Electrochemical Methods

Zenobi Group
Department of Chemistry and Applied Biosciences
https://zenobi.ethz.ch/ 24/09/2020
Electrochemical methods
Dr. Stamatios Giannoukos

1
Electrochemistry
The relationship between chemical reactions and electricity
Ø Certain chemical reactions can produce electricity, e.g. in a battery
Ø Electricity can make certain chemical reactions (that would NOT happen
otherwise) happen
Electricity: movement of electrons e- e- e- e-
e-
Chemical reactions: oxidation reduction
reactions à electrons move between atoms A B
2
Electrochemistry
e-
A B A e- e- B
wire
e-
X X pull push
C D C e- Battery e- D
3
Electrochemical techniques
Techniques in analytical chemistry that measure potential, charge, or current to:
a) determine an analyte's concentration or

b) characterize an analyte's chemical reactivity
Ø Provide qualitative and quantitative analysis
Bulk à measurement of a property of the solution in an electrochemical cell,
e.g. solution conductivity (proportional to the Ctotal of dissolved ions)
Interfacial à potential, charge, or current depend on the interface between a

solution and an electrode
e.g. determination of the pH using a pH electrode
4
Interfacial electrochemical techniques
5
1. Potentiometry
• Measures the potential of an electrochemical cell.
• The potential is then related to the concentration of one or more analytes.
• Selective sensitive to the ion of interest electrodes.
• e.g. glass-membrane electrode in a pH meter.
Zn(s)+2Ag+(aq)⇋2Ag(s)+Zn2+(aq)
6
2. Voltammetry
• Measures the current as a function of a
fixed or variable potential.
• In voltammetry, a time-dependent
potential is applied to an electrochemical
cell and we measure the resulting current
with a 3 electrode system as a function of
that potential.
Types of voltammetry (rep. examples)
linear staircase cyclic

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2. Cyclic Voltammetry
SV = Sisal-like V2O5
BV = bulk V2O5
Cyclic voltammetry of the SV and BV electrodes at a scanning rate of 0.1 mV s−1

between 2.0 and 4.0 V (vs Li/Li+); (c) Nyquist plots of the BV and SV electrodes
after 400 cycles (inset showing the equivalent circuit for the Nyquist plots); and (d)
XRD patterns of BV and SV electrodes after 400 cycles at 1 C. 8
3. Coulometry
• Measures an unknown concentration of an analyte in solution by completely
converting the analyte from one oxidation state to another.
• It is based on an the exhaustive electrolysis of the analyte.
• Forms of coulometry:
i. controlled-potential à a constant potential is applied to the electrochemical cell,
ii. controlled-current à a constant current pass through the electrochemical cell.
During the electrolysis, the total charge Q passing through the electrochemical cell
is proportional to the absolute amount of analyte:
Faraday law: Q = nFNA
n is the number of electrons per mole of analyte,

F is Faraday’s constant (96487 C mol–1),
NA is the moles of analyte
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4. Conductometry
• Conductometry à measurement of the electrolytic conductivity to monitor the
progress of a chemical reaction.
Conductivity of an electrolyte solution is a measure of its ability to conduct

electricity.
It is measured by determining the resistance of the solution between two flat or

cylindrical electrodes separated by a fixed distance.
Example à Conductometric titration in which the electrolytic conductivity of a

reaction mixture is continuously monitored as one reactant is added.
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5. Dielectrometry
• Measures the dielectric constant (or relative permittivity) of a substance resulting
from the orientation of particles (molecules or ions) that have a dipole moment in
an electric field.
• It is the absolute permittivity expressed as a ratio relative to the vacuum

permittivity.
• Used to monitor the purity of dielectrics, e.g. detection of small amounts of

moisture, as an epoxy adhesive cure monitoring method, to identify
pharmaceutical ingredients, etc.
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6. X-Ray Diffraction
v Operando XRD, both
reflection and
transmission modes, can
be used to monitor the
crystal structure of
electrode material
v Special sources
(synchrotron) and special
window materials (Be)
may be necessary
v change and phase
transitions of electrodes
during the electrochemical
process
XRD spectra collected during the first

galvanostatic cycle between 4.0 and 2.9 V.
T:LiFePO4; H:FePO4; *: cell package
7. Raman Spectroscopy
v Vibrational spectroscopy
v Molecular Analysis, works
for analyzing solids
(phonons)
v Works in aqueous
environments
v Operando spectroscopy
LiNi0.33Co0.33Mn0.33O2
8. FTIR Spectroscopy
v Vibrational spectroscopy
v Molecular Analysis, works for
analyzing solids (phonons)
v Aqueous environments:
problematic => special cells
FTIR Spectroscopy / ATR
9. ICP-MS
v Elemental analysis
v Suitable for trace detection
v Can analyze the electrolyte
v Can analyze the solid (sample
preparation = acid digestion)
10. Scanning Electron Microscopy
v High-resolution imaging
method, down to the nm
range
v Elemental analysis with EDX
possible
v Works in vacuum
v Operando / in-situ EM only
with very special cells possible
SEM images of double-shelled

LiNi0.5Co0.2Mn0.3O2 prepared at (a) 800 oC,
(c) 850 oC, (e) 900 oC and normal
LiNi0.5Co0.2Mn0.3O2 at (b) 800 oC, (d) 850
oC, (f) 900 oC..
Transmission Electron Microscopy
v Extremely high resolution method

(atomic resolution) – very small
part of the sample analyzed
v Analysis of various phases
v Pinpoints defects
v ED allows local order
to be established
v Expensive
HRTEM image of phase boundary (marked by red arrows)

between LiFePO4 and FePO4 (= charging end product) along
the [010] direction during lithiation; time = 0 s. (c) At 176 s,
SAED
the thickness of LFP layer increased. (d) Inverse fast Fourier
transform (IFFT) image of (b), showing the distribution of pattern in
dislocations near the phase boundary. LiFePO4
Operando TEM ?
Liquid-cell configuration with battery relevant

liquid electrolyte: Li metal counter electrode,
Si nanowire, and silicon nitride membranes are
deposited on a Si chip.

Electrochemical Methods

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Zenobi Group

Department of Chemistry and Applied Biosciences

Dr. Stamatios Giannoukos

Ø Certain chemical reactions can produce electricity, e.g. in a battery

Electricity: movement of electrons e- e- e- e-

a) determine an analyte's concentration or

Ø Provide qualitative and quantitative analysis

Bulk à measurement of a property of the solution in an electrochemical cell,

e.g. solution conductivity (proportional to the Ctotal of dissolved ions)

Interfacial à potential, charge, or current depend on the interface between a

e.g. determination of the pH using a pH electrode

• The potential is then related to the concentration of one or more analytes.

• Selective sensitive to the ion of interest electrodes.

• e.g. glass-membrane electrode in a pH meter.

Types of voltammetry (rep. examples)

linear staircase cyclic

Cyclic voltammetry of the SV and BV electrodes at a scanning rate of 0.1 mV s−1

• It is based on an the exhaustive electrolysis of the analyte.

Faraday law: Q = nFNA

n is the number of electrons per mole of analyte,

Conductivity of an electrolyte solution is a measure of its ability to conduct

It is measured by determining the resistance of the solution between two flat or

Example à Conductometric titration in which the electrolytic conductivity of a

• It is the absolute permittivity expressed as a ratio relative to the vacuum

• Used to monitor the purity of dielectrics, e.g. detection of small amounts of

XRD spectra collected during the first

SEM images of double-shelled

v Extremely high resolution method

HRTEM image of phase boundary (marked by red arrows)

Liquid-cell configuration with battery relevant

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