A query - if you have to check the expansion vessel when not connected to the system how is that done without draining the system?
You don't need to drain the system, or disconnect - but the fluid pressure should be zero - That way when you have pressure on the air side you know the vessel is full of air.
If the fluid pressure isn't zero you need to open the fluid side, which will release some fluid to release the pressure (sounds like you don't need to though).
We took the expansion vessel pressure in the morning - when the system pressure (according to the gauge) was zero.
You mean you took the expansion vessel [air] pressure? what was it?
Given how the expansion vessel works if it wasn't pressurised then the vessel would be full of fluid yes? This is not the case.
If there was no air pressure then yes, it will likely be full of fluid, which will cause the system pressure to shoot up as soon as it warms up. When you say 'this is not the case' do you mean it IS pressureised, or that it ISN'T full of fluid?
At the moment the pressure gauge on the water side reads zero when the system is cold. When the sun is out and the system is up and running the pressure on that gauge goes up to 2.5 or so
Assuming that's without the panel reaching silly temperatures, then that to me sounds like the pressure vessel is full of fluid.
What you want is (when cool) for the expansion vessel to be full of air.
With the system cold, lets say you pressurise it with air to 0.5bar (and the fluid pressure is less than 0.5bar). When the fluid warms up (and expands) the fluid pressure will rise; when the fluid pressure = 0.5 bar, it will start flowing into the expansion vessel, compressing the air and the pressure will then only rise a tiny amount (as the air is compressible, and only a small %age of the volume will be used by the expanding fluid).
If the fluid boils in the panel then the expansion vessel will have to accommodate the displaced fluid which will cause the pressure to rise more, but hopefully not to vent pressure.