Hybrid Organic/Inorganic Sol-Gel Materials for Proton Conducting Membranes

One important application of hybrid organic-inorganic materials with nano-sized interfaces is the preparation of membranes for Proton Exchange Membrane Fuel Cells (PEMFC) operating at high temperature. Poly (styrene-co-methacrylate)--silica covalent hybrid membranes have been synthesised by copolymerization of monomers (styrene and 2-hydroxyethyl methacrylate), with formation of covalent bonds between hydroxyl group of HEMA and pre-hydrolysed tetraethoxysilane (TEOS). Sulfonation of benzyl groups was applied to endow the membranes of proton conductivity. The incorporation of an inorganic component to a polymeric one modifies properties like thermal, chemical and mechanical stability, and proton conductivity. A compromise between these properties has to be achieved to produce adequate proton conducting membranes with application in PEMFC. The hybrid membrane with 25% SiO₂ combines these properties being a promising candidate for application in PEMFC.     

Preparation and Properties of Hybrid Silane-crosslinked Sulfonated Poly(aryl ether ketone)s as Proton Exchange Membranes

A series of novel organic-inorganic hybrid proton-conducting electrolyte membranes with silane-crosslinked sulfonated poly(aryl ether ketone)(SC-SPAEK) networks was prepared via a simple procedure that includes solution casting and acid treatment. The organosilicon pendants of the silane-grafted SPAEK, which were expected to serve as coupling and crosslinking agents, were found to play a key role in the homogenous dispersion of inorganic particles and improved the performance of hybrid membranes. The hybrid membranes exhibited enhanced proton conductivity, and SC-SPAEK/TiO2-4 showed an extremely high proton conductivity of 0.1472 S/cm at 100℃. The crosslinked hybrid membranes also demonstrated good chemical resistance, oxidative stability, and mechanical properties. The crosslinked hybrid membranes with excellent comprehensive performance may be a promising material for proton exchange membrane fuel cells.     

有机-无机杂化膜的研究进展

有机-无机杂化膜由于具备了无机膜和有机膜各自的特点,具有良好的分离特性和物化稳定性,因而成为当前膜技术领域新型膜材料研究的热点.本文主要介绍了近年来国内外有机-无机杂化膜的研究现状、杂化膜的制备方法、结构和应用.     

Hybrid organic-inorganic nanostructured membranes for high temperature proton exchange membranes fuel cells (PEMFC)

Compared to internal combustion engines, proton-exchange membrane fuel cells (PEMFC) operate with zero emissions of environmental pollutants being this an adequate choice for transportation field. The increase of the operation temperature of PEMFC above 130°C is a great concern for the commercial application of the cells in electric vehicles. Hybrid organic-inorganic nanostructured membranes can combine the main properties to meet this objective: high proton conductivity along with thermal and chemical stability. The possibilities of synthesis of these hybrid structures grow exponentially with the combination of sol-gel chemistry and monomers. Three different approaches have been followed for obtaining hybrid membranes that present the properties needed for application in high temperature PEMFC: development of methacrylate and epoxy structures, and optimization of the inorganic component incorporating phosphorus. Proton conductivity has been endowed on the base of three strategies: a high concentration of hydroxyl groups from inorganic component, groups through sulfonation of phenyl rings, and incorporation of tungstophosphoric acid, H₃[P(W₃O₁₀)₄].     

A Light‐Responsive Metal–Organic Framework Hybrid Membrane with High On/Off Photoswitchable Proton Conductivity

Mimicking biological proton pumps to achieve stimuli‐responsive protonic solids has long been of great interest for their diverse applications in fuel cells, chemical sensors, and bio‐electronic devices. Now, dynamic light‐responsive metal–organic framework hybrid membranes can be obtained by in situ encapsulation of photoactive molecules (sulfonated spiropyran, SSP), as the molecular valve, into the cavities of the host ZIF‐8. The configuration of SSP can be changed and switched reversibly in response to light, generating different mobile acidic protons and thus high on/off photoswitchable proton conductivity in the hybrid membranes and device. This device exhibits a high proton conductivity, fast response time, and extremely large on/off ratio upon visible‐light irradiation. This approach might provide a platform for creating emerging smart protonic solids with potential applications in the remote‐controllable chemical sensors or proton‐conducting field‐effect transistors.     

有机-无机杂化分离膜研究进展

有机-无机杂化膜材料结合了有机膜材料和无机膜材料的优良性能,已成为分离膜材料研究的一个热点。本文以有机、无机组分间相互作用类型对其进行分类,着重介绍组分间以化学键相结合的有机-无机杂化膜的优良特性,总结了影响此类杂化膜结构和性能的主要因素,概括了它在膜分离中的应用,提出了目前研究工作中存在的不足,并做出了简要的述评。     

Crosslinking effects on hybrid organic–inorganic proton conducting membranes based on sulfonated polystyrene and polysiloxane

New hybrid semi‐interpenetrating proton‐conducting membranes were obtained using sulfonated polystyrene (SPS) and inorganic–organic polysiloxane phases with the aim of improving the mechanical and thermal characteristics of the pristine polymer and to study the effects of crosslinking in the latter phase in several of their properties, mainly proton conductivity. Siloxane phases were prepared using poly(dimethylsiloxane) (PDMS) and PDMS with tetraethoxysilane (TEOS) or phenyltrimethoxysilane (PTMS) as crosslinking agents. To study the crosslinking effect, membranes were prepared with different TEOS:PDMS and PTMS:PDMS mole ratios. The films obtained were characterized by FTIR, ²⁹Si‐HPDEC MAS‐NMR, ¹³C‐CP‐MAS NMR, elemental and thermal analyses. Certain properties, such as water uptake (WU), ion exchange capacity (IEC) and the state of the water, were determined. The proton conductivity was measured at different temperatures (30°C and 80°C) and relative humidities (50–95%). The water content of the hybrid membranes declined significantly, compared with the SPS membranes, depending on the nature and amount of siloxane phase added. Nonetheless, the conductivity values remained relatively high (>100 mS cm^?1 at 80°C and 95% RH) when compared to Nafion®117 presumably because of the formation of well developed proton channels, which makes them potentially promising as proton exchange membranes for fuel cells. These membranes proved to be thermally stable up to 350°C. Scanning electron microscopy (SEM) and scanning electrochemical microscopy (SECM) were used to characterize the hybrid membranes microstructures; the latter provided contrast for the conductive domains. Copyright © 2015 John Wiley & Sons, Ltd.     

有机-无机杂化膜的研究进展

有机-无机杂化膜结合了传统有机膜与无机膜的优良性能,已成为膜领域的研究热点之一。本文综述了有机-无机杂化膜的研究现状,归纳了有机-无机杂化膜的分类、制备技术、应用及其优越性,并针对现存的问题及今后的研究发展提出了一些建议。     

Hybrid Organic–Inorganic Thermoelectric Materials and Devices

Hybrid organic–inorganic materials have been considered as a new candidate in the field of thermoelectric materials since the last decade owing to their great potential to enhance the thermoelectric performance by utilizing the low thermal conductivity of organic materials and the high Seebeck coefficient, and high electrical conductivity of inorganic materials. Herein, we provide an overview of interfacial engineering in the synthesis of various organic–inorganic thermoelectric hybrid materials, along with the dimensional design for tuning their thermoelectric properties. Interfacial effects are examined in terms of nanostructures, physical properties, and chemical doping between the inorganic and organic components. Several key factors which dictate the thermoelectric efficiency and performance of various electronic devices are also discussed, such as the thermal conductivity, electric transportation, electronic band structures, and band convergence of the hybrid materials.     

Proton Conducting Organic/Inorganic Sol–Gel Membranes Produced from Phenyltriethoxysilane and 3-Methacryloxypropyl Trimethoxysilane

The increase of the operation temperature in Proton Exchange Membrane Fuel Cells (PEMFC) above 100^∘C would be an important breakthrough for the application of this type of fuel cell in electric vehicles. Hybrid organic-inorganic membranes with nano-sized interfaces can combine all the properties to meet this objective. Membranes using phenyltriethoxysilane and 3-methacryloxypropyl trimethoxysilane have been synthesised by polymerisation of methacrylate groups and inorganic condensation of silanol groups. Sulfonation process to provide proton conductivity affects both proton conductivity and chemical stability of hybrid membranes. Liquid sulfonation during the sol preparation and chlorosulfonic acid as sulfonating agent leads to chain cleavage while trimethylsilyl chlorosulfonate does not affect the polymer backbone. The increase of temperature (up to 120–130^∘C) and relative humidity leads to an increase of proton conductivity close to 10^{− 3} S/cm.     

Preparation and characterization of inorganic–organic hybrid proton exchange membranes based on phosphorylated PVA and PEG-grafted silica particles

We reported proton-conducting membranes with novel microstructure based on partially phosphorylated poly(vinyl alcohol) (P-PVA) and polyethylene glycol (PEG) grafted silica (PEG-SiO₂) particles. The PEG-SiO₂ particles were synthesized through acid catalyzed hydrolysis and condensation reactions. The membranes were characterized for their mechanical, structural, morphological, and electrical properties by employing tensile test, Fourier transform infrared (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), impedance analyzer, respectively. In these membranes, P-PVA acts as the proton source and PEG act as the proton solvent. The PEG-riched phases in the hybrid membrane form continuous ionic conducting pathways and subsequently give high ionic conductivity. The results suggest that the obtained membrane shows good thermal stability, excellent mechanical property and high ionic conductivity, and the low-cost hybrid membrane can be a promising candidate for intermediate temperature fuel cell systems.     

Fabrication and proton conductivity of sulfonated silica composites prepared by postoxidization of mercaptomethoxysilane

Sol–gel derived organic–inorganic hybrids containing phosphotungstic acid (PWA) have been prepared previously to obtain proton conductive membranes. However, leaking of PWA was a serious problem to achieve the higher proton conductivity. In this study, polyelectrolyte membranes functionalized with sulfonic acid groups were fabricated by the sol–gel method. Proton conductivity measurements were performed on an impedance analyzer at 80°C/95% RH. The functionalized polyelectrolyte membranes exhibited the proton conductivity σ ～ 0.9 (S/cm) which was much higher than the previously reported hybrids containing PWA. Although the hybrids exhibited fairly high proton conductivity irrespective to the catalysts used, that under the low relative humidity strongly depends on the catalysts. Among the hybrids prepared in this study, the membrane synthesized with HCl showed outstanding proton conductive properties even at the low humidity thanks to the proton transport channel formed by the swelling of ionic clusters. This fact was confirmed by measuring the ion exchange capacity, water uptake, swelling rate, Fourier transform infrared spectroscopy, atomic force microscopy, and thermogravimetric analysis. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A Light-Responsive Metal–Organic Framework Hybrid Membrane with High On/Off Photoswitchable Proton Conductivity

Mimicking biological proton pumps to achieve stimuli-responsive protonic solids has long been of great interest for their diverse applications in fuel cells, chemical sensors, and bio-electronic devices. Now, dynamic light-responsive metal–organic framework hybrid membranes can be obtained by in situ encapsulation of photoactive molecules (sulfonated spiropyran, SSP), as the molecular valve, into the cavities of the host ZIF-8. The configuration of SSP can be changed and switched reversibly in response to light, generating different mobile acidic protons and thus high on/off photoswitchable proton conductivity in the hybrid membranes and device. This device exhibits a high proton conductivity, fast response time, and extremely large on/off ratio upon visible-light irradiation. This approach might provide a platform for creating emerging smart protonic solids with potential applications in the remote-controllable chemical sensors or proton-conducting field-effect transistors.     

Preparation and characterization of crosslinked PVA/SiO2 hybrid membranes containing sulfonic acid groups for direct methanol fuel cell applications

Organic–inorganic hybrids based on poly(vinyl alcohol) (PVA)/SiO₂ hybrid membranes containing sulfonic acid groups were prepared using the sol–gel process under acidic conditions. The PVA/sulfosuccinic acid (SSA)/silica hybrid membranes were fabricated from different SSA contents. The proton conductivity and methanol permeability of the hybrid membranes were studied with changing SSA content from 5 to 25 wt.%. It was found that the proton conductivity and the methanol permeability were dependent on the SSA content both as a crosslinking agent, and as a donor of the hydrophilic SO₃H group. Up to an SSA content of about 20 wt.%, both of these properties decrease, and above this SSA content, they begin to increase with increasing SSA content. The proton conductivities of the PVA/SSA/silica membranes were in the range of 10⁻³ to 10⁻² S/cm, and the methanol permeabilities ranged between 10⁻⁸ and 10⁻⁷ cm²/s. The presence of silica particles in the organic polymer matrix, which reduce the free water ratio of the membranes, results in hybrids with markedly reduced methanol permeabilities. These characteristics of the PVA/SSA/silica hybrid membranes are desirable for future applications related to direct methanol fuel cells.     

Sulfonic and Phosphonic Acid and Bifunctional Organic–Inorganic Hybrid Membranes and Their Proton Conduction Properties

Hybrid organic–inorganic approaches are used for the synthesis of bifunctional proton exchange membrane fuel cell (PEMFC) membranes owing to their ability to combine the properties of a functionalized inorganic network and an organic thermostable polymer. We report the synthesis of both sulfonic and phosphonic acid functionalized mesostructured silica networks into a poly(vinylidenefluoride‐co‐hexafluoropropylene) (poly(VDF‐co‐HFP) copolymer. These membranes, containing different amounts of phosphonic acid and sulfonic acid groups, have been characterized using FTIR and NMR spectroscopy, SA‐XRD, SAXS, and electrochemical techniques. The proton conductivity of the bifunctional hybrid membranes depends strongly on hydration, increasing by two orders of magnitude over the relative humidity (RH) range of 20 to 100 %, up to a maximum of 0.031 S cm⁻¹ at 60 °C and 100 % RH. This value is interesting as only half of the membrane conducts protons. This approach allows the synthesis of a porous SiO₂ network with two different functions, having  SO₃H and  PO₃H₂ embedded in a thermostable polymer matrix.     

Synthesis,characterization, and proton‐conducting properties of organic–inorganic hybrid membranes based on polysiloxane zwitterionomer

The synthesis and characterization of a series of zwitterionic hybrid membranes based on a zwitterionic siloxane precursor (ZS) are described. Flexible, transparent, optically homogeneous films were prepared. With the further incorporation of poly(ethylene glycol) (PEG), the hybrid films became more flexible but translucent. The structure of the inorganic sides was probed with solid‐state ²⁹Si NMR spectroscopy, and the organic sides and the chemical process involved were characterized with solid‐state ¹³C cross‐polarization/magic‐angle spinning NMR. A higher content of ZS led to higher proton conductivity of the hybrid electrolytes. Moreover, the proton conductivity was enhanced by the addition of the plasticizing component of PEG to the hybrid matrix; this was ascribed to the increased water uptake and free volume of the hybrid matrix and the dissociation of sulfonic acid groups. The proton conductivity of these hybrid membranes could be increased up to 3.5 × 10^?2 S/cm by the temperature and relative humidity being increased to 85 °C and 95%, respectively. The proton‐conduction behavior of these hybrid membranes is also briefly discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3444–3453, 2006     

Chemically stable hybrid polymer electrolyte membranes prepared by radiation grafting,sulfonation, and silane‐crosslinking techniques

To prepare a crosslinked hybrid polymer electrolyte membrane (PEM) with high chemical stability, a silane monomer, namely p‐styryltrimethoxysilane (StSi), was first grafted to poly(ethylene‐co‐tetrafluoroethylene) (ETFE) film by γ‐ray preirradiation. Hydrolysis‐condensation and sulfonation were then performed on the StSi‐grafted ETFE (StSi‐g‐ETFE) films to give them crosslinks and proton conductibility, respectively. Thus, a crosslinked proton‐conducting hybrid PEM was obtained. The crosslinks introduced by the silane‐condensation have an inorganic ? Si? O? Si? structure, which enhance the chemical and thermal stabilities of the PEM. The effect of the timing of the hydrolysis‐condensation (before or after sulfonation) and the sulfonation method (by chlorosulfonic acid or H₂SO₄) on the properties of the resulting hybrid PEMs such as ion‐exchange capacity, proton conductivity, water uptake, chemical stability, and methanol permeability were investigated to confirm their applicability in fuel cells. We conclude that the properties of the new crosslinked hybrid StSi‐grafted PEMs are superior to divinylbenzene (DVB)‐crosslinked styrene‐grafted membranes. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5559–5567, 2008     

Highly Stable,Low Gas Crossover,Proton‐Conducting Phenylated Polyphenylenes

Two classes of novel sulfonated phenylated polyphenylene ionomers are investigated as polyaromatic‐based proton exchange membranes. Both types of ionomer possess high ion exchange capacities yet are insoluble in water at elevated temperatures. They exhibit high proton conductivity under both fully hydrated conditions and reduced relative humidity, and are markedly resilient to free radical attack. Fuel cells constructed with membrane‐electrode assemblies containing each ionomer membrane yield high in situ proton conductivity and peak power densities that are greater than obtained using Nafion reference membranes. In situ chemical stability accelerated stress tests reveal that this class of the polyaromatic membranes allow significantly lower gas crossover and lower rates of degradation than Nafion benchmark systems. These results point to a promising future for molecularly designed sulfonated phenylated polyphenylenes as proton‐conducting media in electrochemical technologies.     

SPEEK-zirconium hydrogen phosphate composite membranes with low methanol permeability prepared by electro-migration and in situ precipitation

Sulfonated poly(ether ether ketone) (SPK)-zirconium hydrogen phosphate (ZrP) composite membranes were prepared by electro-driven migration of Zr(4+) and simultaneous in situ precipitation of ZrP using phosphoric acid under different electrical gradient, in order to avoid loss in its mechanical stability. Degree of sulfonation was estimated from (1)H NMR and ion-exchange capacity study that was found to be 61% and 57%, respectively. In this method Zr(4+) and HPO(4)(2-) were allowed to diffuse within the pores/channels of the preformed SPK membrane under given electrical gradient and ZrP was precipitated within the membrane matrix. ZrP loading density was measured as a function of applied electrical gradient for a definite reaction time (4 h) and electrolytic environment. Membranes with varied ZrP loading densities were characterized for their thermal and mechanical stabilities, physicochemical and electrochemical properties using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), water content, proton conductivity and methanol permeability. No loss in thermal and mechanical stability of membranes was observed due to incorporation of inorganic component (ZrP) in the membrane matrix. Although the composite membranes exhibited low proton conductivity in comparison to SPK membrane at room temperature, but the presence of the inorganic particles led to an improvement in high temperature conductivity. Selectivity parameter of these composite membranes was estimated at two temperatures namely 30 and 70 degrees C, in latter case it was found significantly higher than that for Nafion membrane (0.79 x 10(5) S s cm(-3)) under similar experimental conditions.     

Combination of Organic and Inorganic Electrolytes for Composite Membranes Toward Applicable Solid Lithium Batteries

To meet the demand for long-range electric vehicles with high-energy-density batteries,the solid-state batteries(SSBs)have attracted ever-increasing attention due to their enormous potential in affording the energy density greater than 400 W·h/kg.As the key materials,the solid electrolytes can be classified as inorganic electrolyte and organic electrolyte.The former usually has high ionic conductivity,good stability and mechanical properties,whereas being heavy and brittle.The latter is usually flexible,light and easy to mass produce,nevertheless has poor ionic conductivity and stability.Thus,the combination of the organic and the inorganic electrolytes for the composite membranes has become the inevitable trend to achieve the high energy density and safety of lithium batteries.From the perspective of practical application,this paper discusses how to construct the ideal organic-inorganic composite solid electrolyte with low areal specific resistance,thin texture,wide electrochemical window and high safety for applicable SSBs.Furthermore,the critical challenges and future development directions are prospected for the composite solid electrolytes.