Dual Role of Mo6_{6}S8_{8} in Polysulfide Conversion and Shuttle for Mg–S Batteries

Magnesium–Sulfur batteries are one of most appealing options among the post-lithium battery systems due to its potentially high energy density, safe and sustainable electrode materials. The major practical challenges are originated from the soluble magnesium polysulfide intermediates and their shuttling between the electrodes, which cause high overpotentials, low sulfur utilization, and poor Coulombic efficiency. Herein, a functional Mo$_{6}$S$_{8}$ modified separator is designed to effectively address these issues. Both the experimental results and density functional theory calculations show that the electrochemically active Mo6S8 layer has a superior adsorption capability of polysulfides and simultaneously acts as a mediator to accelerate the polysulfide conversion kinetics. Remarkably, the magnesium–sulfur cell assembled with the functional separator delivers a high specific energy density (942.9 mA h g$^{-1}$ in the 1st cycle) and can be cycled at 0.2 C for 200 cycles with a Coulombic efficiency of 96%. This work demonstrates a new design concept toward high-performance metal–sulfur batteries

A Structurally Flexible Halide Solid Electrolyte with High Ionic Conductivity and Air Processability

In this work, a structurally revivable, chloride-ion conducting solid electrolyte (SE), CsSn$_{0.9}$In$_{0.067}$Cl$_3$, with a high ionic conductivity of 3.45 × 10$^{−4}$ S cm$^{−1}$ at 25 °C is investigated. The impedance spectroscopy, density functional theory, solid-state $^{35}$Cl NMR, and electron paramagnetic resonance studies collectively reveal that the high Cl$^−$ ionic mobility originates in the flexibility of the structural building blocks, Sn/InCl$_6$ octahedra. The vacancy-dominated Cl$^−$ ion diffusion encompasses co-ordinated Sn/In(Cl) site displacements that depend on the exact stoichiometry, and are accompanied by changes in the local magnetic moments. Owing to these promising properties, the suitability of the CsSn$_{0.9}$In$_{0.067}$Cl$_3$, as an electrolyte is demonstrated by designing all-solid-state batteries, with different anodes and cathodes. The comparative investigation of interphases with Li, Li–In, Mg, and Ca anodes reveals different levels of reactivity and interphase formation. The CsSn$_{0.9}$In$_{0.067}$Cl$_3$ demonstrates an excellent humidity tolerance (up to 50% relative humidity) in ambient air, maintaining high structural integrity without compromises in ionic conductivity, which stands in contrast to commercial halide-based lithium conductors. The discovery of a halide perovskite conductor, with air processability and structure revival ability paves the way for the development of advanced air processable SEs, for next-generation batteries

Greener, Safer and Better Performing Aqueous Binder for Positive Electrode Manufacturing of Sodium Ion Batteries

P2-type cobalt-free MnNi-based layered oxides are promising cathode materials for sodium-ion batteries (SIBs) due to their high reversible capacity and well chemical stability. However, the phase transformations during repeated (dis)charge steps lead to rapid capacity decay and deteriorated Na+ diffusion kinetics. Moreover, the electrode manufacturing based on polyvinylidene difluoride (PVDF) binder system has been reported with severely defluorination issue as well as the energy intensive and expensive process due to the use of toxic and volatile N-methyl-2-pyrrolidone (NMP) solvent. It calls for designing a sustainable, better performing, and cost-effective binder for positive electrode manufacturing. In this work, we investigated inorganic sodium metasilicate (SMS) as a viable binder in conjunction with P2-Na0.67Mn0.55Ni0.25Fe0.1Ti0.1O2 (NMNFT) cathode material for SIBs. The NMNFT-SMS electrode delivered a superior electrochemical performance compared to carboxy methylcellulose (CMC) and PVDF based electrodes with a reversible capacity of ~161 mAh/g and retaining ~83 % after 200 cycles. Lower cell impedance and faster Na+ diffusion was also observed in this binder system. Meanwhile, with the assistance of TEM technique, SMS is suggested to form a uniform and stable nanoscale layer over the cathode particle surface, protecting the particle from exfoliation/cracking due to electrolyte attack. It effectively maintained the electrode connectivity and suppressed early phase transitions during cycling as confirmed by operando XRD study. With these findings, SMS binder can be proposed as a powerful multifunctional binder to enable positive electrode manufacturing of SIBs and to overall reduce battery manufacturing costs

Insights into the Degradation Mechanism of the Magnesium Anode in Magnesium–Chalcogen Batteries: Revealing Principles for Anode Design with a 3D-Structured Magnesium Anode

Magnesium–chalcogen batteries are promising post lithium battery systems for large-scale energy storage applications in terms of energy density, material sustainability, safety, and cost. However, the soluble reaction intermediates, such as polysulfides or polyselenides, formed during the electrochemical processes can severely passivate the Mg metal anode, limiting the cycle life of the batteries. It is necessary to rescrutinize the failure in Mg–chalcogen batteries from an anodic perspective. Herein, the Mg metal anode failure mechanism is thoroughly examined, revealing that it is induced by an inhomogeneous Mg deposition promoted by soluble intermediates from chalcogen cathodes. To further confirm the mechanism and solve this anode failure problem, a multifunctional 3D current collector is used to decrease the local current density and regulate the Mg deposition behavior. The present findings are anticipated to provide guidance for anode design, enhance the life-span of Mg–chalcogen batteries, and facilitate the development of other magnesium metal batteries

Surface Engineering of a Mg Electrode via a New Additive to Reduce Overpotential

International audienc

Dual Role of Mo₆S₈ in Polysulfide Conversion and Shuttle for Mg–S Batteries

Magnesium–Sulfur batteries are one of most appealing options among the post‐lithium battery systems due to its potentially high energy density, safe and sustainable electrode materials. The major practical challenges are originated from the soluble magnesium polysulfide intermediates and their shuttling between the electrodes, which cause high overpotentials, low sulfur utilization, and poor Coulombic efficiency. Herein, a functional Mo(6)S(8) modified separator is designed to effectively address these issues. Both the experimental results and density functional theory calculations show that the electrochemically active Mo(6)S(8) layer has a superior adsorption capability of polysulfides and simultaneously acts as a mediator to accelerate the polysulfide conversion kinetics. Remarkably, the magnesium–sulfur cell assembled with the functional separator delivers a high specific energy density (942.9 mA h g(−1) in the 1st cycle) and can be cycled at 0.2 C for 200 cycles with a Coulombic efficiency of 96%. This work demonstrates a new design concept toward high‐performance metal–sulfur batteries

Addressing the Sluggish Kinetics of Sulfur Redox for High‐Energy Mg–S Batteries

A key challenge for practical magnesium–sulfur (Mg–S) batteries is to overcome the sluggish conversion kinetics of sulfur cathodes, achieving a high energy density and long-lasting battery life. To address this issue, a doping strategy is demonstrated in a model Ketjenblack sulfur (KBS) cathode by introducing selenium with a high electronic conductivity. This leads to a significantly enhanced charge transfer in the resultant KBS1−xSex cathodes, giving rise to a higher S utilization and less polysulfide dissolution. Compared to the bare S cathode, the S-Se composite cathodes exhibit a higher capacity, smaller overpotentials, and improved efficiency, serving as better benchmark compounds for high-performance Mg–S batteries. First principles calculations reveal a charge transport mechanism via electron polaron diffusion in the redox end-products, that enhances the reaction kinetics. By suppressing polysulfide dissolution in the electrolyte, the use of the KBS1−xSex cathodes also enables a more uniform anode reaction, and thereby significantly extends the cyclability of the cells. To improve the performance, further efforts are made by implementing a Mo6S8 modified separator into the cell. With an optimized cathode composition of KBS0.86Se0.14, the cell applying modified separator shows an improvement of capacity retention by >50% after 200 cycles