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I'll second the recommendation for Miles Davis.
Also, check out some of the Cafe Del Mar compilations. Not entirely without vocals, but very tasty trip hop.
Aphex twin is also one of my favourites, and his stuff ranges from harsh, static fast tempo, to some really amazing down-tempo stuff. Check out Selected Ambient Works Volume 1 and 2.
And the prodigal ambient record, Brian Eno's Music for Airports.
I don't know if it's really workout music, but it has a lot of backbone and really holds it's own as far as I'm concerned. It may just be what you're looking for.
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