See Earliest Uses of Symbols of Relation for the first occurrence of the equality sign $=$, that was first used by Robert Recorde (c.1510-1558) in 1557 in The Whetstone of Witte, with a link to the image of the original print.
For the equivalence sign, see Earliest Uses of Symbols of Set Theory and Logic, with the origin of $\leftrightarrow$, that was apparently first used in 1933 by Albrecht Becker Die Aristotelische Theorie der Möglichkeitsschlüsse, Berlin, 1933.
The double arrow $\Leftrightarrow$ was first used in 1954 by Nicholas Bourbaki, in: Theorie des ensembles, 3rd edition, Paris, 1954 (see page I.30).
The symbol $\equiv$ for the bi-conditional was firstly used by Gottlob Frege (1848–1925) into his 1879 Begriffsschrift and subsequently "popularized" by Alfred North Whitehead and Bertrand Russell's Principia Mathematica (1910-1913).
Principia uses $=$ followed by Df. on the right-end of the formula for definitional identity.(see page 11 and 15).
We can find the usage of $=_{Def}$ already into Cesare Burali-Forti, Logica Matematica (1894), that uses $=$ for (logical) equivalence (see page 26):
$(a=b) =_{Def} (a \supset b) . (b \supset a)$.