximately 0.6 (at 0.3 M LiTFSI) to approximately 0.15 (at 3.0 M LiTFSI), as shown in Figure 2a.

Figure 2

Figure 2. Simulation results illustrating the effect of the salt concentration on the Li–S cell behavior. (a) Electrochemical performance of a Li–S cell at varying salt concentrations in the electrolyte, evaluated with 80% cathode porosity and 20 vol % sulfur loading. (b) Sulfur fractions of unconverted S42– species and precipitated Li2S in the cathode at different salt concentrations. (c) Evolution of ionic conductivity during discharge for different salt concentrations, where the conductivity is normalized by the maximum ionic conductivity observed during discharge. (d) Electrolyte potential drop during discharge at different salt concentrations. (e) Evolution of PSs during discharge for different salt concentrations.

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The framework captures continuous dissolution and precipitation processes and subsequent microstructural evolution occurring inside the cathode (section S1.2 of the Supporting Information). During discharge, sulfur dissolves into the electrolyte and forms soluble intermediates S82– and S42–, which subsequently precipitate as Li2S. The fraction of unconverted S42– increases markedly with the salt concentration, suppressing Li2S formation and limiting overall sulfur utilization (Figure 2b). At a low salt concentration, a substantial fraction of sulfur converts to Li2S, whereas at a high salt concentration, sulfur remains predominantly trapped as unconverted S42–.
At lower and intermediate salt concentrations (0.3 and 1.0 M), ionic conductivity initially increases in the early stages of discharge due to the formation of highly soluble and mobile S82– species that enhance transport (Figure 2c). As the discharge proceeds and S82– converts into the S42– intermediate, the conductivity begins to decline because of the increased viscosity and hindered ion movement. Once S42– is converted into Li2S, the reduced presence of dissolved intermediates allows Li+ ions to move more freely, partially restoring the conductivity toward the end of discharge. This conductivity recovery occurs later for 1.0 M compared to 0.3 M, consistent with slower reaction kinetics and delayed conversion of the intermediate species. The sharper voltage decay observed at 3.0 M cannot be explained solely by changes in sulfur speciation (Figure 2a). At a 3.0 M salt concentration, ionic conductivity decreases continuously throughout discharge, consistent with enhanced interionic interactions and solvation-limited transport under concentrated conditions. Strong ion–ion associations increase effective viscosity and reduce Li+ mobility, rendering ion transport the limiting mechanism. Consequently, sulfur utilization becomes limited, marking a transition from reaction-controlled to transport-limited operation under concentrated conditions.
Low ionic conductivity in the electrolyte introduces a significant potential drop across the cell, reducing its effective working voltage and capacity (Figure 2d). At a salt concentration of 3.0 M, this potential drop becomes pronounced, consistent with severe ionic transport losses. The resulting increase in electrolyte polarization accelerates voltage decay and limits the complete conversion of intermediate polysulfides to Li2S, leading to premature termination of the discharge. In comparison, for 0.3 and 1.0 M electrolytes, the potential drop initially increases due to the transient accumulation of less soluble S42– species but decreases as these intermediates are consumed. Figure 2e depicts the evolution of sulfur and polysulfide species in both solid and electrolyte phases during discharge for low (0.3 M) and high (3.0 M) concentration electrolytes. Sulfur initially undergoes successive reduction to S82– and S42–, but increasing electrolyte polarization weakens transport, leading to early discharge termination and incomplete intermediate conversion.
To validate the modeling predictions, galvanostatic discharge experiments were performed on Li–S cells containing 0.3, 1.0, and 3.0 M LiTFSI in DOL/DME (1:1, v/v) electrolytes (Figure S5a). An integrated Ketjenblack/sulfur (IKB/S) electrode as a baseline sulfur electrode was used because it can be slurry-coated to high sulfur loading (5.5–6.5 mg cm–2), which is representative of practical Li–S electrodes and makes transport limitations pronounced. It consists of secondary particles of nanomaterials, preserving the high activity of nanosized sulfur hosts while enabling good processability and large-scale slurry-coating fabrication. (63,64) The discharge profiles mirror the simulated trends: cells with 0.3 and 1.0 M electrolytes deliver comparable capacities, whereas the 3.0 M cell exhibits a sharp decline, reflecting severe transport limitations. Electrochemical impedance spectra (Figure 3a and b) show a marked increase in total cell resistance at 3.0 M relative to 0.3–1.0 M, consistent with the simulated rise in electrolyte potential drop. Although ionic conductivity cannot be tracked operando, measurements of the electrolyte containing LiTFSI salt (Figure 3c) reveal a maximum of 12.7 mS cm–1 near 1.0 M and a decline to 3.6 mS cm–1 at 3.0 M, paralleling the predicted conductivity profile. Similarly, viscosity measurements of the same electrolyte indicate that the 0.3 and 1.0 M solutions exhibit much lower viscosity compared to the 3.0 M solution (Figure S5b). Together, the experimental and modeling results confirm that higher LiTFSI concentrations intensify interspecies interactions and viscosity, which suppress ionic mobility, increase electrolyte polarization, and restrict sulfur conversion during discharge.

Figure 3

Figure 3. Nyquist plots of Li–S cells with electrolytes at different LiTFSI concentrations (a) before and (b) after discharge. (c) Experimental ionic conductivity measurement of electrolytes at different LiTFSI concentrations. (d) Simulated sulfur utilization maps as a function of the electrolyte-to-sulfur (E/S) ratio and salt concentration for pristine cathodes with different porosities (60–90 vol %). (e) Map of the salt concentration versus E/S ratio highlighting regions of high sulfur utilization and the “sudden death” zone. (f) Variation in the number of charge carriers and their interactions with changes in the salt concentration and E/S ratio.

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While these results demonstrate improved performance at lower initial salt concentrations, the optimal composition is not universal. Hence, our microstructure-resolved framework is utilized to examine how the salt concentration, E/S ratio, and pristine porosity collectively dictate the local reaction environment and overall cell performance. The performance map (Figure 3d) reveals a strong dependence of cell behavior on the coupled effects of the E/S ratio, salt concentration, and pristine cathode porosity. Although the E/S ratio is intrinsically linked to porosity and sulfur loading, presenting separate maps for different porosities isolates their mechanistic influence on electrochemical behavior. At a fixed porosity of 60 vol %, varying the sulfur loading from 20 to 5% corresponds to an E/S ratio range of approximately 1–4 mL g–1 (for E/S ratio conclusion, we consider the electrolyte present inside the cathode pores only). Within this regime, the use of concentrated electrolytes is particularly detrimental: across most salt concentrations, capacity remains suppressed due to severe transport limitations imposed by the dense microstructure. These transport constraints are further intensified under lean electrolyte conditions. As discharge progresses and the concentration of S42– increases, ionic pathways become increasingly hindered, preventing the realization of any benefit from a high salt concentration.
As the pristine porosity increases to 80% (Figure 3d), the interconnected pore network allows improved electrolyte infiltration and reduced transport resistance. In this case, a wider range of electrolyte formulations, particularly moderate to high salt concentrations with E/S ratios between 2 and 6 mL g–1, provides efficient ion transport. This improvement manifests as a broader region of high sulfur utilization, indicating that transport no longer constrains performance to a narrow conductivity window. When porosity further increases to 90%, sulfur utilization becomes nearly independent of electrolyte composition across the tested range. To gain deeper insight into this behavior, we analyzed the ionic conductivity profile of the electrolyte used in our framework (Figure S1), expressed as a function of the Li+ and S42– concentrations. The resulting conductivity surface exhibits a pronounced peak, which represents an optimal regime where the density of mobile charge carriers is sufficiently high without incurring significant mobility losses.
In Figure 3e, a central zone of high sulfur utilization is observed, flanked by two performance-degrading regimes. The main quantitative criterion used to define the sudden death regime is the discharge capacity value (the sudden death region is defined if the capacity is less than 200 mAh g–1). At one extreme, low salt and lean electrolyte conditions lead to ionic starvation, whereas at the other extreme, very high salt concentrations induce viscosity-driven transport losses. Both extremes yield poor capacity, while intermediate compositions achieve a balanced coupling between charge-carrier density and mobility. Figure 3f explains the potential reasons for the sudden death behavior (due to interionic interactions at high loading and concentration or due to the lack of charge carrier at low loading and low initial salt concentration).
Due to high solubility, higher order and intermediate PSs remain dissolved in the electrolyte. These species migrate across the cathode–separator interface, driven by concentration and electrolyte potential gradients (Figure S2a). Although not all sulfur species crossing the cathode–separator interface react with lithium metal, a fraction undergoes direct chemical reduction at the anode surface. This leads to the capacity defined here as the “shuttle defect”. The electrochemical performance with and without these side reactions (Figure S2b) illustrates the associated energy loss showing inflated voltage plateaus and diminished capacity when shuttling is active.
Two main pathways govern the shuttle activity. In the first, higher order PSs and dissolved sulfur are reduced at the lithium surface to form intermediate PSs that remain soluble and can be reoxidized during charging, causing reversible shuttle loss. In the second, intermediate PSs reduce further to insoluble Li2S, which deposits on the lithium surface and cannot be reoxidized, resulting in irreversible shuttle loss and long-term capacity fade. Figure S2c presents the variation of reaction rates during discharge, where R1, R2, and R3 correspond to reactions S44–S46 of the Supporting Information, with their rate expressions given in reactions S47–S49 in the Supporting Information. Notably, R2 peaks when higher order PSs convert to medium-order species, coinciding with their maximum concentration.
The severity of shuttle loss arises from the interplay between sulfur species transport and their chemical reduction at the anode, both of which depend on the electrolyte’s physicochemical properties. Phase maps of reversible and irreversible shuttle losses (Figure 4a and b) highlight these dependencies across E/S ratios from 1.5 to 6 mL g–1 and salt concentrations ranging from 0.1 to 4.0 M for cathodes with 80% porosity (results for 60 and 90% porosity appear in Figure S3).

Figure 4

Figure 4. (a) Reversible shuttle and (b) irreversible shuttle behavior as functions of the salt concentration and E/S ratio. (c) Key performance descriptors of a Li–S battery and their dependence on the salt concentration. (d) Shuttle influx and consumption at the anode varies with the salt concentration, correlating with transport resistance. Shuttle influx and consumption calculated for (e) 0.1 M and (f) 1.0 M salt concentrations. (g) Variation of irreversible chemical redox reactions with the initial salt concentration.

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In this low-E/S regime, reversible shuttle loss peaks below the 1 M salt concentration. As the LiTFSI concentration increases from 0.1 to 1.0 M, the reversible shuttle effect diminishes across all E/S ratios. At low salt concentrations, excess solvent (DOL/DME) strongly solvates Li+ and PSs, enhancing mobility and intensifying shuttle activity. Increasing the salt concentration incorporates more solvent molecules into Li+ solvation shells, reducing diffusivity and thereby limiting their transport through the electrolyte. Simultaneously, the higher viscosity and lower ionic diffusivity of concentrated electrolytes impose additional resistance to sulfur species transport.
At high salt concentrations and low E/S ratios, strong interspecies interactions hinder both sulfur dissolution and ion transport, producing incomplete cathode conversion and reduced discharge capacity. Overall, increasing the LiTFSI concentration mitigates both reversible and irreversible shuttle losses until near-saturation limits are reached. Irreversible shuttle loss, responsible for Li2S buildup and anode passivation, is also a major contributor to capacity fade during cycling. Figure 4b highlights a high-risk region at elevated E/S ratios (4–6 mL g–1), where a low transport resistance within the cathode permits significant PS migration toward the anode. In this region, even moderate LiTFSI concentrations (∼0.7 M) cause nearly 6% sulfur to precipitate at the anode. The extent of sulfur conversion at the anode is governed by two competing factors: the flux of sulfur species reaching the anode and the fraction reduced to Li2S. While both the E/S ratio and salt concentration influence transport, higher salt concentrations consistently suppress chemical reactions at the anode.
Variations in the E/S ratio and salt concentration modulate sulfur conversion and shuttle behavior, reflecting a composition-dependent balance among PS transport, cathode kinetics, and anode reactivity. Key performance metrics, including unconverted S42–, reversible shuttle contribution, Li2S deposition at the anode, and discharge capacity, are summarized as a function of the E/S ratio for three LiTFSI concentrations: 0.1, 1.0, and 3.0 M (Figure 4c and Figure S4).
At 0.1 M, increasing the E/S ratio lowers unconverted S42– while raising the reversible shuttle, indicating that larger electrolyte volumes enhance PS solubilization and circulation, improving utilization but intensifying the shuttle. At 1.0 M and E/S of ∼1.5 mL g–1, sulfur utilization remains high while the reversible shuttle drops sharply, showing that a moderate ionic strength suppresses PS crossover without hindering cathode kinetics. At 3.0 M under lean E/S conditions, S42– accumulation and restricted ion mobility cause early discharge termination, yet Li2S still deposits at the anode, confirming persistent parasitic reactions despite limited cathode conversion.
A low salt with ample electrolyte results in a high capacity but pronounced shuttle, whereas a moderate salt maintains an efficient conversion with minimal shuttle (Figure 4d). At a very high salt concentration, PS motion is strongly restricted and conversion halts at S42–, yet the anode-side reaction persists, revealing that cathode limitation does not completely suppress chemical reactions at lithium and that transport and surface chemistry can decouple under concentrated conditions.
Anode-side influx and consumption trends (Figure 4e and f) reinforce this behavior. At 0.1 M, both fluxes are large with distinct inflections at a low E/S ratio, consistent with vigorous PS arrival and rapid anode consumption during discharge. At 1.0 M, flux magnitudes drop and the inflection nearly disappears, aligning with moderated transport and reduced shuttle while preserving cathode utilization. The irreversible chemical redox component at the anode (Figure 4g) shows similar dependence: at 0.1 M, irreversible activity is stronger and appears earlier, while at 1.0 M, it is weaker and delayed, reflecting reduced PS access and milder parasitic reactions.
The affinity between solvent molecules and sulfur species is a crucial parameter. This affinity, represented by the solubility product constant (ksp), scales with solvation energy and correlates positively with the concentration of the dissolved active species. Solubility determines the spatial and temporal distribution of sulfur species and, therefore, governs both reaction kinetics and ionic transport. Weakly solvating solvents promote Li+ clustering, reduce diffusivity, and hinder conversion, whereas strong solvents enhance Li+ mobility but facilitate PS transport, increasing shuttle losses (Figure 5a). Experimentally reported sulfur solubility values typically fall within the range of ∼4–10 depending on the electrolyte solvation environment. (65−69) In this work, the ksp sweep is selected to span these experimentally relevant dissolution regimes, enabling controlled evaluation of how solubility-driven speciation affects the kinetics and shuttle. Here, ksp serves as a thermodynamic proxy for solvation-controlled dissolution/dissociation of lithium polysulfides: recent potentiometric measurements show that solvation free energy correlates strongly with ln(ksp) and provide the thermodynamic basis linking the electrolyte solvation strength to an experimentally measurable solubility constant.

Figure 5

Figure 5. (a) Schematic representation depicting the correlation of solvation with Li+ diffusivity; stronger solvation enhances solubility, thereby improving reaction kinetics. (b) Electrochemical performance of the Li–S cell for different ksp values. Species evolution during discharge for electrolytes with (c) ksp = 5, (d) ksp = 7, and (e) ksp = 9. (f) Discharge capacity as a function of solubility (ksp). (g) Sulfur loss due to the shuttle effect as a function of ksp. (h) Qualitative Sankey diagram illustrating the interdependencies and multivariate impact of the cathode architecture, electrolyte properties, and solubility on the mechanistic response of Li–S batteries, including transport, reaction kinetics, capacity, and shuttle loss.

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Electrochemical performance was evaluated across electrolyte systems with ksp values, which was utilized as a modeling parameter. The voltage–capacity profiles for representative solubilities (ksp = 5, 7, and 9) reveal that low-solubility electrolytes (ksp = 5) exhibit depressed upper and lower plateaus, reflecting the limited availability of dissolved PSs. With increasing solubility (ksp = 7 and 9), both plateaus rise and a stronger mid-discharge inflection appears, indicating enhanced formation of medium-order PSs and faster reaction kinetics (Figure 5b–e). The capacity trends (Figure 5f) follow this behavior: low solubility constrains redox activity; moderate solubility boosts conversion, and excessive solubility reverses this gain.
Higher solubility also intensifies the shuttle effect. The fraction of active sulfur lost to irreversible shuttle reactions increases from 0.1 to 0.9% as ksp rises from 3 to 11 (Figure 5g), capturing the trade-off between accelerated kinetics and greater shuttle losses. Thus, solvent design requires a careful balance: solvation must be strong enough to support sulfur dissolution and redox continuity yet moderate enough to preserve transport efficiency and suppress parasitic shuttling.
The interdependence among key design variables is summarized in Figure 5h. Cathode porosity and sulfur loading influence kinetics through their control of accessible active area and active material availability, and they also affect transport pathways by modifying pore structure. The salt concentration and solubility contribute to both channels: higher values improve kinetics through greater Li+ and availability of PSs but concurrently impose viscous and clustering-related transport penalties. The relative strengths of these pathways explain how each parameter ultimately governs capacity and shuttle loss. Achieving high capacity with minimal shuttle requires a synergistic balance, where the cathode architecture promotes redox activity and the electrolyte composition sustains efficient mass transport.
In conclusion, this work integrates pore-scale transport with multi-step sulfur redox and dissolution–precipitation to demonstrate how electrolyte composition and cathode architecture jointly govern the performance of liquid Li–S batteries. By resolving the evolution of elemental sulfur, soluble PSs, and Li2S within a realistic porous network and the link of local speciation to composition-dependent transport, three mechanistic regimes are identified: carrier-limited, transport-limited, and reaction-limited regimes. This study connects the salt concentration, E/S ratio, and solubility with cathode descriptors, such as porosity and sulfur loading, providing a coherent view of how kinetics and mass transport trade off across conditions. Solvent strength exhibits a non-monotonic influence, where excessive solubility accelerates shuttling and clustering. This work provides a quantitative framework that identifies transport-, conversion-, and shuttle-dominated regimes and establishes design maps linking the electrolyte composition with the cathode structure for electrolyte–cathode co-optimization. These mechanistic insights establish a foundation for co-designing electrolyte formulation and cathode structure to achieve stable, high-efficiency liquid Li–S batteries.

Experimental Methods

Experimental methods are presented in section 2.1 of the Supporting Information.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsenergylett.6c00391.

  • Computational framework to predict electrochemical performance (section S1) and experimental methods and results (section S2) (PDF)

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  • Corresponding Author
  • Authors
    • Md Shahriar Nahian - School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907, United States
    • Arpan K. Sharma - School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907, United States;  Orcidhttps://orcid.org/0000-0002-6125-2194
    • Bairav S. Vishnugopi - School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907, United States;  Orcidhttps://orcid.org/0009-0002-6357-9358
    • JiYoung Seo - Energy & Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
    • Lirong Zhong - Energy & Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99354, United States;  Orcidhttps://orcid.org/0000-0001-5052-939X
    • Lili Shi - Energy & Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
  • Author Contributions

    Md Shahriar Nahian and Arpan K. Sharma contributed equally to this work.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This work was supported by the U.S. Department of Energy under Award DE-EE0011166, as part of the Advanced Battery Materials Research (BMR) Program.

References

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  • Abstract

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    Figure 1

    Figure 1. (a) During the Li–S discharge process, species evolution occurs within both the cathode microstructure and the electrolyte. S8(s) first dissolves into the electrolyte, followed by a multi-step electrochemical reduction at the cathode, ultimately leading to the precipitation of solid Li2S. (b) Electrolyte properties influence reaction kinetics, dissolution–precipitation behavior, and species transport in Li–S batteries. Variations in the electrolyte-to-sulfur (E/S) ratio, solvation strength, and LiTFSI concentration modify ion transport and electrochemical reaction pathways, collectively defining the electrolyte signatures governing Li–S performance. Solvation free energies are adapted from Kim et al. (37)

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    Figure 2

    Figure 2. Simulation results illustrating the effect of the salt concentration on the Li–S cell behavior. (a) Electrochemical performance of a Li–S cell at varying salt concentrations in the electrolyte, evaluated with 80% cathode porosity and 20 vol % sulfur loading. (b) Sulfur fractions of unconverted S42– species and precipitated Li2S in the cathode at different salt concentrations. (c) Evolution of ionic conductivity during discharge for different salt concentrations, where the conductivity is normalized by the maximum ionic conductivity observed during discharge. (d) Electrolyte potential drop during discharge at different salt concentrations. (e) Evolution of PSs during discharge for different salt concentrations.

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    Figure 3

    Figure 3. Nyquist plots of Li–S cells with electrolytes at different LiTFSI concentrations (a) before and (b) after discharge. (c) Experimental ionic conductivity measurement of electrolytes at different LiTFSI concentrations. (d) Simulated sulfur utilization maps as a function of the electrolyte-to-sulfur (E/S) ratio and salt concentration for pristine cathodes with different porosities (60–90 vol %). (e) Map of the salt concentration versus E/S ratio highlighting regions of high sulfur utilization and the “sudden death” zone. (f) Variation in the number of charge carriers and their interactions with changes in the salt concentration and E/S ratio.

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    Figure 4

    Figure 4. (a) Reversible shuttle and (b) irreversible shuttle behavior as functions of the salt concentration and E/S ratio. (c) Key performance descriptors of a Li–S battery and their dependence on the salt concentration. (d) Shuttle influx and consumption at the anode varies with the salt concentration, correlating with transport resistance. Shuttle influx and consumption calculated for (e) 0.1 M and (f) 1.0 M salt concentrations. (g) Variation of irreversible chemical redox reactions with the initial salt concentration.

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    Figure 5

    Figure 5. (a) Schematic representation depicting the correlation of solvation with Li+ diffusivity; stronger solvation enhances solubility, thereby improving reaction kinetics. (b) Electrochemical performance of the Li–S cell for different ksp values. Species evolution during discharge for electrolytes with (c) ksp = 5, (d) ksp = 7, and (e) ksp = 9. (f) Discharge capacity as a function of solubility (ksp). (g) Sulfur loss due to the shuttle effect as a function of ksp. (h) Qualitative Sankey diagram illustrating the interdependencies and multivariate impact of the cathode architecture, electrolyte properties, and solubility on the mechanistic response of Li–S batteries, including transport, reaction kinetics, capacity, and shuttle loss.

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  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsenergylett.6c00391.

    • Computational framework to predict electrochemical performance (section S1) and experimental methods and results (section S2) (PDF)


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