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Timothy,
An ENVI .sli file is just a binary array with spectra saved in rows (so it's the same format as a BIP tile).
To read it, you'll need to know the number of spectra (nspec), number of pts per spectrum (npts), the datatype (dt), and whether or not there's an offset. Assuming there's offset=0, and the path to your library file is stored in the variable sli_file, then this should work:
sli = make_array(npts, nspec, type=dt)
openr, lun, sli_file, /get_lun
readu, lun, sli
free_lun, lun
If there's an offset, handle that with a point_lun in between openr and readu.
Jeff
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