JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2018
·Vol. 165
·期 11
·F914
·
IF 3.662
Yangben Cai,Zhouying Yue,Xin Teng,Shiai Xu
A radiation grafting graphene oxide reinforced polybenzimidazole (PBI-RGO) was fabricated and then crosslinked with a self-made crosslinker containing benzimidazole groups by a facile method to obtain crosslinked PBI/RGO (cPBI/RGO) membrane, which was further doped with phosphoric acid (PA) for high temperature proton exchange membrane (HT-PEM) applications. The introduction of benzimidazole groups in the crosslinker results in an increase in PA uptake from 222% to 303% and a reduction of tensile strength of the membrane. The crosslinking structure can effectively improve the tensile strength compared with uncrosslinked membrane at the same PA uptake. The crosslinked membrane shows higher remaining weight after immersion in Fenton's solution for 6 days and PA for 8 days than uncrosslinked membrane, indicating that it has better oxidative and chemical stability. The introduction of RGO and the crosslinking structure can also improve the proton conductivity of membrane. The proton conductivity of PA-doped cPBI/RGO membrane is 58.6 mS·cm−1 at 170°C without humidity, which is increased by 2.6 times compared with that of PA-doped PBI membrane. The crosslinking structure allows the membrane to have better stability and higher proton conductivity, thus making it suitable for HT-PEM applications.
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2020
·
IF 7.183
Jiayu Yang,Xiaobai Li,Chengying Shi,Bairun Liu,Kaiyue Cao,Cengliang Shan,Wei Hu,Baijun Liu
Because of the harsh operating circumstances of high temperature over 100 °C and strong acidity, it is of great significance to explore some new methods on the developments of high-performance membrane materials using in high-temperature proton exchange membrane fuel cells (HT-PEMFCs). In current work, with the assistance of newly designed sulfonated poly (aryl ether ketone) (SPAEK) compatibilizer , some hydrophilic and acidophilic polyhedral-oligosilsesquioxane nanoparticles bearing sulfuric acid groups (SPOSS) were successfully incorporated into a soluble arylether-type polybenzimidazole (Ph-PBI) matrix via an in situ sol-gel process to obtain a new family of hybrid membranes with an improved overall performance. As a result, these hybrid membranes exhibited enhanced acid absorption ability and doping levels at 120 °C, improved acid retention ability and attractive mechanical-dimensional stability. More importantly, the proton conductivity of a phosphoric acid doped hybrid membrane reached 126 mS cm −1 at 200 °C. This membrane was also suitable for membrane electrode assemblies (MEAs), and a maximum power density of 300 mW cm −2 could be achieved at 160 °C without humidity.
研究领域:
材料科学
·
燃料电池技术
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2018
·
IF 4.439
Xue Tian,Shuang Wang,Jinsheng Li,Fengxiang Liu,Xu Wang,Hao Chen,Di Wang,Hongzhe Ni,Zhe Wang
Benzimidazole grafted polybenzimidazole cross-linked membranes (CPBIm-X) with outstanding phosphoric acid (PA) stability are successfully prepared. 2-chloromethyl benzimidazole (CMBelm) is grafted onto PBI mainchains and using 3-glycidoxypropyltrimethoxysilane (KH560) as a cross-linker. The benzimidazole sidechains can not only increase the basic sites but also allow the membrane to achieve higher phosphoric acid uptakes without sacrificing mechanical strength. Moreover, compared with the imidazole rings in the PBI backbone, the side chain with imidazole rings are flexible, which benefit the proton transportation and lower the activation energy. In addition, the mechanical strength of cross-linked membranes is excellent. For example, the tensile strength value of CPBIm-5 is 101.4 MPa, while that of the PBIm is 79.0 MPa. The proton conductivity is enhanced because the hydrolysis of KH560 resulting Si O Si networks structure, which can absorb more phosphoric acid. The Si O Si networks in the matrix can efficiently improve the stability of phosphoric acid (PA), the remaining weight of CPBIm-5 is 57% PA. Taking into account performance comprehensively, the weight of 5% KH560 is the optimum content. For example, the proton conductivity of CPBIm-5 is 0.092 S cm −1 at 180 °C. Compared to the pristine PBI, it is almost three-fold in proton conductivity.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2023
·Vol. 11
·期 24
·12885-12895
·
IF 11.9
Erli Qu,Geng Cheng,Min Xiao,Dongmei Han,Sheng Huang,Zhiheng Huang,Wei Liu,Shuanjin Wang,Yuezhong Meng
A novel acid-base composite membrane consisting of acidic carboxyl-containing polyimide (PI-COOH) and basic polybenzimidazole (OPBI) was fabricated and employed as a high-temperature proton exchange membrane (HT-PEM). PI-COOH was used to prepare HT-PEMs for the first time. The PBI-based acid-base composite membranes and ordinary composite membranes were investigated to elucidate the correlation between the polymer structure and membrane properties, especially in situations where phosphoric acid (PA) is used. The results show that OPBI-xPI-COOH composite membranes (x represents the weight percentage of PI-COOH in the entire membrane) deliver high proton conductivities and superior PA retention due to the continuous hydrogen bond network between OPBI and PI-COOH. The OPBI-50PI-COOH composite membrane revealed a proton conductivity of 89 mS cm−1 under low PA uptake (109%). Compared to the linear OPBI and OPBI-40PI composite membrane, a single cell with a low PA-doped OPBI-50PI-COOH composite membrane presented superior durability and power density (463 mW cm−2) at 160 °C and 0% relative humidity. In a short-term durability test of 369 h, the voltage attenuation rate was only 119 μV h−1. These outstanding outcomes indicate that the obtained acid-base composite membranes can be considered as capable candidates for HT-PEMs with enhanced performance.
研究领域:
材料科学
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能源工程
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2025
·
IF 8.3
Meng-Long Liu,Yan-Hong Shen,Tao Zhou,Xu Han,Wen-Wen He
High-temperature proton exchange membrane fuel cells (HT-PEMFCs) exhibit higher catalytic efficiency and lower hydrogen purification costs. However, the conductivity and stability of high-temperature proton exchange membranes (HT-PEMs) still do not meet the requirements of commercial use. In this work, we synthesize 1,3,5-triphenylbenzene branched poly(terphenyl piperidine) and subsequently graft different ratios of long alkyl piperidine side chains, obtaining a series of novel HT-PEMs with excellent performance. The 1,3,5-triphenylbenzene improves the mechanical properties and chemical stability of membranes. The grafted side chains can increase PA uptake and optimize PA distribution, thereby improving the proton conduction capacity of the membrane. The test result shows that the b-PTP-75MPD membrane can achieve a high proton conductivity (137.7 mS cm −1 ) and high power density (742.9 mW cm −2 ). In conclusion, these strategies pave a new avenue for simple and low-cost method for developing high-performance HT-PEMs.
研究领域:
材料科学
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能源技术
✓ 已验证
产品关联
DOI
高影响因子
Science China-Materials
·
2021
·Vol. 65
·期 4
·904-912
·
IF 8.273
Long Peng,Du Shiqian,Liu Qie,Tao Li,Peng Cong,Wang Tehua,Gu Kaizhi,Xie Chao,Zhang Yiqiong,Chen Ru,Lu Shanfu,Cheng Yi,Feng Wei,Wang Shuangyin
High-temperature proton exchange membrane fuel cells (HT-PEMFCs) bring new opportunities for portable power generation due to their outstanding advantages such as high tolerance to fuel/air impurities and simplified heat/water management. However, carbon-supported nanostructured Pt-based catalysts running at temperatures over 150°C are challenged by the severe aggregation and carbon corrosion, thus leading to poor durability. Herein, we demonstrate that dendritic Pt-Ni nanoparticles supported on fluorinated carbon black (white carbon black) could significantly enhance the performance and durability of HT-PEMFCs as the cathode catalysts running at 160°C due to the strong interaction of the F and Ni atoms to form a Ni x F y interface on Pt-Ni nanoparticles. With the formation of a stable Ni x F y interface, this integrated HT-PEMFC reached peak power densities of 906 mW cm −2 and demonstrated excellent durability at 160°C under anhydrous H 2 /O 2 conditions. This mitigation strategy was applied to Pt-alloy/C electrocatalysts and resulted in the elimination of Pt dissolution in practical fuel cells.
研究领域:
材料科学
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能源技术
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2022
·
IF 7.139
Chang Dong,Xin Xu,Jin Zhang,Haining Wang,Yan Xiang,Haijin Zhu,Maria Forsyth,Shanfu Lu
Introduction of porous structure to high temperature polymer electrolyte membranes is one of effective pathways to increase their proton conductivity under elevated temperature. However, the effect of the porous structure on the proton diffusion mechanism of these membranes is still unclear. In this work, the proton transport behaviour of a series of porous triazole-polysulfone (PSf) membranes under elevated temperature is comprehensively investigated. The functional triazole ring in the framework of porous triazole-PSf acts a proton acceptor to form acid-base pair with phosphoric acid (PA). In addition, the proton diffusion coefficient and proton conductivity of PA-doped porous triazole-PSf is an order of magnitude higher than that of the PA-doped dense triazole-PSf membrane. Percolation theory calculation convinces that the high proton conductivity of PA-doped porous triazole-PSf is due to the formation of continuous long-range proton diffusion channels under high pore connectivity and porosity. On the contrary, excessive pore connectivity also results in high gas permeability , leading to decrease of the open circuit voltage and cell performance of the single cell. Consequently, the optimum porosity for the PA-doped porous triazole-PSf membrane is 75% for fuel cell operating with the maximum peak power density of 550 mW·cm −2 and great durability for 120 h under 140 °C.
研究领域:
材料科学
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能源科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2022
·
IF 10.53
Jian Wang,Guoliang Liu,Ailian Wang,Wenxi Ji,Longgui Zhang,Taoyi Zhang,Jing Li,Hongfei Pan,Haolin Tang,Haining Zhang
Development of simple synthetic strategy for polybenzimidazole-based membranes with high uptake and retention ability of phosphoric acid is essential for long-term practical applications of high temperature proton exchange membrane fuel cells. In this work, N, N -dimethylacetamide is used as both deacid reagent and solvent for N-alkylation reaction to synthesize imidazolium cations-grafted polybenzimidazole. The accordingly formed membranes exhibit the improved uptake and retention ability of phosphoric acid compared to pristine polybenzimidazole membrane. The optimized membrane with grafting degree of 60% has an acid uptake of 361.2 wt% with an anhydrous proton conductivity of 75.2 mS cm −1 at 160 °C, about 4.2 times higher than that of pristine polybenzimidazole membrane. After the acid retention test at 160 °C for 240 h, proton conductivity of the optimized membrane decreases by 7.5%, lower than that of pristine polybenzimidazole membrane under the same conditions (11.9% loss). The thus-assembled single cell delivers the power density of 0.429, 0.596, and 0.708 W cm −2 under 0, 100 and 200 kPa back pressures whereas the values are 0.319, 0.427 and 0.510 W cm −2 for the cell assembled from phosphoric acid-doped pristine polybenzimidazole membrane.
研究领域:
材料科学
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2024
·Vol. 12
·期 22
·13364-13373
·
IF 10.7
Lei Huang,Qian Wang,Zimo Wang,Xi Sun,Jiayu Guan,Jifu Zheng,Shenghai Li,Suobo Zhang
Balancing phosphoric acid (PA) uptake with the dimensional stability of PA-doped membranes is a major challenge in the field of high-temperature proton-exchange membranes. Crosslinking is a common method to solve this problem. However, the construction of conventional crosslinked membranes usually involves a two-step process in which linear polymers are first prepared, followed by the addition of crosslinkers during film formation to generate crosslinked networks. This further complicates the preparation process of crosslinked membranes. In this study, superacid-catalyzed Friedel–Crafts polyhydroxyalkylation was employed to fabricate knitted-network membranes with a high density of alkaline groups in a single step, significantly simplifying the preparation process of crosslinked membranes. Compared with commercial OPBI membrane, the knitted-network membranes exhibited significantly improved mechanical properties; moreover, PA retention was significantly improved, attributable to the formation of three-dimensional crosslinked networks and ultra-microporous structures within the membranes. Additionally, the PA-doped knitted-network membranes exhibited a good conductivity of 186 mS cm−1 at 200 °C and a high peak power density of 850 mW cm−2 at 200 °C without backpressure and humidification. This study is the first to report this in situ polymerization method in which the same precursor monomer is adopted in the subsequent polymerization process to form a crosslinked network. The proposed strategy exhibits significant application potential in the field of high-temperature proton-exchange membrane fuel cells.
研究领域:
化学工程
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材料科学
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能源技术
✓ 已验证
产品关联
DOI
高影响因子
Small
·
2025
·
IF 12.1
Lu Liu,Jiayi Huang,Mingxin Zhang,Yiren Gao,Chen Dong,Pengcheng Cui,Junsheng Yang,Panchao Yin
High-temperature proton exchange membranes (HT-PEMs) are highly desired for fuel cells with high energy density; however, the requirements in balanced anhydrous proton conductivity, mechanical/structural stability, processability and gas-barrier property impose great difficulty for molecular design. Herein, the supramolecular complexation of brush polymers and super acidic metal oxide cluster (H 3 PW 12 O 40 , abbreviation PW 12 ) affords HT-PEMs with comprehensive performance that contributes to the robust performance of high energy density fuel cells. The polymers brush topology enables the decoupling of mechanical properties and proton conduction: the polyethylene glycol (PEG) side chains possess high affinity to PW 12 for proton transport while the rigid backbones help maintain structural stability and mechanical strengths up to 250 °C. The PW 12 clusters can be homogeneously dispersed in PEG with high loadings (≈80 wt.%) and it facilitates proton hopping among the crowded PW 12 for promising anhydrous proton conduction, e.g., 2 × 10 −3 S cm −1 at 200 °C. Their dense supramolecular bonds contribute to enhanced mechanical strength, flexibility and gas barrier property with mitigating hydrogen permeation current as 0.73 mA cm −2 , enabling the feasible processability of PEMs and stable operation of fuel cells. The devices show high power density as 218 mW cm −2 at 180 °C with long-term stable operation.
研究领域:
材料科学
·
能源工程
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF POWER SOURCES
·
2025
·
IF 7.9
Yong Yu,Feng Ji,Shaojie Gao,Chengwei Deng,Bowen Zheng,Weiwei Cai
High-temperature proton exchange membrane fuel cells (HT-PEMFCs) exhibit strong tolerance to impurities in hydrogen, which enhances their potential for practical applications. However, the efficiency of gas, proton, and electron electrocatalytic interfaces remains suboptimal, leading to sluggish cathode reaction kinetics and significantly reducing platinum (Pt) utilization. In this study, quaternary ammonium-functionalized polybenzimidazole (QAPBI), where the quaternary ammonium groups form strong ion pair interactions with phosphate, is employed as a bifunctional ionomer in the cathode catalyst layer (CL). This modification facilitates the regulation of phosphate (PA) distribution within the cathode CL and simultaneously improves proton conduction efficiency. Consequently, well-structured three-phase interfaces are effectively established, and the adsorption of PA onto the catalyst surface is minimized, further enhancing Pt utilization. More importantly, the rapid adsorption of PA onto QAPBI reduces the migration and loss of PA during fuel cell operation, thereby enhancing long-term durability. As a result, the peak power density (PPD) of the QAPBI-based HT-PEMFC is increased by 42 % compared to conventional PTFE-based designs, with a corresponding improvement in durability of 37.5 %.
研究领域:
材料科学
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能源技术
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2019
·
IF 5.155
Lihua Hong,Baolong Wang,Chengji Zhao
A series of poly(arylene ether ketone)- g -quaternized 4-vinylbenzyl chloride copolymers (PAEK-g-QVBC- x ) containing locally and densely quaternized side chains were synthesized. The PAEK- g -QVBC membranes were obtained by solution casting from their reaction mixture and then doped with phosphoric acid (PA) to be used as advanced anhydrous high temperature proton exchange membranes. Compared to the commercial PA doped polybenzimidazole membrane and other main-chain-type quaternized hydrocarbon polymer membranes with the similar proton conductivity, these PA-PAEK-g-QVBC- x membranes possess much lower PA doping level, extremely lower volume swelling ratio, and higher dimensional and oxidative stability. Among them, PA-PAEK-g-QVBC-6.4 membrane with the PA doping level in weight of 101.7% has the highest proton conductivities of 31 mS cm −1 at 120 °C and 65 mS cm −1 at 200 °C, respectively. Surprisingly, its volume swelling ratio is only 7.8%, which is far less than other reported PA doped membranes. The preliminary fuel cell test shows that PA-PAEK-g-QVBC-6.4 membrane has the peak power density of 53 mW cm −2 at 100 °C without any humidification. The results indicate that the anhydrous proton exchange membranes based on comb -shaped polymers with quaternized graft architectures have the potential to resolve the dilemma between demand of high PA doping levels to achieve high proton conductivity and the dimensional and mechanical stability of largely swollen membranes for high temperature fuel cells.
研究领域:
材料科学
·
能源工程
·
化学工程
✓ 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）