Shuttle Effect Of Lithium Polysulfides Research Articles

High-Entropy Alloy Electrocatalysts Bidirectionally Promote Lithium Polysulfide Conversions for Long-Cycle-Life Lithium-Sulfur Batteries.

High-entropy alloys (HEAs) have attracted considerable attention, owing to their exceptional characteristics and high configurational entropy. Recent findings demonstrated that incorporating HEAs into sulfur cathodes can alleviate the shuttling effect of lithium polysulfides (LiPSs) and accelerate their redox reactions. Herein, we synthesized nano Pt0.25Cu0.25Fe0.15Co0.15Ni0.2 HEAs on hollow carbons (HCs; denoted as HEA/HC) by a facile pyrolysis strategy. The HEA/HC nanostructures were further integrated into hypha carbon nanobelts (HCNBs). The solid-solution phase formed by the uniform mixture of the five metal elements, i.e., Pt0.25Cu0.25Fe0.15Co0.15Ni0.2 HEAs, gave rise to a strong interaction between neighboring atoms in different metals, resulting in their adsorption energy transformation across a wide, multipeak, and nearly continuous spectrum. Meanwhile, the HEAs exhibited numerous active sites on their surface, which is beneficial to catalyzing the cascade conversion of LiPSs. Combining density functional theory (DFT) calculations with detailed experimental investigations, the prepared HEAs bidirectionally catalyze the cascade reactions of LiPSs and boost their conversion reaction rates. S/HEA@HC/HCNB cathodes achieved a low 0.034% decay rate for 2000 cycles at 1.0 C. Notably, the S/HEA@HC/HCNB cathode delivered a high initial areal capacity of 10.2 mAh cm-2 with a sulfur loading of 9 mg cm-2 at 0.1 C. The assembled pouch cell exhibited a capacity of 1077.9 mAh g-1 at the first discharge at 0.1 C. The capacity declined to 71.3% after 43 cycles at 0.1 C. In this work, we propose to utilize HEAs as catalysts not only to improve the cycling stability of lithium-sulfur batteries, but also to promote HEAs in energy storage applications.

Flower-like covalent organic frameworks as host materials for high-performance lithium-sulfur batteries

Lithium-sulfur (Li-S) batteries have emerged as a promising alternative energy storage system due to their high energy density and cost-effectiveness. However, practical applications of Li-S batteries are hindered by challenges such as the shuttle effect and sluggish redox kinetics. In this study, a three-dimensional (3D) flower-like diaminoanthraquinone (DAAQ)-covalent organic framework (COF) was developed, featuring nanorod-like petals and enriched with abundant N and O adsorption sites, serving as a host material for the sulfur cathode of Li-S batteries. Through a process of sulfur melting-diffusion, the resulting DAAQ-COF@S cathode material demonstrated a stable 3D cross-linked morphology with a hierarchical pore structure, maximizing the exposure of N/O adsorptive sites and facilitating rapid ion diffusion. This effectively inhibited the shuttling effect of lithium polysulfides (LiPSs) and enhanced rate performance. Consequently, DAAQ-COF@S cathodes exhibited a high initial discharge capacity of 1182.0 mAh g−1 at 0.1 C, with a capacity retention rate of 79.6% after 500 cycles at 2 C. Even at a high current density of 4 C, they maintained a high capacity of 616.8 mAh g−1, surpassing the majority of previously reported COF-based host materials for Li-S batteries. This work underscores the significance of COF micromorphology and advances the development of high-performance cathodes for Li-S batteries.

A Catalytic Electrolyte Additive Modulating Molecular Orbital Energy Levels of Lithium Polysulfides for High-Performance Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have ultrahigh theoretical specific capacity, but the practical application is hindered by the severe shuttle effect and the sluggish redox kinetics of the intermediate lithium polysulfides (LiPSs). Effectively enhancing the conversion kinetics of LiPSs is essential for addressing these issues. Herein, the redox kinetics of LiPSs are effectively improved by introducing 6-azauracil (6-AU) molecules to the organic electrolyte to modulate the molecular orbital energy level of LiPSs. The 6-AU as a soluble catalyst can form complexes with LiPSs via Li-O bonds. These complexes are liable to transform because of the elevated HOMO and the reduced LUMO energy levels as compared to the dissociative LiPSs, resulting in small energy gaps (Egap) and exhibiting stronger redox activity. Benefiting from the rapid conversion kinetics, the shuttling effect of LiPSs is alleviated to a great extent, so that sulfur utilization is improved and the lithium electrode is protected. In addition, the introduction of 6-AU modulates the deposition behavior of Li2S and eases the coverage of the cathode surface by the insulating Li2S layer. The Li-S battery containing 6-AU provides superior capacity retention of 853 mAh g-1 after 150 cycles at 0.2 C and shows remarkable high-rate performance and retains a specific discharge capacity of 855 mAh g-1 at 5 C. This study accelerates the kinetics of Li-S batteries by tuning the HOMO and LUMO energy levels of LiPSs, which opens an avenue for designing functional electrolyte additives.

Heterostructures Regulating Lithium Polysulfides for Advanced Lithium-Sulfur Batteries.

Sluggish reaction kinetics and severe shuttling effect of lithium polysulfides seriously hinder the development of lithium-sulfur batteries. Heterostructures, due to unique properties, have congenital advantages that are difficult to be achieved by single-component materials in regulating lithium polysulfides by efficient catalysis and strong adsorption to solve the problems of poor reaction kinetics and serious shuttling effect of lithium-sulfur batteries. In this review, the principles of heterostructures expediting lithium polysulfides conversion and anchoring lithium polysulfides are detailedly analyzed, and the application of heterostructures as sulfur host, interlayer, and separator modifier to improve the performance of lithium-sulfur batteries is systematically reviewed. Finally, the problems that need to be solved in the future study and application of heterostructures in lithium-sulfur batteries are prospected. This review will provide a valuable reference for the development of heterostructures in advanced lithium-sulfur batteries.

Rational construction of rich coordination-unsaturated Zr-BTB electrocatalyst towards advanced lithium-sulfur batteries

Lithium-sulfur (Li-S) batteries show great potential to achieve high-density energy storage, but their commercial application is severely hindered by the notorious shuttling effect of lithium polysulfides (LiPS) and their sluggish conversion kinetics. Herein, we develop a Quasi Zr-based metal–organic frameworks with the tritopic carboxylate ligand 1,3,5-tris(4-carboxyphenyl)benzene (BTB) microflowers with cross-linked CNTs (Q-Zr-BTB@CNTs). The deficiency of Zr-O coordination at the Zr6 node is realized via a control of the deligandation behavior, which subtly modulates the local environment and electronic structure towards enhanced chemical affinity to polysulfides. Meanwhile, the interweave of the ultrathin Q-Zr-BTB nanosheets and CNTs establishes a porous and conductive network for fast charge transfer as well as a vast exposure of active interfaces. As a result, such a combination of defect engineering and architecture construction imposes strong sulfur adsorption and catalyzation, endowing the S/Q-Zr-BTB@CNTs cathode with a high initial capacity (1130 mAh g−1 at 0.2 C) and an excellent cycling stability (500 cycles at 1 C with 0.05% decay per cycle), as well as a decent electrochemical performance even under a high sulfur loading up to 12.7 mg cm−2. This study provides a novel strategy of designing unsaturated coordination centers to boost sulfur catalysis for high-performance lithium sulfur batteries.

Scalable, flexible and fire-retardant janus membranes for simultaneously inhibiting dendrite growth and catalyzing polysulfide conversion in lithium-sulfur batteries

Shuttle effect of lithium polysulfides (LiPSs) and the problems arising from lithium dendrites impede the practical applications of Li-S batteries. Herein, a scalable and fire-retardant janus membrane (C@OPBI-CeO2//GF) with glass fiber membrane (GF) as substrate and hierarchically porous C@OPBI-CeO2 membrane as the cathode has been constructed. The cathode membrane with porous conductive networks can replace the conventional Al foil and significantly promote Li+ and electron transportation. Meanwhile, the doped CeO2 nanoparticles in the membrane can trap and catalyze LiPSs transformation. The interwoven GF membrane allows the uniform distribution of Li+ on Li plate by redistributing the Li+ flux. It also facilitates the rapid diffusion of Li+ and promotes the reversible Li plating and stripping processes against dendrite growth. Furthermore, the introduction of OPBI and GF improve the structural stability and high temperature resistance of the membrane which are of great significance to realize the commercial application of Li-S batteries. The batteries assembled with the janus membrane have a specific capacity of 620 mA h g − 1 after 550 cycles at a current density of 1 C, and still deliver a capacity of 720 mA h g − 1 after 100 cycles even at a high sulfur loading of 5 mg cm−2.

Engineering single-atom catalysts as multifunctional polysulfide and lithium regulators toward kinetically accelerated and durable lithium-sulfur batteries

Developing electrocatalyst to ameliorate the shuttling effect of lithium polysulfides (LiPSs), sluggish sulfur redox reaction kinetics and the rampant dendrite growth is of paramount importance for lithium-sulfur (Li-S) batteries. Yet still, the utilization of the most mainstream traditional metal electrocatalytic nanoparticles is far below expectation. Herein, we engineer an exclusive single-atom catalyst with planar Co-N4 coupling of nitrogen-doped graphene mesh (SA-Co/NGM) to achieve exceptional atom utilization efficiency for catalytic conversion of LiPSs. High surface area and ultra-thin two-dimensional texture can not only accommodate high concentration monodispersed lithiophilic atomic Co sites, but also guarantee homogenize high-flux Li ion transport, alleviating the formation of Li-dendrites. Critically, the maximized exposure of Co-N4 as a regulator in sulfur electrochemistry can conspicuously suppress the shuttle effect and accelerate bidirectional sulfur redox kinetics via electron delocalization, as demonstrated by a judicious combination of electro-kinetic analysis, in situ spectroscopy and density functional theory (DFT) computations. As expected, the batteries based on a SA-Co/NGM modified separator achieve an ultrahigh rate capability, exceptionally long cycle life and a distinguished favorable areal capacity under high sulfur loading. This work provides a rational design of single-atom catalysts for kinetics-boosted electrocatalysis towards long-lasting Li-S batteries.

Cobalt-loaded three-dimensional ordered Ta/N-doped TiO2 framework as conductive multi-functional host for lithium-sulfur battery

The low electrical conductivity of sulfur and severe shuttling effect of lithium polysulfides (LiPSs) have hindered the practical application of lithium-sulfur (Li-S) batteries. In this work, a conductive Ta/N co-doped TiO2 framework featured with three-dimensional ordered macroporous (3DOM) structure embedded with ZIF-67 derived Co-anchored N-doped carbon (Co-NC) is synthesized as efficient sulfur host material in Li-S batteries. The 3DOM Ta/N-TiO2 backbone has good structural stability, which benefits the electrolyte penetration and sulfur accommodation. Meanwhile, the Ta/N co-doping not only improves the conductivity of TiO2, but also strengthens the adsorption of LiPSs. In addition, the embedded Co-NC increases the active site of 3DOM skeleton towards LiPSs conversion, facilitates the diffusion of Li+ ion, and at the same time provides additional microspores for sulfur confinement. Attributed to these features, the sulfur electrode based on 3DOM Ta/N-TiO2@Co-NC achieves excellent electrochemical performance. The S/3DOM Ta/N-TiO2@Co-NC cell maintains a discharge capacity of 789.2 mAh g−1 after 500 cycles at 1C with a low decay rate of 0.06 % per cycle. Additionally, an initial area capacity of 5.67 mAh cm−2 is obtained under areal sulfur loading of 6.55 mg cm−2. This multistage porous sulfur cathode design has the potential to expedite the development of feasible Li-S battery.

Revealing the Multifunctional Electrocatalysis of Indium‐Modulated Phthalocyanine for High‐Performance Lithium‐Sulfur Batteries

The sluggish kinetics of complicated multiphase conversions and the severe shuttling effect of lithium polysulfides (LiPSs) significantly hinder the applications of Li‐S battery, which is one of the most promising candidates for the next‐generation energy storage system. Herein, a bifunctional electrocatalyst, indium phthalocyanine self‐assembled with carbon nanotubes (InPc@CNT) composite material, is proposed to promote the conversion kinetics of both reduction and oxidation processes, demonstrating a bidirectional catalytic effect on both nucleation and dissolution of Li2S species. The theoretical calculation shows that the unique electronic configuration of InPc@CNT is conducive to trapping soluble polysulfides in the reduction process, as well as the modulation of electron transfer dynamics also endows the dissolution of Li2S in the oxidation reaction, which will accelerate the effectiveness of catalytic conversion and facilitate sulfur utilization. Moreover, the InPc@CNT modified separator displays lower overpotential for polysulfide transformation, alleviating polarization of electrode during cycling. The integrated spectroscopy analysis, HRTEM, and electrochemical study reveal that the InPc@CNT acts as an efficient multifunctional catalytic center to satisfy the requirements of accelerating charging and discharging processes. Therefore, the Li–S battery with InPc@CNT‐modified separator obtains a discharge‐specific capacity of 1415 mAh g−1 at a high rate of 0.5 C. Additionally, the 2 Ah Li–S pouch cells deliver 315 Wh kg−1 and achieved 80% capacity retention after 50 cycles at 0.1 C with a high sulfur loading of 10 mg cm−2. Our study provides a practical method to introduce bifunctional electrocatalysts for boosting the electrochemical properties of Li–S batteries.

Porous Mo2C-Mo3N2 heterostructure/rGO with synergistic functions as polysulfides regulator for high-performance lithium sulfur batteries

Shuttle effect of lithium polysulfides (LiPSs) is among the critical obstacles hampering development of lithium-sulfur batteries. Herein, we present a porous Mo2C-Mo3N2 heterostructure/rGO host and the Mo2C-Mo3N2 heterostructure combines the merits of high adsorption Mo2C and high catalytic Mo3N2 so as to achieve rapid anchoring-diffusion-conversion of LiPSs across the Mo2C-Mo3N2 heterointerface. The Mo2C-Mo3N2 heterointerface boosts the trapping efficiency and conversion to Li2S of LiPSs. rGO provides fast paths for electron transport as well as serves as a protective layer to prevent the structure from being damaged during cycling. Density functional theory (DFT) calculation shows that Mo2C has stronger adsorption ability for Li2S4 than Mo3N2 and Mo3N2 has better reaction kinetic characteristics. Experimentally, Mo2C-Mo3N2/[email protected] electrode respectively shows outstanding rate capability. At high sulfur loadings (3.4 and 5.0 mg cm−2), the capacity retention values are 78%, and 70% at 0.5C after 300 cycles. Mo2C-Mo3N2/rGO sulfur electrodes shows high Li+ diffusion coefficient of 4.56 × 10-7 cm2 s−1, which benefits from the accelerated conversion of LiPSs at interface. Our results reveal the critical role of anchoring-diffusion-conversion of LiPSs in terms of inhibiting the shuttle effect.

Sulfur double encapsulated in a porous hollow carbon aerogel with interconnected micropores for advanced lithium-sulfur batteries

Abstract Due to high theoretical specific capacity, energy density, and low-cost lithium-sulfur (Li-S) batteries became the most potential energy storage devices for the next generation. The harsh shuttling effect, poor electroconductibility of sulfur, and volume change affect the Li-S battery’s practical application. Herein, the rational design of porous hollow carbon aerogel (PHCA) with an ultra-high specific surface area of 2054.5 m2 g−1 and outstanding adsorption ability is firstly fabricated to restrict the shuttling effect of lithium polysulfides (LiPSs) by using commercialized nano-CaCO3 as a template. As a sulfur host, the S/PHCA cathode delivers initially discharge specific capacity of 992.7 mAh g−1 with an average Coulombic efficiency of 97.6%. After 200 cycles, it obtains the reversible specific capacities of 600.1 mAh g−1 for S/PHCA cathode at 0.1C (2.2 mg cm−2) corresponding to 60.45% of their initial discharge specific capacity. As a PHCA interlayer, the Li-S battery with the PHCA interlayer exhibits initially discharge specific capacity of 1267.7 mAh g−1 with an average Coulombic efficiency of 99.36% at 0.1C (3.2 mg cm−2) and maintains at 863.3 mAh g−1 with the discharge specific capacity retention rate of 69.2%. This is an effective strategy to improve the outstanding electrochemical performance which is beyond reported carbon materials, which is attributed to stronger adsorption of LiPSs by the micropore. This work provides a new direction for the modification of a sulfur host and interlayer and simultaneously reveals the relationship between the heteroatom distribution and LiPSs.

Porous honeycomb-like C3N4/rGO composite as host for high performance Li-S batteries

Lithium-sulfur (Li-S) batteries have attracted extensive attention along with the urgent increasing demand for energy storage owing to the high theoretical specific capacity and energy density, abundant reserves and low cost of sulfur. However, the practical application of Li-S batteries is still impeded due to the low utilization of sulfur and serious shuttle-effect of lithium polysulfides (LiPSs). Here, we fabricated the porous honeycomb-like C3N4 (PHCN) through a hard template method. As a polar material, graphitic C3N4 has abundant nitrogen content (∼58%), which can provide enough active sites to mitigate shuttle-effect, and then conductive reduced graphene oxide (rGO) was introduced to combine with PHCN to form PHCN/rGO composite in order to improve the utilization efficiency of sulfur. After sulfur loading, the PHCN/rGO/S cathode exhibited an initial discharge capacity of 1,061.1 mA h g−1 at 0.2 C and outstanding rate performance at high current density of 5 C (495.1 mA h g−1), and also retained 519 mA h g−1 after 400 cycles at 1 C. Even at high sulfur loading (4.3 mg cm−2), the capacity fade rate was only 0.16% per cycle at 0.5 C for 200 cycles. The above results de monstrate that the special design of PHCN/rGO composite as sulfur host has high potential application for Li-S rechargeable batteries.

Insight into the effect of additives widely used in lithium-sulfur batteries.

The interaction between the reactive lithium metal surface and LiNO3 results in the formation of LixNOy clusters, which can protect the Li metal anode and suppress the shuttling effect of lithium polysulfides via the dipole-dipole interaction called the lithium bond.

Improvement of Cycling Performance of Lithium-Sulfur Batteries by Using Magnesium Oxide as a Functional Additive for Trapping Lithium Polysulfide.

Trapping lithium polysulfides formed in the sulfur positive electrode of lithium-sulfur batteries is one of the promising approaches to overcome the issues related to polysulfide dissolution. In this work, we demonstrate that intrinsically hydrophilic magnesium oxide (MgO) nanoparticles having surface hydroxyl groups can be used as effective additives to trap lithium polysulfides in the positive electrode. MgO nanoparticles were uniformly distributed on the surface of the active sulfur, and the addition of MgO into the sulfur electrode resulted in an increase in capacity retention of the lithium-sulfur cell compared to a cell with pristine sulfur electrode. The improvement in cycling stability was attributed to the strong chemical interactions between MgO and lithium polysulfide species, which suppressed the shuttling effect of lithium polysulfides and enhanced the utilization of the sulfur active material. To the best of our knowledge, this report is the first demonstration of MgO as an effective functional additive to trap lithium polysulfides in lithium-sulfur cells.