[SMART CHRONOCOULOMETRY] 20 mai 2011

Proposal for smart chrono-coulometry

A- Description of the requested protocol
1. Apply a potential in the range of -500 to -700 mV vs. Ag/AgCl with a total compliance between -2 to -4 V 2. Potential is applied for a duration of 2 sec (measurement every 0.2 sec) 3. Current is interrupted (open circuit) for a duration of 0.05 sec in which potential is sampled every 97 usec 4. Based on the potential decay ( value at around 0.02 sec after current interrupt) the potential is corrected and value is applied at the next cycle 5. Corrected potential value is applied for the next 2 sec. 6. Charge is measured for every cycle 7. Cycling stops when target total charge was achieved

To summarize, this is a chronocoulometric method (potentiostatitc) with smart adjustment of the applied voltage. The coulometry is measured and when a value (set by the user) is reached the experiment is stopped.

B- Scheme of the protocol

E1 is the applied potential of the step 1; E2 is the applied potential of the step 2; ECI is the potential measured during the OCV period after 20 ms and n is the number of step needed to reach the charge limit.

[SMART CHRONOCOULOMETRY] 20 mai 2011

C- Simplification of the protocol

If the user accepts, it could be possible to simplify the protocol. The OCV period may be reduced to 20 ms (instead of 50 ms), so voltage of interest will be the last point, so we can consider the Emeas or Einit, for example. The modified procedure is described below:

[SMART CHRONOCOULOMETRY] 20 mai 2011

C-1 with EC-Lab (based on linked technique)

This experiment is built with CA (chronocoulometry) and with OCVperiod. Loop technique is added to create step of potential.

The charge limit is controlled in the Experiment limit in the Advanced settings tab.

Advantage: This experiment is already available Drawback: The protocol is changed (ocv period reduce to 20 ms) The sampling rate is 200 s instead of 97 s.

C-2 with EC-Lab Express or DLL (based on Modular pulse technique) For this proposal, the potentio and galvano periods are performed with the Modular Pulse technique (available in V5.50 of EC-Lab Express and V5.27 of DLL).

[SMART CHRONOCOULOMETRY] 20 mai 2011

R&D work: Add the charge limit Advantage: Sampling rate of 97 s can be reached. Drawback: The protocol is changed (ocv period reduce to 20 ms)

D- True protocol
If user cannot accept the previous proposal, only EC-Lab express can do the job (sampling rate is around 100 s).

[SMART CHRONOCOULOMETRY] 20 mai 2011

D-1 with EC-Lab Express 7 (based on Modular pulse technique)

R&D work: Add the charge limit (note the charge of interest is not the charge of the sequence but the total charge, charge of the whole technique) The applied potential in the step n is calculated from the OCV period. In the step n+1, it has to be possible to set smartly the applied potential of n+1 step. E2 has to be E1 + ECI. User should select the time at which the ECI is measured.