Applied Battery Research in Germany - SUNJET II - Moller.pdf · Applied Battery Research in Germany ... German Cultural Center 1F Akasaka 7-5-56, ... Laser Technology ILT Hall Silicate

© Fraunhofer

Dr. Kai-Christian Möller

Fraunhofer Battery Alliance Applied Battery Research in Germany

© Fraunhofer Allianz Batterien

The German Research Landscape Basic and Application-oriented Research

0%

25%

50%

75%

100%

Fraunhofer Helmholtz Leibniz Max-Planck

Drittmittel aus derWirtschaft**

Drittmittel aus Wettbewerb(ohne Wirtschaft)*

Institutionelle Förderung

Source: Paktbericht 2013, Daten aus 2012

base funding

industrial revenue

public sector revenue


The Fraunhofer Gesellschaft Locations in Germany

67 institutes

23 236 employees

budget: 2,010 billion €

(72 % contract research)

patent applications: 603 active patent famailies: 6407

International cooperation via affiliated offices in Europe, USA, Asia and in the Near East institutes

further locations

Status 2013

München

Holzkirchen

Freiburg

Efringen- Kirchen

Freising Stuttgart

Pfinztal Karlsruhe Saarbrücken

St. Ingbert Kaiserslautern

Darmstadt Würzburg

Erlangen

Nürnberg

Ilmenau

Schkopau

Teltow

Oberhausen

Duisburg

Euskirchen Aachen St. Augustin

Schmallenberg

Dortmund

Potsdam Berlin

Rostock

Lübeck Itzehoe

Braunschweig

Hannover

Bremen

Bremerhaven

Jena

Leipzig

Chemnitz

Dresden

Cottbus Magdeburg

Halle

Fürth

Wachtberg

Ettlingen

Kandern

Oldenburg

Freiberg

Paderborn

Kassel

Gießen Erfurt

Augsburg

Oberpfaffenhofen

Garching

Straubing

Bayreuth

Bronnbach

Prien

Hamburg

Leuna


The Fraunhofer Gesellschaft Fraunhofer Representative Offices Asia

Representative Office Tokyo

Seoul Beijing

Bangalore

Tokyo

Jakarta

Ampang

► www.fraunhofer.jp/en.html

German Cultural Center 1F Akasaka 7-5-56, Minato-ku Tokyo 107-0052


Ernst-Mach-Institute EMI

Electron Beam and Plasma Technology FEP

Chemical Technology ICT

Manufacturing Techn. and Appl.Materials Research IFAM

Integrated Circuits IIS

Ceramic Technologies and Systems IKTS

Laser Technology ILT

Silicate Research ISC

Systems and Innovation Research ISI

Integrated Systems and Device Technology IISB

Silica Technology ISIT

Solar Energy Systems ISE

Techno- und Industrial Mathematics ITWM

Transportation and Infrastructure Systems IVI

Mechanics of Materials IWM

Material and Beam Technology IWS

Structural Durability and System Reliability LBF

Wind Energy and Energy System Technology IWES

Manufacturing Engineering and Automation IPA

München

Holzkirchen

Freiburg

Efringen- Kirchen

Freising Stuttgart

Pfinztal Karlsruhe Saarbrücken

St. Ingbert Kaiserslautern

Darmstadt Würzburg

Erlangen

Nürnberg

Ilmenau

Schkopau

Teltow

Oberhausen

Duisburg

Euskirchen Aachen St. Augustin

Schmallenberg

Dortmund

Potsdam Berlin

Rostock

Lübeck Itzehoe

Braunschweig

Hannover

Bremen

Bremerhaven

Jena

Leipzig

Chemnitz

Dresden

Cottbus Magdeburg

Halle

Fürth

Wachtberg

Ettlingen

Kandern

Paderborn

Kassel

Gießen Erfurt

Augsburg

Oberpfaffenhofen

Garching

Straubing

Bayreuth

Bronnbach

Prien

Hamburg

Leuna SCAI

Oldenburg

Freiberg

EMI, ISE, IWM

ICT

IFAM

ICT

IIS, IISB

FEP, IKTS, IVI, IWS ILT

ISC

ISIT

ITWM

LBF

ISI

IPA

Sulzbach- Rosenberg

IWES

Fraunhofer Battery Alliance Members


Materials and Cells

Systems

Testing and Evaluation

Simulation

Fraunhofer Battery Alliance Competences

► + Trainings and Seminars, Studies, Roadmaps, Strategies

../../Presentations/generalBatteryPresentation/BEST_GeoDict2Geometry_longRun2.avi


development of anode and cathode active materials from synthesis to particle modification

development of electrolytes and separators

electrode manufacturing, cell assembly, process development for innovative and economic manufacturing of electrodes and cells, pouch cell pilot production line

characterization, post-mortem analyses , investigation of degradation mechanisms

recycling concepts for batteries

Lithium-Ion, Li-Sulfur, Li-Air, Na-Ion, Redox-Flow, Zinc-Air, Supercaps, Lead Acid, …

Fraunhofer Battery Alliance Materials and Cells


packaging and cell design, module development, connections, sealing, housing

integrated sensors for tests and development, microsensors for temperature and pressure, wireless potential and current sensors

battery prototype production for different applications and requirements

battery managment, battery monitoring, optimized charge strategies, single cell protection, cell balancing, state of charge and capacity determination

Fraunhofer Battery Alliance Systems


electrical characterization, temperature behavior, ageing behavior and mechanisms

electrical, mechanical and thermal abuse tests (VDA specifications for lithium-ion batteries for hybrid electric vehicles, tests for storage and transport (UN Regulations on Transport of Dangerous Goods)

Fraunhofer Battery Alliance Tests


material research

electrode and cell design

safety and durability, calender life

battery system and battery managment

life cycle analyses

methods: quantum-chemical simulations, molecular dynamics, electrochemical continuum simulations, structural mechanics simulation, battery network models

Fraunhofer Battery Alliance Simulation


Roadmap

► www.isi.fraunhofer.de/libroad.php


solid

electrolytes woven

nonwoven

casted separator

polymer

membrane

LiMnPO4 4V

LiNiPO4 5V

LiCoPO4 5V

> 2030 2012 short-

term 2015 mid-term 2020

long-

term

Roadmap

Li4Ti5O12

soft carbon

modified

graphites

Li metal

non-Si alloys

C/alloy

composites Si alloys

Li Me Me Me O2

LiFePO4

S

5V spinel Li Me Me Me O2

high voltage oxygen / air

-SO4F conversion

cathodes

F as MeFx

gel polymer

electrolyte

5V electrolyte

LiPF6-free

electrolyte

ceramic

composites cellulose

chemically

impregnated

C/alloy

composite > 800 mAh/g

4.3 V

LIB

5 V

LIB Li S

Li

Polymer Li air

4.4 V

LIB


> 2030 2012 short-

term 2015

mid-

term 2020

long-

term

Roadmap High Voltage Cells

4.3 V

LIB

5 V

LIB

4.4 V

LIB


Core-shell-materials

Inorganic-organic coating of high voltage cathodes materials

Protected electrode/electrolyte interface

High charging end voltages

Good rate capability

Improved cycling stability

Up scaling to kg batches

Cost-saving coating process

Fraunhofer Battery Alliance High Voltage Cathodes

Galvanostatic cycling of pristine and coated LiNi0,5Mn1,5O2-electrode

► „5 V“ battery w/ commercial available electrolytes 50 nm

LiNi0,5Mn1,5O2

ORMOCER®

Coated LiNi0,5Mn1,5O2-particle


> 2030 2012 short-

term 2015 mid-term 2020

long-

term

Li S Li air

Roadmap Next Generation Lithium-based Technologies


Li-S cells and Li2S-Si cells

► Li-S cells are interesting for their potential high gravimetric energy density

Grav. and vol. energy density of various electrochemical storage systems

Fraunhofer Battery Alliance Next Generation Lithium-based Technologies


Lithium metal deposition (Plating, dendrites)

Charging rate limitations at low temperatures

Ageing effect: irreversible Li deposited on the anode

Safety risk: short circuits caused by dendrite growth

Reasons for plating

Cell operating conditions (Temperature, charge rate)

Cell design factors

Non-uniformities within stack

► Plating is initiated locally: non-uniformities

Overcharged graphite electrode

In-Operandi microscope investigations on graphite electrodes



Lithium Plating

Main factors

Temperature

Charge rate

Rest time (after charging)

Detection methods

Discharge voltage

dV/dQ

Locally through Raman microscopy

► Determine the onset current for irreversible platting Rest time (after charging) effect on

the discharge voltage at -10°C

Charge rate effect on the discharge voltage at 0°C



Lithium conducting glass ceramics for solid electrolytes and separators

LATP-System (Li1+xAlxTi2-x(PO4)3

Lithium-Air and Lithium-Sulfur batteries

Stable in aqueous environments

Conductivities up to 0,4 mS/cm at 25°C

Process technology and applications

Monolithic substrates by tape casting

Films on porous substrates by screen printing

Conducting fillers in polymer based separators


Sintered LATP glass ceramic micro structure with conductivity of 0,3 mS/cm@25°C

► Material synthesis, powder processing and development of sintering routes


Development of new Li-S cell chemistries

Target: high specific energy on cell level:

> 350 Wh kg-1

Cathode concept:

Tailored porous carbons for cathodes with

enhanced sulfur-utilization

Solvent-free dryfilm-process for cathode

production

Ion-selective separators and high capacity silicon anodes for enhanced Li-S-cells are in development

► High specific capacity through tailored cathode

► Modified separators and alternative anodes are in progress

Sulfur / carbon nanocomposite for cathodes in Li-S batteries

Dryfilm-process for electrode production @ Fraunhofer IWS

+ + +

+ +

+ + +




High requirements for sulfur cathodes

► Only high sulfur loads, high sulfur utilization and a low electrolyte/sulfur ratio may push the energy density above the level of commercialized cells!




Fraunhofer ICT focuses on electrode parameters fulfilling the criteria of high

energy density cells high sulfur loads, high sulfur ratio and high sulfur utilization

► Our main target: Reduction of electrolyte amount

[figure caption with explaning informations]



Li-S pouch cell production

Proof of concept – tests in pouch cell

Evaluation of new material concepts in

3 Ah pouch cells

Pouch cell production

3 Ah cells with energy density up to 250 Wh kg-1 are available

New concepts for high energy density > 350 Wh kg-1 are in progress

► High energy Li-S pouch cells in development

► Target specific energy: > 350 Wh kg-1

Performance example of developed Lithium-Sulfur-cells

Dryfilm electrode and Li-S pouch cells (200-250 Wh kg-1)



Process technologies

Electrode production

Dryfilm process and roll-to-

roll coating

Fast cutting by remote laser

“on the fly”

Electrode stacking

Flexible in type

Flexible in shape

Flexible in capacity

► Automated (Li-S) cell processing line (stacked pouch cell)

► Integrated laser cutting and welding technologies

Samples of laser welded tabs Stacking machine with laser welding of tabs

Test channels from 40 up to 300 A



Li/Air Battery Technology

high energy density, but: electrical

rechargable?, efficency?, cycle stability?

Material development:

Li Anode

Cycling of Li Metal, dendrites,

stability and safety, limited

Coulombic efficiencies

Electrolyt

Stability, Li+ - conductivity, O2

solubility

Gas Diffusion Electrodes

Impact of porosity design, Role of

a catalyst

Aprotic Electrolyte

Electrolyte compatibility



GDE development for Li Air

Porosity and wettability:

Development of 3d mesoporous electrode based on Xerogels

No pore clogging, maintain conductivity during discharge

Role of the catalyst:

Discharge / charge kinetics

improved kinetics, surpressing overpotential

Left: Li2O2 deposition/pore clogging as function of porosity; Right: SEM pictures of 3D mesoporous GDE, Toray Paper with Carbon Xerogel *)

top v iew

cross -cut

macropores

meso-/macropores

mesopores

1M LiTFSI / DMSO

MPL (Freudenberg) Vulkan Xerogel



Li/Air Battery Technology: Characterization Methods

In-situ techniques:

in-situ Raman spectroscopy

in-situ Mass spectrometry/Infrared spectroscopy

Inert techniques:

Inert-SEM/EDX (operating in Ar glovebox)

Inert-XPS (Ar glovebox attached to XPS chamber)

Inert-RRDE (operating in Ar glovebox)

System level: Metal-Air test facility

30 channels for operating condition analysis

gases: O2, CO2, Ar, N2

solvent saturation (org./aq.)

-40°C-140°C.

in-situ Raman spectroscopy

Metal-Air test facility



Fraunhofer Battery Alliance

► www.batterien.fraunhofer.de/en.html

Dr. Kai-Christian Möller Deputy Spokesperson for the Alliance Fraunhofer Institute for Chemical Technology ICT Project Group Electrochemical Energy Storage Parkring 6, 85748 Garching b. München, Germany phone: +49 89 540208 - 600 email: [email protected]

Documents

Applied Battery Research in Germany - SUNJET II - Moller.pdf · Applied Battery Research in Germany ... German Cultural Center 1F Akasaka 7-5-56, ... Laser Technology ILT Hall Silicate