Dynamic phase evolution of MoS3 accompanied by organodiselenide mediation enables enhanced performance rechargeable lithium battery.

Considerable efforts have been devoted to Li-S batteries, typically the soluble polysulfides shuttling effect. As a typical transition metal sulfide, MoS2 is a magic bullet for addressing the issues of Li-S batteries, drawing increasing attention. In this study, we introduce amorphous MoS3 as analogous sulfur cathode material and elucidate the dynamic phase evolution in the electrochemical reaction. The metallic 1T phase incorporated 2H phase MoS2 with sulfur vacancies (SVs-1T/2H-MoS2) decomposed from amorphous MoS3 achieves refined mixing with the "newborn" sulfur at the molecular level and supplies continuous conduction pathways and controllable physical confinement. Meanwhile, the in situ-generated SVs-1T/2H-MoS2 allows lithium intercalation in advance at high discharge voltage (≥1.8 V) and enables fast electron transfer. Moreover, aiming at the unbonded sulfur, diphenyl diselenide (PDSe), as a model redox mediator is applied, which can covalently bond sulfur atoms to form conversion-type organoselenosulfides, changing the original redox pathway of "newborn" sulfur in MoS3, and suppressing the polysulfides shuttling effect. It also significantly lowers the activation energy and thus accelerates the sulfur reduction kinetics. Thus, the in situ-formed intercalation-conversion hybrid electrode of SVs-1T/2H-MoS2 and organoselenosulfides realizes enhanced rate capability and superior cycling stability. This work provides a novel concept for designing high-energy-density electrode materials.

Organosulfur Materials for Rechargeable Batteries: Structure, Mechanism, and Application.

Lithium-ion batteries have received significant attention over the last decades due to the wide application of portable electronics and increasing deployment of electric vehicles. In order to further enhance the performance of the batteries and overcome the capacity limitations of inorganic electrode materials, it is imperative to explore new cathode and functional materials for rechargeable lithium batteries. Organosulfur materials containing sulfur-sulfur bonds as a kind of promising organic electrode materials have the advantages of high capacities, abundant resources, tunable structures, and environmental benignity. In addition, organosulfur materials have been widely used in almost every aspect of rechargeable batteries because of their multiple functionalities. This review aims to provide a comprehensive overview on the development of organosulfur materials including the synthesis and application as cathode materials, electrolyte additives, electrolytes, binders, active materials in lithium redox flow batteries, and other metal battery systems. We also give an in-depth analysis of structure-property-performance relationship of organosulfur materials, and guidance for the future development of organosulfur materials for next generation rechargeable lithium batteries and beyond.

Carbon disulfide: A redox mediator for organodisulfides in redox flow batteries.

Organodisulfides (RSSR) are a class of promising active materials for redox flow batteries (RFBs). However, their sluggish kinetics and poor cyclic stability remain a formidable challenge. Here, we propose carbon disulfide (CS2) as a unique redox mediator involving reversible C-S bond formation/breakage to facilitate the reduction reaction of organodisulfides in RFBs. In the discharge of RSSR, CS2 interacts with the negatively charged RSSR-• to promote cleavage of the S-S bond by reducing about one-third of the energy barrier, forming RSCS2Li. In the recharge, CS2 is unbonded from RSCS2Li while RSSR is regenerated. Meanwhile, the redox mediator can also be inserted into the molecular structure of RSSR to form RSCS2SR/RSCS2CS2SR, and these new active materials with lower energy barriers can further accelerate the reaction kinetics of RSSR. With CS2, phenyl disulfide exhibits an exceptional rate capability and cyclability of 500 cycles. An average energy efficiency of >90% is achieved. This strategy provides a unique redox-mediating pathway involving C-S bond formation/breakage with the active species, which is different from those used in lithium-oxygen or other batteries.

Facilitating an Ultrastable O3-Type Cathode for 4.5 V Sodium-Ion Batteries via a Dual-Reductive Coupling Mechanism.

O3-type layered oxides for sodium-ion batteries (SIBs) have attracted extensive attention due to their inherently sufficient Na content, which have been considered as one of the most promising candidates for practical applications. However, influenced by the irreversible oxygen loss and the phase transition of O3-P3, the O3-type cathodes are always limited by low cutoff voltages (typically <4.2 V), restraining the full release of the capacity. In this study, we originally propose a dual-reductive coupling mechanism in a novel O3-type Na0.8Li0.2Fe0.2Ru0.6O2 cathode with the suppressed O3-P3 phase transition, aiming at improving the reversibility of oxygen redox at high voltage regions. Consequently, thanks to the formation of the strong covalent Fe/Ru-(O-O) bonding and inhibited slab gliding from the O to P phase, the cathode delivers the preeminent cyclic stability among the numerous O3-type cathodes within a high voltage of 4.5 V (a capacity retention of 95.4% after 100 cycles within 1.5-4.5 V). More importantly, HAADF-STEM and 7Li solid-state NMR results reveal the absence of transition metal migration and the presence of reversible Li migration during cycling, which further contributes to the improved structural robustness of the cathode. This study proposes an innovative strategy to boost the reversibility of anionic redox and to achieve stable high-voltage O3-type layered oxides, promoting the further development of SIBs.

An Ultrastable Low-Temperature Na Metal Battery Enabled by Synergy between Weakly Solvating Solvents.

The low ionic conductivity and high desolvation barrier are the main challenges for organic electrolytes in rechargeable metal batteries, especially at low temperatures. The general strategy is to couple strong-solvation and weak-solvation solvents to give balanced physicochemical properties. However, the two challenges described above cannot be overcome at the same time. Herein, we combine two different kinds of weakly solvating solvents with a very low desolvation energy. Interestingly, the synergy between the weak-solvation solvents can break the locally ordered structure at a low temperature to enable higher ionic conductivity compared to those with individual solvents. Thus, facile desolvation and high ionic conductivity are achieved simultaneously, significantly improving the reversibility of electrode reactions at low temperatures. The Na metal anode can be stably cycled at 2 mA cm-2 at -40 °C for 1000 h. The Na||Na3V2(PO4)3 cell shows the reversible capacity of 64 mAh g-1 at 0.3 C after 300 cycles at -40 °C, and the capacity retention is 86%. This strategy is applicable to other sets of weak-solvation solvents, providing guidance for the development of electrolytes for low-temperature rechargeable metal batteries.

From Inorganic to Organic Iodine: Stabilization of I+ Enabling High-Energy Lithium-Iodine Battery.

Organic materials have been considered a class of promising cathodes for metal-ion batteries because of their sustainability in preparation and source. However, organic batteries with high energy density and application potential require high discharge voltage, multielectron transfer, and long cycling performance. Here, we report an exceptional lithium-iodine (Li//I2) battery, in which the organic iodine (BPD-HI) cathode formed by the Lewis acid-base coordination between hydroiodic acid (HI) and 4,4'-bipyridine (BPD) allows 2e- transfer via the I-/I0 and I0/I+ redox couples. The I+ stabilized by BPD exhibits a high discharge voltage plateau at ∼3.4 V. Remarkably, from inorganic to organic iodine, it realizes a 2-fold increase in the achieved capacity, up to ∼400 mA h gI-1 (Theor. 422 mA h gI-1 and 245.6 mA h g-1 based on the mass of BPD-HI), and an over 2-fold energy density, reaching 1160 W h kgI-1 (Theor. 1324 W h kgI-1). More importantly, a capacity retention rate of 85% over 850 cycles is attained for the Li//BPD-HI battery at a current density of 2 A gI-1. This facile strategy enables positively charged I+ to be electrochemically active in a rechargeable lithium battery. The new redox chemistry discovered provides new insights for developing organic batteries with high energy density.

An Organic Molecular Cathode Composed of Naphthoquinones Bridged by Organodisulfide for Rechargeable Lithium Battery.

Organic electrodes that embrace multiple electron transfer and efficient redox reactions are desirable for green energy storage batteries. Here, a novel organic electrode material is synthesized, i.e., 2, 2'-((disulfanediylbis (4, 1-phenylene)) bis(azanediyl)) bis (naphthalene-1, 4-dione) (MNQ), through a simple click reaction between common carbonyl and organosulfur compounds and demonstrate its application potential as a high-performance cathode material in rechargeable lithium batteries. MNQ exhibits the aggregation effect of redox-active functional groups, the advantage of fast reaction kinetics from molecular structure evolution, and the decreased solubility in aprotic electrolytes resulting from intermolecular interactions. As expected, the MNQ electrode exhibits a high initial discharge capacity of 281.2 mA h g-1 at 0.5 C, equivalent to 97.9% of its theoretical capacity, and sustains stable long-term cycling performance of over 1000 cycles at 1 C. This work adds a new member to the family of organic electrode materials, providing performance-efficient organic molecules for the design of rechargeable battery systems, which will undoubtedly spark great interest in their applications.

Functional materials for aqueous redox flow batteries: merits and applications.

Redox flow batteries (RFBs) are promising electrochemical energy storage systems, offering vast potential for large-scale applications. Their unique configuration allows energy and power to be decoupled, making them highly scalable and flexible in design. Aqueous RFBs stand out as the most promising technologies, primarily due to their inexpensive supporting electrolytes and high safety. For aqueous RFBs, there has been a skyrocketing increase in studies focusing on the development of advanced functional materials that offer exceptional merits. They include redox-active materials with high solubility and stability, electrodes with excellent mechanical and chemical stability, and membranes with high ion selectivity and conductivity. This review summarizes the types of aqueous RFBs currently studied, providing an outline of the merits needed for functional materials from a practical perspective. We discuss design principles for redox-active candidates that can exhibit excellent performance, ranging from inorganic to organic active materials, and summarize the development of and need for electrode and membrane materials. Additionally, we analyze the mechanisms that cause battery performance decay from intrinsic features to external influences. We also describe current research priorities and development trends, concluding with a summary of future development directions for functional materials with valuable insights for practical applications.

Anchoring and Catalytic Effects of rGO Supported VS2 Nanosheets Enable High-Performance Li-Organosulfur Battery.

As a high-energy-density cathode material, organosulfur has great potential for lithium batteries. However, their practical application is plagued by electronic/ionic insulation and sluggish redox kinetics. Hence, our strategy is to design a self-weaving, freestanding host material by introducing reduced graphene oxide-supported VS2 nanosheets (VS2 -rGO) and carbon nanotubes (CNTs) for lithium-phenyl tetrasulfide (Li-PTS) batteries. Unique host materials not only provide physicochemical confinement of active materials to boost the utilization but also catalyze the conversion of active materials to accelerate redox kinetics. Therefore, Li-PTS cell based on the 3D VS2 -rGO-CNTs (VSGC) host material shows excellent cyclability, with a slow capacity decay rate of 0.08% per cycle over 500 cycles at 0.5 C, and a high areal capacity of 3.1 mAh cm-2 with the PTS loading of 7.2 mg cm-2 . More importantly, the potential for practical applications is highlighted by the flexible pouch cell with a high areal capacity (4.1 mAh cm-2 ) and a low electrolyte/PTS ratio (3.5 µL mg-1 ). This work sheds light on elevating the electrochemical performance of Li-organosulfur batteries through the effective catalytic and adsorbed host material.

MoSe2 @rGO as Highly Efficient Host and Catalyst for Li-Organosulfide Battery.

Organosulfides are promising high-capacity cathode materials for rechargeable lithium batteries. However, sluggish kinetics and inferior utilization impede its practical application in batteries. Rationally designing redox mediators and identifying their active moieties remain formidable challenges. Currently, as a rising star of transition metal dichalcogenides, few-layered MoSe2 decorated reduced graphene oxide (rGO) (MoSe2 @rGO) with high electronic conductivity and narrow energy band is used to manipulate electrocatalytic redox kinetics of organosulfides, thereby enhancing the battery performance. Here, an exotic MoSe2 @rGO is reported with Se defects material obtained from 2D MoSe2 growing on rGO for Li-dipentamethylenethiuram tetrasulfide (Li-PMTT) batteries. MoSe2 @rGO with Se defects has a large specific surface area, and sufficient pores, as well as exce llent catalytic ability for organosulfides conversion reactions. Therefore, the PMTT@MoSe2 @rGO cathode delivers a high reversible capacity of 405 mAh g-1 in the first cycle at 0.5 C and can maintain 238.3 mAh g-1 specific capacity after 300 cycles. This work offers an understanding of organosulfides electrochemistry toward fast and durable performance, holding great promise for developing practically feasible lithium-organosulfides battery material designs.

Long-Life, High-Rate Rechargeable Lithium Batteries Based on Soluble Bis(2-pyrimidyl) Disulfide Cathode.

Organosulfides are promising candidates as cathode materials for the development of electric vehicles and energy storage systems due to their low-cost and high capacity properties. However, they generally suffer from slow kinetics because of the large rearrangement of S-S bonds and structural degradation upon cycling in batteries. In this paper, we reveal that soluble bis(2-pyrimidyl) disulfide (Pym2 S2 ) can be a high-rate cathode material for rechargeable lithium batteries. Benefiting from the superdelocalization of pyrimidyl group, the extra electrons prefer to be localized on the π* (pyrimidyl group) than σ* (S-S bond) molecular orbitals initially, generating the anion-like intermedia of [Pym2 S2 ]2- and thus decreasing the dissociation energy of the S-S bond. It makes the intrinsic energy barrier of dissociative electron transfer depleted, therefore the lithium half cell exhibits 2000 cycles at 5 C. This study provides a distinct pathway for the design of high-rate, long-cycle-life organic cathode materials.

Activation of Bulk Li2 S as Cathode Material for Lithium-Sulfur Batteries through Organochalcogenide-Based Redox Mediation Chemistry.

Lithium sulfide (Li2 S) is considered as a promising cathode material for sulfur-based batteries. However, its activation remains to be one of the key challenges against its commercialization. The extraction of Li+ from bulk Li2 S has a high activation energy (Ea ) barrier, which is fundamentally responsible for the initial large overpotential. Herein, a systematic investigation of accelerated bulk Li2 S oxidation reaction kinetics was studied by using organochalcogenide-based redox mediators, in which phenyl ditelluride (PDTe) can significantly reduce the Ea of Li2 S and lower the initial charge potential. Simultaneously, it can alleviate the polysulfides shuttling effect by covalently anchoring the soluble polysulfides and converting them into insoluble lithium phenyl tellusulfides (PhTe-Sx Li, x>1). This alters the redox pathway and accelerates the reaction kinetics of Li2 S cathode. Consequently, the Li||Li2 S-PDTe cell shows excellent rate capability and enhanced cycling stability. The Si||Li2 S-PDTe full cell delivers a considerable capacity of 953.5 mAh g-1 at 0.2 C.

Electrochemical Reactivation of Dead Li2 S for Li-S Batteries in Non-Solvating Electrolytes.

The use of non-solvating, or as-called sparingly-solvating, electrolytes (NSEs), is regarded as one of the most promising solutions to the obstacles to the practical applications of Li-S batteries. However, it remains a puzzle that long-life Li-S batteries have rarely, if not never, been reported with NSEs, despite their good compatibility with Li anode. Here, we find the capacity decay of Li-S batteries in NSEs is mainly due to the accumulation of the dead Li2 S at the cathode side, rather than the degradation of the anodes or electrolytes. Based on this understanding, we propose an electrochemical strategy to reactivate the accumulated Li2 S and revive the dead Li-S batteries in NSEs. With such a facile approach, Li-S batteries with significantly improved cycling stability and accelerated dynamics are achieved with diglyme-, acetonitrile- and 1,2-dimethoxyethane-based NSEs. Our finding may rebuild the confidence in exploiting non-solvating Li-S batteries with practical competitiveness.

Thiuram Monosulfide with Ultrahigh Redox Activity Triggered by Electrochemical Oxidation.

Organosulfides are promising cathodes for lithium batteries but often suffer from sluggish kinetics and low cycle stability. Herein, we report an electron-deficient organosulfide (ED-OS), which is formed via electrochemical oxidation of thiuram monosulfide, a low-cost sustainable material. The ED structure of (dimethylcarbamothioyl)thio can stretch the electron cloud of the adjacent C═S bond forming an S radical and lead to the cleavage of the S-C bond on the other side forming another S radical. The two (dimethylcarbamothioyl)thio radicals can form S-S bonds individually with low energy barriers, which thus are easy to break and could accommodate lithium ions with ultrafast reaction kinetics. It exhibits an ultralong cyclability of over 8000 cycles with a low capacity-fade rate of 0.0038% per cycle at a high rate of 10C in a lithium cell. In addition, we demonstrate that the same electrochemical oxidation can be applied to other thiuram compounds. This work provides new opportunities in developing ultrahigh-redox-activity organic electrode materials which can be started as needed.

Dynamic 1T-2H Mixed-Phase MoS2 Enables High-Performance Li-Organosulfide Battery.

Achieving high energy density and long cycle life in realistic batteries is still an unmet need, which has triggered research into the discoveries of new electrode materials as well as new storage mechanisms. As a kind of new cathode materials for rechargeable lithium batteries, organosulfide compounds R-Sn -R (n = 3-6) based on conversion chemistries of SS bonds have many advantages and promising prospects; however, poor electric/ionic conductivity and sluggish redox kinetics is a major hinder for their applications. Here an organic-inorganic hybrid cathode by introducing 1T MoS2 grown on reduced graphene oxide to hybridize with phenyl tetrasulfide (Ph-S4 -Ph, theoretical specific capacity 570 mAh g-1 ), enhancing the battery performance is reported. This includes the improved charge transfer, stable long cycles, and close-to-practical energy density in coin cells and pouch cells, which also show high mass loadings and contents, and low electrolyte dependence. Furthermore, the dynamic 1T-2H mixed-phase during the charge/discharge is revealed to be critical for the improved performance. This study proves the hybrid nanomaterials as a promising solution to address the challenges facing lithium-organosulfide batteries.

Isomeric Organodithiol Additives for Improving Interfacial Chemistry in Rechargeable Li-S Batteries.

Lithium-sulfur (Li-S) batteries have a high theoretical specific energy; however, their performance is plagued by the shuttle effect of lithium polysulfides and the instability of the lithium anode interface. Great efforts have been made using electrolyte additives to address the issues. Herein, we report a class of electrolyte additives, i.e., benzenedithiols (BDTs). Among the three isomers of BDTs, 1,4-BDT shows the best effect on the performance improvement of a Li-S battery because it can bond more sulfur atoms than the other two. The functionality of 1,4-BDT on the cathode and anode involves the chemical reactions of thiol groups. The S-S bonds were generated from 1,4-BDT and sulfur through oligomerization, which change the original redox path of sulfur and inhibit the shuttle effect of lithium polysulfides. In addition, 1,4-BDT can form a smooth and stable solid-electrolyte interphase (SEI), which can enable the Li/Li symmetric cell with an ultralow overpotential of 0.08 V at a high current density of 5 mA cm-2 for over 300 h. The Li-S cell with 1,4-BDT displays the highest cycling stability at a C/5 rate, with an initial capacity of 1548.5 mAh g-1 and a reversible capacity of 1306.9 mAh g-1 after 200 cycles. The Li-S pouch cell with 1,4-BDT and 2.8 g of sulfur exhibits an initial capacity of 2640 mAh and a capacity retention rate of 84.2% after 26 cycles at a C/10 rate. This work demonstrates that organodithiol compounds can be used as functional electrolyte additives and provides a new direction to design materials for advanced Li-S batteries.

Simultaneously Homogenized Electric Field and Ionic Flux for Reversible Ultrahigh-Areal-Capacity Li Deposition.

High areal capacity and stable Coulombic efficiency (CE) in lithium metal anodes (LMAs) play pivotal roles in developing high-energy-density rechargeable batteries. However, few reported LMAs delivering high and stable CE (>50 cycles) under ultrahigh areal capacity (>10 mA h cm-2). We demonstrated that the simultaneous homogenization of electric field and Li ion flux by using self-supported and surface-oxidized 3D hollow porous copper fibers (3D-HPCFs) can greatly increase both the areal capacity and reversibility of Li deposition. Li can be easily confined inside the hollow porous fibers and within the interspaces among fibers without uncontrollable Li dendrites. The 3D-HPCF-based anode can be deeply cycled at high capacity of 15 mA h cm-2 with average CE of 98.87% for 53 cycles, enabling a practical cell to realize high capacity retentions at a surplus Li of 10%. This work provides a novel Li deposition-regulation technology in LMAs targeting for next generation high-energy-density batteries.

Organosulfide-Based Deep Eutectic Electrolyte for Lithium Batteries.

Deep eutectic electrolytes (DEEs) are a new class of electrolytes with unique properties. However, the intermolecular interactions of DEEs are mostly dominated by Li⋅⋅⋅O interactions, limiting the diversity of chemical space and material constituents. Herein, we report a new class of DEEs induced by Li⋅⋅⋅N interactions between 2,2'-dipyridyl disulfide (DpyDS) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The strong ion-dipole interaction triggers the deep eutectic phenomenon, thus liberating the Li+ from LiTFSI and endowing the DEEs with promising ionic conductivity. These DEEs show admirable intrinsic safety, which cannot be ignited by flame. The DEE at the molar ratio of DpyDS:LiTFSI=4:1 (abbreviated as DEE-4:1) is electrochemically stable between 2.1 and 4.0 V vs. Li/Li+ , and exhibits an ionic conductivity of 1.5×10-4  S cm-1 at 50 °C. The Li/LiFePO4 half cell with DEE-4:1 can provide a reversible capacity of 130 mAh g-1 and Coulombic efficiency above 98 % at 50 °C.

Organosulfides: An Emerging Class of Cathode Materials for Rechargeable Lithium Batteries.

Lithium-ion batteries have received significant attention over the last decades due to the wide application of portable electronics and increasing deployment of electric vehicles. In order to further increase the energy density of batteries and overcome the capacity limitations (<250 mAh g-1) of inorganic cathode materials, it is imperative to explore new cathode materials for rechargeable lithium batteries. Organic compounds including organic carbonyl, radicals, and organosulfides are promising as they have advantages of high capacities, abundant resources, and tunable structures. In the 1980s, a few organosulfides, in particular organodisulfides, as cathode materials were studied to a certain extent in rechargeable lithium batteries. However, they showed low capacities and poor cycling performance, which made them unappealing then in comparison to transition metal oxide cathode materials. As a result, organosulfides have not been extensively studied like other cathode materials including organic carbonyls and radicals. In recent years, organosulfides with long sulfur chains (e.g., trisulfide, tetrasulfide, pentasulfide, etc.) in the structures have been receiving more attention in conjunction with the development of lithium-sulfur batteries. As a major class of sulfur derivatives, they have versatile structures and unique properties in comparison with elemental sulfur. In this Account, we first generalize the working principles of organosulfides in lithium batteries. We then discuss organosulfide molecules, which have precise lithiation sites and tunable capacities. The organic functional groups can provide additional benefits, such as discharge voltage and energy efficiency enhancement by phenyl groups and cycling stability improvement by N-heterocycles. Furthermore, replacing sulfur by selenium in these compounds can improve their electrochemical properties due to the high electronic conductivity and low bond energy associated with selenium. We list organosulfide polymers consisting of phenyl rings, N-heterocycles, or aliphatic segments. Organosulfides as electrolyte additives or components for forming a solid-electrolyte interphase layer on lithium metal anode are also presented. Carbon materials such as carbon nanotubes and reduced graphene oxide can enhance the battery performance of organosulfide cathodes. We discuss the synthesis methods for polysulfide molecules and polymers. Finally, we show the advantages of organosulfides over sulfur as cathode materials in lithium batteries. This Account provides a summary of recent development, in-depth analysis of structure-performance relationship, and guidance for future development of organosulfides as promising cathode materials for next generation rechargeable lithium batteries.

Electrochemistry of Electrode Materials Containing S-Se Bonds for Rechargeable Batteries.

Sulfur (S) and selenium (Se) have been considered as promising high capacity cathode materials for rechargeable batteries. They have differences in their physical properties (e.g., electronic conductivity) but the same number of electrons in their outermost shells, which leads to similarity in their electrochemical behavior in batteries. In recent years, some efforts have been taken to combine them in electrodes in the hope of improved battery performance. The S-Se bonds of these electrode materials lead to unusual properties and intriguing electrochemical behavior, which have attracted increasing interest. In this Minireview, electrode materials containing S-Se bonds are summarized, including inorganic Sx Sey solid solutions, organic compounds, and organic-inorganic hybrid materials. Our understanding in these materials is still premature, but they have shown unique properties to be electrode materials. We hope this Minireview could provide a new insight into the design, synthesis, and understanding of these materials, which could enable high energy density rechargeable batteries.