bluuebunny/crossref_metadata_2025_split huggingface dataset:
Carbon Paper-Based C:TiOx Anode Material for Rapid Charge Lib Application
Authors: Wang Jyun-Siang , Shen Yu-Min , Huang Jow-Lay , Chang Chia-Chin 
Published: September 2023

As energy issues go viral, the use of lithium-ion batteries is thought to be a practical solution for electric vehicles due to its high specific capacity. However, the poor high-rate capability of the commonly used carbon anodes limits their application. In contrast, we use TiO2 as an anode to mitigate this issue. In the previous work, a non-stoichiometric TiOx nanopowder was fabricated under the influence of a reduced atmosphere to further enhance its capacity. However, due to a lack of interfacial compatibility, the high electrochemical impedance deteriorates the capacity after the first cycle. Thus, in this work, we use the methane treatment to mitigate the issue to enhance the initial coulombic efficiency from 60% to below 30%. The theoretical capacity of TiO2, TiOx, and C:TiOx are all 335 mAh/g. However, with the surface modification, the experimental capacity can improve. Besides, to avoid absorption during X-ray based analyses, we use a carbon paper substrate to mitigate this issue instead of the copper substrate. Herein, we perform an easy and effective method to improve both the ICE and the capacity at the same time by the reduction process followed by carbon doping as the artificial SEI.
The performance of the battery shows that the electrode has a great initial capacity of 1013 mAh/g with 70% ICE, and holds a retention of 700 mAh/g at a rate of 67 mA/g (0.2C) with ~100% CE after formatting. While for the battery without coating, the initial capacity is 752 mAh/g with a 70% ICE and a CE of ~100%, the retention capacity is, however, only 450 mAh/g at the same rate and decreases at a visible speed.
Based on the above ex-situ results, the mechanism during charge and discharge revealed by in-situ measurements is due. We will further use the synchrotron radiation and the in-operando Raman to clarify the phase transformation behavior, especially at a rapid charging rate.
Spatial Confinement of Li Metal in Hollow Microcapsule Hosts Enabled by Heteroatom-Driven Inward Growth
Authors: Kim Siwon , Shin Hong Rim , Lee Jong-Won 
Published: September 2023

In recent years, the demand for advanced batteries with high energy densities has increased significantly, along with the growing demand for electric vehicles. Li metal has garnered considerable research attention as a promising anode material because of its high theoretical specific capacity (3860 mAh g−1) and low electrochemical equilibrium potential (−3.040 V vs. standard hydrogen electrode). However, Li metal batteries still have several hurdles in their practical application because Li metal anodes experience infinite volume expansion, which induces continuous rupture and formation of solid-electrolyte interphase (SEI) layers. This leads to electrolyte consumption and corrosion of Li metal, resulting in a low Coulombic efficiency and poor cycling performance. In addition, the uncontrollable dendrite growth of Li metal may cause early battery failure and safety issues. To address these problems, extensive research efforts have been made, including artificial SEI layers, optimized electrolyte formula, and rational design of three-dimensional (3D) host materials.
Among the various 3D host materials under development, carbon-based materials with hollow structures have been investigated extensively because of their attractive features. The enlarged void space (cavity) of the hollow hosts can accommodate a significant amount of Li deposits, while inhibiting volume changes during plating–stripping cycles. In addition, hollow carbon possesses much lower density than metal-based materials, thereby increasing the specific capacity and energy density. However, the lithiophobic nature of carbon combined with its high resistance to Li+ transport through nanopores on the walls significantly hinders the formation of Li deposits inside the cavity. Li may nucleate on the outer surface of the carbon particles in a nonuniform manner, thereby causing the growth of Li dendrites and electrochemically inactive Li deposits.
In this study, we synthesize metal-organic framework-derived carbon microcapsules with heteroatom clusters (Zn and Ag) on the capsule walls and demonstrate that Ag-assisted nucleation of Li metal alters the outward-to-inward growth in the microcapsule host. The cavity inside the microcapsule host, which was generated by etching with tannic acid, provides large void spaces for Li metal storage. Atomic Ag clusters decorated by a galvanic displacement reaction serve as preferential nucleation sites with a reduced energy barrier and promote the inward growth of Li metal in the cavity, while suppressing nonuniform Li plating on the outer surface. Through combined electrochemical, microstructural, and simulation studies, we verify the beneficial role of Ag-assisted Li nucleation in facilitating inward growth inside the cavity of the microcapsule host, resulting in enhanced electrochemical performance. This study provides new insights into the design of reversible host materials for practical Li-metal batteries.
Multivariate Data Analysis of Multisine Impedimetric Fingerprints in Electroanalysis of Biochemical Compounds
Authors: Ryl Jacek , Bogdanowicz Robert , Pierpaoli Mattia , Niedzialkowski Pawel , Olejnik Adrian , Koterwa Adrian 
Published: September 2023

While Electrochemical Impedance Spectroscopy (EIS) is found as one of the most versatile tools of electrochemical characterization, it suffers a major drawback when the process in question is non-stationary. On the other hand, Dynamic Electrochemical Impedance Spectroscopy (DEIS) offers an ultra-fast measurement time. DEIS utilizes an approach where all the elementary components are superimposed as one multi-component perturbation signal, offering impedance spectra collection in seconds. This particular advantage allows for the effective use of DEIS in the monitoring of the adsorption processes in multiple fields, such as (bio)sensing, corrosion science, energy storage, or AFM-coupled impedance mapping.
This presentation aims at highlighting the DEIS monitoring utility carried out with changes of an independent variable, such as adsorbate concentration or even under linear polarization sweep. Rapid and accurate determination of adsorption isotherms for green organic corrosion inhibitors or Michaelis-Menten constant for enzyme-based glucose (bio)sensors with DEIS operating in galvanostatic mode and under iDC = 0 were already established. When it comes to impedimetric macromolecular electroanalysis, measuring charge transfer resistance upon analyte adsorption is the most common approach. However, the detection may also base on other factors, such as adsorbed layer capacitance or even disturbance in frequency dispersion of capacitance. Most recently, DEIS under polarization sweep mode allowed us to obtain the unique fingerprint of the electric parameter changes, specific to studied macromolecules (such as DNA strings, viral proteins, RNA polymerase, and enzymes). To effectively use our approach DEIS is combined with multivariate data analysis (principal component analysis with partial least square regression). Multivariate data analysis processes large amounts of generated impedimetric data and defines analyte-sensitive conditions (DC polarization, AC amplitude, frequency range, etc.), which can be done just by using the raw data by the singular-value decomposition method to support the sensing mechanisms. The proposed approach neglects some of the reproducibility issues induced by non-specific adsorption and fouling and reveals the measurement conditions that offer the highest variation of studied parameters upon specific analyte adsorption.

The authors acknowledge the financial support of these studies by the National Science Centre (Republic of Poland) under project 2020/37/B/ST7/03262.
Architecting for Mass Transport: It Is More Than Just Tortuosity
Authors: Resing Anton B , Werner Joerg G 
Published: September 2023

Mass transport is performance-defining across energy storage devices. An example of this limitation is evident in energy dense lithium-ion batteries (LIBs), which develop concentration gradients from insufficient transport of lithium-ions (Li-ions) when operated at high current rates. This results in lowered capacity and energy due to underutilized active material and increased overpotential. The movement of Li-ions, or lack thereof is the root cause of the trade-off that exists between energy and power density in LIBs. To alleviate societal demur towards the full adoption of electric vehicles, range anxiety and slow charging are predominant challenges that industry and academia are rushing to overcome. These goals may require reimagined processing methods to move beyond planar electrodes with disorganized and heterogeneous porosity to create architectures that are dense in active material and contain tailored porosity. To maximize the geometric component of diffusion and species flux, porous low-tortuosity channels are a rational design choice, as they act as mass-transport highways for much needed through-plane Li-ion transport.
One such innovative process is hybrid inorganic phase inversion (HIPI), a manufacturing method that is scalable, material-agnostic and results in low-tortuosity free-standing and monolithic architectures with tunable material-to-pore ratios. The HIPI process can enable electrodes with adjustable thicknesses of 100s of µm and relevant micro-architectural feature sizes between 5-40 µm, tailored by tuning the gelation temperature and nucleation density of the inorganic suspension during the nonequilibrium HIPI process. Importantly, the use of a soft organogel casting support results in the unhindered accessibility of the low-tortuosity pores present in the HIPI architectures.
HIPI-architected anode and cathode electrodes exhibit electrochemical and architectural stability over a 1000 cycles in a full-cell battery. Further, mass-transport constraints appear at high current densities, and we identify the lithiation step as rate-performance limiting, a result of insufficient Li-ion supply and concentration polarization. Thus, for energy and power dense LIBs the answer is not simply mass-transport highways as unoptimized low-tortuosity channels, rather in-plane Li-ion demands must be tethered to the through-plane transport. Our results demonstrate the need for and feasibility of tailored electrode architectures where dimensional ratios between low-tortuosity channels, the charge-storing matrix, and electrode thickness are tunable, to both understand multi-scale structure-performance relationships and meet coupled power and energy-storage requirements.
References:
[1] Resing, A. B., et. al., Adv. Mater.

2022

[10.1002/adma.202209694]

Figure 1
Investigation of Sulfide-Based Solid Electrolytes (SSE) Sensitivity Towards Humidity
Authors: Leteyi Mfiban Ivan , Profatilova Irina , Tarnopolskiy Vasily , Reytier Magali 
Published: September 2023

All-solid-state lithium-ion batteries (ASSBs) represent a new generation of energy storage tools containing only solid components. They are of great interest to researchers and manufacturers thanks to their high energy density, which makes them promising candidates for electric transport applications. Among different types of solid-state electrolytes for lithium-ion batteries (LIBs), sulfide-based electrolytes (SSEs) have several advantages, such as high ionic conductivity and malleability [1, 2]. However, one of their main drawbacks is a high sensitivity towards air humidity [3]. Fast reaction of the SSEs with water results in the degradation of their structure and release of toxic gas (H2S) when exposed to even low concentrations of humidity. This factor leads to significant process cost and safety issues associated with mass production of ASSBs with sulfide-based SEs.
The purpose of the present work is to study in details reactivity of SSEs towards humidity by following two main directions:

The development of a flow-through setup that allows a better identification and highly precise quantification of gases (H2S or others) generated during reaction between water (humidity) and commercial SSEs: this flow-through setup intends to solve problems usually encountered when using closed-type setups, which are the most used setups in the literature[3, 4]. These problems include over-concentration of detected gases and low reproducibility of measurements;

Physico-chemical and electrochemical characterizations of pristine and humidity exposed-SSEs in order to reveal the main factors affecting sensitivity towards humidity and to understand the degradation mechanisms.

First, the efficiency of the flow-through gas analysis setup developed had been validated: H2S detection curves obtained for commercial SSE powders (Li6PS5Cl, Li6PS5Br, Li7P3S11, Li3PS4, Li10GeP2S12) in contact with humid Argon (30 to 200 ppm H2O in Ar) are highly reproducible (see example in Fig. 1 and Table 1). Measurements conducted at different humidity levels allowed accessing kinetics of water-induced degradation reactions involved. SSE powders characterizations using XRD, Raman, XPS, SEM, EIS, granulometry before and after exposure to humidity provided an insight into degradation-related phenomena taking place: morphology deterioration, loss of structure and conductive structural groups, drastic increase of ionic resistance. A relationship between the structure of SSE and its reactivity towards water was found and described.

Refs
[1] Energy Storage Mater. 2018, 14, 58–74 ; [2] Nano Energy 2021, 83, 105858 ; [3] Solid State Ion. 2011, 182 (1), 116–119 ; [4] Chem. Mater. 2020, 32 (6), 2664–2672.

Figure 1
(Invited) Electrochemistry of Exceptionally Inert Systems: Determination and Speciation of Arsenic(III) and Arsenic(V)
Authors: Cox James A. , Rutkowska Iwona A. , Kulesza Pawel J. 
Published: September 2023

There has been growing interest in development of new methods for the determination of arsenic oxo species due to their high toxity and increasing population in the environment. Electrochemical methods for the determination of arsenic can be considered as complimentary to spectroscopic and chromoatographic ones because they are fairly simple, and they are subject to different selectivity criteria. In this respect, various stripping voltammetric procedures are becoming popular. The actual stripping voltammetric measurement consists of two steps in which preconcentration of an analyte at the electrode surface is followed by the so called „stripping” step involving electrode reaction recorded in a form of the voltammetric peak. A representative approach involves reduction of the analyte anions upon application of the sufficiently negative potential to form As(0) on the electrode (e.g. gold) surface; this step is followed by voltammetric oxidation (anodic stripping) of the deposit (to As(III)). In a case of so called cathodic stripping voltammetry, the stationary Hanging Mercury Drop Electrode (HMDE) is often used. During the preconcentration step, an insoluble salt (e.g. Cu3As2) is produced on the electrode surface. There is also a need to differentiate between As(III) and As(V) oxo-species, which are relatively more and less toxic, respectively.
Because sensitivity and detection limit in electroanalytical determinations strongly depend on the current densities measured, there is a need to search for specific catalytic materials that would induce otherwise highly slow and irreversible redox processes of As(III) (oxidation) and, in particular, As(V) (reduction). Our research interests concern development of highly specific catalytic systems leading to the enhancement of the electrooxidation of arsenic (III). We explore here the capability of various noble metals nanoparticles (Pt, Rh, Pd) of inducing the arsenic(III) oxidation in acidic medium. The recorded currents have been compared to those observed previously at the electrodes modified with oxocyanoruthenates, the most potent system for the electrocatalytic oxidation of AsIII(OH)3. Reduction of arsenic (V) is even the more inert reaction. Network films of bimetallic (PtRu) nanoparticles (bare and derivatized) permit preconcentration of arsenic(V) species on their surfaces. The stripping step would allow determination of low concentrations of arsenic (10-6 mol/dm-3 or lower).
Promoting Hydrogen Evolution and Oxidation by Reconstructing Hydrogen-Bonding Network of Interfacial Water
Authors: Sun Qiang , Oliveira Nicholas J , Yan Yushan , Kwon Soonho , Goddard William , Li Jingkun , Tyukhtenko Sergiy , Guo Jason , Myrthil Nathalie , Lopez Steven , Kendrick Ian , Mukerjee Sanjeev , Ma Lu , Ehrlich Steven , Jia Qingying 
Published: September 2023

The hydrogen evolution and oxidation reactions (HER/HOR) at the electrode-water control the performance of water electrolyzers and hydrogen fuel cells, two important devices for deep decarbonization of our economy (1). Platinum (Pt) catalyzes the HER/HOR with exceptional activity and stability across a wide pH range. However, its activity progressively decreases by about two orders of magnitude as the pH increases from 0 to 13 (2, 3). The lack of understanding of this pH dependence reflects our fundamental knowledge gaps in electrochemistry and has hindered the advancement of alkaline electrolyzers and fuel cells.
Herein, we promoted the HER/HOR of Pt in base by introducing N-methylimidazoles in the Pt-water interface. In situ spectroscopic characterization of the interface together with computations showed that the N-methylimidazoles form strong hydrogen-bonding with neighboring water molecules thereby reconstructing the H-bond network of interfacial water. We accordingly established a unified mechanism by which the HER/HOR in acid and base proceeds via diffusion of protons and hydroxides, respectively through the H-bond network of interfacial water by the Grotthuss mechanism. This mechanism accounts for the pH-dependent HER/HOR kinetics of platinum, a long-standing puzzle. Utilization of N-methylimidazoles as the HER/HOR probes and promoters not only leads to the elucidation of the HER/HOR mechanism but also holds great promise for applications. We have demonstrated 40% performance improvement of an anion exchange membrane water electrolyzer by adding 10-5 M 1,2-dimethylimidazole into the 0.1 M potassium hydroxide solution fed into its Pt cathode.

Acknowledgements

This work was supported by the Office of Naval Research (ONR) grant N000141712608 (Q.J.)
This research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory Contract DE-SC0012704. Beamline operations were supported in part by the Synchrotron Catalysis Consortium Grant DE-SC0012335.

V. R. Stamenkovic, D. Strmcnik, P. P. Lopes and N. M. Markovic, Nat. Mater., 16, 57 (2017).

J. Durst, A. Siebel, C. Simon, F. Hasché, J. Herranz and H. A. Gasteiger, Energy Environ. Sci., 7, 2255 (2014).

W. Sheng, Z. Zhuang, M. Gao, J. Zheng, J. G. Chen and Y. Yan, Nat. Commun., 6 (2015).

Figure 1
Synthesis of Self-Assembled Molecules Based on Tetraphenylethene-Core Inducing Emission
Authors: Tran Hoang Thi Thuy , Kim Donghwan , Rémond Maxime , Kim Eunkyoung 
Published: September 2023

Aggregation-induced emission (AIE) organic materials have been extensively explored for a future sensible and interactive display to provide high luminescence in ordered states. However, it is challenging for reducing exciton quenching of aggregated materials to achieve high emission and increasing ordered structure to yield high crystallinity as well. To this end, the new structures based on tetraphenylene (TP) core were synthesized by attaching TP with clipping groups (C) consisting of a self-assembling group (SAG) to enhance emission intensity and spectra shift.
As the emissive materials for self-assembly, TPCns with different clip numbers (n=1,2,4) were synthesized through the Wittig-Hörner reaction, where clips consist of extended π-conjugated moiety and the alkyl chain as a segment. The clips could introduce van der Waals interaction to facilitate self-assembly among clips and clip-connected aromatic units. These structures were confirmed and analyzed by different tools including 1HNMR, 13CNMR, FTIR-ATR, element analysis, MALDI-TOF/TOF. The optical properties of TPCns were discussed in solution state and solid state. In terms of photoluminescent emission, the TPC4 showed a more yellowish-green emission (λem = 525nm in THF) and large aggregation-induced emission enhancement (EAIE) in aqueous (fw > 50%) THF solution. The greenish blue emission was realized for TPC1 at the maxima wavelength 481 nm and reached 100% quantum yield in the solid state. Furthermore, due to strong twisted intramolecular charge transfer, TPCn molecules had large Stokes shifts in ranges of 5800–6800 cm−1 for TPC1, TPC2, and 10700–12500 cm−1 for TPC4.
Microneedle Enabled Electrochemical Aptamer-Based Sensing: Real Time Measurements Using Stainless Steel Microneedles
Authors: Downs Alex , Miller Phil , Weaver Bryan , Polsky Ronen , Monteith Hailey , Wolff Nathan 
Published: September 2023

Electrochemical aptamer-based (EAB) sensors are among the only generalizable sensing platforms that resist fouling enough to function directly in bodily fluids and in situ in the living body. Already, these sensors have enabled the real-time measurement of a range of small molecule targets in vivo, including pharmaceuticals and drugs of abuse. EAB sensors consist of an electrode-attached, redox reporter-labeled aptamer that binds to its target species. Target binding causes a shift in electron-transfer rate between the redox reporter and electrode surface, easily detected by a range of electrochemical techniques. Here, we explore the application of EAB sensors to minimally-invasive molecular monitoring. Specifically, we adapt the platform to a microneedle device format. Microneedles can provide direct access to the skin’s interstitial space – a bodily compartment that holds valuable information ranging from drug distribution and immune status. And because microneedles can penetrate into the top layers of the skin with minimal nerve endings, they can avoid eliciting notable pain responses.
In this work, we demonstrate the substantial miniaturization of the sensing platform into electrodes thinner than a human hair, and then integrate them with ultra-fine, hollow microneedles. To ensure needle sterilizability and sharpness while avoiding complex fabrication, we utilize commercial off the shelf stainless steel microneedles. Using an EAB sensor responding to the high-toxicity small molecule drug, vancomycin, as a model system, we achieve quantitative measurements directly in body temperature, undiluted whole blood. Building on this milestone, we explore the application of the sensors when inserted into porcine skin. In porcine skin (a common proxy for human skin), we observe facile microneedle penetration and stable electrochemical signaling. Because of the individual addressability of the sensing electrodes and the generalizability of the aptamer platform, this technology is capable of multiplexed, simultaneous detection of many different molecular targets. Thus, microneedle-enabled aptamer-based sensors offer a promising route forward for non-invasive physiological monitoring – applicable to therapeutic drug monitoring, pain-free biomarker detection, and disease management.