lets first prove a more general thing, i.e,
$\sum_{i = 0}^{x} {n \choose i } {m \choose x - i } = {m + n \choose x}$.
For that, let's suppose we have m apples and n oranges, and now we want to choose x fruits from them, we can do it in ${m + n \choose x}$ ways, and that's RHS. Now we can also select x fruits, by selecting 0 apples and x oranges, 1 apple and x - 1 oranges and so on, and that's exactly LHS, and hence LHS = RHS.
Now just put m = n, and x = n, in the equation, so it becomes
$\sum_{i = 0}^{n} {n \choose i}{n \choose n - i} = {2n \choose n}$
or,
$\sum_{i = 0}^{n} {n \choose i} {n \choose i} = {2n \choose n}$
$\sum_{i = 0}^{n} {n \choose i}^2 = {2n \choose n}$