© 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
© Fraunhofer Allianz Batterien
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
© Fraunhofer Allianz Batterien
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
© Fraunhofer Allianz Batterien
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
© Fraunhofer Allianz Batterien
Materials and Cells
Systems
Testing and Evaluation
Simulation
Fraunhofer Battery Alliance Competences
► + Trainings and Seminars, Studies, Roadmaps, Strategies
© Fraunhofer Allianz Batterien
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
© Fraunhofer Allianz Batterien
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
© Fraunhofer Allianz Batterien
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
© Fraunhofer Allianz Batterien
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
© Fraunhofer Allianz Batterien
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
© Fraunhofer Allianz Batterien
> 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
© Fraunhofer Allianz Batterien
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
© Fraunhofer Allianz Batterien
> 2030 2012 short-
term 2015 mid-term 2020
long-
term
Li S Li air
Roadmap Next Generation Lithium-based Technologies
© Fraunhofer Allianz Batterien
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
© Fraunhofer Allianz Batterien
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
Fraunhofer Battery Alliance Next Generation Lithium-based Technologies
© Fraunhofer Allianz Batterien
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
Fraunhofer Battery Alliance Next Generation Lithium-based Technologies
© Fraunhofer Allianz Batterien
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
Fraunhofer Battery Alliance Next Generation Lithium-based Technologies
Sintered LATP glass ceramic micro structure with conductivity of 0,3 mS/cm@25°C
► Material synthesis, powder processing and development of sintering routes
© Fraunhofer Allianz Batterien
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
+ + +
+ +
+ + +
Fraunhofer Battery Alliance Next Generation Lithium-based Technologies
© Fraunhofer Allianz Batterien
Li-S cells and Li2S-Si cells
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 Battery Alliance Next Generation Lithium-based Technologies
© Fraunhofer Allianz Batterien
Li-S cells and Li2S-Si 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]
Fraunhofer Battery Alliance Next Generation Lithium-based Technologies
© Fraunhofer Allianz Batterien
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)
Fraunhofer Battery Alliance Next Generation Lithium-based Technologies
© Fraunhofer Allianz Batterien
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
Fraunhofer Battery Alliance Next Generation Lithium-based Technologies
© Fraunhofer Allianz Batterien
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
Fraunhofer Battery Alliance Next Generation Lithium-based Technologies
© Fraunhofer Allianz Batterien
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
Fraunhofer Battery Alliance Next Generation Lithium-based Technologies
© Fraunhofer Allianz Batterien
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 Next Generation Lithium-based Technologies
© Fraunhofer Allianz Batterien
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]