Advances in Functional Organosulfur-Based Mediators for Regulating Performance of Lithium Metal Batteries.

Rechargeable lithium metal batteries (LMBs) are promising next-generation energy storage systems due to their high theoretical energy density. However, their practical applications are hindered by lithium dendrite growth and various intricate issues associated with the cathodes. These challenges can be mitigated by using organosulfur-based mediators (OSMs), which offer the advantages of abundance, tailorable structures, and unique functional adaptability. These features enable the rational design of targeted functionalities, enhance the interfacial stability of the lithium anode and cathode, and accelerate the redox kinetics of electrodes via alternative reaction pathways, thereby effectively improving the performance of LMBs. Unlike the extensively explored field of organosulfur cathode materials, OSMs have garnered little attention. This review systematically summarizes recent advancements in OSMs for various LMB systems, including lithium-sulfur, lithium-selenium, lithium-oxygen, lithium-intercalation cathode batteries, and other LMB systems. It briefly elucidates the operating principles of these LMB systems, the regulatory mechanisms of the corresponding OSMs, and the fundamentals of OSMs activity. Ultimately, strategic optimizations are proposed for designing novel OSMs, advanced mechanism investigation, expanded applications, and the development of safe battery systems, thereby providing directions to narrow the gap between rational modulation of organosulfur compounds and their practical implementation in batteries.

P-doped RuSe2 on Porous N-doped Carbon Matrix as Catalysts for Accelerated Sulfur Redox Reactions.

Monocomponent catalysts exhibit the limited catalytic conversion of polysulfides due to their intrinsic electronic structure, but their catalytic activity can be improved by introducing heteroatoms to regulate its electronic structure. However, the rational selection principles of doping elements remain unclear. Here, we are guided by theoretical calculations to select the suitable doping elements based on the balanced relationship between the adsorption strength of lithium polysulfides (LiPSs) and catalytic activity of lithium sulfide. We apply the screening method to develop a new catalyst of phosphorus doped RuSe2, manifesting the further enhanced conductivity compared with original RuSe2, facilitating charge transfer and further modulating the d-band center of RuSe2, thereby augmenting its effectiveness in interacting with LiPSs. Consequently, the assembled cell exhibits an areal capacity of 7.7 mAh cm-2, even under high sulfur loading of 8.0 mg cm-2 and a lean electrolyte condition (5.0 µL mg-1). This rational screening strategy offers a robust solution for the design of advanced catalysts in the field of lithium-sulfur batteries and potentially other domains as well.

Insights into the Optimization of Catalytic Active Sites in Lithium-Sulfur Batteries.

ConspectusLithium-sulfur batteries (LSBs), recognized for their high energy density and cost-effectiveness, offer significant potential for advancement in energy storage. However, their widespread deployment remains hindered by challenges such as sluggish reaction kinetics and the shuttle effect of lithium polysulfides (LiPSs). By the introduction of catalytic materials, the effective adsorption of LiPSs, smooth surface migration behavior, and significantly reduced conversion energy barriers are expected to be achieved, thereby sharpening electrochemical reaction kinetics and fundamentally addressing the aforementioned challenges. However, driven by practical application targets, the demand for higher loadings and reduced electrolyte parameters inevitably exacerbates the burden on catalytic materials during their service. Additionally, given that catalytic materials contribute negligible electrochemical capacity, their incorporation inevitably increases the mass of nonactive components for reducing the energy density of LSBs. A meticulous insight into the lithium-sulfur catalytic reaction reveals that the conversion of LiPSs is dominated by active sites on the surfaces of catalytic materials. These microregions provide the necessary electron and ion transport for the conversion reaction of LiPSs, with their efficacy and quantity directly impacting the conversion efficiency. In light of these considerations, the strategic optimization of active sites emerges as a paramount pathway toward promoting the performance of LSBs while concurrently mitigating unnecessary mass. Here, we outline three strategies developed by our group to optimize active sites of catalytic materials: (1) Augmenting active sites by customizing structural modulation and precise dimensional control to maximize exposure. Emphasis has been placed on the approaches for material synthesis and the essence of reactions for achieving this strategy. (2) Regulating the microenvironment of active sites by integrating the coordination refinement, long-range atomic interactions, metal-support interactions, and other electronic regulation strategies, thereby providing an elevation in the intrinsic catalytic performance. (3) Implementing a self-cleaning mechanism for active sites to counteract deactivation by designing a tandem adsorption-migration-transformation pathway of sulfur contained within the molecular domain. Throughout this process, the intrinsic mechanisms driving performance enhancement through active site optimization strategies have been prominently emphasized, which encompass aspects such as electronic structure, atomic composition, and molecular configuration and significantly expand the comprehension of Li-S catalytic chemistry. Subsequently, considerations demanding heightened attention in future processes of active site optimization for catalytic materials have been delineated, including the in situ evolution patterns and resistance to the poisoning of active sites. It is noteworthy that given the similarity between Li-S catalysis chemistry and traditional electrocatalytic processes, this Account elucidates the concept of active site optimization by drawing insights from representative works and our own works in the field of electrocatalysis, which is relatively rare in previous reviews of LSBs. The proposed insights contribute to uncovering the intrinsic mechanisms of Li-S catalysis chemistry and introducing innovative ideas into active site optimization, ultimately advancing energy density and stability in LSBs.

Rapid Growth of Bi2Se3 Nanodots on MXene Nanosheets at Room Temperature for Promoting Sulfur Redox Kinetics.

Li-S batteries are hampered by problems with their cathodes and anodes simultaneously. The improvement of Li-S batteries needs to consider both the anode and cathode. Herein, a Bi2Se3@MXene composite is prepared for the first time by rapidly growing Bi2Se3 nanodots on two-dimensional (2D) MXene nanosheets at room temperature through simply adding high-reactive hydroxyethylthioselenide in Bi3+/MXene aqueous solution. Bi2Se3@MXene exhibits a 2D structure due to the template effect of 2D MXene. Bi2Se3@MXene can not only facilitate the conversion of lithium polysulfides (LiPSs) but also inhibit their shuttling in the S cathode due to its catalytic effect and adsorption force with LiPSs. Bi2Se3@MXene can also be used as an interfacial lithiophilic layer to inhibit Li dendrite growth in the Li metal anode. Theoretical calculations reveal that Bi2Se3 nanodots in Bi2Se3@MXene can effectively boost the adsorption ability with LiPSs, and the MXene in Bi2Se3@MXene can accelerate the electron transport. Under the bidirectional regulation of Bi2Se3@MXene in the Li metal anode and S cathode, the Li-S battery shows an enhanced electrochemical performance.

One-step growth of ultrathin CoSe2 nanobelts on N-doped MXene nanosheets for dendrite-inhibited and kinetic-accelerated lithium-sulfur chemistry.

The practical application of lithium-sulfur (Li-S) batteries is inhibited by the shuttle effect of lithium polysulfides (LiPSs) and slow polysulfide redox kinetics on the S cathode as well as the uncontrollable growth of dendrites on the Li metal anode. Therefore, both cathode and anode sides must be considered when modifying Li-S batteries. Herein, two-dimensional (2D) ultrathin CoSe2 nanobelts are in situ grown on 2D N-doped MXene nanosheets (CoSe2@N-MXene) via one-step solvothermal process for the first time. Owing to its unique 2D/2D structure, CoSe2@N-MXene can be processed to crumpled nanosheets by freeze-drying and flexible and freestanding films by vacuum filtration. These crumpled CoSe2@N-MXene nanosheets with abundant active sites and inner spaces can act as S hosts to accelerate polysulfide redox kinetics and suppress the shuttle effect of LiPSs owing to their strong adsorption ability and catalytic conversion effect with LiPSs. Meanwhile, the CoSe2@N-MXene film (CoSe2@NMF) can act as a current collector to promote uniform Li deposition because it contains lithiophilic CoSe2 and N sites. Under the systematic effect of CoSe2@N-MXene on S cathode and Li metal anode, the electrochemical and safety performance of Li-S batteries are improved. CoSe2@NMF also shows excellent storage performances in flexible energy storage devices.

Ordered Vacancies as Sodium Ion Micropumps in Cu-Deficient Copper Indium Diselenide to Enhance Sodium Storage.

Unordered vacancies engineered in host anode materials cannot well maintain the uniform Na+ adsorbed and possibly render the local structural stress intense, resulting in electrode peeling and battery failure. Here, the indium is first introduced into Cu2Se to achieve the formation of CuInSe2. Next, an ion extraction strategy is employed to fabricate Cu0.54In1.15Se2 enriched with ordered vacancies by spontaneous formation of defect pairs. Such ordered defects, compared with unordered ones, can serve as myriad sodium ion micropumps evenly distributing in crystalline host to homogenize the adsorbed Na+ and the generated volumetric stress during the electrochemistry. Furthermore, Cu0.54In1.15Se2 is indeed proved by the calculations to exhibit smaller volumetric variation than the counterpart with unordered vacancies. Thanks to the distinct ordered vacancy structure, the material exhibits a highly reversible capacity of 428 mAh g-1 at 1 C and a high-rate stability of 311.7 mAh g-1 at 10 C after 5000 cycles when employed as an anode material for Sodium-ion batteries (SIBs). This work presents the promotive effect of ordered vacancies on the electrochemistry of SIBs and demonstrates the superiority to unordered vacancies, which is expected to extend it to other metal-ion batteries, not limited to SIBs to achieve high capacity and cycling stability.

Self-Zincophilic Dual Protection Host of 3D ZnO/Zn⊂CF to Enhance Zn Anode Cyclability.

Zn dendrite growth and side reactions restrict the practical use of Zn anode. Herein, the design of a novel 3D hierarchical structure is demonstrated with self-zincophilic dual-protection constructed by ZnO and Zn nanoparticles immobilized on carbon fibers (ZnO/Zn⊂CF) as a versatile host on the Zn surface. The unique 3D frameworks with abundant zinc nucleation storage sites can alleviate the structural stress during the plating/stripping process and overpower Zn dendrite growth by moderating Zn2+ flux. Moreover, given the dual protection design, it can reduce the contact area between active zinc and electrolyte, inhibiting hydrogen evolution reactions. Importantly, density functional theory calculations and experimental results confirm that the introduced O atoms in ZnO/Zn⊂CF enhance the interaction between Zn2+ and the host and reduce Zn nucleation overpotential. As expected, the ZnO/Zn⊂CF-Zn electrode exhibits stable Zn plating/stripping with low polarization for 4200 h at 0.2 mA cm-2 and 0.2 mAh cm-2. Furthermore, the symmetrical cell displays a significantly long cycling life of over 1800 h, even at 30 mA cm-2. The fabricated full cells also show impressive cycling performance when coupled with V2O3 cathodes.

Synchronous Regulation of D-Band Centers in Zn Substrates and Weakening Pauli Repulsion of Zn Ions Using the Ascorbic Acid Additive for Reversible Zinc Anodes.

The advanced aqueous zinc-ion batteries (AZIBs) are still challenging due to the harmful reactions including hydrogen evolution and corrosion. Here, a natural small molecule acid vitamin C (Vc) as an aqueous electrolyte additive has been selectively identified. The small molecule Vc can adjust the d band center of Zn substrate which fixes the active H+ so that the hydrogen evolution reaction (HER) is restrained. Simultaneously, it could also fine-tune the solvation structure of Zn ions due to the enhanced electrostatics and reduced Pauli repulsion verified by energy decomposition analysis (EDA). Hence, the cell retains an ultra-long cycle performance of over 1300 cycles and a superior Coulombic efficiency (CE) of 99.5 %. The prepared full cells display increased rate capability, cycle lifetime, and self-discharge suppression. Our results shed light on the mechanistic principle of electrolyte additives on the performance improvement of ZIBs, which is anticipated to render a new round of studies.

Heterogenization-Activated Zinc Telluride via Rectifying Interfacial Contact to Afford Synergistic Confinement-Adsorption-Catalysis for High-Performance Lithium-Sulfur Batteries.

The notorious shuttle effect and sluggish conversion kinetics of intermediate polysulfides (Li2S4, Li2S6, Li2S8) are severely hindered the large-scale development of Lithium-sulfur (Li-S) batteries. Rectifying interface effect has been a solution to regulate the electron distribution of catalysts via interfacial charge exchange. Herein, a ZnTe-ZnO heterojunction encapsulated in nitrogen-doped hierarchical porous carbon (ZnTe-O@NC) derived from metal-organic framework is fabricated. Theoretical calculations and experiments prove that the built-in electric field constructed at ZnTe-ZnO heterojunction via the rectifying interface contact, thus promoting the charge transfer as well as enhancing adsorption and conversion kinetics toward polysulfides, thereby stimulating the catalytic activity of the ZnTe. Meanwhile, the nitrogen-doped hierarchical porous carbon acts as confinement substrate also enables fast electrons/ions transport, combining with ZnTe-ZnO heterojunction realize a synergistic confinement-adsorption-catalysis toward polysulfides. As a result, the Li-S batteries with S/ZnTe-O@NC electrodes exhibit an impressive rate capability (639.7 mAh g-1 at 3 C) and cycling performance (70% capacity retention at 1 C over 500 cycles). Even with a high sulfur loading, it still delivers a superior electrochemical performance. This work provides a novel perspective on designing highly catalytic materials to achieve synergistic confinement-adsorption-catalysis for high-performance Li-S batteries.

Interfacial oxygen atom modification of a PdSn alloy to boost oxygen reduction in zinc-air batteries.

Modifying the surface of a catalyst with heteroatoms can regulate the interfacial atomic valence state and adjust the charge distribution, which is promising for obtaining desirable platinum carbon catalyst (Pt/C)-matched oxygen reduction reaction (ORR) catalytic performance. Here, we developed an efficient method to access O-rich crystalline interfacial-exposed palladium-tin alloy (111) crystal surfaces [Pd3Sn (111)] for highly efficient ORR via direct reduction of Pd/Sn metal salt species that are well dispersed in a nitrogen, phosphorus-doped carbonaceous (NPC) substrate. In addition to the other materials, preembedded Pd/Sn metal salt species in NPC control the release of metal sources upon reduction in the liquid phase, resulting in the grafting of an as-prepared PdSn alloy with many merits, such as efficient electron conduction, short-range crystallinity and increased crystal interface exposure. The presence of a considerable quantity of oxygen atoms at the interface of small-sized PdSn alloys on NPC substrates has been methodically verified by powder X-ray diffraction, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy characterizations. The PdSn-O sample exhibited excellent ORR activity, achieving an onset potential of âˆ¼0.99 V and a half-wave potential of âˆ¼0.88 V at 1600 rpm in O2-saturated 1.0 M KOH. Density functional theory simulations of pure Pd, Pd-O, the PdSn alloy and PdSn-O suggest that interfacial oxygen atom modification is responsible for the significantly improved ORR activity. The assembled zinc-air battery provides a high specific power of 218.9 mW cm-2 and a specific capacity of 810.6 mAh gZn-1. Our approach has the potential to stimulate the preparation of O-rich crystalline interfacial-exposed alloy compounds for other energy conversion applications.