Jodie L. Lutkenhaus

Electrochemically enabled polyelectrolyte multilayer devices: from fuel cells to sensors

With an ever-increasing need for thin, flexible and functional materials in electrochemical systems, the layer-by-layer (LbL) technique provides a simple and affordable route in creating new, active electrodes and electrolytes. The LbL technique, which is based upon the alternate adsorption of oppositely charged species from aqueous solution, possesses unprecedented control of materials selection ( polyelectrolytes, clays, nanoparticles, proteins), materials properties ( conductivity, glass-transition temperature) and architecture ( blends, stratified-layers, pores). These advantages make LbL assemblies excellent candidates for use in proton-exchange membrane and direct methanol fuel-cells, batteries, electrochromic devices, solar cells, and sensors. This review addresses the design of LbL films for electrochemical systems and recent progress.

In Situ One-Step Synthesis of Hierarchical Nitrogen-Doped Porous Carbon for High-Performance Supercapacitors

A hierarchically structured nitrogen-doped porous carbon is prepared from a nitrogen-containing isoreticular metal-organic framework (IRMOF-3) using a self-sacrificial templating method. IRMOF-3 itself provides the carbon and nitrogen content as well as the porous structure. For high carbonization temperatures (950 °C), the carbonized MOF required no further purification steps, thus eliminating the need for solvents or acid. Nitrogen content and surface area are easily controlled by the carbonization temperature. The nitrogen content decreases from 7 to 3.3 at % as carbonization temperature increases from 600 to 950 °C. There is a distinct trade-off between nitrogen content, porosity, and defects in the carbon structure. Carbonized IRMOFs are evaluated as supercapacitor electrodes. For a carbonization temperature of 950 °C, the nitrogen-doped porous carbon has an exceptionally high capacitance of 239 F g(-1). In comparison, an analogous nitrogen-free carbon bears a low capacitance of 24 F g(-1), demonstrating the importance of nitrogen dopants in the charge storage process. The route is scalable in that multi-gram quantities of nitrogen-doped porous carbons are easily produced.

Anisotropic ionic conductivity in block copolymer membranes by magnetic field alignment.

The self-assembly of diblock copolymers provides a convenient route to the formation of mechanically robust films with precise and tunable periodic arrangements of two physically demixed but chemically linked polymeric materials. Chemoselective transport membranes may be realized from such films by selective partitioning of an active species into one of the polymer domains. Here, lithium ions were selectively sequestered within the poly(ethylene oxide) block of a liquid crystalline diblock copolymer to form polymer electrolyte membranes. Optimization of the membrane conductivity mandates alignment of self-assembled structures such that conduction occurs via direct as opposed to tortuous transport between exterior surfaces. We show here that magnetic fields can be used in a very simple and scalable manner to produce highly aligned hexagonally packed cylindrical microdomains in such membranes over macroscopic areas. We systematically explore the dependence of the ionic conductivity of the membrane on both temperature and magnetic field strength. A surprising order of magnitude increase in conductivity relative to the nonaligned case is found in films aligned at the highest magnetic field strengths, 6 T. The conductivity of field aligned samples shows a nonmonotonic dependence on temperature, with a marked decrease on heating in the proximity of the order-disorder transition of the system before increasing again at elevated temperatures. The data suggest that domain-confined transport in hexagonally packed cylindrical systems differs markedly in anisotropy by comparison with lamellar systems.

Controlling Porosity in Lignin‐Derived Nanoporous Carbon for Supercapacitor Applications

Low-cost renewable lignin has been used as a precursor to produce porous carbons. However, to date, it has not been easy to obtain high surface area porous carbon without activation processes or templating agents. Here, we demonstrate that low molecular weight lignin yields highly porous carbon with more graphitization through direct carbonization without additional activation processes or templating agents. We found that molecular weight and oxygen consumption during carbonization are critical factors to obtain high surface area, graphitized porous carbons. This highly porous carbon from low-cost renewable lignin sources is a good candidate for supercapacitor electrode materials.

Optimal temperature for development of poly(methylmethacrylate)

The authors have investigated a range of poly(methylmethacrylate) (PMMA) development temperatures as low as −70°C and characterized their effect on the resolution of PMMA as an electron resist. The results show that cooling, in addition to reducing the sensitivity of the commonly used positive-tone mode of PMMA, also increases the sensitivity of its less commonly used negative-tone mode. They have shown that the resolution-enhancing properties of cold development peak at approximately −15°C as a result of these competing sensitivity changes. At lower temperatures, the high doses required to expose the resist produce significant cross-linking of the polymer, altering its solubility properties and sharply degrading the contrast. If the correct development temperature is used, however, sub-10nm features are readily achievable in PMMA-based scanning electron-beam lithography.

Effect of the layer-by-layer (LbL) deposition method on the surface morphology and wetting behavior of hydrophobically modified PEO and PAA LbL films.

We demonstrate that the surface morphology and surface-wetting behavior of layer-by-layer (LbL) films can be controlled using different deposition methods. Multilayer films based upon hydrogen-bonding interactions between hydrophobically modified poly(ethylene oxide) (HM-PEO) and poly(acrylic acid) (PAA) have been prepared using the dip- and spin-assisted LbL methods. A three-dimensional surface structure in the dip-assisted multilayer films appeared above a critical number of layer pairs owing to the formation of micelles of HM-PEO in its aqueous dipping solution. In the case of spin-assisted HM-PEO/PAA multilayer films, no such surface morphology development was observed, regardless of the layer pair number, owing to the limited rearrangement and aggregation of HM-PEO micelles during spin deposition. The contrasting surface morphologies of the dip- and spin-assisted LbL films have a remarkable effect on the wetting behavior of water droplets. The water contact angle of the dip-assisted HM-PEO/PAA LbL films reaches a maximum at an intermediate layer pair number, coinciding with the critical number of layer pairs for surface morphology development, and then decreases rapidly as the surface structure is evolved and amplified. In contrast, spin-assisted HM-PEO/PAA LbL films yield a nearly constant water contact angle due to the surface chemical composition and roughness that is uniform independent of layer pair number. We also demonstrate that the multilayer samples prepared using both the dip- and spin-assisted LbL methods were easily peeled away from any type of substrate to yield free-standing films; spin-assisted LbL films appeared transparent, while dip-assisted LbL films were translucent.

Thermal transitions in dry and hydrated layer-by-layer assemblies exhibiting linear and exponential growth.

Layer-by-layer (LbL) assemblies are remarkable materials, known for their tunable mechanical, optical, and surface properties in nanoscale films. However, questions related to their thermal properties still remain unclear. Here, the thermal properties of a model LbL assembly of strong polyelectrolytes, poly(diallyldimethylammonium chloride)/poly(styrene sulfonate) (PDAC/PSS), assembled from solutions of varying ionic strength (0-1.25 M NaCl) are investigated using quartz crystal microbalance with dissipation (QCM-D) and modulated differential scanning calorimetry. Hydrated exponentially growing films (assembled from 0.25 to 1.25 M NaCl) exhibited distinct thermal transitions akin to a glass transition at 49-56 °C; linearly growing films (assembled without added salt) did not exhibit a transition in the temperature range investigated and were glassy. Results support the idea that exponentially growing films have greater segmental mobility than that of linearly growing films. On the other hand, all dry LbL assemblies investigated were glassy at room temperature and did not exhibit a T(g) up to 250 °C, independent of ionic strength. For the first time, thermal transitions such as T(g) values can be measured for LbL assemblies using QCM-D by monitoring fluctuations in changes in dissipation, allowing us to probe the films internal structure as a function of film depth.

Oxidatively stable polyaniline:polyacid electrodes for electrochemical energy storage

Conjugated polymers, such as polyaniline, have been widely explored as sensors, electrodes, and conductive fillers. As an electrode material in electrochemical energy storage systems, polyaniline can be subject to irreversible oxidation that reduces cycle life and electrode capacity, thus, limiting its widespread application. Here we present a simple route to produce and prepare polyaniline-based electrodes that are oxidatively stable up to 4.5 V vs. Li/Li(+). The route uses a polyacid to stabilize the fully oxidized pernigraniline salt form of polyaniline, which is normally highly unstable as a homopolymer. The result is an organic electrode of exceptionally high capacity, energy density, power density, and cycle life. We demonstrate that the polyaniline:polyacid electrode stores 230 mA h g(-1) of polyaniline for over 800 cycles, far surpassing homopolymer polyaniline under equivalent conditions. This approach provides a highly stable, electrochemically reversible replacement for conventional polyaniline.

Thermoresponsive layer-by-layer assemblies for nanoparticle-based drug delivery.

Layer-by-layer (LbL) capsules, known for their versatility and smart response to environmental stimuli, have attracted great interest in drug delivery applications. However, achieving a desired drug delivery system with sustained and tunable drug release is still challenging. Here, a thermoresponsive drug delivery system of solid dexamethasone nanoparticles (DXM NPs, 200 ± 100 nm) encapsulated in a model LbL assembly of tunable thickness consisting of strong polyelectrolytes poly(diallyldimethylammonium chloride)/poly(styrenesulfonate) (PDAC/PSS) is constructed. The influence of various parameters on drug release, such as number of layers, ionic strength of the adsorption solution, temperature, and outermost layer, is investigated. Increasing the number of layers results in a thicker encapsulating nanoshell and decreases the rate of dexamethasone release. LbL assemblies created in the absence of salt are most responsive to temperature, yielding the greatest contrast in drug release. Relationships between drug release and LbL architecture are attributed to the size and concentration of free volume cavities within the assemblies. By tailoring the properties of those cavities, a thermoresponsive drug delivery system may be obtained. This work provides a promising example of how LbL assemblies may be implemented as temperature-gated materials for the controlled release of drug, thus providing an alternative approach to the delivery of therapeutics with reduced toxic effects.

Thermochemical properties of free-standing electrostatic layer-by-layer assemblies containing poly(allylamine hydrochloride) and poly(acrylic acid)

Layer-by-layer (LbL) assemblies show promise for global energy and health applications, but their material properties are not well understood. Particularly, little is known about the thermal properties of LbL assemblies because the supporting substrate impedes characterization. It is not initially clear if electrostatic LbL assemblies possess a glass transition temperature or if they are rubbery or glassy at room temperature. Here, large areas of poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA) LbL assemblies were isolated from low surface energy substrates, which facilitates direct thermal characterization via modulated differential scanning calorimetry (MDSC) and thermal gravimetric analysis (TGA). Surprisingly, a glass transition temperature was not observed for the LbL film, regardless of assembly pH, even though homopolymer constituents have well-defined glass transitions. Instead, two endothermic events indicating water loss and covalent cross-linking within the LbL assemblies were observed. TGA and Fourier transform infrared (FTIR) spectroscopy confirm the presence of cross-linking reactions. Results highlight that PAH/PAA LbL films are glassy at room temperature, and have low mobility because of the high density of ion pair crosslinks. The techniques presented here are general, and can be applied to any LbL film.