Electrochemistry centered services for fuel cells and other electrochemical power sources

Transcription

1 Electrochemistry centered services for fuel cells and other electrochemical power sources Group Exhibit Hydrogen, Fuel Cells and Batteries, Technical Forum 24 th of April 2017, Hannover, Germany Dr. Carsten Cremers Team Leader Fuel Cells Fraunhofer Institute for Chemical Technology (ICT) Department for Applied Electrochemistry Joseph-von-Fraunhofer-Str Pfinztal

2 Outline The Fraunhofer ICT and its department for Applied Electrochemistry Why care about electrochemistry Established services for batteries Our offerings for fuel cells

3 Fraunhofer-Gesellschaft, the largest organization for applied research in Europe 69 institutes and research units 24,500 staff 2.1 billion annual research budget totaling. Of this sum, more than 1.9 billion is generated through contract research Roughly two thirds of this sum is generated through contract research on behalf of industry and publicly funded research projects Roughly one third is contributed by the German federal and Länder governments in the form of base funding

4 FRAUNHOFER INSTITUTE FOR CHEMICAL TECHNOLOGY ICT ICT

5 Business areas of the Fraunhofer ICT Energy and environment Chemistry and process engineering Defense, safety and security, air and space travel Automotive and transport technology

6 Organization of the Fraunhofer ICT Director Prof. Dr. P. Elsner Deputy Directors W. Eckl, Prof. Dr. F. Henning Controlling C. Steuerwald Administration Dr. B. Hefer, C. Steuerwald General Management Dr. S. Tröster Energetic Materials Dr. S. Löbbecke Dr. H. Krause Dr. T. Keicher Energetic Systems W. Eckl G. Langer Dr. J. Neutz Applied Electrochemistry Prof. Dr. J. Tübke Prof. Dr. K. Pinkwart Environmental Engineering R. Schweppe S. Rühle Polymer Engineering Prof. Dr. F. Henning Dr. J. Diemert Dr. T. Huber Fraunhofer ICT-IMM, Mainz, Germany Project group for New Drive Systems NAS, Karlsruhe, Germany Fraunhofer Project Center FPC London (Ontario, Kanada) Fraunhofer Project Center for Composites Research, Ulsan, Korea Prof. Dr. Michael Maskos Dr. H.-P. Kollmeier, Prof. Dr. P. Elsner, Prof. Dr. P. Gumbsch (IWM) Prof. Dr. F. Henning

7 Applied Electrochemistry Department Primary and secondary batteries Next generation material and system development e.g. for lithium- or sodium-sulfur, demonstrator set-up, testing and measurement services, safety investigations including gas analytics Redox-flow batteries Investigation and development of alternative electrolytes, stack development, technology consulting, configuration management, simulation Fuel cells Material development for direct alcohol, anion exchange membrane and HTPEM fuel cells, fuel cell system development, APU/range extender and military applications Sensor technology and analysis systems Electrochemical sensors, trace detection, pattern recognition, online analysis, imaging and surface analysis, corrosion investigations and leakage measurements

8 Why care about electrochemistry Though it might appear that power sources can be treated as black boxes in the applications in which they are used, there are a number of reasons to strive for a deeper knowledge of the processes within. Systems are often used over a very broad range of power and under varying environmental conditions. Knowledge of the internal processes helps to prevent failures. For special purpose applications, which are not designed for a purpose power supply, the knowledge about the internal processes helps to adapt common types. In case of an abuse of the system, knowledge about the internal processes helps to develop mitigation strategies and reduce risk and liability. There it is important to care about the electrochemistry.

9 Established services for batteries Electrolyte, ageing and decomposition analytics Pressure Normalized Ion Current / A mbar -1 0,01 1E-3 1E-4 1E-5 7 N 2 14 N 2 / CH 4 + Electrolyte 16 O 2 + Electrolyte 32 O 2 + Electrolyte 34 H 2 S + O 2 33 "Alcohol?" + Electrolyte + 44 DIOX / CO 2 76 CS 2 29 Electrolyte 31 Electrolyte (DME) 1E-6 1E-7 1E-6 1E-7 1E Relative Time / hrs Pressure / mbar Differential electrochemical mass spectroscope (DEMS) Making electrolyte decomposition visible! Detection of gaseous decomposition products at different states of charge What happens at deep discharge or overcharge? Is there gas creation during SEI formation? Fast ageing prediction

10 Established services for batteries Determination of thermal and electrical parameters for your simulations Heat capacity and heat conductivity for all cell types (prismatic, cylindric & pouch cells) Internal resistance, capacity and entropy change for large cell with EIS and pulse discharge Verification of electrical and thermal simulation results Determination of the heat capacity of round and prismatic cells

11 Established services for batteries Safety and abuse tests (1) Safety concepts, fire protection, sensor systems on module and cell level Safety and abuse tests according to international standards (Transport test UN 38.3, IEC62660) Nail penetration, shaker, drop shock test, hydraulic press, overcharge, deep discharge, thermal abuse Air condition and gas washer Documentation of a lithium- ion cell thermal runaway Hydraulic press Climate chamber suitable for battery modules

12 Established services for batteries Safety and abuse tests (2) Determination of the released heat, energy and gas amount of a cell during abuse over the time Important for aggressive Ni rich cathode cells Can the propagation to neighboring cells be stopped? Design of emergency cooling systems

13 Established services for batteries Analytics for battery applications In-situ analytic during safety test (reaction products) or for determination of the electrolyte/electrode composition: Ion chromatographie (HF), micro GC (H 2, O 2, N 2, CO, CO 2, CH y ) Gas chromatograph, mass spectrometer (fluorized hydrocarbons, P-F, org. carbonates, additives), intermediate products FTIR for in-situ battery abuse test measurements SEM:EDX: Electrode material distribution Gas chromatograph Gas chromatograph/mass spectroscope Ion chromatograph

14 Services for fuel cells Catalyst stability testing Accelerated degradation test according to FCCJ, US DoE or EU test protocols Additional uses of DEMS to monitor carbon corrosion I [ma] current / ma % Pt, 0 stress cycles 10% Pt, 8000 stress cycles 10% Pt, stress cycles % Pt/CNT pristine 18% Pt/CNT after 8,000 AST cyles 18% Pt/CNT after 15,000 AST cycles carbon mass loss rate per Pt active area (pg/s)*cm AST cycles x % Pt/C 40% Pt/C 18% Pt/CNT 0,0 0,2 0,4 0,6 0,8 1,0 1,2 electrode potential / V vs. RHE

15 Services for fuel cells Single cell corrosion studies (1) Accelerated degradation tests according to FCCJ, US Doe or EU protocolls Online MS to monitor carbon corrosion Option to discern corrosion of MPL and catalyst support Optional operation with O2-Ar mixture to allow for CO detection (e.g. for Fe/C/N type of catalysts) mass spectrometer Mass spectrometric Ion Current (m/z = 44) corresponding to CO 2 concentration N 2 MFC Humidifier PEM -FC cat hode cathode exhaust (diluted) H 2 MFC Humidifier anode detection point anode exhaust

16 Services for fuel cells Single cell corrosion studies (2) Influence of temperature and humidity ratio of average ion and 0.6 V vs. RHE 60 GDL on Pt (C free CL) GDL on Pt/C (standard CL) ratio protocol cycle number m C loss rate / [ m C * m Pt ] ( [ g C /h] / [mg C *mg Pt ] ) % Pt/CB laboratory 25 C single cell 85 C ratio 70 18% Pt/CNT laboratory 25 C single cell 85 C ratio 620 enlarged / scaled up

17 Services for fuel cells Influence gas borne impurities Test of the tolerance of the catalyst for given impurities Test of possible reaction of the impurities using DEMS Independent evaluation of tolerant catalyst Determination for optimum operation conditions Dimensioning of filters current / A 0,4 0,3 0,2 0,1 0,0 H 2 H kpa toluene 0,0 0,2 0,4 0,6 0,8 1,0 electrode potential / V vs. RHE Ionic Mass Current / na 0,6 0,4 0,2 0,0 81,5 82,0 82,5 83,0 83,5 m/z > E /V Effect of toluene + thiophen on Pt/C under HT-PEMFC conditions 0.06V 0.07V 0.08V 0.09V 0.10V 0.12V 0.14V 0.16V 0.18V 0.20V 0.36V 0.46V 0.56V 0.66V 0.76V 0.86V 0.96V 1.06V

18 Services for fuel cells Influence gas borne impurities (2) Investigation of the effect of methanol cross over in DMFC Pt current density / ma mg -1 Ion current / pa ,0 2,5 2,0 1,5 1,0 0,5 Synthetic air Synthetic air + 2wt% CH 3 OH Synthetic air + 10wt% CH 3 OH 0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 potential / V (vs. RHE) m/z 22: CO 2 Pt Ion current / pa current density / ma mg ,0 4,5 3,0 1,5 0,2 0,4 0,6 0,8 1,0 potential / V (vs. RHE) m/z 22: CO 2 Room temperature: N2 Synthetic air Synthetic air + 10wt% CH 3 OH 0,0 m/z 44: CO 2 (+ HCOOH) 0,20 0,15 0,10 0,05 Ion current / na 0,0 m/z 44: CO 2 (+ HCOOH) 0,15 0,10 0,05 Ion current / na PtCo/C (right) shows better performance and less release of VOC from partial methanol oxidation than Pt/C (left) Ion current / pa 2,0 1,5 1,0 0,5 0,0 m/z 46: HCOOH (+ CO 2 ) m/z 60: HCOOCH 3 0,00 1,0 0,8 0,6 0,4 Ion current / pa Ion current / pa 2,5 2,0 1,5 1,0 0,5 0,0 m/z 46: HCOOH (+ CO 2 ) m/z 60: HCOOCH 3 0,00 0,6 0,4 0,2 Ion current / pa 0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 potential / V (vs. RHE) 0,2 0,0 0,2 0,4 0,6 0,8 1,0 potential / V (vs. RHE)

19 Services for fuel cells Special purpose system design The Fraunhofer ICT supports customers in the development of fuel cell systems for special applications This comprises Selection of the most suitable fuel cell technology Evaluation of commercially available stacks Development of an operation and hybridization strategy based on the requires such as Uptime Durability Useable fuel and oxidant Design of the balance of plant Selection of suitable balance of plant components Set-up and validation of a demonstration system

20 Services for fuel cells Select stack Evaluate stack Task: Fit a 10 bar waterproof 2 kw fuel cell system into this space Built demonstrator Evaluate operating concepts Design and valiadte BoP gas supply system volume / l Rezyklierung 2 bar dead end 2 bar maximum operation time/ h

21 Thank You for Your attention Questions? Contact Dr. Carsten Cremers Department for Applied Electrochemistry Fraunhofer Institute for Chemical Technology Joseph-von-Fraunhofer-Str Pfinztal, Germany carsten.cremers@ict.fraunhofer.de