The T&Cs do mention...
3...other 'low carbon technology at home' including heat pumps and home batteries.
5b...EV charging and any underlying household usage.
5d...Usage in excess of the(se) six hours per day may be charged at the day rate.
I get the impression that Octopus will be flexible as long as they don't see excessive consumption during the low rate periods. One car plus house batteries could easily consume as much or more than a car plus dishwasher, washing, drying etc although if a second car is also included in any particular time period this could flag up enough concurrent consumption for Octopus to investigate. In my case I won't do that so will charge my wife's Fiat 500e predominantly on nights when the Tesla isn't being charged (smaller battery, low daily mileage).
One other point I notice from the app FAQs:
'Why isn't my car going to sleep?" - in my case and based on one day there is no evidence of that happening - SOC still reads 85% from the early morning charge as evidenced from my PV inverter summary below and no additional charge to the car is evident from either grid or solar so even though still plugged in, it doesn't seem to be losing or gaining to any extent (the car will stay plugged in for a while yet before I return - if it did seem to be losing & topping up significantly then I will switch off IO via the app using'Disconnect Vehicle')
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.....incidentally IO has also provided two more additional slots this evening 20.30-21.00 &22.00-22.30 if they were needed (not)