The high theoretical energy density and specific capacity of lithium-sulfur (Li-S) batteries have garnered considerable attention in the prospective market. However, ongoing research on Li-S batteries appears to have encountered a bottleneck, with unresolved key technical challenges such as the significant shuttle effect and sluggish reaction kinetics. This investigation explores the catalytic efficacy of three catalysts for Li-S batteries and elucidates the correlation between their structure and catalytic impacts. The results suggest that the combined utilization of lithium-insertion technology and a proton exchange approach for δ-MnO2 can optimize its electronic structure, resulting in an optimal catalyst (H/Li inserted δ-MnO2, denoted as HLM) for the sulfur reduction reaction. The replacement of Mn sites in δ-MnO2 with Li atoms can enhance the structural stability of the catalyst, while the introduction of H atoms between transition metal layers contributes to the satisfactory catalytic performance of HLM. Theoretical calculations demonstrate that the bond length of Li2S4 adsorbed by the HLM molecule is elongated, thereby facilitating the dissociation process of Li2S4 and enhancing the reaction kinetics in Li-S batteries. Consequently, the Li-S battery utilizing HLM as a catalyst achieves a high areal specific capacity of 4.2 mAh cm-2 with a sulfur loading of 4.1 mg cm-2 and a low electrolyte/sulfur (E/S) ratio of 8 µL mg-1. This study introduces a methodology for designing effective catalysts that could significantly advance practical developments in Li-S battery technology.
The shuttle effect and sluggish redox kinetics of polysulfides have hindered the development of lithium-sulfur batteries (LSBs) as premier energy storage devices. To address these issues, a high-entropy metal phosphide (NiCoMnFeCrP) was synthesized using the sol-gel method. NiCoMnFeCrP, with its rich metal species, exhibits strong synergistic effects and provides numerous catalytic active sites for the conversion of polysulfides. These active sites, possessing significant polarity, can bond with polysulfides. In situ ultraviolet-visible were conducted to monitor the dynamic changes in species and concentrations of polysulfides, validating the ability of NiCoMnFeCrP to facilitate the conversion of polysulfides. The batteries with the NiCoMnFeCrP catalyst as functional separators exhibited minimal capacity decay rates of 0.04 % and 0.23 % after 100 cycles at 0 °C and 60 °C, respectively. This indicates that the NiCoMnFeCrP catalyst possesses good thermal stability. Meanwhile, its area capacity can reach 4.78 mAh cm-2 at a high sulfur load of 4.54 mg cm-2. In conclusion, NiCoMnFeCrP achieves the objective of mitigating the shuttle effect and accelerating the kinetics of the redox reaction, thereby facilitating the commercialization of LSBs.
High interconversion energy barriers, depressive reaction kinetics of sulfur species, and sluggish Li+ transport inhibit the wide development of high-energy-density lithium sulfur (Li-S) batteries. Herein, differing from random mixture of selected catalysts, the composite catalyst with outer delocalized isoelectronic heterostructure (DIHC) is proposed and optimized, enhancing the catalytic efficiency for decreasing related energy barriers. As a proof-of-content, the FeCoOx Sy composites with different degrees of sulfurization are fabricated by regulating atoms ratio between O and S. The relationship of catalytic efficiency and principal mechanism in DIHCs are deeply understood from electrochemical experiments to in situ/operando spectral spectroscopies i.e., Raman, XRD and UV/Vis. Consequently, the polysulfide conversion and Li2 S precipitation/dissolution experiments strongly demonstrate the volcano-like catalytic efficiency of various DIHCs. Furthermore, the FeCoOx Sy -decorated cell delivers the high performance (1413â mAh g-1 at 0.1â A g-1 ). Under the low electrolyte/sulfur ratio, the high loading cell stabilizes the areal capacity of 6.67â mAh cm-2 at 0.2â A g-1 . Impressively, even resting for about 17â days for possible polysulfide shuttling, the high-mass-loading FeCoOx Sy -decorated cell stabilizes the same capacity, showing the practical application of the DIHCs in improving catalytic efficiency and reaching high electrochemical performance.
Li-S batteries have drawn a lot of attention for their high theoretical specific capacity and significant economic benefits. However, the shuttle effect of polysulfides prevents them from being used widely. To tackle this difficulty, a heterogeneous structure based on tubular carbon nitride with evenly dispersed molybdenum dioxide nanoparticles (MoO2/t-C3N4) as the S host is constructed in this work. As a polar material with a large specific surface area, MoO2/t-C3N4 has a strong anchoring effect on polysulfide. Additionally, the heterogeneous material has excellent bidirectional catalytic ability for the redox process of S species based on the action of the built-in electric field formed by electron directional transfer. Not only does it improve the reaction kinetics of the redox process of the polysulfides but it also prevents polysulfides from accumulating on the surface of the modified material and deactivating it, further improving the utilization of the active material. Thus, MoO2/t-C3N4/S shows the high initial-discharge specific capacity of 812.7 mAh g-1 at the current density of 5C, and the Coulombic efficiency is maintained at more than 95% after 400 charge/discharge cycles. Moreover, MoO2/t-C3N4/S achieved a capacity retention of 89% after 100 cycles at the current density of 0.1C under the high S loading. Therefore, the research results of this work provide a trustworthy reference for the future commercial application of Li-S batteries.
The performance promotion of Li-S batteries relies primarily on inhibition of the shuttle effect and improvement of the catalytic-conversion reaction kinetics of polysulfides. Herein, we prepare defect-enriched VS2 nanosheets (VS2-x) as catalysts for Li-S batteries and further study the catalytic mechanism of VS2-x via ex situ X-ray diffraction and in situ UV-vis spectroscopy. A multifunctional S cathode was also obtained by assembling VS2-x on a C cloth to achieve high S loading for Li-S batteries. It was found that VS2-x catalysts undergo a lithiation process in the work voltage of Li-S batteries, and the triggered LiyVS2-x intermediates reciprocate VS2-x with a high catalytic activity so as to enhance the performance of Li-S batteries by promoting the dissociation process of S62- to S3â¢-. Consequently, Li-S batteries with a C/VS2-x/S cathode deliver a high reversible capacity (1471 mAh g-1 at 0.1 C) and good cycling performance (low fading rate of 0.064% per cycle after 400 cycles). Meanwhile, the CC@VS2-x/S cathode with a high S areal loading of 5.6 mg cm-2 can render a satisfactory areal capacity of 4.22 mAh cm-2 at 0.2 C and a cycle stability of over 100 cycles. Therefore, the study on the catalysis of LiyVS2-x intermediates provides a scientific view for revealing the catalysis mechanism of a sulfide-based electrocatalyst and boosting the development of an electrocatalyst for Li-S batteries.
The practical progress of lithium-sulfur batteries is hindered by the serious shuttle effect and the slow oxidation-reduction kinetics of polysulfides. Herein, the ZnFe2O4-Ni5P4 Mott-Schottky heterojunction material is prepared to address these issues. Benefitting from a self-generated built-in electric field, ZnFe2O4-Ni5P4 as an efficient bidirectional catalysis regulates the charge distribution at the interface and accelerates electron transfer. Meanwhile, the synergy of the strong adsorption capacity derived from metal oxides and the outstanding catalytic performance that comes from metal phosphides strengthens the adsorption of polysulfides, reduces the energy barrier during the reaction, accelerates the conversion between sulfur species, and further accelerates the reaction kinetics. Hence, the cell with ZnFe2O4-Ni5P4/S harvests a high discharge capacity of 1132.4 mAh g-1 at 0.5C and displays a high Coulombic efficiency of 99.3% after 700 cycles. The ZnFe2O4-Ni5P4/S battery still maintains a capacity of 610.1 mAh g-1 with 84.4% capacity retention after 150 cycles at 0.1C under a high sulfur loading of 3.2 mg cm-2. This work provides a favorable reference and advanced guidance for developing Mott-Schottky heterojunctions in lithium-sulfur batteries.
Lithium-sulfur (Li-S) batteries are considered a prospective energy storage system because of their high theoretical specific capacity and high energy density, whereas Li-S batteries still face many serious challenges on the road to commercialization, including the shuttle effect of lithium polysulfides (LiPSs), their insulating nature, the volume change of the active materials during the charge-discharge process, and the tardy sulfur redox kinetics. In this work, double transition metal oxide TiNb2O7 (TNO) nanometer particles are tactfully deposited on the surface of an activated carbon cloth (ACC), activating the surface through a hydrothermal reaction and high-temperature calcination and finally forming the flexible self-supporting architecture as an effective catalyst for sulfur conversion reaction. It has been found that ACC@TNO possesses many catalytic activity sites, which can inhibit the shuttle effect of LiPSs and increase the Coulombic efficiency by boosting the redox reaction kinetics of LiPS transformation reaction. As a consequence, the ACC@TNO/S cathode exhibits an impressive electrochemical performance, including a high initial discharge capacity of 885 mAh g-1 at a high rate of 1 C, a high discharge specific capacity of 825 mAh g-1 after 200 cycles with a prominent capacity retention rate of 93%, and a small decay rate of 0.034% per cycle. Although TNO is extensively used in the fields of lithium ion batteries and other rechargeable batteries, it is first introduced as sulfur host materials to boost the redox reaction kinetics of the LiPS transformation reaction and increase the electrochemical performance of Li-S batteries. Therefore, studies of the synergistic effect on the chemical absorption and catalytic conversion effect of TNO for LiPSs of Li-S batteries provide a good strategy for boosting further the comprehensive electrochemical performances of Li-S batteries.
Given the inherent characteristics of transition metal fluorides and open tunnel-type frameworks, intercalation-conversion-type FeF3 ·0.33H2 O has attracted widespread attention as a promising lithium-ion battery cathode material with high operating voltage and high energy density. However, its low electronic conductivity and poor structural stability impede its practical application in high-rate capacity and long-lifetime batteries. Herein, rod-like Nb-substituted FeF3 ·0.33H2 O (Nb-FeF3 ·0.33H2 O@C) nanocrystals with a carbon coating derived from in situ carbonization in an ionic liquid are deliberately designed and prepared. Based on first-principles calculations and electrochemical analysis, it is shown that substitution of Nb into a proportion of Fe sites can dramatically reduce the total energy of the system and the bandgap, thus boosting the structural stability and electronic conductivity of FeF3 ·0.33H2 O. Simultaneously, the combination of a surface conductive carbon coating and assembly of the nanoparticles into a rod-like mesoporous architecture can produce an omni-directional ion/electron transmission network and a robust 3D composite structure. The Nb-FeF3 ·0.33H2 O@C composite with 3% Nb-doping displays high capacity (583.2 mAh g-1 at 0.2 C), good rate capacity (187.8 mAh g-1 at a high rate of 5.0 C), and excellent long-term cycle stability (160.4 mAh g-1 after 300 long cycles).
Nowadays, Li-S batteries are facing many thorny challenges like volume expansion and lithium dendrites on the road to commercialization. Due to the peculiarity of complete lithiation and the capability to match non-lithium anodes, Li2S-based Li-S batteries have attracted more and more attention. Nevertheless, the same notorious shuttle effect of polysulfides as in traditional Li-S batteries and the poor conductivity of Li2S lead to sluggish conversion reaction kinetics, poor Coulombic efficiency, and cycling performance. Herein, we propose the interconnected porous carbon skeleton as the host, which is modified by an atomically dispersed Mn catalyst as well as O, N atoms (named as ON-MnPC) via the melt salt method, and introduce the Li2S nanosheet into the carbon host with poly(vinyl pyrrolidone) ethanol solution. It has been found that the introduction of O, N to bind with Mn atoms can endow the nonpolar carbon surface with ample unsaturated coordination active sites, restrain the shuttle effect, and enhance the diffusion of Li+ and accelerate the conversion reaction kinetics. Besides, due to the ultra-high catalyst activity of atomically dispersed Mn catalysts, the Li2S/ON-MnPC cathode shows good electrochemical performance, e.g., an initial capacity of 534 mAh g-1, a capacity of 514.18 mAh g-1 after 100 cycles, a high retention rate of 96.23%, and a decay rate of 0.04% per cycle. Hence, use of atomically dispersed Mn catalysts to catalyze the chemical conversion reactions of polysulfides from multiple dimensions is a significant exploration, and it can provide a brand-new train of thought for the development and commercialization of the economical, high-performance Li2S-based Li-S batteries.
Li2S-based Li-S batteries are taken as promising energy storage systems due to the high theoretical specific capacity/energy density and nature of a matching Li-metal-free anode. However, the cyclic stability of the Li2S-based Li-S battery is seriously prevented by the shuttle effect of lithium polysulfides (LiPSs). Meanwhile, due to the poor electrical conductivity of Li2S, the Li-S battery displays slow reaction kinetics. In this work, we design 3D-porous carbon (PC) architecture as a host for inhabiting the LiPS shuttle based on physical capture. Furthermore, this porous carbon architecture is modified by introducing two kinds of heteroatoms (N and S) to form dual active sites (named as NSPC) for chemically binding LiPSs and accelerating their conversion. The polyvinyl pyrrolidone-coated Li2SO4·H2O is embedded in the NSPC skeleton and further forms the Li2S/NSPC cathode via a carbothermal reduction process. In consequence, the NSPC architecture possesses continuous electron/ion channels and abundant active sites, which are beneficial to the fast diffusion of Li+ and timely conversion of sulfur species. As a result, the as-prepared Li2S/NSPC cathode exhibits a high initial discharge capacity of 690 mAh g-1 at a high rate of 1C and keeps a capacity of 587 mAh g-1 after 200 cycles with a good capacity retention rate of 85% and low fading rate of 0.075% per cycle. Therefore, this work offers a brand-new platform to understand the synergistic effects of promoting reaction kinetics for Li2S-based Li-S batteries.
Lithium-sulfur (Li-S) batteries have attracted all-time attention because of their supernormal high energy density and low cost, whereas they are still plagued by the severe polysulfide shuttling and sluggish sulfur redox reaction kinetics. Moreover, poor sulfur electrochemical utilization and rapid capacity degradation are top concerns in the high-loading Li-S batteries, which severely hinder their practical applications. Herein, a completely novel porous nanoneedle array NiCo2S4 electrocatalyst grown on a nitrogen-sulfur-doped carbon cloth (NSCC) (NiCo2S4@NSCC) is constructed as a 3D self-supported sulfur host for high-loading Li-S batteries, in which the highest sulfur loading reaches 4.9 mg cm-2. The as-prepared NiCo2S4@NSCC with a typical sulfur loading of around 2.0 mg cm-2 provides a high discharge capacity of 1223 mA h g-1 at 0.2 C and long-term cycle stability with a low capacity decay of 0.046% per cycle over 500 cycles at 1 C. Additionally, NiCo2S4@NSCC/S with a high sulfur loading of 4.9 mg cm-2 delivers an excellent reversible areal capacity of 4.4 mA h cm-2 g over 50 cycles. Noting that such superior electrochemical performance of NiCo2S4@NSCC/S with high-loading sulfur is mainly attributed to high electronic conductivity and the abundant porous structure of NSCC to transport electrons and ions fastly and accommodate sulfur as well as robust absorbability and the outstanding catalytic effect of NiCo2S4 to accelerate the capture and conversion of the polysulfide intermediate. Predictably, this work can provide a guideline to efficiently and rationally design the structure of metal-based compounds with catalytic functions for various applications.
Li-S battery has tremendous application prospect on account of the high theoretical specific capacity and large energy density, while its large-scale application is impeded by the severe shuttle effect and the slow electrochemical kinetics of polysulfides conversion. Herein, the Lewis acidic yttria hollow spheres (YHS) are rationally designed as both sulfur immobilizer and catalyst of polysulfides conversion for the advanced Li-S batteries. It can be known that the Lewis acidic yttria can effectively capture the Lewis basic polysulfides and thus mitigate the shuttle effect of Li-S battery; besides, yttria shows the enhanced catalytic effect for the kinetics of interconversion reaction from polysulfides to Li2S. As a result, either as a sulfur host or as the separator coating, yttria plays a vital part in realizing the high specific discharge capacity and good cycle stability for Li-S battery. In particular, Li-S battery with YHS@C/S cathode and YHS/CNT-0.6- modified separator (2.1 mg cm-2 active material loading) shows a good specific discharge capacity of 912.5 mAh g-1 at 0.5C. Even after 200 steady cycles, the discharge specific capacity can keep as 842.3 mAh g-1, and the capacity decay rate is only 0.038% per cycle. When active material areal loading is increased to 4.24 mg cm-2, it still maintains a considerable areal capacity of 3.79 mAh cm-2. In consequence, the synergy of polysulfides confinement and catalytic conversion reaction provides a meaningful exploration for achieving the high performance of Li-S batteries.
Lithium-sulfur batteries are considered as promising next-generation green secondary batteries. Irrespective of the enhancement of the cycling stability or the suppression of polysulfide species shuttle, although much progress has recently been achieved, improving the conductivity of host materials and capturing the sulfide species as far as possible are still hot topics in the research of lithium-sulfur batteries nowadays. Here, we put forward a novel sulfur host architecture based on Ti2O3 microspheres fabricated by magnesiothermic reduction. The Ti2O3 microspheres possess both high electronic conductivity and excellent ability of anchoring lithium polysulfide species. The high electronic conductivity endowed by a narrow band gap can adequately activate insulative sulfur and reduce the battery resistance so that high specific capacity and excellent rate capability can be achieved, while the polar Ti2O3 could afford abundant polar active sites for the absorption of polysulfides for high capacity retention. As a result, Ti2O3 microspheres are applied in the research of lithium-sulfur batteries; excellent electrochemical performance has been revealed. The initial specific capacity is 1245 mAh g-1 at 0.2C, with 91.57% capacity retention after 180 cycles. Even with a high areal loading of 3.6 mg cm-2, an initial capacity of 665 mAh g-1 at 0.5C and a good capacity retention of 70.98% after 300 cycles could be achieved. Apparently, the preparation and application of Ti2O3 microspheres can not only further extend the application field of the Ti-based compound but also boost the electrochemical performance of lithium-sulfur batteries.
The commercialization of lithium-sulfur (Li-S) batteries is greatly hindered due to serious capacity fading caused by the polysulfide shuttling effect. Optimizing the structural configuration, enhancing reaction kinetics of the sulfur cathode, and increasing areal sulfur loading are of great significance for promoting the commercial applications of Li-S batteries. Herein, the multifunctional polysulfide scavengers based on nitrogen, sulfur co-doped carbon cloth (DCC), which is supported by flower-like MoS2 (1T-2H) decorated with BaMn0.9 Mg0.1 O3 perovskite particle (PrNP) and carbon nanotubes (CNTs), namely, DCC@MoS2 /PrNP/CNTs, are delicately designed and synthesized. The physical confinement, chemical coupling, and catalysis conversion for active sulfur are achieved simultaneously in this polysulfide motif. Due to these merits, the as-fabricated self-supported DCC@MoS2 /PrNP/CNTs/S manifests an excellent reversible areal capacity of 4.75 mAh cm-2 with an ultrahigh sulfur loading of 5.2 mg cm-2 at the 50th cycle. The outstanding cycling stability is obtained upon 800 cycles with a large reversible capacity of 871 mAh g-1 and a negligible fading rate of 0.02% per cycle at a rate of 1.0 C, suggesting its promising prospects for the commercial success of high-performance Li-S batteries toward flexible electronic devices and energy storage equipment.
A high sulfur loading cathode is the most crucial component for lithium-sulfur batteries (LSBs) to obtain considerable energy density for commercialization applications. The major challenges associated with high sulfur loading electrodes are poor material utilization caused via the nonconductivity of the charged product (S) and the discharged product (Li2S), poor stability arisen from dissolution of lithium polysulfides (LiPSs) into most organic electrolytes and pulverization, and structural damage of the electrode caused by large volumetric expansion. A multifunctional synergistic composite enables ultrahigh sulfur content for advanced LSBs, which comprises the sulfur particle encapsulated with an ion-selective polymer with conductive carbon nanotubes and dispersed around Magnéli phase Ti4O7 (MS-3) by the bottom-up method. The ion-selective polymer provides a physical shield and electrostatic repulsion against the shuttling of polysulfides with negative charge, whereas it can permit the transmission of lithium ion (Li+) through the polymer membrane, and the carbon nanotubes twined around the sulfur promote electronic conductivity and sulfur utilization as well as strong chemical adsorption of LiPSs by means of Ti4O7. Because of this hierarchical construction, the cathode possesses a lofty final sulfur loading of 72% and large sulfur areal mass loading of 3.56 mg cm-2, which displays the large areal specific capacity of 4.22 mA h cm-2. In the same time, it can provide excellent cyclic performance with the corresponding capacity attenuation ratio of 0.08% per cycle at 0.5 C after 300 cycles. Especially, while sulfur areal mass loading is sharply enhanced to 5.11 mg cm-2, the MS-3 composite exhibits a large initial areal capacity of 5.04 mA h cm-2 and still keeps a high reversible capacity of 696 mA h g-1 at 300th cycle even at a 1.0 C. The design of high sulfur content cathodes is a viable approach for boosting practical commercialized application of LSBs.
Honeycomb-like nitrogen and sulfur dual-doped hierarchical porous biomass-derived carbon/sulfur composites (NSHPC/S) are successfully fabricated for high energy density lithium-sulfur batteries. The effects of nitrogen, sulfur dual-doping on the structures and properties of the NSHPC/S composites are investigated in detail by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and charge/discharge tests. The results show that N, S dual-doping not only introduces strong chemical adsorption and provides more active sites but also significantly enhances the electronic conductivity and hydrophilic properties of hierarchical porous biomass-derived carbon, thereby significantly enhancing the utilization of sulfur and immobilizing the notorious polysulfide shuttle effect. Especially, the as-synthesized NSHPC-7/S exhibits high initial discharge capacity of 1204â mA h g-1 at 1.0 C and large reversible capacity of 952â mA h g-1 after 300â cycles at 0.5 C with an ultralow capacity fading rate of 0.08 % per cycle even at high sulfur content (85â wt %) and high active material areal mass loading (2.8â mg cm-2 ) for the application of high energy density Li-S batteries.
Biomass , Carbon/chemistry , Electric Power Supplies , Lithium/chemistry , Nitrogen/chemistry , Sulfur/chemistry , Microscopy, Electron, Transmission , Photoelectron Spectroscopy , Porosity , X-Ray Diffraction
