Zentrum für Sonnenenergie- und Wasserstoff-Forschung (ZSW)Baden-Württemberg

Storage Technologies for Smart Mobility

Electrification of Mobility and the Electrical Network

November 20th 2009, Madrid

A. Jossen, J. Garche, W. Tillmetz, L. Jörissen

- 1 -

Zentrum für Sonnenenergie- und Wasserstoff-Forschung

Photovoltaics & Renewable Fuels Stuttgart

Solar Test FeldWidderstall

Electrochemical Energy Technologies, Ulm

• Energy Research & Development in close contact with industry

• Photovoltaics – Thin-Film- technologies, Solar Test Site

• Renewable Fuels• System Analysis & Consulting• Fuel Cell: Technology, Systems test

Center• Batteries & Super Capacitors –

Materials, Systems, Test, Safety

- 2 -

Overview

Electricity generation and distribution

Concepts of electrochemical energy storage systems

What secondary batteries are available

Summary

- 3 -Source: EWE

Electricity Generation and Distribution

Generation

Transmission

Distribution

Consumption

Today Centralized

Tomorrow Distributed

- 4 -

Stand-Alone-SystemsSolar powered water pumpsSolar Home SystemsElectricity supply for remote villagesHybrid systemsElectric vehicles ......

Grid Coupled Systems increasing amount of (distributed) decentralized electricity generation

Consequences:New Grid structuresUse of decentralized energy storage systemsUse of energy management systems

Storage Systems required

Use of Renewable, Distributed Electricity Generation

Storage Systems desired

- 5 -

Power Range of Electricity Storage Technologies

From: http://www.berr.gov.uk/files/file15189.pdf

- 6 -

Challenges in Smart Mobility

Mobility is highly emotionalNormally vehicles are too fast and too big for the actual demandThe majority of all driving distances is below 20 kmLess than 10% of the vehicle fleet is moving

OpportunitiesNew mobility conceptsNew services involving he “non moving fleet”

Non polluting mobilityElectro-mobility

Electricity storageOn board electricity generation (ICE, fuel cell)

- 7 -

Electro-Mobility more than 100 years ago

Ferdinand Porsche developed an all electric vehicle (Lohner-Porsche Elektrowagen).

- considered as a sensation during the 1900 EXPO in Paris

A few years later: AEG started series manufacturing of electric vehicles in Berlin.

Abundant supply of mineral oil combined with ist high energy density in combination with the establishment of highways brought an end to elcoro-mobility

- 8 -

Thomas Edinson – 1883 (a warning before we dig into the details)

The storage battery is, in my opinion, a catchpenny, a sensation, a mechanism for swindling the public by stock companies. The storage battery is one of those peculiar things which appeals to the imagination, and no more perfect thing could be desired by stock swindlers than that very selfsame thing .... Just as Just as soonsoon as a man as a man getsgets workingworking on on thethe secondarysecondary batterybattery itit bringsbrings out his latent out his latent capacitycapacity forfor lyinglying ........

Scientifically, storage is all right, but, commercially, as absolute a failure as one can imagine.

- 9 -

The Most Important Properties of Secondary Batteries

For more than 100 years, batteries of different chemistries are a high volume commercial product used in a plentitude of applications.

For some applications, secondary batteries need to be highly specialized and optimized:

Consumer applications low cost ( < 5ct/Wh => primary batteries + lead-acid)

Automotive high power (up to 2.000W/kg)

Portable (mobile phone ...) high spec. Energy (up to 200 Wh/kg)high energy density (up to 450 Wh/l)

Emergency power high lifetime ( > 15 years)full power available instantaneously

All applications No / little balance of plant (except Redox-Flow)low / no noise, no emission operationlittle heat release during operationhigh round trip efficiency (70 – 95%)electrically rechargeable (existing infrastructure)

- 10 -

Electro-Mobility in the future (back of the envelope calculation)

Let‘s assume:Small and efficient vehicles using 8 kWh traction energy / 100 km (maximum).

This generates the following storage demandBattery 10 kWh/100 kmHydrogen 20 kWh/100 kmGasoline 40 kWh/100 km

Corresponding to weight demandBattery (120 Wh/kg) 83 kg/100 kmHydrogen (10 wt %) 6,0 kg/100 kmHydrogen (5 wt%) 12 kg/100 kmGasoline 3,3 kg/100 km

Volume demandBattery (300 Wh/l) 33 lHydrogen (700 bar) 10.5 lGasoline 4.5 l ~ 95 g CO2 /km

HydrogenMass including tank, excluding FC- SystemJust compressed fuel volume considered, tank volume an FC- System volume are neglected

GasolineJust mass of fuel consideredJust volume of fuel considered

- 11 -

Electro-mobility and Renewable Energies

5000 m2 for Biodiesel with ICE

1000 m2 for Hydrogen from biomass coupled with fuel cell drive train

20 m2 for PV-electricity coupled with battery electric vehicle

500 m2 for hydrogen from wind energy coupled with fuel cell drive train. (Land can still be used for agricultural purposes.)

Land use for renewable fuels necessary to operate a vehicle for 12.000 km per year

- 12 -

1) From: IEA-Statistik 2001-20022) Still available within EU

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

min max min max

[PJ/

yr]

Wind offshore 2)

Wind onshore 2)

Hydropower 2)

PV2)

Solar thermal Power Plants

Use of fuels(transportation 2002) 1) CGH2 LH2

Geothermal 2)

Ocean energy

Road trafficAviationRail

Inland shipping

Technical Potential for the Generation of renewable electricity within the EU

Fuel for Electric Mobility (Hydrogen)

Quelle: LBST

- 13 -

Converter: electrical into chemical energy Chemical

storage unit

Battery charge Battery dischargeAccumulator, secondary battery

Primary battery

Fuel cell

EECEEE

Electrolyzer

Electrical energy Electrical energyChemical energy

Converter: electrical into chemical energy

Electrochemical Energy Storage Concepts

- 14 -

Elektrochemical Energy Storage Options

Internal Chemical Energy StorageClassical secondary batteries

Lead-AcidNickel Metal Hydride, (NiCd, NiZn)

High temperature secondary batteriesSodium-sulfurSodium-Nickel chloride (ZEBRA)

Li-batteriesSuper Capacitors

External Chemical Energy StorageRedox Flow SystemsFuel Cell Systems

- 15 -

Fuel Energy Density

Quelle: Toyota

Gaseous Fuel

Liquid Fuel

Batteries

Volumetric Energy Density / Wh/l

Gra

vim

etric

spec

ific

ener

gy/ W

h/kg

- 16 -

Theoretical Specific Energy of Different Systems of Practical Interest

100

1000

10000

0 1 2 3 4 5

Zellspannung in V

th. s

pezi

fisch

e En

ergi

ein

Wh/

kg

Li-Ion (400-500 Wh/kg)NiMH (240 Wh/kg)

Pb/PbO2 (161 Wh/kg)NiCd (211 Wh/kg)

H2/O (33 kWh/kg) bei Verwendung des Luftsauerstoffs

H2/O (3660 Wh/kg) bei Speicherung von Wasserstoff und Sauerstoff

Ni/H (434 Wh/kg)NiZn (372 Wh/kg)

Li/MnO2 (100Wh/kg)Zn/O (1350 Wh/kg)

Li/S (2500 Wh/kg)

Cell Voltage / V

Theo

retic

al s

peci

fic E

nerg

y / W

h/kg

- 17 -

Requirements for Battery Storage Systems

Cost

LifetimeBattery

Safety

Energy

Power

New materials and new concepts desired

- 18 -

The Three Most Important Secondary Battery Technologies (electrically rechargeable)

Lead Acid + Price + Safety - spec. Energy

Alkaline Systeme: NiCd, NiMH

o Price o Safety

o spec. Energy

Lithium Systems: Li-Ion, Li-Metal ..

+ spec. Energy - Price, Safety

- 19 -

Ragone Diagramm for electrochemical Storage Systems

0.1

1

10

100

1000

1 10 100 1000 10000specific power / W/kg

spec

ific

ener

gy W

h/kg

DLC

Li-Ion

Ni-MeHLead-acid

Redox-flow

High temp.batteries

10h 1h 6 min

0.6 min

discharge time:

Fe-air

- 20 -

Quelle: Hoppecke

Lead-Acid Batteries

- 21 -

Lead-Acid Batteries

Stopper

Space for Debris

Connectors (Poles)

ElectrolyteSeparatorNeg. Plate (pasted grid)

Pos. Plate (tubular plate)

Typical Battery for stationary Applications

Spirally wound cells for Applications requiring high current

Quelle: Exide

Rholab Zelle

- 22 -

Advances in Lead Acid Batteries

-- ++

Cell separator(non conducting)

Pathway of electrond inmonopolar Batteries

Monopolar Configuration

e- e-

-- +

+

Cell separator (bipolar plate)(electronically conducting)

Pathway of electrons in bipolar Batteries

Bipolar Configuration

e- e-

Recent development of bipolar batteries

From: Effpower

- 23 -

Lead-Acid-Batteries „The Workhorse“ also for stationary Use

- 24 -

Summary Lead Acid Batteries

Most important battery technology at the present time

Total market share approximately 50%

Main applications: Automotive (SLI), Stationary, Industrial

Manufacturing capacity available worldwide

AdvantagesInexpensive, safe, longtime experience

DisadvantagesLifetime, limited potential, environment, specific energy

Current development goalsBipolar systems, carbon additives to enhance stability at partial chargeThere are efforts to use lead acid batteries in hybrid vehicles (e.g. Rholab project)

- 25 -

Quelle: Saft

Alkaline Batteries

- 26 -

Negative Elektrode Positive Elektrode

UN,- UN,+

-1,25 Zn MnO2 +0,26

-1,03 Fe O2 (Luft) +0,40

-0,83 MH, H2 NiOOH +0,48

-0,81 Cd Ag2O2 +0,61

Negative Electrode Positive Electrode

Several Combinations are possible

Most important systems today: NiMH, NiCd possibly NiZn increasing interest in metal-Air (Zn-Air)

Alkaline Batteries

- 27 -

1250 W / kg1250 W / kg1250 W / kg

6.5 Ah6.5 Ah6.5 Ah

7.2 V7.2 V7.2 V

1040 g1040 g1040 g

550 W / kg550 W / kg550 W / kg

6.5 Ah6.5 Ah6.5 Ah

7.2 V7.2 V7.2 V

1090 g1090 g1090 g

New PrismaticNew PrismaticNew Prismatic CylindricalCylindricalCylindrical

CapacityCapacity

VoltageVoltage

WeightWeight

880 W / kg880 W / kg880 W / kg

6.5 Ah6.5 Ah6.5 Ah

7.2 V7.2 V7.2 V

1050 g1050 g1050 g

PrismaticPrismaticPrismatic

DimensionDimension285mm(L)19.6mm(W)114mm(H)

285mm(L)285mm(L)19.6mm(W)19.6mm(W)114mm(H)114mm(H)

35mm(f )384mm(L)35mm(35mm(ff ))384mm(L)384mm(L)

275mm(L)19.6mm(W)106mm(H)

275mm(L)275mm(L)19.6mm(W)19.6mm(W)106mm(H)106mm(H)

Specific PowerSpecific Power

1 2 3

1

2

3

New Priusbattery

Current Prius- Battery

Module Development (PEVE)

NiMH-Battery: Standard for HEV

- 28 -

27 MW for 15 Minutes13760 Ni-Cd Cells (Saft)Cost 35 Mio $ Operational since Aug. 2003

Largest stationary Ni-Cd battery system Golden Valley Electric‘s Battery Energy Storage System (Alaska)

Large Scale Ni-Cd-Battery

- 29 -

Vehicles today use NiMH - HEV – EV – SLI -

Technology: NiMH (Panasonic) Energy: ca, 1.6 kWh Power: > 20 kW Warranty: 160 Tkm / 8 years

HEV: Toyota Prius II

Battery 1. Gen.

Battery 2. Gen.

- 30 -

Ni-MH battery electrode composition:

5 - 10 kg/kWh Ni requirement depending on the application.Current cost approx. 10 $/kg, Peak cost (2007) approx. 50 $/kg

Critical for high energy storage facilities in the long run

Cost Problem Nickel

- 31 -

Summary Alkaline Batteries

Currently Ni-MH is the standard technology for hybrid electric vehicles (HEV)

Large systems of alkaline batteries (Ni-Cd; Ni-MH) have been built

Main applications:HEV, industrial traction, aircraft, railways

Only a few manufacturers are available: (Saft, Hawker, Hoppecke, Panasonic …)

Advantages:High cycle life, high specific power (Ni-Cd; Ni-MH)

Disadvantages:Cost, limited development potential

Current development goalsBipolar systems, improved metal hydrides

Alkaline systems are more and more replaced by Li-ion systems.

- 32 -

Lithium Batteries

- 33 -

Li-Systems

Systems with metallic Lithium:

Li-Metal

Systems without metallic Lithium:

Lithium-Ion

Distinction Anode material

Distinction Electrolyte

Liquid Electrolyte:

Li-Metal- liquid

Polymer Electrolyte:

Li-Metal- Polymer

Liquid Electrolyte:

Li-Ion- liquid

Polymer Electrolyte:

Li-Ion- Polymer

button cells only

Little activity Kanada: AVESTOR Fr: Bollore JP: ...

Cells for electronic devices + Power Tools available EV and HEV available as prototypes

Lithium Eigenschaften relat. Atommasse: Ordnungszahl: Schmelzpunkt: Siedepunkt: Oxidationszahl: Dichte: Härte (Mohs):

6,941 3 180,54 °C 1342 °C 1 0,534 g/cm³ 0,6

Li-Battery Systems

- 34 -

Varieties of Li-Ion Battery Systems

4

3

0

1

2

5

4

3

0

1

2

5

LiMn2O4

LiCoO2

LiNiO2

LiFePO4

Li4Ti5O12

LiSiGraphite

Amorphouscarbon

Li-metal

Volta

gevs

. Li

thiu

m m

etal

/ V

MnO2

LixV3O8

4-V Systems

3-V Systems

Positive

Negative

4

3

0

1

2

5

4

3

0

1

2

5

LiMn2O4

LiCoO2

LiNiO2

LiFePO4

Li4Ti5O12

LiSiGraphite

Amorphouscarbon

Li-metal

Volta

gevs

. Li

thiu

m m

etal

/ V

MnO2

LixV3O8

4-V Systems

3-V Systems

Positive

Negative

Many options:

Few systems on the market,high potential,high risk,continuing development

- 35 -

Large Development Efforts Worldwide for Cathode Materials

3V

4V

5V

150 200 250 300

Li(Ni,Co)O 2

LiFePO4

LiCoPO 4

LiCo1/3Ni1/3Mn1/3O 2

Li2MnO 3/1-xMO 2LiNi1/2Mn1/2O 2

MnO 2 – V2O 5

Doped MnO 2

LiMnPO 4

5V LiMn1.5(Co,Fe, Cr)0,5O 4

LiMn2O 4 LiCoO 2

LiMn1.5Ni0.5O 4

3V

4V

5V

150 200 250 300

Li(Ni,Co)O 2

LiFePO4

LiCoPO 4

LiCo1/3Ni1/3Mn1/3O 2

Li2MnO 3/1-xMO 2LiNi1/2Mn1/2O 2

MnO 2 – V2O 5

Doped MnO 2

LiMnPO 4

5V LiMn1.5(Co,Fe, Cr)0,5O 4

LiMn2O 4 LiCoO 2

LiMn1.5Ni0.5O 4

Capacity [Ah/kg]

Pote

ntia

l vs.

Li/L

i+

The cathode material is domination cost, safety, and specific energy.

Other components such as anode material, separator, and electrolytes also are requiring further attention as well as R&D capacity

Potential cathode materials for Li-Ion Batteries

- 36 -

Different Cell Concepts

Different design principles are preferred by different manufacturers.

No final agreement on the most promising design has been found so far.

Prismatic ZCells Cylindrical Cells Pouch-Cells (Coffee-Bag)

- 37 -

GAIA (LTC) – LiFePO4 – HEV Batteries Tomorrows Electric Vehicle?

HP 35Ah cells for plug-in HEV200V, 35Ah battery (7kWh) for a plug-in HEV was demonstrated (electric range of about 50 km)Possibility for grid coupling(charge and discharge)

- 38 -

System ConceptsAltairnano Battery of the Daimler S400 Blue Hybrid

50 Ah Battery module

2 MW / 0.5 MWh Battery system Indianapolis Power & Light

From: Daimler AG

- 39 -

Battery Safety IS an Issue

- 40 -

Summary Lithium Batteries

Lithium Batteries are showing large values of specific energy on a cell level up to 200 Wh/kg.

Li-Ion Cells are produced for the electronics market in large quantities

The market currently is dominated by Japanese, Chinese, and Korean suppliers, Europeans are gradually catching up.

Lithium batteries have a large potential for further improvement. 90% of current battery research is done in the field of Li-batteries.

Upscaling to large stationary or vehicle traction systems is difficult. Further R&D- work is required!

Cost reduction (new materials, manufacturing technologies)Improvement of product safetyImprovement of lifetime (including calendar life)

Current R&D-programs are essential for fast capacity building in R&D and subsequently production.

- 41 -

Li-Ion-Batteries: New Applications >> Significant Challenges

new Materials

& Concepts required

Safety ? Consumer battery: < 90 WhHybrid electric vehicle: 1-2 kWhPlug-In HEV: 6 – 10 kWhBattery electric vehicle: > 20 kWh Cost ?

< 500 €/kWh

Specific energy ? > 200 Wh/kg

Life time ? calendar >10 years > 300 000 Cycles

Operating conditions ? - 30°C bis +50°C, Fast charge,

Vibration, Shock, Crash

Ressources ? Qualified Personnel,

Budget, raw materials

- 42 -

High Temperature Batteries

- 43 -

High Temperature Batteries

Two technologies are showing an advanced state of development

Zebra Battery NaS Battery

NGK (JP)Mes-Dea (CH) Focus: Traction in City busses Focus: stationary

Systems

- 44 -

HT Battery systems are requiring significant auxiliary effort

- 45 -

Summary HT-Batteries

Thermal losses upon low power cycling are a disadvantage

Thermal cycling is critical and might cause rupturing of ceramic electrolyte

Only two manufacturers worldwide, pursuing different technologies

Na-S know-how completely in Japan (ABB backed out in 1995)

Specific energy of 100 Wh/kg and energy density of 250 W/kg achieved on a system level

Cycle life of more than 1000 cycles at a calendar life > 10 years is possible.

Attractive cost in mass manufacturing.

- 46 -

Summary Battery Storage

There is no „universal battery“ each technology has ist own strength and weaknesses

The application is determining the favorite technology

Hybrid vehiclesAlkaline batteries, Li-ion batteries, (lead-acid batteries)

Battery electric vehiclesAlkaline batteries, Li-ion batteries, high temperature batteries, (lead acid batteries)

Stationary systemsAll technologies presented, in addition: flow batteries

R&D work is concentrating on Li-batteries

Major development progress is expected within the next 5 years in Li-ion batteries

- 47 -

The Lossy Way of Electrons in a Hydrogen Economy

100 kWh 85 kWh

100 kWh 25 kWh

But hydrogen is also available from different (chemical) sources

- 48 -

Efficient, emission free mobility

• Several hundreds of vehicles in daily use

• Gradual expansion of current demo fleets.

• R&D to achieve cost reduction

• Implementation of a supply chain

Fuel Cell Powered Electric Vehicles

- 49 -

Challenges in Electro-Mobility

Range of battery electric vehicles will be limitedFuel cell vehiclesHybridization with ICE (not a zero emission option)

Rapid electric refuelingElectric charging stations

2.7 kW from home socket (10 h to full charge)10 kW from home fast charger (~2.5 h to full charge)High power Electric filling stations vs. battery charge acceptance

New potential servicesStationary batteries to assist fast chargingVehicle to grid applications

Public battery charging infrastructureBusiness modelInitially cheaper than hydrogen filling stations, but more expensive at full market penetration

- 50 -

Summary

Development of batteries is driven by applicationsConsumer electronics => Li-IonHybrid Electric Vehicles => NiMH (today) and Li-Ion (in the future)

Stationary storage systems are dominated by lead-acidInexpensive, Comparatively safe, Well known

Li-Ion is the choice for vehicle traction and can become a substitute in stationaryHigh round trip efficiency, high cycle life, butSafety will be a prominent issue in large systems

Redox-flow is a long term option Separation of power and energy

Hydrogen fuel cells are hampered by insufficient round trip efficiency and high costBut they are interesting with respect to fuel storage, safety and environmental issues

- 51 -

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