Since the post-secession Union would have a even higher german percentage than OTL US (in contrast to the Confederacy which was predominantly British settled) it is not unlikely that in such a scenario a revanchist, partially germanized Union would be allied with the CPs and the CSA with the Entente, with WWI producing a thousand mile long trench line across North America.
Let's not forget that there's 50 years between 1864 and 1914 (half a century, or almost a generation) where the world can radically change. Many of these threads tend to forget when people chime in saying "The US will ally with Germany" that in the 1860s there was no Germany, and its' unification under Prussia is not an event set in stone. The politics which lead to OTL's Entente and Central Powers forming are also not set in stone. Prussia/Russia might solidify an alliance putting the rest of Europe at odds with them, France and Britain might come to blows over empire in the late Victorian era and be mutually antagonistic, a divided USA may divide further or turn insular. There's way too much in play over 50 years for the world to look exactly as it did OTL in 1914.
And in truth, Turtledove already wrote those stories and they're pretty good.