Applied Functional Materials and Devices

Energy Storage Devices

Dr. Aravind Vijayaraghavan

Department of Materials
[email protected]

Materials today, 2016, 19, 109-123 1

 Lecture 1
➢ Content

• Background, why energy storage is important?

• Basic concepts of electrochemistry
• Electrolysis cell
• Galvanic or voltaic cell
• Standard electrode potential
• Electrochemical cell potential and free energy
• Nernst equation
• Concentration cell

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 Background
➢ Inconsistency of solar and wind energy requires energy storage before use

Figure 1. (a) Daily profiles of wind power projected by 7 output in April 2005 for the year 2011 in
Tehachapi, California (Courtesy of ISO California). (b) 5 MW PV power over a span of 6 days in Spain
(Courtesy of AES).
Chem. Rev. 2011, 111, 3577–3613
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 Background
➢ Reduction of power station capacity via energy storage

Figure 3. Schematic of balancing generation and demand via load levelling, a typical case of load
shifting (Courtesy of NGK, Inc.).
Chem. Rev. 2011, 111, 3577–3613
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 Background
➢ Classification of potential electrical energy storage for stationary applications

Chem. Rev. 2011, 111, 3577–3613

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Electrochemical energy storage and conversion

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 Basic concepts of electrochemistry
• Electrochemistry is defined as the branch of chemistry that examines the phenomena
resulting from combined chemical and electrical effects.

• This field covers:

➢ -Electrolytic processes: Reactions in which chemical changes occur on the passage of
an electrical current
➢ -Galvanic or Voltaic processes: Chemical reactions that result in the production of
electrical energy
• An electrochemical cell typically consists of:
➢ -Two electronic conductors (also called electrodes)
➢ -An ionic conductor (called an electrolyte)

Charge transport in the electrodes occurs via the motion of electrons (or holes),
Charge transport in the electrolyte occurs via the motion of ions (positive and negative)

At each electrode, an electrochemical reaction occurs. This reaction is called a half cell
reaction (since there are two electrodes in a typical cell at which reactions occur). The
overall chemical reaction of the cell is given by combining the two individual half cell
reactions.
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 Basic concepts of electrochemistry
❖ There are two fundamental types of half cell reactions:
➢ -Oxidation reactions – Loss of an electron from species to electrode
➢ -Reduction reactions – gain of electron from electrode to species

❖ A reaction is classified as oxidation or reduction depending on the direction of

electron transfer

➢ Electrode at which the oxidation reaction occurs is called the anode

➢ Electrode at which the reduction reaction occurs is called the cathode

➢ The electrode at which the reaction of interest occurs is called the working electrode
➢ The electrode at which the other (coupled) reaction occurs is called the counter
electrode
➢ A third electrode, called the reference electrode may also be used

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 Electrolysis Cell
The Electrolysis of Water

Half reactions:

Anode: 2𝐻2 𝑂 𝑙 → 𝑂2 𝑔 + 4𝐻+ 𝑎𝑞 + 4𝑒 − 𝐸 0 𝑎𝑛𝑜𝑑𝑒 = +1.229 𝑉

Cathode: 2𝐻 + 𝑎𝑞 + 2𝑒 − → 𝐻2 𝑔 𝐸 0 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 = 0 𝑉

Overall reaction: 2𝐻2 𝑂 𝑙 → 2𝐻2 (𝑔) + 𝑂2 (𝑔) 𝐸 0 𝑐𝑒𝑙𝑙 = −1.229 𝑉

Electrolyte: H2SO4 Ionic species: H+, SO42−

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https://chem.libretexts.org
 Galvanic or voltaic cell
A galvanic cell or voltaic cell, named after Luigi Galvani or Alessandro Volta, respectively, is an
electrochemical cell that derives electrical energy from spontaneous redox reactions taking place
within the cell.

The Reaction of Metallic Zinc with Aqueous Copper(II) Ions in a Galvanic Cell. https://chem.libretexts.org

Half reactions:

Anode: Z𝑛 𝑠 → 𝑍𝑛2+ 𝑎𝑞 + 2𝑒 − 𝐸 0 𝑎𝑛𝑜𝑑𝑒 = −0.76 𝑉

Cathode: 𝐶𝑢2+ 𝑎𝑞 + 2𝑒 − → 𝐶𝑢 𝑠 𝐸 0 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 = 0.34 𝑉

Overall reaction: Z𝑛 𝑠 + 𝐶𝑢2+ → 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢 (𝑠) 𝐸 0 𝑐𝑒𝑙𝑙 = 1.1 𝑉

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 Standard Electrode Potential
• To develop a scale of relative potentials to predict the direction of an electrochemical reaction.
• Standard cell potential (E0cell), defined as the potential of a cell measured under standard
conditions (1 M) and at a fixed temperature, usually 25°C.
𝐸 0 𝑐𝑒𝑙𝑙 = 𝐸 0 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸 0 𝑎𝑛𝑜𝑑𝑒

• It is impossible to measure the potential of any electrode directly, we can

choose a reference electrode whose potential is defined as 0 V under
standard conditions.
• The standard hydrogen electrode (SHE) is universally used for this
purpose and is assigned a standard potential of 0 V.

https://chem.libretexts.org

E0 = 0 V
SHE consists of a strip of platinum wire in contact with an aqueous solution containing 1 M H+. The [H+] in solution is
in equilibrium with H2 gas at a pressure of 1 atm at the Pt-solution interface. Protons are reduced or hydrogen
molecules are oxidized at the Pt surface. 11
 Standard Electrode Potential
The potential of a half-reaction measured against the SHE under standard conditions is
called the standard electrode potential for that half-reaction.

Half reactions:

Anode: Z𝑛 𝑠 → 𝑍𝑛2+ 𝑎𝑞 + 2𝑒 − 𝐸 0 𝑎𝑛𝑜𝑑𝑒 = −0.76 𝑉

Cathode: 2𝐻+ 𝑎𝑞 + 2𝑒 − → 𝐻2 𝑔 𝐸 0 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 = 0 𝑉

Overall reaction: Z𝑛 𝑠 + 2𝐻+ → 𝑍𝑛2+ (𝑎𝑞) + 𝐻2 (𝑔)

𝐸 0 𝑐𝑒𝑙𝑙 = 0.76 𝑉

𝐸 0 𝑐𝑒𝑙𝑙 = 𝐸 0 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸 0 𝑎𝑛𝑜𝑑𝑒 = 0 𝑉 − −0.76 𝑉 = 0.76 𝑉

https://chem.libretexts.org Therefore, the standard electrode potential for half reaction

Zn2+(aq) + 2e− → Zn(s) is − 0.76 V.

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Standard Electrode Potential

Table of standard electrode potentials.

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https://chem.libretexts.org
 Cell potential and free energy
• Electrochemical cells convert chemical energy to electrical energy and vice versa.
• The total amount of energy produced by an electrochemical cell, depends on both
the cell potential (E) and the total number of electrons that are transferred from the
reductant to the oxidant during the course of a reaction.

One Joule can be defined as the work required to move an electric charge of one coulomb
through an electrical potential difference of one volt,

1J = 1C ∙ 1V
In chemical reactions, however, we need to relate the coulomb to the charge on a mole of
electrons. Multiplying the charge on the electron by Avogadro’s number gives us the
charge on 1 mol of electrons, which is called the faraday constant (F).

6.02214 × 1023
F= 1.6021810−19 C −
= 9.64855 × 104 𝐶 ∙ 𝑚𝑜𝑙 −1 (𝑒 − )
1 𝑚𝑜𝑙 (𝑒 )

The total charge transferred from the reductant to the oxidant is therefore nF, where n is
the number of moles of electrons (mol).

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 Cell potential and free energy
The maximum amount of work that can be produced by an electrochemical cell ( wmax ) is
equal to the product of the cell potential ( E0cell ) and the total charge transferred during
the reaction (nF):
𝑤𝑚𝑎𝑥 = nF𝐸 0 𝑐𝑒𝑙𝑙

Work is expressed as a negative number because work is being done by a system (an
electrochemical cell with a positive potential, e.g. a battery) on its surroundings.

The change in free energy (∆G0) of the electrochemical cell is equal to the amount of
work done by the cell to the surroundings (∆G0 = w)

∆𝐺 0 = −nF𝐸 0 𝑐𝑒𝑙𝑙

A spontaneous redox reaction is therefore characterized by a negative value of ΔG and

a positive value of E0cell .

𝐸 0 𝑐𝑒𝑙𝑙 = 𝐸 0 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸 0 𝑎𝑛𝑜𝑑𝑒 > 0

𝐸 0 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 > 𝐸 0 𝑎𝑛𝑜𝑑𝑒

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 Cell potential and free energy – Examples
➢ Cu-Zn galvanic cell
Half reactions:

Anode: Z𝑛 𝑠 → 𝑍𝑛2+ 𝑎𝑞 + 2𝑒 − 𝐸 0 𝑎𝑛𝑜𝑑𝑒 = 0.76 𝑉

Cathode: 𝐶𝑢2+ 𝑎𝑞 + 2𝑒 − → 𝐶𝑢 𝑠 𝐸 0 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 = 0.34 𝑉

Overall reaction: Z𝑛 𝑠 + 𝐶𝑢2+ (𝑎𝑞) → 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢 (𝑠) 𝐸 0 𝑐𝑒𝑙𝑙 = 1.1 𝑉

∆𝐺 0 = −nF𝐸 0 𝑐𝑒𝑙𝑙 < 0 Spontaneous; release energy

➢ Water electrolysis
Half reactions:

Anode: 2𝐻2 𝑂 𝑙 → 𝑂2 𝑔 + 4𝐻+ 𝑎𝑞 + 4𝑒 − 𝐸 0 𝑎𝑛𝑜𝑑𝑒 = +1.229 𝑉

Cathode: 2𝐻 + 𝑎𝑞 + 2𝑒 − → 𝐻2 𝑔 𝐸 0 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 = 0 𝑉

Overall reaction: 2𝐻2 𝑂 𝑙 → 2𝐻2 (𝑔) + 𝑂2 (𝑔) 𝐸 0 𝑐𝑒𝑙𝑙 = −1.229 𝑉

∆𝐺 0 = −nF𝐸 0 𝑐𝑒𝑙𝑙 > 0 Not Spontaneous; consume energy

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 Nernst equation
Consider the following redox reaction:
Z𝑛 𝑠 + 𝐶𝑢2+ (𝑎𝑞) → 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢 (𝑠) 𝐸 0 𝑐𝑒𝑙𝑙 = 1.1 𝑉

∆𝐺 0 = −nF𝐸 0 𝑐𝑒𝑙𝑙 < 0

What if reaction proceeds and thus concentration of Cu2+ decreases while Zn2+ increases?
Expect driving force for product formation to decrease – LeChatelier Principle
Therefore ΔG increases, and Ecell decreases

➢ Under non-standard conditions, the actual free energy change for a reaction
follows:
∆𝐺 = ∆𝐺 0 + 𝑅𝑇ln𝑄
Reaction quotient Q

−𝑛𝐹𝐸𝑐𝑒𝑙𝑙 = −𝑛𝐹𝐸 0 𝑐𝑒𝑙𝑙 + 𝑅𝑇ln𝑄 aA + bB ⇌ cC + dD

𝑅𝑇 [𝐶]𝑐 [𝐷]𝑑
𝑄=
𝐸𝑐𝑒𝑙𝑙 = 𝐸 0 𝑐𝑒𝑙𝑙 − ln𝑄 [𝐴]𝑎 [𝐵]𝑏
𝑛𝐹
[A]: concentration of A
0.0591 V
𝐸𝑐𝑒𝑙𝑙 = 𝐸0 𝑐𝑒𝑙𝑙 − log𝑄
𝑛 17
 Nernst equation – Example
For a Cu-Zn cell under standard conditions, [Cu2+] = [Zn2+] = 1.0 M, and T = 298 K, the
cell potential (E0) of Zn-Cu redox reaction is 1.10 V. As the reaction proceeds, [Cu2+]
decreases as [Zn2+] increases. After one minute, [Cu2+] = 0.05 M while [Zn2+] = 1.95 M.
Calculate the cell potential after 1 minute.

Z𝑛 𝑠 + 𝐶𝑢2+ (𝑎𝑞) → 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢 (𝑠)

0.0592 V
𝐸 = 𝐸0 − log𝑄
𝑛

[𝑍𝑛2+ ] 1.95 M
𝐸0 = 1.10 V 𝑄= = 𝑛=2
[𝐶𝑢2+ ] 0.05 M

0.0592 V 1.95
𝐸 = 1.10 V − log
2 0.05

𝐸 = 1.05 V

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 Concentration Cell –Example
A voltage can also be generated by constructing an electrochemical cell in which each
compartment contains the same redox active solution but at different concentrations.

Half reactions:
Anode: 𝐴𝑔 𝑠 → 𝐴𝑔+ 𝑎𝑞, 0.1 𝑀 + 𝑒 −
Cathode: 𝐴𝑔+ 𝑎𝑞, 1 𝑀 + 𝑒 − → 𝐴𝑔 𝑠

Overall reaction:
𝐴𝑔+ 𝑎𝑞, 1 𝑀 → 𝐴𝑔+ 𝑎𝑞, 0.1 𝑀

0.0592 V
𝐸 = 𝐸0 − log𝑄
𝑛

0.0592 V 0.1 M
𝐸 =0V− log
1 1M

𝐸 = 0.059 V
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 Summary
• Basic concepts of electrochemistry
• Electrolysis cell: E0 < 0; ∆G > 0; not spontaneous; consume energy
• Galvanic or voltaic cell: E0 > 0; ∆G < 0; spontaneous; release energy
• Standard electrode potential:
• Electrochemical cell potential and free energy
• Nernst equation: determination of cell potential under non-standard
conditions (e.g. concentration differ from 1 M).
• Concentration cell: voltage generated by concentration difference

✓ Reading resources
https://chem.libretexts.org/Courses/University_of_California_Davis/UCD_Chem_002C/UCD_Chem_2C%3A_Larse
n/Text/Unit_1%3A_Electrochemistry

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