Innovative Materialien für Batterien der nächsten

Generation

Dr. Andreas FischerVice President

Battery Research and Electrochemistry

BASF SE, Ludwigshafen

4. SEC 2012Bad Dürkheim

10.05.2012

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Batteries for Stationary Application

Batteries for Mobile Application

Overview

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Batteries for Stationary Application

Batteries for Mobile 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 CO 2 per Kilometer

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162

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Electromobility

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The way to electromobilityMeasures

Cheap renewable energy

� Development of efficient greentechnologies(wind, solar, etc.)

� Optimized gridintegration

Smart and stable grids

� Grid expansion

� Grid management

� Low-losstransmission

Flexible energy storage

� New stationarystorage systems(Batteries…)

� Utilization of carbatteries for storage

Competitive Electric Vehicles

� Development of affordablehigh-performance batterytechnologies

� Energy efficientcomfort elementsand materials

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The battery determines characteristics of an electric v ehicle Range, Costs, Safety, …

The battery allows for differentiation and value crea tionChallenging 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

APPROACHES

� Improved materials for components and cells

� Continued improvement of the Li-ion technologyand development of new battery concepts

ONGOING ACTIVITIES

� International Research Network with renowned scientists and comprehensive industry consortia

� Building a production plant for cathode materials

� Work 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

Pb-Acid

Ni-CdNi-MH

Li-Ion

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+ � LixC6 LiMO2 � Li(1-x)MO2 + xe- + xLi+q

LiPF6

e-

e-

e-

e-

e-

e-

e-

e-

O

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 � 6 C + xe- + xLi+ Li(1-x)MO2 + xe- + xLi+ � LiMO2

4.3

3.0

V

q

e-Graphite Anode Metal oxide cathode

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Cu current collector (12-20 µm)graphite anode (30-150 µm)

separator (16-35µm)

cathode (40-200 µm)

Al current collector (18-25 µm)

-

+

<0.5 mm

Lithium ion batteriesCross section and schematic set up

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� Synthesis of cathode material

� Preparation of slurry

� Electrode coating

� Calendering

� Pouch cell preparation

� 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

� BASF has licensed a broad NCMLi1+x(NiCoMn)1-xO2 patent portfoliofrom ANL.

� Standard NCM-111 will become first BASF product, standard voltage NCM-xyz will follow.

� High-Energy HE-NCM and High-Voltage HV-spinel 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 Facts

� Metal prices dominatecathode cost

� Cobalt content drivestotal metal cost

� Metal prices areheavily fluctuating

$/kg

CobaltNickelManganese

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Chemical CompositionNCM Cathodes – Commercially Relevant Areas

Cost Lifetime

Energy Safety

Cost

Safety

Nickel Cobalt

Manganese

Lower-cost region

High-stability region

High-capacity region

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Lithium ion batteriesCathode materials with higher energy density

Discharge profilesBASF HE-NCM vs. BASF NCM-111

Marked capacity increase at slightly 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]

HE-NCM

NCM-111

Voltage [V]

E = Q × U

Discharge profilesBASF HV spinel vs. BASF NCM-111

Marked voltage increase at slightly 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

NCM-111

HV spinel

E = Q × U

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BASF’s HEDTM HE-NCM vs. graphiteCycling stability in Swagelok cells

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NCM523

HE-NCM

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 HV-spinel 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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Requirements for next generation electrolytes

Performance� Improved energy and power density� Conductivity / Rate capability� Higher voltage window� Low temperature behavior

Safety� Flammability� Overcharge protection� Thermal runaway

Long-term stability� Cycle life� Self discharge

Unfortunately improving one characteristic often leads to worsening another

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Cell type: Pouch cell

Cathode: NCM523 (BASF)

Anode: Graphite

Electrolyte: Carbonates (BASF)

Charge: 4.2V, CCCV, 0.5C

Discharge: 3.2V, CC, 0.5C

Formation: 0.1C at 1st & 2nd Cycle

Temperature: 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 Li-Ionand “next Generation” systems

From Li-Ion to Li/S and Li/Air:The next Generation of Batteries

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Li-Ion

Li-S

Li-Air

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Sulfur-cathodeLi+

S2-

e

e-Li+-ions

Li-anode

Lithium/Sulfur batteriesWorking principle – Discharge

S2--ions

+

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High potential but challenges to be solved

Advantages

� High gravimetricenergy density

� Low cost andabundant raw materials

� Operability atlow temperatures

Lithium/Sulfur batteriesAdvantages and Challenges

Challenges

� Cycle lifeyet too low

� Self dischargeyet too high

� Safety mustbe guaranteed

� Fast charging capabilitiesare essential

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Lithium/Sulfur batteriesJoint Development with Sion Power Corporation

� Sion Power is a global leader inthe development of a new generationof high-energy, rechargeable lithiumsulfur batteries and is locatedin Tuscon, Arizona.

� In 2009 BASF and Sion Power agreedon a joint development program onLi/S battery materials

� The collaboration targets the developmentof materials to improve Li/S batteries’ lifeand energy density

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Field of work

� Several parts and components need further optimizat ion 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, graph enes)

� Improved sulfur utilization and structural stabilit y

Graphite ExpandedGraphite

“Micropockets”for sulfuruptake

SmoothersprayedBASF cathode

Mud crackson standardcathode

5000 : 1 5 µm

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Lithium/Sulfur batteriesCathode development

Higher structural stability results in better cycle life

State of the art Li/S battery with PTFE binder

Li/S batteries with advanced BASF binder

Capacity [mAh/g]

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800

1000

1200

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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

� New electrolytes and additives for improved Li re-p lating

Inhomogenous Li re-plating

Lithium/Sulfur batteriesElectrolyte development

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Lithium/Sulfur batteriesSafety

Safety issues

� At 180°C lithium and sulfur are liquid � fast reaction

� Special protection needed

Li/S batteries with BASF polymer layer

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BASF protective polymer layer enhances safety of Li/S cells

Tcell-Theater [°C]

Temperature [°C]

Sulfurmelting

Limelting

Conventionaldesign

Sion-BASFProtective Layer

Advanceddesign

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Special requirements in EVs because of limited energy availability

Energy efficient comfort elements and materialsExamples

• Light weight constructione.g. fibre-reinforced 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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APPROACHES

� Use of polymer based light weight materials Saving potential of 150 kg per car

� Use in several construction elementslargest impact in load bearing elements like chassis

Goals: Energy saving and increased range

Energy efficient comfort elements and materials – light weight constructionContributions of BASF

ONGOING ACTIVITIES

� Evaluation of new material concepts and technologiesSandwichstructures, fibre-reinforced composites…

� Use of high-performance polymersPolyamides, Polyurethanes…

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Goals: Energy saving and increased comfort

today up to 60 °C

in the future 20-30 °C

Energy efficient comfort elements and materials – heat managementContributions of BASF

APPROACHES

� New heat relecting pigments for shields, paints and interior

� Use of high performance insulating materialsIsolation of cabin and engine compartment

ONGOING ACTIVITIES

� Intense research and development on innovative pigments and new insulating materials

� Insulating materialsPolymer foams

EVs today

up to 35% of energy demand

for operation of air condition

In-cabin temperature

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Electrical energy efficiency― Solar roof with transparent organic solar cells― Transparent organic OLEDs

Goals: maximum energy efficiency, longer driving range and more comfort

Smart Forvision in Cooperation with BASFTechnologies for the Car of Tomorrow

Holistic temperature management― IR-reflecting films/pigments― High performance foams for insulation

Multifunctional lightweight construction ― Lightweight ergonomically designed seats ― Thermoplastic polyamide wheel

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Go online at www.smartforvision.basf.com

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Batteries for Stationary Application

Batteries for Mobile Application

Overview

36Source: 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%

3737

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

Quelle: Grafik – Fraunhofer, Daten – BMU Leitstudie 2007

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2000 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

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40

0

2000 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

Adj

usta

ble

Germany

Energy ProductionChanging the Energy Mix

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Power generation

Energy productionRenewables need storage

Wind and solar are fluctuating and so does the energy harvest.

What are alternatives to buffers:

� Gas peaker plants as back-up

� Grid expansion and distribution

� Steering demand by smart metering

Time

Buffer

Demand

Consumption is fluctuating as well but not accordingly.

Buffer

Chemical Energy

� Hydrogen, Methanol, Methane etc.

ElectrochemicalEnergy

� Lithium-Ionen-Battery

� NaS-Battery

� Redox-Flow-Battery

� Fuel Cells

Mechanical Energy

� Pumped Hydro

� Fly Wheels

� CompressedAir

Thermal Energy

� Hot Water Storage

� Salt Melts

� Phase-Change Materials

Energy storageOptions

Advantages

� Efficient energy storage

� Low costs

BASF expertise

� Electrochemistry

� Chemicals

� Operation of large chemical plants

Energy storageApplying chemical industry technologies

41Source: Prof. Dr. Dirk Uwe Sauer RWTH Aachen

V3+ + e- � V2+

VO2+ + H2O � VO2+ + 2H+ +e-

Electrolyte I Electrolyte II

MembraneElectrode

PumpPump

charge/discharge

+–

Redox-Flow Battery

1.3 Volt3.02 kg V / kWh

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2Na � 2Na+ + 2e-

2Na+ + xS + 2e- � Na2Sx

Source: NGK Insulators Ltd.

Na

Na+

S

Na2Sx

e–

+– – / +

Terminal(-) Terminal(+)

Na-Electrode SolidElectrolyte

S Electrode

β”-Alumina

Charge

Discharge

Source

Load

Sodium -Sulfur Battery

2.06 Volt0.417 kg Na / kWh

43Source: NGK

Sodium -Sulfur Battery

High temperature battery: 2.1 V @ 300 °C, ~ 100 Wh/kg

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Sodium

Sodium-poly-

sulfide

e-

+

Sulfur

Sodium/Sulfur Battery -Research Topic at BASF

2Na � 2Na+ + 2e-

2Na+ + xS + 2e- � Na2Sx

Separation of power and energy Modular approach, aiming at GW range

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Scientific Network on Batteries Joining forces with academia

Task academic partners in the network� Fundamental evaluation of system and components

� Development of a mechanistic understandingof the interaction of components and materials

� Syntheses of materials

� Specific analytics for batteries

Task BASF in the network� Coordination of all work-packages in the network

� Extending the network into BASF

� Benchmarking

� Adoption of respective materials to the system

� Extensive testing options for cells and components

� Scale-up

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Scientific Network on Batteries Partner

� Prof. Jürgen Janek , University of Gießen, GER

� Prof. Hubert Gasteiger , Technical University of Munich, GER

� Prof. Petr Novák , PSI Villigen, CH

� Prof. Doron Aurbach , Bar-Ilan University, ISR

� Prof. Brett Lucht , University of Rhode Island, USA

� Prof. Linda Nazar, University of Waterloo, CAN

� Further partnersabout to be identified

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� Ten scientists working jointly on the developmentof materials and components for next generationof batteries

� First projects related to ceramic ion conductorsas electrolytes and protecting layers for advancedbattery systems

� Scientific supervisors are Prof. J. Janek and Dr. A. Fischer

� The Joint Lab is having 361 m² lab and office space located at KIT Campus North

� All costs of about 12 million Euro over 5 years are shared equally by BASF and KIT

� The Joint Lab is part of the scientific networkon batteries of BASF

Joint Lab BASF / KITBatteries and Electrochemistry Laboratory

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