Nanomaterials
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2022
·Vol. 12
·期 5
·773
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IF 5.719
Erli Qu,Junqiao Jiang,Min Xiao,Dongmei Han,Sheng Huang,Zhiheng Huang,Shuanjin Wang,Yuezhong Meng
As a traditional high-temperature proton exchange membrane (HT-PEM), phosphoric acid (PA)-doped polybenzimidazole (PBI) is often subject to severe mechanical strength deterioration owing to the “plasticizing effect” of a large amount of PA. In order to address this issue, we fabricated the HT-PEMs with a crosslinked network of poly (arylene ether ketone) to confine polybenzimidazole in semi-interpenetration network using self-synthesized amino-terminated PBI (PBI-4NH2) as a crosslinker. Compared with the pristine linear poly [2,2′-(p-oxdiphenylene)-5,5′-benzimidazole] (OPBI) membrane, the designed HT-PEMs (semi-IPN/xPBI), in the semi-IPN means that the membranes with a semi-interpenetration structure andxrepresent the combined weight percentage of PBI-4NH2and OPBI. In addition, they also demonstrate an enhanced anti-oxidative stability and superior mechanical properties without the sacrifice of conductivity. The semi-IPN/70PBI exhibits a higher proton conductivity than OPBI at temperatures ranging from 80 to 180 °C. The HT-PEMFC with semi-IPN/70PBI exhibits excellent H2/O2single cell performance with a power density of 660 mW cm−2at 160 °C with flow rates of 250 and 500 mL min−1for dry H2and O2at a backpressure of 0.03 MPa, which is 18% higher than that of OPBI (561 mW cm−2) under the same test conditions. The results indicate that the introduction of PBI containing crosslinked networks is a promising approach to improve the comprehensive performance of HT-PEMs.Keywords:high-temperature proton exchange membrane;semi-interpenetration network;phosphoric acid;poly [2,2′-(p-oxdiphenylene)-5,5′-benzimidazole]
研究领域:
材料科学
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化学工程
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产品关联
DOI
PubMed
高影响因子
MATERIALS CHEMISTRY AND PHYSICS
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2013
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IF 2.072
Cheng Chen,Chunhui Shen,Gengjin Kong,Shanjun Gao
High temperature anhydrous proton exchange membranes based on phosphonic acid were prepared from epoxycyclohexylethyltrimethoxysilane (EHTMS) and amino trimethylene phosphonic acid (ATMP) by sol–gel process. The structures and properties of membranes with different phosphonic acid content were extensively characterized by FTIR, TG-DSC and XRD . Their proton conductivity under dry condition was also investigated under different temperature. The results show that the proton conductivity of the prepared membranes strongly depends on temperature, and the proton conductivity ranges from 8.81 × 10 −5 S cm −1 at 20 °C to 4.65 × 10 −2 S cm −1 at 140 °C under anhydrous condition. It indicates that the increasing temperature is favorable for congregating of the grafted–PO 3 H 2 and increasing of the proton mobility. In addition, from the results of AFM images, it was confirmed that the continuous distribution of phosphonic acid groups is favorable for the formation of the proton transport channel, which can significantly enhance the proton conductivity of the membranes.
研究领域:
材料科学
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化学工程
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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
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化学工程
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DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Huixuan Wang,Gaofei Pan,Zhunze Ji,Yuwei Ma,Weixiang Shang,Hongxia Li,Fei Ruan,Qingchun Wang,Jinxiao Bao
Increasing the retention of phosphoric acid (PA) may significantly boost the performance of proton exchange membranes (PEMs). In this work, mesoporous titanium dioxide (TiO 2 ) nanoparticles were introduced into polybenzimidazole (PBI) membranes and crosslinked using a silane coupling agent–modified ionic liquid (IL). TiO 2 nanoparticles with high specific volume were combined with ILs to enhance PA retention and inhibit leaching, thereby improving the performance of PEMs. Strong proton conductivity (0.092 S cm −1 , 140 °C) combined with saturated electron transport and outstanding PA retention is made possible by a special proton transfer channel with a silane-bonded titanium dioxide structure. At 140 °C, having an excellent stabilizing current demand of 200 mA cm −2 during 110 h of operation, a hydrogen/oxygen (H 2 /O 2 ) cell founded on the as-fabricated membrane demonstrated outstanding long-term stability and a maximum power density up to 668 mW cm −2 . A high-temperature PEM (HT-PEM) that can function across an extensive temperature spectrum of 80 °C to 200 °C without the need for external humidification is created when stabilized PBI chains are coupled with hydrogen-bonded proton transport channels.
研究领域:
材料科学
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化学工程
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能源技术
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DOI
高影响因子
JOURNAL OF POWER SOURCES
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2023
·
IF 9.2
Yu Bai,Dongmei Han,Min Xiao,Zhiheng Huang,Chengxin Wang,Shuanjin Wang,Yuezhong Meng
Polypyrrolone (PPy) possesses excellent heat resistance and mechanical properties , moreover, the N-heterocycle contained in the PPy allows the absorption of phosphoric acid (PA) for proton conduction. In the present work, PPy is synthesized by a two-step method and evaluated for the first time as the polymeric material for high temperature proton exchange membranes (HT-PEMs). The PA-doped PPy membrane reaches a peak power density of 582 mW cm −2 at 160 °C under fully anhydrous conditions, besides, the fuel cell exhibits excellent durability over a period of 300 h with a load voltage decay of only 0.032% per hour and remains 0.647 V after the test. Further, the PPy-impregnated polyimide (PI) nanofiber mat composite membrane (PI@PPy) with an optimal thickness is fabricated with enhanced dimensional stability, of which acid swelling ratio noticeably declined by 51% in area and 25% in volume. A higher peak power density (634 mW cm −2 ) and less cell voltage reduction is also observed in the composite membrane, benefits from the trade–off between proton conductivity and PA retention ability. The results of the present study may contribute to further studies on polypyrrolone-based HT-PEMs and composite membranes.
研究领域:
材料科学
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能源科学
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DOI
高影响因子
Polymers
·
2023
·Vol. 15
·期 15
·3197
·
IF 5
Yiming Xiao,Haoran Chen,Ranxin Sun,Lei Zhang,Jun Xiang,Penggao Cheng,Huaiyuan Han,Songbo Wang,Na Tang
Despite the outstanding proton conductivity of phosphoric acid (PA)-doped polybenzimidazole (PBI) membranes as high-temperature proton exchange membranes (HT-PEMs), chemical stability is a critical issue for the operation life of PEM fuel cells (PEMFCs). Herein, we introduced polymerized [HVIM]H2PO4ionic liquids (PIL) into an OPBI membrane to accelerate proton transfer and enhance the chemical stability of the membrane. Based on the regulation of the intrinsic viscosity of PIL, the entanglement between PIL chains and OPBI chains is enhanced to prevent the loss of PIL and the oxidative degradation of membrane materials. The PIL/OPBI membrane with the intrinsic viscosity of 2.34 dL·g−1(2.34-PIL/OPBI) exhibited the highest proton conductivity of 113.9 mS·cm−1at 180 °C, which is 3.5 times that of the original OPBI membrane. The 2.34-PIL/OPBI membrane exhibited the highest remaining weight of 92.1% under harsh conditions (3 wt% H2O2; 4 ppm Fe2+at 80 °C) for 96 h, and a much lower attenuation amplitude than the OPBI did in mechanical strength and proton conductivity performance. Our present work demonstrates a simple and effective method for blending PIL with OPBI to enhance the chemical durability of the PA-PBI membranes as HT-PEMs.Keywords:poly(ionic liquid);polybenzimidazole;chemical stability;HT-PEM
研究领域:
材料科学
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化学工程
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DOI
PubMed
高影响因子
Materials Today Chemistry
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2022
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IF 7.613
Hui Guo,Xulei Zhi,Zhongfang Li,Lei Zhang,Peng Sun,Hongchang Pei
High temperature proton exchange membranes with good chemical stability and proton conductivity are desired for practical application. A crosslinkable allyl-cyanuric trisulfonic (ACSA) proton conductor and allyl-mPBI (APBI) are designed and synthesized to approach this aim. More stable basic sites (N) are endowed on ACSA and APBI through the reaction of oxidizable –NH groups to fundamentally achieve anti-free radical oxidation of membranes. The co-crosslinking of ACSA and APBI forms a monolithic crosslinked interpenetrating network in APBI-ACSA membranes, while the abundant basic sites construct dense hydrogen-ionic bond networks with –SO 3 H. The synergy of both networks locks ACSA in networks, avoids leaching and achieves uniform dispersion and high addition level of ACSA, thus providing good membrane stability of mechanical and dimensional. Molecular dynamics simulation shows that the microphase separation structure promotes the formation of continuous proton transport microchannels (including hydrogen-ionic bond network and hydration channel) over wide relative humidity (RH) ranges. Under 100%, 50% and 0% RH, the proton conductivity of APBI-ACSA(40) membrane is 0.158, 0.082 and 0.035 S/cm at 180 °C, respectively. There is almost no decay in conductivity after the durability tests. Meanwhile, APBI-ACSA membranes exhibited good fuel crossover resistance over Nafion membranes for both gas and liquid phase fuels.
研究领域:
材料科学
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化学工程
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
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2020
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IF 8.247
Hongying Tang,Kang Geng,Jinkai Hao,Xiaojuan Zhang,Zhigang Shao,Nanwen Li
Quaternized poly(sulfone)s based on trimethylamine (PSf-TMA-x) and triethylamine (PSf-TEA-x) are developed to form quaternary ammonium (QA)-biphosphate ion pairs as promising high temperature proton exchange membrane (HT-PEM) in H 2 /O 2 fuel cells. The strong QA-biphosphate ion-pair interaction results in high acid absorption and thus high proton conductivity of 78.1 mS cm −1 for PSf-TEA-110/PA membrane at 160 °C in spite of its lower degree of functionalization. Thus, the peak power density of more than 400 mW cm −2 is achieved at 160 °C for the quaternized PSf membranes in H 2 /O 2 fuel cell, which is higher than that of the poly(benzeimidazole) ( m -PBI) membrane (370 mW cm −2 ). Subsequently, the degradation mechanism of the PSf membranes is demonstrated using NMR technique to be occurred in both the polymer backbone and the QA groups. The stability investigation of model compounds further confirms that the degradation of the membranes resulted from the scission of ether linkage and isopropylidene group and the SN2 nucleophilic substitution of QA at operating conditions. Therefore, the significant performance decrease is observed and the lifetime is only less than 30 h at 200 mA cm −2 which is much lower than that of m -PBI membrane (>40 h).
研究领域:
材料科学
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化学工程
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能源科学
✓ 已验证
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2022
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IF 10.53
Ping Li,Hui Guo,Peng Sun,Lei Zhang,Xulei Zhi,Zhongfang Li
Improving the proton conductivity of high temperature proton exchange membrane (HTPEM) over low-medium relative humidity (RH) still remains a challenge. The poly(triazoles-phosphazenes) (PTPP) containing triazoles can function as basic sites and cross-linker. The hydroxyl-terminated SPEEK (SOPEEK) contains abundant –SO 3 H to be applied as proton conductor and bears cross-linking sites with PTPP. The PTPP-SOPEEK composite membranes are obtained by covalent cross-linking between PTPP and SOPEEK, which is expected to realize effective proton conduction. The prepared PTPP-SOPEEK membranes show good physical and chemical stability, dimensional stability, high proton conductivity over low-to-medium RH, and low fuel permeation. At 140 °C and 100% RH, the proton conductivity of PTPP(15)-SOPEEK can reach to 0.223 S cm −1 , while at 180 °C, the proton conductivity is 0.086 S cm −1 at 50% RH, 0.062 at 30% RH, and 0.045 S cm −1 at 0% RH, respectively. After washing with water for 96 h, the conductivity durability of PTPP(15)-SOPEEK shows almost no decay. The gas (H 2 & O 2 ) and liquid (methanol) fuel permeability coefficient of PTPP(15)-SOPEEK membranes is 1–2 orders of magnitude lower than the Nafion membrane. Therefore, the PTPP-SOPEEK membranes can act as promising alternatives for the application in HTPEM.
研究领域:
材料科学
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化学工程
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燃料电池
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Yuyang Han,Yao Xu,Kai Huang,Fei Xu,Jiayuan Ji,Bencai Lin
A series of imidazolium-functionalized poly(phenylene oxide) (QPPO) cross-linked with polybenzimidazole (PBI) (cQPPOx-PBI) membranes were prepared. Compared to the pure PBI membrane without a cross-linked structure nor imidazolium groups, the cQPPOx-PBI membranes showed enhanced toughness, phosphoric acid (PA) retention, and chemical stability. The cQPPOx-PBI membranes showed a enhanced PA uptake than that of PBI membranes, and the cQPPO35-PBI membrane achieves a high conductivity of 139 mS cm −1 at 160 °C, which is much higher than that of PBI membrane under the same conditions (26 mS cm −1 ). The performance of the single fuel cell assembled with the obtained membranes showed a similar trend as their conductivity, and the cell with cQPPO35-PBI showed a maximum power density of 344 mW cm −2 at 140 °C, while the value for PBI membrane was only 175 mW cm −2 under the same conditions. Herein, a straightforward method was developed for introducing imidazolium groups and cross-linked structures, which can be employed to prepare PEMs with enhanced performance for HT-PEMFCs application.
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
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Weiyu Zhang,Jiaqi Ji,Hong Li,Jie Li,Yiming Sun,Yi Tang,Tianqi Yang,Weiyi Jin,Yongqing Zhao,Congshu Huang,Chenliang Gong
Phosphoric acid (PA) leakage and volume expansion are critical factors limiting long-term stable operation of PA-doped polybenzimidazole (PBI) for high-temperature proton exchange membrane fuel cells. Enhancing the interaction between the polymer matrix and PA provides an effective way to minimize PA loss and inhibit excessive membrane swelling. The covalent organic frameworks (COFs) are helpful in improving the performance of PA-PBI membranes due to the robust frameworks, adjustable structures, and good compatibility with polymers. Here, in this work, we synthesized porous COFs named TTA-DFP containing triazine rings and pyridine groups at room temperature for as short as 2 h without oxygen isolation. TTA-DFP was then blended with commercial poly[2,2′-(p-oxidiphenylene)-5,5′-benzimidazole] (OPBI) to prepare composite membranes. The abundant alkaline N sites in TTA-DFP exhibit strong interactions with PA and OPBI, which not only provide more proton transport pathways to promote proton conduction but also immobilize PA in acidophilic micropores to reduce PA leakage. The composite membranes exhibit a much lower volume swelling ratio than that of the OPBI membrane. The PA retention of the composite membrane after 120 h of treatment at 80 °C and 40% relative humidity can reach as high as 84.6%. Particularly, the proton conductivity of the composite membrane doped with 15 wt% TTA-DFP achieves 0.112 S cm–1 at 180 °C without humidification with a swelling ratio of 24.1%. In addition, it has an optimal peak power density of 824.4 mW cm–2 at 180 °C, which is 1.7 times that of the OPBI membrane. The stability of the composite membrane is much better than that of OPBI at a current density of 0.3 A cm–2 at 140 °C for 120 h.
研究领域:
材料科学
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燃料电池工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2023
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IF 9.5
Yutong Zhao,Bo Lv,Wei Song,Jinkai Hao,Junfang Zhang,Zhigang Shao
Conventional high-temperature proton exchange membranes use phosphoric acid (PA) as a proton conductor . However, PA loss, poor mechanical stability, and catalyst poisoning represent major limitations. Solid acids are an alternative to PA that does not require humidification and is less prone to leaching. In this study, we prepared two composite membranes by high-temperature impregnation to investigate the effects of the structure of polybenzimidazole (PBI) on the anchoring of solid acids: a laboratory-synthesized m -PBI/CsH 5 (PO 4 ) 2 and the commercial OPBI/CsH 5 (PO 4 ) 2 . Compared to PA-doped membranes, CsH 5 (PO 4 ) 2 -doped membranes showed excellent mechanical properties , particularly m -PBI/CsH 5 (PO 4 ) 2 . Scanning electron microscopy and energy dispersive spectroscopy images showed that CsH 5 (PO 4 ) 2 was uniformly dispersed on the surface and cross-section of both membranes, conducive to the formation of proton transport channels following the CsH 5 (PO 4 ) 2 melting in both samples. The characterization of the physical structures proved the interaction between the imidazole ring and solid acid. Furthermore, the proton conductivity without humidification was similar in m -PBI/CsH 5 (PO 4 ) 2 and OPBI/CsH 5 (PO 4 ) 2 , demonstrating the suitability of m -PBI for fuel cells production. To test this, we assembled a m -PBI/CsH 5 (PO 4 ) 2 cell that showed competitive performances, with a peak power density of 361.28 mW cm −2 at 160 °C in H 2 /O 2 atmosphere.
研究领域:
材料科学
·
燃料电池工程
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）