Universidad de Oriente

IIBCAUDO
Doctorado en Ciencia de los Materiales
CORROSIÓN AVANZADA

GALVANOSTATIC METHOD AND TO THE CONTROL

DIFFUSION OVERPOTENTIAL

Doctorando: Freddy J Santamaría

V.
Profesor Dr. Mario Ortega, Ph.D.

Jueves 11 de Junio 2015

 Galvanostatic Method
 GALVANOSTATIC INTERMITTENT TITRATION TECHNIQUE
(GITT)
 The GITT procedure consists of a series of current pulses, each followed by
a relaxation time, in which no current passes through the cell. The current is
positive during charge and negative during discharge.
 In a typical GITT measurement, a cell composed of metallic lithium
(counter and reference electrode), electrolyte and positive (working)
electrode is employed. In this way, pieces of information about the
thermodynamics of the active material present in the positive electrode
can be obtained, together with the diffusion coefficient. (Fuente:
Metrohm Autolab, Galvanostatic Intermittent titration Technique.)
 GALVANOSTATIC INTERMITTENT TITRATION TECHNIQUE
(GITT)
During a positive current pulse, the cell potential quickly
increases to a value proportional to the iR drop, where R
is the sum of the uncompensated resistance Run and the
charge transfer resistance Rct. Afterwards, the potential
slowly increases, due to the galvanostatic charge pulse, in
order to maintain a constant concentration gradient. When
the current pulse is interrupted, i.e., during the relaxation
time, the composition in the electrode tends to become
homogeneous by Li-ions diffusion. Consequently, the
potential first suddenly decreases to a value proportional
to the iR drop, and then it slowly decreases until the
electrode is again in equilibrium (i.e., when dE/dt ~ 0) and
the open circuit potential (Voc) of the cell is reached.
Then, the galvanostatic pulse is applied again, followed by
current interruption. (Fuente: Metrohm Autolab,
Galvanostatic Intermittent titration Technique.)
During a negative current pulse, the opposite
holds. The cell potential quickly decreases to a
value proportional to iR. Then, the potential slowly
decreases, due to the galvanostatic discharge
pulse. During the relaxation time, the potential
suddenly increases by a value proportional to iR,
and then it slowly increases, until the electrode is
again in equilibrium (i.e., when dE/dt ~ 0) and the
Voc of the cell is reached. Then, the following
galvanostatic pulse is applied, followed by current
interruption. This sequence of discharge pulse
followed by a relaxation time is repeated until the
battery is fully discharged. (Fuente: Metrohm
Autolab, Galvanostatic Intermittent titration
Technique.)
 METHODS TO CONTROL DIFFUSION
OVERPOTENTIAL
Limitation by diffusion is one of the main obstacles in an electrochemical process.
Therefore one has to limit its influence and increase the limiting current density.
which are by an increase of concentration or by a decrease of the thickness of the
diffusion layer .
Another way is pumping the electrolyte parallel to the electrode or against the
electrode. C

Figure 1, (A) The ideal rotating disk electrode, (B) Schematic representation of a rotating ring–disc electrode (RRDE) and (C) Pine
AFMSRX Electrode Rotator (for use with Rotating Cylinder Electrodes) and Rotating Cylinder Electrode Tip (easily taken apart to replace
metal sample).
METHODS TO CONTROL
OVERPOTENTIAL
• 1) the radius is very large compared to
the momentum boundary layer
thickness,
• 2) all other surfaces within or bounding
the liquid are at a distance large
compared to the radius of the rotating
surface,
• 3) surface irregularities on the disc are
small compared to the momentum
boundary layer thickness,
• 4) the rotation rate for the particular
disc is below the critical Reynolds
number for the onset of turbulence
Rotating-disc electrode
(Fuente: Ernest Yeaqer et
al, “ROTATIING DISC AND
RING-DISC TECHNIQUES”)
DIFFUSION
• In the RRDE technique, the current– • When immersed and rotated in a test
potential characteristics of the disc are solution, the hydrodynamic conditions
unaffected by the presence of the ring. generated by the RCE, even at low
In fact, if the disc current is found to rotation rates, are generally quite
change with the ring potential or turbulent. This makes the RCE an ideal
current, one should suspect a probe for studying corrosion processes
defective RRDE or an undesirable under low velocity but turbulent
coupling of the ring and disc through conditions.
the uncompensated solution
resistance. • The ideal goal is to adjust the rotation
rate so that the laboratory fluid flow
• RRDE experiments are usually carried conditions match (or mimic) those
out with a bipotentiostat, which allows found in the field. Once this is
separate adjustment of ED and ER. accomplished, the corrosion process
However, since most RRDE can be monitored by classic mass loss
measurements involve the steady-state methods or by electrochemical
conditions, it is possible to use an methods such as Linear Polarization
ordinary potentiostat to control the IR Resistance (LPR) or Electrochemical
value and a simple floating power Impedance Spectroscopy (EIS).
supply in ID
Rotating ring-disc
electrodes (Fuente: Sung-
Rotating-cylinder
Jai Lee et
electrodes (Fuente: Pine
al,”Fundamentals of
research Instrumentation,
Rotating Disc and Ring–
review 02 march 2006
Disc Electrode”)
SUMMARY

GALVANOSTATIC INTERMITTENT TITRATION TECHNIQUE (GITT)

 Procedure useful to retrieve both thermodynamics and kinetics parameters.

work to positive current pulse and negative.
The diffusion coefficient is calculated by steps

ROTATING-DISC ELECTRODE (RDE)

Allows study the effects convection (the transport of the reactants in the
solution due to the solvent's flow) and difusion (the transport of the reactants
in the solution due to the non-uniform concentration of the reactants as these
are used up)
SUMMARY

ROTATING RING-DISC ELECTRODO (RRDE)

 The current–potential characteristics of the disc are unaffected by the

presence of the ring.
Since two potentials, the disc potential ED and the ring potential ER.
 Two currents, the disc current ID and the ring current IR.
RRDE experiments are usually carried out with a bipotentiostat, which allows
separate adjustment of ED and ER.
RRDE measurements involve the steady-state conditions, it is possible to use
an ordinary potentiostat to control the IR value and a simple floating power
supply in ID.
SUMMARY

ROTATING CYLINDER ELECTRODE (RCE)

This apparatus includes an electrode rotator and a control unit and electrical contact
with the metal cylinder sample.
Immersed and rotated in a test solution, the hydrodynamic conditions generated by
the RCE, even at low rotation rates, are generally quite turbulent.
By adjusting the RCE rotation rate up or down (typically in the range from 200 to
2000 RPM), it is possible to tune the hydrodynamic conditions adjacent to the metal
sample.
The corrosion process can be monitored by classic mass loss methods or by
electrochemical methods such as Linear Polarization Resistance (LPR) or
Electrochemical Impedance Spectroscopy (EIS).
The RCE has a substantially uniform primary and secondary current density
distribution and lends itself to potentiostatic control of mass transfer in turbulent
flow regimes which are developed at low critical Reynold's numbers (Re).
 Lista Bibliográfica
1) Hongji Li et al, “Synthesis and optical properties of single-crystal MgO nanobelts”, Science Direct, Materials letters 102-103
(2013) 80-82.
2) Haskins et al, “Control of Thermal and Electronic Transport in Defect-Engineered Graphene Nanoribbons”, Acsnano, vol 5,
No5, 3779-3787 (2011).
3) Sutradhar et al, “Controlled Synthesis of Different Morphologies of MgO and Their Use as Solid Base Catalysts”, J. Phys.
Chem. C 2011, 115, 12308-12316.
4) Marquardt et al, “Elastic properties of MgO nanocrystals and grain boundaries at high pressures by Brillouin scattering”,
Physical review B 84, 064131, American Physical Society 2011.
5) Selvamani et al, “Rectangular MgO microsheets with strong catalytic activity”, Materials Chemistry and Physics 129 (2011)
853-861.
6) Zhang Y et al, “Structural Features and Electronic Propieties of MgO Nanosheets and Nanobelts”, J. Phys. Chem. C 2012,
116, 23130−23135.
7) Mohammad Vaseem et al, “ZnO Nanoparticles: Growth, Propierties and Applications”, Vol 5, pages 1-36 2010.
8) Wen Chen et al, “ Recent Research situation in Tin dioxide nanomaterials: Microstructures and propierties” , Front. Mater.
Sci. 2013, 7(3): 203–226.
9) Limin Lu et al, “ A MgO Nanoparticles Composite Matrix-Base Electrochemical Biosensor for Hydrogen peroxide with High
Sensitivity”, Electroanalysis 2010, 22, No. 4, 471 – 477.
10) Mastuli et al, “Growth mechanisms of MgO nanocrystals via a sol-gel synthesis using different complexing agents”,
Nanoscale Research Letters 2014, 9:134.