Signal from lowest concentration that you can detect (detection limit) should be greater than average of electrochemical signal from zero conc. + 3* (Standard deviation of signal from zero conc.)
obtain at least 10 blank electrode response without analyte, then calculate standart deviation of 10 blank electode response, then there is an equation LOD(limit of detection) 3 times of standart deviation """"(3xSD)/m"""" m is the slope of calibration curve. the calculated result is the limit of detection
This paper define the detection limit (LOD), you can calculate the detection limit for an electrochemical sensor using their method, (Thévenot D R, Toth K, Durst R A, et al. Electrochemical biosensors: recommended definitions and classification[J]. Biosensors and Bioelectronics, 2001, 16(1): 121-131).
Sensitivity is a key performance parameter of biosensors, Sensitivity is defined as the slope of change in signal(current) with a change in concentration:
Record series of blank responses without adding analyte and then calculate the St. Dev. for these electrodes. Take the standard deviation and multiply it by 3 and then dived by slope.