Co-reporter:Hong Li;Yijian Wu;Yong Hu;E. Bryan Coughlin
Journal of Materials Science 2015 Volume 50( Issue 12) pp:4280-4287
Publication Date(Web):2015 June
DOI:10.1007/s10853-015-8980-6
Block copolymers, dinonylphenyl end-capped polyethylene glycol-b-polystyrene (DNPE-PEO-b-PSs) were synthesized in a one-step atom transfer radical polymerization (ATRP) of styrene. The PEO block in the DNPE-PEO-b-PS samples (volume fraction of PS: 66.8–93.2 %) was found to be amorphous, which contrasts with DNPE-PEO precursor, traditional methoxide end-capped polyethylene glycol-b-polystyrene (PEO-b-PS) and dinonylphenyl end-capped poly-(ethylene glycol)-b-poly(fluorinated methyl methacrylate)(DNPE-PEO-b-PFMAs). Meanwhile, DNPE-PEO-b-PSs display an intriguing self-assembly behavior in solution. Block copolymer particles with mesoporous internal structures are directly formed by self-assembly of DNPE-PEO-b-PS in tetrahydrofuran/water solutions. It is proposed that DNPE end group has an important effect on the crystallization of the block copolymers as well as their self-assembly behaviors in solution.
Co-reporter:Zhijun Cai, Yanbo Liu, Sisi Liu, Lei Li and Yongming Zhang
Energy & Environmental Science 2012 vol. 5(Issue 2) pp:5690-5693
Publication Date(Web):13 Dec 2011
DOI:10.1039/C1EE02708E
A lithium-ion polymer battery using the lithiated perfluorinated sulfonic ion-exchange membranes swollen with organic non-aqueous solvent as both separator and electrolyte is demonstrated, and shows very good capacity retention compared with the conventional lithium-ion battery using the liquid electrolyte.
Co-reporter:Zhijun Cai, Lei Li, Lijun Su, Yongming Zhang
Electrochemistry Communications 2012 Volume 14(Issue 1) pp:9-12
Publication Date(Web):January 2012
DOI:10.1016/j.elecom.2011.09.022
Supercritical carbon dioxide (Sc-CO2) thermal treatment to enhance performance of Nafion 212 (NR212) commercial membranes for direct methanol fuel cells (DMFCs) is described. It is shown that the microstructure of NR212 membranes is re-organized after the Sc-CO2 treatment, and then the performance of NR212 membranes is improved. Specifically the thinner NR212 membranes after the Sc-CO2 treatments have higher proton conductivity and better capacity of barrier to methanol crossover compared with the thicker Nafion 117 membranes. It is demonstrated that the DMFC performance of the Sc-CO2 treated NR212 membranes is better than that of Nafion 117 membranes.Highlights► Supercritical carbon dioxide treatment was used to enhance performance of NR212. ► The microstructure of NR212 membranes was reorganized after the Sc-CO2 treatment. ► The treated NR212 membranes showed higher proton conductivity than Nafion 117. ► The treated NR212 membranes showed lower methanol permeability than Nafion 117. ► DMFC performance of the treated NR212 membranes was better than Nafion 117.
Co-reporter:Libin Yang, Junke Tang, Lei Li, Xiaoyong Chen, Fei Ai, Wang Zhang Yuan, Li Wang and Yongming Zhang
RSC Advances 2012 vol. 2(Issue 14) pp:5950-5953
Publication Date(Web):08 May 2012
DOI:10.1039/C2RA20318A
A new method to prepare high quality PFSI membranes from their precursor solutions is developed. The obtained membranes exhibit better dimensional stability, higher proton conductivity, and remarkably decreased methanol crossover when compared with those of traditional membranes.
Co-reporter:Lei Li, Lijun Su, Yongming Zhang
International Journal of Hydrogen Energy 2012 Volume 37(Issue 5) pp:4439-4447
Publication Date(Web):March 2012
DOI:10.1016/j.ijhydene.2011.11.110
Supercritical carbon dioxide (Sc-CO2) thermal treatment to enhance performances of both Nafion 212 (NR212) commercial membranes with H-form and Na-form for direct methanol fuel cells (DMFCs) is described. XRD measurements show that the crystallinity of H-form NR212 membranes increases with increasing the treated temperature in the Sc-CO2 system, however, the crystallinity of Na-form NR212 membranes decreases with increasing the treated temperature. Since the bigger crystallites formed after the Sc-CO2 treatments, it improves the mechanical strength and dimensional stability of the Sc-CO2 treated NR212 membranes with H-form and Na-form. Compared with the as-received NR212 membranes, all the Sc-CO2 treated NR212 membranes show higher proton conductivity and better capacity of barrier to methanol crossover. From Fenton test, it can be found that the Sc-CO2 treated NR212 membranes have better chemical stability than that of NR212 membranes. Therefore, NR212 membranes treated by the Sc-CO2 method may be promising candidate electrolytes for DMFC applications.Highlights► NR212 membranes are treated by using supercritical carbon dioxide for DMFCs. ► NR212 membranes with H-form and Na-form are treated. ► Proton conductivity of the treated NR212 membranes is improved. ► Methanol permeability of the treated NR212 membranes is lower than that of NR212. ► The treated NR212 membranes show better chemical stability.
Co-reporter:Lei Li, Fangjian Shang, Li Wang, Supeng Pei and Yongming Zhang
Energy & Environmental Science 2010 vol. 3(Issue 1) pp:114-116
Publication Date(Web):09 Nov 2009
DOI:10.1039/B917352H
The transport properties of PFSA for direct methanol fuel cell application were investigated, including water uptake, proton conductivity, methanol permeability and selectivity of perfluorosulfonic acid (PFSA) membranes as a function of the ion exchange capacity.
Co-reporter:Lijun Su, Lei Li, Hong Li, Yongming Zhang, Wei Yu, Chixing Zhou
Journal of Membrane Science 2009 Volume 335(1–2) pp:118-125
Publication Date(Web):15 June 2009
DOI:10.1016/j.memsci.2009.03.006
Perfluorosulfonic acid (PFSA) membranes were treated by supercritical carbon dioxide (Sc-CO2) method for direct methanol fuel cell application. After the treatment in Sc-CO2 at a desired temperature, the microstructure of the PFSA membranes was changed greatly. Small-angle X-ray scattering measurement indicated that a long-range order developed and the size of the ion cluster in the fully hydrated membranes became much smaller. Wide-angle X-ray diffraction measurement showed that the relative crystallinity of the PFSA membranes increased due to Sc-CO2-induced crystallization. The macro-physical performances of the membranes were also investigated: swelling ratio of the membrane became much smaller; solubility of the membrane in ethanol/water solvent decreased dramatically; density of the wet membrane increased evidently. Differential scanning calorimetry measurement indicated that the nonfreezable water per volume of the fully hydrated membranes increased notably. As a result, the methanol permeability of the PFSA membranes was significantly reduced without the sacrifice of proton conductivity, and the mechanical properties increased evidently. All the results indicated that this novel treatment in Sc-CO2 atmosphere is a promising method to improve the properties of membrane for direct methanol fuel cell application.
Co-reporter:Lijun Su, Lei Li, Hong Li, Junkun Tang, Yongming Zhang, Wei Yu, Chixing Zhou
Journal of Power Sources 2009 Volume 194(Issue 1) pp:220-225
Publication Date(Web):20 October 2009
DOI:10.1016/j.jpowsour.2009.04.070
Polysiloxane modified perfluorosulfonic acid (PFSA) composite membranes are prepared by using (3-mercaptopropyl) methyldimethoxysilane (MPMDMS) as a precursor of silicon alkoxide in supercritical carbon dioxide (Sc-CO2) system. In the Sc-CO2 system with the presence of water, Sc-CO2 is not only used as a solvent and swelling agent, but also functioned as an acid catalyst for the condensation polymerization of MPMDMS. Characteristics of the modified composite membranes are investigated by using attenuated total reflection-infrared spectra, scanning electron microscopy and transmission electron microscopy. The modified membrane with 13.9 wt.% poly(MPMDMS) is the best one among all the modified membranes, whose methanol permeability is extremely lower and selectivity (ratio of proton conductivity to methanol permeability) is about 5.49 times higher than that of pristine membrane and 5.88 times than that of Nafion® 117, respectively. This modified PFSA membrane still can maintain its higher selectivity value than that of Nafion® 117 in the temperature range of 25–65 °C. Therefore, the modified membranes prepared in Sc-CO2 system may be the suitable candidate electrolytes for direct methanol fuel cell applications.
Co-reporter:Yinghao Luan, Heng Zhang, Yongming Zhang, Lei Li, Hong Li, Yangang Liu
Journal of Membrane Science 2008 Volume 319(1–2) pp:91-101
Publication Date(Web):1 July 2008
DOI:10.1016/j.memsci.2008.03.054
To investigate the solution-cast process from concentrated DMF-based perfluorosulfonic ionomer (PFSI) solution to membranes and morphology of the corresponding solution-cast membranes, XRD measurements were conducted on concentrated solutions, gels of various ionomer concentrations and membranes prepared at different temperatures, and small-angle X-ray scattering from the membranes was studied in order to investigate their internal supermolecular structure. It is with interaction of backbones of the ionomer molecules that the PFSI aggregates in the solutions fuse into each other to form gels and membranes, with capillary liquid bridge force and thermal movement of the polymer chains as the driving force on drying. Fusion degree of the ionomer aggregates increases with increasing casting temperature. Accordingly, proton conductivity, water uptake, solubility in ethanol/water mixture and crystallinity of the membranes decrease with increasing casting temperature, whereas dry density and tensile stress at break of the solution-cast membranes increase. SEM and TEM measurements were also conducted to give direct observation of the structure of the membranes. It was also found that morphology of DMF-based solution-cast PFSI membranes is greatly different from that of Nafion® thermo-extruded perfluorosulfonic membranes.
Co-reporter:Yinghao Luan;Yongming Zhang;Heng Zhang;Lei Li;Hong Li;Yangang Liu
Journal of Applied Polymer Science 2008 Volume 107( Issue 1) pp:396-402
Publication Date(Web):
DOI:10.1002/app.27070
Abstract
Perfluorosulfonated ionomer (PFSI) was synthesized and PFSI membranes were prepared via a solution-cast method and annealed at different temperatures from 150 to 230°C. The annealing effect on water content, proton conductivity, and methanol permeability were reported and discussed. X-ray diffraction and small angle X-ray scattering were used to test the structure of the membranes. It was found that annealing increased the proton conductivity of the membranes because heat-treatment helped to free the sulfonic groups that were buried in the polymer segments and form more organized ionic clusters. Water content and methanol permeability of the annealed membranes decreased with increasing annealing temperature. Simultaneously, annealing induced more compact chain packing structure, which eventually affected the transport of the proton and methanol through these ionomer membranes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008
Co-reporter:Yinghao Luan;Yongming Zhang;Lei Li;Heng Zhang;Qing Zhang;Zhongxi Huang;Yangang Liu
Journal of Applied Polymer Science 2008 Volume 107( Issue 5) pp:2892-2898
Publication Date(Web):
DOI:10.1002/app.27150
Abstract
The morphology of perfluorosulfonic ionomer molecules in N,N-dimethylformamide was investigated at different concentrations. Rheological, dynamic light scattering (DLS), and scanning electron microscopy (SEM) measurements were performed on the prepared perfluorosulfonic ionomer solutions or films. The ionomer molecules shrank from rodlike granules to spherelike ones at relatively low concentrations, and the spherelike granules aggregated together to form aggregates at higher concentrations, with capillary liquid bridge force as the driving force. As the solvent evaporated slowly at room temperature, the SEM image showed that the film was loosely stacked by granules and that aggregates formed in the solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008
Co-reporter:Zhong-Xi Huang;Hong Li ;Yan-Gang Liu
Macromolecular Chemistry and Physics 2008 Volume 209( Issue 8) pp:825-831
Publication Date(Web):
DOI:10.1002/macp.200700562
Co-reporter:Zhong Xi Huang;Yong Ming Zhang;Hong Li;Ying Hao Luan ;Yan Gang Liu
Journal of Polymer Science Part A: Polymer Chemistry 2008 Volume 46( Issue 4) pp:1416-1426
Publication Date(Web):
DOI:10.1002/pola.22481
Abstract
Ion exchange resin immobilized Co(II) catalyst with a small amount of soluble CuCl2/Me6TREN catalyst was successfully applied to atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in DMF. Using this catalyst, a high conversion of MMA (>90%) was achieved. And poly(methyl methacrylate) (PMMA) with predicted molecular weight and narrow molecular weight distribution (Mw/Mn = 1.09–1.42) was obtained. The immobilized catalyst can be easily separated from the polymerization system by simple centrifugation after polymerization, resulting in the concentration of transition metal residues in polymer product was as low as 10 ppm. Both main catalytic activity and good controllability over the polymerization were retained by the recycled catalyst without any regeneration process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1416–1426, 2008
Co-reporter:Hong Li;Yong Ming Zhang;Yan Gang Liu
Journal of Applied Polymer Science 2006 Volume 101(Issue 2) pp:1089-1094
Publication Date(Web):25 APR 2006
DOI:10.1002/app.24002
Well-defined poly(vinyl acetate-b-methyl methacrylate) block copolymers were successfully synthesized by the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in p-xylene with CuBr as a catalyst, 2,2′-bipyridine as a ligand, and trichloromethyl-end-grouped poly(vinyl acetate) (PVAc–CCl3) as a macroinitiator that was prepared via the telomerization of vinyl acetate with chloroform as a telogen. The block copolymers were characterized with gel permeation chromatography, Fourier transform infrared, and 1H-NMR. The effects of the solvent and temperature on ATRP of MMA were studied. The control over a large range of molecular weights was investigated with a high [MMA]/[PVAc–CCl3] ratio for potential industry applications. In addition, the mechanism of the polymerization was discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1089–1094, 2006
Co-reporter:Hong-Yan Dou, Hong-Bo Ni, Cheng-Xue Zhao, Yong-Ming Zhang
Journal of Fluorine Chemistry 2005 Volume 126(Issue 8) pp:1130-1133
Publication Date(Web):August 2005
DOI:10.1016/j.jfluchem.2005.04.009
After mixing a methylbenzene 4 with “magic blue” solution in F113 (CClF2CCl2F) containing bis{perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl}nitroxide 2 and perfluoro-1-nitroso-1-[1-(2-fluorosulfonyl)ethoxy]ethane 3 at room temperature, benzylic H-atom of 4 could be selectively abstracted by 2, and benzyl radical 5 thus generated was immediately trapped by 3. Based on hyper-fine splitting constants (hfsc), the structure of the spin adducts perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl benzyl nitroxides 6 derived from seven methylbenzenes have been identified. The mechanism of the H-abstraction/spin trapping process is also discussed.The generation of benzyl nitroxides 6 via H-abstraction/ spin trapping reactions by new “magic blue” (2 + 3) from a series of methylbenzenes 4a–4g are reported.
Co-reporter:Zhong Hui Li;Min Zhao Xue;Yong Ming Zhang;Yan Gang Liu;Lei Zhou
Journal of Polymer Science Part A: Polymer Chemistry 2005 Volume 43(Issue 21) pp:5207-5216
Publication Date(Web):23 SEP 2005
DOI:10.1002/pola.20835
A new catalyst system, CoCl2/tris(2-(dimethyl amino) ethyl)amine (Me6 TREN), was used to catalyze the polymerization of methyl methacrylate (MMA) successfully through atom transfer radical polymerization mechanism. The control over the polymerization was not ideal, the molecular weight distribution of the resulting polymer (PMMA) was relatively broad (Mw/Mn = 1.63–1.80). To improve its controllability, a small amount of hybrid deactivator (FeBr3/Me6TREN or CuBr2/Me6TREN) was added in the cobalt catalyst system. The results showed that the level of control over the polymerization was significantly improved with the hybrid cobalt–iron (or cobalt–copper) catalyst system; the polydispersity index of the resulting polymer was reduced to a low level (Mw/Mn = 1.15–1.46). Furthermore, with the hybrid cobalt–iron catalyst, the dependence of the propagation rate on the temperature and the copolymerization of methacrylate (MA) with PMMA-Br as macroinitiator were also investigated. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5207–5216, 2005