Electrochemistry and energy storage system

Module
ELECTROCHEMISTRY AND ENERGY
1 STORAGE SYSTEM
Syllabus
Electrochemistry and energy storage systems:
Introduction, EMF of the cell, Free Energy, Single electrode Potential-Derivation of Nernst equation,
Numerical problems based on Nernst Equation.
Reference Electrodes: Introduction, construction, working and applications of calomel electrode,
ionselective Electrodes-Glass electrode, determination of pH using a Glass electrode.
Energy Storage Systems: Introduction, Classification of batteries (primary, secondary, and reserved
batteries). Construction, working, and applications of Li-ion batteries. Advantages of Li-ion battery as an
electrochemical energy system for electric vehicles. Recycling of Lithium-ion batteries, Introduction, brief
discussion on direct cycling method, Sodium ion battery – Introduction.
Definitions
1. Define oxidation?
Oxidation is the loss of electrons or an increase in the oxidation state of an atom, an ion, or of certain
atoms in a molecule.
2. Define reduction?
Reduction is the gain of electrons or a decrease in the oxidation state of an atom, an ion, or of certain
atoms in a molecule (a reduction in oxidation state).
3. Define redox reaction?
The oxidation and reduction reactions always occur simultaneously in the redox reaction or Oxidation-
Reduction reaction.
Oxidation - loss of an electron, taking place at the anode.
Reduction - a gain of electron taken place at the cathode.
4. Define EMF of the Cell?
The electromotive force of a cell or EMF of a cell is the maximum potential difference between two
electrodes of a cell. It can also be defined as the net voltage between the oxidation and reduction half-
reactions.
5. Define battery?
Electrochemistry and energy storage system

A battery is a device that’s consists of two or more galvanic cells connected in series or parallel or both which
converts chemical energy into electrical energy through redox reactions.
6. What are Reference Electrodes?
An electrode having fixed potential, which can be used as a reference to measure the potential of another
electrode. Examples: Calomel electrode, Ag/AgCl electrode.
7. Define ion-selective electrode?
An ion-selective electrode is very selective towards a particular type of ions and develops a potential
proportional to the concentration of that ions. The sensitive part of the electrode is its membrane which allows
the exchange of selective ions.
Ex. Glass electrode, crystalline electrodes, Ion-exchange electrodes, Enzyme electrodes, Alkali metal ISE.
Level 2. Six and seven marks questions
1. Explain the electrochemical cell?
The devices in which chemical energy is converted into electrical energy. It is also called galvanic cell
or voltaic cell.
 It consists of a zinc rod dipped in zinc sulphate solution which acts as an oxidation half-cell. The
reduction half-cell, consists of copper rod dipped copper sulphate. Both half-cell are connected with a
salt bridge.

Daniel cell or electrochemical cell

Reaction
At anode:
𝑍𝑛 (𝑠) → 𝑍𝑛2+ (𝑎𝑞) + 2𝑒 −
At cathode:
Electrochemistry and energy storage system

𝐶𝑢2+ (𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠)

Complete reaction:
𝑍𝑛 (𝑠) + 𝐶𝑢2+ (𝑎𝑞) → 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢(𝑠)
A cell is represented as:
𝑍𝑛 (𝑠) ∣ 𝑍𝑛2+ (𝑎𝑞) ∣∣ 𝐶𝑢2+ (𝑎𝑞) ∣ 𝐶𝑢(𝑠)
2. Define electrode potential and cell potential?
Electrode potential
The tendency of an electrode to lose or gain electrons when it is in contact with its own ions in solution is
called electrode potential.
Reduction potential: The tendency to receive the electron.
Oxidation potential: The tendency to release the electron.
Standard electrode potential (EO)
Electrode potential at 25° c, 1 bar pressure, and 1 M solution is known as Standard electrode potential.
Cell potential
The potential difference between the two electrodes of a galvanic cell is called the cell potential or cell
electromotive force.
 The flow of electrons from anode to cathode
 The flow of current from cathode to anode

 emf or cell potential can be calculated from the values of electrode potential of two half cells. The
following three methods are in use

(a). Method 1: When oxidation potential of anode and reduction potential of the cathode is consider
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑜𝑥 (𝑎𝑛𝑜𝑑𝑒) + 𝐸𝑟𝑒𝑑 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒)
(b).Method 2: When the reduction potential of both electrodes are taken into account
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑟𝑒𝑑 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸𝑟𝑒𝑑 (𝑎𝑛𝑜𝑑𝑒)
(c). Method 3: When the oxidation potential of both electrodes are taken into account
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑜𝑥 (𝑎𝑛𝑜𝑑𝑒) − 𝐸𝑜𝑥 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒)
Example: - (1) 𝑍𝑛 (𝑠) + 𝐶𝑢2+ (𝑎𝑞) → 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢(𝑠)
o o o
Emf of the cell = Ecell = ECu2+ − EZn2+
⁄Cu ⁄Zn

3. Derive Nernst equation for single electrode potential?

Electrochemistry and energy storage system

Nernst equation
 Nernst gave a relationship between electrode potential and the concentration of electrolyte solutions.
 If the concentration of the electrolyte is not equal to 1M, then electrode potential is calculated from the Nernst
equation.
Nernst equation for single electrode potential
Consider an electrode in contact with a solution of its ions (consider half-cell reaction). The following
equilibrium is established, for the general electrode.

The Nernst equation is derived from the standard changes in the Gibbs free energy associated with an
electrochemical transformation. From thermodynamics, the 𝛥G can be related to the free energy change under
standard condition 𝛥Go by the relationship.
ΔG=ΔGo +RTlnQc (1)
Cell reaction to be spontaneous, ΔG must be negative, can be written as
ΔG=-nFEel (2)
ΔGo =-nFEoel (3)
[product] [M]
Reaction quotient (Qc) = = [Mn+ ]
[reactant]

Substitute [M]=1 (since the concentration of pure metal is taken as unity)

1
Therefore Qc =
[Mn+ ]

Substitute equation 2, 3, and 4 in 1

1
-nFEel =-nFEoel + RTln
[Mn+ ]
Divided by –nF
RT 1
Eel =Eoel – ln n+
nF [M ]
Or
RT
Eel =Eoel + ln[Mn+ ]
nF
Or
2.303RT
Eel =Eoel + log[Mn+ ]
nF
o
Where Eel = electrode potential, Eel = standard electrode potential, R = gas constant (8.3243 J K-1 mol-1), F
(96485 C mol-1) at 298 K, n = number of electrons involved in the reaction.
Therefore
Electrochemistry and energy storage system

0.059
Eel =Eoel + log[Mn+ ]
n
8. The standard electrode potential of Zn electrode is -0.76V and the concentration [Zn2+] given=0.25M,
Calculate E Zn2+/Zn at 28°C.
Solution:
2.303RT
EZn2+ /Zn =EoZn2+ /Zn + log[Zn2+ ]
nF
2.303×8.3243 ×301
EZn2+ /Zn =-0.76+ log[0.25]=-0.78 V
2×96485
9. Calculate the standard electrode potential of copper, if the potential of Cu electrode immersed in
0.015 M Cu2+solution is 0.296 V at 25°C.
Solution:
0.0591
ECu2+ /Cu =EoCu2+ /Cu + log [Cu2+ ]
n
0.0591
0.296=EoCu2+ /Cu + log [0.015]
2
EoCu2+ /Cu =0.349 V
10. Iron rod immersed in ferrous sulphate of 0.25 M and Cu rod immersed in copper sulphate solution of
0.45 M. Standard potential of Cu and Fe electrodes are 0.34 and -0.41 V respectively. Give cell
representation, cell reaction and calculate EMF of cell at 30°C.
Solution:
Fe (s) + Cu2+ (aq)→Fe2+ (aq) + Cu(s)
Eocell =EoCu2+ – EoFe2+ =0.34–(–0.41)=0.75
⁄ ⁄
Cu Fe

2.303RT [Fe2+ ]
Ecell =Eocell – log
nF [Cu2+ ]
2.303×8.3243 ×303 [0.25]
Ecell =0.75 – log = 0.758 V
2×96485 [0.45]
11. A galvanic cell is formed by the combination of Zn rod immersed in Zinc chloride solution of
concentration 0.5 M and Li rod immersed in lithium chloride solution of concentration 0.15 M. give the
cell representation, cell reactions and calculate EMF of cell at 25°C. The standard electrode potential of
Li and Zn electrode are -3.04 and -0.76 V respectively.
Ans: 2.32 V.
Cell reaction
Anode: 2Li (s) → 2Li+ (aq) + 2e−
Electrochemistry and energy storage system

Cathode: 𝑍𝑛2+ (aq) + 2e− → Zn(s)

Overall reaction: 2Li (s) + 𝑍𝑛2+ (aq) → 2Li+ (aq) + Zn(s)
Cell representation: 𝑍𝑛 (𝑠) ∣ 𝑍𝑛2+ (𝑎𝑞) ∣∣ 𝐿𝑖 + (𝑎𝑞) ∣ 𝐿𝑖(𝑠)

Eocell =EoZn2+ – EoLi+ = –0.76–(–3.04)=2.28

⁄ ⁄
Zn Li

o 2.303RT [𝐿𝑖 + ]2
Ecell =Ecell – log 2+
nF [Zn ]
2.303×8.3243 ×298 [0.15]2
Ecell =2.28 – log = 2.32 V
2×96485 [0.5]
12. Describe the construction and working of Calomel electrodes and applications?
The calomel electrode is an example of the reference electrode and it has fixed potential, which can be used to
measure the potential of another electrode (metal and its alloys).
Construction
 The saturated calomel electrode (SCE) is a reference
electrode based on the reaction between elemental mercury and
mercury chloride.
 The calomel electrode consists of two glass tubes. At the
inside glass tube, there is a paste of mercury and mercurous
chloride (calomel) (Hg2Cl2) at the bottom of a narrow glass tube.
Pure mercury is filled above paste and connected with platinum
wire for electrical connections. This narrow tube was placed inside
an outer glass tube filled with a saturated KCl solution. KCI
solution of 0.1 M or 1 M can also be used. The porous plug at the
bottom of the outer tube acts as a salt bridge.

Calomel electrode is represented as

Hg(l)|Hg2 Cl2 (s)|KCl (aq)

Working:
In calomel electrode, two types of reactions are possible depending upon the nature of another electrode with which
it is coupled.
When it acts as an anode, the electrode reaction is
Electrochemistry and energy storage system

2Hg + 2Cl- → Hg2 Cl2 + 2e-

Oxidation takes place when it is coupled with other electrodes having a lower oxidation potential.
When it acts as a cathode, the electrode reaction is
Hg2 Cl2 + 2e- → 2Hg + 2Cl-
Reduction takes place when it is coupled with other electrodes having a greater oxidation potential.
The net reversible electrode reaction
Hg2 Cl2 (s) + 2e- ↔ 2Hg(s) + 2Cl-
Electrode potential
2.303RT
E =Eo - log[Cl– ] 2
2F
E =Eo -0.0591 log[Cl– ] at 298 K
The electrode potential is decided by the concentration of chloride ions. At 298 K, the electrode potentials are as
follows.
0.1 M KCl electrode (0.334 V)
1 M KCl electrode (0.281 V)
Saturated KCl electrode (0.2422 V)
Applications of calomel electrode:
1. It is used as a reference electrode in the measurement of single electrode potentials.
2. It is used in potentiometric quantitate analysis.
3. The SCE is used in pH measurement, cyclic voltammetry, and general aqueous electrochemistry.
13. How to measure electrode potential using a calomel electrode?

The potential of an electrode is measured by combining with a calomel reference electrode. For example, the
following cell is constructed to measure the potential of the Zn electrode
Electrochemistry and energy storage system

Cell representation:
Zn∣Zn2+ ∣∣KCl∣Hg2 Cl2 ∣Hg
Eocell =Eocathode – Eoanode
Eocell =EoSCE – EoZn
o
If Ecell = 1.0 V
EoZn = 0.2422 V – 1.0 V
o
EZn = −0.76 V
14. Define ion-selective electrodes? Discuss the construction, working, and application of glass electrodes?
Definition: “Ion-selective electrode is very selective towards a particular type of ions and develops a potential
proportional to the concentration of that ions. The sensitive part of the electrode is its membrane which allows the
exchange of selective ions”.
Glass electrode

Construction Glass electrode:

1. Glass electrode is constructed by immersing the Ag-AgCl internal
reference electrode in a glass bulb containing 0.1M HCl solution.
2. The glass bulb is made up of a long glass tube with a thin highly
conducting glass membrane at the bottom.
3. The glass membrane is selective to H+ ions in the solution and is made up
of silicate glass having the composition of 72% SiO2, 22% Na2O, and 6 %
Cao.
The electrode can be represented as
Ag/AgCl/0.1M HCl/Glass membrane
Working of glass electrode:
When a glass electrode is immersed in an acidic solution of different
concentrations, a boundary potential (Eb) is developed across the gel layers
of the glass membrane.
This boundary potential (Eb) arises due to the difference in the concentration of H+ ions inside and outside of the
glass bulb.
C2
Eb = 0.0591 log
C1
C1 = Concentration of H+ inside the bulb, is a constant, C2 = concentration H+ outside the bulb.
Eb = 0.0591 log[C2 ] − 0.0591 log[C1 ]
Substitute − 0.0591 log[C1 ] = K, a constant
Electrochemistry and energy storage system

Then the equation becomes

Eb = K + 0.0591 log[C2 ] = K + 0.0591 log[H + ]
Substitute log (H+) = - pH
The final equation for Eb is obtained as
Eb = K − 0.0591 pH
The potential of glass electrode (EG) includes a contribution from 3 factors
 Boundary Potential (Eb)
 Potential of Ag-AgCl reference electrode dipped inside the bulb E Ag/AgCl
 Asymmetric potential due to slight in the homogeneity of the inner and outer surface of the glass membrane E
Asy.

EG = Eb + EAg/AgCl + EAsy
EG = K − 0.0591 pH + EAg/AgCl + EAsy
EG = L − 0.0591 pH
Where constant L = K + EAg/AgCl + EAsy
15. How to measure the pH of a solution using a glass electrode
Determination of pH using a glass electrode
To measure of pH of an unknown solution a glass electrode is coupled with a calomel electrode and connected to a
potentiometer (or pH meter for reading pH directly)

Determination of pH
The cell formed is represented as
Hg/Hg2Cl2/KCl// solution of unknown pH/Glass electrode
Electrochemistry and energy storage system

The potential established at the glass electrode is higher than that of the calomel electrode hence glass electrode is
taken as a cathode.
E Cell = E Cathode – E anode
E Cell = E G – E SCE
Substituting for EG
E Cell = (L- 0.0591pH) – E SCE
The above equation is arranged to obtain the expression for pH
L-ESCE -Ecell
pH=
0.0591
Measurement of electrode potential using calomel electrode.
16. Define battery? Discuss the basic components required to construct the batteries?
Battery: A battery is a device that’s consists of two or more galvanic cells connected in series or parallel or both
which converts chemical energy into electrical energy through redox reactions.
Example: Zn-Air battery, lead-acid battery, lithium batteries, etc.
Basic components of a battery
A battery consists of four major components. They are anode, cathode, electrolyte, and separator.
Anode: The anode (Negative electrode) is oxidized during the electrochemical reaction and liberates electrons.
M → M n+ + ne−
Cathode: The cathode (Positive electrode) is reduced during the electrochemical reaction which accepts electrons.
M n+ + ne− → M
Electrolyte: The electrolyte provides the medium for the transfer of ions inside the cell between the anode and
cathode. The electrolyte must have good ionic conductivity.
The separator: the material that electronically isolates, It is placed in between the anode and the cathode in a
battery to prevent internal short-circuiting.Example: cellulose, Vinyl polymer, polyolefins
17. What are primary, secondary and Reserve batteries mention their examples each?
Primary batteries: The chemical energy is converted into electrical energy as long as the chemical components
are active. In this battery, the reaction occurs only once and after that, it must be discarded. Ex: Zn- air battery, Dry
cell, Li- MnO2
Secondary batteries: Secondary batteries are those which after discharging can be recharged. These batteries
chemical reactions taking place are reversible
Ex: Lead storage battery, Nickel-cadmium battery, Nickel-metal hydride battery, and Lithium-ion battery.
Reserve Batteries
1. These batteries one of the components is isolated and incorporated into the battery when required.
Electrochemistry and energy storage system

2. The electrolyte is the component that is isolated, but some water-activated batteries contain the electrolyte solute,
and water is added for activation.
3. They are used to deliver high power for relatively short periods of time in applications such as radiosondes (air-
borne instruments to send meteorological information back to earth by radio).
Ex: Mg batteries activated by water (Mg-AgCl, Mg-CuCl), Zn-Ag2O batteries etc.
18. Describe construction, working of Lithium-ion batteries? Mention its application?
Lithium-ion battery: A lithium-ion battery or Li-ion battery is a type of rechargeable battery in
which lithium ions move from the negative electrode through an electrolyte to the positive electrode during
discharge, and back when charging.
Construction: It is constructed with the help of the following components.
Anode: Graphite or carbon
Cathode: Lithium metal oxide (LiCoO2 /LiNiO2/LiMnO2)
Electrolyte: A lithium salt such as LiPF6, LiAsF6, LiClO4, and LiBF4 dissolved in an organic solvent such as
ethylene carbonate dimethyl carbonate or dimethoxyethane.
Separator: Microporous polyethylene or polypropylene.
The operation of this cell does not actually involve true oxidation and reduction. The cell reaction involves the
migration of lithium ions between positive and negative electrodes. Graphite being layered can be accommodated
(or) intercalated with lithium between the atoms.

The cell can be represented as

Electrochemistry and energy storage system

Li ∣ Li+ , C ∣ LiPF6(in ethylene carbonate) ∣ LiCoO2

The cell reaction during discharge or charging are:
At anode:

At cathode:

Overall reaction:

The reverse reaction occurs during charging. Thus lithium ions move back and forth between anode and cathode
during charge and discharge.
It provides a potential of 3.7V
Advantages Lithium ion battery
 High energy density.
 Relatively low self-discharge.
 High cell voltage.
Applications
1. Recharge lithium batteries are found in many cell phones, laptops, digital cameras and electric vehicles.
19. What are the advantages of Li-ion battery as an electrochemical energy system for electric
vehicles
Lithium ions batteries are important energy storage devices for electric vehicles because of their following
properties
 High energy density: High energy per unit mass relative more to other electrical energy storage
systems. Li-ion battery cells can deliver up to 3.6 Volts, 3 times higher than technologies such as Ni-
Cd or Ni-MH.
 Low self-discharge: Lithium-ion cells is that rate of self-discharge is much lower than that of other
rechargeable cells such as Ni-Cad and NiMH forms. It is typically around 5% in the first 4 hours after
being charged but then falls to a figure of around 1 or 2% per month.
 Low maintenance: One major lithium-ion battery advantage is that they do not require and
maintenance to ensure their performance.
 High cell voltage: The voltage produced by each lithium-ion cell is about 3.6 volts. Being higher
than that of the standard nickel-cadmium, nickel-metal hydride, and even standard alkaline cells at
around 1.5 volts and lead-acid at around 2 volts per cell, the voltage of each lithium-ion cell is higher,
Electrochemistry and energy storage system

requiring less cells in many battery applications. For smartphones, a single cell is all that is needed
and this simplifies the power management.
 Load characteristics: The load characteristics of a lithium-ion cell or battery are reasonably good.
They provide a reasonably constant 3.6 volts per cell before falling off as the last charge is used.
 No requirement for priming: Some rechargeable cells need to be primed when they receive their
first charge. One advantage of lithium-ion batteries is that there is no requirement for this they are
supplied operational and ready to go.
 Variety of types available: There are several types of lithium-ion cells available. This advantage of
lithium-ion batteries can mean that the right technology can be used for the particular application
needed. Some forms of lithium-ion battery provide a high current density and are ideal for consumer
mobile electronic equipment. Others can provide much higher current levels and are ideal for power
tools and electric vehicles.
 Most components of lithium-ion batteries can be recycled.

20. Explain the direct recycling of Lithium-ion batteries?

Electric-drive vehicles are relatively new to the auto market, so only a small number of them have
approached the end of their useful lives. As a result, few post-consumer batteries from electric-drive
vehicles are available, thus limiting the extent of battery-recycling infrastructure. As electric-drive
vehicles become increasingly common, the battery-recycling market may expand.
Direct recycling of lithium-ion batteries follows the following steps
 Extraction of electrolyte: Electrolyte is extracted from batteries using a liquid carbon dioxide
extraction system. Gas chromatography is used to evaluate extracted electrolytes.
Electrochemistry and energy storage system

 Harvest of electrode: After extraction of electrolyte, the whole cells are safely shredded. The shredder
residue is placed into a blender vessel with an aqueous wash solution and delaminated from the
copper/aluminum current collectors. The electrode materials were separated from the other
components (plastics, metal casing, copper/aluminum current collectors) by filtration. The collected
electrode material is referred to as“harvested”.
 Cathode healing (Hydrothermal): The harvested cathode is sealed in a pressure vessel with a
saturated lithium aqueous solution. After hydrothermal treatment, the electrode material was removed
from the vessel and rinsed with deionized water.
 Separation of carbon and metal oxides: Harvested material consisted of a mixture of cathode, carbon
black, binder, and graphite. Froth flotation of carbon from LiCoO2 is employed with water and 0.5 g
of a surfactant. The mixture was agitated with a homogenizer for 15–20 s to achieve a visible
separation of carbon (float) and metal oxide (sink). The float is immediately decanted. The metal oxide
settled under gravity and was dried under a vacuum.
 Heating the lithium cobalt oxide: hydrothermally treated cathode is heating under air to 800 °C, time
is 9 h, and final natural cooling to room temperature at approximately.
 Recycled graphite preparation: Graphite recovered from the float rinse in acid (0.25 M nitric acid)
to dissolve trace metals. Subsequent rinse with deionized water and acetone. The product dried at 120o
under vacuum. Final heating at 500 °C under flowing nitrogen was applied to dry the material.
 Extracted materials can be used in the reconstruction of batteries.
21. Write a note on the sodium-ion battery
 Sodium-ion batteries are a type of rechargeable battery that uses sodium ions as charge carriers.
 Sodium-ion battery is relatively young compared to other battery types.
 Sodium-ion batteries are also viable means of energy storage, mainly for large-scale electric storage
applications, due to the following reasons:
 low cost of sodium, compared to that of lithium
 similar chemistry and intercalation kinetics to that of lithium
 the irreversible capacity of carbon anodes in sodium-ion batteries is less than in lithium-ion
batteries
Details component
 Anodes: Hollow carbon nanosphere, Hollow carbon nanowire, Red phosphorus/carbon composite,
Carbon nanosheets, Nitrogen-doped porous carbon nanosheet
 Cathodes: Amorphous LiFePO4 nanoparticles connected with MWCNTs, Na3V2(PO4)3 nanoparticles
with 6 nm carbon coating, Electrospun Na3V2(PO4)3/C nanofibers
 Different electrolytes are used for Na ion batteries such as ethylene carbonate (EC), diethyl Carbonate
(DEC), Propylene carbonate (PC), Dimethyl carbonate (DEC), Ethyl methyl carbonate (EMC),
butylene carbonate, and salt combination LiPF6 and NaClO4.
 Prototypes made with sodium had more charge cycles than lithium-ion.
 It also charged faster and delivered energy more quickly.
Application of sodium-ion battery
 Sodium-ion batteries have shown great promise for the large-scale storage of renewable energy.
 Sodium-ion batteries are cheaper and last longer than cells currently used in gadgets.
Electrochemistry and energy storage system

 These factors price, abundance, and size, make sodium-ion batteries particularly interesting for large-
scale grid storage applications.
Advantages of sodium-ion battery
 Rechargeable sodium ion for energy storage.
 Easier to recycle.
 Low market prices.
 Capable of working at room temperature, good efficiency.
Dis advantages of sodium-ion battery
 Large ionic size Na+ requires more power to keep energy flowing.
 Lower operating voltage.
 Need high temperature for optimal work.