Famous quote about safety: “It will never happen to me” Captain … · 2017. 5. 10. · Famous...

Famous quote about safety: “It will never happen to me” Captain E.J. Smith (1850 – 1912), Captain of the Titanic

Acknowledgements

Federal Ministry of Economics and Technology (BMWi)Federal Ministry for the Environment, Nature Conservation & Nuclear Safety (BMU)

Federal Ministry of Education and Research (BMBF)Economy and Science Ministries of North-Rhine-Westphalia (NRW)

University of Muenster (WWU)Helmholtz Association and Forschungszentrum Jülich GmbH

Funding:German Ministry of Education and Research (BMBF)within the project “Safebatt”

German Ministry of Education and Research (BMBF)within the project “Batterie2020”

German Ministry of Education and Research (BMBF) within the project “Electrolyte Lab 4E”

Acknowledgements

Energy Density, Lifetime and Safety – Not Only an Issue of Lithium Ion BatteriesA. Friesen#, Falko Schappacher # and Martin Winter# x

81. Annual Meeting of DPG and Spring Meeting, Münster, 27 - 31 March 2017

xHelmholtz-Institut Münster (HI MS)#MEET Battery Research Center, Institute for Physical Chemistry, University of MünsterE-mail: [email protected]: [email protected]

Batteries in the Center of a Sustainable Energy Scenario

The Lithium Ion Advantage: High Energy and/or High Power Densities in Comparison to “Conventional” Energy Storage Systems

0.01

110

00

Ener

gy D

ensi

ty(W

h/kg

)

Power Density (W/kg)

100

10 100 1000

100.

1

Lead-acid battery

Ni-Cd battery

Super-capacitor

Phys. capacitor

200

100 200 800300 400 700

00 500 600

400

600

800

1000

1200

Li/O2

Cell

System

Li/S

System

Cell

Cell

System

System

Cell

*

Ener

gy D

ensi

ty /

Wh

L-1

Specific Energy / Wh kg-1

LIB (State of the Art)

LIB (energy optimized)

*Presuming: Li-metal

Wh/L =

Wh/kg

The Lithium Ion Advantage: High Energy Density per Volume in Comparison to Eventual Future Electrochemical Energy Storage Systems**

**Based on Lit. Data

Active and Inactive Materials:From Material Level to Battery Level

[1] D. Andre, S.-J. Kim, P. Lamp, S.F. Lux, F. Maglia, O. Paschos, B. Stiaszny, Fut J. Mater. Chem. A, 3 (2015) 6709-6732.

[1]

Goals for specific energy

Specific energy/energy density of LIBs:

Specific energyWhkg

=Capacity Cell ∗ Cell voltage

Mass active & inactive materials

Energy densityWh

L=

Capacity Cell ∗ Cell voltageVolumen active & inactive material𝑠𝑠

Effect on specific energy/energy density

Increasing amount of inactive

components Decreasing energy density

Active material Electrode Cell Battery module Battery system Application

Material

LIB: State of the Art and Near Future

Page10

LIB: State of the Art and Near Future

Multi Component System

Physical Properties

Electrochemical Properties

Lithium salt Solvent Additive

Energy Power(Temperature)

Costs Durablity Safety

Performance & Costs

Page 10

Multicomponent System

Electrolyte as Key Component of the Battery Cell

Liquid electrolytes need separator: organic and/or ceramic

Electrode

Powdery MaterialsComposite Electrode Structures

Active material Conductive agent

Binder / Porosity / Electrolyte

Current collector

Amount in the composite electrode:Binder: ~ 1-5 wt.%Conductive agent: ~ 1-5 wt.%

Hig

h En

ergy

Performance of LIB:Electrode Level – Active Material

Increasing energy density

High content of active material increases energy density at the

expense of power capability

e-

e-

Hig

h Po

wer

Cathode NCM1:1 (Conductive Agent:Binder)80 µm DFT, 30% porosityAnode Graphite1:1 (Conductive Agent, Binder)80 µm DFT, 30% porosity

0.80 0.85 0.90 0.95 1.00100

120

140

160

180

200

220

240

260

Ener

gy D

ensi

ty (W

ithou

t Cas

ing)

/ W

h kg

-1

Active Material / wt.%

Decreasing resistanceDFT: Dry Film Thickness

Performance of LIB:Electrode Level – Electrode Porosity

Li+

Li+High energyCathode93:3:4 (NCM:Conductive Agent:Binder)80 µm DFTAnode92:1:7 (Graphite:Conductive Agent:Binder)80 µm DFT

0.2 0.3 0.4 0.5 0.6 0.70

50

100

150

200

250

Ener

gy D

ensi

ty (W

ithou

r Cel

lcas

ing)

/ W

h kg

-1

Electrode Porosity / %

Increasing ionic conductivity

Increasing electronic conductivityDFT: Dry Film Thickness

Increasing the electrode thickness increases the energy density but enlarges distances

for ion and electron transportReduced power capabilities

High potential to increasethe energy density

Performance of LIB:Electrode Level – Dry Film Thickness

Li+

e-

Li+

e-

Hig

h En

ergy

Hig

h Po

wer

0 50 100 150 200 250 300 350 4000

50

100

150

200

250

300

Ener

gy D

ensi

ty (W

ithou

t Cel

lcas

ing)

/ W

h kg

-1

DFT / µm

Cathode93:3:4 (NCM:ConductiveAgent:Binder)30% porosityAnode92:1:7 (Graphite:ConductiveAgent:Binder)30% porosity

Increasing Diffusion Distance

Increasing Amount of Inactive Material

Performance of LIB:Electrode Level

High Power Density Electrode

High EnergyDensity ElectrodeHigh Power

Density High Energy

Density

• Porosity (Calendering)• Particle Size (primary and secondary)• Dry Film Thickness (DFT)

• Current collector thickness• Tab position• Tab welding

Variation of parameters

Comparison of Cell Types:Advantages and Disadvantages

Cylindrical

Prismatic

Pouch

Low weightShock- and vibration-tolerantDesign flexibility

Mechanical StabilityExternal pressure required

Heat transferEasy packaging

Slow and complex manufacturingExpensive

High energy densityEasy and fast manufacturing

Fast heating

Battery Line in MEET – 5 Ah (Pouch)

Materials Mixing Coating and Drying Calandering

Type: 5 AhCell AssemblySlitting

Cell Safety

5 2010 20150

1

2

3

4

5

Wor

ldw

ide

EV F

ires

1980 1985 1990 1995 2000 2005 2010 20150

100000

200000

300000

400000

500000

U.S

. Veh

icle

Fire

s

Year

0

100000

200000

300000

400000

500000

Wor

ldw

ide

EV F

ires

U.S.VEHICLE FIRE TRENDS AND PATTERNS

Fire Incidents with ICE und EV

• 90 vehicle fires per billion miles of ICE (only US data)• 12 Total Fire Incidents with EV (Worldwide)• 6 Tesla fires (total) and 3 billion miles driven

2 Tesla fires per billion miles

6x Tesla Model S2x Chevrolet Volt2x Fisker Karma1x Zotye1x BYD e62x Mitsubishi

http://insideevs.com/number-of-fire-related-deaths-per-year-caused-by-evs/

Abuse Behavior of Lithium Ion Cells

QDissipation<

QGeneration

Thermal Runaway

VentingRupture

Fire

Fire/Explosion

Heat Generation

Elevated Temperature

QDissipation>

QGeneration

Safe Outcome

Intelligent design of battery packs(e.g. heat exchange with active/passive heat sink)

Systematic Approach to Lithium Ion Material Safety

Fire is a by-product of combustion (= process of rapid oxidation of fuel). In order to ignite and burn, a fire requires three elements: Heat, Fuel, and Oxygen represented by the "Fire Triangle" (cf. science of fire fighting). The fire is prevented or extinguished by “removing” any one of them. A fire naturally occurs when the elements are combined in the right proportions (e.g., more heat is needed to ignite some fuels).

Sometimes it is useful to consider a fourth essential element of fire, the sustaining Chemical Chain Reaction (⇒ "Fire Tetrahdron")

M. Winter, Li-Ion Batteries and Beyond, Industry Report, 2017http://totalbatteryconsulting.com/industry-reports/Li-Ion-and-beyond-report/overview.html

The Fire Tetrahedron in a Lithium-Ion Cell – Materials View

Heat/Energy Release via• Anode or cathode decomposition• Cell short: internal/external

Combustibles• Li (High surface area)• Electrolyte solvents (and salts) • Gases (Hydrogen-rich)

• Oxygen • Release from layered cathodes

during overcharge• Oxygen access to cell after cell

rupture/opening via gas pressure build-up or external impact


The Fire Tetrahedron in a Lithium-Ion Cell – Materials View: Countermeasures

Heat/Energy Release via• Anode or cathode decomposition• Cell short: internal external

Combustibles• Li (Dendrites)• Electrolyte solvents (and salts)• Gases (Hydrogen-rich)

Oxygen Release from layered

cathodes during overcharge Oxygen access to cell after

cell rupture/opening via gas pressure build-up or external impact

(Radical) Chain Reaction

Material StabilizationCoolingRapid Heat Transfer

Radical scavengersShut-down, etc.(additives, separators)

No Li metalNon-flammable electrolytesGas suppression

Stable cathodes,e.g., LiFePO4

Suppression of gas pressure, etc.


Accelerating Rate Calorimetry (ARC):Thermal Stability of LIB Cells

Bottom Heater

Top Heater

Side

Hea

ter

Side

Hea

ter

Thermocouple

Voltage Tab

• Adiabatic environment

𝑄𝑄𝐺𝐺 → Cell HeatingHeat Generation:

𝑄𝑄𝐷𝐷 = 0 𝐽𝐽Heat Dissipation:

• Measurement of self-sustaining exothermic heat due to decomposition reactions

• No heat dissipation into surrounding

0 200 400 600 8000

100

200

300

T / °

C

t / min

Thermal runaway

High precision

High reproducibility

Only thermal abuse

0 50 100 150 200 250 3000.01

0.1

1

10

100

1000

10000

Self

Hea

t Rat

e / K

min

-1

T / °C

Self

Heat

Rate

(SHR

) / K

min

-1

T / °C

Self-Heat Rate > 10 K min-1: Thermal runaway

0 50 100 150 200 250 3000.01

0.1

1

10

100

1000

10000

Self

Hea

t Rat

e / K

min

-1

T / °C

ARC: Thermal Stability of LIB CellsProcesses at Moderate Temperatures

Anode

Cathode

Electrolyte

Aluminum

Copper

• SEI conversion and decomposition

• Low exothermic heat release

At a stage, where it is easyto counteract

Electrolyte

SEI

Anode

Electrolyte

SEI

Anode

0 200 400 600 8000

100

200

300

T / °

C

t / min

0 50 100 150 200 250 3000.01

0.1

1

10

100

1000

10000

Self

Hea

t Rat

e / K

min

-1

T / °C

• Li (from anode) reacts with electrolyte

• Temperature dependent reaction rate

• Increased gas evolution

Cell venting

Electrolyte

SEI

Anode0 200 400 600 800

0

100

200

300

T / °

C

t / min

O

OO

O

O

O O

O

O

O

O

O

O

CO2

CH4

Electrolyte

SEI

Anode

Anode

Cathode

Electrolyte

Aluminum

Copper

ARC: Thermal Stability of LIB CellsProcesses at Medium Temperatures

0 50 100 150 200 250 3000.01

0.1

1

10

100

1000

10000

Self

Hea

t Rat

e / K

min

-1

T / °C

Layered oxide cathode

0 200 400 600 8000

100

200

300

T / °

C

t / min

Anode

Cathode

Electrolyte

Aluminum

Copper

• Cathode decomposition

• O2 evolution and electrolyte oxidation • Highly exothermic reaction• Generation of large amounts of

gaseous products

Cell rupture, explosion and fire(worst case)

O

O

O

O

OO O

O

O

OO

O

OCO2

CH4

SHR > 10 K min-1

ARC: Thermal Stability of LIB CellsProcesses at Elevated Temperatures

450 500 550 600 650 700 750 800 850

160

180

200

220

240

T Ther

mal

Run

away

/ °C

Volumetric Energy Density / Wh l-1

NCM111NCM523NCM523/LMO

NCM523NCM523/LCO

LCO

NCANCA

NCA

NCM811NCM111/LCO

NCM111NCM523NCM523/LMO

NCM523 NCM523/LCO

LCO

NCANCA

NCA

NCM811

NCM111/LCO

Case Study:Cell Safety of 18650 Cells

Tesla Model S cell (calculation based on NCR18650B)

CATL high power cells for 2017 [3]CATL high energy cells for 2017-2018 [3]

Goal of Renault/Nissan alliance with LIB Tech. [1] LG for 2021 [2]

High/middle power density cellsHigh energy density cells

[1] ZOE Battery Durability, Field Experience and Future Vision, AABC 2017, Mainz, Germany, [2] Advances in High-Energy Density Lithium-ion Polymer Battery for EV, AABC 2016, Mainz, Germany [3] Advanced xEV Battery Development at CATL, AABC 2017, Mainz, Germany

160 180 200 220 240 260 280 300 320 340 360

160

180

200

220

240

T Ther

mal

Run

away

/ °C

Gravimetric Energy Density / Wh kg-1

Layered OxideLCO – LiCoO2NCM111 – LiNi1/3Co1/3Mn1/3O2NCM523 – LiNi0.5Co0.2Mn0.3O2NCM811 – LiNi0.8Co0.1Mn0.1O2NCA - Li(Ni0.8Co0.15Al0.05)O2

SpinelLMO – LiMn2O4

1. Material level

• Energy density determined by materials

• Large variety of materials and combinations

• High research intensity

2. Electrode level

• Power capability determined mostly by the electrode design

• Power increase at the expense of energy density

• Many possibilities to increase both power and energy densities

3. Cell level

• Energy density achievable with thermally less stable materials

• More improvements needed on material and cell level for EV application(both with regard to safety and performance)

Summary

• Dr. Michael M. Thackeray, Argonne National Laboratory• Dr. Kai Vuorilehto, EAS Germany GmbH• Prof. Jeff Dahn, Dalhousie University• Dr. Ann Laheäär, Skeleton Technologies• Prof. Jiang Jiuchun, Beijing Jiaotong University• Prof. Bernd Friedrich, RWTH Aachen University

http://battery-power.eu

28. – 30. März 2017 Welcome in Aachen

Früher war alles besser –aber nicht die BatterienMartin Winter , 30. März 2017

1. Direktor des Helmholtz Institut Münster (HI MS), IEK-12, Forschungszentrum Jülich GmbH, Corrensstraße 46, 48149 Münster, Germany

2. Wissenschaftlicher Direktor des MEET Batterieforschungszentrum, Westfälische Wilhelms-Universität Münster, Corrensstraße 46, 48149 Münster, Germany

Famous quote about safety: “It will never happen to me” Captain … · 2017. 5. 10. · Famous...

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