Block Copolymer-Based Symmetric Membranes for Direct Methanol Fuel Cells
Abstract
:1. Introduction: Setting the Scene
2. Theoretical Background
2.1. How DMFCs Work
2.2. Degradation Mechanisms in DMFCs
2.3. DMFC Challenges
2.4. Beyond Nafion Membranes
3. Block Copolymer Electrolytes
3.1. Synthesis
3.1.1. Postsulfonation of Commercial Block Copolymers
3.1.2. Synthesis of Electrolytes from Poly(arylene Ether)-Based Building Blocks
3.1.3. Poly(arylene Ether Sulfone)-Based Copolymers
3.1.4. Poly(ether Sulfone)-Based Copolymers
3.1.5. Other Systems
3.1.6. Synthesis of Electrolytes from Poly(arylene Ether) and Other Similar Building Blocks
3.1.7. Synthesis of Electrolytes from Poly(styrene) and Other Building Blocks
3.1.8. Synthesis of Electrolytes from Building Blocks Other Than Polystyrene and Poly(arylene Ether)s
3.1.9. Copolymers with Special Shapes
4. Block Copolymer Membranes for DMFCs
4.1. Some Considerations for Transport Mechanisms
4.2. Role of Block Length
4.3. Role of Crosslinking
5. Conclusions and Outlook
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Storage Properties | Methanol | Hydrogen |
---|---|---|
Temperature | 25 °C | −252.8 °C (for liquefied storage) |
Pressure | Atmospheric pressure | 350–700 bar (for gaseous storage) |
Density (at 1 bar) | 792 kg/m3 (at room temperature) | 70 kg/m3 (at liquefaction temperature) |
Specific storage volume | Low | High |
Cost of storage infrastructure | Low | High |
Operating cost of storage | Low | High |
Polymer | Synthesis Reaction | Group | Refs. |
---|---|---|---|
Poly(arylene ether sulfone) | Coupling | [65,66,67,68,69,70,71] | |
Poly(ether sulfone) | Coupling | [72,73] | |
Poly(arylenethioethersulfone) | Coupling | Bai and Dang | [74] |
Poly(arylene ether sulfone ketone) | Coupling | Watanabe | [75,76] |
Poly(phenylene) | Polycondensation | Rikukawa | [77] |
Poly(benzimidazole) | Coupling | Benicewicz | [78] |
Polyimide | Imidization | Watanabe | [79] |
Poly(phenylene) and polyimide | Ni catalysis Copolymerization | Okamoto | [80] |
Poly(arylene ether sulfone) and poly(ether ether ketone) | Nucleophilic coupling | McGrath | [81] |
Poly(arylene ether sulfone) and poly(arylene ether ketone) | Oligomer coupling | McGrath Watanabe | [81,82,83,84] [85] |
Poly(arylene ether sulfone) and polyimide | Oligomer coupling | McGrath | [86] |
Poly(arylene ether sulfone) and polyimide | Imidization coupling | McGrath | [87] |
Poly(arylene ether sulfone) and polybenzimidazole | Oligomer coupling | McGrath Watanabe | [88] [89] |
Poly(arylene ether sulfone) and poly(2,5 benzophenone) | Oligomer coupling and nucleophilic aromatic substitution | McGrath | [90] |
Poly(arylene ether) and poly(benzophenone) | Ni-mediated coupling polymerization | Watanabe | [91] |
Poly(arylene sulfone, thioether) and poly(arylene ether sulfone) | Coupling and oxidation | Jannasch | [92] |
Poly(phenylene sulfone) and poly(phenylene ether sulfone) | Coupling | Meyer | [93] |
Poly(ether ether ketone) and poly(ether sulfone) | Aromatic nucleophilic polycondensation | Liu | [94] |
Poly(ether ether ketone) and poly(butadiene) | Condensation | Yin | [95] |
Polystyrene and hydrogenated polybutadiene | Commercial | Nacher | [96] |
Polystyrene and poly(ethylene-ran-butylene) | Commercial | Kim | [97] |
Polystyrene and poly(isobutylene) | Commercial | Elabd | [98] |
Poly(arylene ether) and poly(styrene-co-acrylonitrile) | Atom transfer radical Polymerization | Jo | [99] |
Poly(arylene sulfone ether ketone) and poly(styrene-co-acrylonitrile) | Condensation and radical polymerization | Jo | [100] |
Polystyrene and poly(p-tert-butylstyrene) | Living anionic | Spontak | [101] |
Polystyrene and poly(hydroxystyrene) | Anionic polymerization | Chao | [102] |
Polystyrene and polyisoprene | Anionic polymerization and sulfonation | Goswami | [103] |
Polystyrene and poly(vinylphosphonic acid) | Anionic polymerization | Jannasch | [104] |
Polystyrene and poly(vinylidene difluoride-co- hexafluoropropylene) | Atom transfer radical polymerization and postsulfonation | Holdcroft | [105,106] |
Polystyrene and poly(vinylidene difluoride) | Atom transfer radical polymerization | Wang | [107] |
Polystyrene and poly(pentafluorostyrene) | (Atom transfer) radical polymerization | Hvilsted Matsuoka | [108] [109] |
Polystyrene and polymethylbutylene | Anionic polymerization | Balsara | [110] |
Poly(norbornenylene ethylstyrene) Poly(styrenesulfonic acid) | Anionic polymerization | Hillmyer | [111] |
Polystyrene and poly(vinyl benzyl phosphonate) | Atom transfer radical polymerization | Müllen | [112] |
Polystyrene and poly(methyl methacrylate) | Atom transfer radical polymerization | Hickner Mezzenga | [113] [114] |
Polystyrene and poly(arylene ether sulfone) | Amide condensation | Lee | [115] |
Polysulfone and poly(vinylidene difluoride) | Polycondensation and postsulfonation | Holdcroft | [116] |
Poly(ethylene oxide) and poly(benzimidazole) | Thiol-ene coupling and ring opening | Jannasch | [117] |
Poly(phenylene oxide) and poly(vinyl benzyl phosphonic acid) | Atom transfer radical Polymerization and Postsulfonation | Müllen | [118] |
Poly(vinylidene fluoride)-g-polystyrene | Atom transfer radical polymerization Postsulfonation | Chung | [119] |
Poly(trifluoroethylene)-g- poly(styrene-co-divinylbenzene) | Atom transfer radical polymerization | Mortensen | [120] |
Poly(vinylidene fluoride)-ter- Poly(hexafluoropropylene)-ter- Trifluoromethacrylic acid Aryl sulfonic acid | Radical terpolymerization and etherification | Ameduri | [121] |
Block Copolymer | Oligomer Mn Ratio a | Theoretical IEC (meq/g) b | IEC by 1H NMR (meq/g) c | Mn d | Mw/Mn d |
---|---|---|---|---|---|
4a | 14,000/14,000 | 2.10 | 2.00 | 68,000 | 2.5 |
4b | 10,000/10,000 | 2.10 | 2.02 | 74,000 | 3.3 |
4c | 6000/6000 | 2.10 | 1.99 | 55,000 | 4.4 |
5a | 14,000/14,000 | 2.10 | 1.95 | 70,000 | 4.1 |
5b | 10,000/10,000 | 2.10 | 1.97 | 60,000 | 3.5 |
5c | 6000/6000 | 2.10 | 1.99 | 84,000 | 4.9 |
Membrane | Proton Conductivity (S cm−1) | Methanol Permeability (10−8 cm2 s−1) |
---|---|---|
PEK-SP10 | 0.045 | 8 |
PEK-SP15 | 0.078 | 22 |
PEK-SP20 | 0.100 | 36 |
PAES-SP18 | 0.122 | 34 |
Nafion 117 | 0.108 | 294 |
Membrane | PSSA (wt%) | D (nm) | PSSA Width (nm) | IEC (mmol/g) | Water Uptake (%) | λ (mol H2O/mol SO3H) |
---|---|---|---|---|---|---|
PEM1a | 36.7 | 41.5 | 18.7 | 1.98 | 118 ± 4 | 33 ± 1 |
PEM2a | 39.1 | 22.6 | 10.8 | 2.06 | 73 ± 12 | 21 ± 4 |
PEM3a | 36.6 | 14.4 | 6.6 | 1.93 | 78 ± 5 | 22 ± 1 |
PEM4a | 36.8 | 28.3 | 13.0 | 1.86 | 73 ± 2 | 20 ± 0.4 |
PEM5a | 37.3 | 19.5 | 9.0 | 1.96 | 42 ± 0.4 | 12 ± 0.1 |
Nafion 117 | - | - | - | - | 34 ± 0.4 | 21 ± 0.2 |
Membrane | IEC | Conductivity (S cm−1) | λ | |||||
---|---|---|---|---|---|---|---|---|
20 °C | 40 °C | 60 °C | 80 °C | 100 °C | 20 °C | 100 °C | ||
SPES-b | 1.54 | 0.09 | 0.19 | 0.27 | 0.43 | 0.77 | 7.81 | 9.02 |
SPES-bn | 1.92 | 0.11 | 0.16 | 0.20 | 0.25 | 0.30 | 9.44 | 8.94 |
Nafion 117 | 0.91 | 0.08 | 0.10 | 0.14 | 0.17 | 0.17 | 9.79 | - |
Crosslinker (DVB) Content (%) | Proton Conductivity (10−2 Scm−1) | MeOH Permeability (10−7 cm2/s) | Water Uptake (%) | Tensile Stress (N/mm2) | Selectivity |
---|---|---|---|---|---|
0 | 4.5 | 8.6 | 75.1 | 4.6 | 1.6 |
2 | 3.1 | 3.4 | 35.8 | 11.0 | 2.7 |
5 | 3.4 | 6.6 | 23.9 | 13.9 | 1.5 |
10 | 2.5 | 4.3 | 25.2 | 17.3 | 1.8 |
Nafion 115 | 9.0 | 27.0 | 26.7 | 13.9 | 1 |
Membrane | Proton Conductivity (mS cm−1) | Methanol Permeability (10−7 cm2/s) |
---|---|---|
A50G4-S10 | 66 ± 2.7 | 12.7 |
A100G4-S10 | 62 ± 3.0 | 8.2 |
A150G4-S10 | 53 ± 2.5 | 5.3 |
Nafion 117 | 62 ± 3.0 | 11.7 |
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Buonomenna, M.G.; Bae, J. Block Copolymer-Based Symmetric Membranes for Direct Methanol Fuel Cells. Symmetry 2024, 16, 1079. https://doi.org/10.3390/sym16081079
Buonomenna MG, Bae J. Block Copolymer-Based Symmetric Membranes for Direct Methanol Fuel Cells. Symmetry. 2024; 16(8):1079. https://doi.org/10.3390/sym16081079
Chicago/Turabian StyleBuonomenna, Maria Giovanna, and Joonwon Bae. 2024. "Block Copolymer-Based Symmetric Membranes for Direct Methanol Fuel Cells" Symmetry 16, no. 8: 1079. https://doi.org/10.3390/sym16081079