I'm not sure that I understand both alternatives.
Is the first option to parallel the entire Leaf pack (96S2P of 33 Ah cells) with the entire Volt pack? They have about the same nominal voltage, but different capacities and seem unlikely to load-share ideally. Or is the first option to use one at a time, switching between them?
Is the second option to reconfigure the Leaf pack to place modules in parallel and then series them into a 48S set, and reconfigure the Volt pack to put modules or more cells in parallel and then series them into another 48S set, then put all of that in series? With the different capacities this seems like a problematic configuration. Or, is the second option to parallel two Leaf cells with a set (3 if the earlier Volt pack, 2 if the later Volt pack) of Volt cells, then put those mixed-source groups in series?
Modules are easy to connect in parallel with other modules, but the Volt modules are big (lots of cells) so it doesn't get even close to cell level parallel connections. Reconfiguring Volt modules at the cell level requires cutting of welds and making some sort of clamped connections. The Leaf modules are only 2S, and because they have a "middle" terminal for the BMS they can be paralleled at the cell level with only bolted connections. But I'm guessing that you already know that...