batteries as enabler for electrification of … · ageing: sanyo ur18650e source: stefan käbitz,...
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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
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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
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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…
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BATTERY TECHNOLOGIES
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LITHIUM-IONEN-BATTERIEN
TRENDS
Seite 525.10.2019
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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
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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
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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!
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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
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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
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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
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THE BATTERY INDUSTRY
• It is a multi-parameter optimization for each and every application!
Application Engineering
Seite 1225.10.2019
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LIHTIUM ION BATTERIES
THE BASICS
Seite 1325.10.2019
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LITHIUM ION BATTERIESWorking Principles
Moritz Teuber, ISEA, RWTH Aachen University
Seite 1425.10.2019
Charging
Charging
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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!
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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−
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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
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AGEING / FATIQUE IN LITHIUM
ION BATTERIES
Seite 1825.10.2019
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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
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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
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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
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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!
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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
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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
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MECHANICAL AGEING IN LIBJelly Roll Expansion/Contraction
Source
Seite 2525.10.2019
0 °
120 °
180 °
0 °
120 °
180 °
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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!
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MECHANICAL AGEING IN LIBCapacity Loss & Jelly Roll Deformation
Seite 2725.10.2019
Micro-Shorts?
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MATERIALS IN LITHIUM ION
BATTERIES
Seite 2825.10.2019
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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.
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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
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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
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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
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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!
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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
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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
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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
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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
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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
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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
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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
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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…
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Seite 4225.10.2019
Thanks!