Unless otherwise stated, all images in this file have been reproduced from:

Blackman, Bottle, Schmid, Mocerino and Wille,

Chemistry, 2012 (John Wiley & Sons)
ISBN: 9 78047081 0866

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 Batteries

Lecture 23 Lecture 24 Lecture 25

Electrolysis Batteries The Haber
Process
 Batteries: commercial uses of redox
We will examine the operation, construction and chemistry of three classes of batteries:
Primary batteries: These are non-reversible and once reactants converted to products
the battery is “dead”.

By Gerhard H Wrodnigg - Own work, CC BY-SA 2.5,

Active electrodes are ok, as they can be consumed.
https://commons.wikimedia.org/w/index.php?curid=542636

Secondary batteries: In these batteries the cell reaction can be reversed and the
battery recharged.

By Kristoferb, CC BY-SA 3.0,https://commons.wikimedia.

Inert or inactive electrodes preferred to allow re-charging.
org/w/index.php?curid=12279456

Fuel cells: Fuel (chemicals) pass through the battery, which converts chemical energy
into electrical energy.
Inert or inactive electrodes needed as reactants (fuel) is provided
By EERE - http://www.hydrogen.energy.gov/permitting/project_considerations.cfm,
Public Domain, https://commons.wikimedia.org/w/index.php?curid=4629990
continuously and electrodes should not be consumed.
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 Primary batteries: dry cells
Zn metal acts as the active anode.
Carbon rod acts as inert or inactive cathode. Graphite rod (cathode)

The electrolyte paste contains solid MnO2 (the oxidant), Electrolyte paste

graphite powder (for electrical conductivity), and NH4Cl Porous spacer

(for ion conductivity).
Zinc metal (anode)

The porous spacer allows Cl– (aq) to reach the anode to Steel shell
steel case

complete the circuit. Figure 12.16 Blackman

Anode: Zn(s) → Zn2+(aq) + 2e– Eº = 0.76 V

Cathode: 2MnIVO2(s) + 2NH4+(aq) + 2e– → MnIII2O3(s) + 2NH3(aq) + H2O(l) Eº = 0.70 V

Zn(s) + 2MnO2(s) + 2NH4+(aq) → Mn2O3(s) + Zn2+(aq) + 2NH3(aq) + H2O(l) Eº = 1.50 V

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Primary batteries: alkaline dry cells
Zn metal acts as the active anode.
Carbon rod acts as inert or inactive cathode. Graphite rod (cathode)

The electrolyte paste contains solid MnO2 (the oxidant), Electrolyte paste

graphite powder (for electrical conductivity), and KOH Porous spacer

(for ion conductivity).
Zinc metal (anode)

The porous spacer allows OH– (aq) to pass from the Steel shell

cathode chamber to the anode to complete the circuit.

Anode: Zn(s) + 2OH–(aq) → ZnO(s) + H2O(l) + 2e– Eº = 1.25 V
Cathode: 2MnIVO2(s) + H2O(l) + 2e– → MnIII2O3(s) + 2OH– (aq) Eº = 0.12 V

Zn(s) + 2MnIVO2(s) → ZnO(s) + MnIII2O3(s) Eº = 1.38 V

Secondary batteries: lead-acid
Anode: Pb0(s) + HSO4–(aq) → PbIISO4(s) + H+(aq) + 2e– Eº = 0.30 V
Cathode: PbIVO2(s) + 3H+(aq) + HSO4–(aq) + 2e– → PbIISO4(s) + 2H2O(l) Eº = 1.63 V
Pb0(s) + PbIVO2(s) + 2H+(aq) + 2HSO4–(aq) → 2PbIISO4(s) + 2H2O(l) Eº = 1.93 V
6 cells in series = 12 V
In this reaction, PbSO4 is deposited on both electrodes. The
reactants are never depleted completely, so it is possible to
recharge the battery by reversing the reaction.
These batteries deliver short bursts of high current because they
have a high surface area and high reactant concentrations.
The cell potential is sensitive to H2SO4 concentration.
Batteries fail or lose capacity because PbSO4 is slowly lost from
the electrode surface, and removed from the circuit.
Worksheet Question 1 6
 Secondary batteries: lithium-ion
Anode: C6Li0 → 6C + Li+ + e– Eº = 2.6 V
Cathode: CoO2 + Li+ + e– → LiICoO2 Eº = 1.1 V
C6Li0 + CoO2 → 6C + LiICoO2 Eº = 3.7 V
The leading battery for mobile devices because
Li is so light, and the cell potential is high.
“Cathode” made of LiCoO2 (CoO2 with Li+ in
interstitial sites).
“Anode” made of graphite (C6 or 6C).
On charging, Li+ is dragged from the positive
electrode to the negative and reduced to Li0.
On discharging, Li0 releases electrons into the
circuit and flows back to the cathode as Li+.
Goodenough and Park, J. Am. Chem. Soc. 2013, 135, 1167-1176 How do lithium ion batteries work? Worksheet Question 2 7
Fuel cells
A fuel cell is a voltaic cell where the reactants are a fuel, e.g. H2, CH4.
The fuel undergoes a normal (overall) combustion reaction. However the two half-
reactions are separated and the electrons harnessed.

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H2/O2 fuel cell
H2O(g)
Anode (–) (+) Cathode
½ O2 + 2 H+ + 2 e–
H2 → 2 H+ + 2 e– → H2O

H2 O2

H+

Electrolyte: KOH
Pt catalyst on
graphite electrodes How do hydrogen fuel cells work? 9
Fuel cells
A fuel cell is a voltaic cell where the reactants are a fuel, e.g. H2, CH4.
The fuel undergoes a normal (overall) combustion reaction. However the two half-
reactions are separated and the electrons harnessed.

Anode: H2 → 2 H+ + 2 e– Eº = 0.0 V
Cathode: ½ O2 + 2 H+ + 2 e– → H2O Eº = 1.23 V
H2(g) + ½ O2(g) → H2O(g) Eº = 1.23 V

Anode: CH4 + 2 H2O → CO2 + 8 H+ + 8 e– Eº = –0.3 V

Cathode: 4×{ ½ O2 + 2 H+ + 2 e– → H2O } Eº = 1.23 V
CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(g) Eº = 0.92 V
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Learning outcomes

After attending this lecture you should be able to:

• Define and distinguish between Primary, Secondary and Fuel Cells.

• Identify the chemical reactions in common batteries.
• Describe the electrochemistry of a lead-acid battery.
• Explain how fuel cells work.

Further Reading: Blackman 12.8

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Extra practice
1. Nickel-Cadmium (NiCd) rechargeable batteries use the following oxidation and reduction half-
reactions:
Anode: Cd (s) + 2 OH– (aq) → Cd(OH)2 (s) + 2 e– E°ox =0.82 V
Cathode: NiO(OH) (s) + H2O (l) + e– → Ni(OH)2 (s) + OH– (aq) E°red =0.6 V
a) Write out the balanced cell reaction.
b) Write out the reaction quotient expression for this redox reaction.
c) Explain why NiCd batteries give stable voltages during discharge. i.e. Why doesn’t the
cell potential change as the reaction proceeds?

2. The oxidation half-reaction for methane is

CH4(g) + 2H2O(l) → CO2(g) + 8H+(aq) + 8e– E°ox= +0.3 V
a) Write out a balanced equation for the spontaneous redox reaction that would occur if this
half-cell was coupled to a standard hydrogen electrode (SHE). (Everything assumed to be
at standard conditions.)
b) Is methane oxidised or reduced by the SHE?

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