bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Metal Oxide Mixed Sulphide of Controlled Crystal Structure As Catalysts for Two-Electron Water Oxidation
Authors: Slesinski Adam , Frackowiak Elzbieta 
Published: February 2024

Conventional catalysts based on noble metals (Pt, Ru) are often used for production of oxygen during water electrolysis in four-electron pathway as they can decrease gas evolution overpotential. Another possible valuable product from water oxidation is hydrogen peroxide obtained via two-electron process. Currently, transition metal oxides, are readily employed to catalyse this reaction. Although they display certain activity, it is still not satisfactory for mass production of H2O2, therefore further optimisations are needed. We suggest in this work, in addition to typical nanostructure modifications of metal oxides (MoO2) such as doping or structural engineering, an application of transition metal dichalcogenides (MoS2). Consequently, the oxide is partially replaced by sulphur. The selection of molybdenum as a centre atom ensures sufficient electrical conductivity of material as an electrode active layer. This combination is intended to provide the benefits thanks to layered materials of tuned interlayer spacing as well as controlled number of active sites. It enables selective adsorption of intermediate products of water oxidation (O∗, OH∗, and OOH∗), and therefore increased preference towards two-electron pathway.
Various chemical approaches are considered to synthesize this material, especially hydrothermal treatment in autoclave and high-temperature sintering of precursors. The catalytic activity of the nanostructured metal oxide is further enhanced by its deposition on conductive high surface area support made of carbon/graphite particles of strictly defined textural parameters and surface chemistry. The final composite is obtained using hydrophobic binders (PVDF and PTFE) to form the electrode and improve the catalyst stability. The measurements are carried out in flow electrolyser unit with an alkaline electrolyte. The amount of produced H2O2, H2 as well as quantity and quality of evolved gases are assessed in terms of faradaic efficiency, pressure and overvoltage measurements.
Benchmarking Activity and Stability of Layered Double Hydroxides (LDHs) Electrocatalysts for Alkaline Water Electrolysis
Authors: Lloret Segura Vicent , Hartert Adrian , Seijas Da Silva Alvaro , Geuß Moritz , Freiberg Anna T.S. , Mayrhofer Karl J. J. , Thiele Simon , Abellán Gonzalo , Cherevko Serhiy 
Published: February 2024

In order to reduce the cost of producing hydrogen through water electrolysis, novel technologies must be improved. Recently, the merging of conventional alkaline electrolysis (AEL) and proton exchange membrane electrolysis (PEM) has led to the development of anion exchange membrane electrolysis (AEMWE), which offers several advantages over AEL and PEM. In a nutshell, this technique employs cheap, abundant, and easily available (non-geostrategic) transition metals with anionic exchange membranes, overcoming the drawbacks of AEL and PEM.[1]
To reach the readiness level of this technology, new and scalable synthetic routes for catalysts that lower the overpotential of the sluggish oxygen evolution reaction (OER) are required. Amongst all the OER catalysts reported in the literature, Layered Double Hydroxides (LDHs) have gained increasing attention due to their low overpotentials and stabilities.[2] Besides, electrochemical protocols to determine the activity and stability of these catalysts in different electrochemical cells must be established to understand their properties. Thus, this work focuses on the advantages and limitations of different electrochemical techniques, such as rotating disk electrode (RDE), three-electrode cells, and single-cell tests, to determine the activity and stability of two different LDHs. Unlike laboratory scale LDHs ‒prepared by hydrothermal treatment (HT-LDH)‒ room temperature synthesized LDHs (RT-LDH) can be prepared in kilogram quantities and present chemical structure and morphology differences. In this work, the LDHs have been characterized with spectroscopic techniques to correlate the chemical structure and morphology of the materials to their electrochemical response by RDE, three-electrode cells, and single-cell measurements.
All in all, the scalable RT-LDH presents higher activity compared to HT-LDH in all three techniques. On the one hand, small current densities can only be reached by RDE, and the short-term stability of the materials is affected by the catalyst layer interface. On the other side, single-cell test measurements require long operational times, and the contribution of the membrane degradation to the overall cell voltage is still unclear. Thus, three-electrode cell measurements offer the possibility of characterizing LDHs at relevant current densities in a fast and straightforward manner, without membrane contributions, and are further employed in this work to study the stability of these systems.

References:

[1] N. Du, C. Roy, R. Peach, M. Turnbull, S. Thiele and C. Bock, Chemical Reviews, 122, 11830 (2022).
[2] R. Sanchis-Gual, A. Seijas-Da Silva, M. Coronado-Puchau, T. F. Otero, G. Abellán, E. Coronado, Electrochimica Acta, 338, 138613 (2021).
Enhanced Oxygen Evolution Reaction Activity and Structural Stability of Sulfur and Manganese Substituted Co(OH)2
Authors: Shamraiz Umair , Etzold Bastian J. M. 
Published: February 2024

The search for efficient, cost-effective, and sustainable energy sources is a crucial challenge for the modern world.1, 2 In this regard, the development of effective electrocatalysts for water splitting, specifically the oxygen evolution reaction (OER), is a critical aspect of renewable energy technology.3, 4 In recent years, layered double hydroxides (LDHs) have emerged as promising materials for electrocatalysis due to their unique structural and electronic properties.5, 6

This study presents the synthesis and characterization of sulfur and manganese substituted Co(OH)2 as electrocatalysts for the oxygen evolution reaction (OER). The research employed a range of structural and physical characterization techniques, including XRD, EDX, SEM, TEM, and XPS to investigate the synthesized materials.
The OER activity was measured via LSV curves in 1 M KOH solution which showed that the S-Mn-Co(OH)2 has significantly low over-potential of 250 and 275 mV for current densities of 10 and 50 mA cm-2 when compared with the Co(OH)2. Additionally, the S–Mn–Co(OH)2 catalyst demonstrated after a 15 hours treatment at 50 mA cm−2 and in 1 M KOH only an overpotential increase of 34 mV and thus excellent stability. High-resolution transmission electron microscopy (HRTEM) analysis confirmed sheet like structure, while the XPS analysis revealed an increase in electron density around the Co owing to the presence of Co2+ and Co3+ in the sample. PXRD and HRTEM analysis also showed a slight reduction in the interlayer gap, indicating further stabilization of the layered structure. Both, stabilized the layered structure and increased electron density around Co could be reason for the enhanced OER performance and be important insights into the role of cation and anion substitution for enhancing LDH OER catalysts.
References

S. Chu and A. Majumdar, nature, 2012, 488, 294-303.

M. M. Rahman, I. Khan, D. L. Field, K. Techato and K. Alameh, Renewable Energy, 2022, 188, 731-749.

Y. Feng, H. Yang, X. Wang, C. Hu, H. Jing and J. Cheng, International Journal of Hydrogen Energy, 2022.

X. Liu, Y. Han, Y. Guo, X. Zhao, D. Pan, K. Li and Z. Wen, Advanced Energy and Sustainability Research, 2022, 3, 2200005.

P. Shandilya, R. Sharma, R. K. Arya, A. Kumar, D.-V. N. Vo and G. Sharma, International Journal of Hydrogen Energy, 2022, 47, 37438-37475.

A. Hameed, M. Batool, Z. Liu, M. A. Nadeem and R. Jin, ACS Energy Letters, 2022, 7, 3311-3328.
Assessing the Stability of Co3O4 Under Oxygen Evolution Reaction Conditions at Low and Mild pH
Authors: Priamushko Tatiana , Franz Evanie , Escalera López Daniel , Brummel Olaf , Libuda Jörg , Kleitz Freddy , Cherevko Serhiy 
Published: February 2024

Water and CO2 electrolysis will play a crucial role in converting renewable energy into value-added chemicals and chemical fuels. To successfully employ and expand these technologies globally, ideally, one should develop Earth-abundant, cost-effective catalysts with high activity and stability. The requirements for the catalysts depend on the configuration of the electrolyzer, and the electrolyte used there. However, especially in CO2 electrolysis, the stability of the catalyst in a certain electrolyte does not guarantee its successful use on a long-term scale, as the pH in the electrolyzer may change during long-term experiments due to ion transfer through the membrane.1 The anode materials should, therefore, be stable across a broad pH range and/or in carbonate-rich electrolytes. Although the earth-abundant, non-noble transition metals, and their compounds are highly stable at higher pH, they are less stable than Ir or Pt at low and (near-)neutral pH.2 Interestingly, recent studies have shown that Co-based oxides exhibit promising stability even at low pH.3, 4 However, the nature of this stability as well as the mechanisms of non-noble metal oxides catalyzing OER at low or near-neutral pH, are yet to be discovered. In this work, we analyze the stability of cobalt oxide under various electrochemical conditions at low pH with the use of a scanning flow cell (SFC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) and differential electrochemical mass spectrometry (DEMS). By using these techniques, we can follow the dissolution of Co online and find potential narrow stability windows before and during the oxygen evolution reaction (OER). Benefiting from the obtained results, mitigating strategies for minimizing Co dissolution are proposed and discussed.
References:
(1) Vass, A.; Kormanyos, A.; Koszo, Z.; Endrodi, B.; Janaky, C. Anode Catalysts in CO2 Electrolysis: Challenges and Untapped Opportunities. ACS Catalysis
2022, 12 (2), 1037-1051. DOI: 10.1021/acscatal.1c04978.
(2) Vass, A.; Endrodi, B.; Samu, G. F.; Balog, A.; Kormanyos, A.; Cherevko, S.; Janaky, C. Local Chemical Environment Governs Anode Processes in CO2 Electrolyzers. ACS Energy Letters
2021, 6 (11), 3801-3808. DOI: 10.1021/acsenergylett.1c01937.
(3) Cherevko, S. Stabilization of non-noble metal electrocatalysts for acidic oxygen evolution reaction. Current Opinion in Electrochemistry
2023, 38. DOI: ARTN 10121310.1016/j.coelec.2023.101213.
(4) Li, A. L.; Kong, S.; Guo, C. X.; Ooka, H.; Adachi, K.; Hashizume, D.; Jiang, Q. K.; Han, H. X.; Xiao, J. P.; Nakamura, R. Enhancing the stability of cobalt spinel oxide towards sustainable oxygen evolution in acid. Nature Catalysis
2022, 5 (2), 109-118. DOI: 10.1038/s41929-021-00732-9.
Electrode Parameterization as an Investigative Tool for Solid Electrolyte Interphase Evolution Monitoring on Commercial Lithium-Ion Battery Electrodes
Authors: Jackowska Roksana , Chen Yongxiu , Spathara Dimitra , Kendrick Emma 
Published: February 2024

The formation process is one of the most critical aspects of lithium-ion battery (LIB) production. It involves the creation of an interface layer known as solid electrolyte interphase (SEI). The layer predominantly forms during the first few charging cycles of the battery, resulting in approximately 10% capacity reduction [1]. However, forming a stable SEI layer is critical in ensuring uniform cell capacity, safe operation, and a long lifetime of LIBs [2].
The thickening of the SEI layer is one of the main contributors to capacity fade over the battery lifetime and strongly depends on electrochemical cycling conditions [1]. Despite its importance, there are still no comprehensive theories and models describing SEI formation and evolution. The difficulties arising from its characterization could explain why various structure models have appeared in the literature [3–5]. Therefore, it is indispensable to go beyond traditional characterization methods to fully elucidate the SEI layer behaviours.
In this work, we investigate changes in the kinetic and thermodynamic electrode parameters with growing SEI layer thickness, deriving relevant variables, such as exchange current density, electrode tortuosity, and lithium diffusion coefficient from experimental data. The measurements are performed on commercially relevant electrodes. Parameter evolution monitoring will contribute to developing a predictive understanding of the SEI layer evolution under different cycling conditions, and to unlocking improvements in LIB sustainability by prolonging their lifetime and enhancing safety.
References:
[1]. Edge, J. S. et al. Lithium ion battery degradation: what you need to know. Physical Chemistry Chemical Physics vol. 23 8200–8221 (2021).
[2]. Wood, D. L., Li, J. & Jin An, S. Formation Challenges of Lithium-Ion Battery Manufacturing. Joule 3, 2884–2888 (2019).
[3]. Peled, E. The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems — The Solid Electrolyte Interphase Model. J. Electrochem. Soc. 126, 2047–2051 (1979).
[4]. Aurbach, D. Review of selected electrode – solution interactions which determine the performance of Li and Li ion batteries. J. Power Sources 89, 206–218 (2000).
[5]. Peled, E., Golodnitsky, D. & Ardel, G. Advanced Model for Solid Electrolyte Interphase Electrodes in Liquid and Polymer Electrolytes. J. Electrochem. Soc. 144, L208–L210 (1997).
Position-Dependent Storage in Mixed Conductors: Generalized Storage Model, Improved Mott-Schottky Analysis and Correct CV-Response
Authors: Xiao Chuanlian , Wang Hongguang , Usiskin Robert , van Aken Peter A , Maier Joachim 
Published: February 2024

In this work, TiO2 and Nb2O5 thin films have been used as model systems to study the fundamental issues related to charge storage and transport in solids. Firstly, the storage capacity of lithium in TiO2 as a function of thickness for various electron-accepting substrates is measured precisely. Contributions from bulk and boundary storage were deconvoluted based on the electrochemistry and electron microscopy results. The results allow for working at three basic points. (1) Such experimental and theoretical investigation of the bulk and interfacial defect chemistry enables deriving the entire profile and embedding bulk and boundary contributions into a common generalized thermodynamic model, and hence a unification of battery intercalation electrode and supercapacitive storage1. (2) Bias-dependent resistance and capacitance measurements across the LixTiO2/electronic conductor interface allow us to improve the Mott-Schottky model by implementing a charge density that has been determined by the preparation conditions2. (3) Cyclic voltammetry (CV) performed at these systems leads to a description that is adjusted to the solid state and deviates significantly from the description in liquids. All these fundamental studies are highly relevant to energy-related application3.
1. C. Xiao, H. Wang, R. Usiskin, P. A. van Aken, J. Maier, submitted.
2. C. Xiao, J. Maier, in preparation.
3. C. Xiao, R. Usiskin, J. Maier, in preparation.
(Invited) Revealing Charge Storage Processes at the Interfaces of Supercapacitor Electrodes
Authors: Wang Xuehang 
Published: February 2024

The fast development of electrochemical energy storage devices has revolutionized almost every aspect of modern life by enabling portable electronic devices, electric vehicles, and grid storage of renewable energy. To satisfy the growing industrial and consumer needs for energy storage systems with high output power and short recharge time, the electrode materials should have excellent high-rate performance.1

Electrical double-layer (EDL) capacitors exhibit high-rate capability and long-cycling life as they store charges electrostatically. Using ionic liquid (IL) as the electrolyte leads to a large voltage window but low capacitance. In this first session of the presentation, I will introduce a mathematical model to simulate the IL ion packing structure in nanopores. This model is capable of estimating the EDLC capacitance based on pore size distribution. Then, we further revealed that mixture IL ions can be selectively driven into the pores of different confinement levels, which was confirmed by solid-state NMR, and further explained by DFT simulation2.
In the second part of the presentation, I will shift to pseudocapacitors, which are expected to have a much higher charge storage capacity than EDL capacitors and a much higher rate than batteries as they store energy through fast surface redox reactions.3 The emerging 2D material family, 2D transition metal carbides/nitrides MXenes, shows outstanding pseudocapacitive performance due to their ionophilicity, metallic conductivity, and highly reactive surfaces. The proper coupling between electrolyte and electrode is critical to increase energy and power density. In the organic electrolyte, we found that the solvent has a strong impact on the ion/solvent arrangement in 2D MXene material and hence the charge storage capability.4 In the aqueous electrolytes, we successfully introduced surface redox reactions to MXene electrodes by using the water-in-salt electrolytes and by adjusting the initial valence of Ti in Ti3C2 MXenes, which dramatically increases the capacitance of MXene in the neutral aqueous electrolytes5.
References

Simon, P.; Gogotsi, Y., Nat. Mater.
2020,
19 (11), 1151-1163.

Wang, X.; Mehandzhiyski, A. Y.; et al., J. Am. Chem. Soc.
2017,
139 (51), 18681-18687.

Fleischmann, S.; Mitchell, J. B.; et al., Chem. Rev.
2020,
120 (14), 6738-6782.

Wang, X.; Mathis, T. S.; et al., Nat. Energy
2019,
4 (3), 241-248.

Wang, X.; Mathis, T. S.; et al., ACS Nano
2021,
15 (9), 15274-15284.
(Invited) Modeling of the Electric Double Layer (EDL) at Li/SEI/Electrolyte Interfaces
Authors: Qi Yue 
Published: February 2024

Liquid electrolytes, consisting of salts, solvents, and additives, must form a stable solid electrolyte interphase (SEI) to ensure the performance and durability of lithium(Li)-ion batteries. However, the electric double layer (EDL) structure near charged surfaces is still unsolved, despite its importance in dictating the species being reduced for SEI formation near a negative electrode. Recently, we have developed an interactive Molecular Dynamics -Density Functional Theory -data statistics (MD-DFT-data) model to investigate the reduction reactions of multicomponent electrolytes within the EDL. We will illustrate the effect of EDL on SEI formation in two essential electrolytes, the carbonate-based electrolyte for Li-ion batteries and the ether-based electrolyte for batteries with Li-metal anodes. Our results reveal that the role of fluoroethylene carbonate (FEC) additive differs drastically in the two electrolytes as an SEI modifier to form the beneficial F-containing SEI component (e.g., LiF). The competition among the cations, anions, and various species in the solvents with a charged surface at different temperatures can all jointly determine the EDL structure and therefore the SEI compositions. [1]
While the classical Poisson–Boltzmann EDL model developed for fully solvated ions face new challenges in high-concentration liquid electrolytes (HCE), localized high-concentration liquid electrolytes (LHCE) as well as solid electrolytes (SE), new theoretical developments are required. We will introduce a new DEL model in SE and SEI by solving the DFT-informed Poisson–Fermi–Dirac equation and demonstrate how it can be used for interlayer thickness design. [2]
[1] Wu, Q.S, McDowell, M.T., & Qi, Y., Journal of the American Chemical Society 145 (4), 2473-2484 (2023)
[2] Swift, M.W., Swift, J.W. & Qi, Y. Modeling the electrical double layer at solid-state electrochemical interfaces. Nat Comput Sci
1, 212–220 (2021)
Interface Induced Fast Ion Conduction in Complex Hydride/Oxide Nanocomposites: Interplay between Hydride and Oxide Properties
Authors: Ngene Peter 
Published: February 2024

Solid-state electrolytes are crucial for next generation batteries with high energy density, long lasting and improved safety. The compatibility of most solid electrolytes with metallic anodes such as Li and Na metals, and cathodes such as sulfur, makes them suitable for high-capacity batteries (e.g., Li-S). They also address the safety concerns of current batteries by eliminating the flammable organic solvents in liquid electrolytes and by preventing/limiting dendrite formation.
The lithium and sodium containing complex metal hydrides (e.g., LiBH4, NaBH4, LiCB11H12) have recently gained attention as solid-state electrolyte. They show high ionic conductivities but only at elevated temperatures (typically above 110 °C). Extending the high ionic conductivities to ambient temperatures is pivotal to the application of this fascinating class of solid electrolytes [1].
In this contribution, we will use LiBH4 and NaBH4 as examples to show that the ionic conductivities of complex hydrides can be greatly enhanced through interface effects resulting from the formation of nanocomposites with metal oxides. This strategy can lead to several orders of magnitude increase in the room temperature ionic conductivity [2]. Using DSC, DRIFT, solid-state NMR, and XRS (Xray Raman scattering), I will discuss how nanocomposite formation and presence of interfaces modifies either the phase stability, the defect concentration and/or leads to the formation of tertiary phase, and thereby increase profoundly the ion mobility of the complex hydrides. Systematic studies with different oxide nanoscaffolds and surface modified metal oxides, reveal that these effects can be optimized by tuning/engineering the nanostructure and interfaces in the nanocomposites. [3-4]. We will show that the effects also depend on a complex interplay between the stability of the metal hydride and surface properties of the metal oxide. Finally, the performance of some of the nanocomposite electrolytes in all-solid-state batteries, will be highlighted [5]

References

[1] L.M de Kort, P. Ngene et al. J. Journal of Alloys and Compounds 901 (2022) 163474
[2] D. Blanchard et al., Advanced Functional Material. 25 (2015), 182.
[3] P. Ngene et al. Physical Chemistry Chemical Physics 21 (40), 22456-22466
[4] L.M de Kort, P. Ngene et al. Journal of Materials Chemistry A 8.39 (2020): 20687-20697
[5] D. Blanchard et al, J. Electrochem. Soc. (2016).