Performance Of Lithium-sulfur Batteries Research Articles

Electrocatalytic tungsten boride quantum dots anchored reduced graphene oxide as the desolvation promotor for efficient sulfur redox kinetics

Lithium-sulfur (Li-S) batteries boast a multitude of compelling attributes, chief among them being their exceptional energy density and relatively low raw material costs. However, the sluggish redox kinetics of sulfur stemming from the considerable desolvation energy barrier and the notorious shuttle effect of lithium polysulfides, pose significant challenges in the commercialization of Li-S batteries. In this work, ultra-fine WB quantum dots were in-situ and uniformly dispersed on reduced graphene oxide nanosheets (WB-rGO) by mild melting-salt method, in which the abundant oxygen-containing functional groups in graphene oxide effectively prevent the agglomeration of WB. Such ultra-fine WB quantum dot as well as dual-active sites stemming from W and electronics-deficient B, confer the WB-rGO composite with improved electrochemical active surface area for dissociating Li+-solvents molecules and catalyzing polysulfides transformations, thus improving cycling and rate performance of Li-S battery. Hence, the cells with WB-rGO@PP maintained a stable long-term cycling (650 mAh g−1 after 900 cycles at 1 C with an average decay rate of 0.038 % per cycle) and an impressive rate capability (740 mAh g−1 at 4 C). Even at a sulfur loading of 4.7 mg cm−2, the cell performed a high areal capacity of 3.6 mAh cm−2 after 200 cycles.

Multifunctional Lithium Phytate/Carbon Nanotube Double-Layer-Modified Separators for High-Performance Lithium-Sulfur Batteries.

Li dendrite and the shuttle effect are the two primary hindrances to the commercial application of lithium-sulfur batteries (LSBs). Here, a multifunctional separator has been fabricated via successively coating carbon nanotubes (CNTs) and lithium phytate (LP) onto a commercial polypropylene (PP) separator to improve the performance of LSBs. The LP coating layer with abundant electronegative phosphate group as permselective ion sieve not only reduces the polysulfide shuttle but also facilitates uniform Li+ flux through the PP separator. And the highly conductive CNTs on the second layer act as a second collector to accelerate the reversible conversion of sulfide species. The synergistic effect of LP and CNTs further increases the electrolyte wettability and reaction kinetics of cells with a modified separator and suppresses the shuttle effect and growth of Li dendrite. Consequently, the LSBs present much enhanced rate performance and cyclic performance. It is expected that this study may generate an executable tactic for interface engineering of separator to accelerate the industrial application process of LSBs.

The benzothiadiazole-based COF/CNT composite as host for efficient Li-S batteries with excellent cycling stability

The cycle stability and dynamic performance of lithium-sulfur (Li-S) batteries have been major challenges, which primarily arise from the dissolution and migration of the soluble reaction intermediates during cycling, as well as the low conductivity of sulfur. In this study, a covalent organic framework containing heteroatoms (B/N/S) is uniformly wrapped on the outer surface of carbon nanotubes to form a nanocomposite (COF@CNT). The composite combines the excellent electrical conductivity of CNTs and the COF material containing evenly distributed heteroatoms that can adsorb and catalyze polysulfides. B atom on COF can be chemically adsorbed by the negatively charged SX2−, S and N atoms can interact with Li+ to reduce the “shuttle effect”. At the same time, the heteroatoms promote the liquid-to-solid phase conversion of the soluble long-chain Li2Sx (4 ≤ x ≤ 8), and the subsequent conversion of solid Li2S2 to Li2S, thereby enhancing the dynamic kinetics. As a cathode material, COF@CNT/S exhibits an initial specific capacity of 1176 mAh/g at 0.2 C, maintaining a capacity of 688 mAh/g after 1000 cycles at 1 C with a Coulombic efficiency of 99.7 %. Notably, a quite low capacity decay rate of 0.029 % per cycle has been achieved, making the COF@CNT/S cathode one of the most stable electrode material for Li-S batteries. This work provides insights into improving cycle performance of Li-S batteries, and also enriches the current study on host materials.

Modeling the dependence of electrolyte design on lithium-sulfur battery performance

Herein, we offer two electrochemical models, a zero-dimensional (0-D) and a one-dimensional (1-D) model, to mechanistically explore the impact of the electrolyte-to-sulfur (E/S) ratio and electrolyte properties on the discharge behavior of a lithium-sulfur (Li-S) cell. The electrochemically active area in both models is defined based on the carbon weight fraction and reference porosity, so the influence of the carbon loading and E/S ratio on the reaction kinetics is included. Mass transfer of the species must be considered to model the reliance of the discharge capacity on the current density. Instead, the 0-D model is more responsive to the influence of the E/S ratio on the discharge capacity. The effect of electrolyte properties can be modeled implicitly through model parameters. The 0-D model is less sensitive to the variance in model parameters than the 1-D model in terms of the predicted capacity.

Interfacial engineering assists dendrite-inhibiting separators for high-safety Li-S batteries

The impediments to the safety and cyclic performance of lithium-sulfur (Li-S) batteries arise from the lithium dendrite growth and “shuttle effect” of polysulfides. Herein, an interfacial engineering was proposed by pre-irradiation grafting acrylic acid (AA) into polypropylene (PP) separator to achieve a dendrite-inhibiting and high stability functional separators. The abundant –COOH groups, introduced to the surface of PP along with AA, effectively modulate lithium dendrite growth by eliminating the local aggregation of Li+ on the surface of the anode and restrain the “shuttle effect” of polysulfides by the physical confinement and electrostatic interaction. Lithium-sulfur batteries with the grafted separator achieved a high initial capacity of 1108.7 mAh g−1 with an ultralow attenuation rate of 0.012 % per cycle at 1C, outperforming the traditional commercial PP separator. Additionally, the grafted separator also appeared a remarkable flexibility owing to the chemical bond between AA and PP-chain. Notably, the pre-irradiation grafting process, characterized by a mild reaction condition and high economic benefit, endowed the grafted separator with outstanding potential for industrialization. Those results showed the practical prospects of the grafted separator, offering a promising new option for high-safety Li-S batteries.

The Role of the Anion in Concentrated Electrolytes for Lithium-Sulfur Batteries

Highly concentrated electrolytes show promise in enhancing lithium-sulfur (Li-S) battery performance by mitigating polysulfide (PS) solubility. The role of the salt anion for the performance improvement(s) is however not well understood. Here a systematic characterization using (concentrated) electrolytes based on three different salts: LiTFSI, LiTf, and LiTDI, in a common DOL:DME solvent mixture is reported for a wide range of physicochemical and electrochemical properties: ionic conductivity, density, viscosity, speciation, and PS solubility. While increased salt concentration in general improves Li-S battery performance, the role of the salt anion introduces complexity. The 2 m LiTDI-based electrolyte, with a slightly higher viscosity and lower PS solubility, outperforms the LiTFSI-based counterpart in terms of accessible reversible capacity. Conversely, the 2 m LiTf-based electrolyte exhibits subpar performance due to the formation of ionic aggregates that renders more free solvent and, therefore higher PS solubility, which, however can be improved by using a 5 m concentrated electrolyte. Hence, using electrolyte salt concentration as a rational design route demands an understanding of the local molecular structure, largely determined/affected by the choice of anion, as well as how it connects to the global properties and in the end improved Li-S battery performance.

A multifunctional solution to enhance capacity and stability in lithium-sulfur batteries: Incorporating hollow CeO2 nanorods into carbonized non-woven fabric as an interlayer

Lithium-sulfur batteries (LSBs) hold promise as the next-generation lithium-ion batteries (LIBs) due to their ultra-high theoretical capacity and remarkable cost-efficiency. However, these batteries suffer from the serious shuttle effect, challenging their practical application. To address this challenge, we have developed a unique interlayer (HCON@CNWF) composed of hollow cerium oxide nanorods (CeO2) anchored to carbonized non-woven viscose fabric (CNWF), utilizing a straightforward template method. The prepared interlayer features a three-dimensional (3D) conductive network that serves as a protective barrier and enhances electron/ion transport. Additionally, the CeO2 component effectively chemisorbs and catalytically transforms lithium polysulfides (LiPSs), offering robust chemisorption and activation sites. Moreover, the unique porous structure of the HCON@CNWF not only physically adsorbs LiPSs but also provides ample space for sulfur’s volume expansion, thus mitigating the shuttle effect and safeguarding the electrode against damage. These advantages collectively contribute to the battery’s outstanding electrochemical performance, notably in retaining a reversible capacity of 80.82 % (792 ± 5.60 mAh g−1) of the initial value after 200 charge/discharge cycles at 0.5C. In addition, the battery with HCON@CNWF interlayer has excellent electrochemical performance at high sulfur loading (4 mg cm−2) and low liquid/sulfur ratio (7.5 µL mg−1). This study, thus, offers a novel approach to designing advanced interlayers that can enhance the performance of LSBs.

Integrated Design for Discrete Sulfur@Polymer Nanoreactor with Tandem Connection as Lithium–Sulfur Battery Cathodes

AbstractApart from electrode material modification, architecture design and optimization are important approaches for improving lithium–sulfur battery performance. Herein, an integrated structure with tandem connection is constructed by confining nanosulfur (NS) in conductive poly(3,4‐ethylenedioxythiophene) (PEDOT) reaction chambers, forming an interface of discrete independent nanoreactor units bonded onto carbon nanotubes (noted as CNT/NS@PEDOT). The unique spatial confinement and concentration gradients of sulfur@PEDOT nanoreactors (SP‐NRs) can promote reaction kinetics while facilitating rapid polysulfide transformation and minimizing dissolution and diffusion losses. Meanwhile, overall ultrahigh energy input and output are achieved through tandem connection with carbon nanotubes, isolation with PEDOT coating, and synergistic multiplicative effects among SP‐NRs. As a result, it delivers a high initial discharge capacity of 1246 mAh g−1 at 0.1 C and 918 mAh g−1 at 1 C, the low capacity decay rate per lap of 0.011 % is achieved at a current density of 1 C after 1000 cycles. This research emphasizes the innovative structural design to provide a fresh trajectory for the further advancement of high‐performance energy storage devices.

Fe3O4-doped mesoporous carbon cathode with a plumber’s nightmare structure for high-performance Li-S batteries

Shuttling of lithium polysulfides and slow redox kinetics seriously limit the rate and cycling performance of lithium-sulfur batteries. In this study, Fe3O4-dopped carbon cubosomes with a plumber’s nightmare structure (SP-Fe3O4-C) are prepared as sulfur hosts to construct cathodes with high rate capability and long cycling life for Li-S batteries. Their three-dimensional continuous mesochannels and carbon frameworks, along with the uniformly distributed Fe3O4 particles, enable smooth mass/electron transport, strong polysulfides capture capability, and fast catalytic conversion of the sulfur species. Impressively, the SP-Fe3O4-C cathode exhibits top-level comprehensive performance, with high specific capacity (1303.4 mAh g−1 at 0.2 C), high rate capability (691.8 mAh gFe3O41 at 5 C), and long cycling life (over 1200 cycles). This study demonstrates a unique structure for high-performance Li-S batteries and opens a distinctive avenue for developing multifunctional electrode materials for next-generation energy storage devices.

Integrated Design for Discrete Sulfur@Polymer Nanoreactor with Tandem Connection as Lithium-Sulfur Battery Cathodes.

Apart from electrode material modification, architecture design and optimization are important approaches for improving lithium-sulfur battery performance. Herein, an integrated structure with tandem connection is constructed by confining nanosulfur (NS) in conductive poly(3,4-ethylenedioxythiophene) (PEDOT) reaction chambers, forming an interface of discrete independent nanoreactor units bonded onto carbon nanotubes (noted as CNT/NS@PEDOT). The unique spatial confinement and concentration gradients of sulfur@PEDOT nanoreactors (SP-NRs) can promote reaction kinetics while facilitating rapid polysulfide transformation and minimizing dissolution and diffusion losses. Meanwhile, overall ultrahigh energy input and output are achieved through tandem connection with carbon nanotubes, isolation with PEDOT coating, and synergistic multiplicative effects among SP-NRs. As a result, it delivers a high initial discharge capacity of 1246 mAh g-1 at 0.1 C and 918 mAh g-1 at 1 C, the low capacity decay rate per lap of 0.011 % is achieved at a current density of 1 C after 1000 cycles. This research emphasizes the innovative structural design to provide a fresh trajectory for the further advancement of high-performance energy storage devices.

Beyond graphene: exploring the potential of MXene anodes for enhanced lithium-sulfur battery performance.

The high theoretical energy density of Li-S batteries makes them a viable option for energy storage systems in the near future. Considering the challenges associated with sulfur's dielectric properties and the synthesis of soluble polysulfides during Li-S battery cycling, the exceptional ability of MXene materials to overcome these challenges has led to a recent surge in the usage of these materials as anodes in Li-S batteries. The methods for enhancing anode performance in Li-S batteries via the use of MXene interfaces are thoroughly investigated in this study. This study covers a wide range of techniques such as surface functionalization, heteroatom doping, and composite structure design for enhancing MXene interfaces. Examining challenges and potential downsides of MXene-based anodes offers a thorough overview of the current state of the field. This review encompasses recent findings and provides a thorough analysis of advantages and disadvantages of adding MXene interfaces to improve anode performance to assist researchers and practitioners working in this field. This review contributes significantly to ongoing efforts for the development of reliable and effective energy storage solutions for the future.

High-Entropy Catalysis Accelerating Stepwise Sulfur Redox Reactions for Lithium-Sulfur Batteries.

Catalysis is crucial to improve redox kinetics in lithium-sulfur (Li-S) batteries. However, conventional catalysts that consist of a single metal element are incapable of accelerating stepwise sulfur redox reactions which involve 16-electron transfer and multiple Li2Sn (n = 2-8) intermediate species. To enable fast kinetics of Li-S batteries, it is proposed to use high-entropy alloy (HEA) nanocatalysts, which are demonstrated effective to adsorb lithium polysulfides and accelerate their redox kinetics. The incorporation of multiple elements (Co, Ni, Fe, Pd, and V) within HEAs greatly enhances the catalytically active sites, which not only improves the rate capability, but also elevates the cycling stability of the assembled batteries. Consequently, HEA-catalyzed Li-S batteries achieve a high capacity up to 1364 mAh g-1 at 0.1 C and experience only a slight capacity fading rate of 0.054% per cycle over 1000 cycles at 2 C, while the assembled pouch cell achieves a high specific capacity of 1192 mAh g-1. The superior performance of Li-S batteries demonstrates the effectiveness of the HEA catalysts with maximized synergistic effect for accelerating S conversion reactions, which opens a way to catalytically improving stepwise electrochemical conversion reactions.

Oxygen-defect-rich ZnV2O4/ZnO heterojunction as multifunctional separator to boost lithium polysulfide adsorption and conversion for superior lithium‑sulfur batteries

Lithium‑sulfur (Li-S) batteries have been recognized as one of the promising energy systems which can meet the large amounts of energy demanding. However, its practical application has been seriously hindered due to the instinct drawbacks such as low conductivity, large volume expansion and notorious “shuttle effect”. Herein, multi-structure lamellar flower-like zinc vanadate/zinc oxide heterojunction (CoNi@ZnV2O4/ZnO-N,C) with abundant oxygen vacancies, CoNi nanoalloys and N-doped carbon (C) layer has been successfully constructed. XPS and ex-situ XRD analysis reveal that the oxygen vacancies can replace lattice oxygen to adsorb lithium polysulfides (LPS), then stabilize the crystal structure. Additionally, with the synergistic catalysis of CoNi nanoalloys and N-doped C layer, the heterojunction can effectively accelerate the conversion of LPS and promote the precipitation of Li2S. When the lamellar flower-like heterojunction is applied as separator modifier, the “shuttle effect” of LPS can be effectively hindered, leading to synergistic enhancement of long cycle performance of Li-S batteries: the initial discharging capacities of 1468.9 and 1394.9 mAh g−1 can be obtained at 0.1 and 1C, respectively. After 1000 long-term cycles at 3C, the discharging capacity can be still maintained at 467.9 mAh g−1, with a capacity loss rate of 0.049 % per cycle, showing a stable high-rate performance.

Synergistic Effect of In2O3/NC-Co3O4 Interface on Enhancing the Redox Conversion of Polysulfides for High-Performance Li-S Cathode Materials at Low Temperatures.

Lithium-sulfur (Li-S) batteries are considered as a promising energy storage technology due to their high energy density; however, the shuttling effect and sluggish redox kinetics of lithium polysulfides (LiPSs) severely deteriorate the electrochemical performance of Li-S batteries. Herein, we report a novel configuration wherein In2O3 and Co3O4 are incorporated into N-doped porous carbon as a sulfur host material (In2O3@NC-Co3O4) using metal-organic framework-based materials to synergistically tune the catalytic abilities of different metal oxides for different reaction stages of LiPSs, achieving a rapid redox conversion of LiPSs. In particular, the introduction of N-doped carbon improved the electron transport of the materials. The polar interface of In2O3 and Co3O4 anchors both long- and short-chain LiPSs and catalyzes long-chain and short-chain LiPSs, respectively, even at low temperatures. Consequently, the Li-S battery with In2O3@NC-Co3O4 cathode materials delivered an excellent discharge capacity of 1042.4 mAh g-1 at 1 C and a high capacity retention of 85.1% after 500 cycles. Impressively, the In2O3@NC-Co3O4 cathode displays superior performances at high current density and low temperature due to the enhanced redox kinetics, delivering 756 mAh g-1 at 2 C (room temperature) and 755 mAh g-1 at 0.1 C (-20 °C).

A Universal Electronic Structure Modulation Strategy: Is Strong Adsorption Always Correlated with High Catalysis?

Unveiling the inherent link between polysulfide adsorption and catalytic activity is key to achieving optimal performance in Lithium-sulfur (Li-S)batteries. Currentresearch on the sulfur reaction process mainly relies on the strong adsorption of catalysts to confine lithium polysulfides (LiPSs) to the cathode side, effectively suppressing the shuttle effect of polysulfides. However, is strong adsorption always correlated with high catalysis? The inherent relationship between adsorption and catalytic activity remains unclear, limiting the in-depth exploration and rational design of catalysts. Herein, the correlation between "d-band center-adsorption strength-catalytic activity" in porous carbon nanofiber catalysts embedded with different transition metals (M-PCNF-3, M=Fe, Co, Ni, Cu) is systematically investigated, combining the d-band center theory and the Sabatier principle. Theoretical calculations and experimental analysis results indicate that Co-PCNF-3 electrocatalyst with appropriate d-band center positions exhibits moderate adsorption capability and the highest catalytic conversion activity for LiPSs, validating the Sabatier relationship in Li-S battery electrocatalysts. These findings provide indispensable guidelines for the rational design of more durable cathode catalysts for Li-S batteries.

Enhanced rate capability in lithium-sulfur batteries using hybrid carbon nanotubes and NZFO-coated separator

Developing lithium-sulfur batteries (LiSBs) performance is vital for sustainable development. This study presents an innovative approach to enhance LiSBs performance by fabricating a sulfur composite cathode using hybrid-carbon nanotubes (CNTs) denoted as M/S-CNT and a nickel-zinc ferrite (NZFO)-coated separator. The batteries with modified separators (M/S-CNT-NZFO) exhibited remarkable achievements, showcasing significantly enhanced high-rate capabilities [∼527 mAh/g at 3350 mA/g (2C)] and a substantial reduction in polarization. Cyclic voltammetry analysis revealed a diffusion-controlled dominated charge storage mechanism, and the modified separator effectively improved lithium-ion transportation, leading to a notable decrease in charge transfer resistance observed in the simulation of electrochemical impedance spectroscopy (EIS) spectra. This work highlights the impressive high-rate capability and reduced polarization achieved in the M/S-CNT-NZFO cells. Recognizing that high-rate capability is crucial for fast-charging devices, this approach stands out as a compelling strategy to establish the electrochemical stability of LiSBs in applications demanding rapid charging.

Triple Effect of "Conductivity-Adsorption-Catalysis" Enables MXene@FeCoNiP to be Sulfur Hosts for Lithium-Sulfur Batteries.

The weak chemical immobilization ability and poor catalytic effect of MXene inhibit its application in lithium-sulfur (Li-S) batteries. Herein, a novel MXene@FeCoNiP composite is rationally developed and utilized as a sulfur host for Li-S batteries. In this well-designed MXene-based nanostructure, the introduction of FeCoNiP in the interlayer of MXene nanosheets can not only effectively inhibit the restacking of MXene nanosheets but also act as an accelerator for the adsorption and catalysis of polysulfides to restrain the shuttling effect and facilitate the transformation of polysulfides. The existence of two-dimensional MXene nanosheets provides more active sites and improves the conductivity, which is beneficial for accelerating the reaction kinetics. Thus, the as-prepared MXene@FeCoNiP composites achieve an outstanding performance for Li-S batteries. This work provides an opportunity to construct an ideal sulfur host with the triple effect of "conductivity-adsorption-catalysis".

Insight into the effect of N-doping level in N-doped carbons modified separator on improving the electrochemical performance of Li-S batteries

Carbon materials are widely applied in lithium-sulfur (Li-S) batteries due to their large specific surface area, high conductivity, and tunable properties. An appropriate heteroatom doping can enhance the adsorption ability and electrochemical activity toward lithium polysulfides, thus improving the overall performance of Li-S batteries. Herein, three nitrogen-doped carbons (NCs) with different nitrogen doping levels are firstly prepared and then used as the model materials to coat the common polypropylene (PP) separator, aiming to elaborate the effect of adsorption behavior from various N-doping level carbons surface toward lithium polysulfides on the subsequent catalytic conversion kinetics. The experimental data demonstrate that the NC800 with appropriate N-doped level shows the moderate adsorption of polysulfides as well as exhibits the best reaction kinetics on polysulfides conversion. In comparison, an assembled Li-S battery with NC800-PP separator delivers high capacity and good cycling stability, achieving an initial specific capacity of ∼ 1302.2 mAh g−1 at 0.2 C and a capacity fading rate of ∼ 0.061 % per cycle after 500 cycles at 1.0 C. Moreover, a Li-S battery using NC800-PP separator still delivers an initial specific capacity of ∼ 1147.6 mAh g−1 at 0.1 C and maintains a stable specific capacity of ∼ 833.5 mAh g−1 even with a sulfur loading of ∼ 3.9 mg cm−2. This study is believed to give better insight to reveal the internal correlation of adsorption and catalytic effect on polysulfides, as well as provide a guidance for rationally designing heteroatom doping carbon materials in Li-S batteries.

Modulating the Coordination Chemistry of Cobalt Catalytic Sites by Ruthenium Species to Accelerate the Polysulfide Conversion Kinetics in Lithium-Sulfur Batteries.

The performance of lithium-sulfur batteries is compromised by the loss of sulfur as dissolved polysulfides in the electrolyte and consequently the polysulfide redox shutting effect. Accelerating the conversion kinetics of polysulfide intermediates into sulfur or lithium sulfide through electrocatalysis has emerged as a root-cause solution. Co-N-C composite electrocatalyst is commonly used for this purpose. It is illustrated here that how the effectiveness can be improved by modulating the coordination chemistry of Co-N-C catalytic sites through introducing Ru species (RuCo-NC). The well-dispersed Ru in the Co-NC carbon matrix altered the total charge distribution over the Co-N-C catalytic sites and led to the formation of electron-rich Co-N, which is highly active for the polysulfide conversion reactions. Using Ru to modulate the electronic structure in the Co-N-C configuration and the additional catalytic sites over the Ru-Nx species can manifest optimal adsorption behavior of polysulfides. Consequently, the sulfur cathode with RuCo-NC can reduce the capacity fade rate from 0.11 % per cycle without catalyst (initial capacity of 701 mAh g-1) to 0.054 % per cycle (initial capacity of 1074 mAh g-1) over 400 cycles at 0.2 C rate. The results of this study provide the evidence for a feasible catalyst modification strategy for the polysulfide electrocatalysis.

Glass-sulfur composite cathodes: A new strategy for improving the performance of lithium-sulfur batteries

In this study, we investigated the potential of glass-sulfur composites to improve lithium–sulfur battery (LSB) performance. Glass-sulfur composites were prepared by the precipitation method, and the effect of varying carbon black content was studied. The results showed that glass addition improved the battery performance due to the high ion-conductivity of its structural motif. The 75 % glass variant demonstrated the best results, in both the low carbon and high carbon cases. The cyclic voltammetry (CV) and electrical impedance spectroscopy (EIS) measurements showed that glass-sulfur composites had lower resistivity than pure sulfur, which was beneficial for battery performance. The XANES analysis revealed that the incorporated glass interacted with and modified the properties of sulfur, leading to a higher proportion of sulfur in the -1 oxidation state (S−1). This suggests that the high proportion of S−1 phase benefitted battery capacity. Overall, glass-sulfur composites prepared using the precipitation method and incorporating a high content of carbon show promise as a novel and improved cathode material for LSBs.