Past exam of the MPhil in micro- and nanotechnology enterprise course of the University of Cambridge / 2020 / Paper 1 / Section B / 11

A lead-acid battery is suitable. Its positive electrode reduces PbO2 to PbSO4 and its negative electrode oxidizes Pb to PbSO4. The net discharge reaction isUsing the supplied rounded potentials gives $E^{\circ }=1.70-(-0.35)=2.05\mathrm{V}$. The Nernst equation, taking solid and water activities as unity, givesAt $\mathrm{pH}=1$ and $298\mathrm{K}$,Thus $1.93\mathrm{V}$ if sulfate activity is assumed unity. The pH alone does not specify sulfate activity, particularly where bisulfate formation and nonideal concentrated acid matter; without that assumption the numerical voltage is underdetermined.

For recharge, reverse both electrode reactions without irreversible loss of active material. Use porous, electronically connected Pb and PbO2 on acid-compatible conducting grids, with enough pore volume for PbSO4 formation and electrolyte transport. Fine, reversible sulfate deposits are desirable; coarse persistent crystals cause sulfation. The separator must remain acid-resistant, electronically insulating and permeable to electrolyte ions while preventing shorts; selective ion exchange is not intrinsically required. A compatible lead-alloy grid is preferable to assuming any metallic substrate survives the positive electrode's oxidizing acidic environment. Control current and charging voltage to limit hydrogen evolution, oxygen evolution, water loss, corrosion, heating and active-material shedding. Nickel hydroxide-based alkaline electrodes are poor choices in this acidic electrolyte because their phase stability and reaction conditions differ from those of their tabulated alkaline half-reactions.

An alkaline zinc-air battery combines a porous Zn negative electrode, aqueous KOH, an ion-permeable separator and a gas-diffusion positive electrode. At discharge, oxygen is reduced at the air electrode:Zinc oxidation can be written $\mathrm{Zn}+4{\mathrm{OH}}^{-}\to {\mathrm{Zn}(\mathrm{OH})}_4^{2-}+2e^{-}$, followed by ZnO precipitation and hydroxide regeneration. The net reaction is $2\mathrm{Zn}+{\mathrm{O}}_2\to 2\mathrm{ZnO}$.

High energy requires high accessible Zn loading and low inactive mass; high power requires short ion paths, good electronic conduction and a large catalytically active gas/electrolyte/electron interface. A porous hydrophobic gas-diffusion layer admits oxygen while controlling electrolyte flooding and drying. Zn morphology and electrolyte composition must avoid premature passivation, excessive corrosion and hydrogen evolution; atmospheric CO2 can carbonate the alkaline electrolyte. A very high loading can impair transport, so energy and power must be optimized together.

Electrical recharge is possible, but is not guaranteed by a primary Zn-air design. It requires reversible Zn deposition with controlled morphology and an oxygen electrode that can evolve oxygen efficiently without rapid catalyst or support corrosion. Dendrites, shape change, ZnO redistribution, gas evolution and large oxygen-reaction overpotentials limit cycling. Bifunctional oxygen catalysts, or separate oxygen-reduction and oxygen-evolution electrodes, help. Mechanical replacement of spent Zn is a different form of refuelling.^[ref]