7z.exe is the command line version of 7-Zip. 7z.exe uses modules from the 7-Zip package which also are used by the 7-Zip File Manager.
7za.exe (a = alone) is a standalone version of 7-Zip. 7za.exe supports only 7z, cab, zip, gzip, bzip2, Z and tar formats. 7za.exe doesn't use external modules.