Fuel Cells
·
2026
·Vol. 26
·期 3
·e70115
·
IF 3.1
Chuyu Zhou,Didi Chu,Wenxing Zeng,Jingze Cheng,Zhengdong Fei
Balancing high proton conductivity with dimensional stability remains a persistent “trade-off” for sulfonated poly(ether ether ketone) (SPEEK) electrolytes. Herein, an amine-triggered self-catalyzed strategy is reported to construct a quaternary ammonium-functionalized siloxane semi-interpenetrating polymer network (semi-IPN) within SPEEK matrix. The in-situ formed rigid Si─O─Si scaffold effectively confines membrane swelling, while the tethered quaternary ammonium sites synergistically facilitate efficient proton hopping through acid–base interactions with sulfonic acid groups. The optimized membrane (GTM-2) yields a peak conductivity of 277.8 mS cm −1 at 80°C, achieves a power density of 746.26 mW·cm −2 in a single fuel cell. Moreover, the semi-IPN membranes maintain favorable mechanical strength (up to 23.3 MPa). This architectural design provides a robust pathway for developing high-performance, non-fluorinated proton exchange membranes.
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DOI
高影响因子
Membranes
·
2025
·Vol. 15
·期 7
·194
·
IF 3.6
Xiaoyao Wang,Benbing Shi
Proton exchange membranes are widely used in environmentally friendly applications such as fuel cells and electrochemical hydrogen compression. In these applications, an ideal proton exchange membrane should have both excellent proton conductivity and mechanical strength. Polymer proton exchange membranes, such as sulfonated poly(ether ether ketone) (SPEEK) membranes with high ion exchange capacity, can lead to higher proton conductivity. However, the ionic groups may reduce the interaction between polymer segments, lower the membrane’s mechanical strength, and even cause it to dissolve in water as the temperature exceeds 55 °C. The porous graphitic C3N4(Pg–C3N4) nanosheet is an important two–dimensional polymeric carbon–based material and has a high content of –NH2and –NH– groups, which can interact with the sulfonic acid groups in the sulfonated SPEEK polymer, form a more continuous proton transfer channel, and inhibit the movement of the polymer segment, leading to higher proton conductivity and mechanical strength. In this study, we found that a SPEEK membrane containing 3% Pg–C3N4nanosheets achieves the optimized proton conductivity of 138 mS/cm (80 °C and 100% RH) and a mechanical strength of 74.1 MPa, improving both proton conductivity and mechanical strength by over 50% compared to the SPEEK membrane.
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DOI
PubMed
高影响因子
ELECTROCHIMICA ACTA
·
2016
·
IF 4.803
Yuxiao Li,Meishan Zhang,Xueyan Wang,Zhun Li,Lianhua Zhao
Sulfonated poly (ether ether ketone) (SPEEK, SP) with tetraethoxysilane (TEOS) and diethylethylammonium trifluoromethanesulfonate ([dema] [OTf]) were used to make SP/SiOx/OTf inorganic–organic composite membranes by the sol–gel method. The composite membranes were studied with respect to their structural, thermal, ionic liquid leeching (ILs), mechanical, and proton conduction properties. Fourier transform infrared spectroscopy (FT-IR) results showed that there exist intermolecular forces between the sulfonic groups, silica, and ILs in the composite membrane. Thermogravimetric (TG) results showed that the thermal stability of the SP/SiOx/OTf composite membrane is better than that of the pristine SPEEK membrane. IL leaching studies showed that the sulfonic group could help to reduce the loss of ILs. The introduction of silica in the SP/SiOx/OTf composite membrane could further reduce the loss of ILs, and also reduce the swelling degree of the composite membrane. Dynamic mechanical analysis (DMA) data showed that the introduction of silica can increase the flexibility of membranes, and improve the mechanical properties. A proton conductivity of 2.003 × 10 −2 S/cm was obtained for a 50 wt% [dema][OTf] doped SP-66/SiOx/OTF-50 composite membranes at 220 °C under anhydrous conditions.
研究领域:
材料科学
·
高分子化学
·
能源材料
·
电化学
·
膜科学
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DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2026
·
IF 3.1
Xi Li,Peng Wei,Fan Yang,Yongfeng Li
The inherent trade-off between proton conductivity and dimensional stability severely limits the practical application of proton exchange membranes (PEMs). To address this issue, a unique sandwich-structured membrane is presented. In this design, its outer surface layers form a rigid skeleton composed of polyimide (PI) nanofibers, which provide physical confinement and effectively suppress excessive water absorption and swelling. The middle functional layer is made up of an ethylenediamine-modified graphene oxide (EGO)/sulfonated poly (ether ether ketone) (SPEEK) composite. Acid–base interactions between amino groups (-NH 2 ) on EGO and sulfonic acid groups ( SO 3 H) in SPEEK allow for the formation of continuous proton-transport pathways. In contrast, this membrane achieves a high proton conductivity of 222.4 mS·cm −1 at 60°C and 100% RH, which is 9.3% higher than that of SPEEK, while area ratio (20.5%) and water uptake (64.6%) are reduced by 56.9% and 39.7%, respectively. The membrane maintains 91.4% of its initial conductivity after a 350-h durability test at 60°C and 100% RH, which is still 26.9% greater than that of SPEEK. Overall, this sandwich-structured approach offers an efficient path toward high-performance PEMs by simultaneously improving proton conductivity and dimensional stability using synergistic physical confinement and interfacial chemical interactions.
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高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2019
·Vol. 44
·期 12
·6148-6159
·
IF 4.084
Xiaoyu Zhang,Shiyuan Yu,Qian Zhu,Lianhua Zhao
The novel SP/IL/AMS composite membrane doped with amino-functionalized mesoporous silica (AMS) was successfully prepared. Sulfonated poly ether ether ketone (SPEEK, SP) was used as the polymer matrix and the ionic liquid (IL) was N -ethylimidazolium trifluoromethanesulfonate (EIm[Tfo]). Its properties were compared with SP/IL/NMS composite membrane doped with non-functionalized mesoporous silica (NMS). Fourier transform infrared spectroscopy (FT-IR) analysis indicated that the components in the composite membrane were bound by intermolecular forces. In addition, an acid-base interaction was formed between -NH 2 in AMS and -SO 3 H in SPEEK. The acid-base pair is beneficial to proton conduction. The anhydrous proton conductivity of SP/IL/3-AMS-7.5 composite membrane is about 4 times higher than that of the SP/IL/NMS-7.5. In addition, the good interfacial compatibility between AMS and polymer matrix is conducive for creation continuous proton transfer channel. Thermogravimetric analysis (TG) showed that all composite membranes were stable at 270 °C. The leaching of IL data indicated that IL can be effectively retained due to the presence of -OH and -NH 2 on the NMS and AMS surfaces. The SP/IL/AMS composite membrane could be used in proton exchange membrane fuel cells under medium temperature and anhydrous conditions.
研究领域:
材料科学
·
高分子化学
·
能源材料
·
燃料电池
·
膜科学
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DOI
高影响因子
ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Xuan Li,Bo He,Ping Li,Shaokun Tang
Sulfonated polyether ether ketone (SPEEK) has been widely investigated in proton exchange membrane fuel cells (PEMFCs) due to its excellent thermal stability, chemical stability, and low cost compared with Nafion. However, excessive degree of sulfonation will easily lead to the decrease in thermal stabilities and mechanical properties of SPEEK membranes, which limits the enhancement of proton conductivity. In this work, a series of Schiff-base networks (SNWs) with different contents are in situ synthesized in the SPEEK membrane by a Schiff-base co-condensation reaction, and then, the composite membranes are soaked in sulfonic acid for further improvement of proton conductivity. The highest doping amount of the SNW filler in SPEEK can reach 20 wt %. High loading and low leaching rate of H2SO4 are easily achieved owing to the similar size between sulfuric acid molecules and micropores in SNW. Moreover, abundant amino and imine groups in SNW networks contribute to the anchoring of H2SO4 into the pores by acid–base interactions. The proton conductivity of the SPEEK/S-SNW-15 composite membrane can reach 115.53 mS cm–1 at 80 °C and 100% RH. Meanwhile, the composite membrane also exhibits satisfied stability and mechanical property.
研究领域:
材料科学
·
燃料电池技术
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产品关联
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2023
·
IF 7.2
Dingbo Han,Jianbo Zhang,Ce Wang,Ping Hu,Yong Liu
A series of novel nanofiber composite proton exchange membranes were fabricated by embedding highly sulfonated poly (ether ketone) (SPEEK) nanofibers in a cross-linked SPEEK matrix, showing both high proton conductivity and excellent stability. Composite membranes were prepared with salt-form SPEEK nanofiber mats filled with acid-form SPEEK solution. After thermal treatment at 180 °C in the presence of dimethyl sulfoxide , the cross-linking reaction occurred in the acid-form SPEEK matrix but not in nanofibers. The dimensional stability, mechanical strength , and oxidative stability of the composite membrane were significantly improved due to thermal cross-linking treatment. The swelling ratio of all the cross-linked membranes was below 30% in hot water, and the maximum tensile strength reached 68 MPa. The nanofibers formed non-cross-linked regions and retained rich sulfonic acid groups to construct fast, long-range proton transport channels. The proton conductivity of the nanofiber composite cross-linked membrane reached 200 mS/cm exceeding the pristine cross-linked membrane (135 mS/cm). The fuel cell performance showed a peak power density of 485 mW/cm 2 at 80 °C under 100% relative humidity.
研究领域:
材料科学
·
能源工程
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DOI
高影响因子
ACS Applied Bio Materials
·
2024
·
IF 4.6
Wei Wei,Jiawen Zhu,Yiting Liu,Liujing Chen,Wenhui Zhu,Hengxing Ji,Zhongle Cheng
Polyetheretherketone (PEEK), particularly its sulfonated form (SPEEK), has emerged as a promising synthetic biomaterial for artificial bone implants, providing an alternative to conventional titanium metal. However, postoperative infections pose a critical challenge, driven by diverse and antibiotic-resistant bacteria. To address this issue, we propose the modification of the SPEEK surface using a thin graphene oxide (GO) film containing silver (Ag) ions. The resulting coating exhibits substantial antibacterial effects against various pathogens, including Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae, and Candida albicans. Experimental assessments elucidate the coating’s impact on bacterial adhesion, biofilm formation, and morphology. The results suggest that hindered bacterial growth stems from reduced biofilm production and the controlled release of Ag ions facilitated by the GO coating. The Ag/GO-SPEEK material holds promise as a bioactive implant, addressing the challenges associated with bacterial targeting in bone tissue engineering applications.
研究领域:
生物材料学
·
医学工程
·
微生物学
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DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2026
·
IF 9.2
Yachao Ji,Yaqi Xu,Xinyu Luo,Zan Chen,Yawei Du,Sibudjing Kawi,Yinhui Li
Hydrogen energy is a promising carrier for decarbonizing energy systems, but its low volumetric energy density requires efficient storage and transportation. Electrochemical hydrogen compression provides quiet and energy-efficient hydrogen compression and purification, relying on proton exchange membranes with high conductivity and mechanical robustness. Herein, sulfonated poly(ether ether ketone) (SPEEK) with a sulfonation degree of 63.5% was prepared by post-sulfonation, and UiO-66-NH 2 (UN) was incorporated to fabricate SPEEK/UN composite membranes. The amino groups, Zr-OH sites, and confined water in UN provide proton-relay sites and regulate the interfacial proton-transport environment. The optimized SPEEK/UN-0.75 membrane exhibited a conductivity of 231.4 mS cm −1 and tensile strength of 57.6 MPa at 60 °C and 100% RH. Its proton selectivity increased from 4.55 to 13.89, and an outlet pressure of 2.37 MPa was achieved, outperforming SPEEK and Nafion 115. This membrane design provides a promising strategy for developing proton exchange membranes for electrochemical hydrogen compression.
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高影响因子
POLYMER
·
2023
·
IF 4.6
Peng Wei,Dong Huang,Chen Luo,Yang Sui,Xi Li,Qingkun Liu,Bensheng Zhu,Chuanbo Cong,Qiong Zhou,Xiaoyu Meng
Due to its uncomplicated manufacturing procedure for large-scale industrialization and adaptable conductivity, the competitive proton exchange membrane (PEM) matrix employed is sulfonated poly (ether ether ketone). However, the conflict between the strong proton conductivity and high stability of SPEEK-based PEM constantly upsets the equilibrium; the primary chain of SPEEK will conduct more protons if additional sulfonic acid is introduced, but it also causes a high swelling ratio and lowers stability. To tackle this challenging issue, we coupled the high intrinsic proton conductivity of phosphotungstic acid (HPW) and the excellent stability of polyimide (PI) nanofibers in a single PEM. In particular, sandwich-structure hybrid membranes (PI/SPEEK + HPW) were created to reduce HPW loss under operational conditions, further improving stability. Consequently, the swelling ratio and conductivity of the premium sandwich-structure PI/SPEEK + HPW-20 were 29% and 223.4 mS cm −1 under 60 °C and 100% RH, their respective values were 8% larger than those of SPEEK. Its proton conductivity reached 170.9 mS cm −1 during 13 days of exposure under 60 °C and 100% RH, which would be 30% better than that of SPEEK over the same treatment. Protons in these membranes were transported through Grotthus and vehicle mechanism, and the establishment of an acid-rich layer at the surface among PI nanofiber with HPW/SPEEK, which was confirmed by FTIR, XPS , and TEM , is responsible for these superior performances. From our point of view, our findings might encourage more studies into the creation of high-performance PEM.
研究领域:
材料科学
·
高分子化学
·
能源材料
·
电化学
·
膜科学与技术
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DOI
高影响因子
ELECTROCHIMICA ACTA
·
2017
·
IF 4.798
Xueyan Wang,Mingshi Jin,Yuxiao Li,Lianhua Zhao
Anhydrous proton conducting membranes made of different ionic liquids (ILs), sulfonated poly (ether ether ketone) (SPEEK), and mesoporous silica (SiO 2 ) are successfully prepared. Influences of different ionic liquids on the properties of composite membranes doped with 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF 4 ]), 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([BMIm][Tfo]), 1-butyl-3-methylimidazolium chloride ([BMIm]Cl), diethylmethylammonium trifluoromethanesulfonate ([dema][Tfo]), and 1-ethylimidazolium trifluoromethanesulfonate ([EIm][Tfo]) ionic liquids are described. Fourier transform infrared spectroscopy (FT-IR) analysis showed that there were interactions between ionic liquids, SPEEK and mesoporous silica. IL leaching studies demonstrated that IL loss decreased significantly after doping with SiO 2 . The proton conductivity study showed that both anions and cations of IL influenced the proton conductivity of the composite membranes. Proton conductivity of composite membranes displayed a positive correlation with the number of hopping sites within IL cation structures. Of all the conducting membranes studied, SP/SiO 2 -7.5/[BMIm][BF 4 ]-50 showed the highest anhydrous proton conducting ability (15 mS cm −1 at 200 °C). Therefore, it is expected to find applications in proton exchange membrane fuel cells under medium temperature, anhydrous conditions.
研究领域:
材料科学
·
化学工程
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DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2026
·
IF 9.2
Ying Ou,Zaijun Gan,Jiying Wang,Yalian Wang,Meiling Fan,Jie Wang,Fan Cheng,Hai Liu,Guoliang Liu
Developing novel proton exchange membranes that combine superior proton conductivity and low methanol permeation for direct methanol fuel cells is of great significance. Herein, an in-situ ionically crosslinked membrane was prepared by blending sulfonated polybenzimidazole (SPBI, DS = 200%) and sulfonated poly(ether ether ketone) (SPEEK, DS = 80%) utilizing ionic interactions between protonated imidazole rings and -SO 3 H. The ionic crosslinking suppresses the water solubility of the highly sulfonated SPEEK while enhancing the water uptake of the blend membrane, promoting the formation of continuous hydrophilic channels within the membrane. Meanwhile, due to the restriction of segmental motion by ionic crosslinking, the mechanical properties and methanol barrier performance of the blended membranes were notably enhanced. As a result, the assembled DMFC single cell with SPBI/SPEEK-H + -20% blended membrane exhibits a power density of 117.24 mW cm −2 and low methanol crossover current density of 254.18 mA cm −2 under 80°C with a 2 M methanol concentration.
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高影响因子
危险品化学品经营许可证（带存储）