Session S33: Ion Containing Polymer Membranes

Proton conducting, high modulus polymer electrolyte membranes by polymerization-induced microphase separation

Robust solid-state polymer electrolyte membranes (PEMs) are vital for designing next-generation lithium-ion batteries and high-temperature fuel cells. However, the performance of diblock polymer electrolytes is generally limited by poor mechanical stability and network defects in the conducting pathways. We present the \textit{in-situ} preparation of robust cross-linked PEMs via polymerization-induced microphase separation, and incorporation of protic ionic liquid (IL) into one of the microphase separated domains. The facile design strategy involves a delicate balance between the controlled growth of polystyrene from a poly(ethylene oxide) macro-chain transfer agent (PEO-CTA) and simultaneous chemical cross-linking by divinylbenzene in the presence of IL. Small angle X-ray scattering and transmission electron microscopy confirmed the formation of a disordered structure with bicontinuous morphology and a characteristic domain size of order 20 nm. The long-range continuity of the PEO/protic IL conducting nanochannels and cross-linked polystyrene domains imparts high thermal and mechanical stability to the PEMs, with elastic modulus approaching 10 MPa and a high ionic conductivity of 15 mS/cm at 180 \textdegree C.   

The role of tortuosity on ion conduction in block copolymer electrolyte thin films

This talk discusses the role of grain tortuosity on ion conductivity in block copolymer electrolyte (BCE) thin films. In particular, we studied lamellae forming BCEs with both domains oriented perpendicular to the substrate surface and connected directly from one electrode to another -- i.e., tortuosity of one. The BCE is composed of ion-conducting, poly(2-vinyl n-methylpyridinium) blocks and non-ionic polystyrene blocks. Prior to creating the BCE, the pristine block copolymer, poly(styrene-$b$-2-vinyl pyridine), was directly self-assembled (DSA) on topographical or chemical patterns via graphoepitaxy and chemoepitaxy. A chemical vapor infiltration reaction modified the P2VP block into positively charged, fixed quaternary ammonium groups paired with mobile counteranions. The graphoepitaxy process utilized topographical interdigitated gold nanoelectrodes (100s of nanometers spacing between electrodes) created via e-beam lithography. Alternatively, chemical patterns had gold electrodes incorporated into them with 10s to 100s of microns spacing using conventional optical lithography. The interdigitated gold electrodes enabled in-plane ion conductivity measurements of the DSA BCEs to study the role of grain tortuosity on ion conductivity.   

Building non-tortuous ion-conduction pathways using self-assembled block copolymers

Ion-containing polymers with self-assembled morphologies are becoming important ingredients of a wide range of electrochemical devices such as lithium-ion batteries, fuel cells and electroactive actuators. Although several studies have reported the relationship between morphologies and ion transport properties of such polymers, the most of quantitative analysis have been limited to two-dimensional morphologies as they occupy a large window of the phase diagrams. In present study, we investigated the effects of morphology on the ion transport efficiency with a focus on three-dimensional symmetry. A range of three-dimensional self-assembled morphologies, i.e., ill-defined cubic, orthorhombic network (O$^{\mathrm{70}})$, and face-centered cubic phases (fcc) were achieved for a single sulfonated block copolymer upon the addition of non-stoichiometric ionic liquids. The type of three-dimensional lattice was found out to play a crucial role in determining the ion transport properties of composite membranes, where the most efficient ion-conduction was demonstrated for fcc phases with lowest tortuosity of 1 over orthorhombic networks phases (tortuosity:1.5). This intriguing result suggests a new avenue to designing polymer electrolytes with improved transport properties.   

Nanostructured anion conducting block copolymer electrolyte thin films

Lamellae forming block copolymer electrolyte (BCE) thin-films with perpendicular aligned orientation were registered with high fidelity over large areas via a self-assembly process followed by a novel chemical vapor infiltration reaction (CVIR) technique. In this scheme, poly(styrene-$b$-2-vinyl pyridine) (PS$b$P2VP) block copolymers were self-assembled with perpendicular orientations on neutral chemical brushes using solvent vapor annealing. The ionic groups were selectively introduced into the P2VP block via a Menshutkin reaction that converted the nitrogen in the pyridine to n-methylpyridinium - anion carrier groups. FTIR-ATR and XPS tools confirmed the formation of the aforementioned ionic moieties post CVIR process and structure imaging tools (e.g., SEM and AFM imaging, GI-SAXS and RSOXs) established that incorporation of the ionic groups did not alter the self-assembled nanostructured films nor did subsequent ion-exchange processes. Electrochemical impedance spectroscopy determined the in-plane ion conductivity of different counteranions in the BCE thin films and alteration to the symmetry of the block copolymer film substantially improved (or hindered) BCE ion conductivity if the P2VP block's volume fraction was slightly greater than (or less than) 0.5.   

Surface Structure of Thin Films of Multifunctional Ionizable Copolymers

Phase segregation results in a rich variety of structures in co-polymers where interfacial forces often dominate the structure of thin films. Introduction of ionizable segments often drives the formation of compounded structures with multiple blocks residing at the interfaces. Here we probe thin films, 40-50nm, of an A-B-C-B-A co-polymer where C is a randomly sulfonated polystyrene with sulfonation fractions of 0, 26 and 52 mole {\%}, B is poly (ethylene-r-propylene), and A is poly (t-butyl styrene) as the sulfonation level and temperature are varied using Neutron Reflectivity AFM, and surface tension measurements. As cast films form layers with both hydrophobic blocks dominating the solid and air interfaces and the ionizable block segregating to the center. Following annealing at 170$^{0}$C, above Tg of styrene sulfonate, the films coarsen, with surface aggregation dominating the structure, though interfacial regions remain dominated by the hydrophobic segments. We show that in contrast to non-ionic co-polymers, formation of micelles dominated the structure of these ionic structured films.   

Effects of repeated wet/dry cycling on the structure and performance of sulfonated pentablock copolymer membranes.

Sulfonated block copolymers have shown potential as membranes for water purification. However, the performance of these materials under cyclic wet/dry conditions is not well understood. We measured the membrane structure, mechanical properties, and water vapor transport rates in a sulfonated pentablock copolymer as a function of the number of wet/dry cycles. The polymer is synthesized with an ABCBA block sequence, where A is poly(t-butyl styrene), B is poly(hydrogenated isoprene), and C is poly(styrene sulfonate). The ion exchange capacity is 2 meq, and membranes were prepared by coating from a solution. Using small angle X-ray scattering, we find the structure in as-prepared membranes resembles disordered micelles, and the characteristic length scale swells slightly with each wet/dry cycle. This lattice swelling is likely constrained by the glassy end-blocks. We also detect a lower yield point and less overall tensile strength with repeated cycling. Water vapor transport rates vary with the number of wet/dry cycle, however no specific trend was observed.   

Influence of Substrate on PFSA Thin-Film Morphology

Perfluorosulfonic-acid (PFSA) ionomers are the most commonly used electrolyte for polymer-electrolyte fuel cells (PEFCs) due to their high conductivity and good electrochemical and thermo-mechanical stability. A PFSA's chemical structure is comprised of a polytetrafluoroethylene (PTFE) backbone that provides mechanical and chemical stability, and randomly placed tethered perfluoroether side chains terminated with sulfonic-acid groups, which impart its remarkable proton-conduction capabilities. Controlled by substrate/film interactions, long-range structural order in PFSAs change when confined to thin films (\textless 200 nm), as does its transport and mechanical properties. The nature of change is substrate dependent, where stronger interactions create a more dramatic change in properties. In this talk, grazing-incidence c-Ray scattering (GIXS) is used to demonstrate induced structural order on metallic substrates, which is not present on other substrates like silicon and carbon. The higher degree of ordering is correlated with measured changes in mechanical properties for the thin films. Scattering data is also modeled using the recently released program high-performance GISAXS (HipGISAXS), to estimate the size and distribution of the ordered domains. -/a   

Structure and Properties of a Semi-crystalline Cationic Polymer for Anion Exchange Membranes

Nafion has long been studied in order to understand its combination of good mechanical properties, chemical resistance, and excellent charge transport characteristics. In the past decade, uncertainty regarding the morphological behavior of Nafion has largely been resolved, allowing researchers to mimic and improve on the structure of this material. In this presentation, work to incorporate key characteristics of Nafion into a model cation-containing polymer will be described. In these new materials, semi-crystalline atactic poly(norbornene) is used to introduce good mechanical properties to anion-exchange membranes, analogous to the PTFE crystallites in Nafion. The ether linkages between the charged species and backbone are also utilized to place the cationic species (trimethylamine) in our materials into a mechanically soft environment. The resulting polymer shows some characteristics that are similar to those of Nafion. In this presentation, the synthesis, alkaline stability, mechanical properties, morphological behavior and charge transport properties will all be described.   

Exploring the Parameters Controlling the Crystallinity-Conductivity Correlation of PFSA Ionomers

Perfluorosulfonic-acid (PFSA) ionomers are the most commonly used solid-electrolyte in electrochemical energy devices because of their remarkable conductivity and chemical/mechanical stability, with the latter imparted by their semi-crystalline fluorocarbon backbone. PFSAs owe this unique combination of transport/stability functionalities to their phase-separated morphology of conductive hydrophilic ionic domains and the non-conductive hydrophobic backbone, which are connected via pendant chains. Thus, phase-separation is governed by fractions of backbone and ionic groups, which is controlled by the equivalent weight (EW). Therefore, EW, along with the pendant chain chemistry, directly impact the conductive vs non-conductive regions, and consequently the interrelation between transport and stability. Driven by the need to achieve higher conductivities without disrupting the crystallinity, various pendant-chain chemistries have been developed. In this talk, we will report the results of a systematic investigation on hydration, conductivity, mechanical properties and crystallinity of various types and EWs of PFSA ionomers to (i) develop a structure/property map, and (ii) identify the key parameters controlling morphology and properties. It will be discussed how the pendant-chain and backbone lengths affect the conductivity and crystallinity, respectively. Lastly, the data set will be analyzed to explore universal structure/property relationships for PFSAs.   

Water's Role in the Relaxation of Polyelectrolyte Complexes and Multilayers

In the last decade, evidence for an intriguing glass-transition-like phase transition has emerged in hydrated polyelectrolyte complex precipitates and polyelectrolyte multilayers. Although the transition is weak, it stimulates large-scale macroscopic phenomena such as multilayer shrinking, swelling, and rearrangement. To date, there is not a clear consensus on what causes this transition, although a growing body of evidence indicates that salt and water are key parameters. Recent simulations of hydrated polyelectrolyte complexes show that water molecules form a stabilizing hydrogen-bonded network and that this network is disrupted by dehydration of the polyanion at the thermal transition, leading to segmental relaxation of polymer chains. If true, this would explain the transition's dependence on water and extrinsic compensation as well as its glass transition-like character. This talk will focus upon water's role in the transition, in which a strong dependence on hydration is observed. Quartz crystal microbalance with dissipation (QCM-D) and modulated differential scanning calorimetry (MDSC) are used to track the transition in polyelectrolytes complexes as a function of hydration.   

Probing the mechanism of non-linear growth of polyelectrolyte multilayers

We report a study of the non-linear growth of electrostatically assembled polyelectrolyte multilayer films (PEM). PEM films were assembled by the layer-by-layer (LbL) technique using poly(methacrylic acid) as a polyanion and quaternized poly-2-(dimethylamino)ethyl methacrylate as a polycation. During film build-up, the thickness evolution as well as water uptake of PEM films were measured by in situ ellipsometry, whereas neutron reflectometry was used to probe the evolution of film internal structure as a function of deposition time. First, we found that during non-linear growth, films remain in a highly swollen hydrogel-like state, but the swelling ratio demonstrated an odd/even effect, with much larger hydration of the PEM when the terminal layer was the polycation. Second, while polycation chains were able to diffuse into the bulk of the film with a diffusion constant several orders of magnitude lower than in their free, unbound state, polyanion invasion was limited to the film surface. The amounts of the polycation and the polyanion adsorbed per deposition cycle were also drastically different. We quantify chemical composition and water content in the film, and correlate these data with the depth polyelectrolyte chains penetrate within the film during PEM construction.   

Effect of Aggregation on the Mechanical Properties of Ionomers from MD Simulations

Ionomers are polymers with a small fraction of charged monomers; these bound ions, along with free counterions, tend to aggregate together strongly in the absence of solvent. Ionic aggregates can act like temporary cross-links, giving rise to interesting mechanical properties. We perform coarse-grained molecular dynamics simulations of ionomers with various spacings of charges along the chain, representing experimental precisely spaced, neutralized poly(ethylene-co-acrylic acid) materials. We calculate aggregate morphology, dynamics, and scattering profiles and study the systems during uniaxial tensile strain to understand how aggregate structure changes under deformation and affects mechanical properties. Anisotropic structure factors (parallel and perpendicular to the direction of pull) and visualization shows that the aggregates align, in qualitative agreement with experimental findings. Stress-strain curves at different strain rates are also obtained. A modification of the model to account for unneutralized acid groups by adjusting their Lennard-Jones interaction strengths with each other and with ionic groups will also be discussed.   

Structure and ionic conductivity of block copolymer electrolytes over a wide salt concentration range

Block copolymer electrolytes are promising materials for safe, long-lasting lithium batteries because of their favorable mechanical and ion transport properties. The morphology, phase behavior, and ionic conductivity of a block copolymer electrolyte, SEO mixed with LiTFSI was studied over a wide, previously unexplored salt concentration range using small angle X-ray scattering, differential scanning calorimetry and ac impedance spectroscopy, respectively. SEO exhibits a maximum in ionic conductivity at twice the salt concentration that PEO, the homopolymer analog of the ion-containing block, does. This finding is contrary to prior studies that examined a more limited range of salt concentrations. In SEO, the phase behavior of the PEO block and LiTFSI closely resembles the phase behavior of homopolymer PEO and LiTFSI. The grain size of the block copolymer morphology was found to decrease with increasing salt concentration, and the ionic conductivity of SEO correlates with decreasing grain size. Structural effects impact the ionic conductivity-salt concentration relationship in block copolymer electrolytes. SEO: polystyrene-\textit{block}-poly(ethylene oxide); also PS-PEO LiTFSI: lithium bis(trifluoromethanesulfonyl imide   

Role of Acid Functionality and Placement on Morphological Evolution and Strengthening of Acid Copolymers

Functional polymers with specific interactions produce hierarchical morphologies that directly impact mechanical properties. We recently reported that the formation of acid-rich layered morphologies in precise poly(ethylene-co-acrylic acid) copolymers improves tensile strength. We now explore the generality of this phenomenon through variations in pendant acid chemistries, acid content and precision in placement of acid groups in polyethylene-based copolymers. In situ X-ray scattering measurements during tensile deformation reveal that the precision in acid group placement is critical to forming well-defined layered morphologies. This phenomenon was observed in both semi-crystalline and amorphous precise acid copolymers with varied acid chemistries (acrylic, geminal acrylic and phosphonic acids). Compositionally identical polymers but with pseudo random acid placement do not form layered morphologies. Acid chemistry and acid content influence morphological evolution predominately though modification of the copolymer Tg and crystallinity. Our results indicate that hierarchical layered structures, commensurate with improved mechanical properties, form in the presence of uniformity in chemical structure and sufficient chain mobility to strongly align during deformation.   

States of Salt Water in Polyampholyte Hydrogel Networks at Ice Forming Temperatures

The behavior of water in polymers, including ice formation, is of increasing interest. For example, one can achieve improved longevity of water-borne polymeric coatings and aqueous electrolytes that operate at low temperature by understanding the polymer-water interaction. Water molecules that are bound to hydrophilic polymer backbones are known to be non-freezable at extremely low temperatures such as -100\textdegree C, whereas non-bound water is still freezable at higher temperatures. Polyampholyte, which contains both cationic and anionic groups in its backbone, is an interesting class of anti-fouling coating material with a hygroscopic nature and self-healing ability. In real operational condition, for example in maritime petroleum production in the arctic climate, multiple species of salt ions can complicate the ice formation, but their effect has not been exhaustively studied. Using a random copolymer of sodium p-styrenesulphonate (NaSS) and 3-(methacryloylamino)propyl-trimethylammonium chloride as a model system to study the phase behavior of NaCl salt in the hydrogel, this work presents (i) intriguing mechanical and electrical properties of polyelectrolytes at low temperature (\textless -20\textdegree C), (ii) differential scanning calorimetry studies on the effects of salt concentration, polymer chain density, degree of polymerization, and (iii) effect of dialysis on microstructure and phase water behavior in the polyampholyte hydrogel.