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Related Concept Videos

Ladder Diagrams: Redox Equilibria01:30

Ladder Diagrams: Redox Equilibria

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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.
Consider the Fe3+/Fe2+ half-reaction, which has a standard-state potential of +0.771 V. At potentials more positive than +0.771 V, Fe3+ predominates, whereas Fe2+...
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Balancing Redox Equations02:58

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Electrochemistry is the science involved in the interconversion of electrical and chemical reactions. Such reactions are called reduction-oxidation, or redox reactions. These important reactions are defined by changes in oxidation states for one or more reactant elements and include a subset of reactions involving the transfer of electrons between reactant species. Electrochemistry as a field has evolved to yield sufficient insights on the fundamental principles of redox chemistry and multiple...
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Redox Equilibria: Overview01:23

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A reduction-oxidation reaction is commonly called a redox reaction. In a redox reaction, electrons are transferred from one species to another rather than being shared between or among atoms. The reducing agent or reductant is the species that loses electrons and gets oxidized in the process. The species that gains electrons and gets reduced in the process is the oxidizing agent or oxidant. Redox reactions are represented as two separate equations called half-reactions, where one equation...
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Standard Electrode Potentials03:02

Standard Electrode Potentials

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On comparing the reactivity of silver and lead, it is observed that the two ionic species, Ag+ (aq) and Pb2+ (aq), show a difference in their redox reactivity towards copper: the silver ion undergoes spontaneous reduction, while the lead ion does not. This relative redox activity can be easily quantified in electrochemical cells by a property called cell potential. This property is commonly known as cell voltage in electrochemistry, and it is a measure of the energy which accompanies the charge...
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The Nernst Equation02:59

The Nernst Equation

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Nonstandard Reaction Conditions
The interconnection between standard cell potentials and various thermodynamic parameters such as the standard free energy change ΔG° and equilibrium constant K has been previously explored. For example, a redox reaction involving zinc(II) and tin(II) ions at 1 M concentration with Eºcell = +0.291 V and ΔG° = −56.2 kJ is spontaneous.
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Electrolysis03:00

Electrolysis

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In a galvanic cell, the electrical work is done by a redox system on its surroundings as electrons produced by the spontaneous redox reactions are transferred through an external circuit. Alternatively, an external circuit does work on a redox system by imposing a voltage sufficient to drive an otherwise nonspontaneous reaction in a process known as electrolysis. For instance, recharging a battery involves the use of an external power source to drive the spontaneous (discharge) cell reaction in...
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Related Experiment Video

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Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
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Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes.

Tammo K Schwietert1, Violetta A Arszelewska1, Chao Wang1

  • 1Storage of Electrochemical Energy, Faculty of Radiation Science and Technology, Delft University of Technology, Delft, the Netherlands.

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Safer all-solid-state lithium-ion batteries are enabled by understanding solid electrolyte stability. This study reveals indirect decomposition pathways, expanding the electrochemical stability window and explaining battery capacity.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Solid-State Batteries

Background:

  • All-solid-state lithium-ion batteries offer enhanced safety and energy density.
  • Limited understanding of solid electrolyte electrochemical stability hinders development.
  • Detrimental reactions at the electrolyte-electrode interface are a key concern.

Purpose of the Study:

  • To elucidate the electrochemical decomposition pathways of solid electrolytes.
  • To rationalize the observed electrochemical stability windows of solid electrolytes.
  • To explain the redox activity and cycling capacity contributions in solid-state batteries.

Main Methods:

  • Investigated argyrodite-, garnet-, and NASICON-type solid electrolytes.
  • Analyzed decomposition pathways through (de)lithiated intermediate states.
  • Correlated proposed mechanisms with observed electrochemical stability and cycling behavior.

Main Results:

  • Identified indirect decomposition via (de)lithiated states as the favorable pathway.
  • Demonstrated that this indirect pathway leads to a larger electrochemical stability window than direct decomposition.
  • Showcased metastable phases in argyrodite electrolytes contributing to cycling capacity.

Conclusions:

  • The indirect decomposition mechanism explains the observed stability of solid electrolytes.
  • Metastable phases play a crucial role in the redox activity and capacity of solid-state batteries.
  • This fundamental understanding is key for designing advanced solid electrolytes and interfaces for next-generation batteries.