A triple-synergistic small-molecule sulfur cathode promises energetic Cu-S electrochemistry.

Metal-sulfur batteries have received great attention for electrochemical energy storage due to high theoretical capacity and low cost, but their further development is impeded by low sulfur utilization, poor electrochemical kinetics, and serious shuttle effect of the sulfur cathode. To avoid these problems, herein, a triple-synergistic small-molecule sulfur cathode is designed by employing N, S co-doped hierarchical porous bamboo charcoal as a sulfur host in an aqueous Cu-S battery. Expect the enhanced conductivity and chemisorption induced by N, S synergistic co-doping, the intrinsic synergy of macro-/meso-/microporous triple structure also ensures space-confined small-molecule sulfur as high utilization reactant and effectively alleviates the volume expansion during conversion reaction. Under a further joint synergy between hierarchical structure and heteroatom doping, the resulting sulfur cathode endows the Cu-S battery with outstanding electrochemical performance. Cycled at 5 A g-1, it can deliver a high reversible capacity of 2,509.8 mAh g-1 with a good capacity retention of 97.9% after 800 cycles. In addition, a flexible hybrid pouch cell built by a small-molecule sulfur cathode, Zn anode, and gel electrolytes can firmly deliver high average operating voltage of about 1.3 V with a reversible capacity of over 2,500 mAh g-1 under various destructive conditions, suggesting that the triple-synergistic small-molecule sulfur cathode promises energetic metal-sulfur batteries.

Amidation-Dominated Re-Assembly Strategy for Single-Atom Design/Nano-Engineering: Constructing Ni/S/C Nanotubes with Fast and Stable K-Storage.

An amidation-dominated re-assembly strategy is developed to prepare uniform single atom Ni/S/C nanotubes. In this re-assembly process, a single-atom design and nano-structured engineering are realized simultaneously. Both the NiO5 single-atom active centers and nanotube framework endow the Ni/S/C ternary composite with accelerated reaction kinetics for potassium-ion storage. Theoretical calculations and electrochemical studies prove that the atomically dispersed Ni could enhance the convention kinetics and decrease the decomposition energy barrier of the chemically-absorbed small-molecule sulfur in Ni/S/C nanotubes, thus lowering the electrode reaction overpotential and resistance remarkably. The mechanically stable nanotube framework could well accommodate the volume variation during potassiation/depotassiation process. As a result, a high K-storage capacity of 608 mAh g-1 at 100 mA g-1 and stable cycling capacity of 330.6 mAh g-1 at 1000 mA g-1 after 500 cycles are achieved.

Anion-Regulated Sulfur Conversion in High-Content Carbon Layer Confined Sulfur Cathode Maximizes Voltage and Rate Capability of K-S Batteries.

Potassium-sulfur (K-S) batteries have attracted attention in large-scale energy storage systems. Small-molecule/covalent sulfur (SMCS) can help to avoid the shuttle effect of polysulfide ions via solid-solid sulfur conversion. However, the content of SMCS is relatively low (≤40%), and solid-solid reactions cause sluggish kinetics and low discharge potentials. Herein, SMCS is confined in turbo carbon layers with a content of ≈74.1 wt% via a C/S co-deposition process. In the K-S battery assembled by using as-fabricated SMCS@C as cathode and KFSI-EC/DEC as an electrolyte, anion-regulated two-plateau solid-state S conversion chemistry and a novel high discharge potential plateau at 2.5-2.0 V with a remarkable reversible capacity of 384 mAh g-1 at 3 A g-1 after 1000 cycles are found. The SMCS@C||K full cell showed energy and power density of 72.8 Wh kg-1 and 873.2 W kg-1, respectively, at 3 A g-1. Mechanism studies reveal that the enlarged carbon layer space enables the diffusion of K+-FSI- ion pairs, and the coulombic attraction between them accelerates their diffusion in SMCS@C. In addition, FSI- regulates sulfur conversion in situ inside the carbon layers along a two-plateau solid-state reaction pathway, which lowers the free energy and weakens the S─S bond of intermediates, leading to faster and more efficient S conversion.

Room-Temperature Potassium-Sulfur Batteries Enabled by Microporous Carbon Stabilized Small-Molecule Sulfur Cathodes.

Potassium-sulfur (K-S) batteries are a promising alternative to lithium ion batteries for large-area energy storage applications, owing to their high capacity and inexpensiveness, but they have been seldom investigated. Here we report room-temperature K-S batteries utilizing a microporous carbon-confined small-molecule sulfur composite cathode. The synergetic effects of the strong confinement of microporous carbon matrix and the small-molecule sulfur structure can effectually eliminate the formation of soluble polysulfides and ensure a reversible capacity of 1198.3 mA h g-1 and retain 72.5% after 150 cycles with a Coulombic efficiency of ∼97%. The potassium-storage mechanism was investigated by X-ray photoelectron spectroscopy analysis and theoretical calculations. The results suggest that K2S is the final potassiation product along with the reaction of 2K + S ↔ K2S, giving a theoretical capacity of 1675 mA h g-1. Our findings not only provide an effective strategy to fabricate high-performance room-temperature K-S batteries but also offer a basic comprehension of the potassium storage mechanism of sulfur cathode materials.