ACS Applied Energy Materials
·
2024
·
IF 5.4
Yi Zhang,Feng Ji,Jing Li,Miaoling Zhang,Chengwei Deng,Hansong Cheng,Zhiming Cui,Weiwei Cai
Phosphoric acid (PA) leakage restricts the commercialization process of polybenzimidazole (OPBI)-based high-temperature proton-exchange membrane fuel cells (HT-PEMFC). In this work, sulfonated iron–titanium oxide (sFTO) is employed in the OPBI membrane to improve the PA retention ability due to the Lewis base ability of sFTO. The sFTO/OPBI composite membrane therefore exhibits a 237% lower PA leakage than the pristine OPBI membrane resulting from the hydrogen bonding between PA and the Fe–O–Ti network with a high density of vacancies and unpaired electrons. As a result, the sFTO/OPBI membrane reveals a proton conductivity of 0.18 S/cm at 180 °C, which is 257% higher than that of the pristine OPBI membrane due to the stable and rapid proton-conductive channel created in the membrane matrix. HT-PEMFC equipped with sFTO/OPBI can therefore outperform the pristine OPBI membrane by 72% with a maximum power density of 576.18 mW/cm2 at 180 °C. Above all, this work identifies a membrane design route for HT-PEMFC applications.
研究领域:
材料科学
·
电化学
·
燃料电池技术
✓ 已验证
产品关联
DOI
高影响因子
Materials Chemistry Frontiers
·
2025
·
IF 6.4
Xinxin Huang,Yongkui Chen,Yuling Zhao,Yang Zhao,Jianji Wang
Covalent organic frameworks (COFs) have gained significant research attention as promising proton conducting materials due to the prominent properties such as remarkable specific surface area, regular structure and minimal density. Herein, a series of polyethyleneimine (PEI) functionalized COF (TpPa-SO3H@PEI-wt%) with high amino density were designed and synthesized to promote the proton hopping in COF hexagonal nanopores, where the flexibile polyethyleneimine (PEI) has a strong proton capture and release capability, which can improve the continuity of the hydrogen-bonding networks and provide a low energy barrier pathway for proton hopping in the system, and thus improving proton transfer efficiency. Importantly, the proton conductivity can be well modulated by varying the molecular weight and grafted amount of PEI, among which, TpPa-SO3H@PEI600-40% exhibited a remarkable proton conductivity of as high as 5.9×10-3 S cm-1 along with low activation energy of 0.14 eV at 98% RH and 80 °C thanks to Grotthuss mechanism for proton conduction. In addition, TpPa-SO3H@PEI600-40% showed excellent stability in water vapor environment and no obvious conductivity decrease was observed even after 72 hours of continuous conductivity measurements. This demonstrates good potential in the development and application of high proton conductive materials.
研究领域:
材料科学
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化学
·
纳米技术
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电化学
·
高分子科学
✓ 已验证
产品关联
DOI
高影响因子
MATERIALS RESEARCH INNOVATIONS
·
2016
·
IF 0
W. Li,C. Shen,X. Zhang,G. Kong,C. Chen
The development of proton exchange membranes (PEMs) with excellent performance becomes an important issue for proton exchange membrane fuel cells (PEMFCs). Acid–base hybrid high-temperature PEMs were prepared from aminopropyltriethoxysilane (APTES) and amino trimethylene phosphonic acid (ATMP) by sol–gel process. Fourier-transform infrared (FTIR) spectra revealed that phosphonic acid and amino group could have been protonized, and siloxane groups were hydrolysed and condensed to yield Si–O–Si network. These membranes were thermally stable up to 200°C and showed excellent dimensional stability in water. In addition, SEM analysis revealed that many nanoparticles appeared in the membranes, and energy dispersive spectrum (EDS) results proved that many phosphate ions were present on the surface of the nanoparticles. This phenomenon became obvious with increasing acidity of sol in sol–gel process. Proton conductivity results indicated that the above structure was favourable for the formation of hydrogen bond and the proton conductivity increases with the increase in temperature, the highest conductivity can reach 4.93 × 10− 2 S cm− 1 at 140°C under anhydrous condition.
研究领域:
材料科学
·
燃料电池研究
✓ 已验证
产品关联
DOI
RSC Advances
·
2015
·Vol. 5
·期 113
·93480-93490
·
IF 3.84
Yanxu Zhao,Yuqin Fu,Yao He,Bo Hu,Lingdi Liu,Jianhua Lü,Changli Lü
Sulfonated polymer brush functionalized graphene oxide (SPB-FGO) was prepared by reversible addition fragmentation chain transfer (RAFT) polymerization, and then was introduced into a sulfonated poly(ether sulfone) (SPES) matrix to fabricate composite proton exchange membranes (PEMs). The influence of the loading content of SPB-FGO on the properties of the composite membranes was intensively studied. It was demonstrated that the properties, including proton conductivity, thermal stability, mechanical property and oxidative stability for the composite membranes, were improved as compared with those of a pristine SPES membrane. Meanwhile, the methanol permeability of the composite membranes was lower than that of the pristine membranes. The proton conductivity of SPES/SPB-FGO-2 was nearly doubled as compared with that of the pristine membrane at 25 °C. This result could be attributed to the fact that the SPB-FGO was well-distributed within the SPES membrane matrix and the ion clusters were relatively uniform in size, which made the SPB-FGO fillers create broad ionic pathways through the sulfonic acid groups in polymer brushes via interfacial interactions. Our study demonstrated that the incorporation of an appropriate amount of SPB-FGOs could improve the properties of PEMs, opening up a new design concept to fabricate organic–inorganic composite PEMs.
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
Advanced Composites and Hybrid Materials
·
2023
·Vol. 6
·期 2
·1-14
·
IF 20.1
Zhang Wenxing,Zhao Shengqiu,Wang Rui,Zhang Aojie,Huang Yi,Tang Haolin
The development of rapid and dependable proton transport channels is crucial for proton exchange membrane fuel cells (PEMFCs) operating in low humidity conditions. Herein, a metal–organic framework (NH-Zr framework) consisting of 1H-pyrazole-3, 5-dicarboxylic acid (PZDC), and zirconium chloride octahydrate (ZrOCl 2 ·8H 2 O) rich in basic sites was in situ constructed in a perfluorosulfonic acid (PFSA) solution, and hybrid proton exchange membranes were prepared (PFSA-NH-Zr). The introduced NH-Zr framework successfully induced proton conducting groups (-SO 3 H) reorganization along the NH-Zr framework, resulting in the formation of fast ion transport channels. Meanwhile, under low humidity, the acid–base pairs between N–H (NH-Zr framework) and -SO 3 H (PFSA) promoted the protonation/deprotonation and the subsequent proton leap via the Grotthuss mechanism. Especially, the hybrid membrane PFSA-NH-Zr-1 with suitable NH-Zr content had a promising proton conductivity of 0.031 S/cm at 80 °C, 40% relative humidity (RH), and 0.292 S/cm at 80 °C, 100% RH, which were approximately 33% and 40% higher than the pristine PFSA membrane (0.023 S/cm and 0.209 S/cm), respectively. In addition, the maximum power density of the hybrid proton exchange membrane was 0.726 W/cm 2 , which was nearly 20% higher than the pristine PFSA membrane (0.604 W/cm 2 ) under 80 °C, 40% RH. Thus, PFSA-NH-Zr may be promising membrane materials for potential applications in fuel cells. This work established a referable strategy for developing high-performance proton exchange membranes under low RH conditions. Graphical Abstract
研究领域:
材料科学
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化学
·
能源工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2018
·
IF 6.14
Fengxiang Liu,Shuang Wang,Hao Chen,Jinsheng Li,Xue Tian,Xu Wang,Tiejun Mao,Jingmei Xu,Zhe Wang
A series of composite cross-linked membrane based on fluorine-containing polybenzimidazole (6FPBI) and a cross-linkable polymeric ionic liquid (cPIL) have been prepared for high temperature proton exchange membrane (HT-PEM) applications. Particularly, the obtained composite cross-linked membranes showed excellent phosphoric acid doping ability and proton conductivity. On the basis of the trade-off between mechanical strength and proton conductivity of composite membranes, the optimal content of cPIL is 20 wt % (6FPBI-cPIL 20 membrane). For instance, the 6FPBI-cPIL 20 membrane with a PA doping level of 27.8 exhibited a proton conductivity of 0.106 S cm–1 at 170 °C, which is much higher than that of pristine 6FPBI membrane. The most outstanding contribution of this work is that the 6FPBI-cPIL membranes showed improved phosphoric acid retention and long-term conductivity stability under harsh conditions (80 °C/40% RH) for 96 h. In particular, the proton conductivity and PA doping level of the 6FPBI-cPIL 20 membrane remained at a high level of 0.064 S cm–1 and 8.5 after 96 h of the test, respectively.
研究领域:
材料科学
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化学工程
·
电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2016
·
IF 6.333
Xiaobai Li,Hongwei Ma,Yanchao Shen,Wei Hu,Zhenhua Jiang,Baijun Liu,Michael D. Guiver
Phosphoric acid–doped polybenzimidazole (PA- m -PBI) membranes are widely investigated for high temperature proton exchange membrane fuel cells because of their low cost and high performance. For this system, a major challenge is in achieving a good compromise between the phosphoric acid doping level and the membrane dimensional-mechanical stability. Different from the established PA- m -PBI system, the present work investigates two types of PA-PBI membranes incorporating flexible ether linkages and asymmetric bulky pendants (phenyl and methylphenyl), which exhibit much better dimensional-mechanical stability after immersing in PA solution, even at high temperature for an extended period. This superior stability allowed higher acid doping levels (20.6 and 24.6) to be achieved, thus increasing proton conductivity (165 and 217 mS cm −1 at 200 °C under anhydrous conditions) as well as significantly improving fuel cell performance . The peak power densities in hydrogen/air fuel cell were 279 and 320 mW cm −2 at 160 °C, without humidification . Molecular simulation , density and fractional free volume, and wide-angle X-ray diffraction were used to investigate their structure-property relationships.
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
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2014
·Vol. 39
·期 28
·16123-16131
·
IF 2.93
Yufei Wang,Shuanjin Wang,Min Xiao,Shuqin Song,Dongmei Han,Michael A. Hickner,Yuezhong Meng
Novel sulfonated poly (fluorenyl ether ketone) with pendant quaternary ammonium groups (SPFEKA) was successfully synthesized by one-pot copolymerization of bis(4-fluoro-3-sulfophenyl)sulfone disodium salt, 4,4′-difluorobenzophenone, bisphenol fluorene and 2,2′-dimethylaminemethylene-9,9′-bis(4-hydroxyphenyl) fluorene (DABPF). The chemical structures were confirmed by FT-IR, and 1 H NMR. The thermal properties were fully investigated by TGA . The synthesized copolymers SPFEKAs are soluble in aprotic solvents, and can be cast into membranes on a glass plate from their N,N′-dimethylacetamide (DMAc) solution. A new kind of amphoteric ion exchange membrane (AIEM) was obtained by immersed SPFEKA into 1 M sulfuric acid. The proton conductivities of these membranes are comparable to the most reported sulfonated polymers under the same conditions. The permeability of vanadium ions in vanadium redox flow battery (VRB) was effectively suppressed by introducing quaternary ammonium groups for Donnan exclusion effect . AIEM-20% possess a only 4.4% vanadium ion permeability of Nafion 115. Cell performance tests showed that the VRB assembled with AIEM-20% shows the highest coulombic efficiency (CE) at the current density of 50 mA/cm 2 , because of its lowest VO 2+ permeability. In conclusion, these ionomers could be promising candidates for ion-exchange membranes for VRB applications.
研究领域:
材料科学
·
电化学
·
能源存储
·
高分子化学
·
膜科学
✓ 已验证
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2025
·
IF 9
Panlong Zhou,Bin Zhang,Linjian Sang,Hang Zhang,Xi Sun,Heguo Han,Yaohan Chen,Xiaofeng Li,Jifu Zheng,Shenghai Li,Suobo Zhang
Low phosphoric acid (PA) retention and conductivity are the inherent drawbacks for PA-doped polybenzimidazole (OPBI) membranes, which are applied in high-temperature proton exchange membrane fuel cells (HT-PEMFCs). In this work, we designed and synthesized a type of covalent organic framework linked with quaternary ammonium alkyl chains (COF-BQA) and organically combined it with OPBI to prepare composite membranes, which utilized strong ion-pair interaction between quaternary ammonium groups and H 2 PO 4 − to increase PA retention. Meanwhile, the composite membranes formed ordered microstructures to store PA and ordered ion transport nanochannels to increase proton conductivity. This synergistic effect showed that COF-BQA (5 %)-PA/OPBI could obtain good anhydrous proton conductivity of 121 mS cm −1 , high phosphoric acid retention of 70.1 %, good humidity cycle stability and high peak cell power density of 733.3 mW cm −2 , which was significantly better than that of pristine PA/OPBI.
研究领域:
材料科学
·
能源工程
·
燃料电池技术
·
聚合物纳米复合材料
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2024
·
IF 8.4
Jinsheng Li,Zhao Jin,Fengxiang Liu,Xue Wang,Wenjing Li,Meiling Xiao,Changpeng Liu,Wei Xing,Jianbing Zhu
Rationally constructing proton transport channel within high temperature proton exchange membranes (HT-PEMs) plays a critical role in lowering the mass transfer resistance and thus improving the performance of HT-PEM fuel cells (HT-PEMFCs). We herein designed a microphase-separated structure to promote proton transmitting by incorporating 1,4-Diazabicyclo[2.2.2]octane (DABCO) cationic polymer into tetramethyl poly(aryl ether ketone) (TMPAEK). The flexible and cationic segments afforded a polarity difference from TMPAEK, resulting in easier phosphoric acid adsorption. High proton conductivity of 135 mS cm −1 was obtained under anhydrous conditions at 150 °C. Besides, the hydrophilic domains that containing N-heterocycle could stabilize phosphoric acid through hydrogen bonding interactions, resulting in high phosphoric acid retention of ∼80 % after 288 h test. A Peak power density of 496 mW cm −2 was achieved in non-humidified H 2 /O 2 without back pressure at 140 °C, which was higher than that of m -PBI under the same conditions. This work not only paved a way to tailor the ion conductivity of membrane, but also provided a highly competitive membrane for HT-PEMFCs.
研究领域:
材料科学
·
化学工程
·
能源技术
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POLYMER RESEARCH
·
2021
·Vol. 28
·期 12
·1-15
·
IF 3.097
Zhao Xuhui,Nan Bohua,Lu Yunhua,Zhao Chunyan,Xu Shiai
A novel phosphorylated graphene oxide (PGO)-reinforced polybenzimidazole (PBI) composite membrane was prepared for high-temperature proton exchange membrane fuel cell (HT-PEMFC). PGO was prepared by phosphorylation of graphene oxide (GO) with phosphoric acid (PA), and its structure was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), energy dispersive spectrometry (EDS), and ion exchange capacity (IEC) measurement. Then, PGO was added into PBI to prepare composite membranes, with excellent oxidation and thermal stability, outstanding mechanical properties, strong PA uptake and high proton conductivity. The PBI composite membrane with 1.5 wt.% of PGO exhibits the highest tensile strength (38.4 MPa) and excellent proton conductivity (17.6 mS·cm −1 at 180 ℃ without moisture) after immersion in PA aqueous solution, which is 1.31 and 1.15 times higher than that of pure PBI and PBI/GO composite membranes, respectively. Thus, PGO-reinforced PBI composite membranes have promising applications in HT-PEMFC.
研究领域:
材料科学
·
电化学
·
能源材料
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Energy Materials
·
2022
·
IF 6.959
Xiaorui Wang,Di Wang,Shuang Wang,Jinsheng Li,Geng Liu,Yinghe Cui,Dan Liang,Xiaodong Wang,Zhipeng Yong,Zhe Wang
Herein, composite proton exchange membranes based on block polybenzimidazole (bPBI) and a phosphotungstic acid-ionic liquid (PWA-IL) organic–inorganic filler have been prepared. The bPBI was prepared by block copolymerization of poly[2,2′-(p-phenylene)-5,5′-benzimidazole] and poly(4,4′-diphenylether-5,5′-bibenzimidazole) oligomers. bPBI combined the advantages of both rigid and flexible segments. The block structure of the segmented block copolymer helped build proton transmission channels and made the transmission of protons easier. The PWA-IL was evenly distributed in the membranes. The PWA-IL has good electrochemical properties and can also form hydrogen bonds with phosphoric acid (PA), which is beneficial to proton conduction. The membranes had excellent mechanical properties (11 MPa) owing to the low acid doping level (ADL). Moreover, the membranes exhibit 0.05 S cm–1 proton conductivity at 170 °C at a low ADL and exhibit over 60% PA retention.
研究领域:
材料科学
·
化学工程
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）