innovative€materials for today‘s and€future generations … · 2011-12-01 ·...
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Innovative materials fortoday‘s and futuregenerations of batteries
Dr. Andreas FischerBASF SEDPG AKE Herbstsitzung 2011, Bad Honnef, 21.10.2011
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Batteries forStationary Application
Batteries forMobile Application
Overview
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Batteries forStationary Application
Batteries forMobile Application
Overview
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Global Challenges… require new concepts
MEGATRENDS
Energy demand &climate protection
Growingpopulation
Urbanization Globalization &Developing Markets
New concepts for Mobility
AffordableEnergyefficient
Lowemission
Suitedfor daily use
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CO2 emission by propulsion conceptPotentials for optimization
Assumption energy demand: 4,5 l/100 km ICE today, ICE optimized 20%, 18 kWh/100 kmSource: Studien UBA, Agentur für Erneuerbare Energien, BMU, IES, Stand: 9/2008.
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ICE today ICE optimzed EV Electricity fromhard coal
EV Electricity Germanenergy mix
EV Electricity fromrenewables
Gramm CO2 per Kilometer
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Electromobility
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The way to electromobilityMeasures
Cheap renewable energy
n Development ofefficient greentechnologies(wind, solar, etc.)
n Optimized gridintegration
Smart and stable grids
n Grid expansionn Grid managementn Lowloss
transmission
Flexible energy storage
n New stationarystorage systems(Batteries… )
n Utilization of carbatteries for storage
Competitive Electric Vehicles
n Development of affordablehighperformance batterytechnologies
n Energy efficientcomfort elementsand materials
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The battery determines characteristics of an electric vehicleRange, Costs, Safety, …
The battery allows for differentiation and value creationChallenging technology and chance for chemistry / engineering / OEMs
Materials are the heart of the battery cellChemistry plays a central role as materials supplier
Materials Components Cells Batteries Electric Car
Improved Battery TechnologyBattery as key components in electric vehicles
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Improved Battery TechnologyContributions of BASF
APPROACHESn Improved materials for components and cellsn Continued improvement of the Liion technology
and development of new battery concepts
ONGOING ACTIVITIESn International Research Network with renowned
scientists and comprehensive industry consortia
n Building a production plant for cathode materials
nWork on new generations of cell chemistry
Goals: higher energy density, safety,and life time at lower costs
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0 20 40 60 80 100 120 140 160 180 200Specific Energy (~Driving Range) Wh/kg
PbAcid
NiCd NiMH
LiIon
Comparing different battery technologiesPower versus energy
Specific Power (~Torque), W/kg
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+
4.3
3.0
V
Li+
e
6 C + xe + xLi+ g LixC6 LiMO2 g Li(1x)MO2 + xe + xLi+q
LiPF6
e
e
e
e
e
e
e
eO
O
OO O
O
Li+ containingElectrolyte
Lithium ion batteriesWorking principle charging
Graphite Anode Metal oxide cathode
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LiPF6
Li+ containingElectrolyte
+Li+
O
O
OO O
O
e
e
e
e
e
e
e
e
A
Lithium ion batteriesWorking principle discharging
LixC6 g 6 C + xe + xLi+ Li(1x)MO2 + xe + xLi+g LiMO2
4.3
3.0
V
q
eGraphite Anode Metal oxide cathode
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Cu current collector (1220 µm)graphite anode (30150 µm)
separator (1635µm)
cathode (40200 µm)
Al current collector (1825 µm)
+
<0.5 mm
Lithium ion batteriesCross section and schematic set up
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n Synthesis of cathode material
n Preparation of slurry
n Electrode coating
n Calendering
n Pouch cell preparation
n Electrochemical characterization
NCM
From raw material to lithium ion batteriesPreparation steps
1000 : 120 µm
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5000 : 15 µm
5000 : 15 µm
5000 : 15 µm
Lithium ion batteriesCathode materials roadmap
n BASF has licensed a broad NCMLi1+x(NiCoMn)1xO2 patent portfoliofrom ANL.
n Standard NCM111 will becomefirst BASF product, standard voltageNCMxyz will follow.
n HighEnergy HENCM andHighVoltage HVspinel materialsas well as Li iron phosphates LFPare in the pipeline.
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00 01 02 03 04 05 06 07 08 09 10
Metal PricesHistoric Development
Key Factsn Metal prices dominate
cathode cost
n Cobalt content drivestotal metal cost
n Metal prices areheavily fluctuating
$/kg
CobaltNickelManganese
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Chemical CompositionNCM Cathodes –Commercially Relevant Areas
CostLifetime
EnergySafety
CostSafety
Nickel Cobalt
Manganese
Lowercost region
Highstability region
Highcapacity region
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Lithium ion batteriesCathode materials with higher energy density
Discharge profilesBASF HENCM vs. BASF NCM111
Marked capacity increase atslightly lower voltage “High Energy”
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
0 50 100 150 200 250 300Capacity [Ah/kg]
HENCM
NCM111
Voltage [V]
E = Q × U
Discharge profilesBASF HV spinel vs. BASF NCM111
Marked voltage increase atslightly lower capacity “High Voltage”
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
0Capacity [Ah/kg]
Voltage [V]
50 100 150
NCM111
HV spinel
E = Q × U
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BASF’s HEDTM HENCM vs. graphiteCycling stability in Swagelok cells
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0 100 200 300 400 500 600 700 800 900 1000
NCM523
HENCM
Specific capacity [Ah/kg]
Cycle No.
25°C, 0,5 C
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0 100 200 300 400 500 600 700Cycle No.
25°C, 1.0 C
4.25V –4.80V
BASF’s HEDTM HVspinel vs. graphiteCycling stability in pouch cells
Specific capacity [Ah/kg]
Standard cell chemistry
Cell chemistry 1 (“additives”)
Cell chemistry 2 (“modification”)
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Requirementsfor next generation electrolytes
Performancen Improved energy and power densityn Conductivity / Rate capabilityn Higher voltage windown Low temperature behavior
Safetyn Flammabilityn Overcharge protectionn Thermal runaway
Longterm stabilityn Cycle lifen Self discharge
Unfortunately improving one characteristicoften leads to worsening another
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Cell type: Pouch cellCathode: NCM523 (BASF)Anode: GraphiteElectrolyte: Carbonates (BASF)Charge: 4.2V, CCCV, 0.5CDischarge: 3.2V, CC, 0.5CFormation: 0.1C at 1st & 2nd CycleTemperature: Room temperature
High cycle stability successfully demonstrated
Lithium ion batteriesCathode material and electrolyte from BASF used
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100
Cycle No.
Capacity [mAh/g] Efficiency [%]
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Specific Energy / Wh/kg
Specific Power / W/kg
BASF battery research focuses on advanced LiIonand “next Generation”systems
From LiIon to Li/S and Li/Air:The next Generation of Batteries
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0 100 200 300 400 500 600 700 800 900 1000
LiIon
LiSLiAir
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SulfurcathodeLi+
S2
e
eLi+ions
Lianode
Lithium/Sulfur batteriesWorking principle –Discharge
S2ions
+
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High potentialbut challenges to be solved
Advantagesn High gravimetric
energy density
n Low cost andabundant raw materials
n Operability atlow temperatures
Lithium/Sulfur batteriesAdvantages and Challenges
Challengesn Cycle life
yet too low
n Self dischargeyet too high
n Safety mustbe guaranteed
n Fast charging capabilitiesare essential
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Lithium/Sulfur batteriesJoint Development with Sion Power Corporation
n Sion Power is a global leader inthe development of a new generationof highenergy, rechargeable lithiumsulfur batteries and is locatedin Tuscon, Arizona.
n In 2009 BASF and Sion Power agreedon a joint development program onLi/S battery materials
n The collaboration targets the developmentof materials to improve Li/S batteries’lifeand energy density
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Field of work
u Several parts and components need further optimization and improvement
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Lithium/Sulfur batteriesCathode development
Evaluation of special cathode preparation techniquesas spraying, doctor blading, screen printing
New cathode additives (e.g. expanded graphites, graphenes)
u Improved sulfur utilization and structural stability
Graphite ExpandedGraphite
“Micropockets”for sulfuruptake
SmoothersprayedBASF cathode
Mud crackson standardcathode
5000 : 1 5 µm
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Lithium/Sulfur batteriesCathode development
Higher structural stabilityresults in better cycle life
State of the art Li/S batterywith PTFE binder
Li/S batterieswith advanced BASF binder
Capacity [mAh/g]
600
800
1000
1200
1400
00 10 20 30 40 50Cycle No.
Capacity [mAh/g]
600
800
1000
1200
1400
00 10 20 30 40 50Cycle No.
capacity drop ~ 20%
capacity drop ~ 50%
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Cycle no.10095908580757065605550454035302520151050
Cap
acity
/mA
h
1.400
1.300
1.200
1.100
1.000
900
800
700
600
500
400
300
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0
Advanced electrolytebased on BASF materials
Standard electrolytebased on DME, DOL, LiTFSI
u New electrolytes and additives for improved Li replating
Inhomogenous Li replating
Lithium/Sulfur batteriesElectrolyte development
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Lithium/Sulfur batteriesSafety
Safety issuesn At 180°C
lithium and sulfur are liquidg fast reaction
n Special protection needed
Li/S batterieswith BASF polymer layer
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100 120 140 160 180 200 220
BASF protective polymer layerenhances safety of Li/S cells
TcellTheater [°C]
Temperature [°C]
Sulfurmelting
Limelting
Conventionaldesign
SionBASFProtectiveLayer
Advanceddesign
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Special requirements in EVs because of limited energy availability
Energy efficient comfort elements andmaterialsExamples
• Light weight constructione.g. fibrereinforced composites
• Heat managementreflecting paints/shields,high performance insulating materials
• Energy by sun lightOrganic Photovoltaics
• New lighting systemsLEDs
• Innovative cooling systemsMagneto caloric
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1
3
45
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APPROACHESn Use of polymer based light weight materials
Saving potential of 150 kg per car
n Use in several construction elementslargest impact in load bearing elements like chassis
Goals: Energy saving andincreased range
Energy efficient comfort elements andmaterials –light weight constructionContributions of BASF
ONGOING ACTIVITIESn Evaluation of new material concepts and
technologiesSandwichstructures, fibrereinforced composites…
n Use of highperformance polymersPolyamides, Polyurethanes…
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Goals: Energy saving andincreased comfort
todayup to 60 °C
in the future2030 °C
Energy efficient comfort elements andmaterials –heat managementContributions of BASF
APPROACHESn New heat relecting pigments
for shields, paints and interior
n Use of high performance insulating materialsIsolation of cabin and engine compartment
ONGOING ACTIVITIESn Intense research and development
on innovative pigments and new insulating materials
n Insulating materialsPolymer foams
EVs todayup to 35% of energy demandfor operation of air condition
Incabin temperature
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Batteries forStationary Application
Batteries forMobile Application
Overview
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35Source: IEA Energie Statistics
Energy ProductionWorldwide Energy Mix 2007
19,855 TWh
Hydro 15.9%
Waste 0.34%
Nuclear 13.7%
Gas 20.8%
Biomass 0.96%
Coal 41.4%
Geothermal 0.31%
Oil 5.6%
Wind 0.87%
Solar PV 0.02%
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3636
Energy productionChanging the energy mix
Today: 1 / 6 fluctuating / adjustableYear 2050: 2 / 1 fluctuating / adjustable
Quelle: Grafik –Fraunhofer, Daten –BMU Leitstudie 2007
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80
40
02000 2005 2010 2015 2020 2040 2050
Bruttoleistung [GW]
EU Verbund EE
Kernenergie
Photovoltaik
Wind an Land
Wind Offshore
Laufwasser
Biomasse, Biogase
Geothermie
KWk, fossil
Gas Kond.
Kohle Kond.
foss
ilre
gene
rativ flu
ktui
eren
dko
ntin
uier
lich
rege
lbar
200
160
120
80
40
02000 2005 2010 2015 2020 2040 2050
Bruttoleistung [GW]
EU Verbund EE
Kernenergie
Photovoltaik
Wind an Land
Wind Offshore
Laufwasser
Biomasse, Biogase
Geothermie
KWk, fossil
Gas Kond.
Kohle Kond.
foss
ilre
gene
rativ flu
ctua
ting
Adju
stab
le
Germany
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Powergeneration
Energy productionRenewables need storage
Wind and solar are fluctuating and so does the energy harvest.
What are alternativesto buffers:n Gas peaker plants
as backup
n Grid expansionand distribution
n Steering demandby smart metering
Time
Buffer
Demand
Consumption is fluctuating as well but not accordingly.
Buffer
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38Source: Prof. Dr. Dirk Uwe Sauer RWTH Aachen
V3+ + e D V2+
VO2+ + H2O D VO2+ + 2H+ +e
Electrolyte I Electrolyte II
Membrane Electrode
PumpPump
charge/discharge
+–
RedoxFlow Battery
1.3 Volt3.02 kg V / kWh
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2Na D 2Na+ + 2e
2Na+ + xS + 2e D Na2Sx
Source: NGK Insulators Ltd.
Na
Na+
S
Na2Sx
e–
+– –/ +
Terminal() Terminal(+)
NaElectrode SolidElectrolyte
S Electrode
β”Alumina
Charge
Discharge
Source
Load
SodiumSulfur Battery
2.06 Volt0.417 kg Na / kWh
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40Source: NGK
SodiumSulfur Battery
High temperature battery:2.1 V @ 300 °C, ~ 100 Wh/kg
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Scientific Network on BatteriesJoining forces with academia
Task academic partners in the networkn Fundamental evaluation of system and componentsn Development of a mechanistic understanding
of the interaction of components and materialsn Syntheses of materialsn Specific analytics for batteries
Task BASF in the networkn Coordination of all workpackages in the networkn Extending the network into BASFn Benchmarkingn Adoption of respective materials to the systemn Extensive testing options for cells and componentsn Scaleup
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Scientific Network on BatteriesPartner
n Prof. Jürgen Janek, University of Gießen, GER
n Prof. Hubert Gasteiger, Technical University of Munich, GER
n Prof. Petr Novák, PSI Villigen, CH
n Prof. Doron Aurbach, BarIlan University, ISR
n Prof. Brett Lucht, University of Rhode Island, USA
n Further partnersabout to be identified
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n Ten scientists working jointly on the developmentof materials and components for next generationof batteries
n First projects related to ceramic ion conductorsas electrolytes and protecting layers for advancedbattery systems
n Scientific supervisors are Prof. J. Janek and Dr. A. Fischer
n The Joint Lab is having 361 m² lab and office spacelocated at KIT Campus North
n All costs of about 12 million Euro over 5 years areshared equally by BASF and KIT
n The Joint Lab is part of the scientific networkon batteries of BASF
Joint Lab BASF / KITBatteries and Electrochemistry Laboratory
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