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Materials Today Energy · 2024 · IF 9

Improving the ohmic polarization of high-temperature proton exchange membrane fuel cells using crosslinked polybenzimidazole membranes containing acidophilic quaternary ammonium groups synthesized by one-step strategy

Jin Li,Guoliang Liu,Fangfang Zhang,Jun Liao,Haolin Tang,Haining Zhang

Ingenious crosslinked network structure in phosphoric-acid-doped polybenzimidazole membranes can mitigate the mutual restriction of proton conductivity and mechanical properties. However, the complicated synthesis of tailored macromolecular crosslinker and the time-consuming post-treatment hinder their practical application as high-temperature proton exchange membranes. Herein, crosslinked polybenzimidazole membranes are synthesized using small molecular crosslinkers containing acidophilic quaternary ammonium groups through a one-step crosslinking strategy. After doping with phosphoric acid, the quaternary ammonium-biphosphate ion-pair coordination and the crosslinked structure result in the improved anhydrous proton conductivity, oxidation stability, and mechanical strength of the formed membranes compared to the sample without the crosslinking structure. A membrane with the optimized degree of crosslinking exhibits an anhydrous conductivity of 72.27 mS/cm at 160 °C, with a tensile strength of 12.14 MPa. Benefiting from the crosslinked structure and high proton conductivity, the accordingly formed membrane electrode assembly possesses a high open-circuit voltage of 1.01 V and animproved ohmic polarization, delivering a peak power density of 0.66 W/cm 2 using hydrogen as fuel and air as oxidant.

研究领域: 材料科学 · 能源技术
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

NH2-UiO66 functionalized polyimide nanofiber to anchor HPW and fabricate high-performance sandwich-structure membrane for achieving excellent durability

Peng Wei,Yang Sui,Dong Huang,Bensheng Zhu,Xiaoyu Meng,Qiong Zhou

Sulfonated poly ether ether ketone (SPEEK) was used to fabricate proton exchange membrane (PEM) due to its adaptable proton conductivity. However, PEM cannot simultaneously enhance its conductivity and stability. To solve the problem mentioned above, phosphotungstic acid (HPW) with strong inherent proton conductivity was chosen to add to the SPEEK matrix, but it still faces the leaky problem. NH 2 -UiO-66 (NU6) with a large surface area and chemical stability was synthesized in situ on the surface of polyimide (PI) nanofiber to create NU6@PI nanofiber, which can be used to anchor HPW. Meanwhile, the stability of proton transport channel may be further enhanced by the sandwich structure, which may be advantageous for proton transport. The NU6@PI/SPEEK + HPW-20 exhibited a conductivity of 174.9 mS·cm −1 and a swelling ratio of 19 % at 60 °C and 100 % RH. After 6 weeks of testing, its conductivity decreased to 151.2 mS·cm −1 which was 24 % higher than that of SPEEK, while the swelling ratio increased to 31 % which was lower than that of SPEEK. The outcome demonstrates that the sandwich-structure NU6@PI/SPEEK + HPW membrane may really boost proton conductivity and stability at the same time. By using XPS and TEM, it is possible to confirm the acid-base interaction and acid-rich layer that exist at the interfaces of NU6@PI nanofiber and HPW/SPEEK matrix. After 6-weeks of usage, the sandwich-structure composite membrane with nanofiber at both the top and bottom of PEM can still maintain high proton conductivity and high stability, offering a novel research idea for resolving the issue that PEM cannot simultaneously achieve significant proton conductivity as well as elevated stability.

研究领域: 材料科学 · 化学工程 · 电化学 · 纳米技术
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JOURNAL OF MEMBRANE SCIENCE · 2021 · IF 8.742

Spindle-like MOFs-derived porous carbon filled sulfonated poly (ether ether ketone): A high performance proton exchange membrane for direct methanol fuel cells

Honghao Huang,Yefei Ma,Zhongqing Jiang,Zhong-Jie Jiang

The sulfonated spindle-like carbon derived from metal-organic framework, MOF- C -SO 3 H, has been employed as a filler for the SPEEK membrane. The obtained MOF- C -SO 3 H@SPEEK membrane shows improved properties as a PEM for DMFCs . In particular, with the presence of 3.0 wt% of MOF- C -SO 3 H, the MOF- C -SO 3 H@SPEEK membrane can exhibit higher proton conductivity and much lower methanol permeability than Nafion 115. The specific porous and sulfonated carbon structure is believed to play an important role in the high performance of the MOF- C -SO 3 H@SPEEK membrane. It helps the good dispersion of MOF- C -SO 3 H in the SPEEK matrix, decreasing the swelling ratio and methanol permeability of the membrane, and promotes the transport of protons through the membrane, improving the proton conductivity of the membrane. More interestingly, when used in the DMFCs , it can give maximum power density of 83.91 mW cm −2 , which is ~50% higher than that of Nafion 115. This, together with its higher stability of the DMFC with the MOF- C -SO 3 H@SPEEK membrane than that with Nafion 115, suggests that the MOF- C -SO 3 H@SPEEK membrane is a promising proton exchange membrane for fuel cells.

CAS / MDL: 64-17-5 127-19-5 68-12-2
研究领域: 材料科学 · 电化学 · 能源工程 · 高分子科学
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ACS Applied Materials & Interfaces · 2022 · IF 10.383

Rapid Gas-Phase Synthesis of the Perovskite-Type BaCe0.7Zr0.1Y0.1Yb0.1O3−δ Proton-Conducting Nanocrystalline Electrolyte for Intermediate-Temperature Solid Oxide Fuel Cells

Zeyun Wu,Yiyang Zhang,Zuoqing Liu,Haorui Ma,Xing Jin,Guangming Yang,Yixiang Shi,Zongping Shao,Shuiqing Li

Perovskite-type proton-conducting materials, such as BaCe0.7Zr0.1Y0.1Yb0.1O3−δ (BCZYYb), are very attractive for the next-generation equipment of electrochemical energy conversion and storage owing to their excellent conductivity in the intermediate-temperature range (300–750 °C), as well as good thermo-chemical stability, coking resistance, and sulfur tolerance. However, the lack of a reliable and cost-effective synthesis method for such multi-component co-doping oxides limits their large-scale application. In this study, for the first time, we successfully synthesize BCZYYb electrolyte nanopowders by using a rapid, scalable flame-based gas-phase synthesis method with two different barium precursors Ba(NO3)2 and Ba(CH3COO)2, named as BCZYYb (N) and BCZYYb (CA). The as-synthesized nanoparticles exhibit good crystallinity of the pure orthorhombic perovskite BCZYYb phase. BCZYYb (CA) shows more uniform doping with the element ratio of 1:0.74:0.12:0.08:0.1, which is very close to the theoretical value. The shrinkage and surface SEM (scanning electron microscope) results indicate that the flame-made powders have superior sinterability compared to the sol–gel-made powders because of the smaller primary particle size (∼20 nm). Electrochemical impedance spectroscopy tests show that BCZYYb (CA) sintered at 1450 °C has the highest protonic conductivity of 1.31 × 10–2 S cm–1 in wet H2 when operating at 600 °C and still maintains a high-level conductivity of 1.19 × 10–2 S cm–1 even when the sintering temperature is reduced to 1350 °C, which is mainly attributed to uniform doping and good sinterability. The activation energy for the conductivity of BCZYYb (CA) is also significantly lower than that of conventional electrolytes, which suggests much better conductivity in the intermediate (∼600 °C) and even lower operating temperature. The excellent conductivity performance combined with the high-throughput production capability makes the swirling spray flame a promising synthesis method for promoting the BCZYYb electrolytes from lab to industrial-scale solid oxide fuel cells.

研究领域: 材料科学 · 电化学 · 能源转换与存储
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ADVANCES IN POLYMER TECHNOLOGY · 2020 · IF 1.539

Semi-interpenetrating Network Membrane from Polyethyleneimine-Epoxy Resin and Polybenzimidazole for HT-PEM Fuel Cells

Chao Meng,Sheng Huang,Dongmei Han,Shan Ren,Shuanjin Wang,Min Xiao

In the present work, a semi-interpenetrating network (semi-IPN) high-temperature proton exchange membrane based on polyethyleneimine (PEI), epoxy resin (ER), and polybenzimidazole (PBI) was prepared and characterized, aiming at their future application in fuel cell devices. The physical properties of the semi-IPN membrane are characterized by thermogravimetric analysis (TGA) and tensile strength test. The results indicate that the as-prepared PEI-ER/PBI semi-IPN membranes possess excellent thermal stability and mechanical strength. After phosphoric acid (PA) doping treatment, the semi-IPN membranes show high proton conductivities. PA doping level and volume swelling ratio as well as proton conductivities of the semi-IPN membranes are found to be positively related to the PEI content. High proton conductivities of are achieved at 160°C for these PA-doped PEI-ER/PBI series membranes. H2/O2 fuel cell assembled with PA-doped PEI-ER(1 : 2)/PBI membrane delivered a peak power density of 170 mW cm-2 at 160°C under anhydrous conditions.

CAS / MDL: 872-50-4 7664-38-2
研究领域: 材料科学 · 电化学 · 能源技术
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JOURNAL OF MEMBRANE SCIENCE · 2024 · IF 8.4

Sulfonated poly(aryl ether) proton exchange membrane with excellent dimensional stability for hydrogen production by water electrolysis

Zhipeng Xu,Junyao Wang,Zhihao Lin,Daohui He,Yixiang Yu,Qiuping Wang,Meng Wang,Junbin Liao,Huimin Ruan,Jiangnan Shen

The use of proton exchange membrane water electrolysis (PEMWE) for hydrogen production is considered a promising technology due to its high theoretical current density, gas purity, and energy efficiency. In this study, a fluorinated sulfonated hydrocarbon polymer was used to prepare hydrocarbon−based membranes for PEMWE that displayed exceptional stability. Notably, the SFPAE-60 membrane has a proton conductivity of up to 293.1 mS cm −2  at 80 °C and 100%RH, but its volumetric swelling ratio is only 47 %. Its dimensional stability is significantly better than that of previously reported sulfonated poly (aryl ether)−based proton exchange membranes (>100 %). The PEMWE based on the SFPAE-60 membrane achieves a current density of over 4800 mA cm −2  at 2.0V, confirming the membrane's applicability in actual water electrolysis. The results indicate that the electrolyte membrane of fluorinated sulfonated hydrocarbon polymer performs well in the PEM electrolyzer.

CAS / MDL: 1478-61-1
研究领域: 材料科学 · 电化学 · 可再生能源
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JOURNAL OF MEMBRANE SCIENCE · 2025 · IF 9

Construction of high conductivity poly(aryl ether ketone sulfone) proton exchange membrane by incorporating zwitterion-modified MOFs

Yuzhe Guo,Qingyuan Shi,Jiaxin Li,Youwei Huang,Jingmei Xu

In this paper, the zwitterion ADPS was modified on UiO-66-COOH by amidation reaction, and the functional UiO-66-ADPS that was produced was added to the matrix of sulfonated poly(aryl ether ketone sulfone) (SPAEKS), and the series of composite membranes of SPAEKS-UiO-66-ADPS (abbreviated as SPAEKS-U-A-X%) were successfully prepared. The UiO-66-ADPS and the series of composite membranes were characterized and evaluated. The composite membranes created exhibit excellent electrochemical performance, as well as superior water uptake and mechanical properties. Among them, at 90 °C, the proton conductivity of SPAEKS-U-A-0.75% reached 268.31 mS cm -1 , and the power density was 1553.10 mW/cm 2 , which was much higher than that of the SPAEKS membrane (302.65 mW/cm 2 ). The results show that UiO-66-ADPS significantly improved the electrochemical performance of the PEMs.

研究领域: 材料科学 · 高分子化学 · 能源材料 · 燃料电池 · 纳米复合材料
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2022 · IF 7.139

Constructing a long-range proton conduction bridge in sulfonated polyetheretherketone membranes with low DS by incorporating acid-base bi-functionalized metal organic frameworks

Jiashu Long,Xiaocan Zhang,Siqin Zeng,Tong Pei,Huixiao Ma,Xuesong Li,Xiaoyu Meng

Functionalized metal-organic frameworks (MOFs) are being extensively developed as viable fillers to enhance the proton conductivity of proton exchange membranes . Herein, an amino-pendant sulfonic acid bi-functionalized MOFs material (UNCS)-doped SPEEK membrane with low degree of sulfonation (DS) can improve the proton conductivity as well as maintain the membrane dimensional stability. UNCS can act as bridges of proton donors and acceptors to reduce the activation energy barrier and shorten the distance of long-range proton conduction. Among all as-prepared membranes, SPEEK/UNCS-3 exhibited the highest proton conductivity of 186.4 mS·cm −1  at 75 °C and 100% relative humidity (RH), which is much greater than that of pristine SPEEK and Nafion 117. Benefiting from the acid-base pair interaction between the amino groups of UNCS and the sulfonic acid groups of SPEEK, the dimensional stability and mechanical properties of the composite membranes were enhanced. More interestingly, STEM-HAADF and SAXS characterization consistently revealed that UNCS served as bridges among proton channels in the composite membranes for continuous proton transport.

研究领域: 材料科学 · 化学 · 电化学 · 高分子科学
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EUROPEAN JOURNAL OF INORGANIC CHEMISTRY · 2015 ·Vol. 2015 ·期 28 ·4708-4714 · IF 2.942

Intercalation of Lamellar Mineral Kaolinite with 2-Picolinic Acid: Facile Preparation, Crystal Structure Optimization, and Proton Conductivity

Xiao-Qing Huang,Hao Yang,Shun-Ping Zhao,Jian-Lan Liu,Xiao-Ming Ren

Graphical An anhydrous proton conductor is achieved by inserting 2-picolinic acid into the layer space of kaolinite, and the proton transport in this intercalated hybrid material is mainly through the vehicle mechanism owing to the absence of a dense H-bond network. Kaolinite intercalated with 2-picolinic acid was prepared and characterized by scanning electron microscopy, powder X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The proton conductivity ( σ ) of the material is 1.85 × 10 –10 S cm –1 at 353 K and gradually increases to 1.7 × 10 –7 S cm –1 at 393 K under N 2 (anhydrous environment) with an activation energy of E a = 1.93 eV, whereas σ = 1.56 × 10 –7 S cm –1 under 80 % relative humidity at 353 K with E a = 0.91 eV. The crystal structure optimized with the Cambridge Sequential Total Energy Package discloses the absence of a dense H-bond network in the layer space of kaolinite, which explains the low proton conductivity and high proton transfer activation energy of the intercalated proton conductor.

CAS / MDL: 78-96-6
研究领域: 材料科学 · 化学 · 固体物理
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ACS Nano · 2024 · IF 15.8

High-Performance Proton Field-Effect Transistor Based on Two-Dimensional Cd Vacancy-Resided Cd0.85PS3Li0.15H0.15

Wenhao Shi,Xitang Qian,Chuankai Zou,Meng Zhang,Chenhui Huang,Xiangshui Miao,Lei Ye

Ion transport is a critical phenomenon underpinning numerous biological, physical, and chemical systems. Proton transistors leveraging proton transport face significant limitations, such as a low on–off ratio and deficient carrier mobility, which restrict their applicability in biological and other scenarios. This study explores the use of two-dimensional (2D) vacancy-residing transition metal phosphorus trichallcogenide-based membranes as the active layer for proton field-effect transistors. The synthesized Cd0.85PS3Li0.15H0.15 membrane exhibits a well-organized layered structure and high hydrophilicity, with nanometer-sized interlayers containing interconnected water networks. These distinct features facilitate proton conduction, leading to a high proton conductivity value of 0.83 S cm–1 at 98% relative humidity and 90 °C, with an activation energy of 0.26 eV. The Cd0.85PS3Li0.15H0.15-based proton transistor demonstrates tunability via gate voltage, thereby enabling effective modulation of proton flow across source and drain electrodes. The transistor notably showcases superior switching characteristics, with an on/off ratio surpassing 5.51 and a carrier mobility of 8.84 × 10–2 cm2 V–1 s–1. The underlying mechanism for this performance enhancement is attributed to electric-field-induced switching in Cd vacancies. This research boosts the development of highly versatile ionotropic devices by introducing advanced 2D ion-conductive membranes.

CAS / MDL: 7447-41-8
研究领域: 材料科学 · 电子学 · 纳米技术 · 质子学 · 器件物理
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JOURNAL OF MEMBRANE SCIENCE · 2021 · IF 8.742

Highly conductive quaternary ammonium-containing cross-linked poly(vinyl pyrrolidone) for high-temperature PEM fuel cells with high-performance

Huijuan Bai,Jin Zhang,Haining Wang,Yan Xiang,Shanfu Lu

Poly(vinyl pyrrolidone) (PVP)-based high-temperature polymer electrolyte membranes (HT-PEMs) doped with phosphoric acid (PA) present an attractive prospect for high-temperature fuel cell. However, its proton conductivities and mechanical properties are inversely dependent on PVP content in membranes. Herein, chloromethyl-polysulfone is used as a polymeric crosslinker to fabricate cross-linked PVP. The effects of chloromethylation degree of polysulfone on PVP cross-linking degree, free volume and other parameters are studied. The quaternary amine groups introduced by cross-linking reaction enhances PA adsorption and retention capacity of membrane. The increased molar free volume created by polymeric crosslinker can accommodate more PA storage and reduce the polymer main chain plasticization. Thus, the mechanical properties of membranes are maintained. When compared to uncross-linked C-PVP-0/PA, the cross-linked C-PVP-13.7%/PA exhibits improved mechanical strength with increasement of 140% (4.5 MPa) and enhanced proton conductivity with increasement of 119% (120.0 mS cm −1 @160 °C). Also, these superior characteristics allow a significantly enhanced H 2 –O 2 fuel cell performance with the membrane of 724.9 mW cm −2 @160 °C, which has increasement of 50% in comparison with that of the C-PVP-0%/PA membrane, and excellent durability. These praiseworthy results suggest that the cross-linked membrane within moderately molar free volume is potential to act as HT-PEMs materials for real-world applications.

研究领域: 材料科学 · 化学工程 · 能源技术
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SENSORS AND ACTUATORS B-CHEMICAL · 2014 · IF 3.84

Novel sulfonated polysulfone ion exchange membranes for ionic polymer–metal composite actuators

Yongjun Tang,Zhigang Xue,Xingping Zhou,Xiaolin Xie,Chak-Yin Tang

A series of sulfonated polysulfone (SPSU) membranes with different degrees of sulfonation were prepared for fabricating cost-effective and high-performance ionic polymer–metal composite (IPMC) actuators. The experimental results show that the ion exchange capacity and water uptake of SPSU membranes increase with increasing their degree of sulfonation, and the proton conductivities of these hydrated membranes are subsequently enhanced. Compared with the commercial Nafion 117 ion exchange membrane, these SPSU membranes have higher ion exchange capacity and water uptake ability. Furthermore, the higher molecular rigidity of the SPSU membranes leads to higher tensile moduli in both dry and wet states than the Nafion membrane. The IPMC actuators made of the SPSU membranes demonstrate the large bending strain, fast response and excellent fatigue resistance under electric stimulation. Their electromechanical behaviors can be controlled by adjusting the sulfonation level of the SPSU ion exchange membranes.

研究领域: 材料科学 · 电化学 · 高分子科学 · 致动器技术
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