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Hi, any advice or opinions would be much appreciated. We are looking at buying a Toyota Prius 2006 (70,000km). Was it a good model, reliable etc.? Is maintenance costly? Should I be concerned about battery replacement etc.? Thanks in advance!

There was nothing much wrong with the Prius but I'm not sure an aging Prius would be a good bet.
General maintenance is no more than a conventional car, but as you point out, when they age battery replacement (in the event of a failure) could be a very big cost.
Also, there are so many small, economical and environmentally-friendly conventional vehicles available, that the additional complexity of an aging hybrid could perhaps be difficult to justify.

Have also been looking at a 2006 Toyota Prius with less than 50k on the clock. Environmentally and economically what makes would suit someone doing 50k per annum please??

50,000km per annum is very high mileage, and it would depend on the type of use as to which type of car would best suit your needs. If a majority of that mileage is inner city (eg; taxi use or similar), then a Toyota hybrid makes sense as it can be used in EV mode in slow moving traffic.
If it's all open road use, then the Toyota hybrid system offers very little advantage, and perhaps a Honda hybrid might make sense, as the Honda IMA system is better at higher speeds, whereas the Toyota system is better down low.

Great, thanks!