Linear accelerators have been employed in space. While "voltage" is perhaps not the right term, precisely, these do generate very high energy beams, and frequently using means (like RF, etc) other than direct acceleration by a high voltage DC supply.
There are current proposals to develop a 1MeV RF linac for experiments in space. Early experiments in the 1970s used standard DC high voltage supplies to generate beams of up to 40keV, injecting pulses into the ionosphere using sounding rockets.
Spacelab-1 also had a 7.5keV accelerator on board for a series of particle accelerator experiments.
There was also the BEAM experiment in 1989 that produced a 1MeV neutral hydrogen beam. This had a 30keV injector to the RF accelerator - I'd expect this probablythat used a standard DC accelerator gridsupply at 30kV. Like the sounding rocket experiments in the '70s, this was also deployed on a similar voltagesub-orbital rocket to a maximum altitude of 195km - so "in space", but I'm not certainin orbit.