Electrical engineering

Nanotechnology

Electrode

Pseudocapacitance

Engineering

Faraday efficiency

Physical chemistry

Differential capacitance

Chemical physics

Chemistry

Materials science

Capacitive sensing

Double-layer capacitance

Pseudocapacitor

Electrolyte

Dielectric spectroscopy

Capacitance

Electrochemistry

Supercapacitor

Nature Energy

The capacitance of the electrochemical interface has traditionally been separated into two distinct types: non-Faradaic electric double-layer capacitance, which involves charge induction, and Faradaic pseudocapacitance, which involves charge transfer. However, the electrochemical interface in most energy technologies is not planar but involves porous and layered materials that offer varying degrees of electrolyte confinement. We suggest that understanding electrosorption under confinement in porous and layered materials requires a more nuanced view of the capacitive mechanism than that at a planar interface. In particular, we consider the crucial role of the electrolyte confinement in these systems to reconcile different viewpoints on electrochemical capacitance. We propose that there is a continuum between double-layer capacitance and Faradaic intercalation that is dependent on the specific confinement microenvironment. We also discuss open questions regarding electrochemical capacitance in porous and layered materials and how these lead to opportunities for future energy technologies. Electrochemical charge storage in a confined space is often interpreted as either electrostatic adsorption or Faradaic intercalation. Here the authors propose that the storage mechanism is a continuous transition between the two phenomena depending on the extent of ion solvation and ion–host interaction.

Continuous transition from double-layer to Faradaic charge storage in confined electrolytes