Use loc for setting with enlargement:
df.loc['mean'] = df.mean()
The resulting output:
diode1 diode2 diode3 diode4
Time
0.53 7.0 0.0 10.0 16.0
1.218 17.0 7.0 14.0 19.0
1.895 13.0 8.0 16.0 17.0
2.57 8.0 2.0 16.0 17.0
3.24 14.0 8.0 17.0 19.0
3.91 13.0 6.0 17.0 18.0
4.594 13.0 5.0 16.0 19.0
5.265 9.0 0.0 12.0 16.0
5.948 12.0 3.0 16.0 17.0
6.632 10.0 2.0 15.0 17.0
mean 11.6 4.1 14.9 17.5