For cases, 3D print one, for comfortably less than 200€ you can get a Open-Source Hardware Certified Ender 3, and that's with DHL shipping already.
Laminated glass is an option.
I know someone who 3D-printed a phone case with a consumer printer he got for Christmas, and it fell apart within a few days.
That said I don't think 3D printing phone cases is worth doing for any reason other then the cool factor. I'd expect 3rd parties to start selling cases for it fairly quickly, there just might not be a huge range of colors/options/prices
Then that's his fault, because millions of people made durable flexible material things with their consumer 3D printers.
A bad workman always blames his tools...
Then it turns out that the vital piece which fits the requirements does not exist at all (or does not exist for small time customer), or is incompatible with the architecture which has a lot of resources invested in.
Not saying that this will be what happens and most likely Librem team are already well aware of this risk, but it is certainly a possibility.
I wish them well but I’m sceptical. Still, it would be great to be surprised.