R-3 Repository :: Browsing by Author "Terlier, Tanguy"

Browsing by Author "Terlier, Tanguy"

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Characterization of polymeric surfaces and interfaces using time-of-flight secondary ion mass spectrometry
(Wiley, 2022) Mei, Hao; Laws, Travis S.; Terlier, Tanguy; Verduzco, Rafael; Stein, Gila E.; Shared Equipment Authority
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is used for chemical analysis of surfaces. ToF-SIMS is a powerful tool for polymer science because it detects a broad mass range with good mass resolution, thereby distinguishing between polymers that have similar elemental compositions and/or the same types of functional groups. Chemical labeling techniques that enhance contrast, such as deuterating or staining one constituent, are generally unnecessary. ToF-SIMS can generate both two-dimensional images and three-dimensional depth profiles, where each pixel in an image is associated with a complete mass spectrum. This Review begins by introducing the principles of ToF-SIMS measurements, including instrumentation, modes of operation, strategies for data analysis, and strengths/limitations when characterizing polymer surfaces. The sections that follow describe applications in polymer science that benefit from characterization by ToF-SIMS, including thin films and coatings, polymer blends, composites, and electronic materials. The examples selected for discussion showcase the three standard modes of operation (spectral analysis, imaging, and depth profiling) and highlight practical considerations that relate to experimental design and data processing. We conclude with brief comments about broader opportunities for ToF-SIMS in polymer science.
Impact of fabrication methods on binder distribution and charge transport in composite cathodes of all-solid-state batteries
(IOP Publishing Ltd, 2023) Emley, Benjamin; Wu, Chaoshan; Zhao, Lihong; Ai, Qing; Liang, Yanliang; Chen, Zhaoyang; Guo, Liqun; Terlier, Tanguy; Lou, Jun; Fan, Zheng; Yao, Yan
The manufacturing process of all-solid-state batteries necessitates the use of polymer binders. However, these binders, being ionic insulators by nature, can adversely affect charge transport within composite cathodes, thereby impacting the rate performance of the batteries. In this work, we aim to investigate the impact of fabrication methods, specifically the solvent-free dry process versus the slurry-cast wet process, on binder distribution and charge transport in composite cathodes of solid-state batteries. In the dry process, the binder forms a fibrous network, while the wet process results in binder coverage on the surface of cathode active materials. The difference in microstructure leads to a notable 20-fold increase in ionic conductivity in the dry-processed cathode. Consequently, the cells processed via the dry method exhibit higher capacity retention of 89% and 83% at C/3 and C/2 rates, respectively, in comparison to 68% and 58% for the wet-processed cells at the same rate. These findings provide valuable insights into the influence of fabrication methods on binder distribution and charge transport, contributing to a better understanding of the binder’s role in manufacturing of all-solid-state batteries.
Impact of Processing Effects on Surface Segregation of Bottlebrush Polymer Additives
(American Chemical Society, 2022) Lee, Dongjoo; Charpota, Nilesh; Mei, Hao; Terlier, Tanguy; Pietrzak, Danica; Stein, Gila E.; Verduzco, Rafael
The surface properties of polymeric materials govern interactions with the surroundings and are responsible for various application-relevant properties. Recent studies have shown that bottlebrush polymers can be used to modify the surface chemistry of the polymers because they spontaneously segregate to the interfaces when they are blended with the linear polymers, driven in large part by entropic effects that arise from the unique architecture of bottlebrush polymers. However, while prior work has largely focused on equilibrium segregation profiles, kinetic and processing effects can also drive bottlebrush additives to surfaces and interfaces. In solution-cast blends of polymers and colloids, vertical stratification is controlled by the relative Péclet (Pe) numbers of the constituents, i.e., the relative rates of solvent evaporation and solute diffusion. Herein, we studied processing effects that drive bottlebrush additives to interfaces when blended with linear polymers. We prepared blends of bottlebrush polystyrene (BBPS) and linear perdeuterated polystyrene (dPS), where the BBPS side-chain length was fixed at Nsc = 48, the BBPS backbone length ranged from Nb = 30–260, and the dPS chain length ranged from Nm = 40–548. The relative Pe numbers of BBPS and dPS were varied by changing the solvent and sizes of BBPS and dPS. In contrast to other binary blends where the constituents have disparate sizes (e.g., colloid/colloid, polymer/colloid, and polymer/polymer), we found that the relative Pe number cannot account for the degree of segregation observed in these bottlebrush and linear polymer blends. For a fixed BBPS side-chain length, we observe stronger surface segregation of bottlebrush additives when the blend is cast using lower boiling point solvents and/or for blends with longer bottlebrush polymers. We further show that solvent annealing of the film can increase the enrichment of bottlebrush additives near surfaces. This study provides insight into the interplay of processing effects and blend thermodynamics that govern surface segregation of bottlebrush polymer additives.
Nanostructured Films of Oppositely Charged Domains from Self-Assembled Block Copolymers
(American Chemical Society, 2020) Fultz, Brandon A.; Terlier, Tanguy; Dunoyer de Segonzac, Beatriz; Verduzco, Rafael; Kennemur, Justin G.
The exploration of poly(tert-butyl methacrylate)-block-poly(4-vinylpyridine), PtBMA-b-P4VP, as a precursor material for the creation of nanostructured films with oppositely charged domains is reported. Thin films of hexagonally packed P4VP cylinders were self-assembled perpendicular to the surface and subsequently treated with bromoethane vapor at various times to quaternize pyridinyl nitrogens. The PtBMA matrix was then partially hydrolyzed to poly(methacrylic acid), PMAA, through HCl vapor treatment followed by neutralization by brief submersion in KOH solution. Under optimal treatment conditions, atomic force microscopy and contact angle measurements confirm that the film morphologies remain intact and become more hydrophilic. Time-of-flight secondary ion mass spectrometry confirms the presence and location of specific anions and cations within each domain throughout the block copolymer film and corroborates successful ionization during each treatment step. These results bolster the viability of PtBMA-b-P4VP as a suitable material for creating self-assembled nanostructures bearing oppositely charged domains under relatively facile conditions and open the door to future investigations for their potential application in charged mosaic membranes.
Prelithiation Effects in Enhancing Silicon-Based Anodes for Full-Cell Lithium-Ion Batteries Using Stabilized Lithium Metal Particles
(American Chemical Society, 2023) Nguyen, Quan Anh; Haridas, Anulekha K.; Terlier, Tanguy; Biswal, Sibani Lisa
Silicon (Si) has been considered as one of the most promising replacements for graphite anodes in next-generation lithium-ion batteries due to its superior specific capacity. However, the irreversible consumption of lithium (Li) ions in Si-based anodes, which is associated with a large volume expansion upon lithiation and the continuous formation of the solid electrolyte interphase (SEI), is especially detrimental to full-cell batteries, whose Li-ion reserve is limited. This study demonstrates the application of stabilized lithium metal particles (SLMPs) as a prelithiation method for Si anodes that can be readily incorporated into large-scale industrial battery manufacturing. Particularly, a surfactant-stabilized SLMP dispersion was designed to be spray-coated onto prefabricated Si composite anodes, forming a uniformly distributed and well-adhered SLMP layer for in situ prelithiation. In full-cells with lithium iron phosphate (LFP) cathodes, the Si-based anodes demonstrated an improved 1st cycle Coulombic efficiency and cycle life with SLMP prelithiation using capacity-control cycling. However, when cycling over the full potential range, prelithiation with high SLMP loading was found to initially increase battery capacity while inducing accelerated fading in later cycles. This phenomenon was caused by Li trapping in the Li–Si alloy associated with higher SLMP-enabled Li diffusion kinetics. Additionally, cycled Si anodes from full-cells were also examined by surface analysis techniques, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS), demonstrating SLMP effects in modifying the SEI by increasing the inorganic content, particularly LiF, which had been widely credited with improving SEI morphology and Li-ion diffusion through the interphase. Our findings provide valuable insights into the design of prelithiation and cycling strategies for high-capacity Si-based full-cell batteries to utilize the benefits of SLMP while avoiding the Li trapping phenomenon.
Solution-Deposited and Patternable Conductive Polymer Thin-Film Electrodes for Microbial Bioelectronics
(Wiley, 2022) Tseng, Chia-Ping; Liu, Fangxin; Zhang, Xu; Huang, Po-Chun; Campbell, Ian; Li, Yilin; Atkinson, Joshua T.; Terlier, Tanguy; Ajo-Franklin, Caroline M.; Silberg, Jonathan J.; Verduzco, Rafael
Microbial bioelectronic devices integrate naturally occurring or synthetically engineered electroactive microbes with microelectronics. These devices have a broad range of potential applications, but engineering the biotic–abiotic interface for biocompatibility, adhesion, electron transfer, and maximum surface area remains a challenge. Prior approaches to interface modification lack simple processability, the ability to pattern the materials, and/or a significant enhancement in currents. Here, a novel conductive polymer coating that significantly enhances current densities relative to unmodified electrodes in microbial bioelectronics is reported. The coating is based on a blend of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) crosslinked with poly(2-hydroxyethylacrylate) (PHEA) along with a thin polydopamine (PDA) layer for adhesion to an underlying indium tin oxide (ITO) electrode. When used as an interface layer with the current-producing bacterium Shewanella oneidensis MR-1, this material produces a 178-fold increase in the current density compared to unmodified electrodes, a current gain that is higher than previously reported thin-film 2D coatings and 3D conductive polymer coatings. The chemistry, morphology, and electronic properties of the coatings are characterized and the implementation of these coated electrodes for use in microbial fuel cells, multiplexed bioelectronic devices, and organic electrochemical transistor based microbial sensors are demonstrated. It is envisioned that this simple coating will advance the development of microbial bioelectronic devices.
Tannic Acid as a Small-Molecule Binder for Silicon Anodes
(American Chemical Society, 2020) Sarang, Kasturi T.; Li, Xiaoyi; Miranda, Andrea; Terlier, Tanguy; Oh, Eun-Suok; Verduzco, Rafael; Lutkenhaus, Jodie L.
Increasing demand for portable electronic devices, electric vehicles, and grid scale energy storage has spurred interest in developing high-capacity rechargeable lithium-ion batteries (LIBs). Silicon is an abundantly available anode material that has a theoretical gravimetric capacity of 3579 mAh/g and a low operating potential of 0–1 V vs Li/Li+. However, silicon suffers from large volume variation (>300%) during lithiation and delithiation that leads to pulverization, causing delamination from the current collector and battery failure. These issues may be improved by using a binder that hydrogen bonds with the silicon nanoparticle surface. Here, we demonstrate the use of tannic acid, a natural polyphenol, as a binder for silicon anodes in lithium-ion batteries. Whereas the vast majority of silicon anode binders are high molecular weight polymers, tannic acid is explored here as a small molecule binder with abundant hydroxyl (−OH) groups (14.8 mmol of OH/g of tannic acid). This allows for the specific evaluation of hydrogen-bonding interactions toward effective binder performance without the consideration of particle bridging that occurs otherwise with high molecular weight polymers. The resultant silicon electrodes demonstrated a capacity of 850 mAh/g for 200 cycles and a higher capacity when compared to electrodes fabricated by using high molecular weight polymers such as poly(acrylic acid), sodium alginate, and poly(vinylidene fluoride). This work demonstrates that a small molecule with high hydrogen-bonding capability can be used a binder and provides insights into the behavior of small molecule binders for silicon anodes.

Browsing by Author "Terlier, Tanguy"

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