Electrification of Mobility and the Electrical Network November 20th 2009, Madrid

Storage Technologies for Smart Mobility A. Jossen, J. Garche, W. Tillmetz, L. Jörissen Zentrum für Sonnenenergie- und Wasserstoff-Forschung (ZSW) Baden-Württemberg

Zentrum für Sonnenenergie- und Wasserstoff-Forschung • Energy Research & Development in close contact with industry • Photovoltaics – Thin-Filmtechnologies, Solar Test Site • Renewable Fuels • System Analysis & Consulting • Fuel Cell: Technology, Systems test Center • Batteries & Super Capacitors – Materials, Systems, Test, Safety

Photovoltaics & Renewable Fuels Stuttgart -1-

Solar Test Feld Widderstall

Electrochemical Energy Technologies, Ulm

Overview Electricity generation and distribution

Concepts of electrochemical energy storage systems

What secondary batteries are available

Summary

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Electricity Generation and Distribution Today Centralized

Generation

Transmission

Distribution

Consumption

-3-

Source: EWE

Tomorrow Distributed

Use of Renewable, Distributed Electricity Generation Stand-Alone-Systems Solar powered water pumps Solar Home Systems Electricity supply for remote villages Hybrid systems Electric vehicles ......

Storage Systems required

Grid Coupled Systems increasing amount of (distributed) decentralized electricity generation Consequences: New Grid structures Use of decentralized energy storage systems Use of energy management systems -4-

Storage Systems desired

Power Range of Electricity Storage Technologies

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

Challenges in Smart Mobility Mobility is highly emotional Normally vehicles are too fast and too big for the actual demand The majority of all driving distances is below 20 km Less than 10% of the vehicle fleet is moving Opportunities New mobility concepts New services involving he “non moving fleet” Non polluting mobility Electro-mobility Electricity storage On board electricity generation (ICE, fuel cell)

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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 -7-

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 soon as a man gets working on the secondary battery it brings out his latent capacity for lying .... Scientifically, storage is all right, but, commercially, as absolute a failure as one can imagine.

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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

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

Automotive

Æ high power (up to 2.000W/kg)

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

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

All applications

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

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Electro-Mobility in the future (back of the envelope calculation) Let‘s assume: Hydrogen Small and efficient vehicles using Mass including tank, excluding FC8 kWh traction energy / 100 km System (maximum). Just compressed fuel volume This generates the following storage demand considered, tank volume an FCBattery 10 kWh/100 km System volume are neglected Hydrogen 20 kWh/100 km Gasoline Gasoline 40 kWh/100 km Just mass of fuel considered Corresponding to weight demand Just volume of fuel considered Battery (120 Wh/kg) 83 kg/100 km Hydrogen (10 wt %) 6,0 kg/100 km Hydrogen (5 wt%) 12 kg/100 km Gasoline 3,3 kg/100 km Volume demand Battery (300 Wh/l) 33 l Hydrogen (700 bar) 10.5 l Gasoline 4.5 l ~ 95 g CO2/km

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Electro-mobility and Renewable Energies Land use for renewable fuels necessary to operate a vehicle for 12.000 km per year

5000 m2 for Biodiesel with ICE 1000 m2 for Hydrogen from biomass coupled with fuel cell drive train 500 m2 for hydrogen from wind energy coupled with fuel cell drive train. (Land can still be used for agricultural purposes.) 20 m2 for PV-electricity coupled with battery electric vehicle

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Fuel for Electric Mobility (Hydrogen) Technical Potential for the Generation of renewable electricity within the EU PV2) Solar thermal Power Plants

20000

[PJ/yr]

18000 16000

Rail

Ocean energy Geothermal 2) Wind onshore 2)

Inland shipping Aviation Road traffic

14000

Wind offshore 2)

12000 10000 8000 6000 4000 2000

Quelle: LBST 0

Use of fuels (transportation 2002) 1)

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min

max

CGH2

min

Hydropower

max1) 2)

LH2

2)

From: IEA-Statistik 2001-2002 Still available within EU

Electrochemical Energy Storage Concepts

Electrical energy

Chemical energy

EE

Electrical energy

EE

CE Converter: electrical into chemical energy

Battery charge

Chemical storage unit

Converter: electrical into chemical energy

Battery discharge Accumulator, secondary battery Primary battery

Electrolyzer

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Fuel cell

Elektrochemical Energy Storage Options Internal Chemical Energy Storage Classical secondary batteries Lead-Acid Nickel Metal Hydride, (NiCd, NiZn) High temperature secondary batteries Sodium-sulfur Sodium-Nickel chloride (ZEBRA) Li-batteries Super Capacitors External Chemical Energy Storage Redox Flow Systems Fuel Cell Systems

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Gravimetric specific energy / Wh/kg

Fuel Energy Density

Liquid Fuel Gaseous Fuel

Batteries

Volumetric Energy Density / Wh/l - 15 -

Quelle: Toyota

Theoretical specific Energy / Wh/kg th. spezifische Energiein Wh/kg

Theoretical Specific Energy of Different Systems of Practical Interest H2/O (33 kWh/kg) bei Verwendung des Luftsauerstoffs

10000

H2/O (3660 Wh/kg) bei Speicherung von Wasserstoff und Sauerstoff Li/S (2500 Wh/kg) Zn/O (1350 Wh/kg)

Li/MnO2 (100Wh/kg)

1000 Ni/H (434 Wh/kg)

NiZn (372 Wh/kg) Li-Ion (400-500 Wh/kg) NiMH (240 Wh/kg) Pb/PbO2 (161 Wh/kg)

NiCd (211 Wh/kg)

100 0

1

2

3

Zellspannung in V Cell Voltage /V

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4

5

Requirements for Battery Storage Systems Safety Power

Battery

Lifetime

Energy Cost

New materials and new concepts desired - 17 -

The Three Most Important Secondary Battery Technologies (electrically rechargeable)

Lead Acid + Price + Safety - spec. Energy

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Alkaline Systeme: NiCd, NiMH

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

o Price o Safety o spec. Energy

+ spec. Energy - Price, Safety

Ragone Diagramm for electrochemical Storage Systems discharge time:

1000

6 min

1h

10h

specific energy Wh/kg

High temp. batteries Li-Ion

Fe-air 100

0.6 min

Redox-flow 10

Ni-MeH Lead-acid DLC

1

0.1 1

10

100 specific power / W/kg

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1000

10000

Lead-Acid Batteries

Quelle: Hoppecke

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Lead-Acid Batteries Spirally wound cells for Applications requiring high current

Typical Battery for stationary Applications Stopper Connectors (Poles) Electrolyte Separator Neg. Plate (pasted grid) Pos. Plate (tubular plate) Space for Debris

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Quelle: Exide

Rholab Zelle

Advances in Lead Acid Batteries Monopolar Configuration

- +

- +

Recent development of bipolar batteries

e-

e-

Cell separator (non conducting) Pathway of electrond in monopolar Batteries Bipolar Configuration

From: Effpower

-

+ +

-

e-

e-

Cell separator (bipolar plate) (electronically conducting)

Pathway of electrons in bipolar Batteries - 22 -

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

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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 Advantages Inexpensive, safe, longtime experience Disadvantages Lifetime, limited potential, environment, specific energy Current development goals Bipolar systems, carbon additives to enhance stability at partial charge There are efforts to use lead acid batteries in hybrid vehicles (e.g. Rholab project)

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Alkaline Batteries

Quelle: Saft

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Alkaline Batteries Several Combinations are possible

Negative NegativeElektrode Electrode

Positive Positive Elektrode Electrode

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

Most important systems today: NiMH, NiCd possibly NiZn increasing interest in metal-Air (Zn-Air) - 26 -

NiMH-Battery: Standard for HEV

Module Development (PEVE)

New Prismatic

Cylindrical

7.2 V

7.2 V

Capacity

6.5 Ah

6.5 Ah

6.5 Ah

Weight

1040 g

1050 g

1090 g

1250 W / kg

880 W / kg

550 W / kg

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

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

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

1

New Prius Current Priusbattery Battery

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2

7.2 V

Dimension

3

Prismatic

Voltage

Specific Power

2

1

3

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

27 MW for 15 Minutes 13760 Ni-Cd Cells (Saft) Cost 35 Mio $ Operational since Aug. 2003 - 28 -

Vehicles today use NiMH - HEV – EV – SLI HEV: Toyota Prius II

Battery 1. Gen. Technology: Energy: Power: Warranty:

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NiMH (Panasonic) ca, 1.6 kWh > 20 kW 160 Tkm / 8 years

Battery 2. Gen.

Cost Problem Nickel 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 Æ Critical for high energy storage facilities in the long run - 30 -

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 goals Bipolar systems, improved metal hydrides Alkaline systems are more and more replaced by Li-ion systems.

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Lithium Batteries

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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

Distinction Anode material

Li-Battery Systems Li-Systems

Systems with metallic Lithium:

Li-Metal

Distinction Electrolyte

Lithium-Ion

Liquid Electrolyte:

Polymer Electrolyte:

Liquid Electrolyte:

Polymer Electrolyte:

Li-Metalliquid

Li-MetalPolymer

Li-Ionliquid

Li-IonPolymer

button cells only

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Systems without metallic Lithium:

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

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

Varieties of Li-Ion Battery Systems

Many options: 5

5

Voltage vs. Lithium metal / V

LiCoO2 4 4-V Systems

4 LiMn2O4

Positive

LiNiO2 LiFePO4

3

3 3-V Systems

MnO2 2

LixV3O8

Li4Ti5O12

Amorphous carbon

1

2

1

Negative

Li-metal 0

- 34 -

Graphite

LiSi

0

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

Potential vs. Li/Li+

Large Development Efforts Worldwide for Cathode Materials Potential cathode materials for Li-Ion Batteries

5V LiM n 1.5 (C o,Fe, C r) 0,5 O 4

5V

LiC oP O 4 Li2 M nO 3 /1-xM O 2 LiN i 1/2 M n 1 /2 O 2 LiM n 1.5 N i 0.5 O 4

LiC o 1/3 N i 1/3 M n 1 /3 O 2

LiM nP O 4

4V

LiM n 2 O 4 LiC oO 2

Li(N i,C o)O 2

LiFeP O 4 D oped M nO 2

3V

M nO 2 – V 2 O 5

150

200

250

300

Capacity [Ah/kg] 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 - 35 -

Different Cell Concepts

Prismatic ZCells

Cylindrical Cells

Pouch-Cells (Coffee-Bag)

Different design principles are preferred by different manufacturers. No final agreement on the most promising design has been found so far.

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GAIA (LTC) – LiFePO4 – HEV Batteries Tomorrows Electric Vehicle? HP 35Ah cells for plug-in HEV 200V, 35Ah battery (7kWh) for a plug-in HEV was demonstrated (electric range of about 50 km) Possibility for grid coupling(charge and discharge)

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System Concepts Altairnano

Battery of the Daimler S400 Blue Hybrid

50 Ah Battery module

From: Daimler AG

2 MW / 0.5 MWh Battery system Indianapolis Power & Light

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Battery Safety IS an Issue

- 39 -

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&Dwork is required! Cost reduction (new materials, manufacturing technologies) Improvement of product safety Improvement of lifetime (including calendar life) Current R&D-programs are essential for fast capacity building in R&D and subsequently production.

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

Specific energy ? > 200 Wh/kg

Cost ? < 500 €/kWh

new Materials & Concepts required

Safety ? Consumer battery: < 90 Wh Hybrid electric vehicle: 1-2 kWh Plug-In HEV: 6 – 10 kWh Battery electric vehicle: > 20 kWh

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

Ressources ? Qualified Personnel, Budget, raw materials - 41 -

Life time ? calendar >10 years > 300 000 Cycles

High Temperature Batteries

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High Temperature Batteries Two technologies are showing an advanced state of development Zebra Battery

Mes-Dea (CH) Focus: Traction in City busses - 43 -

NaS Battery

NGK (JP) Focus: stationary Systems

HT Battery systems are requiring significant auxiliary effort

- 44 -

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.

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Summary Battery Storage There is no „universal battery“ each technology has ist own strength and weaknesses The application is determining the favorite technology Hybrid vehicles Alkaline batteries, Li-ion batteries, (lead-acid batteries) Battery electric vehicles Alkaline batteries, Li-ion batteries, high temperature batteries, (lead acid batteries) Stationary systems All 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

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The Lossy Way of Electrons in a Hydrogen Economy

100 kWh

100 kWh

85 kWh

25 kWh

But hydrogen is also available from different (chemical) sources - 47 -

Fuel Cell Powered Electric Vehicles 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

- 48 -

Challenges in Electro-Mobility Range of battery electric vehicles will be limited Fuel cell vehicles Hybridization with ICE (not a zero emission option) Rapid electric refueling Electric 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 services Stationary batteries to assist fast charging Vehicle to grid applications Public battery charging infrastructure Business model Initially cheaper than hydrogen filling stations, but more expensive at full market penetration

- 49 -

Summary Development of batteries is driven by applications Consumer electronics => Li-Ion Hybrid Electric Vehicles => NiMH (today) and Li-Ion (in the future) Stationary storage systems are dominated by lead-acid Inexpensive, Comparatively safe, Well known Li-Ion is the choice for vehicle traction and can become a substitute in stationary High round trip efficiency, high cycle life, but Safety 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 cost But they are interesting with respect to fuel storage, safety and environmental issues

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Thank You Very Much for Your Kind Attention Zentrum für Sonnenenergie- und Wasserstoff-Forschung www.zsw-bw.de

Applied Reseach for Sustainable Energy Technologies Batteries – Fuel Cells – Photovoltaics – Renewable Fuels Materials – Modelling – Components – Systems – Test Center

Stuttgart - 51 -

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Ulm