Shuttling Effect Research Articles

Constructing Orbital Coupling-Modulated Homogeneous Dual-Atom Fe-Fe Sites for Boosting Bidirectional Conversion of Polysulfides.

Homogeneous dual-atom catalysts (HDACs) have garnered significant attention for their potential to overcome the shuttling effect and sluggish reaction kinetics in lithium-sulfur (Li-S) batteries. However, modulating the electron structure of metal atomic orbitals for HDACs to dictate the catalytic activity toward polysulfides has remained meaningful but unexplored so far. Herein, an interfacial cladding strategy is developed to obtain a new type of dual-atom iron matrix with a unique FeN2P1-FeN2P1 coordination structure (Fe2@NCP). The 3d orbital electrons of the Fe centers are redistributed by incorporating phosphorus atoms into the first coordination sphere. The theoretical calculations disclose that the strong coupling between the Fe d orbital and the S p orbital exhibits an enhanced Fe-S bond and improved reactivity toward polysulfides. Moreover, the Fe2@NCP catalyst achieves robust adsorption ability toward Li2Sn (1 ≤ n ≤ 8) and significantly boosts bidirectional sulfur redox reaction kinetics by lowering the Li2S deposition/decomposition energy barriers. Consequently, the assembled Li-S batteries present a high retention ratio of 77.3% after 500 cycles at 1C. Furthermore, the Li-S pouch cell also exhibits good performance at 0.1C (80.2% retention over 100 cycles) for practical application with a sulfur loading of 4.0 mg/cm2. The outcome of this study will facilitate the design of homogeneous dual-atom catalysts for Li-S batteries.

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).

The Role of Transition Metal Versus Coordination Mode in Single-Atom Catalyst for Electrocatalytic Sulfur Reduction Reaction.

Electrocatalytic sulfur reduction reaction (SRR) is emerging as an effective strategy to combat the polysulfide shuttling effect, which remains a critical factor impeding the practical application of the Li-S battery. Single-atom catalyst (SAC), one of the most studied catalytic materials, has shown considerable potential in addressing the polysulfide shuttling effect in a Li-S battery. However, the role played by transition metal vs coordination mode in electrocatalytic SRR is trial-and-error, and the general understanding that guides the synthesis of the specific SAC with desired property remains elusive. Herein, we use first-principles calculations and machine learning to screen a comprehensive data set of graphene-based SACs with different transition metals, heteroatom doping, and coordination modes. The results reveal that the type of transition metal plays the decisive role in SAC for electrocatalytic SRR, rather than the coordination mode. Specifically, the 3d transition metals exhibit admirable electrocatalytic SRR activity for all of the coordination modes. Compared with the reported N3C1 and N4 coordinated graphene-based SACs covering 3d, 4d, and 5d transition metals, the proposed para-MnO2C2 and para-FeN2C2 possess significant advantages on the electrocatalytic SRR, including a considerably low overpotential down to 1 mV and reduced Li2S decomposition energy barrier, both suggesting an accelerated conversion process among the polysulfides. This study may clarify some understanding of the role played by transition metal vs coordination mode for SAC materials with specific structure and desired catalytic properties toward electrocatalytic SRR and beyond.

Synergistic engineering of structural and electronic regulation in necklace-like UiO-66/ACNT structure toward lithium-sulfur batteries with fast polysulfide redox

Although UiO-66-based metal-organic framework (MOF) composites have been widely applied in the entrapment and catalytic effect toward lithium polysulfides (LiPSs), the synergistic engineering of structural and electronic regulation strategy has not been carefully considered. Herein, we optimize the internal cluster structure, rational regulate the size of UiO-66, and design the necklace-like structure composed of UiO-66 nanoparticles and acid-treated carbon nanotube (UiO-66/ACNT) through simple hydrothermal reaction and thermal treatment strategy. According to experiments and density universal function theory calculations, the improved UiO-66/ACNT architecture effectively provides more polarity to capture polysulfides via exposing more active sites and effectively delivers electrocatalytic activity of polysulfide conversion. Furthermore, systematic electrocatalytic kinetics, in situ Raman spectroscopy and in-situ impedance analysis indicate the functional separator can inhibit the shuttling effect, and catalyze the conversion of lithium polysulfide. As a result, Li-S batteries with functional separators exhibit excellent electrochemical performance (low fading rate over 1000 cycles of 0.06 % per cycle at 1C, high areal capacity of 4.01 mAh cm−2 at 0.2C). This work offers insight into the rational design of UiO-66-based metal-organic frameworks (MOFs) through synergistic engineering for high-performance Li-S batteries.

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.

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".

Suppressing Shuttle Effect via Cobalt Phthalocyanine Mediated Dissociation of Lithium Polysulfides for Enhanced Li‐S Battery Performance

AbstractCationic lithium polysulfides (LiPSs) within ether‐based electrolytes are essential intermediates pivotal in instigating the shuttle effect. Suppressing the generation of cationic LiPSs is crucial for enhancing the performance of high‐energy‐density Li‐S batteries in practical applications. Herein, for the first time, it is demonstrated that cobalt phthalocyanine (CoPc) can significantly enhance the dissociation of LiPSs, leading to a decrease in cationic LiPSs species within the electrolyte. Employing NMR and in‐situ Raman spectroscopy, it is observed that CoPc interacts with sulfur anions within LiPSs, modifying the dissociation equilibrium of LiPSs in 1,2‐dimethoxyethane (DME)/1,3‐dioxolane (DOL) electrolyte. This CoPc‐mediated shift toward dissociation equilibrium reduces the concentration of cationic LiPSs, effectively suppressing the electromigration of LiPSs intermediates toward the Li anode during the charging process of Li‐S battery. As a result, the Li‐S battery enabled a high reversible areal capacity of 4.2 mAh cm−2 at a high sulfur loading of 5.0 mg cm−2 and a low electrolyte/sulfur (E/S) ratio of 3 µL mgs−1. This work affords a promising strategy for tackling the fundamental challenges regarding Li‐S batteries.

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.

Multifunctional tri-layer aramid nanofiber composite separators for high-energy-density lithium-sulfur batteries

Lithium-sulfur (Li-S) battery has attracted much attention due to their high theoretical energy density. However, severe shuttling effect, sluggish reaction kinetics and uncontrolled dendrite formation of Li anode greatly deter their practical applications. Different to conventional separator engineering strategies that are always focused on surface coating of functional interlayer on commercial polyolefin separators, herein, we proposed a structural engineering tactic by rationally tuning the porous structure and composition of the p-aramid nanofiber (ANF) composite separator to address simultaneously the above problems. A two-step film-casting process combined with a phase inversion approach was developed to fabricate a multifunctional tri-layer ANF composite separator. This innovative separator was especially engineered to comprise a conductive and catalytic NiFe2O4 modified multi-walled carbon nanotubes/ANF layer for rapid and efficient conversion of lithium polysulfides, a microporous ANF layer for fast ion transport, and a dense nanoporous ANF layer for lithium dendrite inhibition. This tri-layer ANF-based separator possessed high porosity, excellent thermal stability, and superb electrolyte wettability. Batteries with the tri-layer ANF- based separator exhibited outstanding cyclic stability with high capacity of >3 mAh cm−2 at high sulfur loading (4 mg cm−2) and high current density (4 mA cm−2). This work opens up new opportunities for design of functional separators based on high performance polymers using the structural engineering strategy.

Encasing Few-Layer MoS2 within 2D Ordered Cubic Graphitic Cages to Smooth Trapping-Conversion of Lithium Polysulfides for Dendrite-Free Lithium-Sulfur Batteries.

The industrialization of lithium-sulfur (Li-S) batteries faces challenges due to the shuttling effect of lithium polysulfides (LiPSs) and the growth of lithium dendrites. To address these issues, a simple and scalable method is proposed to synthesize 2D membranes comprising a single layer of cubic graphitic cages encased with few-layer, curved MoS2. The distinctive 2D architecture is achieved by confining the epitaxial growth of MoS2 within the open cages of a 2D-ordered mesoporous graphitic framework (MGF), resulting in MoS2@MGF heterostructures with abundant sulfur vacancies. The experimental and theoretical studies establish that these MoS2@MGF membranes can act as a multifunctional interlayer in Li-S batteries to boost their comprehensive performance. The inclusion of the MoS2@MGF interlayer facilitates the trapping and conversion kinetics of LiPSs, preventing their shuttling effect, while simultaneously promoting uniform lithium deposition to inhibit dendrite growth. As a result, Li-S batteries with the MoS2@MGF interlayer exhibit high electrochemical performance even under high sulfur loading and lean electrolyte conditions. This work highlights the potential of designing advanced MoS2-encased heterostructures as interlayers, offering a viable solution to the current limitations plaguing Li-S batteries.

Configuring single-layer MXene nanosheet onto natural wood fiber via C–Ti–C covalent bonds for high-stability Li-S batteries

Lithium-sulfur batteries (LSBs) are considered promising candidates for next-generation battery technologies owing to their outstanding theoretical energy density and cost-effectiveness. However, the low conductivity and polysulfide shuttling effect of S cathodes severely hamper the practical performance of LSBs. Herein, in situ-generated single layer MXene nanosheet/hierarchical porous carbonized wood fiber (MX/PCWF) composites are prepared via a nonhazardous eutectic activation strategy coupled with pyrolysis-induced gas diffusion. The unique architecture, wherein single layer MXene nanosheets are constructed on carbonized wood fiber walls, ensures rapid polysulfide conversion and continuous electron transfer for redox reactions. The C–Ti–C bonds formed between MXene and PCWF can considerably expedite the conversion of polysulfides, effectively suppressing the shuttle effect. An impressive capacity of 1301.1 mA h g−1 at 0.5 C accompanied by remarkable stability is attained with the MX/PCWF host, as evidenced by the capacity maintenance of 722.6 mA h g−1 after 500 cycles. Notably, the MX/PCWF/S cathode can still deliver a high capacity of 886.8 mA h g−1 at a high S loading of 5.6 mg cm−2. The construction of two-dimensional MXenes on natural wood fiber walls offers a competitive edge over S-based cathode materials and demonstrates a novel strategy for developing high-performance batteries.

MoC‐MoSe2 Heterostructures as Multifunctional Catalyst Toward Promoting the Stepwise Polysulfide Conversion for Lithium‐Sulfur Batteries

AbstractCatalyzing polysulfides conversion for lithium‐sulfur batteries is an efficient strategy to overcome the sluggish kinetics of polysulfides conversion as well as its serious shuttling effect. Due to the multistep and complicated phase transformation of sulfur species, the monofunctional catalyst can hardly promote the overall polysulfides redox process. Herein, a molybdenum‐based heterostructure is proposed, that facilitates the entire reduction process by tandemly catalyzing liquid‐liquid conversion and liquid‐solid conversion. It is uncovered that the MoC physiochemically immobilizes the soluble long‐chain polysulfide and accelerates the conversion between S8 to Li2S4 through adsorbing Li2S8 and extending its S─S bond distance. Then, the kinetics of Li2S precipitation is enhanced by facilitating the migration of Li2S4 from MoC to MoSe2. This is driven by the internal electric field at the heterogeneous interface and the low diffusion energy barrier on MoSe2 for Li2S4. Moreover, MoC‐MoSe2 exhibits the smallest degree of Li2S2 disproportionation throughout the reduction process. Consequently, the cell with MoC‐MoSe2/C/S cathode delivers an initial discharge‐specific capacity of 841.1 mAh g−1 and long‐term cycling stability with a capacity attenuation rate of 0.08% per cycle at 1.0 C. This work presents a novelty view to design a rational multifunction catalyst for sequentially accelerating the stepwise conversion of polysulfides.

Suppressing the Shuttle Effect of Aqueous Zinc-Iodine Batteries: Progress and Prospects.

Aqueous zinc-iodine batteries are considered to be one of the most promising devices for future electrical energy storage due to their low cost, high safety, high theoretical specific capacity, and multivalent properties. However, the shuttle effect currently faced by zinc-iodine batteries causes the loss of cathode active material and corrosion of the zinc anodes, limiting the large-scale application of zinc-iodine batteries. In this paper, the electrochemical processes of iodine conversion and the zinc anode, as well as the induced mechanism of the shuttle effect, are introduced from the basic configuration of the aqueous zinc-iodine battery. Then, the inhibition strategy of the shuttle effect is summarized from four aspects: the design of cathode materials, electrolyte regulation, the modification of the separator, and anode protection. Finally, the current status of aqueous zinc-iodine batteries is analyzed and recommendations and perspectives are presented. This review is expected to deepen the understanding of aqueous zinc-iodide batteries and is expected to guide the design of high-performance aqueous zinc-iodide batteries.

In-situ constructing cathode protective film toward high performance of Li-S batteries at high sulfur loadings

Shuttle effect of lithium polysulfide (LiPSs) and low sulfur loadings encumber practical application of Li-S batteries. Sulfur cathode coating is a direct and effective strategy to alleviate the problem. However, it is difficult for the available ex-situ coating to suppress shuttle effect at high sulfur surface loading. In the present work, diphenylamine (DPA) is used as an electrolyte additive, which can undergo electropolymerization and form an in-situ PDPA film on sulfur cathode, thereby inhibiting LiPSs diffusion. More importantly, computations and experiments prove that DPA-LiPSs complexes are formed in the electrolyte, increasing the solubility of LiPSs and improving the conversion kinetics. Benefit from the above, the capacity of DPA battery reaches 1029.5 mAh g−1 with sulfur loading of 3 mg cm−2 at 1 C rate, and keeps 762.1 mAh g−1 after 1000 cycles. Excellent cycling performance is achieved even at a high sulfur loading of up to 7 mg cm−2. This work provides a new strategy for suppressing the LiPSs shuttle effect under high sulfur surface loadings.

Pinpointing the Cl Coordination Effect on Mn-N3-Cl Moiety Toward Boosting Reaction Kinetics and Suppressing Shuttle Effect in Li-S Batteries.

Single atom catalysts (SACs) are highly favored in Li-S batteries due to their excellent performance in promoting the conversion of lithium polysulfides (LiPSs) and inhibiting their shuttling. However, the intricate and interrelated microstructures pose a challenge in deciphering the correlation between the chemical environment surrounding the active site and its catalytic activity. Here, a novel SAC featuring a distinctive Mn-N3-Cl moiety anchored on B, N co-doped carbon nanotubes (MnN3Cl@BNC) is synthesized. Subsequently, the selective removal of the Cl ligands while inheriting other microstructures is performed to elucidate the effect of Cl coordination on catalytic activity. The Cl coordination effectively enhances the electron cloud density of the Mn-N3-Cl moiety, reducing the band gap and increasing the adsorption capacity and redox kinetics of LiPSs. As a modified separator for Li-S batteries, MnN3Cl@BNC exhibits high capacities of 1384.1 and 743mAhg-1 at 0.1 and 3C, with a decay rate of only 0.06% per cycle over 700cycles at 1C, which is much better than that of MnN3OH@BNC. This study reveals that Cl coordination positively contributes to improving the catalytic activity of the Mn-N3-Cl moiety, providing a fresh perspective for the design of high-performance SACs.

Cobalt-iron layered double hydroxides/CNTs composite modified separator enabling high-performance lithium–sulfur batteries

The active material loss and capacity degeneration resulted from severe shuttle effect and sluggish redox reaction kinetics of lithium polysulfides (LiPSs) have greatly hindered the further development of high-performance lithium–sulfur batteries (LiSBs). Herein, the functional polymer separator consisting of cobalt-iron layered double hydroxides (CoFe LDH)/carbon nanotubes (CNTs) modified polymer separator is developed. This CoFe LDH/CNTs composite combines the advantages of enhanced chemical bonding between CoFe LDH and LiPSs and improved conductivity, which can significantly suppress the shuttling effect of LiPSs and accelerate the redox reaction kinetics. Therefore, LiSBs assembled by CoFe LDH/CNT-modified separators exhibit superior electrochemical performance with high initial capacity (961.4 mAh g−1) and excellent cycling stability during 200 cycles at 0.5 C rate. The results demonstrate that the Co-Fe LDH/CNTs composites are efficient functional separators for for high-performance LiSBs.

Secondary Amines Functionalized Organocatalytic Iodine Redox for High-Performance Aqueous Dual-Ion Batteries.

Aqueous dual-ion batteries (ADIBs) based on the cooperative redox of cations and iodine anions at the anode and cathode respectively, are attracting increasing interest because of high capacity and safety. However, the full-cell performance is limited by the sluggish iodine redox kinetics between iodide and polyiodide involving multiple electron transfer steps, and the undesirable shuttling effect of polyiodides. Here, this work reports a versatile conjugated microporous polymer functionalized with secondary amine groups as an organocatalytic cathode for ADIB, which can be positively charged and electrostatically adsorb iodide, and organocatalyze iodine redox reactions through the amine groups. Both theoretical calculations and controlled experiments confirm that the secondary amine groups confine (poly)iodide species via hydrogen bonding, which is essential for accelerating iodine redox kinetics and reducing the polyiodide shuttling effect. The ADIB achieves an ultrahigh capacity of 730 mAh g-1 with an ultrasmall overpotential of 47mV at 1 A g-1 , which also exhibits excellent rate performance and long cycling stability with a capacity retention of 74% after 5000 cycles at a high current density of 5 A g-1 . This work demonstrates the promise of developing organocatalysts for accelerating electrochemical processes, which remains a virtually unexplored area in electrocatalyst design for clean energy applications.

Achieving a Quasi‐Solid‐State Conversion of Polysulfides via Building High Efficiency Heterostructure for Room Temperature Na–S Batteries

AbstractThe practical application of room temperature sodium–sulfur (RT Na–S) batteries are prevented by the sulfur insulation, the severe shuttling effect of high‐order sodium polysulfides (Na2Sn, 4 ≤ n ≤ 8), and the sluggish reaction kinetics. Therefore, designing an ideal host material to suppress the polysulfides shuttle process and accelerate the redox reactions of soluble NaPSs to Na2S2/Na2S is of paramount importance for RT Na–S batteries. Here, a quasi‐solid‐state transformation of NaPSs is realized by building high efficiency MoC‐W2C heterostructure in freestanding multichannel carbon nanofibers via electrospinning and calcination methods (MoC‐W2C‐MCNFs). The multichannel carbon nanofibers are interlinked micro‐mesoporous structures that can accommodate volume change of electrode materials and confine the entire redox process of NaPSs (restraining the polysulfides shuttle process). Meanwhile, the MoC‐W2C heterostructure with abundant heterointerfaces can facilitate electron/ion transport and accelerate conversion of NaPSs. Consequently, the S/MoC‐W2C‐MCNFs cathode delivers a high capacity of 640 mAh g−1 after 500 cycles at 0.2 A g−1 and an excellent reversible performance of 200 mAh g−1 after ultralong 3500 cycles at 4 A g−1. What's more, the heterostructure catalytic mechanism (a quasi‐solid‐state transformation) is proposed and confirmed in carbonate electrolyte by combining experimentally and theoretically.

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.

Demonstration of a Gel-Polymer Electrolyte-Based Electrochromic Device Outperforming Its Solution-Type Counterpart in All Merits: Architectural Benefits of CeO2 Quantum Dot and Nanorods.

For years, solution-type electrochromic devices (ECDs) have intrigued researchers' interest and eventually rendered themselves into commercialization. Regrettably, challenges such as electrolyte leakage, high flammability, and complicated edge-encapsulation processes limit their practical utilization, hence necessitating an efficient alternate. In this quest, although the concept of solid/gel-polymer electrolyte (SPE/GPE)-based ECDs settled some issues of solution-type ECDs, an array of problems like high operating voltage, sluggish response time, and poor cycling stability have paralyzed their commercial applicability. Herein, we demonstrate a choreographed-CeO2-nanofiller-doped GPE-based ECD outperforming its solution-type counterpart in all merits. The filler-incorporated polymer electrolyte assembly was meticulously weaved through the electrospinning method, and the resultant host was employed for immobilizing electrochromic viologen species. The filler engineering benefits conceived through the tuned shape of CeO2 nanorod and quantum dots, along with the excellent redox shuttling effect of Ce3+/Ce4+, synchronously yielded an outstanding class of GPE, which upon utilization in ECDs delivered impressive electrochromic properties. A combination of features possessed by a particular device (QD-NR/PVDF-HFP/IL/BzV-Fc ECD) such as exceptionally low driving voltage (0.9 V), high transmittance change (ΔT, ∼69%), fast response time (∼1.8 s), high coloration efficiency (∼339 cm2/C), and remarkable cycling stability (∼90% ΔT-retention after 25,000 cycles) showcased a striking potential in the yet-to-realize market of GPE-based ECDs. This study unveils the untapped potential of choreographed nanofillers that can promisingly drive GPE-based ECDs to the doorstep of commercialization.