JOURNAL OF MEMBRANE SCIENCE
·
2022
·
IF 10.53
Tao Ban,Maolian Guo,Yajie Wang,Yiyang Zhang,Xiuling Zhu
Fabrication of aromatic proton exchange membrane (PEM) with excellent conductivity and stability is a long-standing challenge. Here, we propose an aromatic PEM containing multiple sulfonated alkyl side chains (SAFPAEK-x and SAFPAEF-x), and then implement an ideal strategy to address the trade-off between conductivity and stability by optimizing the side chain length and main chain polarity. Specifically, the synthesized PEMs achieve an efficient proton transport (proton conductivity >0.124 S cm −1 at 80 °C) under the synergistic effect of multiple pendant sulfonate groups and a pronounced microphase separation structure. Meanwhile, regulating the polarity of the hydrophobic domain via introducing fluorinated structures can effectively suppress the swelling behavior, so that SAFPAEF-x display excellent dimensional stability (swelling ratio <10% at 80 °C). The theoretical calculations of molecular models and ex-situ experiments demonstrate that appropriate increases in side chain length and main chain polarity lead to noticeably improved radical stability of aromatic PEMs. Finally, the laboratory-assembled direct borohydride fuel cell using our rationally designed PEMs reaches the highest peak power density of 191.17 mW m −2 at room temperature, outperforming the Nafion 115 (95.87 mW m −2 ) under the same conditions. Therefore, this membrane design strategy stimulates great potential in designing high-performance aromatic PEMs for fuel cells.
研究领域:
材料科学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2015
·Vol. 5
·期 101
·83320-83330
·
IF 3.84
Lishuang Xu,Hailan Han,Meiyu Liu,Jingmei Xu,Hongzhe Ni,Hailong Zhang,Da Xu,Zhe Wang
Sulfonated poly(arylene ether ketone sulfone) containing pendant amino groups (Am-SPAEKS)/phosphotungstic acid (HPW) composite membranes with different HPW content were prepared by the solution blend method as proton exchange membranes (PEM) for proton exchange membrane fuel cells (PEMFCs) that operate at medium–high temperatures. Am-SPAEKS was synthesized successfully by adjusting the molar feed ratio, which was confirmed by Fourier transform infrared (FT-IR) and 1H NMR spectroscopy. FT-IR spectroscopy showed that there were acid–base interactions between the amino groups and HPW, as well as between HPW and the sulfonic groups. These interactions could stabilize HPW in the composite membranes, which was confirmed by SEM images. The water uptake and thermal stability of the composite membranes were improved compared with the Am-SPAEKS membranes. The water retention capacity and the mechanical property of the composite membranes also met the requirement for proton exchange membranes. The proton conductivity of the Am-SPAEKS/HPW30% composite membrane was as high as 0.091 S cm−1 at 120 °C. These results indicate that the Am-SPAEKS/HPW composite membranes have potential to be used as alternative proton exchange membrane materials for proton exchange membrane fuel cells at medium–high temperature conditions.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2013
·
IF 4.675
Hao Jiang,Xin Guo,Gang Zhang,Jing Ni,Chengji Zhao,Zhongguo Liu,Liyuan Zhang,Mingyu Li,Shuai Xu,Hui Na
In this paper, a series of proton exchange membranes prepared by “Click Reaction” are reported. The cross-linked membranes are based on water soluble sulfonated poly (ether ether ketone) containing dipropenyl groups (SDPEEK-nE/nH). Compared with self-crosslinked membranes (SDPEEK-nS), this “Click” cross-linked membranes using 1,2-Ethanedithiol and 1,6-Hexanedithiol as the cross-linker exhibit extremely reduced water uptake and swelling ratio. The lowest proton conductivity at 80 °C of the “Click” cross-linked membranes reaches to 0.168 S cm −1 , and the highest methanol permeability of the “Click” cross-linked SDPEEK-8E is only 4.13 × 10 −7 cm 2 s −1 , which is 5 times lower than that of Nafion 117 membrane. All the results imply that the cross-linked membranes with novel thiol cross-linker are promising alternative material for fuel cell application .
研究领域:
材料科学
·
能源工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2022
·Vol. 169
·期 2
·024502
·
IF 4.386
Chao Meng,Dongmei Han,Shan Ren,Shuanjin Wang,Min Xiao,Yuezhong Meng
In the present work, a cross-linked high-temperature proton exchange membrane based on poly [2, 2'-(p-oxydiphenylene)-5, 50-benzimidazole] (OPBI), imidazole (Im) and hexachlorocyclotriphosphazene (HCCP) was prepared and characterized, aiming at their future application in fuel cell devices. The composite membranes were characterized by Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscope (SEM), energy dispersive X-ray (EDX) and thermogravimetric analysis (TGA). The results show that the PBI are successfully cross-linked by the cross-linking agent, and the membranes are uniform and compact, with excellent thermal stability. Phosphoric acid (PA) doped crosslinked membranes have excellent mechanical properties and proton conductivities. The tensile strength of PA-doped PBI-ImCCP-20% at room temperature is 20 MPa, and the proton conductivity reaches 53 mS cm−1 at 160 °C without humidification. H2/O2 fuel cell assembled with PA-doped PBI-ImCCP-20% membrane delivered a peak power density of 749 mW cm−2 at 160 °C under anhydrous conditions. The excellent performance of PBI-ImCCP series cross-linked membranes makes them potential candidate for HT-PEMFC applications.
研究领域:
材料科学
·
能源工程
✓ 已验证
产品关联
DOI
高影响因子
Nanomaterials
·
2023
·Vol. 13
·期 2
·266
·
IF 5.3
Erli Qu,Min Xiao,Dongmei Han,Sheng Huang,Zhiheng Huang,Wei Liu,Shuanjin Wang,Yuezhong Meng
A semi-aromatic polybenzimidazole (DPBI) is synthesized via polycondensation of decanedioic acid (DCDA) and 3,3-diaminobenzidine (DAB) in a mixed phosphorus pentoxide/methanesulfonic acid (PPMA) solvent. Ascribing to in-situ macromolecular crosslinker of ploly((vinylbenzyl chloride) (PVBC), a robust crosslinked DPBI membrane (DPBI-xPVBC,xrefers to the weight percentage of PVBC in the membrane) can be obtained. Comprehensive properties of the DPBI and DPBI-xPVBC membranes are investigated, including chemical structure, antioxidant stability, mechanical strength, PA uptake and electrochemical performances. Compared with pristine DPBI membrane, the PA doped DPBI-xPVBC membranes exhibit excellent antioxidative stability, high proton conductivity and enhanced mechanical strength. The PA doped DPBI-10PVBC membrane shows a proton conductivity of 49 mS cm−1at 160 °C without humidification. Particularly, it reveals an enhanced H2/O2single cell performance with the maximum peak power density of 405 mW cm−2, which is 29% higher than that of pristine DPBI membrane (314 mW cm−2). In addition, the cell is very stable in 50 h, indicating the in-situ crosslinked DPBI with a macromolecular crosslinker of PVBC is an efficient way to improve the overall performance of HT-PEMs for high performance HT-PEMFCs.Keywords:polybenzimidazole;crosslinked membrane;high temperature proton exchange membrane;high temperature fuel cell
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF POWER SOURCES
·
2023
·
IF 9.2
Qingting Liu,Yuqing Luo,Shoukun Yang,Yuyue Xiong,Rongxin Wang,Xudong Fu,Rong Zhang,Shengfei Hu,Xujin Bao,Chenxi Xu
The preparation of traditional graphene oxide (GO)-based proton exchange membrane (PEM) composites asks for multiple transfer steps due to the different solvent requirements of GO preparation and polymer synthesis . Moreover, GO is easy to agglomerate in polymer matrix , it is difficult to give full play to the excellent proton conductivity of single/few-layered nanosheets . Herein, a novel transfer-free in-situ method is developed to prepare poly(2,5-benzimidazole) (ABPBI)-grafted electrolytic graphene oxide (EGO) composites (ABPBI-EGO) for high-temperature (HT) PEM fuel cells applications . The process involves the in-situ electrochemical oxidation and exfoliation of graphite foil into single/few-layered EGO in Eaton's reagent and followed by in-situ synthesis of ABPBI-grafted-EGO composites in the same reagent. This strategy leads to a single or few-layered dispersion of EGO nanosheets in ABPBI matrix, thus significantly improving the physicochemical performance. By constructing fast proton-conducting channels through single/few-layered GO nanosheets , composite membranes without free phosphoric acid exhibit superior proton conductivities over the whole temperature range of 120–180 °C. ABPBI-0.5EGO composite membrane-based fuel cell achieves a power density of 349 mW/cm 2 at 180 °C, which is nearly 2.3 times higher than the original ABPBI membrane. Thus, this transfer-free in-situ strategy shows great promise for developing high-performance HT-PEMs.
研究领域:
材料科学
·
能源工程
✓ 已验证
产品关联
DOI
高影响因子
Joule
·
2023
·
IF 39.8
Hai Liu,Zhuang Zhang,Jinjie Fang,Mengxuan Li,Marshet Getaye Sendeku,Xian Wang,Haoyang Wu,Yaping Li,Junjie Ge,Zhongbin Zhuang,Daojin Zhou,Yun Kuang,Xiaoming Sun
Proton exchange membrane (PEM) water electrolysis shows advantages including high current density, high efficiency, and compact configuration but suffers from the scarcity and high price of iridium (Ir)-based anodic catalysts. Herein, insoluble niobium (Nb)-incorporated RuO 2 with a high valence state was designed as an Ir-free catalyst for active and stable acidic oxygen evolution reaction (OER). Nb 0.1 Ru 0.9 O 2 exhibited a low overpotential (204 mV) and superb stability with an ultralow degradation rate (25 μV/h) over a 360-h durability test at 200 mA cm −2 , which is only 1/100th of the decay rates of other Ru-based catalysts measured at 10 mA cm −2 . The PEM electrolyzer with Nb 0.1 Ru 0.9 O 2 as an anode survived from a 100-h operation at 300 mA cm −2 . The strengthened adsorption of oxygen intermediates to active Ru sites reduced the OER energy barrier, while the enhanced electron transfer to Ru by Nb doping and formation of Nb 5+ during the OER process extended catalyst’s durability.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2018
·
IF 8.097
Ruiyi Han,Peiyi Wu
Porous organic cage, a kind of newly emerging soluble crystalline porous material, is introduced to proton-exchange membrane by in situ crystallization. The crystallized Cage 3 with intrinsic water-meditated three-dimensional interconnected proton pathways working together with Nafion matrix generates a composite membrane with highly improved proton conductivity. Different from inorganic crystalline porous materials, like metal–organic frameworks, the organic porous material shows better compatibility with Nafion matrix due to the absence of inorganic elements. In addition, Cage 3 can absorb water up to 20.1 wt %, which effectively facilitates proton conduction under both high- and low-humidity conditions. Meanwhile, the selectivity of Nafion–Cage 3 composite membrane is also elevated upon the loading of Cage 3. The proton conductivity is evidently enhanced without obvious increased methanol permeability. At 90 °C and 95% RH, the proton conductivity of NC3-5 reaches 0.27 S·cm–1, highly improved compared to 0.08 S·cm–1 of recast Nafion under the same condition. This study offers a new strategy for modifying proton-exchange membrane with crystalline porous materials.
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
PubMed
高影响因子
ACS Nano
·
2019
·
IF 13.903
Jiaman Liu,Liwei Yu,Xingke Cai,Usman Khan,Zhengyang Cai,Jingyu Xi,Bilu Liu,Feiyu Kang
Two-dimensional (2D) hexagonal boron nitride (h-BN) has attracted great interest due to its excellent chemical and thermal stability, electrical insulating property, high proton conductivity, and good flexibility. Integration of 2D h-BN into commercial proton exchange membranes (PEMs) has the potential to improve ion selectivity while maintaining the proton conductivity of PEMs simultaneously, which has been a longstanding challenge in membrane separation technology. Until now, such attempts are only limited in mechanically exfoliated small area h-BN and in proof-of-concept devices, due to the difficulty of growing and transferring large area uniform h-BN monolayers. Here, we develop a space-confined chemical vapor deposition approach and achieve the growth of wafer-scale uniform h-BN monolayer films on Cu rolls. We further develop a Nafion functional layer assisted transfer method which effectively transfers as-grown h-BN monolayer films from the Cu roll to sulfonated poly(ether ether ketone) (SPEEK) membrane. The as-fabricated Nafion/h-BN/SPEEK sandwich structure is used as the membrane and compared with the pure SPEEK membrane for flow batteries. Results show that the sandwich membrane exhibits ion selectivity 3-fold greater than that of a pure SPEEK membrane (i.e., 32.1 × 104vs 9.7 × 104 S min cm–3). In addition, we fabricate vanadium flow batteries using the Nafion/h-BN/SPEEK sandwich membrane and find that the sandwich structure does not affect the proton transport but inhibits vanadium crossover at low current density (<120 mA cm–2) due to the selective blocking of vanadium ions by 2D h-BN. As a result, the sandwich membrane exhibits a significantly improved Coulombic efficiency and energy efficiency, ∼95% and ∼91%, respectively. Our results suggest that a functional layer/2D film/target substrate-based sandwich structure shows clear potential for future 2D material-based membranes in separation technologies.
研究领域:
材料科学
·
能源技术
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2021
·
IF 8.742
Xin Liu,Yi Li,Mengyuan Li,Na Xie,Junfeng Zhang,Yanzhou Qin,Yan Yin,Michael D. Guiver
The chemical stability of proton exchange membranes (PEMs) is a pivotal factor to effectuate reliable and practical durability in proton exchange membrane fuel cells (PEMFCs). Recently, we discovered unexpectedly robust chemical stability of PEMs, which was demonstrated to be attributable to the radical scavenging ability of the ferrocyanide‒ferricyanide (Fc (II)‒Fc (III)) redox cycle. In these previous studies, the Fc (II)‒Fc (III) redox species were introduced into polymer matrices using a strategy of ligand exchange, which somewhat restricts the applicable scope of available polymers. Herein, via an alternative route of physical incorporation, Fc (II)/Fc (III) species are introduced into a variety of perfluorosulfonic acid (PFSA) and sulfonated hydrocarbon PEM matrices. The resulting composite membranes display enhanced durability in PEMFC evaluations, compared with pristine membranes, even considerably beyond the composite membranes using US Department of Energy approved state-of-the-art antioxidant Ce ions. Moreover, the incorporation of Fc (II)/Fc (III) species simultaneously introduces additional proton sites after membrane acidification, thereby increasing both ex situ conductivity and in situ power output. In addition, due to hydrogen bonding between the less ionized protons on Fc (II)/Fc (III) species and the sulfonic groups of the polymer matrices, these additives show adequate retention in the composite membranes. The strategy proposed in the present work appears promising as a universal method to greatly improve the chemical oxidative stability of both PFSA and hydrocarbon-based PEMs.
研究领域:
材料科学
·
能源工程
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2024
·
IF 8.1
Hongsheng Liu,Hengyue Li,Bin Huang,Yange Yang,Haibo Guo,Yan Xiao,Weiguang Yang
To enhance the proton conductivity and durability of Ce-based hybrid proton exchange membranes (PEMs), this study fabricates modified perfluorosulfonic acid (PFSA) hybrid membranes by incorporating the dual-function γ-AlOOH@Ti-supported CeO 2 composite oxide (γ-AlOOH@Ti/CeO 2 ). In addition to combining the inherent proton conductivity of γ-AlOOH with the excellent radical scavenging ability of CeO 2 , both the proton conductivity and durability of Ce-based PEMs are further improved by introducing Ti-dopant, which not only increases hydrogen vacancies on the surface of γ-AlOOH, which facilitate proton conduction, and induces electron transfer from γ-AlOOH@Ti to CeO 2 , which enhance free radical adsorption. As results shown, the proton conductivity and the fluoride release value of the resulting hybrid membrane are about 76 % higher and 35.25 % lower than those of the PFSA-CeO 2 membrane, respectively. Moreover, the performance of cells shows that, after accelerated degradation testing, the PFSA-γ-AlOOH@Ti/CeO 2 membrane exhibits the lowest peak power density decrease rate, the impedance increase rate and hydrogen crossover current density, with 11.79 %, 27.54 % and 3.04 mA cm −2 , respectively. These results suggest that compared to CeO 2 -hybrid PEMs, γ-AlOOH@Ti/CeO 2 -based hybrid PEMs exhibit higher proton conductivity and superior chemical stability, indicating the potential application of γ-AlOOH@Ti/CeO 2 -based hybrid PEMs in proton exchange membrane fuel cells.
研究领域:
材料科学
·
能源化学
·
电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2012
·
IF 1.289
Pei Chen,Xinbing Chen,Zhongwei An
Crosslinkable sulfonated poly(arylene ether sulfone)s (SPAESs) were synthesized by copolymerization of 4,4′-biphenol with 2,6-difluorobenzil, 4,4′-difluorodiphenyl sulfone, and 3,3′-disulfonated-4,4′-difluorodiphenyl sulfone disodium salt. The corresponding covalent-ionically crosslinked SPAESs were prepared via the cyclocondensation reaction of benzil moieties in polymer chain with 3,3′-diaminobenzidine. The crosslinking significantly improved the membrane performance, that is, the crosslinked membranes had the lower membrane dimensional swelling, lower methanol permeability, and higher oxidative stability than the corresponding precursor membranes, with keeping the reasonably high proton conductivity. The crosslinked membrane ( CS5 ) with measured ion exchange capacity of 1.47 meq g −1 showed a reasonably high proton conductivity of 112 mS cm −1 with water uptake of 42 wt % at 80°C, and exhibited a low methanol permeability of 2.1 × 10 −7 cm 2 s −1 for 32 wt % methanol solution at 25°C. The crosslinked SPAES membranes have potential for PEFC and DMFCs. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
研究领域:
材料科学
·
能源科学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）