For example:
$Xe^{+}+e^{-} \rightarrow Xe + \mbox{energy}$
Assuming that the electron has a kinetic energy $\neq 0$.
Is the released energy a photon or heat?
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1$\begingroup$ Recombination usually does emit photons. In this case it may be useful to think of this emission as of Bremsstrahlung. $\endgroup$– RuslanCommented Aug 12, 2013 at 13:27
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The extra kinetic energy appears as heat, which is vibration-energy at the atomic scale.
Energy forms like this is largely where much of the chemical energy comes from. The heat derived is then used to drive an engine of some form, which produces mechanical, and then prehaps, electrical, energy.