Raichu has been with Volkner since Volkner was a young boy and Raichu was a Pikachu.
As a Pikachu, Raichu was once involved in a battle with a Houndoom used by a Pokémon Poacher. The Poacher appeared as well in the same episode as the flashback, which was Flint Sparks the Fire, and revealed that battling Volkner and Flint all those years ago had made him have a change of heart and he decided to stop Pokémon poaching.
Raichu was often seen outside his Poké Ball. He was shown to be very affectionate towards Flint, being about as close to him as Volkner was, and jumped into his arms for a hug. Despite being Volkner's main Pokémon, Raichu merely watched Volkner's battle with Ash instead of participating in it.
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- Volkner's Raichu is the only signature Pokémon to be used by a Gym Leader that was not used in a battle with Ash.