Bottom up synthesis of boron-doped graphene for stable intermediate temperature fuel cell electrodes

Tennyson, Wesley D.; Tian, Mengkun; Papandrew, Alexander B.; Rouleau, Christopher M.; Puretzky, Alexander A.; Sneed, Brian T.; More, Karren Leslie; Veith, Gabriel M.; Duscher, Gerd J. M.; Zawodzinski, Thomas A.; Geohegan, David B.

doi:10.1016/j.carbon.2017.08.002

Title: Bottom up synthesis of boron-doped graphene for stable intermediate temperature fuel cell electrodes

Journal Article · Fri Aug 04 00:00:00 EDT 2017 · Carbon

DOI:https://doi.org/10.1016/j.carbon.2017.08.002· OSTI ID:1489107

^[1]; Tian, Mengkun ^[2]; Papandrew, Alexander B. ^[2];

^[1];

^[1]; Duscher, Gerd J. M. ^[3]; Zawodzinski, Thomas A. ^[3];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

The high surface area and electrical conductivity of few-layered graphene would make it an ideal catalyst support and electrode in fuel cells apart from its susceptibility to oxidative corrosion. Here we report the single-step, bottom-up synthesis of oxidation-resistant boron-doped graphene and show its increased stability in the aggressive electrochemical environment of intermediate temperature solid acid fuel cells (SAFCs). Boron was shown to alter the growth mode of single walled carbon nanohorns by laser vaporization to produce high yields of thin (<20 layer) boron-doped (2–3 at.%) crystalline flakes of turbostratic graphene (B-GLF). Alternatively, adding partial pressures of hydrogen less effectively shifted the growth mode of SWCNHs toward planar, turbostratic graphene-like flakes (GLFs). Thermogravimetric analysis indicates that boron-doping enhances the oxidation resistance of few-layer GLFs by >140 °C, with large fractions of multilayered B-GLFs surviving 10 °C/min ramps to 1000 °C. These B-GLFs provided a stable Pt catalyst support and electrode over 40 h operation in SAFCs with cesium dihydrogen phosphate electrolyte operating at 250 °C, as opposed to undoped GLFs or SWCNHs which were nearly completely consumed. Furthermore, the facile synthesis and oxidation-resistant properties of boron-doped GLF appear promising for graphene applications in oxidizing environments.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725; AR0000499

OSTI ID:: 1489107

Alternate ID(s):: OSTI ID: 1547093

Journal Information:: Carbon, Vol. 123, Issue C; ISSN 0008-6223

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 20 works

Citation information provided by
Web of Science

References (73)

Progress in material selection for solid oxide fuel cell technology: A review Mahato, Neelima; Banerjee, Amitava; Gupta, Alka Progress in Materials Science, Vol. 72 https://doi.org/10.1016/j.pmatsci.2015.01.001	journal	July 2015
Solid acid proton conductors: from laboratory curiosities to fuel cell electrolytes Haile, Sossina M.; Chisholm, Calum R. I.; Sasaki, Kenji Faraday Discuss., Vol. 134 https://doi.org/10.1039/B604311A	journal	January 2007
High-Performance Solid Acid Fuel Cells Through Humidity Stabilization Boysen, D. A. Science, Vol. 303, Issue 5654 https://doi.org/10.1126/science.1090920	journal	January 2004
Glycerol electro-oxidation on a carbon-supported platinum catalyst at intermediate temperatures Ishiyama, Keisuke; Kosaka, Fumihiko; Shimada, Iori Journal of Power Sources, Vol. 225 https://doi.org/10.1016/j.jpowsour.2012.10.035	journal	March 2013
Ruthenium as a CO-tolerant hydrogen oxidation catalyst for solid acid fuel cells Papandrew, Alexander B.; Atkinson III, Robert W.; Unocic, Raymond R. Journal of Materials Chemistry A, Vol. 3, Issue 7 https://doi.org/10.1039/C4TA06451H	journal	January 2015
Advanced Electrodes for Solid Acid Fuel Cells by Platinum Deposition on CsH ₂ PO ₄ Papandrew, Alexander B.; Chisholm, Calum R. I.; Elgammal, Ramez A. Chemistry of Materials, Vol. 23, Issue 7 https://doi.org/10.1021/cm101147y	journal	April 2011
Activity and Evolution of Vapor Deposited Pt-Pd Oxygen Reduction Catalysts for Solid Acid Fuel Cells Papandrew, Alexander B.; Chisholm, Calum R. I.; Zecevic, Strahinja K. Journal of The Electrochemical Society, Vol. 160, Issue 2 https://doi.org/10.1149/2.002303jes	journal	December 2012
Support materials for PEMFC and DMFC electrocatalysts—A review Sharma, Surbhi; Pollet, Bruno G. Journal of Power Sources, Vol. 208 https://doi.org/10.1016/j.jpowsour.2012.02.011	journal	June 2012
Nanostructured carbon electrocatalyst supports for intermediate-temperature fuel cells: Single-walled versus multi-walled structures Papandrew, Alexander B.; Elgammal, Ramez A.; Tian, Mengkun Journal of Power Sources, Vol. 337 https://doi.org/10.1016/j.jpowsour.2016.10.093	journal	January 2017
Carbon Corrosion in Proton-Exchange Membrane Fuel Cells: Effect of the Carbon Structure, the Degradation Protocol, and the Gas Atmosphere Castanheira, Luis; Silva, Wanderson O.; Lima, Fabio H. B. ACS Catalysis, Vol. 5, Issue 4 https://doi.org/10.1021/cs501973j	journal	March 2015
A robust fuel cell cathode catalyst assembled with nitrogen-doped carbon nanohorn and platinum nanoclusters Zhang, Linwei; Zheng, Ning; Gao, Ang Journal of Power Sources, Vol. 220 https://doi.org/10.1016/j.jpowsour.2012.08.009	journal	December 2012
Porous structures in stacked, crumpled and pillared graphene-based 3D materials Guo, Fei; Creighton, Megan; Chen, Yantao Carbon, Vol. 66 https://doi.org/10.1016/j.carbon.2013.09.024	journal	January 2014
Quantitative evaluation of delamination of graphite by wet media milling Damm, Cornelia; Nacken, Thomas J.; Peukert, Wolfgang Carbon, Vol. 81 https://doi.org/10.1016/j.carbon.2014.09.059	journal	January 2015
A review on mechanical exfoliation for the scalable production of graphene Yi, Min; Shen, Zhigang Journal of Materials Chemistry A, Vol. 3, Issue 22 https://doi.org/10.1039/C5TA00252D	journal	January 2015
Mass-production of highly-crystalline few-layer graphene sheets by arc discharge in various H2–inert gas mixtures Chen, Yani; Zhao, Hongbin; Sheng, Leimei Chemical Physics Letters, Vol. 538 https://doi.org/10.1016/j.cplett.2012.04.020	journal	June 2012
Production of few-layer graphene through liquid-phase pulsed laser exfoliation of highly ordered pyrolytic graphite Qian, Min; Zhou, Yun Shen; Gao, Yang Applied Surface Science, Vol. 258, Issue 22 https://doi.org/10.1016/j.apsusc.2012.06.006	journal	September 2012
Scientific Aspects of Polymer Electrolyte Fuel Cell Durability and Degradation Borup, Rod; Meyers, Jeremy; Pivovar, Bryan Chemical Reviews, Vol. 107, Issue 10 https://doi.org/10.1021/cr050182l	journal	October 2007
Carbon Corrosion in Proton-Exchange Membrane Fuel Cells: From Model Experiments to Real-Life Operation in Membrane Electrode Assemblies Castanheira, Luis; Dubau, Laetitia; Mermoux, Michel ACS Catalysis, Vol. 4, Issue 7 https://doi.org/10.1021/cs500449q	journal	May 2014
Characterisation of boron-doped coal-derived carbon foams and their oxidation behaviour Rodríguez, Elena; García, Roberto Fuel, Vol. 93 https://doi.org/10.1016/j.fuel.2011.08.028	journal	March 2012
Inhibition of catalytic oxidation of carbon/carbon composites by boron-doping Wu, Xianxian; Radovic, Ljubisa R. Carbon, Vol. 43, Issue 8 https://doi.org/10.1016/j.carbon.2005.02.029	journal	July 2005
Boron/phosphorus doping for retarding the oxidation of reduced graphene oxide Yuan, Bihe; Xing, Weiyi; Hu, Yixin Carbon, Vol. 101 https://doi.org/10.1016/j.carbon.2016.01.080	journal	May 2016
Oxidation inhibition effects of phosphorus and boron in different carbon fabrics Lee, Young-Jae; Radovic, Ljubisa R. Carbon, Vol. 41, Issue 10 https://doi.org/10.1016/S0008-6223(03)00199-4	journal	January 2003
Efficient Reduction of Graphite Oxide by Sodium Borohydride and Its Effect on Electrical Conductance Shin, Hyeon‐Jin; Kim, Ki Kang; Benayad, Anass Advanced Functional Materials, Vol. 19, Issue 12 https://doi.org/10.1002/adfm.200900167	journal	June 2009
Studies on X-ray diffraction and Raman spectra of B-doped natural graphite Hagio, T.; Nakamizo, M.; Kobayashi, K. Carbon, Vol. 27, Issue 2 https://doi.org/10.1016/0008-6223(89)90132-2	journal	January 1989
Influence of boron on carbon fiber microstructure, physical properties, and oxidation behavior Jones, L. E.; Thrower, P. A. Carbon, Vol. 29, Issue 2, p. 251-269 https://doi.org/10.1016/0008-6223(91)90076-U	journal	January 1991
Formation of Boron-Carbon Nanosheets and Bilayers in Boron-Doped Diamond: Origin of Metallicity and Superconductivity Polyakov, S. N.; Denisov, V. N.; Mavrin, B. N. Nanoscale Research Letters, Vol. 11, Issue 1 https://doi.org/10.1186/s11671-015-1215-6	journal	January 2016
Growth and characterization of boron doped graphene by Hot Filament Chemical Vapor Deposition Technique (HFCVD) Jafari, A.; Ghoranneviss, M.; Salar Elahi, A. Journal of Crystal Growth, Vol. 438 https://doi.org/10.1016/j.jcrysgro.2015.12.038	journal	March 2016
Flexible Boron-Doped Laser-Induced Graphene Microsupercapacitors Peng, Zhiwei; Ye, Ruquan; Mann, Jason A. ACS Nano, Vol. 9, Issue 6 https://doi.org/10.1021/acsnano.5b00436	journal	May 2015
Raman Spectroscopy of Boron-Doped Single-Layer Graphene Kim, Yoong Ahm; Fujisawa, Kazunori; Muramatsu, Hiroyuki ACS Nano, Vol. 6, Issue 7 https://doi.org/10.1021/nn301728j	journal	June 2012
High-concentration boron doping of graphene nanoplatelets by simple thermal annealing and their supercapacitive properties Yeom, Da-Young; Jeon, Woojin; Tu, Nguyen Dien Kha Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep09817	journal	May 2015
Effects of boron-doping and heat-treatment on the electrical resistivity of carbon nanohorn-aggregates Harada, Manabu; Inagaki, Takayuki; Bandow, Shunji Carbon, Vol. 46, Issue 5 https://doi.org/10.1016/j.carbon.2008.02.001	journal	April 2008
Facile synthesis of sandwich-like polyaniline/boron-doped graphene nano hybrid for supercapacitors Hao, Qingli; Xia, Xifeng; Lei, Wu Carbon, Vol. 81 https://doi.org/10.1016/j.carbon.2014.09.090	journal	January 2015
The Preparation of BN-Doped Atomic Layer Graphene via Plasma Treatment and Thermal Annealing Xu, Jiao; Jang, Sung Kyu; Lee, Jieun The Journal of Physical Chemistry C, Vol. 118, Issue 38 https://doi.org/10.1021/jp504773h	journal	September 2014
Preparation and characterization of $B_{x}$ $C_{1 - x}$ thin films with the graphite structure Way, B. M.; Dahn, J. R.; Tiedje, T. Physical Review B, Vol. 46, Issue 3 https://doi.org/10.1103/PhysRevB.46.1697	journal	July 1992
The role of substitutional boron in carbon oxidation Radovic, Ljubisa R.; Karra, Murthy; Skokova, Kristina Carbon, Vol. 36, Issue 12 https://doi.org/10.1016/S0008-6223(98)00156-0	journal	January 1998
Ultrasensitive gas detection of large-area boron-doped graphene Lv, Ruitao; Chen, Gugang; Li, Qing Proceedings of the National Academy of Sciences, Vol. 112, Issue 47 https://doi.org/10.1073/pnas.1505993112	journal	November 2015
Platinum–boron doped graphene intercalated by carbon black for cathode catalyst in proton exchange membrane fuel cell Yang, H. N.; Lee, D. C.; Park, K. W. Energy, Vol. 89 https://doi.org/10.1016/j.energy.2015.06.019	journal	September 2015
Large-Scale Production of Single-Wall Carbon Nanohorns with High Purity Azami, Takeshi; Kasuya, Daisuke; Yuge, Ryota The Journal of Physical Chemistry C, Vol. 112, Issue 5 https://doi.org/10.1021/jp076365o	journal	February 2008
Cumulative and continuous laser vaporization synthesis of single wall carbon nanotubes and nanohorns Puretzky, A. A.; Styers-Barnett, D. J.; Rouleau, C. M. Applied Physics A, Vol. 93, Issue 4 https://doi.org/10.1007/s00339-008-4744-3	journal	December 2008
Buffer gas optimization in CO2 laser ablation for structure control of single-wall carbon nanohorn aggregates Yuge, Ryota; Yudasaka, Masako; Toyama, Kiyohiko Carbon, Vol. 50, Issue 5 https://doi.org/10.1016/j.carbon.2011.12.043	journal	April 2012
Growth dynamics of single-wall carbon nanotubes and nanohorn aggregates by CO2 laser vaporization at room temperature Kokai, F.; Takahashi, K.; Kasuya, D. Applied Surface Science, Vol. 197-198 https://doi.org/10.1016/S0169-4332(02)00434-8	journal	September 2002
Laser vaporization synthesis of polyhedral graphite Kokai, F.; Takahashi, K.; Kasuya, D. Applied Physics A: Materials Science & Processing, Vol. 77, Issue 1 https://doi.org/10.1007/s00339-003-2128-2	journal	June 2003
Raman study on defective graphene: Effect of the excitation energy, type, and amount of defects Eckmann, Axel; Felten, Alexandre; Verzhbitskiy, Ivan Physical Review B, Vol. 88, Issue 3 https://doi.org/10.1103/PhysRevB.88.035426	journal	July 2013
Interlayer spacing anomaly of single-wall carbon nanohorn aggregate Bandow, S.; Kokai, F.; Takahashi, K. Chemical Physics Letters, Vol. 321, Issue 5-6 https://doi.org/10.1016/S0009-2614(00)00353-5	journal	May 2000
Quantification of thin graphene sheets contained in spherical aggregates of single-walled carbon nanohorns Irie, Michiko; Nakamura, Maki; Zhang, Minfang Chemical Physics Letters, Vol. 500, Issue 1-3 https://doi.org/10.1016/j.cplett.2010.10.018	journal	November 2010
A molecular dynamics simulation of the fullerene formation process Yamaguchi, Yasutaka; Maruyama, Shigeo Chemical Physics Letters, Vol. 286, Issue 3-4 https://doi.org/10.1016/S0009-2614(98)00102-X	journal	April 1998
The growth mechanism of few-layer graphene in the arc discharge process Qin, Bin; Zhang, Tengfei; Chen, Honghui Carbon, Vol. 102 https://doi.org/10.1016/j.carbon.2016.02.074	journal	June 2016
Three nanostructured graphitic particles and their growth mechanisms from high-temperature carbon vapor confined by Ar gas Kokai, F.; Koshio, A.; Kasuya, D. Carbon, Vol. 42, Issue 12-13 https://doi.org/10.1016/j.carbon.2004.05.022	journal	January 2004
Investigations of single-wall carbon nanotube growth by time-restricted laser vaporization Puretzky, Alex A.; Schittenhelm, Henrik; Fan, Xudong Physical Review B, Vol. 65, Issue 24 https://doi.org/10.1103/PhysRevB.65.245425	journal	June 2002
Condensed phase growth of single-wall carbon nanotubes from laser annealed nanoparticulates Geohegan, D. B.; Schittenhelm, H.; Fan, X. Applied Physics Letters, Vol. 78, Issue 21 https://doi.org/10.1063/1.1371796	journal	May 2001
Nanotube and nanohorn nucleation from graphitic patches: Tight-binding molecular-dynamics simulations Kawai, Takazumi; Miyamoto, Yoshiyuki; Sugino, Osamu Physical Review B, Vol. 66, Issue 3 https://doi.org/10.1103/PhysRevB.66.033404	journal	July 2002
Graphitic cones and the nucleation of curved carbon surfaces Krishnan, A.; Dujardin, E.; Treacy, M. M. J. Nature, Vol. 388, Issue 6641 https://doi.org/10.1038/41284	journal	July 1997
Carbon nanocones: A variety of non-crystalline graphite Heiberg-Andersen, H.; Skjeltorp, A. T.; Sattler, K. Journal of Non-Crystalline Solids, Vol. 354, Issue 47-51 https://doi.org/10.1016/j.jnoncrysol.2008.06.120	journal	December 2008
A grand canonical Monte Carlo study of hydrogen adsorption in carbon nanohorns and nanocones at 77K Gotzias, A.; Heiberg-Andersen, H.; Kainourgiakis, M. Carbon, Vol. 49, Issue 8 https://doi.org/10.1016/j.carbon.2011.02.062	journal	July 2011
Efficient growth of multi-walled carbon nanotubes by continuous-wave laser vaporization of graphite containing B4C Kokai, Fumio; Nozaki, Iori; Okada, Takashi Carbon, Vol. 49, Issue 4 https://doi.org/10.1016/j.carbon.2010.11.033	journal	April 2011
Synthesis and Raman characterization of boron-doped single-walled carbon nanotubes McGuire, K.; Gothard, N.; Gai, P. L. Carbon, Vol. 43, Issue 2 https://doi.org/10.1016/j.carbon.2004.11.001	journal	January 2005
Doping Graphitic and Carbon Nanotube Structures with Boron and Nitrogen Stephan, O.; Ajayan, P. M.; Colliex, C. Science, Vol. 266, Issue 5191 https://doi.org/10.1126/science.266.5191.1683	journal	December 1994
Boron- and nitrogen-doped single-walled carbon nanohorns with graphite-like thin sheets prepared by CO2 laser ablation method Yuge, Ryota; Bandow, Shunji; Yudasaka, Masako Carbon, Vol. 111 https://doi.org/10.1016/j.carbon.2016.10.049	journal	January 2017
First-Principles Simulations of Boron Diffusion in Graphite Suarez-Martinez, I.; El-Barbary, A. A.; Savini, G. Physical Review Letters, Vol. 98, Issue 1 https://doi.org/10.1103/PhysRevLett.98.015501	journal	January 2007
Dehydration behavior of the superprotonic conductor CsH2PO4 at moderate temperatures: 230 to 260 °C Taninouchi, Yu-ki; Uda, Tetsuya; Awakura, Yasuhiro Journal of Materials Chemistry, Vol. 17, Issue 30 https://doi.org/10.1039/b704558c	journal	January 2007
Dehydration of CsH2PO4 at temperatures higher than 260 °C and the ionic conductivity of liquid product Taninouchi, Yu-ki; Uda, Tetsuya; Awakura, Yasuhiro Solid State Ionics, Vol. 178, Issue 31-32 https://doi.org/10.1016/j.ssi.2007.10.017	journal	January 2008
Phase Relationship of CsH[sub 2]PO[sub 4]–CsPO[sub 3] System and Electrical Properties of CsPO[sub 3] Taninouchi, Yu-ki; Hatada, Naoyuki; Uda, Tetsuya Journal of The Electrochemical Society, Vol. 156, Issue 5 https://doi.org/10.1149/1.3086755	journal	January 2009
Microstructure effects on the electrochemical corrosion of carbon materials and carbon-supported Pt catalysts Cherstiouk, O. V.; Simonov, A. N.; Moseva, N. S. Electrochimica Acta, Vol. 55, Issue 28 https://doi.org/10.1016/j.electacta.2010.07.047	journal	December 2010
Electrochemical carbon corrosion in high temperature proton exchange membrane fuel cells Oh, Hyung-Suk; Lee, Jin-Hee; Kim, Hansung International Journal of Hydrogen Energy, Vol. 37, Issue 14 https://doi.org/10.1016/j.ijhydene.2012.04.095	journal	July 2012
Electrochemical corrosion behavior of carbon black in phosphoric acid Antonucci, P. L.; Romeo, F.; Minutoli, M. Carbon, Vol. 26, Issue 2 https://doi.org/10.1016/0008-6223(88)90037-1	journal	January 1988
Electrocatalytic Corrosion of Carbon Support in PEMFC Cathodes Roen, L. M.; Paik, C. H.; Jarvi, T. D. Electrochemical and Solid-State Letters, Vol. 7, Issue 1 https://doi.org/10.1149/1.1630412	journal	January 2004
Carbon substrates for phosphoric acid fuel cell cathodes Stonehart, P. Carbon, Vol. 22, Issue 4-5 https://doi.org/10.1016/0008-6223(84)90015-0	journal	January 1984
Properties of high-temperature PEFC Celtec®-P 1000 MEAs in start/stop operation mode Schmidt, Thomas J.; Baurmeister, Jochen Journal of Power Sources, Vol. 176, Issue 2 https://doi.org/10.1016/j.jpowsour.2007.08.055	journal	February 2008
Carbon support oxidation in PEM fuel cell cathodes Maass, S.; Finsterwalder, F.; Frank, G. Journal of Power Sources, Vol. 176, Issue 2 https://doi.org/10.1016/j.jpowsour.2007.08.053	journal	February 2008
Effect of boron doping in the carbon support on platinum nanoparticles and carbon corrosion Acharya, Chethan K.; Li, Wei; Liu, Zhufang Journal of Power Sources, Vol. 192, Issue 2 https://doi.org/10.1016/j.jpowsour.2009.03.020	journal	July 2009
Dynamics of single-wall carbon nanotube synthesis by laser vaporization Puretzky, A. A.; Geohegan, D. B.; Fan, X. Applied Physics A: Materials Science & Processing, Vol. 70, Issue 2 https://doi.org/10.1007/s003390050027	journal	February 2000
Electrochemical Hydrogen Separation via Solid Acid Membranes Papandrew, Alexander B.; Wilson, David L.; M. Cantillo, Nelly Journal of The Electrochemical Society, Vol. 161, Issue 5 https://doi.org/10.1149/2.078405jes	journal	January 2014
Ruthenium-Alloy Electrocatalysts with Tunable Hydrogen Oxidation Kinetics in Alkaline Electrolyte St. John, Samuel; Atkinson, Robert W.; Unocic, Raymond R. The Journal of Physical Chemistry C, Vol. 119, Issue 24 https://doi.org/10.1021/acs.jpcc.5b03284	journal	June 2015

Cited By (2)

In situ determination of the electrochemically active platinum surface area: key to improvement of solid acid fuel cells Lohmann-Richters, Felix P.; Abel, Bernd; Varga, Áron Journal of Materials Chemistry A, Vol. 6, Issue 6 https://doi.org/10.1039/c7ta10110d	journal	January 2018
Laser Synthesis, Processing, and Spectroscopy of Atomically-Thin Two Dimensional Materials Geohegan, David B.; Puretzky, Alex A.; Boulesbaa, Aziz Advances in the Application of Lasers in Materials Science https://doi.org/10.1007/978-3-319-96845-2_1	book	January 2018