Smallest negative value expressed in 8 bit 2 complement from is $-128$ [ 1000 0000 ]
Now if we add it with itself :
1000 0000 $(-128)$
1000 0000 $(-128)$
1 0000 0000 $(-256)$
Note: Here we can see overflow came because when we add two binary numbers there must be an overflow when :
X Y Z
0 0 1
1 1 0
Where X → Sign bit of first number
Y → Sign bit of second number
and, Z → Sign bit of Resultant