Practicing AlwaysOn on SQL Server 2014 - Windows 10 Home
SQL Server 2016 will allow for Availability Groups without a domain, but sorry, I don't think your operating system is going to cut it. 

To support your scenario, you could put an eval of a proper server OS in a virtual machine or dual boot scenario, but to really test AGs, you'd need multiple copies of Windows in order to understand failover, availability modes, etc. And if you're trying to beef up your skills for a potential job, this edge case scenario is probably not the type of thing a company serious about HA/DR would have any interest in, because they're unlikely to be avoiding domains...