bluuebunny/crossref_metadata_2025 huggingface dataset:
Formation of the Heterojunction Based on Titania Modified with Ni and Ag Sulfide Via SILAR Method - Electrochemical and Photoelectrochemical Activity
Authors: Lipinska Wiktoria , Shinnur Manjunath , Grochowska Katarzyna , Crisp Ryan , Siuzdak Katarzyna
Published: February 2024

The great interest of TiO2 nanotubes (TiNT) is justified by large surface area, high degree of ordering, facilitated charge transport along the nanotube, mechanical strength, strong UV absorption and light scattering due to the pore specific arrangement well as wide range of potential applications in solar cells, photocatalysis and sensors [1]. However, due to the wide energy band gap of TiO2 (3.2 eV) its photoactivity is limited and therefore titania based heterojunction are formed with the photoabsorber being active in the visible range [2]. In line with this strategy, we present electrochemical and photoelectrochemical activity of TiNT modified by NiS and AgS.

The electrode is fabricated via electrochemical anodization of Ti foil, thermal annealing providing anatase phase and finally Successive Ionic Layer Adsorption and Reaction (SILAR) was carried out using silver, nickel and sulfur ions precursor and with different number of deposition cycles. The characteristic Ag-S, Ag-O and S-O peaks appearing on Raman spectra indicating successful SILAR modification. The cyclic voltammetry curves for TiNT, NiS/TiNT, AgS/TiNT and AgS/NiS/TiNT electrode were registered in 0.5 M Na2SO4 (Fig.1a). Peaks found on the anodic branch of the AgS/NiS/TiNT electrode at 0 V and +0.3 V vs. Ag/AgCl/0.1 M KCl are assigned to oxidation of Ag0 to Ag1+ and Ag1+ to Ag2+, respectively. When the scan went towards cathodic direction, peak located at +0.1 V and -0.1 V indicates reduction of Ag2+ to Ag1+ and Ag1+ to Ag0, respectively [3]. Furthermore, the linear voltammetry measurements performed under visible light illumination in 0.5 M Na2SO4 is presented in Fig.1b. The best photoactivity was reached for the AgS/NiS/TiNT electrode when only 5 deposition cycles for each metal precursor was applied. The photocurrent registered at +0.5 V reaches ca. 40 µA/cm2 which is 20 times higher than for pure TiNT.

Summing up, modification of titania nanotubes by nickel and silver sulfides significantly enhanced material photoelectrochemical response under visible light. Moreover, it has been proved that this synergetic effect originated from the titania/metal sulphide heterojunction that can be achieved using SILAR method.

Research is financed by National Science Centre (Poland): Grant no. 2020/39/I/ST5/01781

[1] K. Siuzdak et al. RSC Advances, 5 (2015) 50379, DOI:10.1039/c5ra08407e

[2] S. Chandrasekaran et al. Chemical Society Reviews, 48 (2019) 4178, DOI:10.1039/c8cs00664d

[3] J.R.N. Santos et al. Electrocatalysis, 13 (2022) 713, DOI: 10.1007/s12678-022-00754-2

Figure 1
Effect of pH on the Selectivity of γ-MnO2 Electrocatalysts Towards Oxygen Evolution Reaction in the Presence of Chloride Ions in Alkaline Environment
Authors: Baturina Olga A , Finn Matthew , Weathers Brandice
Published: February 2024

Pt-Nb anodes utilized in the cathodic protection system onboard of Naval ships generate NaOCl (and eventually Cl2) that (1) limits the materials that can be used in the vicinity of the anodes and (2) has a severe impact on living organisms in the marine environment. The environmentally-friendly oxygen evolution reaction (OER) from H2O is thermodynamically more favorable due to a lower equilibrium potential [1]. However, chlorine evolution successfully competes with the OER due to faster kinetics. One of a few catalysts that demonstrates high selectivity towards the OER in the presence of chloride ions in alkaline environment (pH 12) is g-MnO2 [2]. In this presentation, we will (1) compare activities and selectivities towards the OER of electrodeposited and chemically synthesized g-MnO2 and (2) determine how pH affects selectivity in the pH range from 8 to 12.

References

[1] F. Dionigi, T. Reier, Z. Pawolek, M. Gliech, P. Strasser, Chemsuschem, 9 (2016) 962.

[2] K. Fujimura, T. Matsui, K. Izumiya, N. Kumagai, H. Habazaki, A. Kawashima, K. Asami, K. Hashimoto, Materials Science and Engineering a-Structural Materials Properties Microstructure and Processing, 267 (1999) 254.
Electrospun Polymer Supported Cux O Nanostructures for CO2 Reduction Reaction
Authors: Elbataioui Adam , Abdalaziz Aljabour , Wurster Stefan , Bautista Daniel , Schlögl Sandra , Eckert Jürgen , Rafailovic Lidija D.
Published: February 2024

The reduction of carbon dioxide (CO2) to value-added products is a promising approach for mitigating the impact of CO2 emissions on the environment [1]. Copper oxide (CuO) and copper oxide (Cu2O) have been identified as effective catalysts for CO2 reduction reaction (CO2RR) due to their unique electronic properties [2]. Electrospinning is a versatile and efficient technique for the fabrication of high surface area polymer (P) nanofibers which enables a promising range of applications in energy storage and conversion [3].

In this study, we investigate the synthesis of CuxO-incorporated polyacrylonitrile (PAN) and PAN/polyaniline (PANI) nanofibers via electrospinning and evaluate their performance as a catalyst for CO2RR. The CuxO/P nanofibers were characterized by various techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy.

The results revealed that CuxO nanoparticles were dispersed on the surface of the polymer nanofibers. The XRD analysis confirmed the presence of crystalline CuxO nanoparticles in the nanofibers. The FTIR spectra indicated that CuxO was successfully incorporated into the polymer nanofibers without new chemical bond formation between CuxO and PAN.

The catalytic performance of CuxO/P nanofibers was evaluated for CO2RR in a three-electrode electrochemical cell. The CuxO/P nanofibers showed a significantly enhanced catalytic activity for CO2RR. Moreover, the CuxO/P nanofibers showed good stability during the electrochemical CO2RR.

The enhanced catalytic performance of CuxO/P nanofibers can be attributed to the unique electronic properties of CuxO nanoparticles, which can facilitate the adsorption and activation of CO2 molecules. Furthermore, the high surface area and porous structure of the polymer nanofibers provide abundant active sites for the CO2RR. The dispersion of CuxO nanoparticles on the surface of the polymer nanofibers can also enhance electron transfer and reduce charge transfer resistance during the CO2RR.

In conclusion, CuxO-incorporated polymer nanofibers were successfully synthesized by electrospinning and showed excellent catalytic activity for CO2RR. The CuxO/P nanofibers exhibited high selectivity and stability for the electrochemical reduction of CO2 to useful chemicals. These findings suggest that CuxO/P nanofibers have great potential as an efficient catalyst for CO2RR and could contribute to the development of sustainable energy conversion and storage systems.

[1] A. Aljabour, D. H. Apaydin, H. Coskun, F. Ozel, M. Ersoz, P. Stadler, N. S. Sariciftci, and M. Kus, ACS Applied Materials & Interfaces, 8 (46), 31695-31701 (2016).

[2] R. W. Abebe, H. Zanling, Z. Pengxiang, H. Liangsheng, A. Didier, Coordination Chemistry Reviews, 454, 214340 (2022).

[3] A. Aljabour, ChemistrySelect
5, 7482 (2020).

Figure 1
The Electronic Structure of Transition Metal (TM) Oxides for the Oxygen Evolution Reaction: The Critical Role of TM 3d Hole State
Authors: Oropeza Freddy , Wang Hongxia , Zhang Kelvin Hongliang , Hofmann Jan Philipp , de la Peña O'Shea Victor A.
Published: February 2024

Electrolysis of water to produce hydrogen and oxygen is a promising pathway for the storage of renewable energy in form of chemical fuels. The efficiency of the overall process is usually limited by the sluggish kinetics of the oxygen evolution reaction (OER) due to a complex four-electron/proton transfer mechanism. Therefore, the most crucial step for water electrolysis to become a widespread industrial process is to develop efficient electrocatalysts capable of driving the OER at a low overpotential.[1,2]

In this talk, I will summaries the key electronic features that induces high catalytic activity towards the oxygen evolution reaction of trivalent transition metal (TM) oxides with perovskite structure, such as LaCoO3
[3] and LaFeO3.[4] The partial substitution of La for Sr in LaTMO3 results in the oxidation of TM3+ to TM4+ and substantially enhances OER catalytic activity. A comprehensive X-ray spectroscopic study, based on in-situ XPS and XAS, reveals a strong correlation of the enhanced OER catalytic activity with the presence of cations in the 4+ oxidation state. Increasing the concentration of TM cations in the 4+ oxidation state leads to a more covalent TM–O bond due to higher TM 3d–O 2p orbital hybridization and shifts the energy position of the valence band (VB) closer to the Fermi level (E
F). Such an electronic modulation optimizes the surface adsorption energetics of *OH intermediates, contributing to faster OER kinetics. Furthermore, the oxidation of TM3+ to TM4+ creates a new unoccupied state (hole state) below the conduction band, associated with the formation of TM 3d empty electronic states. This hole states reduce the energy barrier for electron transfer associated with the OER, as illustrated in the figure below, thereby facilitating charge transfer at the interface during the reaction.

Figure 1: Key electronic features of transition metal (TM) oxides for the oxygen evolution reaction

References:

[1] M. Cui, X. Ding, X. Huang, Z. Shen, T. L. Lee, F. E. Oropeza, J. P. Hofmann, E. J. M. Hensen, K. H. L. Zhang, Chem. Mater.
2019, 31, 7618.

[2] H. Wang, K. H. L. Zhang, J. P. Hofmann, V. A. de la Peña O’Shea, F. E. Oropeza, J. Mater. Chem. A
2021, 9, 19465.

[3] Z. Shen, M. Qu, J. Shi, F. E. Oropeza, V. A. de la Peña O’Shea, G. Gorni, C. M. Tian, J. P. Hofmann, J. Cheng, J. Li, K. H. L. Zhang, J. Energy Chem.
2022, 65, 637.

[4] Z. Shen, Y. Zhuang, W. Li, X. Huang, F. E. Oropeza, E. J. M. Hensen, J. P. Hofmann, M. Cui, A. Tadich, D. Qi, J. Cheng, J. Li, K. H. L. Zhang, J. Mater. Chem. A
2020, 8, 4407.

Figure 1
Construction of Dendrite-Free Metallic Lithium Anodes: From Static Lithiophilic Adsorption to Dynamic Electrochemical Diffusion Kinetics
Authors: Wang Jian , Lin Hongzhen , Passerini Stefano
Published: February 2024

Lithium metal batteries (LMBs) possess high theoretical energy density, becoming a promising next-generation energy storage system.1, 2 However, the applications of Li metal anodes are restricted by the Li dendrite formation, repeated formation and fracturing of solid electrolyte interphase (SEI), and large volume expansion, resulting in severe “dead lithium” and subsequent short circuiting.3, 4 Herein, differing from conventional interfacial engineering or current-collector designs with numerous lithiophilic site, fundamental novel insights of Li plating kinetics via using single-atomic catalyst (SAC) activators to boost Li diffusion behaviors is proposed to realize delocalized deposition.5, 6 Specifically, via the aid of series of characterizations and theoretical simulations, the SACs have the ability in decreasing barriers of desolvation, Li ion transport or Li atom diffusion and we have unambiguously depicted that the SACs serve as kinetic activators in propelling the surface spreading and lateral redistribution of the lithium atoms for achieving dendrite-free plating morphology.

Reference:

Wang, J.; Hu, H.; Zhang, J.; Li, L.; Jia, L.; Guan, Q.; Hu, H.; Liu, H.; Jia, Y.; Zhuang, Q.; Cheng, S.; Huang, M.; Lin, H. Hydrophobic lithium diffusion-accelerating layers enables long-life moisture-resistant metallic lithium anodes in practical harsh environments. Energy Storage Mater.
2022,
52, 210-219.

Zhang, J.; He, R.; Zhuang, Q.; Ma, X.; You, C.; Hao, Q.; Li, L.; Cheng, S.; Lei, L.; Deng, B.; Li, X.; Lin, H.; Wang, J. Tuning 4f-Center Electron Structure by Schottky Defects for Catalyzing Li Diffusion to Achieve Long-Term Dendrite-Free Lithium Metal Battery. Adv. Sci. (Weinh)
2022,
9, (23), e2202244.

Wang, J.; Li, L.; Hu, H.; Hu, H.; Guan, Q.; Huang, M.; Jia, L.; Adenusi, H.; Tian, K. V.; Zhang, J.; Passerini, S.; Lin, H. Toward Dendrite-Free Metallic Lithium Anodes: From Structural Design to Optimal Electrochemical Diffusion Kinetics. ACS Nano
2022,
16, 17729−17760.

Zhang, J.; You, C.; Lin, H.; Wang, J. Electrochemical Kinetic Modulators in Lithium–Sulfur Batteries: From Defect‐Rich Catalysts to Single Atomic Catalysts. Energy & Environmental Materials
2022,
5, (3), 731-750.

Wang, J.; Zhang, J.; Cheng, S.; Yang, J.; Xi, Y.; Hou, X.; Xiao, Q.; Lin, H. Long-Life Dendrite-Free Lithium Metal Electrode Achieved by Constructing a Single Metal Atom Anchored in a Diffusion Modulator Layer. Nano Lett.
2021,
21, (7), 3245-3253.

Wang, J.; Zhang, J.; Duan, S.; Jia, L.; Xiao, Q.; Liu, H.; Hu, H.; Cheng, S.; Zhang, Z.; Li, L.; Duan, W.; Zhang, Y.; Lin, H. Lithium Atom Surface Diffusion and Delocalized Deposition Propelled by Atomic Metal Catalyst toward Ultrahigh-Capacity Dendrite-Free Lithium Anode. Nano Lett.
2022,
22, (19), 8008-8017.
Investigations on the Initial-Stages of Lithium Deposition/Dissolution Processes in Sulfolane Based Electrolytes
Authors: Genov Ivan , Tesfaye Alexander , Ivanov Svetlozar , Bund Andreas
Published: February 2024

Li metal could be the ideal anode for rechargeable battery technologies, due to its negative redox potential (ca. -3 V vs. SHE), high specific capacity (3860 mAh g−1), and low density (0.534 g cm−3) [1-3]. Recent advances show a new design concept where there are no initial active materials in the anode (no carbon, Si, or Li metal) and the corresponding Li quantity is directly deposited on the current collector during charging. This approach will result in important practical advantages such as enhanced volumetric and gravimetric specific energies, ease of manufacturing and reduced complexity/safety concerns of the recycling process (ideally Li is completely removed in the discharged state). However, the applicability of the Li-metal batteries is constrained by the nonuniform lithium deposition, accompanied by dendrite growth and the formation of dead lithium during long-term cycling, which lead to low Coulombic efficiency and even cell failure [2]. The initial structure and morphology of the Li deposit has a vital influence on the later progression of the Li layer [4]. This underpins the importance of a fundamental understanding of the electrodeposition process. However, the presence of a solid-electrolyte interphase (SEI) makes such investigations difficult, since after the transport of the Li ions through the SEI, a subsequent charge transfer and nucleation growth process at the substrate-SEI interface, instead of substrate-liquid electrolyte interface occurs. This contribution will discuss lithium electrodeposition in a sulfolane based, localized high concentrated electrolyte system. Possible phase formation mechanisms as well as kinetic and thermodynamic aspects during the initial stages of the process are studied by classical electrochemical methods (Fig. 1, left). Furthermore, the mass-charge balance during deposition and stripping was monitored (Fig. 1, right) via in-situ microgravimetry (electrochemical quartz crystal microbalance). In the contribution we will discuss these transients in terms of lithium layer growth and SEI formation.

References:

[1] X. Cheng et al., (2017) Chemical Reviews, 117 (15), p. 10403-10473.

[2] J. Cui et al., (2017) Chinese Chemical Letters, 28 (12), p. 2171-2179.

[3] Z. Hu et al., (2020) Frontiers in chemistry 8, p. 409.

[4] A. Pei et al., (2017) Nano Letters, 17 (2), p. 1132–1139.

Figure 1
Synthesis and Interface Stabilization of Chalcogenide-Based Solid Electrolytes in Solid-State Sodium Batteries
Authors: Wang Hui
Published: February 2024

Rechargeable sodium (Na) batteries that utilizing solid-state ion conductors have attracted intense attentions for large-scale energy storage systems due to the abundant resources of Na compounds and electrochemical voltage (2.70 V vs. 3.05V for Li). So far, the most popular inorganic Na-ion SEs include oxides, halides, and chalcogenides such as Na3PhCh4 (Ph=P, Sb; Ch=S, Se) etc. In specific, Na3SbCh4 (Ch=S, Se) chalcogenide conductors exhibit impressive ionic conductivity at room temperature due to vacancy-assisted three-dimensional (3D) ion transport channels. In this talk, we will introduce our works on the studies on in-situ synthesis of Na chalcogenide solid electrolytes (SEs) and several strategies for interface stabilization of such SEs towards Na anode. The in-situ synthesis studies of Na3SbCh4 (Ch=S, Se) reveal the structural evolutions during the solid-state reaction process.1 Besides, efficient interface stabilization strategies have been demonstrated to enable solid-state Na metal batteries that using Na as the anode, and metal sulfide (TiS2 or FeS2) as the cathode.2, 3 For instance, phase transition interlayer (PEG-PPG-PEG) has been successfully proved to prevent the side reactions between the Na3SbS4 SE and Na metal and contribute to the uniform Na deposition at interface to prevent dendrite formation and growth. The goal of our work is to develop novel chalcogenide Na conductors and promote their applications in solid-state Na batteries.

Halacoglu, S.; Chertmanova, S.; Chen, Y.; Li, Y.; Rajapakse, M.; Sumanasekera, G.; Narayanan, B.; Wang, H., Visualization of Solid-State Synthesis for Chalcogenide Na Superionic Conductors by in-situ Neutron Diffraction. ChemSusChem
2021,
14 (23), 5161-5166.

Li, Y.; Arnold, W.; Halacoglu, S.; Jasinski, J. B.; Druffel, T.; Wang, H., Phase-Transition Interlayer Enables High-Performance Solid-State Sodium Batteries with Sulfide Solid Electrolyte. Advanced Functional Materials
2021,
31 (28), 2101636.

Li, Y.; Halacoglu, S.; Shreyas, V.; Arnold, W.; Guo, X.; Dou, Q.; Jasinski, J. B.; Narayanan, B.; Wang, H., Highly efficient interface stabilization for ambient-temperature quasi-solid-state sodium metal batteries. Chemical Engineering Journal
2022,
434, 134679.
In-Operando Detection Method for Lithium Metal Deposition during Fast Charging of Lithium-Ion Batteries Derived from Impedance Modeling
Authors: Keilhofer Josef , Dorau Filip Adam , Hsiao Hao-Chen , Daub Rüdiger , Suthar Bharatkumar
Published: February 2024

Lithium-ion batteries play a key role in the electrification of the transport sector. However, to replace combustion engines with battery-powered electric drive trains, the fast charging capability is essential. Therefore, it is necessary to identify the optimum operating window for lithium-ion cells. A strict criterion for optimization is to prevent lithium metal deposition at the anode, as this undesired side reaction can pose serious safety risks. An efficient technique to optimize charging strategies while tracking lithium plating is needed, as existing approaches have limitations such as a lack of in-line capability, low time precision, or complex experimental setups. In this study, a simple lithium metal deposition detection method is derived from a three-electrode setup. This in-operando method is applied during fast charging using dynamic electrochemical impedance spectroscopy. To model the acquired impedance spectra, a novel equivalent circuit is developed. The model is used to elucidate characteristic impedance features of anodes with deposited lithium metal. These observed characteristic features are then applied to a simplified measurement method in full cells using a single-frequency signal. The precision and high temporal resolution of both methods are demonstrated through validation. Furthermore, the simplified method can be applied in in-operando applications, making it suitable for diverse research and industrial contexts.
(Invited) Engineering Local Chemical Environments in Electrolytes and at Electrode-Electrolyte Interface for Efficient Aqueous Batteries
Authors: Lukatskaya Maria R.
Published: February 2024

Electrolytes are an essential component of energy storage devices. Electrolyte composition has a significant impact on the environmental footprint, safety, price and performance of a battery. Aqueous electrolytes are non-flammable and can offer safer battery operation and lower toxicity. However, they suffer from a smaller electrochemical stability window compared to traditional organic electrolytes, which leads to lower energy density. To circumvent the small electrochemical stability window, highly concentrated “water-in-salt” (WIS) electrolytes, which demonstrate significantly wider stability window, were proposed and successfully applied to various aqueous energy storage systems including Li-ion and Zn metal batteries that are highly attractive for grid energy storage. However, since WIS electrolytes require large amounts of salt (often toxic) and have dramatically increased viscosity, it in turn limits their transport properties, charge-discharge rates, and usability in batteries.

In this talk, the use of highly concentrated "water-in-salt" (WIS) electrolytes as a means of achieving increased charging efficiency and a wider stability window will be discussed in the context of aqueous Li-ion and Zn metal batteries. Further, we elaborate the role of cation solvation environment, electrolyte structure and hydrogen bonding on the physicochemical properties and electrochemical response of the system. We show that electrolyte composition affects the interfacial kinetics of Zn plating/stripping as well as the kinetics of the parasitic processes of electrolyte decomposition. Finally, we discuss how relatively dilute electrolytes can be engineered for efficient aqueous batteries.

References

Suo, O. Borodin, T. Gao, M. Olguin, J. Ho, X. Fan, C. Luo, C. Wang and K. Xu, Science, 2015, 350, 938

Yamada, K. Usui, K. Sodeyama, S. Ko, Y. Tateyama and A. Yamada, Nat. Energy, 2016, 1, 16129

R. Lukatskaya, J.I. Feldblyum, D.G. Mackanic, F. Lissel, D.L. Michels, Y. Cui, Z. Bao, Energy Environ. Sci., 2018, 11, 2876-2883

D.G. Vazquez, T. P. Pollard, J. Mars, J.M. Yoo, H.G. Steinrück, S. E. Bone, O. V. Safonova, M. F. Toney, O. Borodin, M.R. Lukatskaya, Energy Environ. Sci., 2023, DOI: 10.1039/D3EE00205E
Combined Operando Investigations Reveal Correlation between Formation Parameters and Transport Mechanisms in Solid Electrolyte Interphases of Lithium-Ion Battery Anodes
Authors: Stich Michael , Valdes Landa Jesus Eduardo , Pantenburg Isabel , Roling Bernhard , Bund Andreas
Published: February 2024

Despite its thickness being only in the nanometer range, the solid electrolyte interphase (SEI) of lithium-ion battery anodes has proven to be a crucial component, contributing critically to the battery’s longevity and long-term rate capability. This is due to the SEI’s passivating properties, protecting the battery electrolyte from further decomposition during operation while maintaining a good conductivity for lithium ions to be intercalated into the active anode material. Notwithstanding prolonged scientific efforts, a reliable SEI characterization is still very challenging, due to its fragile and inherently unstable nature which can easily lead to the introduction of artifacts in its evaluation, when dried, rinsed, or exposed to ambient atmospheric conditions. Thus, the relation between SEI formation parameters and the resulting morphological, compositional, and electrochemical properties is still poorly understood.

To overcome the limitations of often-employed ex-situ methods, we developed an interlocked combination of several non-destructive operando characterization methods consisting of atomic force microscopy (AFM), electrochemical quartz-crystal microbalance (EQCM) and electrochemical impedance spectroscopy (EIS) to provide a plethora of information on the SEI’s morphological evolution, mass and thickness development and its viscoelastic and electrochemical properties like charge transfer resistance. All this information is gathered in the same electrochemical cell during the SEI formation on carbon model electrodes in typical LIB electrolytes containing 1 M LiPF6 in various carbonate mixtures.

The combination of AFM, EQCM and EIS data gives us the opportunity to correlate the different growth modes during formation and resulting compositions of the SEI with its dominant transport mechanisms. Additional redox probe experiments help to further distinguish the transport parameters for lithium ions, solvent molecules, and redox molecules. A better understanding of these correlations allows battery researchers to find optimized SEI formation procedures and SEI forming additives, which reduce the formation duration during battery production and can thus contribute to lowering costs of lithium-ion batteries.
Theoretical and Experimental Performance Characterization of Battery Anodes Comprised of Coal Derived Graphite
Authors: Paul Abigail , Magee Regan , Wilczewski Warren , Wolfe Kody D , Wichert Nathan , Wang Fengkun , Trembly Jason , Staser John A. , Garrick Taylor R.
Published: February 2024

As demand for energy storage expands, securing reliable supply-chains for raw battery materials is critical in mitigating the threats of delayed manufacturing and inflated manufacturing costs. These issues have pushed researchers and industry to consider alternative sources for traditional lithium-ion battery materials, such as graphite. Commonly available sources of graphite for Li-ion anodes include natural graphite and petroleum coke derived synthetic graphite. While many carbon sources have been studied, most require complicated processing and result in sub-par graphite anode materials. This talk highlights raw coal and coal derived materials as promising graphite sources thanks to their abundance of sp2 hybridized carbon, resulting in simpler processing, and low material costs.

We show that coal derived graphite can be implemented as a lithium-ion anode, however, many chemical, microstructural, and morphological considerations are necessary to compare with commercial graphite performance. We will experimentally compare the morphology at the microstructure for graphite from various carbon sources, and then apply the virtual microstructure analysis method as detailed by Lopata et al to quantify potential differences between the anode microstructures with respect to effective active material particle size (diffusion length calculation), the electrochemical surface area, and the tortuosity of the liquid phase domain. These calculations from representative 3D microstructures can then be extended to a porous electrode model as detailed in Garrick et al to probe the impact in ionic, kinetic, and ohmic losses in the system.

References

Joseph S. Lopata et al 2023 J. Electrochem. Soc.
170 020530

Taylor R. Garrick et al 2021 J. Electrochem. Soc.
168 010530
Adaptation of a Vanadium Redox Flow Battery for Thermal Applications Using a Solid Capacity Booster
Authors: Berling Sabrina , Hidalgo Jose Manuel , Mavrikis Sotirios , Patil Nagaraj , Garcia - Quismondo Enrique , Palma Jesus , Ponce de Leon Carlos
Published: February 2024

In this work a novel approach for the use of the Vanadium Redox Flow Batteries (VRFB) is made by viewing it as a dual system with the ability to store both electrical and thermal energy. Electrical energy is thanks to the electrochemical reactions of the vanadium ions dissolved in the electrolyte, while thermal energy will use the sensible heat of the electrolyte mass.

The performance of VRFB has been widely studied over the last 40 years and there is an extensive bibliography on the subject regarding the electrochemical performance attending only to the conventional energy storage requirements, but the hybrid electrical-thermal function is a novel subject that has been scarcely explored. One of the most critical aspects is the narrow operating temperature range of these batteries (15-40°C) that strongly limits their thermal energy storage capacity.

Practical vanadium electrolytes operate with electrolytes containing a vanadium concentration between 1.6 and 2.0 M, and usually also employ cooling and heating systems to maintain the temperature between 15 and 40ºC. In particular, at temperatures below 15ºC the slower reaction kinetics, high viscosity and reduced conductivity of the concentrated electrolytes introduce remarkable energy losses in the battery. On the other hand, at temperatures over 35ºC the positive electrolyte is not stable due to the limited solubility of VO2
+ species. High temperatures also boost the kinetics of parasitic reactions such as hydrogen and oxygen evolution, thus increasing energy losses.

In this study, we address these limitations aiming to open up new possibilities of a successful integration of vanadium redox flow batteries into thermal applications. For this, the functionality and stability limits of a diluted vanadium electrolyte are analyzed for an extended operational temperature window from 5ºC to 50ºC and compared to commercial electrolyte formulations. In a second step, the use of a solid capacity booster is investigated to compensate the loss of energy density due to electrolyte dilution.

[1] S. Berling, S. Mavrikis, N. Patil, E. García – Quismondo, J. Palma, C. Ponce de León “Lignin as redox-targeted catalyst for the positive vanadium electrolyte”, Electrochemistry Communications 142 (2022) 107339.

[2] S. Berling, J. M. Hidalgo, N. Patil, E. García - Quismondo, J. Palma, C.Ponce de León, “A mediated vanadium flow battery: Lignin as redox-targeting active material in the vanadium catholyte”. Submitted
Manufacturing Strategies for Engineering Carbon Electrodes Via Non-Solvent Induced Phase Separation
Authors: Jacquemond Remy Richard , Wan Charles Tai-Chieh , Brushett Fikile R. , Forner-Cuenca Antoni
Published: February 2024

Porous electrodes are at the core of emerging electrochemical systems and tuning the electrode properties is critical to overcome system-specific limitations. To meet the stringent performance and cost requirements, there is a need for tailored microstructures generated through inexpensive and scalable synthesis methods with precursors originating from reliably-sourced, globally-abundant feedstocks. To this end, we recently introduced a manufacturing route using non-solvent induced phase separation (NIPS), yielding porous carbon electrodes with multimodal and interconnected porosity. The synthesized NIPS electrodes demonstrated a beneficial trade-off between transport properties (permeability, mass transfer) and electrochemically active surface area (ECSA) resulting in high performance in iron and all-vanadium redox flow batteries (RFBs)[1,2]. Moreover, NIPS manufacturing offered control over electrode characteristics (pore size, surface area) which are critical parameters for broader electrochemical devices. Besides its use for RFB application, we hypothesize that the electrode morphologies resulting from NIPS could be applied to a broader range of electrochemical systems employing porous electrodes. Consequently, here we focus on extending the library of electrode microstructures achievable via NIPS through the alteration of simple process parameters.

In this presentation, I will discuss our latest advances on the bottom-up manufacturing of porous electrodes using NIPS targeting porosity gradients and high ECSA materials. For the former, we introduce the use of a control layer, casted on top of the NIPS polymer solution at the interface with the coagulation bath, thereby altering the rate of the phase separation process. We investigate various process parameters such as the composition, viscosity, and thickness of the control layer and assess their effect onto the resulting microstructures. The NIPS method assisted by a control layer generates porosity gradients, resulting in a slight increase of the electrode ECSA at the cost of a higher pressure drop. To further increase the ECSA of the prepared electrodes, we also propose nano-patterning approaches to significantly enhance ECSA through addition of nano-scale porosity without compromising the pressure drop through the porous structure. Finally, both porosity gradient and nano-patterned NIPS electrodes are tested in a all-vanadium redox flow cell to extract microstructure-performance relationships. Despite being in its early technological stage, this work illustrates the versatility of NIPS to manufacture porous electrodes through a very broad microstructural design space.

References

[1] R. R. Jacquemond, C. T.-C. Wan, Y.-M. Chiang, Z. Borneman, F. R. Brushett, K. Nijmeijer, A. Forner-Cuenca, Cell Reports Physical Science
2022, 3, 100943.

[2] C. T. Wan, R. R. Jacquemond, Y. Chiang, K. Nijmeijer, F. R. Brushett, A. Forner‐Cuenca, Adv. Mater.
2021, 33, 2006716.
Deposition of Composite Nanoparticle-Based Thin Films for Gas Sensing
Authors: Capek Jiri , Shaji Kalyani , Haviar Stanislav , Zeman Petr
Published: February 2024

Working principle of conductometric gas sensors is based on modulation in electrical conductivity of the sensing material due to adsorption-desorption reactions between the target gas and the sensor surface. Nano-structuring the sensing material increases the effective surface area for interaction between the target gas and the sensing material thereby enhancing the sensorial response. Metal oxide semiconductors (MOS) have shown remarkable sensing performance to oxidizing and reducing gases. The combination of different MOS has often demonstrated to synergistically improve the gas sensing performance via the formation of highly sensitive heterojunctions at their interface.

In this work, we deposited thin films composed of nanoparticles (NPs) of p-type CuOx and n-type WOx to enhance the effective surface area of the material and to realize the maximum number of nano p-n heterojunctions in the material. The films were prepared using the Nanogen-Trio NP source equipped with three 1′′ magnetrons, mounted on a custom-built deposition chamber and sputtered by a DC power supply. Depositions were executed in Ar+O2 gas mixture. The O2 admixture may significantly enhance the mass flux of NPs. Furthermore, the O2 admixture allows one to tune the desired stoichiometry of the respective metal oxides. On the other hand, the pronounced hysteresis complicates the deposition of WOx NPs. The deposition process was controlled using an in-house developed software to prepare thin films composing a mixture of NPs with a defined volumetric ratio of the individual materials.

This work demonstrates the versatility of our custom-built gas aggregation source that facilitates the preparation of multi-composite NP-based thin film giving the best sensorial response.
Fabrication of a Palladium Hydride pH Microelectrode with an Extended Lifetime
Authors: Li Yuanjiao , Mauzeroll Janine , Perry Samuel Charles
Published: February 2024

Stable miniaturized pH microelectrodes are crucial in exploring localized pH changes, but most suffer from instability and short lifetimes. Palladium hydride in a mixer phase has been reported to measure the solution pH taking advantage of the interaction between the alloyed hydrogen atoms and hydrogen ions in the solution. However, with the escape of the hydrogen atoms from the palladium lattice, the palladium hydride will transition to single phase and become invalid for pH measurement. The duration of the mixer-phase palladium hydride is even shorter as the sensor is made small. A method to stabilize the mixer-phase is needed for the development of palladium hydride sensors.

A method of synthesizing the mixer-phase palladium hydride in dimethylformamide at an elevated temperature has been reported. The synthesized palladium hydride can be stable under aerobic conditions. We used the stable palladium hydride to fabricate a pH microelectrode. In contrast to electrochemically generated palladium hydride microelectrodes, chemically generated palladium hydride microelectrodes are longer lasting and importantly have good an analytical performance under aerobic conditions. Chemically generated palladium hydride microelectrodes perform best in acid to neutral electrolytes devoid of Cl-. They can readily be produced on 10 µm diameter disk platinum microelectrodes, which makes them attractive candidates for future localized electrochemical studies.
Fabrication of a Capacitive BaTiO3-PDMS Hand Sign Language Sensor and Its Signal Classification Aided by Machine Learning
Authors: Fernandez Frances Danielle , Yoon Sukeun , Yim Jin-Heong , Choi Hong Kyoon , Kim Jihoon
Published: February 2024

The detection of sign language signals is an important aspect in the life of people with hearing and speaking impairment. It is one important application in the fabrication of capacitive strain sensors. In these kinds of sensors, the change in electrical properties such as capacitance depicts the change in a body’s movement. It is one of the variables along with sensitivity, repeatability, response time, fabrication cost, and ease of fabrication which are the important factors to consider in the fabrication of sensors. This paper presents the fabrication of multi-strain sensors that can be integrated into hand gloves to monitor hand sign language gestures. The designed sensor is composed of barium titanate oxide (BaTiO3) which served as the sensing material and polydimethylsiloxane (PDMS) as the stretchable substrate. The silver electrodes were inkjet printed on top of the prepared BaTiO3-PDMS composite after surface treatment to allow the adhesion of silver ink. The capacitance values of the sensors were continuously measured and recorded using an Inductance-Capacitance-Resistance (LCR) meter while bending the sensors at different bending angles for multiple cycles. The fabricated BaTiO3-PDMS capacitive sensors exhibited a high response of 42.85%, linearity of 0.941, fast response and recovery time of ~1s, and low hysteresis of less than 2%, and good stability over a thousand cyclic test. Its application as a hand sign language sensor was demonstrated to have a unique combination of sensing signals with respect to specific finger flexion angles that correspond to a specific hand sign language of the English alphabet. The interpretation of the sensing signals were aided by machine learning and depicted a classification accuracy of 92% signifying the ability of the sensor to detect a particular letter from the English alphabet.
High-Sensitivity Hydrogen Sulfide Electrochemical Gas Sensor Based on CNT/Pt Cluster Electrode
Authors: Kwon JinBeom , Jung Daewoong , Ha Yuntae , Choe SuJi , Baek Soobeen , Jung Dong Geon , Kang Byoungho
Published: February 2024

Recently, due to the development of industrial technology, harmful gases discharged from industrial sites are gradually increasing, and as a result, inconvenience and civil complaints due to odor in the community are rapidly increasing. Among several types of harmful gases, hydrogen sulfide (H2S) is a colorless representative harmful gas that can cause pain through irritation of the mucous membranes of the eyes and respiratory tract, and can cause central nerve paralysis and suffocation at the same time when exposed to high concentrations. In addition, H2S is not only harmful to the human body, but also can create an unpleasant feeling by causing an odor even in a very small amount. Therefore, in order to manage H2S, research on a gas sensor capable of quickly and stably detecting H2S has been actively conducted. Most of the sensors that have been studied in the past are metal oxide-based semiconductor H2S gas sensors, which have high sensitivity, but have disadvantages in that low selectivity and high-temperature operating conditions are required. On the other hand, the electrochemical gas sensor can measure H2S gas with high selectivity because a chemical reaction occurs with respect to a specific gas depending on the type of electrolyte and electrode, and a potential difference due to electrons generated thereby is measured. Therefore, in this study, a CNT/Pt-based electrochemical H2S gas sensor capable of detecting at room temperature with high selectivity for H2S was developed. After forming a CNT thin film on a PTFE membrane, Pt was deposited through an E-beam to fabricate a working electrode capable of selectively detecting only H2S, and applied to an electrochemical H2S gas sensor using sulfuric acid (H2SO4) electrolyte. H2S was measured at a concentration of 100 to 10 ppm in units of 10 ppm using the manufactured CNT/Pt-based electrochemical H2S gas sensor. As a result, the amount of current change was confirmed to be 100uA at a concentration of 100 ppm, and the response time and recovery time were confirmed to be about 10 seconds.

This work was supported by the Korea Innovation Foundation(INNOPOLIS) grant funded by the Korea government(MSIT) (2020-DD-UP-0348). This study has been conducted with the support of the Korea Institute of Industrial Technology as "Development of a thermal convection-type flow sensor with high-sensitivity for emergency patients breathing monitoring in real-time" (Kitech UI-23-0012).
High-Sensitivity Mechanochromic Sensor Using Core-Shell Colloidal Crystals
Authors: Kim Young-Seok , Lee SangHoon , Park Shin Geun , Lee Wonmok
Published: February 2024

The Colloidal Crystals-based mechanochromic sensor changes color as the arrangement of colloidal particles changes in response to mechanical deformation, which can be detected through optical measurement. This type of sensor can be used in various applications, such as automobile collision detection, structural deformation detection, and medical equipment, among others. In this study, we prepared a stretchable film by dispersing surface-functionalized colloidal particles in an elastic polymer matrix. Surface of silica colloidal particle was modified with an initiator for Atom Transfer Radical Polymerization (ATRP), followed by surface-initiated ATRP of poly(t-butyl methacrylate) (PtBMA). The core-shell colloidal particles were composited with various acrylic monomers, to fabricate crystalline colloidal array which transforms to elastic film by photopolymerization exhibiting structural color. The prepared film showed a clear color change for deformation within 10%, and the peak reflectance showed more than 30%.
Understanding Neurotransmission Using Single Vesicle Electrochemistry
Authors: Li Xianchan
Published: February 2024

Exocytosis is one of the essential steps for chemical signal transmission between neurons. In this process, vesicle docks and fuses with the plasma membrane and release the stored neurotransmitters through exocytotic pore into the extracellular space, and all of these steps are governed with various molecules, such as proteins, ions and even lipids. Quantitatively monitoring vesicular neurotransmitter release in exocytosis and initial neurotransmitter storage in individual vesicles are significant in order to study mechanisms of neurotransmission and malfunction in disease. Recently, we developed new approaches to characterize the contents of mammalian vesicles isolated, in situ or in vivo, termed as intracellular vesicle impact electrochemical cytometry.[1] In this approach, nanoscale mammalian vesicles are allowed to adsorb to electrodes and subsequently rupture thereby expelling their contents eliciting an oxidation current that can be used to quantify the catecholamine contents of the vesicles.[
2-5] Combined with exocytotic release measurements with single cell amperometry, it is a unique technique for understanding neuronal transmission and investigating the pharmacology or toxicology of drugs on chemical signaling related biological functions, for example, learning and memory.[6-15]

References

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[2] Li, X.; Dunevall, J.; Ren, L.; Ewing A. G.* Anal. Chem. 2017, 89, 9416−9423.

[3] Li, X.; Ren, L.; Dunevall, J.; Ye, D.; White, H. S.; Edwards, M. A.; Ewing, A. G.* ACS Nano, 2018, 12, 3010−3019.

[4] Li, X;# Dunevall, J.;# Ewing A. G.* Acc. Chem. Res. 2016, 49, 2347−2354.

[5] Phan, N. T. N.; Li, X.; Ewing A. G.* Nat. Rev. Chem. 2017, 1, 0048.

[6] Li, X.; Dunevall, J.; Ewing, A. G.* Angew. Chem., Int. Ed. 2016, 55, 9041−9044.

[7] Mohammadi, A. S.;# Li, X;# Ewing A. G.* Anal. Chem. 2018, 90, 8509−8516.

[8] Xiao, T.; # Li, X.; # Wei, H.; Ji, W.; Yue, Q.; Yu, P.; Mao, L.*. Anal. Chem. 2018, 90, 13783-13789.

[9] Wang, D.;# Li, X.; #Jiang, Y.; Jiang, Y.; Ma, W.; Yu, P.; Mao, L.*. ACS Chem. Neurosci. 2019, 10, 2576-2583.

[10] Yue, Q.; # Li, X.;# Wu, F.; Ji, W.; Zhang, Y.; Yu, P.; Zhang, M.; Ma, W.; Wang, M.; Mao, L.* Angew. Chem., Int. Ed. 2020, 59, 11061−11065.

[11] Thomen, A.; Najafinobar, N.; Penen, F.; Kay, E.; Upadhyay, P. P.; Li X.; Phan, N. T. N.; Malmberg, P.; Klarqvist, M.; Andersson, S.; Kurczy, M. E.*, Ewing, A. G.* ACS Nano 2020, 14, 4, 4316-4325.

[12] Liu, Y.; Du, J.; Wang, M.; Zhang, J.; Liu, C.*; Li, X.*
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[13] Yue, Q.; # Wang, K.; # Guan, M.; Zhao, Z.; Li, X.;* Yu, P.; Mao, L.* Angew. Chem. Int. Ed. 2022, 61, e202117.

[14] Wang, M.; Liu, Y.; Du, J.; Zhou, J.; Cao, L.; Li, X.*
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[15] Zhou, J.; # Zhang, J.; # Cao, L.; Liu, Y.; Liu, L.; Liu, C.*; Li, X.* Chem. Commun. 2023, 59, 3087-3090.
(Invited) Paper-Based SERS Quantitative Analysis for Cancer Diagnosis and Subtyping
Authors: Li Ming
Published: February 2024

Paper-based biosensors are typically low-cost and user-friendly, which enable fast and easy detection of biomarkers of pathological significance for disease point-of-care diagnosis and therapeutic monitoring. Quantitative analysis of biomarkers in body fluids provides a good opportunity for early diagnosis, prompt treatment and longitudinal therapeutic surveillance of diseases such as cancer. Surface-enhanced Raman spectroscopy (SERS) is a powerful spectroscopic analytical technique capable of ultrasensitive and nondestructive analysis of biomarkers directly in biological samples with a multitude of advantages, including high sensitivity, molecular specificity, powerful multiplex detection capability, and excellent chemo/photostability. This talk will present our recent work on the development of paper-based SERS biosensing platforms for quantitative analysis of biomarkers. We have successfully innovated a series of paper-based SERS biosensing platforms, including (i) a freestanding SERS biosensor with excellent condensing enrichment capability for quantitative label-free detection of trace fentanyl in biofluids, (ii) a SERS-vertical flow biosensor for multiplexed quantitative profiling of exosomal proteins in clinical serum samples of patients, realizing noninvasive breast cancer subtyping and longitudinal treatment monitoring, and (iii) SERS-lateral flow biosensors for quantification of specific biomarkers (e.g., serum exosomes, proteins) of disease diagnosis and post-operative assessment. We demonstrate exceptional performances of these paper-based SERS biosensors for diverse biosensing applications. We believe that these paper-based SERS biosensors could be promising tools for point-of-care diagnosis in both clinical and field settings.

References:

(1) Xiaoming Su, Xinyu Liu, Yangcenzi Xie, Mingyang Chen, Chao Zheng, Hong Zhong,* Ming Li,* Integrated SERS-vertical flow biosensor enabling multiplexed quantitative profiling of serological exosomal proteins in patients for accurate breast cancer subtyping, ACS Nano
2023, 17(4), 4077–4088.

(2) Xiaoming Su, Xinyu Liu, Yangcenzi Xie, Mingyang Chen, Hong Zhong,* Ming Li,* Quantitative label-free SERS detection of trace fentanyl in biofluids with a freestanding hydrophobic plasmonic paper biosensor, Analytical Chemistry, 2023, 95(7), 3821-3829.

(3) Xiang Pan, Linhu Li, Hangduo Lin, Jiayi Tan, Haitao Wang, Mengling Liao, Caiju Chen, Beibei Shan, Yingfan Chen, Ming Li,* A graphene oxide-gold nanostar hybrid based-paper biosensor for label-free SERS detection of serum bilirubin for diagnosis of jaundice, Biosensors and Bioelectronics, 2019, 145, 111713.
(Invited) Optical Paper-Based Microfluidic Devices for Point-of-Care Testing
Authors: Wu Nianqiang
Published: February 2024

Colorimetric paper-based microfluidic devices are well known for point-of-care testing of pregnancy and COVID-19 infection. However, colorimetric transduction makes devices low-sensitivity and poor resistance to interference of biomolecules in complex sample matrices. This presentation will discuss how to use utilize fluorescence and surface-enhanced Raman scattering to improve sensitivity and resistance to background interference.