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I'm not sure if Calibre can do what you want. You can use it as an WiFi home-server to download your books, but not as a remote library with free access from everywhere.
And if you are already at home it is much easier and faster to get your books via USB.
On the other hand Pocketbook in combination with Calibre offers excellent ways of storing big numbers of books easily accessible on the device by creating a decent folder structure.
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