© Fraunhofer ICT
Fraunhofer Institute for Chemical Technology ICTDr. Duygu Karabelli, M.Sc. Burak Caglar
Thomas Berger, Dr. Peter Fischer, Dr. Carsten Cremers, Dr. Karsten Pinkwart, Dr. Jens Tübke
DEPARTMENT OFAPPLIED ELECTROCHEMISTRY
© Fraunhofer ICT
Applied Electrochemistry-Fraunhofer ICT
Established 1972
Location Pfinztal-Berghausen
Staff (full-time equivalent) 80 (approx. 45)Scientists, PhD candidates 28Graduates, laboratory technicians 19Workshop and laboratory assistants 10Administration 2Trainees 21
Budget 2010 (only ICT Pfinztal) 3.8 million €
Total site area 700 m2
Laboratories, pilot plants approx. 500 m2
Test sites approx. 200 m2
Stand 31.12.2010
© Fraunhofer ICT
Batteries
T. Berger
Fuel Cells
Dr. C. Cremers
Redox-Flow-Batteries
Dr. P. Fischer
Sensors andAnalytical Systems
P. Rabenecker
Director
Dr. J. Tübke, Dr. K. Pinkwart
Project Group „Mobility“ Wolfsburg
Dr. J. Tübke
Applied Electrochemistry
Project Group „Electrochemical Storage Systems“
Dr. J. Tübke, Dr. Kai-Christian Möller
© Fraunhofer ICT
Applied Electrochemistry – Research since 1970
1970
Electrochemical direct conversion of ammonia for fuel cells
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Applied Electrochemistry – Research since 1970
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Measurement methods for the comparative study of primary batteries
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© Fraunhofer ICT
1981
Solar power generator for low power range
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Applied Electrochemistry – Research since 1970
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Hydrogen storage with reversible metalhydrid
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Applied Electrochemistry – Research since 1970
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© Fraunhofer ICT
2007
Redox-Flow Batteries for renewable energy storage
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Applied Electrochemistry – Research since 1970
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© Fraunhofer ICT
2010
Methylated spirits for fuel cells
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Applied Electrochemistry – Research since 1970
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2012
Active and passive measurements for intrinsically safe lithium-ion batteries
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Applied Electrochemistry – Research since 1970
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© Fraunhofer ICT
Materials• Test cell development.
material tests• Solid state ion
conductors• S- und O- cathodes• Alkaline -anodes
Cell Development• Pouch cells• Cell design > 40 Ah• Electrical and thermal
cell characterisation
Safety andPerformance• Standard tests up to
40 kWh / module• Customer – specific
measurements• Gas analysis• Simulation
Applied ElectrochemistryBatteries
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© Fraunhofer ICT
Lithium Batteries
Electrode materials Cathodes for Li-S and Li-O batteries
Electrolytes and separators Ionic liquids, polymer gel electrolytes and
ceramic separators, e.g. for lithium-ion andlithium batteries
Material tests
Testing and benchmarking of electrode materials, electrolytes and separators
Construction of laboratory test cells
Construction of sample cells Demonstrator cells with a pouch design
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© Fraunhofer ICT
Advantages of the Li-S system
Sulfur is cheap (70-600 $/t [1] ; LIB-material >10.000 $/t [2] )
Abundant resources
Highest theoretical capacity of solid cathode materials (1672 mAh/g sulfur)
Energy densities between 200-500 Wh/kg
Cathode production with existing Li-Ion technology
1: U.S. Geological Survey, Mineral Commodity Summaries, January 2009
2: W.F. Howard, R.M. Spotnitz: Journal of Power Sources 165 (2007) 887–891
Disadvantages of the Li-S Systems
Low cell voltage (2.2 V vgl. LIB ~3.7V)
High self discharge
Sulfur is isolator
Low cycle stability(~200 cycles)
Shuttle mechanism
Lithium-Sulfur High Energy Cells
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© Fraunhofer ICT
Lithium-Sulfur Batteries - Targets
Lower costs for electrode compared to LIB
Higher energy density than LIB ( 300-600 Wh/kg)
Comparable cycle life (> 2000 cycles)
Solving of the „shuttle mechanism“
Problem (self discharge, no full charge)
Lithium-anode
Separator
Sulfur cathode
Current collector
Current collector
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© Fraunhofer ICT
CNT electrode (side view) CNT-S electrode (bird‘s eye view)
Lithium-Sulfur Batteries – Fraunhofer Approach
Ni substrate
CNT
CNT
sulfur‐coated CNT
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Vertical alligned CNT synthesized directly on the current collector
No binder, no additional conductive carbon
80 - 90 % sulfur weight percentage of electrode!
© Fraunhofer ICT
Experiment Results - Capacity – organic electrolyte
90 % sulfur in electrode
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© Fraunhofer ICT
Li-O2 Batteries
Advantages of the Li-O system
Very high possible energy densities ~ 1,000 Wh/kg
Oxygen can be taken out of the air
Cost effective catalysts
Higher average discharge voltage than Li-S (2.7 V)
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© Fraunhofer ICT
Energydensity
Cost Lifetime Safety
State of theart
Theoretical: 11680 Wh/kg
Pratical: 1700 Wh/kg
Ratio: 14,5%
Cost-effectivecatalysts
Demonstratedlife up to about
50
Thermal runaway not
possible
Lithium metal: well-known
safety problem
Future research
Increase of theratio
Increase of thevolumetric
energy density
Development ofmanufacturing
equipment
Better design
Higher numberof charge cycles
needed
Safer anodealternatives
Lithium-Air Batteries - Targets
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© Fraunhofer ICT
Air electrode: coated carbon cloth with high specific surface area
Composition of the air electrode 5% PTFE 30% MnO2 nanowires 65% Carbon
Lithium-Air Batteries – Fraunhofer Approach
High capacity Good capacity retention
Capacity over cycle life at 0.1 mA/cm2 in 0.7 M LiTFSI/TEGDME. Catalyst: 30% MnO2. Capacity in mAh/gelectrode (carbon + catalyst + PTFE, without substrate)
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© Fraunhofer ICT
Batteries – Safety Tests
FreedomCAR – Electrical Energy Storage Systems Abuse Test Manual for Electricand Hybrid Vehicle
VDA test specification for lithium ion batteries for hybrid vehicle
Tests for the UN Regulations on Transport of Dangerous Goods ADR 2003, IATA DGR 2003 und IMDG Code 2002)
Other tests (e.g. UL 1642)
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© Fraunhofer ICT
EUCAR Hazard Level´s
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© Fraunhofer ICT
What do we offer?
Mechanical Abuse Tests
Controlled crash, Penetration, Fall tests, Immersion…
Electrical Abuse Tests
Overcharging, Short-circuiting/partial short-circuiting, Forced discharge/voltage reversal
Thermal Abuse Tests
Thermal stability, Simulated fuel fire, Storage at high temperature
Rapid charging/discharging, Rapid temperature cycling
Analytical Methods and Equipment
Climate and test chambers, Corrosion (saltfog or noxious gases)
Cyclic voltammetry, Impedance spectroscopy
Differential electrochemical mass spectroscopy
Battery testing facility for safety investigations © Fraunhofer ICT
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Climate chamber© Fraunhofer ICT
Inflated pouch cell© Fraunhofer ICT
© Fraunhofer ICT
Non-Destructive Testing
Cell Tester -64 Channels
Voltage ± 5 V, Current ± 3 A
Integrated impedance measurement up to 300 kHz
Cell Tester -16 Channels
Voltage -3 bis +10 V
Current ± 4 A
Cell Tester -8 Channels
Voltage 0 bis 6 V
Current ± 40 A
Module Testing Unit
6 channels, regenerative, impedance measurement
Data logger (voltage, temperature)
Voltage 0 – 60 V
Current ± 300 A
Battery module developed at Fraunhofer ICT
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© Fraunhofer ICT
Non-Destructive Testing
Pack Testing Unit
2 channels, regenerative
Data logger (voltage, temperature)
Voltage 10 – 1000 V
Current ± 300 A
Shaker Unit with Sliding Table
Frequency range 5 – 3000 Hz
Sine-wave/random noise 18 kN, Schock40 kN
Vibration amplitude +/- 26,0 mm
Acceleration 833 m/s² under shock operation with test sample mass up to 25 kg
Maximum test sample load 300 kg
Sliding table surface 600 x 600 mm
Shaker unit with sliding table© Fraunhofer ICT
Drop-Shock Tester
Test sample masses of up to 85 kg
Semi sine-wave 150 g Duration: 6 mm
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© Fraunhofer ICT
MaterialMaterial StackStack SystemSystem SimulationSimulation
• Development • Test and
Characterization• Alternative battery-
chemistry• Long-Term durability
tests
• Cell- and Stack design
• Prototype-development
• Characterization• Aging tests
• System design• Demonstrator• Automation• Battery-
management• Thermal Balance
• Coupled models of electrochemistry and flow
• Leak-current simulation
• Microgrids
Applied ElectrochemistryRedox-Flow-Batteries
© Fraunhofer ICT
Redox-Flow Battery
Material development and testing Electrode materials Separators Electrolytes Long-duration tests, simulations, aging
Stacks and systems Stack design and development Construction of prototypes Feasibility studies System integration, battery
management
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© Fraunhofer ICT
Vanadium Redox-Flow-Batteries
High efficiency (>75 %) Long calendar life, excellent cycle
ability (> 10.000) Flexible design (power/energy
separate scalable) Modular design possible Fast response time (μs – ms) Over charge and over discharge
tolerant Low maintenance costs Low self discharge Low energy density (15-25 Wh/L) Corrosive media
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© Fraunhofer ICT
Vanadium / Air Redox-Flow-Batteries
MEA
Electrode
Pump
Load
- +
Electrode
Electrolyte
Air
Anode: V2+ V3+ + e-
Cathode: O2 + 4e- + H+ 2H2O
- 0,255 V vs. NHE
+ 1,2 V vs. NHE
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© Fraunhofer ICT
Redox Flow Battery – Comparison of Redox Systems
Type Energy
Density of Electrolyte
[Wh/L]
Current Density
[mA/cm²]
Power Density [W/m²
electrode]
Cell Voltage [V] (25°C, 1 mol/L
electrolyte conc.)EE
Vanadium / Vanadium 30 80 ~ 800 1,40-1,60 70 – 90 %
Vanadium / Bromine 35-70 1,34 66 – 75 %
Iron / Chromium 40 40 ~ 200 1,18 75 %
Polysulfide / Bromine 80 60 ~ 800 1,52 60 – 75 %
Zinc / Bromine 80 >100 ~ 1000 1,85 65 – 75 %
Uranium 1,00
Neptunium 1,00-1,10
Cerium / Zinc 12-20 400-500 1200-2500 2,00-2,40
Lead 75 ~ 1000 2,00
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© Fraunhofer ICT
Materials Testing
Characterization of bipolar plates, membrane materials, felt electrodes and electrolyte chemistry in cell test
columbic efficiency
energy efficiency
discharge power density
Development of commercial test rig for redox flow batteries with standardized test cell
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© Fraunhofer ICT
Materials (Bipolar plates)
Thermoplastic and thermoset bipolar plates Injection molded
Compression molded
Fillers Natural and synthetic graphite
Carbon nanotubes
Carbon fibers…
Coated metallic bipolar plates Substrates Fe, Ti, Al
Metal doped diamond-like carbon (Me-DLC) / boron doped diamond Dopants transition metals (IV-Vi)
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© Fraunhofer ICT
Stack Development and Production
600 cm² active area, 22 cells, 18 – 35 V
max. 60 A, 1,5 kW
Simple stack design
Simple assembly of stacks
Process technologies for flow frame production (injection molding)
Systems up to 30 kW
Design of demonstrators and test rigs
Systems for home PV
IPS systems with hybrid of Supercap bank + RFB
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© Fraunhofer ICT
Simulation & Modeling
Simulation of flow through of cells/
battery stacks
Electrochemical battery model 2D of
V-RFB/ VOFC
Electrochemical battery model 3D of
V-RFB under development
Evaluation via in-situ measurements
Segmented cell for the measurement
of local current densities
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© Fraunhofer ICT
System (Redox-Wind)
2 MW wind turbine with a 2 MW/ 20 MWh
All-Vanadium-Redox-Flow-Battery at the
ground of ICT
Junction / DC coupling of wind turbine and
battery
Development /adaption of the battery to the
wind turbine
Synergies with a new design of the electrical of
cost effective production technologies
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© Fraunhofer ICT
Energy Systems
Energy optimization
Analysis and optimization with respect to
Electricity, heating, and cooling requirements of the company + public areas
Utilization of surpluses
Integration of distributed generation and energy storage
Shifting of loads to reduce peak demand
Efficient use of energy
Visualization of energy flows
Integrated Optimization
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© Fraunhofer ICT
Increasing the self-supply for electricity and heat demand
Utilization of surpluses
Reduction of peak loads
Visualization of energy consumption and management of energy data
Specific savings goals only possible after analysis of potential
Simulation Analysis Definition of goals
Practical implementation
Energy Systems
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© Fraunhofer ICT
Energy optimization
Secure energy costs through distributed generation and energy storage
Transparency and understanding for own consumption
Keeping investment costs low by contracting models with public utilities
Savings through the use of energy surpluses
Reduction in procurement costs through peak load reduction
Load shift: The highest peak power in the load curve determines the amount of kWh price
Added value through networking activities
Energy Systems
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© Fraunhofer ICT
Design and simulation of a hybrid power supply for an observatory tower in Oman (desert) to 3000 m altitude:
Modeling with photovoltaics, small wind power, generator and battery (redox flow / lead-acid battery)
Simulation of one year operation term
Design of the components for a commercial operation
Energy Systems
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© Fraunhofer ICT
Energy Optimized Research Centre
Simulation ICT campus electrical supply by:
Wind turbine with redox flow battery, CHP and power grid
Simulation of future operational scenarios
Investigation of the degree of self-sufficiency
Extension of the model to the heat supply and an intelligent interaction of the components
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© Fraunhofer ICT
Materials• Electrocatalyst• Support material• Membrane electrode
assembly (MEA)• Bipolar plates
Characterization• Materials• Degradation• System tests
System• DAFC Systems up
to 5 kW• Reforming• Degradation, Aging• Simulation
Applied ElectrochemistryFuel Cells
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© Fraunhofer ICT
Development and Evaluation of Materials
Electrocatalyst
Alcohol oxidation in alkaline FCs Oxygen reduction in alkaline FCs (PGM free) Alcohol oxidation in HT-PEMFC Sulfur-containing reformat in HT-PEMFC PEM-Electrolysis
Support materials
PEMEL Anodes HT-PEMFC
Binder materials for alkaline membrane fuel cells
TEM image of electrocatalyst
SEM image of catalyst layer in electrode
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© Fraunhofer ICT
Fraunhofer ICT designed a flow through DEMS Cell
The quantification of CO2 production including in alkaline media
Determination of the alcohol oxidationproduct spectrum
Investigation of reactions for the electrochemical synthesis
Investigation of support and binder corrosion
HT-DEMS
Only at Fraunhofer ICT DEMS measurements in the gas phase at elevated
temperature Characterization of catalysts for HT-PEMFC under
realistic conditions
Development and Evaluation of Materials
HT-DEMS cell for the characterization ofcatalyst
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© Fraunhofer ICT
Development of membrane electrode assemblies (MEA)
LT-PEMFC HT-PEMFC AEMFC PEMEL
Development of adapted coating processes
Binder selection Ink formulation Spraying conditions Thermal treatment
Partially automated spray-coater for small series
Membrane Electrode Assemblies
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© Fraunhofer ICT
Single cell tests Current - Voltage Impedance spectroscopy Current density distribution measurement Determination of the electrochemically active surface Product analysis with online MS Offline analysis with GC or HPLC
Measuring stations LT-PEMFC/PEMEL HT-PEMFC DAFC
Investigation of mass transport in PEMFC electrodes for automotive applications
Analysis of transient corrosion processes by online mass spectrometry
0 50 100 150 200 250 300 350 400 450
0,2
0,4
0,6
0,8
1,0
cell
pote
ntia
l / V
current density / mA cm-2
Alkaline Anion Exchange Membrane Direct Ethanol Fuel Cell Performance
0
20
40
60
80
100
120
pow
er d
ensi
ty /
mW
cm
-2
Membrane Electrode Assemblies
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© Fraunhofer ICT
Stacks and System Integration
Direct alcohol fuel cell systems for portable applications
Fuel cell based range-extenders and APUs
HT-PEMFC petrol steam reformer as APU for electric vans
Reformed methanol fuel cells as range extender for compact class car
Hydrogen PEMFC range-extenders
Fuel cells for military applications
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© Fraunhofer ICT
© Fraunhofer ICT
THANK YOU FOR YOUR ATTENTION!
Dr. Duygu Karabelli
Tel.: +49 (721) 4640827Email: [email protected]
M.Sc. Burak Caglar
Tel.: +49 (721) 4640514Email: [email protected]
Applied ElectrochemistryFraunhofer-Institute for Chemical TechnologyJoseph-von-Fraunhofer-Str. 776327 Pfinztal
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