bluuebunny/crossref_metadata_2025_split huggingface dataset:
Bottom-up Design of Organic Selenide Interfaces for Sensitive Electrocatalytic Detection of Peroxynitrite: A Fundamental Investigation and Application
Authors: Kalil Haitham , Curtis William , Menches Victoria , Azeroual Sami , Fouad Farid , Bayachou Mekki 
Published: November 2022

Peroxynitrite (PON) is a potent oxidative stress species that has been linked with both oxidation and nitration reactions in biological systems. It emerged as a major cytotoxic agent that is implicated in a host of pathophysiological conditions. Reports emphasized the deleterious physiological reactivity of peroxynitrite with different cellular targets including DNA, proteins, and lipids in cell membranes. This oxidant has also been linked to cytoprotective roles under certain conditions. The balance between the deleterious reactivity and its potential cytoprotective roles of peroxynitrite depends on the dynamic concentration of this species. However, accurate determination of peroxynitrite concentration is inherently difficult particularly in biological systems. Various methods for peroxynitrite determination have been reported including indirect spectroscopic assays and, recently, direct electrochemical methods. While the development of electrochemical sensors for PON is currently a very active field, viable electrochemical probes for PON detection and quantification are still relatively illusive.
In this work, we prepared and characterized a series of functional thin film materials based on organic diphenyl selenides on graphite electrodes and used these interfaces to compare and contrast their performance in terms of electrochemical determination of peroxynitrite.
We will describe the preparation and grafting of the catalytic material based on the electrodeposition of various organic aminodiphenyl selenides on graphite electrodes. Several physicochemical methods including Scanning Electron Microscopy (SEM), Energy Dispersive X-ray spectroscopy (EDX) and X-ray Photoelectron Spectroscopy (XPS) were used to characterize the resulting modified interfaces. We will describe the performance of resulting selenide thin films as peroxynitrite sensing interfaces using voltammetry and amperometry. The grafted thin film materials show a significant enhancement in peroxynitrite oxidative current compared to controls under the same conditions. For all selenides tested, we show that the enhancement in peroxynitrite signal is the result of an electrocatalytic mechanism where the grafted aniline selenide-based material at the oxidized state mediates the electrocatalytic oxidation of peroxynitrite. We will compare and contrast the performance of the various selenide systems and explore if the modulation of the electronic properties of the selenium catalytic center results in proportional changes in PON catalytic efficiency.

Figure 1
The Effects of Ionic Liquid Addition on the Heat of Polymerization of Additive Manufacturing Resins
Authors: Dobyns Breanna M , Duranty Edward , Reichert W. Matthew 
Published: November 2022

Ionic liquids can be utilized in stereolithography (SLA) additive manufacturing resins to adjust multiple parameters of the resulting polymer, such as chemical stability, temperature stability, and other key physical properties. While studies into these properties are ongoing, little is known about the effects the presence of these ILs has on the polymerization process. This study intends to use a new technique incorporating acoustic levitation, FLIR thermography, and differential scanning calorimetry (DSC) to provide insight into heat of polymerization of the resins utilizing an approach previously developed in the Duranty laboratory. This technique allows a small amount of liquid to levitate in standing sound waves generated by transducers at the top and bottom of a 3D printed scaffolding. This novel approach maximizes the probability of heat transfer via convection (through the air/surrounding medium) while preventing heat transfer via conduction (through direct contact) that is normally observed in container methods, allowing for direct thermal imaging of the captured droplets. Two 405 nm lasers, mounted at the top and bottom of the apparatus, are utilized to mimic the lasers of SLA 3D printing which initiate the polymerization process. This apparatus allows for the direct observation of the temperature changes during the polymerization process.
A variety of ionic liquids were used in this investigation in order to study to effects of structure changes and ion effects. The study observed the effects of alkyl chain length, functional groups on the alkyl chain, anion effects, aromatic vs. non-aromatic, and potential co-polymer ionic liquids. Each ionic liquid was added to the commercial Clear V4 resin from Formlabs in the amount of 10 to 50 wt% ionic liquid. Once the mixtures were homogenous, 5 µL of each IL/resin mixture was suspended in the acoustic field. Thermographic data was collected before, during, and after the polymerization process which was initiated by exposure to 405 nm lasers. The heats of polymerization for each sample were calculated using heat capacity data collected via DSC along with the change in temperature of the droplet observed by FLIR thermographic imaging of the suspended droplet during polymerization. Thermal degradation temperatures of the resulting polymer matrices were determined via thermal gravimetric analysis (TGA). The combination of this data revealed that the addition of some of the ionic liquids targeted in this study reduced the heat of polymerization, while others increased it. Therefore, the cation and anion structures greatly impact the heat of polymerization.

Figure 1
(Invited) Understanding Transport Properties of Ionic Liquids By Targeted Modifications of Ion Structures
Authors: Welton Tom , Philippi Frederik , Koutsoukos Spyridon , Rauber Daniel , Kay Christopher , Hunt Patricia 
Published: November 2022

Ionic liquids have been of great interest throughout this century and continue to find new applications in both academia and industry. This is largely due to their great versatility, with millions of potential combinations of cations and anions, which has led to them being described as 'designer solvents'. However, this leads to its own problems when it comes to choosing the optimum ionic liquid for any given application. To fully exploit this versatility, it is imperative to understand how the properties of ionic liquids arise from their constituent ions.
To derive meaningful structure-property relationships for ionic liquids is a complex task. It can be particularly difficult to isolate the cause of any property change arising from even simple modifications of ions. For example, changing the length of the alkyl chain of a cation in an ionic liquid also changes the volume and mass of the ion, all of which can affect a property such as ion mobility and consequent properties such as the viscosity and conductivity of the ionic liquid. A ‘targeted modification’ is a deliberate change in the structure of an ionic liquid ion that is designed to minimise the introduction of such confounding factors. The change must isolate what is of interest, so that we can study only one concept at a time. Once these structure-property relationships have been clearly defined, it will be possible to use these as design elements for new ionic liquids.
As well as experimental observations, it is possible to apply the targeted modification approach to a computer simulation. This provides both insight into experimental observations and predictions of potential targeted modifications before complex synthesis is attempted. Together, theory and experiment will enable the concept of ionic liquids as designer solvents to be realised.
In this presentation we apply the targeted modifications approach to the transport properties of ionic liquids.
(Invited) Mechanically Extreme Batteries: From Flexible to Structural
Authors: Yang Yuan 
Published: November 2022

Batteries with extreme mechanical properties are attractive for unique applications. On the soft side, flexible and stretchable batteries are attractive for wide applications, such as health care and flexible electronics. It is challenging to realize high flexibility/stretchability and high energy density simultaneously. In this talk, I will talk about feasible and scalable strategies to fabricate flexible lithium-ion batteries, which can concurrently have high energy density and high mechanical flexibility, including bendability, foldability, twistability and stretchability. Inspired by the structure of animal spine, the vertebrae-like hard segments with multiple layers of conventional anode/separator/cathode stack to offer energy storage are interconnected by the soft components as marrow with the monolayer stack to provide flexibility.
On the other hand, mechanically strong batteries are also important as they may replace structural components in vehicles and aircrafts for lightweighting. I will discuss a scalable and feasible tree-root-like lamination at the electrode/separator interface, which effectively transfers load between different layers of battery components and thus dramatically enhances the flexural modulus of pouch cells from 0.28 to 3.1 GPa. A graphite/LiNi0.5Mn0.3Co0.2O2 full cell with such interfacial lamination delivers a steady discharge capacity of 148.6 mAh g−1 at C/2 and 95.5% retention after 500 cycles. A prototype of “electric wings” is also demonstrated, which allows an aircraft model to fly steadily.
(Invited) Textile Composite Electrodes for Wearable Batteries and Beyond
Authors: Zheng Zijian 
Published: November 2022

Abstract

Wearable energy storage devices are indispensable corner stones for future wearable electronics. Current energy storage technologies are based on materials and devices that are rigid, bulky, and heavy, making them difficult to wear. On the other hand, fibers are flexible and lightweight materials that can be assembled into different textiles and have been worn by human beings thousands of years. Different from conventional two-dimensional thin films and foils, the three-dimensional fibre and textile structures not only provide superior wearing ability, but also much larger surface areas. This talk will introduce how our research group makes use of the attributes of fibres for high-performance wearable energy storage devices. We will demonstrate the strategies and discuss the perspectives to modify fibers and textiles for making wearable capacitators and batteries with excellent mechanical durability, electrochemical stability, and high energy/power density. We will also show that the fibrous materials can significantly enhance the stability and energy density of battery for wearable applications and others such as Na battery.

References

[1] Q. Huang, D. Wang, Z. J. Zheng*, Adv. Energy Mater. 2016, 6, 1600783.
[2] Y. Gao, C. Xie, Z. J. Zheng*, Adv. Energy Mater. 2020, 2002838
[3] L. Liu, Y. Yu, C. Yan, K. Li, Z. J. Zheng*, Nat. Commun. 2015, 6, 7260.
[4] Y. Yu, C. Yan, Z. J. Zheng*, Adv. Mater. 2014, 26, 55085516.
[5] Y. Yang, Q. Huang, L. Niu, D. Wang, C. Yan, Y. She, Z. J. Zheng*, Adv. Mater. 2017, 160667.
[6] J. Chang, Z.J.Zheng* et al., Nat. Commun. 2018, 2018, 9, 4480.
[7] J. Chang, Q. Huang, and Z. J. Zheng*, Joule 2020, 4, 7, 1346
[8] J. Chang, Q. Huang, Y. Gao, Z. J. Zheng*, Adv. Mater. 2021, 202004419.
[9] Y. Gao, H. Hu, J. Chang, Q. Huang, Q. Zhuang, P. Li, Z. J. Zheng*, Adv. Energy Mater. 2021, 2101809.
[10] L. Wang, J. Shang, Q. Huang, H. Hu, Y. Zhang, C. Xie, Y. Luo, Y. Gao, H. Wang, Z. J. Zheng*, Adv. Mater. 2021, 2102802.
Electrolyte Additive Enabled Low Temperature Lithium Metal Batteries
Authors: Zhang Yiwen , Li Weiyang 
Published: November 2022

One of the key challenges in the development of energy storage devices is the ability to operate efficiently under extremely cold environments (i.e. below -20 °C), especially for batteries in temperature-sensitive applications such as portable electronic devices, transportation, and stationary energy storage. As reported, at low temperature, the increased internal resistance and sluggish ion diffusion in batteries lead to declined charge-delivering capability, which deteriorates cell performance and eventually terminates the power output. Although lithium (Li) metal battery (LMB) with ether electrolyte is considered promising in overcoming these issues due to the low viscosity of ether solvent and its distinctive electrode structure, the low-temperature performance of LMBs remains unsatisfactory. A series of problems are observed upon the anode-electrolyte interphase, including aggravated side reactions, abnormal Li deposition, and dramatically increased solid-electrolyte interphase (SEI) resistance. Thus, building a stable SEI layer on the Li metal anode is critical for the development of low-temperature LMBs.
Here, we demonstrate a dioxolane (DOL)-based electrolyte with dimethyl sulfoxide (DMSO) as the low-temperature additive, which helps to construct a robust SEI layer that possesses uniform structure and good composition consistency even under extremely cold condition. In this electrolyte, DOL works as the primary electrolyte component that defines the basic electrochemical properties, while DMSO further tunes the SEI composition to boost the low-temperature performance. To elucidate the modified microstructure and chemical composition of the SEI film, cryogenic transmission electron microscopy, X-ray photoelectron spectroscopy, and energy-dispersive X-ray spectroscopy are conducted to make a comprehensive investigation. Moreover, a series of electrochemical tests are conducted under extremely cold environments, and results demonstrate that the adjusted SEI is resilient to the stripping and plating cycles of Li metal at temperatures as low as -80 °C. Full cells with lithium iron phosphate as the cathode material are assembled and good electrochemical performance is achieved at -40 °C at 0.2 C. The solvation structure of DMSO added electrolyte is also investigated to fundamentally understand how it affects the SEI formation. Our work establishes fundamental insights into the low-temperature electrolyte additives and paves the road to the further applications of LMBs in harsh environments.
Correlating Computation and Structural Analysis for LiFePO4 through Operando Characterization of Lithium-Ion Pouch-Cell Batteries
Authors: Long Jeffrey W. , DeBlock Ryan H. , Carter Rachel Elizabeth , Chervin Christopher N. , Love Corey T. , Johannes Michelle D. 
Published: November 2022

X-ray absorption spectroscopy (XAS) is a powerful technique for exploring the electronic and structural characteristics of battery materials. Historically, XAS measurements require synchrotron-based photon sources to achieve necessary sensitivity and energy control, but with breakthroughs in X-ray optics, laboratory-based XAS systems are now available on the commercial market. The Chemistry Division at the Naval Research Laboratory recently acquired an easyXAFS™ system, a laboratory-scale spectrometer that is capable of collecting XANES (X-ray Absorption Near-Edge Spectroscopy) and EXAFS (Extended X-ray Absorption Fine Structure) measurements in the 5–18 keV energy window. This energy range covers K-edge absorptions for the first-row transition metals that are of primary interest for electrochemical energy storage. In order to demonstrate the utility of such a laboratory-based XAS, we perform operando measurements on pouch-cell batteries containing the common lithium-ion battery cathode, LiFePO4 (LFP; lithium iron phosphate), tracking Fe oxidation state and bonding environment as a function of state-of-charge. X-ray absorption spectra collected with the easyXAFS™ compare favorably to those from prior investigations of LFP cells analyzed at synchrotron sources [1]. In parallel with XAS measurements, we perform DFT (Density Functional Theory) computation of the LFP structure. Calculations of LFP show that hole-polaron formation during charging alters the local environment around the Fe ion, decreasing the Fe–O bond length. Bond contraction increases with the addition of the Hubbard "U", which also increases the valence difference (formally 2+/3+). We further refine the computational model for the LFP system by tuning the DFT input parameter “U” to correlate with experimental XAS data.
[1] C. T. Love, A. Korovina, C. J. Partridge, K. E. Swider-Lyons, M. E. Twigg, and D. E. Ramaker, J. Electrochem. Soc. 160 (2013) A3153.
Bragg Coherent Diffraction Imaging Studies of Pt Nanograins Under Electrochemical Control Using Pipette Cells
Authors: Sheyfer Dina , Highland Matthew , Hruszkewycz Stephan , You Hoydoo , Cha Wonsuk , Harder Ross , Mariano Ruperto , Kanan Mathew , Kawaguchi Tomoya 
Published: November 2022

Deeply penetrating X-rays are well suited to investigate the electrochemical systems and interfaces under in-situ / operando environments. In particular, a recently developed X-ray Bragg Coherent Diffractive Imaging (BCDI) is a powerful tool for 3D imaging of internal structures of nano-size particles, [1,2] and the internal compositions of alloy nanoparticles. [3-5] Further, the well-annealed alloy nanoparticles can be electrochemical treated to increase the surface strain and to enhance the certain electrocatalytic activities such as oxygen reduction reaction (ORR). [6] After introduction of the technique and examples, we will focus on how strain in a single Pt nano-grain evolves in response to applied potential. The strain responses then will be discussed within the context of surface oxidation and oxygen-evolution reaction (OER).
For Pt nanograins of a film grown on a substrate, the strain response is tightly related to the place-exchange surface oxidation and electrochemical double layer to the applied potential range relevant to OER. During polarization, marked changes in surface strain arise from the Coulombic attraction between the electrode surface and electrolyte ions, while the strain in the bulk of the crystal remained unchanged. The concurrent surface redox reactions have a strong influence on the magnitude and nature of the strain dynamics under polarization.
In careful BCDI analyses, we found that only the top 10 nm of Pt at the grain/electrolyte interface responded sensitively to applied potential, while a much more muted response was observed for the remainder of the bulk Pt grain. The potential-dependent strain responses were not present at grain boundaries locked to the neighbor grains and at the bottom interface in contact to the substrate, neither of which were exposed to electrolyte. Our measurements further suggested that even highly stable electrodes such as Pt are subject to irreversible structural changes during polarization, highlighting the importance of in-situ/operando techniques to draw faithful structure-activity relationships in electrochemistry. These observations were possible due to the high strain sensitivity of BCDI combined with the near-zero X-ray scattering background of the submicron scale nanopipette electrochemical cell.
[1] Y. Liu et al., Nano Letters 17, 1595 (2017).
[2] W. Cha, Y. Liu, H. You, G. B. Stephenson, and A. Ulvestad, Advanced Functional Materials 27, 1700331 (2017).
[3] T. Kawaguchi et al., Physical Review Letters 123, 246001 (2019).
[4] T. Kawaguchi, W. Cha, V. Latyshev, S. Vorobiov, V. Komanicky, and H. You, Journal of the Korean Physical Society 75, 528 (2019).
[5] S. Choi et al., Nano Letters 20, 8541 (2020).
[6] T. Kawaguchi, V. Komanicky, V. Latyshev, W. Cha, E. R. Maxey, R. Harder, T. Ichitsubo, and H. You, Nano Letters 21, 5945 (2021).
Effect of Covalent Modification on Proton-Coupled Electron Transfer at Quinone-Functionalized Carbon Electrodes
Authors: Owhoso Fiki V , Kwabi David G. 
Published: November 2022

Electrodes functionalized with molecularly well-defined reactive/catalytic species have become attractive for promoting a wide variety of electrochemical energy conversion processes or systems, such as electrocatalytic CO2 and O2 reduction, as well as metal-sulfur and redox-flow batteries.1-3 Critical to the performance of these electrodes is the interaction between the electric field, and the molecular species at the electrical double layer. Nevertheless, elucidating the potential/electric field experienced at the functionalized interface is challenging. We show in this work that the acid-base thermochemical (i.e. Pourbaix) behavior of molecular quinones can vary depending on their mode of covalent attachment to a carbon electrode and ionic strength of the electrolyte, in a manner that sheds light on the experienced interfacial electric field. This work can inform strategies for effective pH modulation at electrified interfaces in ways that can enhance the electrocatalytic processes and systems mentioned above, and enable newer applications such as pH-swing-based electrochemical CO2 capture using appropriately chemically modified electrodes.4

References
1 Ren, G. et al. Porous Core–Shell Fe3C Embedded N-doped Carbon Nanofibers as an Effective Electrocatalysts for Oxygen Reduction Reaction. ACS Applied Materials & Interfaces
8, 4118-4125, doi:10.1021/acsami.5b11786 (2016).
2 Zhang, S., Fan, Q., Xia, R. & Meyer, T. J. CO2 Reduction: From Homogeneous to Heterogeneous Electrocatalysis. Accounts of Chemical Research
53, 255-264, doi:10.1021/acs.accounts.9b00496 (2020).
3 Zhao, C.-X. et al. Semi-Immobilized Molecular Electrocatalysts for High-Performance Lithium–Sulfur Batteries. Journal of the American Chemical Society
143, 19865-19872, doi:10.1021/jacs.1c09107 (2021).
4 Jin, S., Wu, M., Gordon, R. G., Aziz, M. J. & Kwabi, D. G. pH swing cycle for CO2 capture electrochemically driven through proton-coupled electron transfer. Energy & Environmental Science, doi:10.1039/D0EE01834A (2020).
(Invited) Potassium (co)Intercalation in Graphite: How Electrolyte Concentration May Trigger Different Cation Insertion Mechanisms
Authors: Le Pham Phuong Nam , Gabaudan Vincent , Boulaoued Athmane , Avall Gustav , Monconduit Laure , Johansson Patrik , Stievano Lorenzo 
Published: November 2022

Recently, potassium-ion batteries (KIB) have been considered as a potential alternative of Li-ion batteries due to the cost effectiveness and the variety of electrode materials. Graphite – the well-known anode in LIB – has gained numerous attention from KIB scientists owing to its ability of intercalating K+ ion to form KC8 with high theoretical capacity (278 mAh/g) and good cycling retention.
KFSI in DME has been considered as a promising electrolyte for KIB due to its compatibility with not only K metal but also the electrode materials. However, the electrolyte concentration strongly affects the electrochemistry of graphite. A change in the intercalating species as increasing the salt concentration, going from the cointercalation of [K(DME)x]+ (observed at 1M) to the simple intercalation of bare K+ ions (at 5M), was confirmed by galvanostatic profiles and operando XRD.
By a complementary theoretical-experimental approach combining Raman spectroscopy with quantum chemistry, we provide here an insightful and coherent explanation of the occurring of the two different mechanisms, showing that they depend upon the solvation of K+ ions in DME rather than on the different SEI formed, as usually observed in lithium batteries.
In some specific conditions, it was also possible to observe the co-existence of the two mechanisms, with the partial formation of staged intercalated-cointercalated layers, proving without doubt that the nature of the solvated species can be a major driving force driving specific ion insertion mechanisms.