It was 2009 I went, we spent a few days in the Triglavski National park, the Soca Valley and then Lake Bled, I really enjoyed it all, although Bled was very touristy tacky.
I do recall people being very friendly and welcoming, fuel was easily available like anywhere else in Europe, don't recall any tolls whatsoever. But I do recall traffic being minimal, however Slovenia and Croatia are now much more popular and they may well have changed.
Never quite felt I explored Slovenia properly, on my list to return to.