Yes, I 100% agree with you that “append()” vs “concat()” are certainly no less confusing in their differences than “/=“ vs “+=“ (and the latter are arguably less confusing due to the mnemonic effect you mention).
In fact, to generalize, I think we can fairly say that operator overloads are akin to extremely short function names; in some cases they may work out great when there is not much ambiguity implicit in the underlying problem, but in other cases a longer and more explicitly descriptive name is required to disambiguate. In this case, “append” and “concat” seem quite poor names for different functions, given that they are virtually synonymous and therefore do nothing to describe or distinguish their differences of behavior.
So my claim is that we can do significantly better at resolving ambiguity with carefully named functions (or other approaches) than operators, or tersely/ambiguously named functions (like “append” and “concat”). Of course, this does come at the cost of code verbosity. Just where we should draw the line between too ambiguous vs too verbose, is of course a difficult subjective matter.