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

133

110

162

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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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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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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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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]

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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

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100

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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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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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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

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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Energy productionChanging the energy mix

Today: 1 / 6 fluctuating / adjustableYear 2050: 2 / 1 fluctuating / adjustable

Quelle: Grafik –Fraunhofer, Daten –BMU Leitstudie 2007

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

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

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

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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