An extensive SAXS investigation of the 3M perfluorinated sulfonic acid ionomer was performed to investigate the morphological changes that occur during and after annealing at temperatures above the T α. The effect of film thickness in the range studied, 11–45 μm, was found to be negligible. These properties were studied as a function of equivalent weight from 700 to 1100 and correlated with the water uptake as measured by dynamic vapor sorption. Isoscattering points were observed in dynamic annealing experiments of the unboiled annealed films at q = 0.023, 0.096 Å–1. On initial water uptake these films also showed isoscattering points at q = 0.024, 0.220 Å–1; q = 0.029, 0.223 Å–1; and q = 0.030, 0.211 Å–1 at 50, 80, or 95 °C, respectively, indicating a decrease in the symmetry of the scattering objects in these size regimes. Isoscattering points were absent in similar water uptake experiment for the films after boiling.

a b s t r a c tAnion exchange membranes (AEM) are promising solid polymer electrolytes utilized in alkali fuel cells and electrochemical energy conversion devices. AEMs must efficiently conduct ions while maintaining chemical and mechanical stability under a range of operating conditions. The ionic nature of AEMs leads to stiff and brittle membranes under dry conditions while at higher hydrations, water sorption causes significant softening and weakening of the membrane. In this work, a new polyethylene-b-poly(vinylbenzyl trimethylammonium) polymer (70 kg/mol) was cast into large (300 cm 2 ), thin (12 7 3 μm) membranes. These membranes exhibited improved elasticity over previously tested AEMs, minimal dimensional swelling, and moderate ionic conductivity (5 7 2 mS/cm at 50°C, 95% RH in the bromide form). Extensional testing indicated a 95% reduction in Young's modulus between dry and hydrated states. Further investigation of the complex modulus as a function of hydration, by dynamic mechanical analysis, revealed a sharp decrease in modulus between dry and hydrated states. Mechanical softening was reversible, but the location of the transition displayed hysteresis between humidification and dehumidification. Conductivity increased after membrane softening; suggesting bulk mechanical properties can identify the hydration level required for improved ion transport. Understanding the relationship between ion conduction and mechanical properties will help guide AEM development and identify operating conditions for sustained performance.

Alkali anion exchange membrane (AEM) based devices have the potential for electrochemical energy conversion using inexpensive catalysts and a variety of fuel types. Membrane stability and anion transport must be improved in AEMs before these devices can be fully realized. Mechanical failure of the membrane can contribute to failure of the device, thus membrane durability is critical to overall system design. Here, a study of the mechanical properties of three well-established AEMs uses a modified extensional rheometer platform to simulate tensile testing using small membrane samples. Mechanical properties were tested at 30 and 60 • C under dry or water saturated gas conditions. Water in the membrane has a plasticizing effect, softening the membrane and reducing strength. PEEK membrane reinforcement limits swelling producing negligible softening and only a 9% decrease in strength from dry to hydrated conditions at 30 • C. Higher cation concentration increases water uptake resulting in significant softening, a 57% reduction in Young's modulus, and a 67% reduction in strength when hydrated at 30 • C. In a working electrochemical device, AEMs must maintain integrity over a range of temperatures and hydrations, making it critical to considering mechanical properties when designing new membranes. Polymer electrolyte membrane fuel cells and electrolyzers are potentially disruptive technologies that will replace traditional heat engines such as internal combustion engines for transportation applications, portable electronics, and are scalable to larger energy storage facilities. Polymer electrolyte membrane fuel cells are suitable for transportation applications due to their low temperature start-up and operation, high power density, and quick refueling.1-3 Proton exchange membranes (PEMs) have dominated polymer electrolyte membrane fuel cell development in the last several decades, resulting in the development of relatively stable, well performing membranes.1-4 Current PEM fuel cells remain cost prohibitive due to high catalysts costs, as well as long-term durability issues. 3,5,6 Anion exchange membranes (AEMs) can also be utilized in polymer electrolyte membrane devices and have several potential benefits over PEMs. AEM fuel cells benefit from increased kinetics in an alkali media allowing more complex fuels then hydrogen and have the potential to utilize non-platinum catalysts to reduce costs. 7-11However, a number of challenges must be overcome before AEMs reach the performance and durability necessary for fuel cells and other electrochemical energy conversion devices. Hydroxide present in the AEM degrades many of the proposed cationic groups and some polymer backbones, making development of chemically stable AEMs difficult. 9,11,12 Additionally, transport of hydroxide in AEMs is inherently slower than protons in PEMs, 13 to compensate, the concentration of ionic groups is often increased in AEMs.8 Increasing ion concentration in AEMs increases water sorption in the polymer and can result in significant dimensional...

An alkaline exchange membrane (AEM) based on an aminated trimethyl poly(phenylene) is studied in detail. This article reports hydroxide ion conductivity through an in situ method that allows for a more accurate measurement. The ionic conductivities of the membrane in bromide and carbonate forms at 90 °C and 95% RH are found to be 13 and 17 mS cm−1 respectively. When exchanged with hydroxide, conductivity improved to 86 mS cm−1 under the same experimental conditions. The effect of relative humidity on water uptake and the SAXS patterns of the AEM membranes were investigated. SAXS analysis revealed a rigid aromatic structure of the AEM membrane with no microphase separation. The synthesized AEM is shown to be mechanically stable as seen from the water uptake and SAXS studies. Diffusion NMR studies demonstrated a steady state long‐range diffusion constant, D∞ of 9.8 × 10−6 cm2 s−1 after 50–100 ms. © 2012 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1743–1750, 2013

Anion exchange membranes (AEM) are solid polymer electrolytes that facilitate ion transport in fuel cells. In this study, a polystyrene-b-poly(vinylbenzyl trimethylammonium) diblock copolymer was evaluated as potential AEM and compared with the equivalent homopolymer blend. The diblock had a 92% conversion of reactive sites with an IEC of 1.72 6 0.05 mmol g 21 , while the blend had a 43% conversion for an IEC of 0.80 6 0.03 mmol g 21 . At 50 C and 95% relative humidity, the chloride conductivity of the diblock was higher, 24-33 mS cm 21 , compared with the blend, 1-6 mS cm 21 . The diblock displayed phase separation on the length scale of 100 nm, while the blend displayed microphase separation ($10 lm). Mechanical characterization of films from 40 to 90 microns thick found that elasticity and elongation decreased with the addition of cations to the films. At humidified conditions, water acted as a plasticizer to increase film elasticity and elongation. While the polystyrene-based diblock displayed sufficient ionic conductivity, the films' mechanical properties require improvement, i.e., greater elasticity and strength, before use in fuel cells.

Ion exchange membranes are a promising class of materials for use in fuel cells, barrier layers, and water splitting devices. While the majority of research related to anion exchange membranes is on improving the chemical stability and increasing ionic conductivity, the mechanical performance under relevant operating conditions is vital to device lifetime. Using tensile testing and humidity cycling, we report the mechanical performance of Nafion 115, polyethylene-b-polyvinyl benzyl trimethylammonium diblock copolymer (PEb-PVBTMA), poly[t-butyl styrene-b-hydrogenated isoprene-b-vinyl benzyl trimethylammonium-b-hydrogenated isoprene-b-t-butyl styrene] (QP43), and aminated tetramethyl polyphenylene (ATMPP). Nafion 115 serves as a well-studied material to compare with the developmental anion exchange membranes. A home-built environmental chamber attached to a rheometer was utilized to perform all measurements under elevated temperature and relative humidity conditions. Standard mechanical properties are important to understanding membrane performance, but a simple metric comparing the mechanical elongation in a dry condition with the in-plane swelling percentage in liquid water can be used to predict how membranes will perform under hygral cycling. While chemical degradation remains a significant issue for membrane stability in anion exchange membranes (AEMs), mechanical stability is also an integral factor in fuel cell lifetime.1 The polymer needs to be processed into thin, durable membranes and withstand the stresses inside a fuel cell at operating conditions. Microcracks formed from repeated hydration and dehydration cycles in a fuel cell are the most common form of mechanical failure. Several attempts have been made to correlate mechanical failure with a common mechanical property, such as elongation at break 2,3 or Young's modulus and yield strength. 4 Cycling the humidity correlated well with a reduction in the strain at failure even though the yield stress and yield strain remained largely unchanged. 3Most of the available literature on mechanical properties of ion conducting polymer membranes is limited to stress-strain curves in various states of hydration. [5][6][7][8] Tensile strength and Young's modulus decrease as the polymer absorbs water. The elongation at break increases due to plasticizing effect of the absorbed water.7 Also noted by Marestin et al. 5 is the lack of a comprehensive study of mechanical properties including the combined effect of water content and temperature. Custom environmental chambers built around a mechanical tester are common for detailed exploration of properties at different humidities, 9-11 and the testing is usually performed at a constant temperature and relative humidity; time dependence is not considered. Bauer et al. investigated the dynamic mechanical response to Nafion 117 under different temperature and relative humidity conditions, concluding water acts as a plasticizer at lower temperatures, but stiffens the membrane at higher temperatures.11 Creep measurements are...

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Anion exchange membranes (AEMs) are a promising class of materials for applications that require selective ion transport, such as fuel cells, water purification, and electrolysis devices. Studies of structure–morphology–property relationships of ion‐exchange membranes revealed that block copolymers exhibit improved ion conductivity and mechanical properties due to their microphase‐separated morphologies with well‐defined ionic domains. While most studies focused on symmetric diblock or triblock copolymers, here, the first example of a midblock quaternized pentablock AEM is presented. A symmetric ABCBA pentablock copolymer was functionalized to obtain a midblock brominated polymer. Solution cast films were then quaternized to obtain AEMs with resulting ion exchange capacities (IEC) ranging from 0.4 to 0.9 mmol/g. Despite the relatively low IEC, the polymers were highly conductive (up to 60 mS/cm Br− at 90 °C and 95%RH) with low water absorption (<25 wt %) and maintained adequate mechanical properties in both dry and hydrated conditions. X‐ray scattering and transmission electron microscopy (TEM) revealed formation of cylindrical non‐ionic domains in a connected ionic phase. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 612–622