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Ladder diagrams are useful tools for understanding redox equilibrium reactions, especially the effects of concentration changes on the electrochemical potential of the reaction. The vertical axis in the redox ladder diagrams represents the electrochemical potential, E. The area of predominance is demarcated using the Nernst equation.
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Besides iodine, other oxidizing or reducing agents can serve as titrants in redox titrations. Common oxidizing titrants include KMnO4, cerium(IV), and K2Cr2O7. The choice of oxidizing titrants depends on factors like stability, cost, analyte strength, and reaction rate between the analyte and titrant. KMnO4 is a strong oxidizing titrant that reduces from Mn(VII) to Mn(II) in a highly acidic solution, simultaneously oxidizing the analyte to a higher oxidation state. In this case, KMnO4 acts as a...
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Acid halides are reduced to alcohols in the presence of a strong reducing agent like lithium aluminum hydride.
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Protocol of Electrochemical Test and Characterization of Aprotic Li-O2 Battery
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Tunable Redox Mediators for Li-O2 Batteries Based on Interhalide Complexes.

Graham Leverick1, Shuting Feng2, Pedro Acosta3

  • 1Department of Mechanical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, Massachusetts 02139, United States.

ACS Applied Materials & Interfaces
|January 31, 2022
PubMed
Summary

Researchers developed new redox mediators for lithium-oxygen batteries. These interhalide mediators, like iodine-bromine mixtures, enhance charging efficiency and reduce unwanted side reactions, overcoming solvent limitations.

Keywords:
Li−O2 batteryinterhalideredox mediator

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Area of Science:

  • Electrochemistry
  • Materials Science
  • Energy Storage

Background:

  • Lithium-oxygen (Li-O2) batteries offer higher energy density than Li-ion batteries but face challenges with charging efficiency due to discharge product oxidation.
  • Soluble inorganic redox mediators (RMs) can improve round-trip efficiency in Li-O2 batteries, but solvent choice is constrained by stability and reactivity requirements.
  • Optimizing RM performance is difficult when solvent selection is limited, hindering practical application of Li-O2 battery technology.

Purpose of the Study:

  • To demonstrate the use of interhalide redox mediators for tuning the oxidizing power in Li-O2 battery systems.
  • To overcome the limitations of solvent selection in optimizing redox mediator performance for Li-O2 batteries.

Main Methods:

  • Investigated interhalide redox mediators based on LiI/LiBr and LiI/LiCl mixtures.
  • Utilized DEMS (Differential Electrochemical Mass Spectrometry) measurements during charging of Li-O2 cells.
  • Assessed the chemical oxidizing power of interhalide RMs against Li2O2 and LiOH.

Main Results:

  • I-Br interhalides (I2Br- to IBr2-) showed tunable and increasing chemical oxidizing power toward Li2O2 and LiOH with higher bromide content.
  • DEMS analysis revealed that I-Br interhalide RMs promoted increased O2 evolution compared to LiI alone.
  • These interhalide RMs resulted in reduced charging potentials and suppressed CO2 evolution compared to LiBr.

Conclusions:

  • Interhalide redox mediators offer a strategy to tune oxidizing power within a given solvent for Li-O2 batteries.
  • This approach circumvents the need for solvent redesign to achieve optimal redox mediator performance.
  • The developed I-Br interhalides enhance charging efficiency and mitigate parasitic reactions in Li-O2 batteries.