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A thermoelectric generator maintains hot and cold junctions of two materials with different Seebeck coefficients. Mobile charge carriers redistribute in the temperature gradient, producing an open-circuit voltage of magnitude $|V|=|S_p-S_n|\Delta T$ for constant coefficients. A load permits electric current; pairs of p-type and n-type legs are commonly connected electrically in series and thermally in parallel. Maintaining the output requires continuous heat transfer from the hot reservoir and rejection of heat to the cold reservoir. The thermoelectric figure of merit $ZT=S^2\sigma T/\kappa$ expresses the favorable combination of large Seebeck coefficient, large electrical conductivity and small thermal conductivity. Contact losses, Joule heating and parasitic heat leaks reduce practical efficiency.

A pyroelectric generator instead exploits a change of spontaneous electric polarization with temperature. If the relevant component of the pyroelectric coefficient is $p=d{P}_s/dT$, an electrode of area $A$ receives a short-circuit electric current approximately $I=pAdT/dt$. A heating stroke and a cooling stroke produce opposite charge changes. Rectification or a synchronized electrical cycle can transfer energy to storage. A spatial temperature difference drives the thermoelectric device; a temporal temperature change drives the pyroelectric device. Uniform, constant temperature gives no continuing current from pyroelectricity even if the material is hot. Reported nanowire generators deliberately use changing temperature, rather than infer continuous generation from a static hot specimen.^[ref]

Both approaches can be compact, silent and free of macroscopic moving parts. The thermoelectric generator gives continuous output under a sustained gradient, but needs two effective thermal contacts and sufficient heat flow; very small $\Delta T$ gives a small voltage and thermal contacts can consume much of the available gradient. Thin films exhibiting pyroelectricity can respond to intermittent heating without a permanently maintained hot/cold separation across their thickness, but require repeated thermal cycling, low electrical leakage and suitable charge extraction. Their thermal time constant limits useful cycling frequency, and sensible heating/cooling can dominate the heat budget. A steady hot pipe with an available cold sink favors a thermoelectric generator; periodic radiative heating can favor a pyroelectric generator. Neither converts equilibrium thermal motion at a single fixed temperature into sustained useful work.

A thermoelectric generator uses the Seebeck effect and needs a spatial temperature gradient: a couple develops $V\simeq (S_p-S_n)\Delta T$ between hot and cold junctions. It can deliver continuous power under a steady thermal gradient and has no moving parts, but requires sustained heat flow and adequate hot- and cold-side thermal contacts. Thermal conduction, internal electrical resistance and the material's thermoelectric figure of merit limit conversion.

A pyroelectric generator responds to a time-dependent spontaneous electric polarization. Under approximately uniform heating or cooling, $I=pAdT/dt$ when the electrical boundary condition allows charge flow. It can harvest temporal thermal fluctuations without a persistent spatial gradient. However, at a constant uniform temperature its ordinary pyroelectric current stops; practical extraction needs cycling, low-leakage electronics and a suitable load. A large open-circuit voltage is not evidence of a large available average power. Temperature-driven nanowire measurements provide a primary experimental example of this distinction.^[ref]

A pyroelectric material has a spontaneous electric polarization that changes with temperature. electrodes collect the resulting change in compensating charge. For a uniform element,Consequently temperature variation in time, rather than a steady temperature difference alone, drives a pyroelectric generator. A cyclic thermal input and a suitable electrical circuit are needed for repeated energy extraction.

The primary pyroelectric effect is the change of electric polarization at fixed strain. The secondary pyroelectric effect arises because thermal expansion strains a piezoelectric crystal and thereby changes its electric polarization. In component notation its contribution iswith piezoelectric coefficients $e_{ij}$ and thermal-expansion coefficients ${\alpha }_j$. Choosing orientation, mechanical constraint and substrate expansion so that the secondary contribution reinforces the primary one can increase the response; the signs can instead oppose one another.

An array of slender nanowires can expand more freely than a film clamped to a substrate and can exchange heat rapidly because of its high surface-to-volume ratio. Reduced clamping can recover a secondary response suppressed in the film. Faster thermal cycling can also increase electric current through $dT/dt$. This is a geometrical opportunity rather than a universal increase of the intrinsic coefficient: screening, leakage, orientation and the actual thermal excursion must be compared. ZnO nanowire generators provide an experimental realization of pyroelectric energy conversion.^[ref]