Membranes for Energy Conversion and Energy Storage with Fuel Cells and Batteries
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1 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
2 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
3 BWT We go for 98.5% 3 3
4 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
5
6 Membrane Humidifier Water-to-Gas and Gas-to-Gas humidifier: 1 kw 3 kw 5 kw 10 kw 100 kw 6 6
7 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
8 New FUMATECH production site New membrane production site in Bietigheim-Bissingen from
9 Membranes for Energy Conversion 9 9
10 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
11 Low and medium temperature FC on hydrogen / air fumapem F
12 fumion F - perfluorinated ionomer fumion F CF 2 CF 2 x CF CF 2 O y long side-chain perfluorosulfonic acid polymer EW = g / eq (IEC = 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)
13 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 Power density / mwcm -2
14 Reinforced Membranes F-940rf fumapem F-rf FUMATECH Water Technologies for a Better Life Fuel Cell Technologies for a Better Quality of Life 14
15 Reinforced Membranes F-940rf 1 Membrane = PTFE supported PFSA (thickness = 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, Current density / macm -2 FUMATECH Water Technologies for a Better Life Fuel Cell Technologies for a Better Quality of Life 15
16 Zirconium phosphate Zr(HPO 4 ) 2 H 2 O sol-gel method insoluble in water acidic sites (conductivity and water content) layered structure
17 Performance of fumapem FZP in MT-PEMFC RH / % fumapem FZP E-Modulus / Pa 10 8 PFSA without ZrP 10 7 fumapem FZP KE279 fumapem F950 Nafion 115 Nafion 117 Nafion T / C
18 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 Current density / macm -2
19 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 hrs Hydrogen cross-over at 630 hrs: 0,2 ma/cm 2 0, Time / hrs FUMATECH Water Technologies for a Better Life Fuel Cell Technologies for a Better Quality of Life 19
20 High temperature reformate / air fumapem AM ABPBI
21 Milestones of fumapem AM in HT-PEMFC 100 H N N n Modulus / MPa 10 H N H N N N n 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
22 Performance of fumapem AM at 160 C 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 Stromdichte / A cm -2
23 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, time / hrs
24 Durability of fumapem AM cycling at 160 C 1 End: ,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) time / hrs
25 Durability of fumapem AM cycling at 180 C Test protocol: T = 180 C Cycling 5 0,4 A/cm 2 1 0,0 A/cm A/cm 2 no gas BOL = 0,953 V EOL = 0,922 V Decay = -147,6 µv/h
26 Catalyst Coated Membranes for Water Electrolysis
27 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
28 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)
29 Performance fumea EF-40 new catalysts
30 Membranes for Energy Storage in Flow Batteries 30 30
31 Redox flow battery as possible solution: Working principle Anode: Cathode:
32 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
33 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 µm ~180 1,09 92,05 ~2 ml/h F µm ~270 3,40 99,10 ~ 0,7 ml/h FX µm ~280 1,35 97,50 ~0,6 ml/h VM µm ~350 2,70 99,50 ~0,1 ml/h FAP 35 µm ~298 1,28 99,05 ~0,15 ml/h
34 34 34
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