Should work with the Hub 3. Note however if you are not on the top tiers, you will be charged £5 pm. Best to buy your own wifi solution to keep, rather than rent something you will never own.
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Try and update to Volt and they are free for all, also I am pretty sure if the App backed up you had a black spot the POD is free for one of them at least.
I cannot say for sure as the App has not worked (does not support) since I got a HUB4 long ago.
Thanks for your post welcome to the forums. It's great having you on board with us in the Community.
I'm sorry to hear you've had an issue getting a second WiFi pod added to your account. We can certainly help with this. I have sent you a private message regarding this and will investigate further once I receive your reply. Just click on the little plum envelope at the top right hand side of the page to access your inbox.