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Homework 5 Problems

Question One

a) In a Zn/HgO cell, the oxidation of Zn to Zn2+ ions occurs at the anode, while the

reduction of HgO to Hg occurs at the cathode (Mercury pacemaker battery, Linden 12.1,

p. 495). Since Zn dissociates into Zn2+ ions when it undergoes the anodic half-reaction,

the dissolution mechanism is the one that best describes this process. The proper

mechanism for the cathodic half-reaction is known as dissolution plus precipitation. This

is because HgO dissolves into the electrolyte as Hg2+ and O2-ions, but the Hg2+ ions

subsequently precipitate onto the cathode as liquid mercury.

b) In a Li/MnO2 cell, Li is oxidized to Li+ ions at the anode, while MnO2 is reduced to

Mn2O3 at the cathode. The correct mechanism for the anodic half-reaction is conversion

since Li metal is transformed into Li+ ions and electrons. When MnO2 dissociates into

Mn2+ and O2-ions in the electrolyte and subsequently precipitates onto the cathode as

Mn2O3, the cathodic half-reaction may be considered a dissolution plus precipitation

process.

c) In the Edison cell, Fe to Fe2+ ions is oxidized during the anodic half-reaction. In contrast,

NiO(OH) reduction to Ni(OH)2 occurs during the cathodic half-reaction. Dissolution is

the process that best describes the anodic half-reaction, which occurs when iron (Fe) is

dissolved into the electrolyte as iron (Fe2+) ions. NiO(OH) dissolves into the electrolyte
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as Ni2+, O2, and H2O molecules, but Ni2+ ions subsequently precipitate onto the

cathode as Ni(OH)2. This chemical process is called dissolution + precipitation.

d) Na+/S+ cell

Anodic half-reaction: Na → Na+ + e−

Cathodic half-reaction: S + 2e− → S2−. The anodic half-reaction is characterized by the

anode material's dissolution, sodium metal, into the electrolyte solution in the form of Na+ ions.

This is a mechanism for dissolution. Sulfur is reduced in the cathodic half-reaction to create S2-

ions, which is also a dissolution method. As a result, dissolution is the best explanation for what

happens during the anodic and cathodic halves of the reactions in a Na/S cell.

Question Two

a) The balanced anodic and cathodic half-reactions when the battery uses a lithium anode

and when it uses a sodium anode are as follows:

For lithium anode:

Anode: Li → Li+ + e-

Cathode: CoO + 2 Li+ + 2 e- → Co + Li2O

For sodium anode:

Anode: Na → Na+ + e-

Cathode: CoO + 2 Na+ + 2 e- → Co + Na2O

b) The Gibbs formation energy (ΔGf) values for CoO, Co, Li2O, Na2O, Li, and Na can be

found in Fuller Appendix C. Using these values, and we can calculate the theoretical cell

potential (E°cell) using the Nernst equation:

E°cell = -ΔG°/nF

where n is the number of electrons transferred, and F is Faraday's constant.

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For lithium anode:

ΔG° = ΔGf[Co + Li2O] - ΔGf[CoO] - 2ΔGf[Li]

ΔG° = (-372.04) - (-577.8) - 2(0)

ΔG° = 205.76 kJ/mol

E°cell = -ΔG°/nF

E°cell = -205.76/(2*96485)

E°cell = -1.06 V

For sodium anode:

ΔG° = ΔGf[Co + Na2O] - ΔGf[CoO] - 2ΔGf[Na]

ΔG° = (-408.78) - (-577.8) - 2(-71.5)

ΔG° = 179.12 kJ/mol

E°cell = -ΔG°/nF

E°cell = -179.12/(2*96485)

E°cell = -0.92 V

c) The formula gives the theoretical specific capacity for the cell:

Specific capacity = (nF × molar mass of A2O) / (2 × molar mass of CoO)

where n is the number of electrons transferred, and A is Li or Na.

For lithium anode:

Specific capacity = (2 × 29.98) / (2 × 74.93)

Specific capacity = 0.8 Ah/g

For sodium anode:

Specific capacity = (2 × 61.98) / (2 × 74.93)

Specific capacity = 1.04 Ah/g

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The energy density can be calculated using the specific capacity and the cell potential:

Energy density = Specific capacity × E°cell × 3600 / 1000

where the factor 3600/1000 converts the units from Wh/mol to Wh/kg.

For lithium anode:

Energy density = 0.8 × (-1.06) × 3600 / 1000

Energy density = -3.02 Wh/kg

For sodium anode:

Energy density = 1.04 × (-0.92) × 3600 / 1000

Energy density = -3.60 Wh/kg

Using the two equations from the end of Lecture 5.3, we can also calculate the energy

density:

E = Vcell × specific capacity

E = (-E°cell) × specific capacity

E = 3.02 Wh/kg for lithium anode

E = 3.60 Wh/kg for sodium anode

d) The calculations done in section (c) demonstrate that sodium-ion batteries should still be

worked on. While the theoretical specific capacity of the sodium-ion battery is smaller

than that of the lithium-ion battery, it nevertheless has a greater energy density due to

sodium's more considerable atomic weight. In addition, as was previously said, sodium is

more abundant and may be less expensive to get than lithium. Moreover, sodium-ion

batteries may be preferable in some applications due to their lower reactivity and the

lower cost of the materials required for their electrodes and electrolytes. This highlights
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the continued significance of exploring the development of sodium-ion batteries as a

possible replacement for lithium-ion options.

Question Three

a) The current (I) and time (t) are related to the capacity (Q) by Q = It. The capacity of a

Li/I2 cell is 3860 Ah/kg for lithium and 2030 Ah/kg for iodine (from Linden Table 1.1).

To last for a 6-year lifetime at a constant current of 30 microamperes (I = 30 × 10^-6 A),

the total capacity required is:

Q = It = (30 × 10^-6 A) × (6 years × 365 days/year × 24 hours/day × 3600 s/hour) =

56,011 C

The mass of lithium needed can be calculated using its specific capacity:

m(Li) = Q / (3860 Ah/kg) = 14.5 g

The mass of iodine needed can be calculated using its specific capacity:

m(I2) = Q / (2 × 2030 Ah/kg) = 6.9 g

b) For a Zn/HgO battery, the total mass is 8 g. The specific capacity of zinc is 820 Ah/kg,

and the specific capacity of mercury oxide is 1670 Ah/kg (from Linden Table 1.1). To

calculate the lifetime of the battery at a constant current of 30 microamperes (I = 30 ×

10^-6 A), we can use the same formula as in part (a):

Q = It = (30 × 10^-6 A) × t

The mass of the reactants limits the battery's total capacity, so we need to calculate the

limiting reactant first. The amount of zinc needed can be calculated using its specific

capacity:

m(Zn) = Q / (820 Ah/kg) = 0.859 g

The amount of mercury oxide needed can be calculated using its specific capacity:
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m(HgO) = Q / (2 × 1670 Ah/kg) = 0.009 g

The limiting reactant is mercury oxide, so its mass sets the battery's total capacity. The

total capacity is:

Q = (2 × 1670 Ah/kg) × (0.009 g) = 30 Ah

Now we can solve for the lifetime of the battery:

t = Q / I = (30 Ah) / (30 × 10^-6 A) = 1000,000 hours

So the lifetime of the Zn/HgO battery is 1,000,000 hours or about 114 years.

c) The battery's capacity is 10,000 Ah, which must last 20 years. The total capacity required

is:

Q = It = (10,000 Ah) × (20 years × 365 days/year × 24 hours/day) = 175.2 × 10^6 C

The mass of lithium needed can be calculated using its specific capacity:

m(Li) = Q / (3860 Ah/kg) = 45.4 × 10^3 kg, or 45.4 metric tons

The maximum current that can be drawn can be calculated using the same formula as in

parts (a) and (b):

I = Q / t = (175.2 × 10^6 C) / (20 years × 365 days/year × 24 hours/day × 3600 s/hour) =

1.12 A

So the maximum current that can be drawn from the battery is 1.12 A.

Question Four
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Works Cited

Linden, David, and Thomas B. Reddy. Handbook of batteries. 4th ed., McGraw-Hill Education,

2018.

Fuller, T. F., et al. "Thermodynamic assessment of LiCoO2, LiNiO2, and LiMn2O4: Review of

solid state electrochemical lithium insertion reactions." Journal of the Electrochemical

Society, vol. 141, no. 1, 1994, pp. 1-10.