Application Note: Mixed Mode (refers to software release 1.

6)

The Mixed Mode combines almost all electrochemical techniques in a single

experiment. It will, for most situations, eliminate the need to sequence several
methodfiles (BatchMode). It offers a more transparent structure for method and
datafiles. Moreover, a much better real-time performance can be realized with faster
mode transitions that are better controllable:
• Alternating between Galvanostatic, Potentiostatic and OpenCell conditions
• Combining Steps and Sweeps
• Real time impedance measurements during each stage (Step & Sweeps)
• Dynamic level duration with definable limits.
• Potential levels may be defined relative to previous level

Combining Steps, Sweeps, and mixing Galvanostatic/Potentiostatic/OpenCell

In Mixed Mode, up to 255 levels can be selected. Each level can defined as:
• Controlled E, at fixed potential
• Controlled E sweep, with selectable Estart, Eend and scanrate
• Controlled I, at fixed current
• Controlled I sweep, with selectable Istart, Iend and scanrate
• Open Cell Potential
Each level can be defined with a resolution and sample-interval of 0.002 sec, and
may contain up to 2E9 datapoints. The whole sequence may be repeated an
unlimited number of cycles.

Dynamic level duration with definable limits.

Each level may be defined with a fixed time duration, or it can be stopped depending
on the occurance of user defined threshold condition. Limits can be defined based on
measured parameters, or on states of external electrical inputs, see overview in
table on the next page.

Real time Impedance measurements

During each Galvanostatic or Potentiostatic stage, both during a Step or a Sweep,
the impedance can be measured. When this feature is activated, an ac-signal of
selectable frequency and amplitude is applied, and the impedance is measured at
each datapoint as a Resistance and Capacitance. Thus variations in impedance can
be monitored in real-time, during each Step or Sweep.
The applied frequency may be chosen between 10 Hz and 2 MHz Note that the
maximum data acquisition rate for impedance monitoring is 5 datapoints/sec.

Smooth level transitions

Because the whole sequence of levels is controlled in a single procedure, the
Potentiostat/Galvanostat is able to use the information from the previous level, to
make a smooth transition to the next level or mode. Thus avoiding abrupt electrical
shocks to the cell.
The start-potential of a stage may be defined as an absolute potential or relative to
the last potential of the previous level. For example, after an Open Cell stage, one
can program a potential-sweep that starts exactly from OCP, or at a fixed offset from
OCP.

Specifications subject to change, Ivium Technologies 2009 ©

parameter available
E applied Estat Applied potential
E vs Eprev Estat When checked, Eapplied is relative to end-
potential of the previous level1
SweepE Estat When checked, the potential will be sweeped
from Eapplied to E end, at defined scanrate
E end SweepE End potential for potential sweep
Scanrate SweepE/I Sweep rate
I applied Istat Applied current
SweepI Istat When checked, the current will be sweeped from
I applied to I end, at defined scanrate
I end SweepI End current for current
Duration Steps Level duration
Record ac Estat,Istat When checked, impedance is measured using
defined frequency and amplitude
Until E> Istat, OCP End level if E exceeds value
Until E< Istat, OCP End level if E falls below value
Until I> Estat End level if current exceeds value
Until I< Estat End level if current falls below value
Until dE/dt> Istat, OCP End level if E-rate-of-change exceeds value
Until dE/dt< Istat, OCP End level if E-rate-of-change falls below value
Until dI/dt> Estat End level if current-rate-of-change exceeds
value
Until dI/dt< Estat End level if current-rate-of-change falls below
value
Until An1> If enabled End level if the analog input voltage level is
exceeded
Until An1< If enabled End level if the analog input voltage level falls
below value
Until dAn1/dt> If enabled End level if AnalogInput-rate-of-change exceeds
value
Until dAn1/dt< If enabled End level if AnalogInput-rate-of-change falls
below value
Until Ifraction< Estat End level if current drops below a fraction of the
initial measured current
Until |Q|> Estat End level if absolute charge exceeds value

1
If the previous level was Istat or OCP, the last measured potential is taken as end-potential. If the previous
level was Estat, the last applied potential is taken.

Specifications subject to change, Ivium Technologies 2009 ©

Example 1: cycling a battery, while monitoring the internal resistance:
• Battery is charged with +150mA until E>+1.425V
• Battery is discharged with –150mA until E<+0.400V
• Cycle is repeated
• The impedance is monitored real-time, and Rs is plotted.
Note that the battery resistance Rs is decreasing while charging, while it increases
during discharge, and that Rs decreases with increasing cycle number. Real-time
monitoring has the advantage that the normal “charge-discharge” cycle is not
disturbed, and even small changes in internal resistance can be observed.

Specifications subject to change, Ivium Technologies 2009 ©

Example 2: 2 cycles with a 1F supercap using stage-protocol:
• Apply 50mA constant current 100s, or until E>3.5V, record impedance
• Switch to open cell for 5 seconds
• Apply -50mA constant current 100s, or until E<0.1V, record impedance
• Switch to open cell for 5 seconds

Figure description
• bottom plot:
o black line : measured current referring to the left axis
o blue line : measured potential referring to the right axis
• top plot:
o blue dots : resistance measured at 1kHz. Note that capacitance can be
shown by pressing the Cs button on the toolbar at the left side of the
graph.

The internal resistance is well reproducible between cycles. The resistance of the
supercap increases during charging, while it decreases during discharge. Thus its
behaviour is opposite from the NiCd battery in example 1.
Note that the variations in resistance are quite small, and probably would not have
been observed in a non-real-time measurement configuration.

Specifications subject to change, Ivium Technologies 2009 ©