Immobilized hindered amine radical scavenger for durability enhancement of perfluorosulfonic acid membrane in PEMFCs

Pang, Yang; Duan, Yuting; Li, Qijia; Liu, Binghui; Hu, Xinyue; Liu, Qian; Zhao, Chengji

doi:10.1016/j.memsci.2023.121999

Cited by 24 publications

(5 citation statements)

References 43 publications

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“…This may result from the dense hydrogen bonding network constructed between the amine/imino group on CeO 2 @Ph-PEI and -SO 3 H in the matrix, which restricted the migration of the chain segments and boosted the mechanical strength of the membrane. However, incorporating inorganic nano llers slightly reduced the elongation at the break of the hybrid membranes, in line with previously reported research [42]. Hence, attention needs to be paid to balancing the relationship between strength and toughness.…”

Section: Physical and Chemical Properties Of Obtained Membranessupporting

confidence: 88%

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Phosphate-grafted polyethyleneimine-induced multifunctional cerium oxide as an antioxidant for simultaneously enhancing the proton conductivity and durability of proton exchange membranes

Zhao,

Liao,

Wang

et al. 2024

Preprint

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Free radical attack on Proton exchange membranes (PEM) is detrimental to the long-term durability of proton exchange membrane fuel cells (PEMFCs), and although state-of-the-art cerium-based antioxidants defend against free radical attack, potentially impairing the proton conductivity of PEM limits their more comprehensive application. To break the "trade-off" between the durability and proton conductivity of PEM, a functionalized cerium oxide (CeO2@Ph-PEI) composite with a synergistic enhancement of durability and proton conductivity has been synthesized induced by phosphate-grafted polyethyleneimine (Ph-PEI). Owing to the strong adsorption of phosphate groups on transition metal hydroxides/oxides, Ph-PEI was firmly anchored on the particle surface during the transition from sol-gel to oxide, which suppressed the further aggregation of CeO2 nanoparticles and thus retained abundant active sites for free radical scavenging. Moreover, due to the extra proton transport sites in the anchored Ph-PEI functional shells, the hybrid membrane fabricated with CeO2@Ph-PEI as the antioxidant additive exhibited a high proton conductivity up to 0.242 S cm− 1, which was approximately 1.32 times higher than that of the unmodified CeO2-based hybrid membrane. Consequently, CeO2@Ph-PEI-based PEMs exhibited an OCV decay rate of 0.32 mV h− 1, a maximum power density of 1.19 W cm− 2, an H2 crossover value of 2.12 mA cm− 2, and thickness retention (93.7%) after 200 hours of accelerated degradation testing. This strategy synergistically improves the proton conductivity of PEMs and the lifetime of PEMFCs through CeO2 functionalization, providing a promising solution for next-generation fuel cell-based energy storage techniques.

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Section: Physical and Chemical Properties Of Obtained Membranessupporting

confidence: 88%

“…The CeO 2 @Ph-PEI-based PEMs showed outstanding performance in terms of OCV decay rate compared to previously reported work (Fig. 4e), [10,18,19,22,23,42,[47][48][49][50][51][52][53][54][55][56][57] illustrating that CeO 2 @Ph-PEI is an antioxidant with promising applications.…”

Section: Insight Into the Functioning Mechanism Of Ceo 2 @Ph-peimentioning

confidence: 53%

Phosphate-grafted polyethyleneimine-induced multifunctional cerium oxide as an antioxidant for simultaneously enhancing the proton conductivity and durability of proton exchange membranes

Zhao,

Liao,

Wang

et al. 2024

Preprint

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“…7 These free radicals attack the PFSA and cause significant degradation, thereby severely reducing the life of the PFSA membrane. In recent years, the incorporation of variable valence cations (for example, Ce 3+ and Zr 2+ ) 1,8 and their oxides (such as CeO 2 and ZrO 2 ), 5,9 resveratrol, 10 MOFs, 11,12 and caffeic acid 13 as free radical scavengers has been used to effectively mitigate the chemical degradation of PFSA. However, these metal ions initially exchange with protons from the –SO 3 H groups in PFSA, degrading proton conduction during device operation.…”

Section: Introductionmentioning

confidence: 99%

A composite proton exchange membrane with a three-dimensionally-reinforced hydrogen bonding network for durable hydrogen fuel cells

Dong,

Feng,

Xie

et al. 2024

Inorg. Chem. Front.

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“…The stability decay of Fe-N-C catalysts mainly results from the oxidation of carbon substrates and poisoning of active Fe-N x . , During the ORR process, the superoxide (•HO 2 – ) and hydroxyl (•OH) radicals generated by the activation and incomplete reduction of oxygen greatly damage the Fe-N x site via oxidizing carbon to carbon dioxide or poisoning Fe–N x sites. , Thus, mitigating the attack of radicals on the Fe–N x sites is of the utmost importance in the improvement of ORR stability. − Recently, researchers have explored effective strategies to proactively scavenge radicals and, thus, balance the activity and stability of the Fe-N-C catalysts. Specifically, adding other oxide species into Fe-N-C can proactively scavenge radicals and maintain efficient ORR activity .…”

Section: Introductionmentioning

confidence: 99%

“…17,18 During the ORR process, the superoxide (•HO 2 − ) and hydroxyl (•OH) radicals generated by the activation and incomplete reduction of oxygen greatly damage the Fe-N x site via oxidizing carbon to carbon dioxide or poisoning Fe−N x sites. 19,20 Thus, mitigating the attack of radicals on the Fe−N sites is of the utmost importance in the improvement of ORR stability. 21−23 Recently, researchers have explored effective strategies to proactively scavenge radicals and, thus, balance the activity and stability of the Fe-N-C catalysts.…”

Section: Introductionmentioning

confidence: 99%

Mn Single-Atom Tuning Fe-N-C Catalyst Enables Highly Efficient and Durable Oxygen Electrocatalysis and Zinc–Air Batteries

Ran,

Xu,

Zhu

et al. 2023

ACS Nano

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Fe-N-C catalyst is one of most promising candidates for oxygen electrocatalysis reaction in zinc–air batteries (ZABs), but achieving sustained high activity is still a challenging issue. Herein, we demonstrate that introducing Mn single atoms into Fe-N-C (Mn1@Fe-N-C/CNTs) enables the realization of highly efficient and durable oxygen electrocatalysis performance and application in ZABs. Multiple characterizations confirm that Mn1@Fe-N-C/CNTs is equipped with Mn-N2O2 and Fe-N4 sites and Fe nanoparticles. The Mn-N2O2 sites not only tune the electron structure of Fe-N x sites to enhance intrinsic activity, but also scavenge the attack of radicals from Fe-N x sites for improvement in ORR durability. As a result, Mn1@Fe-N-C/CNTs exhibits enhanced ORR performance to traditional Fe-N-C catalysts with high E 1/2 of 0.89 V vs reversible hydrogen electrode (RHE) and maintains ORR activity after 15 000 CV. Impressively, Mn1@Fe-N-C/CNTs also presents excellent OER activity and the difference (ΔE) between E 1/2 of ORR and OER potential at 10 mA cm–2 (E j10) is only 0.59 V, outperforming most reported catalysts. In addition, the maintainable bifunctional activity of Mn1@Fe-N-C/CNTs is demonstrated in ZABs with almost unchanged cycle voltage efficiency up to 200 h. This work highlights the critical role of Mn single atoms in enhancing ORR activity and stability, promoting the development of advanced catalysts.

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Immobilized hindered amine radical scavenger for durability enhancement of perfluorosulfonic acid membrane in PEMFCs

Cited by 24 publications

References 43 publications

Phosphate-grafted polyethyleneimine-induced multifunctional cerium oxide as an antioxidant for simultaneously enhancing the proton conductivity and durability of proton exchange membranes

Phosphate-grafted polyethyleneimine-induced multifunctional cerium oxide as an antioxidant for simultaneously enhancing the proton conductivity and durability of proton exchange membranes

A composite proton exchange membrane with a three-dimensionally-reinforced hydrogen bonding network for durable hydrogen fuel cells

Mn Single-Atom Tuning Fe-N-C Catalyst Enables Highly Efficient and Durable Oxygen Electrocatalysis and Zinc–Air Batteries

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