All-Solid-State Lithium-Sulfur Batteries Enhanced by Redox Mediators.
Journal of the American Chemical Society
Redox mediators (RMs) play a vital role in some liquid electrolyte-based electrochemical energy storage systems. However, the concept of redox mediator in solid-state batteries remains unexplored. Here, we selected a group of RM candidates and investigated their behaviors and roles in all-solid-state lithium-sulfur batteries (ASSLSBs). The soluble-type quinone-based RM (AQT) shows the most favorable redox potential and the best redox reversibility that functions well for lithium sulfide (Li2S) oxidation in solid polymer electrolytes. Accordingly, Li2S cathodes with AQT RMs present a significantly reduced energy barrier (average oxidation potential of 2.4 V) during initial charging at 0.1 C at 60 °C and the following discharge capacity of 1133 mAh gs-1. Using operando sulfur K-edge X-ray absorption spectroscopy, we directly tracked the sulfur speciation in ASSLSBs and proved that the solid-polysulfide-solid reaction of Li2S cathodes with RMs facilitated Li2S oxidation. In contrast, for bare Li2S cathodes, the solid-solid Li2S-sulfur direct conversion in the first charge cycle results in a high energy barrier for activation (charge to 4 V) and low sulfur utilization. The Li2S@AQT cell demonstrates superior cycling stability (average Coulombic efficiency 98.9% for 150 cycles) and rate capability owing to the effective AQT-enhanced Li-S reaction kinetics. This work reveals the evolution of sulfur species in ASSLSBs and realizes the fast Li-S reaction kinetics by designing an effective sulfur speciation pathway.
View details for DOI 10.1021/jacs.1c07754
View details for PubMedID 34677957
- Wheat Bran Derived Carbon toward Cost-Efficient and High Performance Lithium Storage ACS SUSTAINABLE CHEMISTRY & ENGINEERING 2020; 8 (42): 15898–905
Incorporating the nanoscale encapsulation concept from liquid electrolytes into solid-state lithium-sulfur batteries.
Lithium-sulfur (Li-S) batteries are attractive due to their high specific energy and low-cost prospect. Most studies in the past decade are based on these batteries with liquid electrolytes, where many exciting material/structural designs are realized at the nanoscale to address problems of Li-S chemistry. Recently, there is a new promising direction to develop Li-S batteries with solid polymer electrolytes, although it is unclear whether the concepts from liquid electrolytes are applicable in the solid state to improve battery performance. Here we demonstrate that the nanoscale encapsulation concept based on Li2S-TiS2 core-shell particles, originally developed in liquid electrolytes, is very effective in solid polymer electrolytes. Using in situ optical cell measurement and sulfur K-edge X-ray absorption near edge spectroscopy, we find that polysulfides form and are well trapped inside individual particles by the nanoscale TiS2 encapsulation. This TiS2 encapsulation layer also functions to catalyze the oxidation reaction of Li2S to sulfur, even in solid-state electrolytes, proved by both experiments and density functional theory calculations. A high cell-level specific energy of 427 W∙h∙kg-1 at 60 °C (including the mass of the anode, cathode, and solid-state electrolyte, but excluding the current collector and packaging) is achieved by integrating TiS2 encapsulated Li2S cathode with ultrathin polyethylene oxide-based solid polymer electrolyte (10~20 m) and lithium metal anode. The solid-state cells show excellent stability over 150 charge/discharge cycles at 0.8 C at 80 °C. This study points to the fruitful direction of borrowing concepts from liquid electrolytes into solid-state Li-S batteries.
View details for DOI 10.1021/acs.nanolett.0c02033
View details for PubMedID 32515973
Promoting H2O2 production via 2-electron oxygen reduction by coordinating partially oxidized Pd with defect carbon.
2020; 11 (1): 2178
Electrochemical synthesis of H2O2 through a selective two-electron (2e-) oxygen reduction reaction (ORR) is an attractive alternative to the industrial anthraquinone oxidation method, as it allows decentralized H2O2 production. Herein, we report that the synergistic interaction between partially oxidized palladium (Pdδ+) and oxygen-functionalized carbon can promote 2e- ORR in acidic electrolytes. An electrocatalyst synthesized by solution deposition of amorphous Pdδ+ clusters (Pd3δ+ and Pd4δ+) onto mildly oxidized carbon nanotubes (Pdδ+-OCNT) shows nearly 100% selectivity toward H2O2 and a positive shift of ORR onset potential by ~320 mV compared with the OCNT substrate. A high mass activity (1.946 A mg-1 at 0.45 V) of Pdδ+-OCNT is achieved. Extended X-ray absorption fine structure characterization and density functional theory calculations suggest that the interaction between Pd clusters and the nearby oxygen-containing functional groups is key for the high selectivity and activity for 2e- ORR.
View details for DOI 10.1038/s41467-020-15843-3
View details for PubMedID 32358548
View details for PubMedCentralID PMC7195490
Enhancing C–C Bond Scission for Efficient Ethanol Oxidation using PtIr Nanocube Electrocatalysts
View details for DOI 10.1021/acscatal.9b02039