In fact, Li-ion batteries were used in hand held devices and laptops long before they were used in cars. Marc Tarpenning and Martin Eberhard, the founders of Tesla, made their previous fortunes in the PDA/E-Book business. So they were comfortable with the technology. Just needed to scale it up.
They started up Tesla on the heels of the crushing of the EV-1s and other EVs, bypassed NiMH, and went straight to Li-ion for the Tesla Roadster. The rest is history.