Performance and stability of supported liquid membranes using LIX 984N for copper transport

The transport of copper through supported liquid membranes (SLM) using Celgard and Accurel membranes as supports and a novel commercial extractant LIX 984N as a carrier was investigated. LIX 984N provides good overall transport performance for copper from the acidic and dilute solution to the concentrated copper sulfuric acid. The instability of the supported liquid membranes using Celgard 2500 as the membrane support has been studied. It has been demonstrated that initially the surface shear forces due to stirring are a main cause for membrane liquid loss leading to SLM instability. However, during long term permeation no single instability mechanism dominants. The instability of long term operation involves a complex interaction of a number of factors, including surface shear forces, Marangoni effects, changes to membrane morphology, Bernard instabilities and membrane preparation protocal.     

Preparation and characterization of monovalent cation selective sulfonated poly(ether ether ketone) and poly(ether sulfone) composite membranes

Highly charged cation permeable composite membranes were prepared by blending of sulfonated poly(ether sulfone) (SPES) with sulfonated poly(ether ether ketone) (SPEEK) in 0 to 90% weight ratio, to adjust the hydrophobic properties and ion selective nature. Extent of sulfonation was confirmed by 1H NMR and ion exchange capacity and degree of sulfonation depending on blending composition. These membranes were characterized as a function of weight fraction of SPEEK by recording ion-exchange capacity, water uptake, thermogravimetric analysis, membrane conductivity and membrane potential in equilibration with different electrolytic solutions. Membrane permselectivity and solute flux were estimated using these data on the basis of non-equilibrium thermodynamic principles and for observing the selectivity of different membranes for mono- or bivalent counter-ions. It was observed that relative selectivity for monovalent in comparison to bivalent counter-ions were increased with the decrease in SPEEK content in the composite membrane matrix. The range of SPEEK content in the blend from 60 to 80% appears the most suitable for the selective separation of monovalent ions from bivalent ions. Furthermore, highly charged nature and stabilities of these membranes extend their applications for the electro-assisted separations of similarly charged ions as well as other electro-membrane processes.     

Sulfonated poly(ether ether ketone)/polyaniline composite proton-exchange membrane

Sulfonated poly(ether ether ketone) (PEEK) was prepared by sulfonation of commercial Victrex^@ PEEK and degree of sulfonation was found to be about 44.5% by ¹H NMR. Sulfonated PEEK/polyaniline composite membranes, in order to prevent methanol crossover, were prepared by chemical polymerization of a thin layer of polyaniline (PANI) in the presence of a high oxidant concentration on a single face modification. FTIR and PANI coating density studies confirmed the loading of PANI in sulfonated PEEK membrane matrix. PANI composite membranes with different polymerization time were prepared and subjected to thermogravimetric analysis as well as electrochemical and methanol permeability study to compare with sulfonated PEEK and Nafion 117 membrane. Ion-exchange capacity, water uptake, proton transport numbers and proton conductivities for different PANI composite sulfonated PEEK (SPEEK) membranes were found to be dependent on the coating density of the PANI in the membrane matrix and were slightly lower than that of Nafion 117 membrane. Methanol permeability of these membranes (especially SPEEK/PANI-1.5) was about four times lower than Nafion 117 membrane. Among the all SPEEK membranes synthesized in this study, SPEEK-1.5 appears to be more suitable for direct methanol fuel cell (DMFC) application considering optimum physicochemical and electrochemical properties, thermal stability as well as very low methanol permeability. Above all, the cost-effective and simple fabrication technique involved in the synthesis of such composite membranes makes their applicability quite attractive.     

Structural and transport phenomena of urocanate-based proton carrier in sulfonated poly(ether ether ketone) membrane composite

Proton transport is one of crucial phenomena in electrolytic part highly considered to overcome a limit in fuel cell efficiency improvement. Proton conducting organic electrolyte was modeled and simulated at atomistic level of calculation by doping of butyl urocanate (C4U), a composite material with imidazole substructure, with sulfonated poly(ether ether ketone) (SPEEK) amorphous membrane at various working temperature. Molecular dynamics simulations were used to investigate structural and dynamics characteristic of C4U in the membrane comparing with the SPEEK-hydronium membrane model as a control. From simulations, thermal effect on water and proton carriers cluster surrounding the sulfonate groups was explored. At higher temperature, the more transport dynamics of C4U ions in SPEEK membranes were found than that of hydronium ions in the control system. Likewise, phase separation of hydrophobic and hydrophilic parts was taken into consideration here. A critical role of the enhancing proton conductivity by increasing the diffusion coefficient at temperature beyond C4U melting point in composite polymer membrane was emphasized. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1625–1635     

Sulfonated poly(ether ether ketone) composite membranes based on amino-modified halloysite nanotubes that effectively immobilize phosphotungstic acid

In this work, we prepared amino-modified halloysite nanotubes (PEI-DHNTs) via the co-deposition of self-polymerized dopamine and polyethylenimine (PEI) on the surface of nanotubes, which was confirmed by X-ray photoelectron spectroscopy (XPS) and Thermogravimetric analysis (TGA). A series of composite proton exchange membranes (PEMs) were prepared by incorporating PEI-DHNTs and phosphotungstic acid (HPW) into sulfonated poly(ether ether ketone) (SPEEK). It was found that both PEI-DHNTs and HPW were well dispersed in the polymer matrix, exhibiting excellent filler-matrix compatibility. The composite membranes demonstrated enhanced proton conductivity, reaching as high as 0.078 S cm⁻¹ with 33.3 wt.% HPW loading, which was ~90% higher than that of SPEEK control membrane. Such improvement was mainly attributed to the strong acid–base pairs formed by PEI-DHNT with both SPEEK and HPW, which shortened proton hopping distance and created more continuous proton conduction pathways. Furthermore, the membrane conductivity remained almost constant after 1 year's immersion in liquid water, indicating the successful immobilization of HPW in the composite membranes.     

Novel sulfonated poly (ether ether ketone)/silica coated carbon nanotubes high‐performance composite membranes for direct methanol fuel cell

The major risk of using carbon nanotubes (CNTs) to modify proton exchange membranes (PEMs) in fuel cells is possible short‐circuiting due to the excellent electrical conductivity of CNTs. In this article, silica‐coated CNTs (SiO₂@CNTs) were successfully prepared by a simple sol–gel process and then used as a new additive in the preparation of sulfonated poly (ether ether ketone) (SPEEK)‐based composite membranes. The insulated and hydrophilic silica coated on the surface of CNTs not only eliminated the risk of short‐circuiting, but also enhanced the interfacial interaction between CNTs and SPEEK, and hence promoted the homogeneous dispersion of CNTs in the SPEEK matrix. Moreover, compared to the methanol permeability of the pure SPEEK membrane (3.42 × 10^?7 cm² s^?1), the SPEEK/SiO₂@CNT composite membrane with a SiO₂@CNT loading of 5 wt% exhibits almost one order of magnitude decrease of methanol crossover, while the proton conductivity still remained above 10^?2 S cm^?1 at room temperature. The obtained results expose the possibility of SPEEK/SiO₂@CNT membranes to be served as high‐performance PEMs in direct methanol fuel cells. Copyright © 2015 John Wiley & Sons, Ltd.     

Preliminary evaluation of sulfonated poly(ether ether ketone)/monoethanolamine/adipic acid composite membranes for direct methanol fuel cell applications

A series of sulfonated poly(ether ether ketone)/monoethanolamine/adipic acid (SPEEK/MEA/AA) composite membranes are prepared and investigated to assess their possibility as proton exchange membranes in direct methanol fuel cells (DMFCs). A preliminary evaluation shows that introducing MEA and AA into SPEEK matrix decreases the thermal stability of membrane. However, the degradation temperatures are still above 260 °C, satisfying the requirement for fuel cell operation. Compared with the pure SPEEK membrane, the composite membranes exhibit not only lower water uptake and swelling ratios but also better mechanical property and oxidative stability. Noticeably, the methanol diffusion coefficient of the composite membranes decrease significantly from 3.15 × 10^?6 to 0.76 × 10^?6 cm²/s with increasing MEA and AA content, accompanied by only a small sacrifice in proton conductivity. Although both the methanol diffusion coefficient and the proton conductivity of composite membranes are lower than those of pure SPEEK and Nafion® 117 membranes, their selectivity (conductivity/methanol diffusion coefficient) are higher. In addition, the composite membranes show excellent stability in aqueous methanol solution. The good thermal and chemical stability, low swelling ratio, excellent mechanical property, low methanol diffusion coefficient, and high selectivity make the use of these composite membranes in DMFCs quite attractive. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2871–2879, 2007     

全钒液流电池用磺化聚醚醚酮/锂皂石质子膜的结构及性能

通过溶液流延法制备了磺化聚醚醚酮/锂皂石(SPEEK/Lap)复合膜, 对其物理化学性质、 机械性能、 化学稳定性及单电池性能进行了测试. 在SPEEK基质中引入的Lap有效改善了复合膜的质子传导率、 溶胀率和机械性能. 当Lap添加量(质量分数)从0.2%增到1.5%时, 复合膜的质子传导率随之增加(19.9~23.6 mS/cm). SPEEK/Lap-0.2复合膜的自放电时间为57.2 h, 是Nafion 117膜的2.4倍和纯SPEEK膜的1.5倍. 在80 mA/cm ²电流密度下, SPEEK/Lap-0.2复合膜的电压效率(VE, 86.5%)和能量效率(EE, 84.0%)明显高于Nafion 117膜(VE: 83.8%, EE: 80.7%)和纯SPEEK膜(VE: 81.4%, EE: 78.9%). 同时, SPEEK/Lap-0.2复合膜经100次充放电循环测试后具有良好的循环稳定性和结构稳定性.     

Nano oxides incorporated sulfonated poly(ether ether ketone) membranes with improved selectivity and stability for vanadium redox flow battery

Three kinds of sulfonated poly(ether ether ketone) (SPEEK)/nano oxide (Al₂O₃, SiO₂, and TiO₂) composite membranes are fabricated for vanadium redox flow battery (VRFB) application. The composite membranes with 5 wt% of Al₂O₃, SiO₂, and TiO₂ (S/A-5 %, S/S-5 %, and S/T-5 %) exhibit excellent cell performance in VRFB. Incorporation of nano oxides (Al₂O₃, SiO₂, and TiO₂) in SPEEK membrane improves in aspect of thermal, mechanical, and chemical stabilities due to the hydrogen bonds’ interaction between SPEEK matrix and nano oxides. The energy efficiencies (EEs) of composite membranes are higher than that of Nafion 117 membrane, owing to the good balance between proton conductivity and vanadium ion permeability. The discharge–capacity retentions of composite membranes also overwhelm that of Nafion 117 membrane after 200 cycles, indicating their good stability in VRFB system. These low-cost SPEEK/nano oxide composite membranes exhibit great potential for the application in VRFB.     

Sulfonated poly(ether ether ketone) as an alternative charged material to poly(vinyl chloride) in the design of ion-selective electrodes

To date, poly(vinyl chloride) (PVC) is the most used polymer in the design of ion selective electrode (ISE) membranes. This paper is focused on the use of sulfonated poly(ether ether ketone) (SPEEK) as an alternative material to PVC for the design of ISEs. SPEEK of the desired degree of sulfonation is synthesized from poly(ether ether ketone) (PEEK). An NH₄⁺-ISE has been chosen as a model electrode to study the efficiency of SPEEK as polymer matrix of the membrane. The material was evaluated in ionophore free ion exchanger membranes as well as in ion-selective electrodes membranes containing nonactine as ionophore. Analytical performance parameters of the prepared electrodes were evaluated. The electrodes show a slope between 50 and 60 mV dec⁻¹ depending on both the calibration medium and the membrane composition. A linear range of response between 10⁻⁴ and 1.0 M and a lifetime of 1-2 months were obtained. The interferences of cations such us Ca²⁺, Na⁺, Li⁺ and K⁺ over the prepared ISEs are studied as well. Although the plasticizer in the SPEEK based membrane matrix is not necessary, its presence improves the sensibility. This makes SPEEK a good potential choice over alternative membrane matrices reported in the literature and a promising platform for the establishment of membrane components.     

Polyaniline decorated graphene oxide on sulfonated poly(ether ether ketone) membrane for direct methanol fuel cells application

In direct methanol fuel cells (DMFC), methanol crossover is a major issue which has reduced the performance of polymer electrolyte membrane (PEM) for energy generation. In this study, graphene oxide (GO) and conductive polyaniline decorated GO (PANI-GO) were used as additives in fabrication of sulfonated poly(ether ether ketone) (SPEEK) nanocomposite PEM membrane to reduce methanol crossover. PANI-GO was synthesized by in situ polymerization method and the formation of PANI coated GO nanostructures was confirmed by surface morphology and crystallinity analysis. The membrane morphology and topography analysis confirmed that GO and PANI-GO were well dispersed on the surface of SPEEK membrane. 0.1 wt% PANI-GO modified SPEEK nanocomposite membrane exhibited the highest water uptake and ion exchange capacity of 40% and 1.74 meq g^?1, respectively. The oxidative stability of the nanocomposite membranes also improved. Lower methanol permeability of 4.33 × 10^?7 cm^?2S^?1 was noticed for 0.1 wt% PANI-GO modified SPEEK membrane. PANI-GO modified SPEEK membrane enhanced the proton conductivity, which was due to the existence of acidic and hydrophilic group present in PANI and GO. PANI-GO modified SPEEK membrane held higher selectivity of 1.94 × 10⁴ S cm^?3 s^?1. Overall, these studies revealed that PANI-GO modified SPEEK membrane is a potential material for DMFC applications.     

自交联型磺化聚醚醚酮质子交换膜的合成

以含3,3'-二烯丙基双酚 A 结构单元的聚醚醚酮为基膜材料, 通过自由基加成反应在取代基上引入磺酸基团, 合成侧链型磺化聚醚醚酮(SPEEK)质子交换膜. 用傅里叶变换红外(FTIR)光谱、 核磁共振氢谱(¹H NMR)、 热重分析(TG)和扫描电子显微镜(SEM)等方法对 SPEEK 的结构进行表征. 实验结果表明, 巯基丙磺酸被接枝在聚醚醚酮侧基上, SPEEK 膜具有明显的亲水疏水微相分离形貌, 磺酸基团相互聚集形成离子通道. SPEEK 膜离子交换容量为 2.12 mmol/g, 钒离子渗透率为 1.54×10^-6 cm²/min, 低于Nafion117 膜的钒离子渗透率, 阻钒能力优于 Nafion117 膜. 以 SPEEK-4 膜组装电池的自放电时间约为130 h, 长于 Nafion117 膜的 66 h. 电池充放电循环 50 次, SPEEK-4 膜的库仑效率、 电压效率和能量效率没有明显降低, 显示出良好的稳定性.     

Preparation and characterization of nanofiltration membranes by coating polyethersulfone hollow fibers with sulfonated poly(ether ether ketone) (SPEEK)

A new type of nanofiltration membrane is reported based on coating a sulfonated poly(ether ether ketone) (SPEEK) layer on top of a polyethersulfone support. The membranes were characterized by dextran mixtures, salt solutions as well as negatively charged dyes. The SPEEK coated nanofiltration membranes showed molecular weight cutoff for dextran in the range of ultrafiltration, however, rather high rejection for sodium sulfate; retention for salts in the order of RNa₂SO₄>RNaCl>RMgCl₂$R_{\text{N}{\text{a}}_2\text{S}{\text{O}}_4}>R_{\text{NaCl}}>R_{\text{MgC}{\text{l}}_2}$; in addition, the membranes showed a 97–100% retention to the organic dyes. The rejection rates were improved by an increase in the coating thickness and the polymer concentration in the coating solution at the penalty of permeability decrease. Furthermore, it was found that pore penetration of SPEEK into the support membrane effectively constrained the swelling rate of SPEEK and increased the retention. The Donnan–Steric Pore Model was used to describe the transport properties of the membrane. Modeling identified a very tortuous passage within the active separation layer.     

Sulfonated Poly(ether ether ketone) and Poly(ethylene glycol) Diacrylate Based Semi-Interpenetrating Network Membranes for Fuel Cells

Polymer electrolyte membranes are prepared from novel semi-interpenetrating polymer network material where the sulfonated poly (ether ether ketone) (SPEEK) is the linear polymer and the poly (ethylene glycol) diacrylate (PEGDA) is the cross-linking constituent. The semi-IPN is prepared by in situ polymerization of PEGDA in the presence of sulfonated poly (ether ether ketone). SPEEK is prepared by direct sulfonation of commercial PEEK (Gatone? 1100) by reported procedures. SPEEK with degree of sulfonation 63% (calculated from FT-NMR) is selected as the base membrane and different semi-IPN membranes were prepared by varying the PEGDA and SPEEK ratio. The degree of sulfonation of SPEEK and the formation of semi-IPN were confirmed by spectroscopy studies. The various semi-IPN membranes were characterized for ion-exchange capacity, water uptake, hydrolytic stability, proton conductivity and thermal stability for evaluating the suitability of these membranes for fuel cells. The proton conductivity of the membranes decreased with increasing PEGDA content. The Semi-IPN membranes exhibited conductivities (30°C) from 0.018 S/cm to 0.006 S/cm. These interpenetrating network membranes showed higher hydrolytic stability than the pure SPEEK membrane. This study shows that semi-IPN membranes based on PEGDA and SPEEK can be viable candidates for electrolyte membranes.     

Promotion of PEM self-humidifying effect by nanometer-sized sulfated zirconia-supported Pt catalyst hybrid with sulfonated poly(ether ether ketone)

A self-humidifying membrane based on low-cost sulfonated poly (ether ether ketone) (SPEEK) hybrid with sulfated zirconia (SO4(2-)/ZrO2, SZ)-supported platinum catalyst (Pt-SZ catalyst) was investigated for fuel cell applications. The SZ particle, a solid-state superacid with hygroscopic and high proton conductivity properties, was employed as the catalyst support. The SPEEK/Pt-SZ self-humidifying membrane was characterized by TEM and SEM coupled with EDX. FT-IR was conducted to verify the effect of SPEEK/Pt-SZ membrane on catalytic combination of crossover hydrogen and oxygen. To display the advantages of Pt-SZ catalyst as the additive, the IEC, water uptake, proton conductivity, single-cell performance, and areal resistance measurements were compared between the plain SPEEK membrane, SPEEK/Pt-SiO2 membrane, and the SPEEK/Pt-SZ membrane. The SPEEK/Pt-SZ membrane exhibited the highest IEC value, proton conductivity, single-cell performance, and the lowest areal resistance relative to the plain SPEEK and SPEEK/Pt-SiO2 membranes. The SPEEK/Pt-SZ self-humidifying membrane exhibited peak power density of 1.0 W/cm2 under dry operation condition compared with 0.89 W/cm2 and 0.58 W/cm2 of SPEEK/Pt-SiO2 and plain SPEEK membranes, respectively. The incorporation of the catalytic, hygroscopic and proton conductive Pt-SZ catalyst in the SPEEK/Pt-SZ self-humidifying membrane facilitated water balance and proton conduction, and accordingly improved its single cell performance under dry operation. In addition, the enhanced OCV and the decreased areal ohmic resistance confirmed the promotion effect of Pt-SZ catalyst in the self-humidifying membrane on suppressing reactant crossover and the membrane self-humidification.     

Sulfonated montmorillonite/sulfonated poly(ether ether ketone) (SMMT/SPEEK) nanocomposite membrane for direct methanol fuel cells (DMFCs)

A nanocomposite membrane of sulfonated montmorillonite/sulfonated poly(ether ether ketone) (SMMT/SPEEK) is proposed for direct methanol fuel cells (DMFCs). The SMMT is clay modified with silane of which the structure consists of a sulfonic acid group for proton conductivity improvement. The micro- and nano-scaled morphologies of the membranes perform the increase in inorganic aggregation with SMMT loading content as confirmed by SEM and AFM. The membrane stability, i.e., the liquid uptake in water and in methanol aqueous solution, as well as the mechanical stability increases with the SMMT loading content whereas thermal stability does not improve significantly. The methanol permeability reduction is obtained when the SMMT loading content increases for various methanol concentrations (1.5–4.5 M). A comparative study of the SPEEK nanocomposite membranes with SMMT and with pristine MMT shows fourfold proton conductivity enhancement after sulfonation. The DMFC single cell tests inform us that all nanocomposite membranes give the significant performance revealed by the plot of current density–voltage and power density.     

磺化聚醚醚酮/三羧基丁烷膦酸锆复合质子交换膜的研究

通过在磺化聚醚醚酮(SPEEK)中掺杂1,2,4-三羧基丁烷-2-膦酸锆(Zr(PBTC))制备出SPEEK/Zr(PBTC)复合质子交换膜.结果表明,与纯SPEEK膜相比,Zr(PBTC)的掺杂能降低复合膜的吸液量及甲醇透过系数,且随着Zr(PBTC)含量的增加,这种作用越趋明显.在室温至80℃范围内,复合膜的甲醇透过系数在10-7cm2.s-1数量级上,远小于Nafion115膜.在饱和湿度下,当温度大于90℃时,含40wt%Zr(PBTC)的复合膜电导率超过Nafion115膜,并在160℃时达到0.36S.cm-1.使用温度的提高及在高温下的高电导率表明该复合膜适合在高温DMFC中使用.     

可逆加成-断裂链转移自由基聚合法合成梳型磺化聚醚醚酮

以带双硫酯取代基聚醚醚酮为大分子链转移剂, 采用可逆加成-断裂链转移自由基聚合(RAFT)法合成不同接枝率的磺化聚醚醚酮(g-SPEEK), 并对其结构进行表征. 在单体/链转移剂/引发剂的投料比(摩尔比)为50:4:1, 温度为70 ℃, 反应24 h, 得到聚合物膜的离子交换容量和吸水率分别为1.312 mmol/g和43.51%, 其溶胀率为5.05%, 低于Nafion膜的11.50%. 热重分析(TGA)结果表明该梳型g-SPEEK具有较好的热力学稳定性, 且该聚合物膜具有与Nafion膜相当的抗氧化性. 在相同的离子交换容量下, 梳型g-SPEEK比主链型SPEEK具有更好的H⁺离子透过性能.     

Synthesis of the block sulfonated poly(ether ether ketone)s (S-PEEKs) materials for proton exchange membrane

To improve the proton conductivity of sulfonated poly(ether ether ketone)s (SPEEK) with low sulfonated degrees, a series of block SPEEK copolymers were prepared by a two-stage one pot process: first the hydrophobic block was prepared with the desired length, then the monomers for the hydrophilic block were added to the first reactive flask to form block copolymers. Membranes were cast from their DMF solutions, and characterized by determining the ion-exchange capacity, water uptake, proton conductivity and mechanical properties. Block-3 with the longer hydrophobic chain shows enhanced performance than the random one in usage for PEM. SAXS was employed to investigate the microstructure effects on the above properties. Larger ionic cluster size and larger proton transport channel in block-3 SPEEK membranes are detected from the result of SAXS. It is believed that this microstructure feature attributes to the enhanced proton conductivity values of block-3 membrane at low IEC.     

Fabrication of blend hydrophilic polyamide imide (Torlon®)-sulfonated poly (ether ether ketone) hollow fiber membranes for oily wastewater treatment

Blend hydrophilic polyamide imide (PAI)-sulfonated poly (ether ether keton) (SPEEK) hollow fiber membranes were fabricated for oil-water emulsion separation. The structure and performance of the membranes were examined by FESEM analysis, N₂ permeation, overall porosity, collapsing pressure, water contact angle, pure water flux, molecular weight cutoff (MWCO), and oil rejection tests. By studying ternary phase diagrams of polymer/solvent-additive/water system, the higher phase-inversion rate was confirmed for the solutions prepared at higher PAI/SPEEK ratio. A more open structure with larger finger-likes was observed by increasing PAI/SPEEK ratio. Mean pore size of 81 nm, overall porosity of 79% and water contact angle of 58° were obtained for the improved membrane prepared by PAI/SPEEK ratio of 85/15. Increasing SPEEK ratio resulted in lower mechanical stability in terms of collapsing pressure. Pure water flux of about 2.5 times of the plain PAI membrane was found for the improved membrane. MWCO of 460 kDa was found for the improved blend membrane. From oil rejection test, all the membranes demonstrated an oil rejection of over 95%. The improved membrane showed a lower rate of permeate flux reduction compared to the plain membrane which was related to the smaller fouling possibility. Less fouling resistance of the improved membrane was related to the higher flux recovery ratio (about 92%). For all the membranes, the dominant fouling mechanism was found to be the cake filtration. The improved PAI-SPEEK hollow fiber membranes was found to be practical for ultrafiltration of oily wastewaters.