The activation overpotential, ηact, is the potential required to overcome the energy barrier for an

electrochemical reaction to occur. It is a function of the following factors:

● Exchange current density (i0): The exchange current density is the current density that
flows at equilibrium, when there is no net reaction. The higher the exchange current
density, the lower the activation overpotential.
● Current density (i): The current density is the rate at which charge is transferred across
the electrode-electrolyte interface. The higher the current density, the higher the activation
overpotential.
● Temperature (T): The temperature affects the rate of the electrochemical reaction. The
higher the temperature, the faster the reaction and the lower the activation overpotential.
● Electrode material: The electrode material can have a significant impact on the activation
overpotential. Some materials are better catalysts for certain reactions than others.
● Electrolyte composition: The electrolyte composition can also affect the activation
overpotential. For example, the concentration of reactants and products, as well as the pH
of the electrolyte, can all play a role.

In general, the activation overpotential can be reduced by:

● Increasing the exchange current density

● Decreasing the current density
● Increasing the temperature
● Using a more efficient electrode material
● Optimizing the electrolyte composition

The following are some specific examples of how the factors listed above can affect the
activation overpotential:

● Exchange current density: The exchange current density is affected by the nature of the
electrochemical reaction and the electrode material. For example, the exchange current
density for the hydrogen evolution reaction (HER) on platinum is much higher than on
stainless steel. This means that the activation overpotential for the HER will be lower on
platinum.
● Current density: The current density is affected by the applied potential and the
resistance of the electrolyte. Increasing the applied potential will increase the current
density, but it will also increase the activation overpotential. Increasing the resistance of
the electrolyte will decrease the current density, but it will also increase the ohmic
overpotential.
● Temperature: The temperature affects the rate of the electrochemical reaction through the
Arrhenius equation. Increasing the temperature will increase the rate of the reaction and
decrease the activation overpotential. However, it is important to note that increasing the
temperature can also lead to other problems, such as increased corrosion and decreased
selectivity.
● Electrode material: The electrode material can have a significant impact on the activation
overpotential. Some materials are better catalysts for certain reactions than others. For
 example, platinum is a very good catalyst for the HER, while nickel is a better catalyst for
the oxygen evolution reaction (OER).
● Electrolyte composition: The electrolyte composition can also affect the activation
overpotential. For example, the concentration of reactants and products can affect the rate
of the electrochemical reaction. The pH of the electrolyte can also affect the activation
overpotential, as it can affect the adsorption of reactants and products on the electrode
surface.

By understanding the factors that affect the activation overpotential, it is possible to design
electrochemical systems that are more efficient and less susceptible to failure.