Soluble Polysulfides Research Articles

Porous Carbon Interlayer Derived from Traditional Korean Paper for Li-S Batteries.

A carbonized interlayer effectively helps to improve the electrochemical performance of lithium-sulfur (Li-S) batteries. In this study, a simple and inexpensive carbon intermediate layer was fabricated using a traditional Korean paper called "hanji". This carbon interlayer has a fibrous porous structure, with a specific surface area of 91.82 m2 g-1 and a BJH adsorption average pore diameter of 26.63 nm. The prepared carbon interlayer was utilized as an intermediary layer in Li-S batteries to decrease the charge-transfer resistance and capture dissolved lithium polysulfides. The porous fiber-shaped carbon interlayer suppressed the migration of polysulfides produced during the electrochemical process. The carbon interlayer facilitates the adsorption of soluble lithium polysulfides, allowing for their re-utilization in subsequent cycles. Additionally, the carbon interlayer significantly reduces the polarization of the cell. This simple strategy results in a significant improvement in cycle performance. Consequently, the discharge capacity at 0.5 C after 150 cycles was confirmed to have improved by more than twofold, reaching 230 mAh g-1 for cells without the interlayer and 583 mAh g-1 for cells with the interlayer. This study demonstrates a simple method for improving the capacity of Li-S batteries by integrating a functional carbon interlayer.

Lithium Sulfur Batteries: Insights from Solvation Chemistry to Feasibility Designing Strategies for Practical Applications

Rechargeable lithium–sulfur (Li–S) batteries, featuring high energy density, low cost, and environmental friendliness, have been dubbed as one of the most promising candidates to replace current commercial rechargeable Li‐ion batteries. However, their practical deployment has long been plagued by the infamous “shuttle effect” of soluble Li polysulfides (LiPSs) and the rampant growth of Li dendrites. Therefore, it is important to specifically elucidate the solvation structure in the Li–S system and systematically summarize the feasibility strategies that can simultaneously suppress the shuttle effect and the growth of Li dendrites for practical applications. This review attempts to achieve this goal. In this review, we first introduce the importance of developing Li–S batteries and highlight the key challenges. Then, we revisit the working principles of Li–S batteries and underscore the fundamental understanding of LiPSs. Next, we summarize some representative characterization techniques and theoretical calculations applied to characterize the solvation structure of LiPSs. Afterward, we overview feasible designing strategies that can simultaneously suppress the shuttle effect of soluble LiPSs and the growth of Li dendrites. Finally, we conclude and propose personal insights and perspectives on the future development of Li–S batteries. We envisage that this timely review can provide some inspiration to build better Li–S batteries for promoting practical applications.

Hyphae‐mediated bioassembly of carbon fibers derivatives for advanced battery energy storage

AbstractIngenious design and fabrication of advanced carbon‐based sulfur cathodes are extremely important to the development of high‐energy lithium‐sulfur batteries, which hold promise as the next‐generation power source. Herein, for the first time, we report a novel versatile hyphae‐mediated biological assembly technology to achieve scale production of hyphae carbon fibers (HCFs) derivatives, in which different components including carbon, metal compounds, and semiconductors can be homogeneously assembled with HCFs to form composite networks. The mechanism of biological adsorption assembly is also proposed. As a representative, reduced graphene oxides (rGOs) decorated with hollow carbon spheres (HCSs) successfully co‐assemble with HCFs to form HCSs@rGOs/HCFs hosts for sulfur cathodes. In this unique architecture, not only large accommodation space for sulfur but also restrained volume expansion and fast charge transport paths are realized. Meanwhile, multiscale physical barriers plus chemisorption sites are simultaneously established to anchor soluble lithium polysulfides. Accordingly, the designed HCSs@rGOs/HCFs‐S cathodes deliver a high capacity (1189 mA h g−1 at 0.1 C) and good high‐rate capability (686 mA h g−1 at 5 C). Our work provides a new approach for the preparation of high‐performance carbon‐based electrodes for energy storage devices.

Exploiting Natural Diatom Shells as an Affordable Polar Host for Sulfur in Li-S Batteries

<p>Given the high theoretical capacity (1,675 mAh g<sup>−1</sup>) and the inherent affordability and ubiquity of elemental sulfur, it stands out as a prominent cathode material for advanced lithium metal batteries. Traditionally, sulfur was sequestered within conductive porous carbons, rooted in the understanding that their inherent conductivity could offset sulfur’s non-conductive nature. This study, however, pivots toward a transformative approach by utilizing diatom shell (DS, diatomite)—a naturally abundant and economically viable siliceous mineral—as a sulfur host. This approach enabled the development of a sulfur-layered diatomite/S composite (DS/S) for cathodic applications. Even in the face of the insulating nature of both diatomite and sulfur, the DS/S composite displayed vigorous participation in the electrochemical conversion process. Furthermore, this composite substantially curbed the loss of soluble polysulfides and minimized structural wear during cycling. As a testament to its efficacy, our Li-S battery, integrating this composite, exhibited an excellent cycling performance: a specific capacity of 732 mAh g<sup>−1</sup> after 100 cycles and a robust 77% capacity retention. These findings challenge the erstwhile conviction of requiring a conductive host for sulfur. Owing to diatomite’s hierarchical porous architecture, eco-friendliness, and accessibility, the DS/S electrode boasts optimal sulfur utilization, elevated specific capacity, enhanced rate capabilities at intensified C rates, and steadfast cycling stability that underscore its vast commercial promise.</p>

Establishing reaction networks in the 16-electron sulfur reduction reaction.

The sulfur reduction reaction (SRR) plays a central role in high-capacity lithium sulfur (Li-S) batteries. The SRR involves an intricate, 16-electron conversion process featuring multiple lithium polysulfide intermediates and reaction branches1-3. Establishing the complex reaction network is essential for rational tailoring of the SRR for improved Li-S batteries, but represents a daunting challenge4-6. Herein we systematically investigate the electrocatalytic SRR to decipher its network using the nitrogen, sulfur, dual-doped holey graphene framework as a model electrode to understand the role of electrocatalysts in acceleration of conversion kinetics. Combining cyclic voltammetry, in situ Raman spectroscopy and density functional theory calculations, we identify and directly profile the key intermediates (S8, Li2S8, Li2S6, Li2S4 and Li2S) at varying potentials and elucidate their conversion pathways. Li2S4 and Li2S6 were predominantly observed, in which Li2S4 represents the key electrochemical intermediate dictating the overall SRR kinetics. Li2S6, generated (consumed) through a comproportionation (disproportionation) reaction, does not directly participate in electrochemical reactions but significantly contributes to the polysulfide shuttling process. We found that the nitrogen, sulfur dual-doped holey graphene framework catalyst could help accelerate polysulfide conversion kinetics, leading to faster depletion of soluble lithium polysulfides at higher potential and hence mitigating the polysulfide shuttling effect and boosting output potential. These results highlight the electrocatalytic approach as a promising strategy for tackling the fundamental challenges regarding Li-S batteries.

Pitaya peel-derived carbon film through one-step carbonization as a functional interlayer for lithium sulfur battery

To address the persistent challenge of soluble lithium polysulfides (LiPSs) migration in lithium-sulfur batteries, this study introduces a functional conductive interlayer derived from a cost-effective porous carbon film, innovatively synthesized through one-step carbonization of pitaya peel waste. The porous structure and abundant oxygen-containing functional groups in the resulting film successfully restrict LiPSs diffusion and boost the redox dynamics of LiPSs. Electrochemical evaluation reveals that the sulfur cathode with the proposed interlayer outperforms a pure sulfur cathode, exhibiting superior discharge capacity and cycling stability. The research presents a simplified and economical method for interlayer fabrication, contributing to sustainable advancements in lithium-sulfur battery technology.

Nitrogen-doped carbon encapsulated trimetallic CoNiFe alloy nanoparticles decorated carbon nanotube hybrid composites modified separator for lithium‑sulfur batteries

The large-scale applications of lithium sulfur batteries have been limited by their rapid capacity loss, which can be attributed to the dissolution of polysulfide intermediates and subsequent irreversible shuttling effect. Several strategies have been attempted to the solve these problems by designing novel cell structure, including the modification of separator. Herein, a hybrid composite consisting of trimetallic CoNiFe alloy nanoparticles encapsulated with nitrogen doped carbon decorated carbon nanotubes (NC@CoNiFe/CNTs) was designed and coated on polypropylene (PP) separator for lithium sulfur batteries. The conductivity of mesoporous CNTs provide fast electronic transport and improve the sulfur utilization. The NC@CoNiFe nanoparticles can further adsorb the soluble polysulfides and serve as catalysts to promote the redox kinetics of polysulfides conversion. Benefiting from the synergism of physical confinement, chemical adsorption, and catalytic conversion, the lithium sulfur cell based NC@CoNiFe/CNTs-PP delivers excellent electrochemical performance at high sulfur loading. The lithium sulfur cell with NC@CoNiFe/CNTs-PP under 3.8 mg cm−2 sulfur loading exhibits a high initial capacity of 785.4 mAh g−1 at 0.5C and sustain a capacity of 572.4 mAh g−1 after 240 cycles, corresponding to a retention rate of 72.9 %. The cell with a high sulfur loading of 8.9 mg cm−2, it shows a discharge capacity of 8.89 mAh cm−2 and still maintains 7.24 mAh cm−2 over 100 cycles.

Encapsulation of Titanium Disulfide into MOF-Derived N,S-Doped Carbon Nanotablets Toward Suppressed Shuttle Effect and Enhanced Sodium Storage Performance.

Titanium disulfide (TiS2) is a promising anode material for sodium-ion batteries due to its high theoretical capacity, but it suffers from severe volume variation and shuttle effect of the intermediate polysulfides. To overcome the drawbacks, herein the successful fabrication of TiS2@N,S-codoped C (denoted as TiS2@NSC) through a chemical vapor reaction between Ti-based metal-organic framework (NH2-MIL-125) and carbon disulfide (CS2) is demonstrated. The C─N bonds enhance the electronic/ionic conductivity of the TiS2@NSC electrode, while the C─S bonds provide extra sodium storage capacity, and both polar bonds synergistically suppress the shuttle effect of polysulfides. Consequently, the TiS2@NSC electrode demonstrates outstanding cycling stability and rate performance, delivering reversible capacities of 418/392mAhg-1 after 1000 cycles at 2/5Ag-1. Ex situ X-ray photoelectron spectroscopy and transmission electron microscope analyses reveal that TiS2 undergoes an intercalation-conversion ion storage mechanism with the generation of metallic Ti in a deeper sodiation state, and the pristine hexagonal TiS2 is electrochemically transformed into cubic rock-salt TiS2 as a reversible phase with enhanced reaction kinetics upon sodiation/desodiation cycling. The strategy to encapsulate TiS2 in N,S-codoped porous carbon matrices efficiently realizes superior conductivity and physical/chemical confinement of the soluble polysulfides, which can be generally applied for the rational design of advanced electrodes.

Enhancing lithium-sulfur battery performance through electronic/ionic co-conductive multi-walled carbon nanotubes/lithium lanthanum titanium oxide separator modification

As one of the most promising energy storage devices, lithium-sulfur batteries (LSBs or Li-S batteries) are still facing obstacles due to the notorious shuttling of soluble polysulfide intermediates, accompanied by low S utilization, corrosion of the lithium anode, and rapid capacity fading, leading to a short cycling life. To overcome these issues and achieve high-performance LSBs, we introduce a modified separator composed of multi-walled carbon nanotubes/lithium lanthanum titanium oxide (MWCNTs/LLTO). The proposed MWCNTs/LLTO-modified separator improves the redox reaction kinetics from soluble higher-order lithium polysulfides to insoluble lower-order ones and ultimately to Li2S, thereby reducing the polysulfides dissolved in the electrolyte. It also serves as a physical barrier to adsorb polysulfides, efficiently preventing their diffusion from the cathode to the anode. LSBs adopting the MWCNTs/LLTO-modified separator exhibit higher ionic and electronic conductivity than their un-modified counterparts, leading to an initial specific capacity of 1496 mA/h/g (∼90% of the theoretical capacity) at 0.1 C, excellent rate capability performance, and a remarkable capacity retention of 80% after 200 cycles. Furthermore, the cells with S loading reaching up to 4.18 mg/cm2 further confirmed the beneficial impact of the MWCNTs/LLTO-modified separator.

Cubic CoSe2@carbon as polysulfides adsorption-catalytic mediator for fast redox kinetics and advanced stability lithium-sulfur batteries

Although lithium-sulfur batteries (LSBs) are an attractive next-generation rechargeable battery with high theoretical energy density (2600 Wh kg−1) and specific capacity (1675 mA h g−1), the shuttle of soluble lithium polysulfides (LiPSs) is still the protruding obstacle to accelerate the redox reaction of LSBs. Here, cubic cobalt diselenide@carbon (CoSe2@C) derived from zeolite imidazole framework-67 (ZIF-67) was employed as the functional coating of polypropylene (PP) separator to efficiently adsorb and catalyze polysulfides, inhibit “shuttle effect” and improve the electrochemical reaction kinetics of LSBs. The CoSe2@C offers larger mesopore proportion of 77.19 % and abundant active sites to ensure space as a secondary reaction region, and infiltration of electrolyte and rapid transport of Li+. The involved adsorption and catalysis effect are discussed by static adsorption experiment, XPS, and Li2S nucleation kinetics analysis. The results show that CoSe2@C exhibits strong adsorption effect and catalytic activity on LiPSs, and CoSe2@C/PP cells display fast Li+ diffusion and improved redox kinetics (high Li2S nucleation peak current of 0.27 mA and deposition capacity of 148.46 mA h g−1). Ascribe to these advantages, the CoSe2@C/PP cell provides an initial discharge specific capacity of 1335.01 mA h g−1 at 0.1 C and a fine reversible capacity at 5.0 C, and achieves stable and durable lifespan with an average capacity decay rate of 0.12 % over 400 cycles at 0.5 C. This work could promote the practical application of metal selenides in the key components and devices for LSBs.

Metal-organic-framework derived NiS2/C hollow structures for enhanced polysulfide redox kinetics in lithium-sulfur batteries.

To cope with the shuttling of soluble lithium polysulfides in lithium-sulfur batteries, confinement tactics, such as trapping of sulfur within porous carbon structures, have been extensively studied. Although performance has improved a bit, the slow polysulfide conversion inducing fast capacity decay remains a big challenge. Herein, a NiS2/carbon (NiS2/C) composite with NiS2 nanoparticles embedded in a thin layer of carbon over the surface of micro-sized hollow structures has been prepared from Ni-metal-organic frameworks. These unique structures can physically entrap sulfur species and also influence their redox conversion kinetics. By improving the reaction kinetics of polysulfides, the NiS2/carbon@sulfur (NiS2/C@S) composite cathode with a suppressed shuttle effect shows a high columbic efficiency and decent rate performance. An initial capacity of 900 mAh g-1 at the rate of 1 C (1 C = 1675 mA g-1) and a low-capacity decline rate of 0.132% per cycle after 500 cycles are obtained, suggesting that this work provides a rational design of a sulfur cathode.

Controllable Sulfurization of MXenes to In‐Plane Multi‐Heterostructures for Efficient Sulfur Redox Kinetics

AbstractAlthough in‐plane heterostructure with high ion transport pathway and unique interfacial atomic structure offers endless possibilities in the catalysis field, it is still challenging to directly synthesize MXene‐based in‐plane heterostructure due to the differences in crystal structures and growth conditions. Here, Mo2C–MoS2 in‐plane multi‐heterostructures are synthesized by topological conversion of sandwich‐like mesoporous Mo2C–SiO2 layers in sulfur vapor and subsequent removal of SiO2. During the conversion process, the exposed Mo2C will efficiently converted to 2H phase MoS2, meanwhile, the covered Mo2C remained stable, affording metallic Mo2C MXene and semiconducting MoS2 in‐plane multi‐heterostructures compatible in one layer. The resultant Mo2C–MoS2 layer has multiple heterointerfaces, build‐in electric fields as well as abundant defects. Such structural features enable to improve of the electrochemical active surface area (16.4 mF cm−2), which not only facilitates the bidirectional sulfur electrochemistry between solid Li2S and soluble lithium polysulfides, but also enhances the transfer kinetics of electrons and ions, giving rise to a high‐rate performance (642 mAh g−1 at 5 C) and a long‐term cycle life (1000 cycles at 5 C) in lithium–sulfur batteries.

Selective Reduction of Multivariate Metal-Organic Frameworks for Advanced Electrocatalytic Cathodes in High Areal Capacity and Long-Life Lithium-Sulfur Batteries.

Lithium-sulfur batteries hold great promise as next-generation high-energy-density batteries. However, their performance has been limited by the low cycling stability and sulfur utilization. Herein, we demonstrate that a selective reduction of the multivariate metal-organic framework, MTV-MOF-74 (Co, Ni, Fe), transforms the framework into a porous carbon decorated with bimetallic CoNi alloy and Fe3O4 nanoparticles capable of entrapping soluble lithium polysulfides while synergistically facilitating their rapid conversion into Li2S. Electrochemical studies on coin cells containing 89 wt % sulfur loading revealed a reversible capacity of 1439.8 mA h g-1 at 0.05 C and prolonged cycling stability for 1000 cycles at 1 C/1060.2 mA h g-1 with a decay rate of 0.018% per cycle. At a high areal sulfur loading of 6.9 mg cm-2 and lean electrolyte/sulfur ratio (4.5 μL:1.0 mg), the battery based on the 89S@CoNiFe3O4/PC cathode provides a high areal capacity of 6.7 mA h cm-2. The battery exhibits an outstanding power density of 849 W kg-1 at 5 C and delivers a specific energy of 216 W h kg-1 at 2 C, corresponding to a specific power of 433 W kg-1. Density functional theory shows that the observed results are due to the strong interaction between the CoNi alloy and Fe3O4, facilitated by charge transfer between the polysulfides and the substrate.

Soluble inorganic quantum dots as an electrolyte additive to boost lithium-sulfur battery performance.

Herein, MoS2 quantum dots (QDs) are constructed to serve as electrolyte additives for lithium-sulfur batteries, which can 'solidify' soluble polysulfides by chemisorption and promote sulfur conversion chemistry by electrocatalysis. The Li-S cell with MoS2 QDs shows high retained capacity and high-rate capability, much better than the counterpart without MoS2 QDs.

Influence of Nd-MOF/CNF-derived Nd2O3-C/CNF composite on lithium-sulfur batteries.

The shuttle effect of soluble lithium polysulfide (LiPS) is a major obstacle to the practical application of lithium-sulfur (Li-S) batteries. In order to reduce the negative impact of the shuttle effect, Nd-MOF was combined with carbon nanofibers (CNFs) so that Nd-MOF was embedded in the CNFs and the Nd2O3-C/CNF composite was realized as a separation modification material. This embedded structure made the combination between Nd2O3-C and CNFs tighter, and it exhibited better synergistic effects to inhibit the shuttle effect of polysulfides while also enhancing the tensile strength of the separator and improving the safety performance of the battery. Based on these advantages, a lithium-sulfur coin cell with the Nd2O3-C/CNF-modified separator exhibited excellent electrochemical performance.

Theoretical investigation of synergistically boosting the anchoring and electrochemical performance of lithiophilic/sulfiphilic transition metal carbides for lithium-sulfur batteries.

Lithium-sulfur (Li-S) battery is one of the most promising next-generation energy-storage systems with a high energy density and low cost. However, their commercial applications face several challenges, such as the shuttle effect caused by the soluble lithium polysulfide (LiPSs) intermediates and the sluggish sulfur redox reaction. In this article, we systematically investigated the anchoring and electrochemical performance of a series of transition metal carbides (TMCs: TiC, VC, ZrC, NbC, HfC, TaC) as cathode materials for Li-S batteries by theoretical calculations. The lithiophilic/sulfiphilic non-polar (001) surfaces of TMCs can offer moderate binding strength with LiPS intermediates, ensuring good performance of sulfur immobilization. These TMCs can also facilitate lithium diffusion, indicating the good rate performance of Li-S batteries. We also demonstrated that the studied TMCs can be classified into two classes according to their catalytic activity for Li2S decomposition which originated from their different electronic structural features. Furthermore, TiC, ZrC, and HfC exhibited excellent bifunctional electrochemical activity through reducing the Gibbs free energy for sulfur reduction reactions (SRRs) and lowering the barrier for Li2S decomposition which facilitates accelerating electrode kinetics and elevating utilization of sulfur. Our results offer a systematic approach to designing and screening non-polar materials for high-performance Li-S batteries, based on the rational electronic structure and lattice match strategy.

A gel polymer electrolyte functionalized separator for high-performance lithium-sulfur batteries.

Lithium-sulfur (Li-S) batteries, featuring ultrahigh specific theoretical energy density with low-cost raw materials, have been deemed one of the most promising candidates for next-generation energy storage and conversion devices. However, the shuttle effect of soluble Li polysulfides (LiPSs) has seriously hindered their practical deployment. Herein, we report that tris(pentafluorophenyl)borane (TPFPB) is used to modify the separator (TPFPB/Al2O3) for suppressing the shuttle effect of LiPSs. In detail, the introduction of TPFPB induces 1,3-dioxolane solvent ring-opening polymerization to form a gel layer between the S cathode and separator for suppressing the shuttle effect of Li polysulfides, effectively improving the electrochemical performance of Li-S batteries. The Li-S batteries using the TPFPB/Al2O3 separator demonstrate outstanding cycling stability and high capacity retention rates. This work provides a useful guideline for separator modification using a functional interface layer to design high-performance Li-S batteries.

SO3-COF@Al2O3 modified cathode electrode materials enhance the cycling ability of lithium sulfur batteries.

Herein, a covalent organic framework (SO3-COF) containing sulfonic acid groups has been developed on the surface of alumina by a one-step method, labeled as SO3-COF@Al2O3. The experimental results show that SO3-COF@Al2O3 can effectively inhibit the shuttle effect of soluble lithium polysulfide (LiPSs) in LSBs after loading the active material sulfur, and exhibits better cycling behavior than the initial polymer SO3-COF. The initial discharge specific capacity of this electrode material at 0.05C is as high as 1141 mA h g-1, and the capacity can be maintained at 466 mA h g-1 after 500 cycles with a capacity decay rate of 0.08% per cycle.

Defect engineering of a TiO2 anatase/rutile homojunction accelerating sulfur redox kinetics for high-performance Na-S batteries.

Room-temperature sodium-sulfur (RT Na-S) batteries have the drawbacks of the poor shuttle effect of soluble sodium polysulfides (NaPSs) as well as slow sulfur redox kinetics, which result in poor cycling stability and low capacity, seriously affecting their extensive application. Herein, defect engineering is applied to construct rich oxygen vacancies at the interface of a TiO2 anatase/rutile homojunction (OV-TRA) to enhance sulfur affinity and redox reaction kinetics. Combining structural characterizations with electrochemical analysis reveals that OV-TRA well alleviates the shuttle effect of NaPSs and precipitates the deposition and diffusion kinetics of Na2S. Consequently, S/OV-TRA provides excellent electrochemical performance with a reversible capacity of 870 mA h g-1 at 0.1 C after 100 cycles and a long-term cycling capability of 759 mA h g-1 at 1 C after 1000 cycles. This work provides an effective interfacial defect engineering strategy to promote the application of metal oxides in RT Na-S batteries.

Toward robust lithium-sulfur batteries via advancing Li2S deposition.

Lithium-sulfur batteries (LSBs) with two typical platforms during discharge are prone to the formation of soluble lithium polysulfides (LiPS), leading to a decrease in the cycling life of the battery. Under practical working conditions, the transformation of S8 into Li2S is cross-executed rather than a stepwise reaction, where the liquid LiPS to solid Li2S conversion can occur at a high state of charge (SOC) to maintain the current requirement. Therefore, advancing Li2S deposition can effectively reduce the accumulation of LiPSs and ultimately improve the reaction kinetics. Herein, a "butterfly material" GeS2-MoS2/rGO is used as a sulfur host. Rich catalytic heterointerfaces can be obtained via the abundant S-S bonds formed between GeS2 and MoS2. MoS2 (left wing) can enhance LiPS adsorption, while the lattice-matching nature of Fdd2 GeS2 (right wing) and Fm3̄m Li2S can induce multiple nucleation and regulate the 3D growth of Li2S. Li2S deposition can be advanced to occur at 80% SOC, thereby effectively inhibiting the accumulation of soluble LiPSs. Attributed to the synergistic effect of catalytic and lattice-matching properties, robust coin and pouch LSBs can be achieved.