We show that over any ring, the double Ext-orthogonal class to all flat Mittag-Leffler modules contains all countable direct limits of flat Mittag-Leffler modules. If the ring is countable, then the double orthogonal class consists precisely of all flat modules, and we deduce, using a recent result of Saroch and Trlifaj, that the class of flat Mittag-Leffler modules is not precovering in Mod-R unless R is right perfect.