Definitely not. Rhodey's character in the comics was never depicted as a Skrull. His role and development were consistent without this element of transformation.
In some comic arcs, the Skrull can be seen as bad due to their actions and motives. However, there are also instances where they have more complex and nuanced roles.
One possible reason could be a misunderstanding during a mission. Maybe Rhodey made a decision that put Tony in danger without realizing it at first, and later realized his mistake. For example, if Rhodey called for backup in a situation where it attracted more enemies towards Tony. Another reason might be something related to their personal relationship outside of the hero stuff. Perhaps Rhodey said something unkind about Tony's new technology, not knowing how much effort Tony had put into it.