Fundamentals - of - Electrochemical S2020

Energy Storage
Lecture 7:
Fundamentals of Electrochemical Storage
Winter Term 2015/2016
Carsten Agert
NEXT ENERGY
Lectures: last week
Date Lecture
12. Okt. 15 power grids and motivation for storage
19. Okt. 15 (no lecture)
26. Okt. 15 storage for buildings, including heat pump and CHP (Herena)
2. Nov. 15 storage for buildings, including heat pump and CHP (Herena)
9. Nov. 15 compensating RE fluctuations - the transmission grid level
16. Nov. 15 compensating RE fluctuations - the distribution grid level
23. Nov. 15 non-electrochemical electricity storage: overview
30. Nov. 15 fundamentals of electrochemical storage
7. Dez. 15 electrochemical electricity storage devices (except batteries)
14. Dez. 15 batteries: primary cells
4. Jan. 16 batteries: secondary cells
11. Jan. 16 course summary & exam preparation // electric cars (I)
18. Jan. 16 electric cars (II)
25. Jan. 16 exam
only for internal use (storage lecture) Lecture 7: Fundamentals of Electrochemical Storage 2
Categorization of energy storage technologies, option 1:
The kind of energy that is actually stored.
Electricity storage
Mechanical energy Chemical energy Electrical energy

 Capacitors
Potential energy  Batteries
 SMES
 Pumped hydro  Hydrogen
(Superconducting
 Compressed air  Synthetic methane magnetic
energy storage)
Kinetic energy  (Fossil energy carriers)
 Fly wheels  (Biomass)
Categorization of energy storage technologies, option 2:
The application field in the electricity grid.
Quick response (ms) Slow response (min-h)

High power density High energy density
Last week: Storage technologies that are not based on
electrochemistry
Mechanical ES
CAES (compressed air energy storage) Potential energy
PHS (pumped hydro storage) Potential energy
Flywheels Kinetic energy storage
Electrical energy storage

SMES (superconductive magnetic energy storage) Magnetic field
Electrical (and electrochemical) energy storage

Capacitors & Double layer capacitors/super caps) Electrostatic ES
Comparison of the presented technologies
Brief exercise from homework:
Assume a rotating cylinder in a
flywheel application with
m=50kg, f=16000 rpm,
r1 = 30 cm, r2 = 40 cm.
=> energy stored Erot = 2.4 kWh

Lectures
Date Lecture
25. Jan. 16 exam
Fundamentals of batteries
Battery fundamentals and electrochemistry
Manufacturing
Volta‘s crown of cups (~1800)
Volta placed a zinc and a silver plate into

salt-water and noticed a continous flow of
electricity.
Higher voltages were achieved by series
connection.
When trying different metal
combinations, Zn/Ag and Zn/Cu
appeared to be particularly well-suited.
Volta‘s crown of cups (and his “pile”) was
the first current source that could deliver
significant currents over longer times. It
was a real breakthrough for electricity.
Battery Fundamentals: What is the underlying principle?
Thermodynamics drives chemical reactions between so-

called redox couples. Those redox reactions combine an
oxidation (one partner losing an electron) and a
reduction (the other partner gaining an electron).
Exemplary overall reaction: Zn + Cu2+ -> Zn2+ + Cu. When

Zinc is placed in a copper sulfate (CuSO4) solution,
metallic copper will be deposited on the zinc while Zn 2+
goes into solution.
Zinc is being oxidised, copper ions are being reduced.

The redox reaction/electron exchange takes place as
heterogeneous reaction on the Zn surface. The reaction
enthalpy is released as heat.
Thermodynamics drives chemical reactions between so-

called redox couples. Those redox reactions combine an
oxidation (one partner losing an electron) and a
reduction (the other partner gaining an electron).
In a battery, the overall redox reaction is being split

into its two partial reactions, with oxidation and
reduction happening spatially separated.
While the electron moves via an external electrical
circuit, charge equalisation requires ion transport
in an electrolyte (e. g. a salt in solution).
This is the underlying principle of every battery.
It converts chemical directly into electrical energy .
Basic elements of all modern batteries
In principle, all modern batteries follow the same construction principle:
» Two electrodes being in contact with an electrolyte (ion-conductor).

NB: Electronic and ionic conductivity „meet“ at the electrodes.
» A separator inbetween the electrodes in order to avoid direct contact
» The active material (redox couple) as part of the electrodes
» The (negative) electrode, where the oxidation takes place, is called anode.
» The (positive) electrode, where the reduction takes place, is called cathode.
In rechargeable batteries this definition would mean that the electrodes would
change their names while charging. For simplicity, the electrode nomenclature
in batteries always follows the discharge situation.
In brief, a battery is an electrochemical cell that converts chemical energy into

electrical energy.
What are the basic elements of all modern batteries?
negative electrode / anode
positive electrode / cathode
electrolyte
separator
housing

electrical energy.
The anode or negative electrode
provides electrons to the external
circuit and is oxidized during the
electro-chemical (discharge)
reaction. It is generally a metal or
an alloy but e. g. hydrogen is also
used. The anodic process is the
oxidation of the metal to form
metal ions.

electrical energy.
The cathode or positive electrode
(the oxidizing electrode) accepts
electrons from the external circuit
and is reduced during the electro-
chemical (discharge) reaction. It is
usually a metallic oxide or a sulfide
but oxygen is also used. The
cathodic process is the reduction of
the oxide to leave the metal.

electrical energy.
electrolyte
The electrolyte (the ionic conductor)
is the medium for transfer of charge
(ions) inside the cell between the
anode and cathode. The electrolyte
is typically a solvent containing
dissolved chemicals providing ionic
conductivity. It should be an isolator
for electrons to avoid self-discharge
of the cell.

electrical energy.
electrolyte
Separator
The separator electrically isolates
the positive and negative electrodes.
But first of all: The theory behind it
Active materials, redox reactions and the Electrochemical Series
Faraday Law
Kinetic principles (I-V-characteristic)
Electrodes as highly porous three-phase boundary

(active material / electrolyte / electronic conductor)
Exemplary Redox-Couple: Zinc/Hydrogen
Redox-Couple 1: Standard-Hydrogen-Electrode (Ion-/Gas-Electrode)

2H+ + 2e-  H2
This electrode is realised by placing an inert metal such as Pt
in an ion-solution (i. e. an acid) while purging it with the gas.
(Note: The standard-hydrogen-electrode is a reference
electrode with no commercial significance.)
Redox-Couple 2: Zn  Zn2+ + 2e-
In summary: 2H+ + Zn  H2 + Zn2+
The arrangement would normally be

employed for the measurement of
potentials (i. e. no current flow).
(If charge transfer was allowed, the
zinc would be dissolved while
additional hydrogen bubbles emerge.)
The Electrochemical Series
Electrochemical potentials can not be

defined for a single electrode but only
between two different electrodes. The
standard hydrogen electrode is
generally used as reference point.
The smaller the potential, the stronger

is the reducing effect of an active
material (e. g. Lithium);
the higher the potential , the stronger
is the oxidising effect (e. g. Fluorine).
The open circuit voltage of a reaction

can easily be calculated from the table,
e. g. Zn/Cl2: 1.36 V – (-0.76 V) = 2.12 V
Typical active materials / redox couples
Want to oxidize Want to reduce

(lose electrons) (gain electrons)
some common chemicals used for battery electrodes arranged in order of their relative electrode potentials
Faraday‘s law:
Proportionality between „mass and electricity”
Given the nature of the redox reactions, the number of electrons/ions

produced is obviously proportional to the number of involved molecules
of active material. This is described by Faraday‘s law: Q  n  z  F
Q: electric charge, n: amount of active material,

z: number of electrons per molecule, F: Faraday constant (F=96487As/mol)
Example:
A NiCd-battery with a capacity of 1 Ah (3600 As) must contain at least
n  3600 A / 2  96487 As / mol  0.01866mol
of Cd. With 112.4 g/mol for Cd, this gives 2.091 g.
The I-V-characteristic of a battery: Overvoltages
If I = 0, the cell voltage is called “OCV” (open circuit voltage).
When a battery is being charged, the terminal voltage is higher than OCV,
during discharge it is lower than OCV.
The related losses are called “Overvoltages” and have a number of reasons:
» The electrical conductivities of the cell materials are limited.
=> “Ohmic overvoltage”
» Ion-transport/mass transport has a finite velocity.
=> “diffusion overvoltage”
» The electrochemical reactions are associated with an activation energy.
=> “Activation overvoltage”
These phenomena and the resulting I-V-characteristic will be described.

I-V-characteristic: Ohmic losses
The Ohmic overvoltage describes the Ohmic resistances in the battery:

» The resistance of the metallic current collector
» The resistance of the electrolyte
» The resistance of the active/electrode material
Ohmic resistances follow Ohm’s law, i. e. they show a linear behaviour.
The largest contribution stems from the electrolyte.
The resistance of the active material is often a function of the

state-of-charge.
The overall resistance often increases through ageing of the battery:

loss of electrolyte, increasing boundary layer resistances, interface films, etc.
I-V-characteristic: Diffusion Overvoltage
It can be shown that the open circuit voltage of a

battery is a function of the ion concentration at the
electrode (Nernst-Equation).
The reaction at the electrode involves ions. The con-

centration of ions close to the electrode is therefore
either higher or lower compared to the concentration
further away from the electrodes.
The driving force for ion transport is diffusion.

Diffusion is described by Fick’s laws: J   D  c  x  c  t  D  
2
c
x 2
» The diffusion properties determine the related voltage

loss, i. e. the diffusion overvoltage.
I-V-characteristic: Diffusion Overvoltage
Example for diffusion effects:

When starting a car with a weak
Discharge current I: battery (e. g. in winter), the starting
behavior will recover after a
I0 = 0 and I1 < I2 < I3 reasonable pause.
I-V-characteristic: Activation Overvoltage
At the electrode there is a charge transfer between electronic and ionic

conduction.
At zero current density, the related reactions still take place, but have the same
rates, so that their current densities compensate each other. This current
density i0 is the „exchange current density“: an essential parameter of any
electrode.
The fact, that i0 has a finite value, means that any current over the surface of an
electrode will be associated with a voltage loss / overvoltage.
This voltage loss can be described by the semi-empirical so-called Tafel equation:
i
Vact  A  ln 
 i0 
The constant A can be shown as RT/nαF, in which α is a symmetry factor,
T: Temp, F: Faraday, R: gas constant, n: no. of electrons exchanged,
i0: exchange current density.
I-V-characteristic: Activation Overvoltage
i
Vact  A  ln 
 i0 
Example of a fuel cell:

Graph of cell voltage against
current density, assuming losses
are due only to the activation
overvoltage at one electrode, for
three different values of
exchange current density i0.
I-V-characteristic: Resulting discharge behaviour of a battery
Ideal voltage limit

Ohmic Losses
Activiation Losses
Diffusion Losses
Cell potential in equilibrium and including polarization effects

(overvoltages / voltage losses)
On discharge, the potential is always less than thermodynamics
Modified from: Julian Schwenzel, Entwicklung alone predicts. It can be calculated by the equation:
und Charakterisierung von Dünnschicht-Akku-
mulatoren auf Basis von Festkörpermaterialien. Vcell = E – Vohm – Vact – Vdiff with E: rev. OCV
Electrical double layer capacity
A number of effects leads to the formation of a charge

double layer at the electrode/electrolyte interface.
Its static effect is described by the activation over-

voltage. However, the situation also represents an
electrical capacitor and has dynamic consequences.
As a result, the activation overvoltage does not

immediately follow the current, but needs a few
(milli-)seconds to reach its final equilibrium value.
When measuring the resistance at approximately

1000 Hz, diffusion and activation overvoltages usually do
not contribute to the overall voltage loss. Hereby, one
gains direct access to the Ohmic resistance.
Electrodes as highly porous phase boundary
Electrodes are the phase boundary of the

active material, the electronic conductor and
the ion conductor (electrolyte).
All electrochemical reactions take place at the

boundary of the active material and the
electrolyte.
For a small current density (i. e. a small

voltage loss), the surface area must be
maximised (many sqm of surface area per
gramm active material). Therefore the active
material is employed in a highly porous form.
Source of picture:
http://www.organische-chemie.ch/ I. e. about 50% of the volume of an elec-
chemie/2006sep/lithiumbatterien.shtm
trode is filled with the electrolyte.
Electrodes as highly porous phase boundary
The porous active material is usually

deposited on a metallic conductor as
electrical connection to the outside world.
As electrons are created in the active

material, this material must also be an
electron conductor.
Sometimes this is achieved by additives.
During charge and discharge the electrodes

often undergo volume changes. The porous
structure must be able to compensate the
mechanical stress.
Source of picture: D. Sauer, Electrochemical storage systems, Tutorial "Propulsion
systems for hybrid and fuel cell electric vehicles", 12th European Conference on
Power Electronics and Applications, Aalborg, 02.09.2007
Different electrode structures in commercial batteries
Bobbin Electrodes Flat Plate Electrodes
Spiral Wound Electrodes (Also called Jelly- Stacked Electrodes

roll or Swiss-roll construction)
The classification of cell casings for primary batteries
Cylindrical Cells Multi-cell Batteries Thin film battery
Button Cells and Coin Cells Prismatic Cells Pouch Cells
Classification of batteries
Primary battery
In primary cells the electrochemical reaction is not reversible. During
discharging the chemical compounds are permanently changed and
electrical energy is released until the original compounds are completely
exhausted. Thus the cells can be used only once.
Secondary battery (rechargeable battery)

In secondary cells the electrochemical reaction is reversible and the original
chemical compounds can be reconstituted by the application of an electrical
potential between the electrodes injecting energy into the cell. Such cells can be
discharged and recharged many times.
Classification of batteries
Zn/MnO2 battery
Alkaline manganese battery
Primary Battery Zn/Ag2O battery
Zn/Air battery
(Non-rechargeable) Li primary batteries
electrical energy
Others
Chemical Batteries
chemical energy
Lead-Acid battery
Ni-Cd battery
Secondary Battery Ni-MH battery
(Rechargeable) Li-ion battery
High-temperature secondary battery
Others
Some Definitions and Terms: Voltage and Capacity
OCV is the voltage difference

between the anode and cathode
Working voltage is the current.
without actual cell voltage between
two electrodes in the discharge processes.
Open circuit voltage Final
(OCV) discharge voltage is the voltage at which
the battery's discharge limit is reached.
Working voltage
Voltage Final charge voltage is the voltage at which the
Final discharge voltage battery's charge limit is reached.
Final charge voltage
Capacity is the amount of electrical energy that can be
supplied by a battery or cell, expressed in mAh, and in
specified discharge conditions, which can be defined as the
product of the discharge current and the discharge time.
Theoretical
Example: A battery with a capacity of 1200 mAh (= 1.2 Ah) capacity of the battery is the maximum battery capacity and
can provide a current of 1.2 A during 1 hour. only depends on the theoretical capacity of the electrode materials. It
can be estimated by using Faraday’s
Nominal dischargelaw.
capacity is rated at
Specific capacity 0.2C
is the(see
capacity that can limited
C-rate) to the be discharge
derived per unit weight
voltage. of the cell or per unit
Theoretical capacity weight of the active electrode material.
Capacity Nominal discharge capacity

Specific capacity
Some more Definitions and Terms: Charge and Discharge
Charge is the process that stores the energy of an Charge current is the current a battery requires to be
electrical current into a battery. fully recharged within a specific time.
Charge Charge current Discharge current is the current a battery can

deliver during a specified time. Usually the
Discharge is the process that converts the stored energy discharge current is specific for 5 hours.
from a battery into an electrical current.
Discharge current Self discharge is the loss of

capacity over time of a battery
Discharge Self discharge when it is unused.
Discharge Curve
The discharge curve is a plot of voltage against

percentage of capacity discharged. A flat discharge
curve is desirable as this means that the voltage
remains constant as the battery is used up.
Even more Definitions and Terms
Energy density
The energy density is the energy that can be derived per unit volume or
weight of the cell (Wh/Kg or Wh/L).
Power density
The power density is the power that can be derived per unit weight or unit
volume of the cell (W/kg).
Cell resistance
The cell resistance is the internal resistance of a battery. It is composed of the
Ohmic resistance (RΩ) and the electrochemical overpotential resistance (Rf).
C-rate
The proportion the current (mA) bears to the nominal capacity (mAh).
Example: A 3C battery with a capacity of 1000mAh can deliver a current of 3 A.
Manufacturing a battery
(example: Li-Ion)
Electrode architecture and requirements
Requirements:
High electronic and ionic conductivity
Mechanical stability
Chemical stability
High surface area

Active material 85-90%
High gravimetric capacity

Binder 5-10%
Conductive additives 5-10%
Current collector
Electrode manufacture on lab scale
Slurry preparation Pretreatment of the Collector Casting
http://www.clipartguide.com
Compressing Drying
Cell assembly
Cell production chain
Anode
Separator Stacking/Winding
Cathode
Addition of
Electrolyte and Casing and
Case Sealing in Dry Assembly
Room conditions
Scource: www.gm-volt.com
Formation
Video on cell and battery manufacturing (example: Li-Ion technology)
Lectures
Date Lecture
25. Jan. 16 exam

Fundamentals - of - Electrochemical S2020

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Energy Storage

Mechanical energy Chemical energy Electrical energy

 Fly wheels  (Biomass)

Quick response (ms) Slow response (min-h)

Electrical energy storage

Electrical (and electrochemical) energy storage

Comparison of the presented technologies

=> energy stored Erot = 2.4 kWh

Battery fundamentals and electrochemistry

Volta placed a zinc and a silver plate into

Thermodynamics drives chemical reactions between so-

Exemplary overall reaction: Zn + Cu2+ -> Zn2+ + Cu. When

Zinc is being oxidised, copper ions are being reduced.

Thermodynamics drives chemical reactions between so-

In a battery, the overall redox reaction is being split

In principle, all modern batteries follow the same construction principle:

» Two electrodes being in contact with an electrolyte (ion-conductor).

In brief, a battery is an electrochemical cell that converts chemical energy into

In brief, a battery is an electrochemical cell that converts chemical energy into

In brief, a battery is an electrochemical cell that converts chemical energy into

In brief, a battery is an electrochemical cell that converts chemical energy into

In brief, a battery is an electrochemical cell that converts chemical energy into

Active materials, redox reactions and the Electrochemical Series

Kinetic principles (I-V-characteristic)

Electrodes as highly porous three-phase boundary

Redox-Couple 1: Standard-Hydrogen-Electrode (Ion-/Gas-Electrode)

Redox-Couple 2: Zn  Zn2+ + 2e-

In summary: 2H+ + Zn  H2 + Zn2+

The arrangement would normally be

Electrochemical potentials can not be

The smaller the potential, the stronger

The open circuit voltage of a reaction

Want to oxidize Want to reduce

Given the nature of the redox reactions, the number of electrons/ions

Q: electric charge, n: amount of active material,

If I = 0, the cell voltage is called “OCV” (open circuit voltage).

These phenomena and the resulting I-V-characteristic will be described.

The Ohmic overvoltage describes the Ohmic resistances in the battery:

Ohmic resistances follow Ohm’s law, i. e. they show a linear behaviour.

The largest contribution stems from the electrolyte.

The resistance of the active material is often a function of the

The overall resistance often increases through ageing of the battery:

It can be shown that the open circuit voltage of a

The reaction at the electrode involves ions. The con-

The driving force for ion transport is diffusion.

» The diffusion properties determine the related voltage

Example for diffusion effects:

At the electrode there is a charge transfer between electronic and ionic

Example of a fuel cell:

Ideal voltage limit

Cell potential in equilibrium and including polarization effects

A number of effects leads to the formation of a charge

Its static effect is described by the activation over-

As a result, the activation overvoltage does not

When measuring the resistance at approximately

Electrodes are the phase boundary of the

All electrochemical reactions take place at the

For a small current density (i. e. a small

The porous active material is usually

As electrons are created in the active

During charge and discharge the electrodes

Bobbin Electrodes Flat Plate Electrodes

Spiral Wound Electrodes (Also called Jelly- Stacked Electrodes