Structurally modulated and functionalized carbon nanotubes as potential filler for Nafion matrix toward improved power output and durability in proton exchange membrane fuel cells operating at reduced relative humidity

Vinothkannan Mohanraj; Ae Rhan Kim; Sung Kwan  Ryu; Dong Jin Yoo

doi:10.1016/j.memsci.2022.120393

Structurally modulated and functionalized carbon nanotubes as potential filler for Nafion matrix toward improved power output and durability in proton exchange membrane fuel cells operating at reduced relative humidity

Vinothkannan Mohanraj, Ae Rhan Kim, Sung Kwan Ryu, Dong Jin Yoo

Jeonbuk National University

Research output: Contribution to journal › Article › peer-review

74 Citations (Scopus)

Abstract

Development of a high-performance and durable proton exchange membrane (PEM) for low relative humidity (RH) operation is imperative for further commercialization of hydrogen-air fuel cell (HAFC). In this work, we reported the synthesize of carbon nanotubes-unzipped carbon nanotubes (CNTs-UCNTs) hybrid via calcination process with ammonium fluoride. Further, the 4-benzenediazonium sulfonate was used to sulfonate both CNTs and UCNTs to form sulfonated CNTs-sulfonated UCNTs (SCNTs-SUCNTs) hybrid. The unzipping enlarged the surface area of CNTs-UCNTs hybrid and facilitated the accommodation of a large density of sulfonic acid (-SO ₃H) groups during sulfonation. Thus, SCNTs-SUCNTs hybrid incorporation with the host Nafion matrix results a uniform composite membrane with high density of –SO ₃H groups per unit volume. It positively impacts thermal, mechanical and oxidative stabilities, and physicochemical performances of composite membrane. Besides, Nafion/SCNTs-SUCNTs composite membrane afforded credible proton conductivity, current output, power output, and durability, which are 0.015 S cm ⁻¹, 1.000 A cm ⁻², 0.343 W cm ⁻², and 0.15 mV h ⁻¹, respectively when operating the HAFC at 60 °C under 20% RH. In contrast, bare Nafion, Nafion/CNTs, and Nafion-212 membranes exhibited inferior proton conductivity, current output, power output, and durability under identical HAFC operating conditions.

Original language	English
Article number	120393
Number of pages	11
Journal	Journal of Membrane Science
Volume	649
Early online date	23 Feb 2022
DOIs	https://doi.org/10.1016/j.memsci.2022.120393
Publication status	Published - 5 May 2022
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2022 Elsevier B.V.

Funder

This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning ( NRF-2020R1A2B5B01001458 ). This research was supported by Basic Science Research through the National Research Foundation of Korea (NRF) funded by the Ministry of Education ( NRF-2021R1I1A1A01050905 ). This work was supported by Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government (MOTIE) (No. 20214000000040 , Innovation Research Center for Next Generation Battery-based Materials, Parts and Applied Technology).

High-resolution-transmission electron microscopy (HR-TEM) (JEOL, JEM-2010) and high resolution-scanning electron microscopy (HR-SEM) (JEOL, JSM-6400) were used to image the micromorphology of pristine CNTs, CNTs-UCNTs, and SCNTs-SUCNTs particles and corresponding membrane samples. Powder X-ray diffractometry (XRD, Panalytical, X'pert Pro Powder), Brunauer–Emmett–Teller (BET) analysis (Micromeritics, Gemini 2375), and X-ray photoelectron spectroscopy (XPS, Axis-Nova, Kratos Inc.) were utilized to study the crystallinity, surface area, and elemental composition, respectively, of additive samples. Thermogravimetric analysis (TGA, TA instruments, Q500), differential scanning calorimetry (DSC, TA instruments, Q20), dynamic mechanical analysis (DMA, TA instruments, Q800), and universal test machine (UTM, LR5K plus 5 kN, Ametek-Lloyd Instruments) were used to confirm the thermal and mechanical properties of membranes. All the aforenoted instruments were installed at Korea Basic Science Institute (KBSI) and Center for University-wide Research Facilities (CURF) at Jeonbuk National University (JBNU). Detailed descriptions regarding water adsorption, contact angle, water uptake, swelling ratio, ion exchange capacity (IEC), and proton conductivity measurements are provided in supporting information. Experiments related to membrane electrode assembly (MEA) preparation, HAFC performance, and durability are also given in supporting information.This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (NRF-2020R1A2B5B01001458). This research was supported by Basic Science Research through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2021R1I1A1A01050905). This work was supported by Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government (MOTIE) (No.20214000000040, Innovation Research Center for Next Generation Battery-based Materials, Parts and Applied Technology).

Funding

This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning ( NRF-2020R1A2B5B01001458 ). This research was supported by Basic Science Research through the National Research Foundation of Korea (NRF) funded by the Ministry of Education ( NRF-2021R1I1A1A01050905 ). This work was supported by Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government (MOTIE) (No. 20214000000040 , Innovation Research Center for Next Generation Battery-based Materials, Parts and Applied Technology). High-resolution-transmission electron microscopy (HR-TEM) (JEOL, JEM-2010) and high resolution-scanning electron microscopy (HR-SEM) (JEOL, JSM-6400) were used to image the micromorphology of pristine CNTs, CNTs-UCNTs, and SCNTs-SUCNTs particles and corresponding membrane samples. Powder X-ray diffractometry (XRD, Panalytical, X'pert Pro Powder), Brunauer–Emmett–Teller (BET) analysis (Micromeritics, Gemini 2375), and X-ray photoelectron spectroscopy (XPS, Axis-Nova, Kratos Inc.) were utilized to study the crystallinity, surface area, and elemental composition, respectively, of additive samples. Thermogravimetric analysis (TGA, TA instruments, Q500), differential scanning calorimetry (DSC, TA instruments, Q20), dynamic mechanical analysis (DMA, TA instruments, Q800), and universal test machine (UTM, LR5K plus 5 kN, Ametek-Lloyd Instruments) were used to confirm the thermal and mechanical properties of membranes. All the aforenoted instruments were installed at Korea Basic Science Institute (KBSI) and Center for University-wide Research Facilities (CURF) at Jeonbuk National University (JBNU). Detailed descriptions regarding water adsorption, contact angle, water uptake, swelling ratio, ion exchange capacity (IEC), and proton conductivity measurements are provided in supporting information. Experiments related to membrane electrode assembly (MEA) preparation, HAFC performance, and durability are also given in supporting information.This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (NRF-2020R1A2B5B01001458). This research was supported by Basic Science Research through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2021R1I1A1A01050905). This work was supported by Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government (MOTIE) (No.20214000000040, Innovation Research Center for Next Generation Battery-based Materials, Parts and Applied Technology).

Funders	Funder number
Jeonbuk National University
Ministry of Education	NRF-2021R1I1A1A01050905
Ministry of Trade, Industry and Energy	20214000000040
Ministry of Science and ICT	NRF-2020R1A2B5B01001458
National Research Foundation of Korea
University Technology Malaysia
Korea Institute of Energy Technology Evaluation and Planning
Jeonbuk National University

Keywords

Hydrogen-air fuel cells
Low relative humidity
Nafion composite membrane
SCNTs-SUCNTs hybrid

ASJC Scopus subject areas

General Materials Science
Biochemistry
Physical and Theoretical Chemistry
Filtration and Separation

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Mohanraj, V., Kim, A. R., Ryu, S. K., & Yoo, D. J. (2022). Structurally modulated and functionalized carbon nanotubes as potential filler for Nafion matrix toward improved power output and durability in proton exchange membrane fuel cells operating at reduced relative humidity. Journal of Membrane Science, 649, Article 120393. https://doi.org/10.1016/j.memsci.2022.120393

Structurally modulated and functionalized carbon nanotubes as potential filler for Nafion matrix toward improved power output and durability in proton exchange membrane fuel cells operating at reduced relative humidity. / Mohanraj, Vinothkannan; Kim, Ae Rhan; Ryu, Sung Kwan et al.
In: Journal of Membrane Science, Vol. 649, 120393, 05.05.2022.

Research output: Contribution to journal › Article › peer-review

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title = "Structurally modulated and functionalized carbon nanotubes as potential filler for Nafion matrix toward improved power output and durability in proton exchange membrane fuel cells operating at reduced relative humidity",

abstract = "Development of a high-performance and durable proton exchange membrane (PEM) for low relative humidity (RH) operation is imperative for further commercialization of hydrogen-air fuel cell (HAFC). In this work, we reported the synthesize of carbon nanotubes-unzipped carbon nanotubes (CNTs-UCNTs) hybrid via calcination process with ammonium fluoride. Further, the 4-benzenediazonium sulfonate was used to sulfonate both CNTs and UCNTs to form sulfonated CNTs-sulfonated UCNTs (SCNTs-SUCNTs) hybrid. The unzipping enlarged the surface area of CNTs-UCNTs hybrid and facilitated the accommodation of a large density of sulfonic acid (-SO 3H) groups during sulfonation. Thus, SCNTs-SUCNTs hybrid incorporation with the host Nafion matrix results a uniform composite membrane with high density of –SO 3H groups per unit volume. It positively impacts thermal, mechanical and oxidative stabilities, and physicochemical performances of composite membrane. Besides, Nafion/SCNTs-SUCNTs composite membrane afforded credible proton conductivity, current output, power output, and durability, which are 0.015 S cm −1, 1.000 A cm −2, 0.343 W cm −2, and 0.15 mV h −1, respectively when operating the HAFC at 60 °C under 20% RH. In contrast, bare Nafion, Nafion/CNTs, and Nafion-212 membranes exhibited inferior proton conductivity, current output, power output, and durability under identical HAFC operating conditions.",

keywords = "Hydrogen-air fuel cells, Low relative humidity, Nafion composite membrane, SCNTs-SUCNTs hybrid",

author = "Vinothkannan Mohanraj and Kim, {Ae Rhan} and Ryu, {Sung Kwan} and Yoo, {Dong Jin}",

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year = "2022",

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doi = "10.1016/j.memsci.2022.120393",

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AU - Ryu, Sung Kwan

AU - Yoo, Dong Jin

PY - 2022/5/5

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AB - Development of a high-performance and durable proton exchange membrane (PEM) for low relative humidity (RH) operation is imperative for further commercialization of hydrogen-air fuel cell (HAFC). In this work, we reported the synthesize of carbon nanotubes-unzipped carbon nanotubes (CNTs-UCNTs) hybrid via calcination process with ammonium fluoride. Further, the 4-benzenediazonium sulfonate was used to sulfonate both CNTs and UCNTs to form sulfonated CNTs-sulfonated UCNTs (SCNTs-SUCNTs) hybrid. The unzipping enlarged the surface area of CNTs-UCNTs hybrid and facilitated the accommodation of a large density of sulfonic acid (-SO 3H) groups during sulfonation. Thus, SCNTs-SUCNTs hybrid incorporation with the host Nafion matrix results a uniform composite membrane with high density of –SO 3H groups per unit volume. It positively impacts thermal, mechanical and oxidative stabilities, and physicochemical performances of composite membrane. Besides, Nafion/SCNTs-SUCNTs composite membrane afforded credible proton conductivity, current output, power output, and durability, which are 0.015 S cm −1, 1.000 A cm −2, 0.343 W cm −2, and 0.15 mV h −1, respectively when operating the HAFC at 60 °C under 20% RH. In contrast, bare Nafion, Nafion/CNTs, and Nafion-212 membranes exhibited inferior proton conductivity, current output, power output, and durability under identical HAFC operating conditions.

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Structurally modulated and functionalized carbon nanotubes as potential filler for Nafion matrix toward improved power output and durability in proton exchange membrane fuel cells operating at reduced relative humidity

Abstract

Bibliographical note

Funder

Funding

Keywords

ASJC Scopus subject areas

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