BATTERIES AS ENABLER FOR ELECTRIFICATION OF
MOBILITY – DEVELOPMENT TRENDS OF MATERIALS
AND SYSTEMS
10/10/2019
EGBERT FIGGEMEIER
HELMHOLTZ INSTITUTE MÜNSTER (HI MS), IEK-12 & ISEA, RWTH AACHEN UNIVERSITY
WHY THE HYPE ABOUT BATTERIES?Batteries connect industries
Quelle Frankfurter Allgemeine Zeitung 2018. :https://www.faz.net/aktuell/wirtschaft/schneller-schlau/schneller-schlau-woher-kommt-deutsches-oel-her-
infografik-15914568.html
Seite 225.10.2019
Crude Oil Supply Germany 2018
Convergency of Energy Supply andMobility
BATTERY TECHNOLOGIES
• 1780: Luigi Galvani – Frog legs react when in touch with Cu and Fe
• 1799-1800: Volta pile by Alessandro Volta
• 1859: Invention of the rechargeable lead acid battery
• 1866: Leclanche Zelle (Zn/MnO2)
• 1899: Invention of the nickel-cadmium battery
• 1901: Invention of the nickel-iron battery
• 1990: First commercialization of nickel-metal hydride battery
• 1991: First commercialization of Lithium-ion battery by Sony
Look at the time frames of battery developments!!!
It´s a long story…..
….and the Nobel-price 2019…
BATTERY TECHNOLOGIES
LITHIUM-IONEN-BATTERIEN
TRENDS
Seite 525.10.2019
THE BATTERY INDUSTRY - TRENDS´Technology Switch in Automotive Industry at ….not behind…the Horizon
Source: Avicienne Energy, 2017
Seite 625.10.2019
• Larger numbers, faster assembly
• Cost is key for automotive applications!
• Cell price for OEMs at100 €/kWh
• Trend to larger cells (bis 150 Ah)….?
Speciality Commodity
THE BATTERY INDUSTRY - TRENDSFast growth – even accelerating
Source: Avicenne Energy 2018
Seite 725.10.2019
• And expected CAGR til 2025: 17 %.
• 520 GWh market in 2025
• > 500 Billion€ marketin 2025
THE BATTERY INDUSTRY – TRENDSExciting times……
Quelle: Clayton M. Christensen, „The Innovator´s Dilemma“, Harper Business, 2000.
Seite 825.10.2019
1. Technology – „Combustion Engines“
2. Technology – „Battery Electric Vehicles“
Time and/or Engineering Effort
Pro
duct
Perf
orm
ance We are here!
LITHIUM ION BATTERIESCustomer Expecations….????
Seite 925.10.2019
MarketM
iles p
er
hour
120
Market
Market
Mile
s
Seconds
2010 2015
2010 2015
2010 2015
300
10Customer segment decides!
Market
Range vs Costs
100 €/kWh
2010 2015
Driving Range
Top Speed
Acceleration
Price
SWITCH OF TECHNOLOGYReaching Maturity for Mass Market
Source: Volkswagen AG
Seite 1025.10.2019
Modular Electric Building Block (MEB)
e.g. for VW I.D.VW Golf – Internal Combustion Engine
22 kWh120 km
36 kWh>200 km
50 kWh>300 km
At same costs and price!
2014 2017 2020
THE BATTERY INDUSTRY - TRENDS
• Hybrids and battery electric vehicle sales
pick up speed
• China leading the pack: Strategic decision of
China to go for full electric
• EU requirements on CO2-emissions together
with cost decrease render battery electric
vehicles competitive
• US Tesla technology lead out of the niche…..
• BEV with > 40 kWh battery pack compared
to ca 0.015 kWh for a smartphone!
Automotive is the driver….and it´s a global trend picking up speed
Source: Avicenne Energy 2018
Seite 1125.10.2019
THE BATTERY INDUSTRY
• It is a multi-parameter optimization for each and every application!
Application Engineering
Seite 1225.10.2019
LIHTIUM ION BATTERIES
THE BASICS
Seite 1325.10.2019
LITHIUM ION BATTERIESWorking Principles
Moritz Teuber, ISEA, RWTH Aachen University
Seite 1425.10.2019
Charging
Charging
LITHIUM ION BATTERIESWorking Principles
Seite 1525.10.2019
Li
𝑒− 𝑒−Li
+𝑒−+𝑳𝒊+
Electrolyte Anode
LiMC
Solid-Electrolyte-Interphase (SEI)
LiF
LiCO3
> 4 V: Decomposition of electrolyte Passivation!
LITHIUM ION BATTERIESCharge-Discharge-Efficiencies
Source: F. Aupperle, G. G. Eshetu, E. Figgemeier et al. Accepted in Ápplied Energy Materials, 2019.
Seite 1625.10.2019
0 100 200 300 400 500 600 700 8002.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
Pote
ntial (V
)
Capacity (mAh)
1 cycle
100 cycle
200 cycle
300 cycle
400 cycle
0 100 200 300 400 500 600 700 8002.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
Pote
ntial (V
)
Capacity (mAh)
1 cycle
100 cycle
200 cycle
300 cycle
400 cycle
0 100 200 300 40090
95
100
105
110
without TEOSCN
with TEOSCN
Coulo
mbic
Effic
iency (
%)
Cycles
0 100 200 300 400
300
400
500
600
700
800
without TEOSCN
with TEOSCNDis
charg
e C
ap
acity (
mA
h)
Cycles
a) b)
c) d)
• Charge-Discharge-Efficiency > 99,999 %• >> 1000 Full Cycles!• 0,0001 %: Side reactions, electrolyte
decomposition, lithium inventory loss
Side Reactions! 𝑒−
LITHIUM-IONEN-BATTERIENMechanische Arbeit
Seite 1725.10.2019
Li
𝑒− 𝑒−+𝑒−
+𝑳𝒊+
Elektrolyt AnodeSolid-Electrolyte-Interphase (SEI)
Einlagerung von Lithium in Graphit Volumenänderung!
Li
AGEING / FATIQUE IN LITHIUM
ION BATTERIES
Seite 1825.10.2019
LITHIUM-ION-BATTERIESAgeing and Safety
Seite 1925.10.2019
Window of Stability Smaller
than Window of Safety
Stability Determines Business
Case
Safety Defines Application
Tem
pera
tur
Side Reactions/Thermal Runaway
Lithium Plating -Dendrites
Source: L. Lu et al. / Journal of Power Sources 226 (2013) 272e288
LITHIUM-ION-BATTERIES
• NMC/Graphite
• 2.05 Ah nominal capacity
• 2012-2014: Intensive ageing matrix
• Complete parametrization of electrochemical
models (porosity, electrode design,
impedance etc.)
• Project: E-Performance: Audi/RWTH
Ageing: Sanyo UR18650E
Source: Stefan Käbitz, Dissertation, RWTH Aachen Universität, 2016. ISEA.
Seite 2025.10.2019
LITHIUM-ION-BATTERIESAgeing: Test Matrix – Sanyo UR18650E
Source: Stefan Käbitz, Dissertation, RWTH Aachen Universität, 2016
Seite 2125.10.2019
0 20 40 60 80 1000
10
20
30
40
50
60
70
80
90
100
DOD [%]
SO
C [%
]
T = 35 °CCycling1 C / 1 C
LITHIUM-ION-BATTERIESThermal Management and Ageing
Source: Master Thesis Carl Felix Braun, BatterieIngenieure GmbH, RWTH Aachen 2018.
2225.10.2019
• Air cooling is not able to ensure
homogeneous temperature within
stack of cells
• Capacity loss of cells at higher
temperature insight module higher!
LITHIUM-ION-BATTERIESThermal Management
Quelle: Master Thesis Carl Felix Braun, BatterieIngenieure GmbH, RWTH Aachen 2018.
Seite 2325.10.2019
• Stack liquid cooled
• Significantly better thermal
homogenity
• Low capacity loss
Capacity fade comparison between two battery modules
Air Cooled
Liquid Cooled
LITHIUM-ION-BATTERIESAgeing
Vetter, J., Novák, P., Wagner, M. R., Veit, C., Möller, K. C., Besenhard, J. O., Winter, M.... & Hammouche, A. (2005). Ageing mechanisms in lithium-ion
batteries. Journal of power sources, 147(1), 269-281. Pfrang, Figgemeier et al, Journal of Power Sources 392 (2018) 168–175.
Seite 2425.10.2019
Electrochemical/Chemical Geometric/Mechanical
Ageing Mechanisms
MECHANICAL AGEING IN LIBJelly Roll Expansion/Contraction
Source
Seite 2525.10.2019
0 °
120 °
180 °
0 °
120 °
180 °
MECHANICAL AGEING IN LIBJelly Roll Deformation and Electrode Delamination
Pfrang, Figgemeier et al, Journal of Power Sources 392 (2018) 168–175
Seite 2625.10.2019
Deformations Desorption - Cathode ….Anode almost always comes off….
• Mechanical stress on current collectors!
MECHANICAL AGEING IN LIBCapacity Loss & Jelly Roll Deformation
Seite 2725.10.2019
Micro-Shorts?
MATERIALS IN LITHIUM ION
BATTERIES
Seite 2825.10.2019
MATERIALS IN LIBA hot topic……
Seite 2925.10.2019
• Copper• Aluminum• Lithium• Organic solvents• Polymeric separators• Transition metals: Cobalt,
Nickel, Manganese etc.• Fluor (LiPF6)• Etc.
ANODE MATERIALS
10/25/2019 30
• Various graphites lead to optimized performances for applications
Natural Graphite
Synthetic Graphite
Time for Charge/Dischargeslow fast
Synthetic &
natural
Graphite
Sp
ecific
Ca
pa
city
in m
Ah/g
http://brussels-scientific.com/?p=4120
http://asbury.com/images/vein6.jpg
Advanced Materials 21(45):4593 - 4607 · December 2009
CATHODE MATERIALS
Material Energy
Density
Power
Density
Safety Stability Costs per
Ah
Example
LCO –
Lithium
Cobalt Oxide
0 + -- 0 -- Consumer
electronics
NCA – Nickel
Cobalt
Aluminum
+ + -- - 0 Tesla
NMC – Nickel
Manganese
Cobalt
0 0 - - 0 BMWi3
LMO –
Manganese
Cobalt
-- + 0 -- 0 ?
LFP – Iron
Phosphate
-- + + + + Busses in
China
Scale: Very bad -- / - / 0 / + / ++ very good
LITHIUM ION BATTERY MATERIALS ROADMAP
32
LMO (NMC111/4.1 V)
Graphit
LMO (NMC111/4.2V)
Graphite
HE-NMC(622/4.4V)
Graphite/Si (<20 %)
HE-NMC(622/4.4V)
Graphite/Si (>20 %)
2016 2018 2020 2022199X - 2010
HE-NMC (811>4.6V)
Graphite/Si (>40 %)
>4.5 V / Si- or
Lithium metal
anode + solid state
electrolyte /
separator
Energy Density
Year
Lower Cobalt – Higher Voltages
LCO/Graphite
Engineering
higher energy
density
LIB – TRENDS
• Nano-Materials enable high power due to
high surface area
• Nano-Materials suffer from high rate of
side reactions Degradation!
• Published data is almost never enough to
judge the promise of the material for real
applications
Nano Materialien is a great hype…..
Quelle: Chem. Rev. 2014, 114, 11444−11502
Seite 3325.10.2019
Nano does not solve the problem!
ALUMINUM IN LIB
• Cathode: NCA active material (e.g. Tesla/Panasonic Cells)
• Anode: Aluminum as active material
• Casing:
• Hard case prismatic cells
• Pouch bag cells
• Current collector
Plenty…..
Seite 3425.10.2019
ALUMINUM IN LIB
• Requirements:
• Cathode material with high adhesion
• High tear strength Fast continuous coating process
• Corrosion resistant….whatever that means at such voltages
Current Collector
Seite 3525.10.2019
ALUMINUM IN LIB
• HF created in-situ leads to corrosion of Al-current-collector in LiB
• Water-free electrodes and carbon coatings as preventive measures
Current Collector Corrosion
Source: C. Rahe, DU Sauer, E. Figgemeier et al., Journal of Power Sources Volume 433, 1 September 2019, 126631.
Seite 3625.10.2019
Source: J. Mater. Chem., 2011, 21, 9891–9911 | 9893
ALUMINUM IN LIB
• Up to µm-thick carbon coatings for preventing corrosion of Al-current-collector in LiB
• Most commonly wet-deposition of carbon slurry
• Improves adhesion ande corrosion properties
• Commercial products: e.g. – „Cambridge Energy Solutions:
• Conductive carbon coating
• Double side coating with 1 micron thickness each side
• Density: 0.5 g/m²
• Surface resistivity: < 30 ohms per 25 um²
• Substrate of Aluminum foil
• Purity > 99.9%
• Aluminium Thickness: 16 micron
Current Collector – Carbon Coating
Seite 3725.10.2019
ALUMINUM IN LIB
• Pouch bag foils:
• Multilayer architecture: PE-Al-PP, sometimes mechanically enhanced by….
• Tab sealing remains a challenge
• Cooling along the rim is difficult
• Notorious for electrolyte leakage
• Prismatic cell casings:
• Laser welded sealing
• Sometimes coatings insight for corrosion inhibition
Casings and Pouch Cell Bags
Seite 3825.10.2019
ALUMINUM IN LINAluminum as anode active material
Source: M.N. Obrovac, Leif Christensen, Dinh Ba Le and J.R. Dahn, J. Electrochem. Soc. 154 (2007) A849
Seite 3925.10.2019
High energy density! Potentially low cost and abundant material
ALUMINUM IN LIBAnode active material
Source: Lukas Well, Egbert Figgemeier, Haohao Yi,, ISEA, RWTH Aachen University, 2019.
Seite 4025.10.2019
Very slow insertion of Li into Al / Large irreversiblity / Pulverization of foil
SUMMARY
• Batteries market is growing double-digit and will grow for at least the next 10 years to come: Automotive is the
driver, but many applications come with it…..
• Current developments are cost not performance driven!
• Development times for new battery technologies are counted in decades Don´t wait for a revolution! …it
won´t come….
• Development times for new materials in established battery technologies: > 5 years!....minimum
• Multiple ageing mechanisms: Chemical, electrochemical, mechanical….
Pfrang, Figgemeier et al, Journal of Power Sources 392 (2018) 168–175
Seite 4125.10.2019
Aluminum plays a major role!
….maybe even more in the future…
Seite 4225.10.2019
Thanks!