Detangling electrolyte chemical dynamics in lithium sulfur batteries by operando monitoring with optical resonance combs.

Challenges in enabling next-generation rechargeable batteries with lower cost, higher energy density, and longer cycling life stem not only from combining appropriate materials, but from optimally using cell components. One-size-fits-all approaches to operational cycling and monitoring are limited in improving sustainability if they cannot utilize and capture essential chemical dynamics and states of electrodes and electrolytes. Herein we describe and show how the use of tilted fiber Bragg grating (TFBG) sensors to track, via the monitoring of both temperature and refractive index metrics, electrolyte-electrode coupled changes that fundamentally control lithium sulfur batteries. Through quantitative sensing of the sulfur concentration in the electrolyte, we demonstrate that the nucleation pathway and crystallization of Li2S and sulfur govern the cycling performance. With this technique, a critical milestone is achieved, not only towards developing chemistry-wise cells (in terms of smart battery sensing leading to improved safety and health diagnostics), but further towards demonstrating that the coupling of sensing and cycling can revitalize known cell chemistries and break open new directions for their development.

Achieving Superior Tensile Performance in Individual Metal-Organic Framework Crystals.

Rapid advances in the engineering application prospects of metal-organic framework (MOF) materials necessitate an urgent in-depth understanding of their mechanical properties. This work demonstrates unprecedented recoverable elastic deformation of Ni-tetraphenylporphyrins (Ni-TCPP) MOF nanobelts with a tensile strain as high as 14%, and a projected yield strength-to-Young's modulus ratio exceeding the theoretical limit (≈10%) for crystalline materials. Based on first-principles simulations, the observed behavior of MOF crystal can be attributed to the mechanical deformation induced conformation transition and the formation of helical configuration of dislocations under high stresses, arising from their organic ligand building blocks in the crystal structures. The investigations of the mechanical properties along with electromechanical properties demonstrate that MOF materials have exciting application potential for biomechanics integrated systems, flexible electronics, and nanoelectromechanical devices.

Interlayer Structure and Chemistry Engineering of MXene-Based Anode for Effective Capture of Chloride Anions in Asymmetric Capacitive Deionization.

Negatively charged surfaces and readily oxidizabile characteristics fundamentally restrict the use of MXene building blocks as anodes for anion intercalation. Herein, by embedding bacterial cellulose nanofibers with conformal polypyrrole coating (BC@PPy) and populating them between MXene (Ti3C2Tx) interlayers, we enable the fabricated MXene/BC@PPy (MBP) composite films to be highly efficient anodes for Cl--capturing in asymmetric capacitive deionization (CDI) systems. Performance gains are realized due to the surface electronegativity of MXene nanosheets becoming compensated by positively charged BC@PPy nanofibers, alleviating electrostatic repulsion, thus realizing reversible Cl- intercalation. More crucially, the anodization voltage of MBP is effectively enhanced as a result of the increase of the Ti valence state in MXene nanosheets with the addition of the BC@PPy spacer. Furthermore, BC@PPy nanopillars effectively enlarge the interlayer space for facile Cl- de-/intercalation, improve the vertical electron transfer between loosely deposited MXene nanosheets, and perform as additional active materials for Cl--capturing. Consequently, the MBP anode exhibits a promising desalination capacity of up to 17.56 mg g-1 at 1.2 V with a high capacity retention of 94.6% after 30 cycles in an asymmetric CDI system. This work offers a simple and effective strategy to unlock the application potential of MXene building blocks as anodes for Cl--capturing in electrochemical desalination.

Simplifying Electrode Design for Lithium-Ion Rechargeable Cells.

In the race to increase lithium-ion cell manufacturing, labor and energy costs quickly ascend to become chief concerns for building new facilities, as conventional electrode designs need significant resources during fabrication. Complicating this issue is an empirical trade-off between environmental friendliness and ethical sourcing. To circumvent this paradox, modified cell designs that employ foils and textiles can significantly change manufacturing considerations if their simple construction can be matched with competitive performance. In this work, we demonstrate one possible cell design for a lithium-ion device that utilizes a fabric and a foil for the cathode and the anode, respectively. For the anode, a prelithiated aluminum foil is chosen, as the room-temperature solubility range of the LiAl phase is well-suited to uptake and release lithium, all while reducing energy or cost-intensive production steps. The cathode is composed of activated carbon fiber textiles, which offer a scalable path to realize sustainability. With such benefits, this device design can potentially change the calculus for the mass production of energy storage devices.

Exploring the Reversibility of Phase Transformations in Aluminum Anodes through Operando Light Microscopy and Stress Analysis.

Aluminum is well-known to possess attractive properties for possible use as an anode material in Li-ion batteries (LIBs), but effort is still needed to understand how and why it degrades. Herein, investigations of the delithiation and the re-lithiation processes in Al thin films using an established operando light microscopic platform are pursued. Operando videos highlight that the extraction of Li from the ß phase (LiAl) is accompanied by fracture and crack formation leading to the detachment of the α phase (Al) from the rest of the electrode. The evolution of mechanical stress in Al thin film electrodes is tracked and shows severe stress asymmetry as phase transformations progress. Combining with the observations from light and electron microscopy, the mechanical stress during dealloying can be explained by Li solubility with the ß phase, formation of cracks and of a highly porous Al nanostructure. Although the results pave a difficult path for utilization of the Al/LiAl/Al (α/ß/α) phase transformations in future LIBs, they also suggest excellent opportunities when structural changes can be prevented, which otherwise impact the stability of Al-based electrodes.

The Limits of Electromechanical Coupling in Highly-Tensile Strained Germanium.

Speculations regarding electronic and photonic properties of strained germanium (Ge) have perpetually put it into contention for next-generation devices since the start of the information age. Here, the electromechanical coupling of <111> Ge nanowires (NWs) is reported from unstrained conditions to the ultimate tensile strength. Under tensile strain, the conductivity of the NW is enhanced exponentially, reaching an enhancement factor of ∼130 at ∼3.5% of strain. Under strains larger than ∼2.5%, the electrical properties of Ge also exhibit a dependence on the electric field. The conductivity can be further enhanced by ∼2.2× with a high bias condition at ∼3.5% of strain. Cyclic loading tests confirm that the observed electromechanical responses are repeatable, reversible, and related to the changing electronic band structure. These tests reveal the excellent prospects for utilizing strained Ge NWs in photodetector or piezoelectronic transistor applications, but significant challenges remain to realize strict direct band gap devices.

Impact of high UV fluences on the mechanical and sensing properties of polymer optical fibers for high strain measurements.

PMMA-based fibers are widely studied for strain measurements and show repeatable results for Fiber Bragg Gratings (FBGs) inscribed using 325 nm laser and 248 nm laser. However, there is no available material mechanical behavior characterization of the UV source impact on the fiber properties. In this manuscript, fibers are irradiated with high fluence of 325 nm and 248 nm lasers and the fibers properties are investigated using dynamic mechanical analysis and tensile strain for potential use of these fibers past the yield point. It is demonstrated that the UV sources shifted the ultimate tensile strength and changed the strain hardening behavior. Tensile strain measurements show excellent repeatability for gratings inscribed with these two sources with similar sensitivity of 1.305 nm/mɛ for FBG inscribe with 325 nm laser, and 1.345 nm/mɛ for grating written with 248 nm laser in the range 0 to 1.5 % elongation. Furthermore, tests far beyond the yield point (up to 2.8 % elongation) show that grating inscribed with lower UV wavelength exhibit hysteresis. Finally, we demonstrate that 248 nm laser fluence shall be chosen carefully whereas even high 325 nm laser fluence do not critically impact the sensor properties.

Improvement of the Cycling Performance of Aluminum Anodes through Operando Light Microscopy and Kinetic Analysis.

Aluminum is an attractive anode material for lithium-ion batteries (LIBs) owing to its low cost, light weight, and high specific capacity. However, utilization of Al-based anodes is significantly limited by drastic capacity fading during cycling. Herein, a systematic study is performed to investigate the kinetics of electrochemical lithiation of Al thin films to understand the mechanisms governing the phase transformation, by using an operando light microscopy platform. Operando videos reveal that nuclei appear at random positions and expand to form quasi-circular patches that grow and merge until the phase transformation is complete. Based on this direct evidence, models of the lithiation processes in Al anodes are discussed and reaction-controlled kinetics are suggested. The growth rate of LiAl depends on the potential and increases considerably as higher overpotentials are approached. Lastly, improved cycling performance of Al-based anodes can be realized by two approaches: 1) by controlling the lithiation extent, the cycling life of Al thin film is extended from 5 cycles to 25 cycles; 2) the performance can be optimized by adjusting the kinetics. Together, this work offers a renewed promise for the commercialization of Al-based anodes in LIBs where the performance requirements are compatible with the proposed cycle life-extending strategies.

Performance Recovery in Degraded Carbon-Based Electrodes for Capacitive Deionization.

Limitations of capacitive deionization (CDI) and future commercialization efforts are intrinsically bound to electrode stability. In this work, thermal treatments are explored to understand their ability to regenerate aged CDI electrodes. We demonstrate that a relatively low thermal treatment temperature of ∼500 °C can sufficiently recover the lost salt adsorption capacity of degraded electrodes. Furthermore, a systematic study of electrode replacement clarifies that the desalination ability loss and regeneration for a CDI cell are isolated to the aged anode, as expected. Characterizations of surface functionalities support that the acidic oxygen-containing functional groups formed in situ during cycling undergo thermal decomposition during treatment. The modified Donnan model quantitatively confirms that the surface charges originate from the formation/decomposition of functional groups. Accordingly, the lost pore volume and the increased resistance are recovered during thermal treatments, while the surface morphologies and pore structure of the electrodes are well-preserved. Therefore, thermal treatment can be applied practically to extend the lifetime of aged electrodes. This study also offers insights into strategies for minimizing electrode degradation or in situ regeneration such that the technology gains momentum for future commercialization.

Leveraging Titanium to Enable Silicon Anodes in Lithium-Ion Batteries.

Silicon is a promising anode material for lithium-ion batteries because of its high gravimetric/volumetric capacities and low lithiation/delithiation voltages. However, it suffers from poor cycling stability due to drastic volume expansion (>300%) when it alloys with lithium, leading to structural disintegration upon lithium removal. Here, it is demonstrated that titanium atoms inside the silicon matrix can act as an atomic binding agent to hold the silicon atoms together during lithiation and mend the structure after delithiation. Direct evidence from in situ dilatometry of cosputtered silicon-titanium thin films reveals significantly smaller electrode thickness change during lithiation, compared to a pure silicon thin film. In addition, the thickness change is fully reversible with lithium extraction, and ex situ post-mortem microscopy shows that film cracking is suppressed. Furthermore, Raman spectroscopy measurements indicate that the Si-Ti interaction remains intact after cycling. Optimized Si-Ti thin films can deliver a stable capacity of 1000 mAh g-1 at a current of 2000 mA g-1 for more than 300 cycles, demonstrating the effectiveness of titanium in stabilizing the material structure. A full cell with a Si-Ti anode and LiFePO4 cathode is demonstrated, which further validates the readiness of the technology.

Ultra-fast polymer optical fibre Bragg grating inscription for medical devices.

We report the extraordinary result of rapid fibre Bragg grating inscription in doped polymer optical fibres based on polymethyl methacrylate in only 7 ms, which is two orders of magnitude faster than the inscription times previously reported. This was achieved using a new dopant material, diphenyl disulphide, which was found to enable a fast, positive refractive index change using a low ultraviolet dose. These changes were investigated and found to arise from photodissociation of the diphenyl disulphide molecule and subsequent molecular reorganization. We demonstrate that gratings inscribed in these fibres can exhibit at least a 15 times higher sensitivity than silica glass fibre, despite their quick inscription times. As a demonstration of the sensitivity, we selected a highly stringent situation, namely, the monitoring of a human heartbeat and respiratory functions. These findings could permit the inscription of fibre Bragg gratings during the fibre drawing process for mass production, allowing cost-effective, single-use, in vivo sensors among other potential uses.

Formation of single tiers of bridging silicon nanowires for transistor applications using vapor-liquid-solid growth from short silicon-on-insulator sidewalls.

Single tiers of silicon nanowires that bridge the gap between the short sidewalls of silicon-on-insulator (SOI) source/drain pads are formed. The formation of a single tier of bridging nanowires is enabled by the attachment of a single tier of Au catalyst nanoparticles to short SOI sidewalls and the subsequent growth of epitaxial nanowires via the vapor-liquid-solid (VLS) process. The growth of unobstructed nanowire material occurs due to the attachment of catalyst nanoparticles on silicon surfaces and the removal of catalyst nanoparticles from the SOI-buried oxide (BOX). Three-terminal current-voltage measurements of the structure using the substrate as a planar backgate after VLS nanowire growth reveal transistor behaviour characteristics.