Loughborough University Institutional Repository Mechanical integration of a PEM fuel cell for a multifunctional aerospace structure ThisitemwassubmittedtoLoughboroughUniversity’sInstitutionalRepository by the/an author. Additional Information: • A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy of Loughborough University. Metadata Record: https://dspace.lboro.ac.uk/2134/21513 Publisher: (cid:13)c Wasim Bhatti Rights: This work is made available according to the conditions of the Cre- ative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/ Please cite the published version. LOUGHBOROUGH UNIVERSITY Mechanical integration of a PEM fuel cell for a multifunctional aerospace structure By Wasim Bhatti Submitted as partial fulfilment of the requirements for the award of Doctor of Philosophy of Loughborough University 2/6/2016 © Wasim Bhatti 2016 Acknowledgments This research project has been a rollercoaster ride, with challenge, after challenge, both personal and professional, a game of endurance and shear will power. The journey could not have been completed without God almighties (Allah s.w.t) guiding hand. I’m a firm believer that everybody has a place in life and people come in and out of one’s life for a reason, to guide you, to support you, to believe in you, and sometimes not too. I would like to acknowledge and express my appreciation and gratitude for those supervisors, academics, and people of knowledge and experience who have worked with me, lent their ear, and contributed in any way small or large to the success of this project. I would like to thank the various academic institutions, industrial companies, and research funding groups for their support over the years. I would specially like to thank those people (and industrial companies) who contributed to this project simply because they wanted to help a research student out or had an interest in the research area but did not specifically gain anything in return. I would like to thank all my friends and family for believing in me, encouraging me, and backing me over the years. To those who believed in me And to those who did not Please read on 1 Contents Abstract ................................................................................................................... 12 Introduction ............................................................................................................ 13 Chapter 1 Literature review ................................................................................... 15 1.1 Fuel cell fundamentals ...................................................................................... 15 1.2 PEM fuel cell arrangement ................................................................................ 17 1.3 Bipolar plates ................................................................................................... 18 1.4 Membrane electrode assembly (MEA) ............................................................... 19 1.5 MEA – Electrode ............................................................................................... 20 1.6 Fuel cell polarisation curves ............................................................................. 21 1.6.1 Activation polarisation .......................................................................................................... 23 1.6.2 Ohmic polarisation .................................................................................................................. 24 1.6.3 Concentration polarisation .................................................................................................. 25 1.6.4 Other losses................................................................................................................................ 27 1.7 Hydrogen production road map ........................................................................ 28 1.8 Fuel cell systems for UAVs ................................................................................ 32 1.8.1 Thermal management ............................................................................................................ 34 1.8.2 Hydrogen storage .................................................................................................................... 35 1.8.3 Hydrogen generator ............................................................................................................... 37 1.8.4 Anode purge .............................................................................................................................. 38 1.8.5 Weight breakdown .................................................................................................................. 39 1.8.6 Clamping pressure .................................................................................................................. 42 1.8.7 Fuel cell shape ........................................................................................................................... 43 1.9 Structural power .............................................................................................. 45 1.9.1 Multifunctional fuel cells ...................................................................................................... 45 1.9.2 Pultruded and VARTM fuel cell .......................................................................................... 47 1.10 Wing rib loads ................................................................................................ 49 1.11 Summary and knowledge gap ......................................................................... 53 Chapter 2 Structural fuel cell development ............................................................ 55 2.1 Current fuel cell systems .................................................................................. 55 2.2 Structural fuel cell concept ............................................................................... 56 2.3 Structural fuel cell ............................................................................................ 57 2.4 Structural fuel cell design and development ...................................................... 58 2 2.5 Cantilever concept and terminology .................................................................. 59 2.6 Conceptual design ............................................................................................ 60 2.6.1 Bipolar plates ............................................................................................................................ 60 2.6.2 End plates ................................................................................................................................... 62 2.6.3 Initial FEA ................................................................................................................................... 63 2.7 Structural fuel cell design ................................................................................. 66 2.7.1 Bipolar plate and Gasket ....................................................................................................... 68 2.7.2 Gas inlet/out sealing............................................................................................................... 69 2.7.3 Gasket ........................................................................................................................................... 70 2.7.4 Membrane Electrode Assembly (MEA) manufacture ................................................ 71 2.7.5 GDE misalignment ................................................................................................................... 74 2.7.6 Electrical insulation ................................................................................................................ 75 2.7.7 Gas tightness .............................................................................................................................. 76 Chapter 3 - Experimental setup and results ........................................................... 79 3.1 Fuel cell operating conditions ........................................................................... 79 3.1.1 Consumption of Oxygen ........................................................................................................ 80 3.1.2 Consumption of Hydrogen ................................................................................................... 82 3.1.3 Water production .................................................................................................................... 83 3.2 Water management .......................................................................................... 84 3.3 Humidification ................................................................................................. 86 3.4 Thermal management ...................................................................................... 88 3.5 Experimental parameters ................................................................................. 93 3.6 Experimental apparatus ................................................................................... 96 3.7 Experimental loads........................................................................................... 99 3.7.1 Manual application of loads ................................................................................................. 99 3.7.2 Digital image correlation – Bending .............................................................................. 101 3.7.3 Digital image correlation – Tip ........................................................................................ 105 3.7.4 Digital image correlation – Torsion ............................................................................... 108 3.8 Strain measurements ..................................................................................... 111 3.8.1 Strain comparison with and without clamping bolts ............................................. 113 3.9.1 Actuator accuracy ................................................................................................................. 118 3.10 MEA activation ............................................................................................. 122 3.10.1 Initial MEA polarisations ................................................................................................ 123 3 3.10.2 Investigation ........................................................................................................................ 128 3.10.3 Experimental apparatus .................................................................................................. 128 3.10.4 MEA manufacturing procedure .................................................................................... 129 3.10.5 Hot pressing ......................................................................................................................... 130 3.10.6 Interfacial contact resistance ........................................................................................ 132 3.10.7 Performance benchmark comparison ....................................................................... 135 3.10.8 MEA- Quality and repeatability .................................................................................... 137 3.10.9 Conclusion of investigation ............................................................................................ 138 3.11 Experimental results .................................................................................... 139 3.11.1 Experimental procedure ................................................................................................. 139 3.11.2 Static bending – Cathode compression ...................................................................... 142 3.11.3 Static bending – Anode compression ......................................................................... 145 3.11.4 Static torsion ........................................................................................................................ 148 3.11.5 Dynamic bending – 3mm deflection ........................................................................... 151 3.11.6 Dynamic bending – 5mm deflection ........................................................................... 156 3.11.7 Dynamic bending – 7mm deflection ........................................................................... 161 3.11.8 Dynamic torsion – 3.4° ..................................................................................................... 168 3.11.9 Dynamic torsion – 5° ........................................................................................................ 172 3.12 Discussion .................................................................................................... 177 3.12.1 Dynamic bending comparison ...................................................................................... 177 3.12.2 Dynamic torsion comparison ........................................................................................ 180 3.12.3 MEA recovery ...................................................................................................................... 183 3.12.4 MEA examination ............................................................................................................... 185 Chapter 4 - Corrosion of bipolar plates ................................................................ 188 4.1 Initial test run ................................................................................................ 188 4.2 Investigation .................................................................................................. 188 4.2.1 SEM and EDS ........................................................................................................................... 190 4.2.2 Anode surface analysis – figure 4.3 ............................................................................... 195 4.2.3 Cathode surface analysis –figure 4.4 ............................................................................. 195 4.2.4 MEA surface analysis – figure 4.5 ................................................................................... 196 4.2.5 Overall analysis ..................................................................................................................... 197 4.2.6 Results post corrosion protection .................................................................................. 199 4.2.7 Conclusion ............................................................................................................................... 212 4 Chapter 5 - Finite element analysis ...................................................................... 214 5.1 Further finite element modelling .................................................................... 214 5.2 Coordinate system.......................................................................................... 214 5.3 Initial simplified model ................................................................................... 215 5.4 Material specification ..................................................................................... 215 5.5 Boundary conditions ...................................................................................... 215 5.6 Loading and additional constraints ................................................................. 215 5.7 Simplified model results ................................................................................. 218 5.8 Detailed model ............................................................................................... 220 5.8.1 End plates and bipolar plates ....................................................................... 220 5.8.2 Contact behaviour ................................................................................................................ 222 5.8.3 FE sensitivity analysis ......................................................................................................... 223 5.8.4 Boundary conditions and steps ....................................................................................... 226 5.8.5 Clamping bolt constraints ................................................................................................. 227 5.8.6 Detailed model ....................................................................................................................... 228 5.9 Model validation ............................................................................................ 242 5.9.1 Strain values ........................................................................................................................... 242 5.9.2 Load verses displacement ................................................................................................. 244 Chapter 6 – Conclusions and future work............................................................. 246 6.1 Conclusions .................................................................................................... 246 6.2 Future works ................................................................................................. 249 Publications ......................................................................................................... 251 References ............................................................................................................. 252 5 Table of figures Figure 1.1 - Electrochemical reaction within PEM fuel cells [19] ............................................. 16 Figure 1.2 - Components within a conventional single PEM fuel cell and a stack .............. 17 Figure 1.3 - Biologically inspired flow filed design [18] ............................................................... 18 Figure 1.4 - MEA component interaction ............................................................................................ 20 Figure 1.5 - A typical polarisation curve with voltage losses ..................................................... 22 Figure 1.6 - Breakdown of MEA layers ................................................................................................ 25 Figure 1.7 - Global hydrogen production [79] .................................................................................. 28 Figure 1.8 – Global CO production [81] ............................................................................................. 30 2 Figure 1.9 - Roadmap hydrogen production technology mix [81] ........................................... 31 Figure 1.10 - Fuel cell system based sodium borohydride [15] ................................................ 37 Figure 1.11 - Experimentally derived hydrogen purge [1] .......................................................... 38 Figure 1.12 - UAV system weight breakdown [1]............................................................................ 39 Figure 1.13 - Sodium borohydride fuel cell system [39] .............................................................. 40 Figure 1.14 - Assembly procedure of the cylinder shaped air-breathing PEMFC [14] ..... 43 Figure 1.15 - Polarization curves for planar PEMFC and Cy-PEMFC [14] ............................. 44 Figure 1.16 - Composite structural fuel cell [30] ............................................................................. 46 Figure 1.17 - Cross section of multifunctional composite fuel cell ........................................... 47 Figure 1.18 - Concept of pultruded fuel cell [35] ............................................................................. 48 Figure 1.19 - Key wing structural components [43] ...................................................................... 50 Figure 1.20 - Wing twisting and wing bending [42] ....................................................................... 51 Figure 2.1 - Chemical hydride based fuel cell system [37] .......................................................... 55 Figure 2.2 - Fuel cell replacement of the Rear Rib structure highlighted in red ................. 57 Figure 2.3 - Exploded view of a conventional fuel cell arrangement ....................................... 58 Figure 2.4 - Cantilever arrangement with terminology ................................................................ 59 Figure 2.5 - Structural fuel cell stainless steel bipolar plates ..................................................... 60 Figure 2.6 - Structural fuel cell aluminium end plates .................................................................. 62 Figure 2.7 - Finite element modelling steps ...................................................................................... 63 Figure 2.8 - End plate displacement ..................................................................................................... 64 Figure 2.9 - Redesigned structural fuel cell end plate ................................................................... 66 Figure 2.10 - Bipolar plate and Gasket re-designed ....................................................................... 68 Figure 2.11 - Gas inlet, end plate, and bipolar plate arrangement............................................ 69 Figure 2.12 - Application guide [52] ..................................................................................................... 70 Figure 2.13 - MEA and Gasket ................................................................................................................. 71 Figure 2.14 - MEA manufacturing process ......................................................................................... 73 Figure 2.15 - GDE misalignment ............................................................................................................ 74 Figure 2.16 - MEA7 Batch 3 ...................................................................................................................... 74 Figure 2.17 - Clamping bolts and short and long bolt insulation bushes ............................... 75 Figure 2.18 - Exploded view of the new structural fuel cell ........................................................ 76 Figure 2.19 - Structural fuel cell gas tightness achieved .............................................................. 78 Figure 3.1 - Production and transportation of water content [2] ............................................. 84 Figure 3.2 - Passive humidification with internal recirculation of water .............................. 85 6 Figure 3.3 - Humidify bottle and dual temperature controller .................................................. 86 Figure 3.4 - Humidifier gas outlet temperature / flow rate against dew point [78].......... 87 Figure 3.5 - Structural fuel cell with a flexible silicone heating element attached ............. 90 Figure 3.6 - Three heating elements bonded to each end plate ................................................. 92 Figure 3.7 - Gas humidifiers in close proximity to the structural fuel cell............................. 94 Figure 3.8 - Structural fuel cell experimental setup ....................................................................... 97 Figure 3.9 - Structural fuel cell mounted on the mechanical loading assembly .................. 98 Figure 3.10 - Manual application of loads ....................................................................................... 100 Figure 3.11 - Surfaces spray painted for digital image correlation ....................................... 101 Figure 3.12 - DIC image of structural fuel cell under bending loads of zero to 232N .... 102 Figure 3.13 - DIC image of structural fuel cell under bending loads of 276N to 365N .. 103 Figure 3.14 - DIC image of fuel cell tip under bending loads of 54N to 98N ...................... 105 Figure 3.15 - DIC image of fuel cell tip under bending loads of 147N to 365N ................. 106 Figure 3.16 - Bending loads against average DIC displacement measurements .............. 107 Figure 3.17 - Deformation magnitude and x-plane displacement - 1.6 degree of twist. 109 Figure 3.18 - Deformation magnitude and x-plane displacement ......................................... 110 Figure 3.19 - Strain gauges attached to the structural fuel cell. ............................................. 111 Figure 3.20 - Strain measurements - top and bottom end plate ............................................. 114 Figure 3.21 - Strain measurements - top end plate and bottom end plate ......................... 115 Figure 3.22 - Clamping bolts, horizontal rib, and strain gauge positons ............................. 116 Figure 3.23 - Gimson robotics GLA750 screw type actuator ................................................... 117 Figure 3.24 - Experimental setup for actuator accuracy measurements ............................ 118 Figure 3.25 - Actuator tested with structural fuel cell attached ............................................. 119 Figure 3.26 - Experimental setup for torsion loads and bending loads ............................... 121 Figure 3.27 - Five activation curves for MEA1-B1 (Batch 1) ................................................... 124 Figure 3.28 - Activation curves for MEA3-B2 (Batch 2) ............................................................ 125 Figure 3.29 - Activation curves for MEA4-B2 ................................................................................ 126 Figure 3.30 - A selection of activation polarisation curves for MEA6-B2 ........................... 127 Figure 3.31 - Breakdown of MEA layers - convective and diffusive mass transfer ......... 130 Figure 3.32 - Damage to MEA’s from batches one and two post hot pressing .................. 131 Figure 3.33 - Bolting sequence for the structural fuel cell ........................................................ 132 Figure 3.34 - Polarisation curve for MEA T1 .................................................................................. 134 Figure 3.35 - Polarisation curves for the 25cm2 Pragma and Structural fuel cells.......... 135 Figure 3.36 - Actuator control - static and dynamic bending loads ...................................... 140 Figure 3.37 - Peak power against deflection .................................................................................. 142 Figure 3.38 - Static bending from 6mm back to zero deflection. ............................................ 143 Figure 3.39 - Peak power against deflection and peak power against bending load ..... 144 Figure 3.40 - Polarisation curves for static bending -1mm to -7mm deflection .............. 145 Figure 3.41 - Peak power against deflection .................................................................................. 146 Figure 3.42 - Peak power against deflection .................................................................................. 146 Figure 3.43 - Polarisation curves for static torsion 0° to 5° ..................................................... 148 Figure 3.44 - Peak power against torsion ........................................................................................ 149 Figure 3.45 - Cell performance after multiple rounds of torsional loading ....................... 150 7 Figure 3.46 - Peak power 0 to 100 cycles ........................................................................................ 151 Figure 3.47 - Polarisation curves for 500 to 1000 cycles .......................................................... 152 Figure 3.48 - Peak power performance from 250 to 1000 cycles .......................................... 152 Figure 3.49 - Polarisation curves for 1100 to 2000 cycles ....................................................... 154 Figure 3.50 - Peak power performance from 1100 to 2000 cycles ....................................... 155 Figure 3.51 - Peak power performance from 125 to 400 cycles ............................................ 156 Figure 3.52 - Polarisation curves for 500 to 1000 cycles .......................................................... 157 Figure 3.53 - Peak power performance from 500 to 1000 cycles .......................................... 158 Figure 3.54 - Polarisation curves for 1100 to 1500 cycles ....................................................... 159 Figure 3.55 - Polarisation curves for 1600 to 2000 cycles ....................................................... 159 Figure 3.56 - Peak power performance from 1100 to 2000 cycles ....................................... 160 Figure 3.57 - Polarisation curves for 125 to 200 cycles ............................................................. 161 Figure 3.58 - Peak power performance from 125 to 500 cycles ............................................ 162 Figure 3.59 - Polarisation curves for 500 to 1000 cycles .......................................................... 163 Figure 3.60 - Peak power performance from 250 to 1000 cycles .......................................... 164 Figure 3.61 - Polarisation curves for 1100 to 2000 cycles ....................................................... 166 Figure 3.62 - Peak power performance from 1100 to 2000 cycles ....................................... 167 Figure 3.63 - Polarisation curves for 500 to 1000 cycles .......................................................... 168 Figure 3.64 - Peak power performance from 250 to 1000 cycles .......................................... 169 Figure 3.65 - Polarisation curves for 1600 to 2000 cycles ....................................................... 170 Figure 3.66 - Peak power performance from 1100 to 2000 cycles ....................................... 171 Figure 3.67 - Polarisation curves for 50 to 100 cycles ............................................................... 172 Figure 3.68 - Polarisation curves for 500 to 1000 cycles .......................................................... 173 Figure 3.69 - Peak power performance from 250 to 1000 cycles .......................................... 174 Figure 3.70 - Polarisation curves for 1100 to 2000 cycles ....................................................... 175 Figure 3.71 - Peak power performance from 1100 to 2000 cycles ....................................... 176 Figure 3.72 - Peak power performance between each group of bending cycles .............. 177 Figure 3.73 - Peak power percentage losses from zero cycles to 2000 cycles .................. 178 Figure 3.74 - Peak power change from zero cycles to 2000 cycles ....................................... 179 Figure 3.75 - Peak power performance between each group of torsional cycles. ........... 180 Figure 3.76 - Peak power change from zero cycles to 2000 cycles ....................................... 181 Figure 3.77 - Peak power percentage losses from zero cycles to 2000 cycles .................. 182 Figure 3.78 - Demonstration of recovery behaviour of the MEA ........................................... 184 Figure 3.79 - MEA’s after 2000 torsional load cycles at 3.4 and 5° ....................................... 185 Figure 3.80 - Damage to MEA7-B3 after 2000 bending cycle at 5mm deflection ............ 187 Figure 3.81 - Damage to MEA6-B3 after 2000 bending cycle at 7mm deflection ............ 187 Figure 4.1 - Unknown deposits on MEA and bipolar plate surfaces. .................................... 189 Figure 4.2 - Anode, Cathode, and MEA samples in SEM/EDS machine ................................ 191 Figure 4.3 - SEM and EDS analysis of anode surface ................................................................... 192 Figure 4.4 - SEM and EDS analysis of cathode surface ............................................................... 193 Figure 4.5 - SEM and EDS analysis of MEA surface ...................................................................... 194 Figure 4.6 - Post application of Gold protective coating system ............................................ 199 Figure 4.7 - Second polarisation curve produced approximately 24hrs after the first. 200 8
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