I replaced the old corrugated fibre/cement roof on the garage at our old place with insulated box profile steel - well worth the effort as it made it much warmer in the winter and cooler in the summer, but expensive!
25mm Celotex/Kingspan would make a difference, I would think, either stuck to the underside of the roofing boards with no gap for condensation to form, or with an air gap, only needs to be an inch or so, ventilated to stop condensation between the insulation and the roofing boarding.
Bear in mind that standard Celotex/Kingspan is a fire risk, especially if you're grinding etc.
You can get fire resistant Celotex/Kingspan though, and foil covered, which lessens the risk.
Polystyrene would really be considered a no-no, I would think, as it burns really well - I doubt your insurance company would look favourably on a claim if you've lined your roof with polystyrene!
My current 'barn', 72mx32m was built with 3" of fibreglass insulation inside the walls and roof, and the temperature is very stable and is easy to warm up in the winter
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