Membranes for Energy Conversion and Energy Storage with Fuel Cells and Batteries

Membranes for Energy Conversion and Energy Storage with Fuel Cells and Batteries Dr. Bernd Bauer / FUMATECH FuMA-Tech Gesellschaft für funktionelle Membranen und Anlagentechnologie 1 1

There are no alternatives to water, but there are various alternatives to energy. Water Technologies for a Better Life! Fuel Cell and Battery Technologies for a Better Quality of Life! 2 2

BWT We go for 98.5% 3 3

FUMASEP Membranes fumasep Ion-exchange membranes Micro-heterogeneus anion- and cation exchange membranes IEx-membranes for electrodialysis and donnan dialysis Bipolar membranes Oxidation stable and chlorine tolerant anion-exchange membranes Membranes for capacitive electrodeionisation Membranes for RED energy production Membranes for sea water desalination Perfluorinated membranes for electrolysis Membrane humidifiers Flat sheet membranes for ERV applications 4 4

Membrane Humidifier Water-to-Gas and Gas-to-Gas humidifier: 1 kw 3 kw 5 kw 10 kw 100 kw 6 6

FUMAPEM Membranes fumion membrane polymers and ionomers for MEA fabrication fumapem membranes for fuel cells, batteries and electrolysers: F-series fully fluorinated membranes for LT-PEM AM-series acid doped membranes for HT-PEM S, ST and P-series hydrocarbon type membranes for DMFC FAA anion exchange membranes for alkaline fuel cells FAAM anion exchange membranes for alkaline electrolysers FAP anion membranes for vanadium redox batteries fumea catalyst-coated membranes for water electrolysis 7 7

New FUMATECH production site New membrane production site in Bietigheim-Bissingen from 2013 8 8

Membranes for Energy Conversion 9 9

Shortcomings with todays PEM Today s market hurdles for PEM fuel cells Hydrogen infrastructure (renewable H 2, reformate, ) Durability, reliability and life-time Cost Reduction of Pt-loading, non noble metal catalysts (AFC) Lower cost materials (hydrocarbon membranes, ) System simplification Non humidified operation (dry proton conductors, ) Increased operation temperature (improved PFSA, ) FUMATECH Water Technologies for a Better Life Fuel Cell Technologies for a Better Quality of Life

Low and medium temperature FC on hydrogen / air fumapem F

fumion F - perfluorinated ionomer fumion F CF 2 CF 2 x CF CF 2 O y long side-chain perfluorosulfonic acid polymer EW = 820 1100 g / eq (IEC = 1.2 0.9 meq / g) CF 2 CF CF 3 O CF 2 CF 2 SO 3 H glass transition temperature T g ~ 110 C (EW = 900) end-group protected by polymerisation high molecular weight, low PD membrane thickness 30, 40 and 50 μm reinforcement (optional)

Durability of fumapem f-950 in LT-PEMFC 1 Durabilty test: 600cycles:1h 0.5A/cm 2,2h 0A/cm 2 PEMFC at 65 C, 7-layer MEA 25cm 2 F950, 20wt%Fumion 1bara, λ H2 :1.5(85% r.h.), λ air :2.5(85% r.h.) c p :1N/mm 2, cathode:0.4 mg Pt/cm 2 (HS13100,SGL10DC) anode:0.15 mg PtRu/cm 2 (HS10100,SGL10CC) 400 0,9 350 Voltage / V 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0 run from OCV to short circuit scan rate: 0.5A/5s OCV BOL : 955 OCV EOL : 953 0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 Current density / Acm -2 Cell voltage BOL Cell voltage BOL goal Cell voltage EOL goal Cell voltage EOL target point Power density BOL Power density BOL goal Power density EOL goal Power density EOL 300 250 200 150 100 50 0 Power density / mwcm -2

Reinforced Membranes F-940rf fumapem F-rf FUMATECH Water Technologies for a Better Life Fuel Cell Technologies for a Better Quality of Life 14

Reinforced Membranes F-940rf 1 Membrane = PTFE supported PFSA (thickness = 30-40 µm) Test cell: QuickConnect 25 cm², Air: λ = 2.5; 100% r.h.; H 2 : λ = 1.5, 100% r.h., pressure = 1 bara; electrode = E-Tek GDE 250 EW 0,5mg/cm² Pt 0,9 0,8 0,7 Voltage / V 0,6 0,5 0,4 PTFE supported membrane 0,3 0,2 F940 0,1 0 0 100 200 300 400 500 600 700 Current density / macm -2 FUMATECH Water Technologies for a Better Life Fuel Cell Technologies for a Better Quality of Life 15

Zirconium phosphate Zr(HPO 4 ) 2 H 2 O sol-gel method insoluble in water acidic sites (conductivity and water content) layered structure

Performance of fumapem FZP in MT-PEMFC RH / % 12.8 6.0 3.0 1.8 10 9 fumapem FZP E-Modulus / Pa 10 8 PFSA without ZrP 10 7 fumapem FZP KE279 fumapem F950 Nafion 115 Nafion 117 Nafion 212 40 60 80 100 120 T / C

Performance of fumapem FZP in MT-PEMFC 1 fumapem FZP-930 Test cell: QuickConnect 25 cm², Air: λ = 2.5; H 2 : λ = 1.5, humidifier: (A) 80 C - (C) 65 C pressure = 1 bara, GDL = H2315 C2 0,9 0,8 0,7 Voltage / V 0,6 0,5 0,4 0,3 0,2 0,1 65 C 80 C 100 C 110 C 120 C 65 C EOL 0 0 100 200 300 400 500 600 700 800 Current density / macm -2

Stabilized Membranes F-940xs 1 PFSA membrane fumapem F-940 with a stabiliser Cell potential / V 0,8 0,6 0,4 OCV-hold test: T (cell)= 65 C cell, humidifier 20 C (20% r.h.) utilisation H 2 /Air = 1,5/2,5 OCV Lost: 200 µv/hr until 350 hrs, 10 µv/ hr in 350-630 hrs Hydrogen cross-over at 630 hrs: 0,2 ma/cm 2 0,2 0 0 100 200 300 400 500 600 Time / hrs FUMATECH Water Technologies for a Better Life Fuel Cell Technologies for a Better Quality of Life 19

High temperature reformate / air fumapem AM ABPBI

Milestones of fumapem AM in HT-PEMFC 100 H N N n Modulus / MPa 10 H N H N N N n 1 100 120 140 160 180 T / C Start time / MEA generation 10/2007-1/1 1/2008 1/2 4/2008 1/3 8/2008 2/1 10/2008 Peak power / mw/cm 2 330 370 400 520

Performance of fumapem AM at 160 C 1000 900 800 fumapem AM membrane with fumea electrodes ambient pressure operation non-humidified conditions H 2 / air T = 160 C gas utilisation: hydrogen 83%, air 50 % 700 Zellspannung / V 600 500 400 300 200 100 0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 Stromdichte / A cm -2

Durability of fumapem AM at 180 C 1 0,95 0,9 160 C T= 180 C 0,85 cell potential / V 0,8 0,75 0,7 0,65 0,6 0,55 0,2 A/cm2 fumapem AM membrane with fumea electrodes ambient pressure operation non-humidified conditions H 2 / air T = 180 C λ(h 2 ) = 1.5, λ(air) = 2.0 0,5 0 50 100 150 200 250 300 350 time / hrs

Durability of fumapem AM cycling at 160 C 1 End: 2355 0,95 cell potential / V 0,9 0,85 0,8 0,75 0,7 0,65 0,6 0,55 0,5 Cycling conditions: OCV (4 min) 0,3 A/cm2 (16 min) 500 1000 1500 0 100 200 300 400 500 600 700 800 900 time / hrs

Durability of fumapem AM cycling at 180 C Test protocol: T = 180 C Cycling 5 h @ 0,4 A/cm 2 1 h @ 0,0 A/cm 2 1 h @ 0 A/cm 2 no gas OCV @ BOL = 0,953 V OCV @ EOL = 0,922 V Decay = -147,6 µv/h

Catalyst Coated Membranes for Water Electrolysis

Fumapem membranes for water electrolysis 2,1 2 Effect of CCM's thickness; conditions: T= 25 C and atmospheric pressure standard coating procedure and standard coating materials; reinforced membrane 1,9 cell potential / V 1,8 1,7 1,6 CCM 360 µm 1,5 CCM 240 µm 1,4 CCM 130 µm 1,3 0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4 current density / A.cm -2

Purity of gases on various CCM Laboratory / CCM EF-10 EF-40 EF-50 (135 micron) (240 micron) (360 micron) Company A 0,7 % (10 bar) 0,2 % (20 bar) n.d. (low perf.) Company B 0,5 % (10 bar) 0,3 % (10 bar) < 0,05 % (10 bar) Company C < 0,01 % (1 bar) 0,5 % (50 bar)

Performance fumea EF-40 new catalysts

Membranes for Energy Storage in Flow Batteries 30 30

Redox flow battery as possible solution: Working principle Anode: Cathode:

Guideline for membrane s choice Cation-exchange vs. Anion-exchange Cation exchange membranes Low selectivity High conductivity High electrolyte transfer High oxidation stability High cost for PFSA Anion exchange membranes High selectivity Medium conductivity Low electrolyte transfer Medium to good oxidation stability Medium to low cost

Characterisation of VRB Membranes Membrane thickness AC - R m [m *cm²] DC - R c [ *cm²] CE [%] Liquid transfer Reference 125 µm ~275 1,29 92,50 ~0,8 ml/h F-1050 50 µm ~180 1,09 92,05 ~2 ml/h F-1860 60 µm ~270 3,40 99,10 ~ 0,7 ml/h FX-7050 55 µm ~280 1,35 97,50 ~0,6 ml/h VM-20 20 µm ~350 2,70 99,50 ~0,1 ml/h FAP 35 µm ~298 1,28 99,05 ~0,15 ml/h

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