Piperidinium-Based Anion-Exchange Membranes with an Aliphatic Main Chain for Alkaline Fuel Cells

Xu, Fei; Su, Yue; Yuan, Wensen; Han, Jizhong; Ding, Jianning; Lin, Bencai

doi:10.1021/acs.iecr.0c02736

Cited by 16 publications

(12 citation statements)

References 51 publications

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“…Generally, the increases of SD and WU of AEMs are usually associated with the increase of membranes IEC. [33][34][35] The swelling behavior affects the dimensional stability of AEMs, which directly determines whether the membrane is suitable for the fabrication of membrane electrode assembly (MEA). The importance of WU on the AEMs performance has also been extensively recognized.…”

Section: Ion Exchange Capacity Swelling Degree and Water Uptakementioning

confidence: 99%

Conductivity and Stability Properties of Anion Exchange Membranes: Cation Effect and Backbone Effect

et al. 2021

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The rise of heterocycle cations, a new class of stable cations, has fueled faster growth of research interest in heterocycle cation-attached anion exchange membranes (AEMs). However, once cations are grafted onto backbones, the effect of backbones on properties of AEMs must also be taken into account.In order to comprehensively study the influence of cations effect and backbones effect on AEMs performance, a series of AEMs were prepared by grafting spacer cations, heterocycles cations, and aromatic cations onto brominated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO) or poly(vinylbenzyl chloride) (PVB) backbones, respectively. Spacer cation [trimethylamine (TMA), N,N-dimethylethylamine (DMEA)]-attached AEMs showed general ion transportation and stability behaviors, but exhibited high cationic reaction efficiency. Heterocycle cation [1-methylpyrrolidine (MPY), 1-methylpiperidine (MPrD)]-attached AEMs showed excellent chemical stability, but their ion conduction properties were unimpressive. Aromatic cation [1-methylimidazole (MeIm), N,N-dimethylaniline (DMAni)]-attached AEMs exhibited superior ionic conductivity, while their poor cations stabilities hindered the application of the membranes. Besides, it was found that PVB-based AEMs had excellent backbone stability, but BPPO-based AEMs exhibited higher OH À conductivity and cation stability than those of the same cations grafted PVB-based AEMs due to their higher water uptake (WU). For example, the ionic conductivities (ICs) of BPPO-TMA and PVB-TMA at 80 °C were 53.1 and 38.3 mS cm À 1 , and their WU was 152.3 and 95.1 %, respectively. After the stability test, the IC losses of BPPO-TMA and PVB-TMA were 21.4 and 32.2 %, respectively. The result demonstrated that the conductivity and stability properties of the AEMs could be enhanced by increasing the WU of the membranes. These findings allowed the matching of cations to the appropriate backbones and reasonable modification of the AEM structure. In addition, these results helped to fundamentally understand the influence of cation effect and backbone effect on AEM performance.

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Section: Ion Exchange Capacity Swelling Degree and Water Uptakementioning

confidence: 99%

Conductivity and Stability Properties of Anion Exchange Membranes: Cation Effect and Backbone Effect

et al. 2021

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“…Previous studies have mainly focused on the alkaline stability of cations. A large number of reports have confirmed that quaternary ammonium (QA) cations are unstable under alkaline conditions because of their degradation. − The alkaline stability of AEMs could be enhanced by synthesizing cations with bulky steric hindrance and (or) constructing side-chain structures of polymers, which has been confirmed by recent reports. − Many AEMs with different structures have been reported due to the development of polyether backbones, for example, poly(phenylene oxide), poly(ether imide), poly(ether sulfone), and poly(ether ether ketone), which exhibit good comprehensive performance. − However, a recent study reported that polar groups such as ether present in the main chain backbones of AEMs are vulnerable to OH – attack because of their strong inductive effect of QA, thereby degrading the main chain. − Thus, the synthesis of polymers without polar groups has become a popular method.…”

Section: Introductionmentioning

confidence: 83%

Polyfluorene/Poly(vinylbenzyl chloride) Cross-Linked Anion-Exchange Membranes with Multiple Cations for Fuel Cell Applications

Chen

et al. 2022

ACS Appl. Energy Mater.

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An ideal anion-exchange membrane (AEM) must possess good dimensional stability, excellent alkaline stability, and good ionic conductivity. In this study, polyfluorene/poly-(vinylbenzyl chloride) (PVBC) cross-linked AEMs with multiple cations are prepared. A cross-linked structure is introduced to enhance the mechanical strength (>30 MPa) and dimensional stability (swelling ratio < 15%) of these AEMs. All PHF x TP 100−x − PVBC-and PMF x TP 100−x −PVBC-based AEMs exhibit excellent alkaline stability after treating with 2 M KOH at 80 °C for 30 days, which is attributed to the ether-free backbone and cross-linked structure. The long hydrophobic alkyl side chains of PHF 10 TP 90 − PVBC favors the construction of microphase separation within the membrane, leading to higher conductivity and cell performance (64.56 mS cm −1 and 323 mW cm −2 , at 80 °C) than those of the PMF 10 TP 90 −PVBC (57.56 mS cm −1 and 100 mW cm −2 at 80 °C).The results indicate that polyfluorene/PVBC cross-linked AEMs with multiple cations are prospective membrane materials for fuel cells.

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“…(2) The OH – transfer direction is opposite to the fuel permeation direction, which can avoid internal short circuits in the cell . However, the anion exchange membrane (AEM), the “heart” of the AEMFC, has obvious defects such as poor alkali stability and low ionic conductivity, which hinder the commercial application of AEMFCs. , …”

Section: Introductionmentioning

confidence: 99%

“…5 However, the anion exchange membrane (AEM), the "heart" of the AEMFC, has obvious defects such as poor alkali stability and low ionic conductivity, which hinder the commercial application of AEMFCs. 6,7 The alkali stability of an AEM is the key to the long-term stable operation of AEMFCs. The current methods for improving the alkali stability of AEMs mainly focus on the improvement of the alkali stability of the cationic group and the optimization of connection of the main and side chains.…”

Section: Introductionmentioning

confidence: 99%

Preparation and Characterization of Non-N-Bonded Side-Chain Anion Exchange Membranes Based on Poly(2,6-dimethyl-1,4-phenylene oxide)

Chen

Zhang

Shen

et al. 2022

Ind. Eng. Chem. Res.

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Due to the polyether structure on the main chain, the alkali resistance of quaternized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) anion exchange membranes (AEMs) needs to be improved. Through the Williamson etherification reaction, we synthesized a new type of PPO-based AEM with a quaternized piperidine cation side chain, which has good ionic conductivity (63.5 mS cm–1 at 80 °C). Due to being non-N-bonded, it has good alkali resistance, and the conductivity loss is less than 10% when immersed in 1 mol L–1 KOH solution for 480 h. In addition, we also prepared other two AEMs (N-bonded) for comparison and studied their degradation mechanism by Fourier transform infrared spectroscopy. The study found that the non-N-bonded PPO-based AEM has the lowest OH– conductivity loss and its C–N retention is the highest after soaking in alkali, which shows that the non-N bond and the ether bond can effectively improve alkali resistance, while the conductivity is not lower than that of the AEM with N-bonded cations.

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Piperidinium-Based Anion-Exchange Membranes with an Aliphatic Main Chain for Alkaline Fuel Cells

Cited by 16 publications

References 51 publications

Conductivity and Stability Properties of Anion Exchange Membranes: Cation Effect and Backbone Effect

Conductivity and Stability Properties of Anion Exchange Membranes: Cation Effect and Backbone Effect

Polyfluorene/Poly(vinylbenzyl chloride) Cross-Linked Anion-Exchange Membranes with Multiple Cations for Fuel Cell Applications

Preparation and Characterization of Non-N-Bonded Side-Chain Anion Exchange Membranes Based on Poly(2,6-dimethyl-1,4-phenylene oxide)

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