animated feature film Tangled, she only hits Eugene with the skillet. Every other skillet attack was done by Eugene or some of the ruffians from the Snuggly Duckling.
However, in the made for Disney Channel short animated film Tangled Before Ever After, Rapunzel definitely knocks out one villian with a similar cast iron skillet.
Also, in many episodes of Tangled the Series (since retitled Rapunzel's Tangled Adventure) there are many scenes where Rapunzel does attack various villians using the cast iron skillet as her weapon of choice. I'd have to go back and re-watch to see if any of those did indeed cause any believed to be deaths of said villians.