There is a true or false question that asks if A is a n x n matrix and if Ax=0 has only the trivial solution, then the system Ax = b has a unique solution for every b that is real.
I believe that this is true. But in order to show it I want to verify the statement "if Ax=0 has only the trivial solution" implies that there are no free variables. Hence Ax = b will have unique solutions since rank(A) = the number of variables in the system.
As for proof of the equivalence of the two specific conditions you cite without referring to other conditions... consider doing so by contrapositive. Suppose that there exists some $b$ such that $Ax=b$ has more than one solution, in other words there exist $x_1\neq x_2$ such that $Ax_1=Ax_2=b$. Then subtracting, we have $A(x_1-x_2)=Ax_1-Ax_2=b-b=0$ and so $Ax=0$ has a solution different than the trivial solution, namely $x_1-x_2$.
In the other direction, supposing that $Ax=0$ has a solution different than the trivial solution, namely some $x_1$ for which $Ax_1=0$, then here we have both $A0=0$ and $Ax_1=0$ and so letting $b=0$ we have an example of a $b$ for which there is more than one solution.