Beruflich Dokumente
Kultur Dokumente
Lecture
Winter Term 2017/18
Introduction
Basic Reactions
Side Reactions
VRLA (Valve-Regulated Lead-Acid Battery)
Electrolyte
Ageing Mechanisms
Voltage, Energy, Power
Grid and Plate Design
Cell and Battery Design
Recommendations for Usage
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180111 | University of Ulm | EST-III | LAB | MW
Lead Acid Battery Development
The LAB’s history dates back to 1789, with its birthdate being debated being
either 1854 or 1859.
1854 1859 1973 Today
W.J. Sinsteden G. Planté F&E world record 40 Wh/kg
0.1 Wh/kg 9 Wh/kg Japan Storage 200 W/kg
70.5 Wh/kg 500 cycles (SFUDS*)
100 cycles Charging time
50% in 5 min
80% in 15 min
150 USD/kWh
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Lead Acid Battery Development
Milestones
2000 Lead acid batteries ready to power the global communication highways.
1990 Lead acid batteries power the cellular telephone revolution.
1980 Stationary VRLA batteries based on AGM technology are developed.
1968 The maintenance free SLI battery is developed.
1965 Polypropylene SLI battery cases start to be used.
1958 Jache describes the gel VRLA battery.
1951 Lead calcium alloys are used in telephone exchange stationary lead acid batteries.
1918 Shimadzu describes the ball mill oxide.
1915 Willard introduces rubber separators.
1910 The iron-clad or tubular plate construction is introduced.
1907 A lead calcium alloy is patented.
1904 Red cedar wood is used as battery separator.
1882 Gladstone and Tribe describe the so called double-sulfate theory i.e. the basis of
operation of the lead acid battery. Tudor operates a lead acid battery factory in
Luxembourg.
1881 Faure discovers the pasted plate which yields a mayor breakthrough in capacity. A
lead antimony alloy is used the first time to give strength.
1859 Planté improves the capacity of the lead acid batteries with a technique still in use
today (Planté type plates).
1854 Sinsteden uses for the first time lead plates in sulfuric acid to store, i.e. accumulate,
electricity
1800 Volta demonstrates to Napoleon the Volta pile, a primary, non rechargeable battery.
1789 Galvani carries out his frog leg experiments.
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General Properties
Pros:
High cell voltage (~ 2 V)
High safety at normal and at abuse conditions
Long calendar life is possible in certain conditions (especially in charge sustaining
mode)
Good power (100 – 200 W/kg, high-power LAB up to 1000 W/kg for short periods)
Large system variety: sizes from 12 V, 0.5 Ah for camcorder batteries all the way up to
2 V 12.000 Ah for submarine battery cells.
Good recycleability, since all components are rich in Pb
Low costs (from 50 €/kWh)
Cons:
Low specific energy (25 Wh/kg for stationary LAB to 45 Wh/kg for SLI LAB)
Low cycle life for heavy cyclic duty
Limited storage times
Ventilation of storage room is required, since H2 and O2 may evolve
Self discharge (approx. 3% per month at 20°C)
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180111 | University of Ulm | EST-III | LAB | MW
Types of Lead Acid Batteries
By Basic Design
Continuous improvements:
• Low maintenance
• No maintenance Absorbant glass mat Gel-Type
(AGM) • Electrolyte immobilisation
• Electrolyte immobilisation as silica gel
in glass microfibre fleece
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180111 | University of Ulm | EST-III | LAB | MW
Types of Lead Acid Batteries
By Application
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180111 | University of Ulm | EST-III | LAB | MW
Contents
Introduction
Basic Reactions
Side Reactions
VRLA (Valve-Regulated Lead-Acid Battery)
Electrolyte
Ageing Mechanisms
Voltage, Energy, Power
Grid and Plate Design
Cell and Battery Design
Recommendations for Usage
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180111 | University of Ulm | EST-III | LAB | MW
Basic Reactions
discharge
Cell reaction:
Pb + PbO2 + 2SO42– + 4H+ 2PbSO4 + 2H2O
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Basic Reactions
discharge
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Electrode Potentials and Nominal Cell Voltage
4
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Electrode
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180111 | University of Ulm | EST-III | LAB | MW
Contents
Introduction
Basic Reactions
Side Reactions
VRLA (Valve-Regulated Lead-Acid Battery)
Electrolyte
Ageing Mechanisms
Voltage, Energy, Power
Grid and Plate Design
Cell and Battery Design
Recommendations for Usage
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180111 | University of Ulm | EST-III | LAB | MW
Side Reactions
Grid (Pb)
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180111 | University of Ulm | EST-III | LAB | MW
Gas Formation Reactions
U / V vs. SHE
Pourbaix diagramme
(potential vs. pH)
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180111 | University of Ulm | EST-III | LAB | MW
Potentials and Kinetics of Side Reactions
Flooded
VRLA
Equilibrium potentials (dependent
on acid concentration)
Basic charge / discharge reactions of Pb and PbO2: fast kinetics (high current rates even at small deviations from
equilibrium potentials)
O2 and H2 evolution: high overvoltages required: low current rates at normal conditions, gradual current increase with
electrode polarisation (especially important at overcharge conditions)
Oxygen recombination (oxygen reduction): „limiting current“ (reaction rate is determined by rate of oxygen diffusion from
positive to negative electrode) D. Berndt, „Valve-Regulated Lead-Acid Batteries“; J. Power Sources 100 (2001) 29.
P.T. Moseley, D.A.J. Rand, in „Valve Regulated Lead-Acid Batteries“, Elsevier, 2004; (Fig. 1.5).
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180111 | University of Ulm | EST-III | LAB | MW
Contents
Introduction
Basic Reactions
Side Reactions
VRLA (Valve-Regulated Lead-Acid Battery)
Electrolyte
Ageing Mechanisms
Voltage, Energy, Power
Grid and Plate Design
Cell and Battery Design
Recommendations for Usage
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180111 | University of Ulm | EST-III | LAB | MW
Working Principle of VRLA
Oxygen Recombination
gas channels
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Immobilised Electrolyte in VRLA
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180111 | University of Ulm | EST-III | LAB | MW
VRLA
Recombination does not work with 100% efficiency, therefore slowly gas
pressure builds up; if pressure becomes too high (approx. 100 - 150 mbar
overpressure) gas is released by short opening of valve ( valve-regulated
LAB)
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180111 | University of Ulm | EST-III | LAB | MW
Working Potential Ranges
Flooded
VRLA
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180111 | University of Ulm | EST-III | LAB | MW
VRLA – Where the Name Comes from …
Resealable Valve
Resealable valve
1: Sealing edge
2: Synthetic-rubber plate
3: Spring
4: Flame-resistant porous
disc
5: O-ring gasket
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180111 | University of Ulm | EST-III | LAB | MW
Comparison of Gel and AGM-Technology
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180111 | University of Ulm | EST-III | LAB | MW
Contents
Introduction
Basic Reactions
Side Reactions
VRLA (Valve-Regulated Lead-Acid Battery)
Electrolyte
Ageing Mechanisms
Voltage, Energy, Power
Grid and Plate Design
Cell and Battery Design
Recommendations for Usage
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180111 | University of Ulm | EST-III | LAB | MW
Electrolyte
Dilute H2SO4
Working concentrations:
Flooded LAB: charged 1.24 – 1.28 g/cm3 (33 – 37%, 4.2 – 4.8 M)
discharged: ~ 1.1 g/cm3 (~ 15%, ~ 1.6 M)
VRLA: charged 1.30 – 1.32 g/cm3 (40 – 42%, 5.2 – 5.5 M)
discharged: 1.05 – 1.1 g/cm3 (8 – 15%, 0.85 – 1.6 M)
Acid acts as active material, i.e. battery capacity determines minimum amount of
electrolyte which is required
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180111 | University of Ulm | EST-III | LAB | MW
Dilute H2SO4
Concentration Conversion Table
Concentration Density Concentration Concentration Refractive Relative
Wt.% g/cm3 g/L mol/L index viscosity
A. Jossen, W. Weydanz: Moderne Akkumulatoren richtig einsetzen; Leipheim and Munich (Germany), 2006.
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Electrolyte Conductivity
as Function of Concentration and Temperature
Conductivity / -1cm-1
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Open Circuit Voltage (OCV)
as Function of Acid Density
OCV according to
Nernst equation
Linear approximation
A. Jossen, W. Weydanz: Moderne Akkumulatoren richtig einsetzen; Leipheim and Munich (Germany), 2006.
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180111 | University of Ulm | EST-III | LAB | MW
Freezing Point
as Function of Electrolyte Density
In fully discharged state freezing point lies around -10°C.
Freezing point / °C Risk of freezing in winter!
VRLA
(SOC = state of charge)
A. Jossen, W. Weydanz: Moderne Akkumulatoren richtig einsetzen; Leipheim and Munich (Germany), 2006.
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180111 | University of Ulm | EST-III | LAB | MW
Low Temperature Performance of SLI Batteries
Engine
load
Battery
capacity
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180111 | University of Ulm | EST-III | LAB | MW
Contents
Introduction
Basic Reactions
Side Reactions
VRLA (Valve-Regulated Lead-Acid Battery)
Electrolyte
Ageing Mechanisms
Voltage, Energy, Power
Grid and Plate Design
Cell and Battery Design
Recommendations for Usage
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180111 | University of Ulm | EST-III | LAB | MW
Ageing Mechanisms
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180111 | University of Ulm | EST-III | LAB | MW
Sulfation during Storage in Discharged State
recrystallisation
Same volume
Half surface area
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Sulfation During HRPSoC Operation
At high rates negative electrode tends to form a dense PbSO4 layer at the surface, which
prevents complete discharge and results in increased electrode polarisation
• During discharge Pb reacts with sulfuric acid to give PbSO4
• At low rates sulfuric acid which is consumed in electrode bulk can be replenished by diffusion from
electrolyte bulk into electrode. Electrode is homogeneously discharged.
• At high rates sulfuric acid is consumed faster in electrode bulk than it can diffuse into the electrode.
Discharge reaction is concentrated on the surface. Dense PbSO4 layer at surface impedes diffusion of
sulfuric acid even more.
• During following charge electrode potential becomes more negative and hydrogen evolution
increases.
Low rate discharge High rate discharge Recharge following a high rate discharge
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180111 | University of Ulm | EST-III | LAB | MW
D.A.J. Rand, P.T. Moseley: Lead Acid Systems Overview, in J. Garche (ed.): Encycl. of Electrochem. Power Sources, Elsevier, Amsterdam, 2009, Vol. 4, p. 550.
Sulfation – Counter Measures
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180111 | University of Ulm | EST-III | LAB | MW
UltraBattery
by SCIRO / Furukawa Batteries
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Acid Stratification
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Acid Stratification
Accelerated ageing
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Contents
Introduction
Basic Reactions
Side Reactions
VRLA (Valve-Regulated Lead-Acid Battery)
Electrolyte
Ageing Mechanisms
Voltage, Energy, Power
Grid and Plate Design
Cell and Battery Design
Recommendations for Usage
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180111 | University of Ulm | EST-III | LAB | MW
Typical Discharge Voltage Curve
Spannungssack: due to
crystal nucleation, only
for fully charged cells Rapid voltage decrease due to
consumption of reactants and
Normal operation region: quasi-linear further increase of internal
voltage decrease (due to OCV decrease resistance
and increase of internal resistance)
Voltage / V
Time / h
A. Jossen, W. Weydanz: Moderne Akkumulatoren richtig einsetzen; Leipheim and Munich (Germany), 2006.
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Rate Capability
n = Peukert parameter
Discharge time / h
High power LAB
(n = 1.12)
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180111 | University of Ulm | EST-III | LAB | MW
Rate Capability and Peukert’s Law
Ideal battery:
Discharge time / h
Discharge time scales linearly with current. High power LAB
(n = 1.12)
(I.e. double current means half discharge time.)
167 Wh/kg
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180111 | University of Ulm | EST-III | LAB | MW
Contents
Introduction
Basic Reactions
Side Reactions
VRLA (Valve-Regulated Lead-Acid Battery)
Electrolyte
Ageing Mechanisms
Voltage, Energy, Power
Grid and Plate Design
Cell and Battery Design
Recommendations for Usage
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180111 | University of Ulm | EST-III | LAB | MW
Plate Types
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180111 | University of Ulm | EST-III | LAB | MW
Plate Types
Grid Plates
Use:
● Both as negative and positive plate
Design:
● Casted grids or expanded metal grids
● Low cost, high rate capability, lower cycle life as
active material is not well fixed
Manufacture:
● Grid plate made by casting (gravity casting or
injection molding).
● Flat pasted plates, some-times in combination
http://www.tpub.com/content/doe/hdbk with tubular grids, are standard in most
1084/ (last access 01/2011): application.
● Cast grids increasingly substituted by expanded
wrought grids (mainly for negative electrode).
● Very thin grids (pure Pb) are used for spirally
wound cells.
Applications:
● SLI batteries, automotive, marine, industrial
trucks, light duty traction, emergency back-up
systems
D. Pavlov: Lead-Acid Batteries, Elsevier, Amsterdam, 2011, p. 203.
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180111 | University of Ulm | EST-III | LAB | MW
Plate Types
Grid Plates
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180111 | University of Ulm | EST-III | LAB | MW
AM Utilisation as Function of Current Collector Shape
[%] D A C
16
80
8
C 3.87g Pb = 1 Ah
60
conventional tubular
40 B
A
B 1 D
0,1
0,2
20
1 2 3 4 5 6
Average electron path way [mm] Expanded metal fibres
Increasing utilisation of active mass (AM) with P. Faber, in Power Sources 4, Proceedings of the 8th
International Symposium held at Brighton, Sept. 1972, pg.
decreasing length of electron path way (in AM) 525 – 540. D. H. Collins, ed., Oriel Press, 1973
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180111 | University of Ulm | EST-III | LAB | MW
Plate Types
Tubular Plates
Use:
Especially for positive plates (in combination
with conventional negative plates)
Design:
Metal tab surrounded by active material and
contained in cloth tube or separator tube
Round shapes prefered in flooded LAB
Rectangular shapes prefered for VRLA, due to
better contact with immobilised electrolyte layer
Manufacture:
Grid made by casting or injection-molding of
http://www.tpub.com/content/doe/hdbk1084/ (last access 01/2011): spines attached to a connector bus and lug.
Fiber glass sheaths or multi-tube gauntlets are
placed over the spines and filled with mass
powder or slurry.
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180111 | University of Ulm | EST-III | LAB | MW
Plate Types
Planté Type Plates
Design:
Large surface area
Manufacture:
Made by crimping or rolling lead strips into
rosettes inserted in holes of cast plates, or by
cutting grooves into lead plates, and
electrolytical formation.
Applications:
Simple design and production, poor capacity,
high reliability, long life during float duties
Standby emergency power, load levelling,
telephone exchange, signaling, uninterruptible
power systems (UPS), …
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180111 | University of Ulm | EST-III | LAB | MW
Plate Manufacturing
+ H2SO4
+ O2 Paste
“Leady oxide” + additives “Basic lead sulfates”
Pb ingot
(ball mill or (PbO + Pb) (= xPbO•PbSO4•yH2O)
furnace) + PbO + Pb + H2SO4
may be added to
“Red lead oxide” positive electrode paste
Pb3O4
Curing
Pasting Flash drying at controlled temperature and humidity
Cured plate
onto Pb grid → Formation of hard porous mass (“skeleton”)
from paste particles
→ Oxidation of residual Pb
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Electrode Additives
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Contents
Introduction
Basic Reactions
Side Reactions
VRLA (Valve-Regulated Lead-Acid Battery)
Electrolyte
Ageing Mechanisms
Voltage, Energy, Power
Grid and Plate Design
Cell and Battery Design
Recommendations for Usage
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Separators
Requirements: Materials:
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Battery Housings
Materials:
Mainly polymers: PP, polycarbonate, styrene-acrylonitrile (SAN) copolymer,
acrylonitrile-butadiene-styrene copolymer
Polycarbonate and SAN are transparent and allow visual control of acid level
(flooded battery)
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180111 | University of Ulm | EST-III | LAB | MW
Components of Flooded LAB and VRLA
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180111 | University of Ulm | EST-III | LAB | MW
Plate Sets in Stacked Cells
+ −
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Stacked Plate-Design (SLI, Start-Stop)
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180111 | University of Ulm | EST-III | LAB | MW
Stacked Plate-Design
Maintenance-Free SLI Type
State-of-the-art SLI
Source:http://www.tpub.com/content/doe/hdbk1084/
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180111 | University of Ulm | EST-III | LAB | MW
Comparison of Typical SLI Batteries
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180111 | University of Ulm | EST-III | LAB | MW
Gel-Type VRLA
(Hagen Drysafe)
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Cyclindrical AGM-VRLA
Thin Plate Spiral Wound Design (EXIDE)
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Cyclindrical Lead Acid Battery
Thin Plate Spirally Wound Design - OPTIMA 24 Ah/36V
Weight, kg 25
Impedance, mOhm (1 kHz @ 23 C) 14.6
DC Resistance, mOhm (400 A @ 23 C) 23.2
Reserve Capacity, Ah 18
C/20 Capacity, Ah 24
CCA, A (30 s @ 0F, > 21.6 V) 350
Maximum Continuous Discharge, A (25 C) 300
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Bipolar Designs
?
e e
- -
? e Partition wall Positive ?
e -
- Active
?
Paste
Negative
Active
Paste
? ?
e- e- ?
Separator
2 + 2
V V
Monopolar 4 V Bipolar 4 V Pseudo-bipolar 4 V
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180111 | University of Ulm | EST-III | LAB | MW
Bipolar Battery
(Effpower)
Effpower
Hybrid Battery
12 V
Width 230 mm
Height 167 mm
Length 118 mm
Weight 3,9 kg
W/Kg 800
Source: EffPower
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180111 | University of Ulm | EST-III | LAB | MW
Contents
Introduction
Basic Reactions
Side Reactions
VRLA (Valve-Regulated Lead-Acid Battery)
Electrolyte
Ageing Mechanisms
Voltage, Energy, Power
Grid and Plate Design
Cell and Battery Design
Recommendations for Usage
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180111 | University of Ulm | EST-III | LAB | MW
Recommendations for Usage
Long Life:
Discharge LAB only as far as needed, avoid deep discharge
Do not fully discharge LAB before recharging
Recharge LAB as soon as possible after discharge
If LAB is used in a cyclic duty around a middle state of charge (PSoC, partial
state of charge), fully recharge LAB regularly (at least once a month)
The lower the temperature the higher the calendar life, but below -5°C risk of
freezing
Storage: in fully charged state at low temperature (< 25°C), recharge battery
regularly (every 3 to 6 months)
Safety:
Ventilate rooms with lead acid batteries (H2 and O2 evolution!)
Avoid sparks and flames near lead acid batteries (H2 and O2 evolution!)
LAB must be recycled
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Further Reading
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Acknowledgements
Parts of this lecture are based on a lecture by Andreas Jossen (TU München).
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Thank you for your attention!
mario.wachtler@zsw-bw.de
www.zsw-bw.de