To emphasize what DiapDealer said ...
KindleUnpack will "unpack" an azw3 to an "epub-like" structure, but is is not a real converter in and of itself. If the azw3 was created by passing in a valid epub3 or epub2, Kindleunpack it unpack it to a valid epub3 (or epub2) or something very very close to valid.
If however someone passed in an old mobi or some other format (such as a non-valid epub) into kindlegen to create the azw3, then KindleUnpack will not produce a valid epub.
That said ... KindleUnpack will produce something that should be importable into Sigil (or Calibre) as an epub so that it can be validated and any problems fixed.
So you may have run into one of those azw3 that were not generated with a valid epub and therefore the output of KindleUnpack will need to be validated and fixed in Sigil or Calibre or by hand, to get a proper valid epub.
KevinH
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