Membranes for water electrolysis and for flow batteries Bernd Bauer, Tomas Klicpera FuMA-Tech GmbH Hannover, April 13 th 2015 1
Introduction of Fumatech as part of BWT Background of decision in participation at energy storage and energy conversion concepts Membranes for water electrolysis Membranes for battery systems 2 2 2
Frischwasser-Stress 3 Quelle: Assessing Water Risks, WWF 2011, Philippe Rekacewicz, February 2006, http://maps.grida.no/go/graphic/water-scarcity-index 3 3
Facts and possible outcome regarding water consumption Consumption of water has risen 6-fold in last 100 years and in next 20 years will be yet doubled. The crisis that concerned only developing countries are affecting even the most developed ones (look at California drought that lasts for 8 months). Availability of water that is clean enough might likely limit the development of economy regardless the region. Smaller innovative decentralized system of water treatment will be 4 possibly set as standard one and might become matter of regulation or indirectly matter of lawmaker actions due to the public pressure. 4 4
A said, B follows: and what happens if there is not enough clean water? More energy is necessary to invest and that could become at certain point critical Our conclusion: reduction of CO 2 footprint and higher utilization of produced energy has surprisingly more in common with link between energy and water than what one would expect. Those two reasons has triggered the interest at Fumatech in the energyrelated matters about 15 years ago. Fumatech actively follows the power-to-gas (P2G) concept of energy conversion (= electrolysis) and concept of energy storage (= batteries) 5 5 5
Our vision Approach of Fumatech: Utilisation and development of our key competences that contributes to both water treatment and energy storage / energy conversion Key competence: development and production of membranes plus increasing their value by an action such as catalyst coating (CCM) for electrolysis or building membrane-electrode assembly (MEA) for water treatment. 6 6 6
Portfolio of Fumatech s membranes for energy application Redox Flow Batteries FAP membranes F 930 rfd, F 1075 PK Hybrid membranes AEM (50 75 C) FAA 3 LTPEM (50 90 C) F 940 rfs SPS membranes MTPEM (90 120 C) FS 720 rfs Composite membranes HTPEM (150 180 C) A membrane Alk. Water electrolysis FAAM 75 rf PEM water electrolysis Membranes: F 9100 rf, F 9120 rf, F 9180 rf CCM: fumea EF 10 DMFC (50 80 C) F 1850 E 730 7
PEM water electrolysis membranes 8 8 8
Request on membrane properties: Specific resistance of membrane: less than 200 mohm.cm 2 Good mechanical properties: high Young modulus (> 1000 MPa), high tensile strength Low Hydrogen permeation Reinforced membranes preferred Thickness 75-250 µm; which is depending on application, pressure difference etc. Remark: The membranes are utilized for production of own CCM fumea, but all of them are also freely commercially available 9 9 9
Typical performance of WE membranes Membrane Resistance / Thickness / µm Dim. Swelling / mohm.cm 2 % U @ 2 A/cm2 @ 80 C in V F-1075-PK 90 70-75 < 1 1,79 F-10100-PK 125 95-100 < 2 1,84 F-10120-PK 155 115-120 < 2 1,90 F-10180-PK 190 170-180 < 3 2,00 F-9240-PTFE 240 235-245 < 10 2,05 The higher pressure / pressure difference the thicker membrane 10 is necessary. 10 10
Customer s durability data 11 Membrane F-9240-PTFE (fumea EF-40), idle filtered. 11 11
Membranes for vanadium-redox-flow batteries 12 12 12
VRB application: one of the technologies that has enjoyed just limited funding, but it has been brought to commercial scale. The size of modularly scalable and ranges from 10kW up to 10MW. The VRB has by far the largest energy efficiency among all electrochemical processes focused on energy storage and it fits well to wind/solar renewables Key components: carbon electrode, carbon bipolar plates and membrane -> no limitation by precious metals 13 13 13
Vanadium-Redox-Flow Batteries + - 14 14
Membrane s types -Cation exchange (abbr. CEM), PFSA-based ones -> electrolyte crossover direction V (5+) -Anion exchange (abbr. AEM), proprietary polymers -> electrolyte crossover direction V (2+) The choice depends on following factors: -Operation range of current densities -Target efficiencies -Periphery for equalising the electrolytes -Required mechanical robustness -Target price The decission is based on characterisation of each candidate by defined protocol 15
VRB membranes made by Fuma Membrane Resistance Coul. Eff. / Ohm.cm 2 % EOP µl/(cm2.hr) OP µl/(cm2.hr) Cross-over direction FAP-450 650 97 10 5 Cathode No FAP-330 390 93 15 11 Cathode No PE FAP-375 630 95 11 6 Cathode No PE F-930rfd 520 99 21 1 Anode Yes F-1070 PK 670 99 21 0,2 Anode Yes F-1850 1500 99 12 0,1 Anode No Develop. 250 94 18 3,8 Anode No 16 Changes of electrolyte conc. 16 16
Example of short-time cycling 17 Cation-exchange membrane F-930rfd: performance loss about 0,3% per cycle 17 17
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Membrane Dispersion Polymer www.fumatech.de fumion fumion FF fumapem F fumapem S fumapem FZP fumapem AM fumasep FAA fumasep FAP fumasep FBM fumasep fumea ionomer resin as granular polymer, in solution form or in dispersion granular perfluorosulfonyl fluoride resin for extrusion perfluorosulfonic acid membranes for PEMFC hydrocarbon membranes for DMFC and PEMFC hybrid membranes for medium temperature PEMFC membranes for high temperature PEMFC anion-exchange membrane for alkaline DEFC anion-exchange membrane for redox flow batteries bipolar membrane ion-exchange membranes for humidifers, electrodialysis and electrolysis catalyst coated membranes for water electrolysis