bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) The Electrochemical-Mechanical Coupled Interface Contacts during Lithium Plating and Stripping
Authors: Qi Yue , Feng Min , Liu Xing 
Published: August 2024

The current density during battery operation is often assumed uniform across the entire electrode surface. This may be valid for conformal solid/liquid interfaces; however, solid/solid interfaces generally have imperfect contacts. By introducing the contact area ratio, γ, to the electrochemical model, it can be demonstrated clearly that the effective current density scales linearly with the 1/γ and the overpotential scales exponentially with contact area loss, 1-γ.
The calculation of surface contact area must consider the multi-length-scale nature of surface roughness. Assuming surface roughness is self-affine, Bo Persson’s multiscale contact mechanics model for elastic materials can be used for the cathode/solid electrolyte interface to predict the necessary pressure to maintain the original contact area. [1]
However, the most challenging process is Li-stripping, as the vacancy generated by each Li atom removed from the interfaces can accumulate and generate voids, reducing the contact area. However, under an applied stack pressure, the self-affine property will reach a steady state interface contact ratio (γo.) in different length scales. Thus, we proposed a coupled atomistic-and-continuum model, which will capture Li striping and vacancy hopping and accumulation near the Li/SE interface with Density Functional Theory (DFT) informed Kinetic Monte Carlo (KMC) simulations and predict the macroscopic contact area evolution according to the macroscopic creep law with finite element simulations (FEM). The creep rate will be mapped to preferred forward hopping rates for all the Li atoms at the atomic scale. Solving these models iteratively leads to a steady contact area ratio (γo.). Generally, lithiophilic interface requires less stack pressure to maintain a flat surface while a higher stack pressure is needed at lithiophobic interfaces to accelerate Li vacancy diffusion into the bulk and maintain a flat surface. This critical stack pressure needs to be high enough to alter the Li forward-and-backward hopping barriers at the interface. This predictive multiscale simulation scheme was able to combine multiple chemical-mechanical effects during Li stripping morphology evolution. [2,3]

[1] Hong-Kang Tian and Yue Qi, Electrochem. Soc. 2017, 164, E3512

[2] T. Yang and Y. Qi, Chem. Mat. 2021, 33, 2814-2823

[3] Feng, C.T. Yang, and Y. Qi, J. Electrochem. Soc. 2022, 169, 090526
Microstructure-Aware Mesoscale Modeling of Chemomechanical Stress Evolution during Cycling in Solid Electrolyte-Cathode Composite
Authors: Wang Bo , Feng Longsheng , Kim Kwangnam , Wood Marissa , Wan Liwen , Wood Brandon C. , Heo Tae Wook 
Published: August 2024

The volume change of cathode active materials during charge-discharge cycling is responsible for the capacity fading of all-solid-state Li batteries due to mechanical degradation in the cathode such as delamination and crack formation. Many strategies to alleviate the chemomechanical stress buildup have been proposed in experiments but rationale of the stress release mechanisms at the mesoscale remain elusive. In this presentation, we present a microstructure-aware mesoscale model to quantitatively predict the stress distribution during cycling in a secondary particle agglomerate of the cathode active material embedded within a solid electrolyte matrix, taking the LiCoO2-Li7La3Zr2O12 (LCO-LLZO) as a model system. We find that the mechanical stress hotspots develop at different stages within the grain boundaries of the LCO agglomerate and the LCO-LLZO interfaces. We investigate the influences of microstructural morphology (columnar versus equiaxial), grain orientations (textured versus random), mechanical properties at the grain boundaries and heterogeneous interfaces, and anisotropy of chemical expansion on the stress hotspot evolution and provide optimal mitigation strategies. The theoretical results can help gain mechanistic understanding on cathode degradation and inform guidelines for experimental design of mechanically optimized cathode materials for long-life solid-state batteries.
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 and 22-ERD-043.
Electrochemical Embrittlement Accelerates Dendrite Growth in Ceramic Electrolytes
Authors: Fincher Cole D. , Gilgenbach Colin , Roach Christian , Osmundsen Rachel , Sheldon Brian W. , Carter W. Craig , LeBeau James , Chiang Yet-Ming 
Published: August 2024

Although solid-state batteries with metal anodes promise to enable safer, higher energy density batteries, metal protrusions (dendrites) grow when charging faster than a critical current density[1,2]. It is generally believed that dendrites grow when plating-induced stresses exceed that required for fracture of the solid-electrolyte[2–4]. Although the electrolyte's fracture toughness is commonly taken as a constant[2–4], here we show that the effective fracture toughness depends markedly upon the metal deposition current density. Based upon operando birefringence microscopy[5], we directly measure dendrite-induced stresses and obtain the mechanical driving force for failure, as well as the electrolyte fracture toughness. We find that increasing current densities embrittle the solid electrolyte—diminishing the fracture toughness by as much as 70%. Cryogenic Scanning Transmission Electron Microscopy (Cryo-STEM) reveals decomposed electrolyte phases at the dendrite tip. This decomposition is associated with a volume contraction consistent with embrittlement of the electrolyte. All experiments were conducted on the most electrochemically stable Li-ion conducting solid electrolyte (tantalum-doped lithium lanthanum zirconium oxide); the fracture toughness of less stable electrolytes (e.g., agryodites) may be even more susceptible to such embrittlement. The collective results indicate that “electrochemical embrittlement” markedly weakens the electrolyte, enabling dendrite growth—even when such degradation has negligible effect on bulk electrochemical properties.
References:

Sudworth, J. L., Hames, M. D., Storey, M. A., Azim, M. F. & Tilley, A. R. An analysis and laboratory assessment of Two Sodium Sulfur Cell Designs. Power Sources 4, 1–18 (1972).

Sharafi, A., Meyer, H. M., Nanda, J., Wolfenstine, J. & Sakamoto, J. Characterizing the Li–Li7La3Zr2O12 interface stability and kinetics as a function of temperature and current density. J. Power Sources 302, 135–139 (2016).

Fincher, C. D. et al. Controlling dendrite propagation in solid-state batteries with engineered stress. Joule 6, 2794-2809 (2022).

Porz, L. et al. Mechanism of lithium metal penetration through inorganic solid electrolytes. Adv. Energy Mater. 7, 1701003 (2017).

Athanasiou†, C. E., Fincher†, C. D. et al. Operando measurements of dendrite-induced stresses in ceramic electrolytes using photoelasticity. Matter (2023).
Multiple Strategies for Producing and Utilizing Ammonia Using Electrochemical Methods Using Transition Metal Based Electrocatalysts
Authors: Kim Jeehye , Jang Ji Hee , Doucet Mathieu , Wang Hanyu , Browning Jim , Jang Youn Jeong , Lee Jae Sung 
Published: August 2024

Ammonia is one of the most important chemicals in fertilizer and industrial chemical production, stands as the world’s second-largest synthetic chemical (> 200 million tons). Additionally, its potential as a clean energy source is gaining attentions due to its carbon neutrality, high energy density, and ease of transport. Electrochemical ammonia production emerges as a 'green' method which minimize the carbon footprint. However, the development of effective systems to produce and utilize 'green' ammonia remains a significant challenge [1,2].
To enhance the efficiency of electrochemical systems, modifications in both catalyst and system design are mandatory. This presentation will introduce the electrochemical nitrogen reduction reaction (eNRR) using Cu-based catalysts [3]. For catalyst modification, we addressed copper’s challenge of its low affinity and activation potential for stable dinitrogen (N2) molecules. This was achieved through phosphorus activation, which enhance the adsorption and activation of N2 by creating electron-deficient Cu sites on the catalyst surface. System-wise, the poor solubility of nitrogen in aqueous electrolytes limits it’s the performance of the system. Addressing this, we applied a gas diffusion electrode (GDE) coated with polytetrafluoroethylene (PTFE) into the eNRR system. This setup establishes an efficient three-phase boundary among liquid water, gaseous N2, and the solid catalyst, thus facilitating nitrogen access to the catalytic sites. Our novel catalyst in a flow-type cell attains a Faradaic efficiency of 13.15% and an ammonia production rate of 7.69 μg h-1 cm-2 at -0.2 VRHE. These figures represent 3.56- and 59.2-times improvements, respectively, over a pristine Cu electrode in a conventional electrolytic cell.
Additionally, the presentation will provide a brief introduction to the amorphous Ni-Cu electrocatalyst for electrochemical ammonia oxidation, which is an essential reaction for ammonia utilization [4]. We highlight its doubled ammonia removal efficiency compared to the Ni-Cu LDH electrocatalyst, underlining the potential of these developments.
[1] Y. Zeng, C. Priest, G. Wang, G. Wu, Restoring the Nitrogen Cycle by Electrochemical Reduction of Nitrate: Progress and Prospects, Small Methods, 4 (2020) 2000672.
[2] B. Yang, W. Ding, H. Zhang, S. Zhang, Recent Progress in Electrochemical Synthesis of Ammonia from Nitrogen: Strategies to Improve the Catalytic Activity and Selectivity, Energy Environ. Sci., 14 (2021) 672-687.
[3] J. Kim, C.H. Lee, Y.H. Moon, M.H. Lee, E.H. Kim, S.H. Choi, Y.J. Jang, J.S. Lee, Enhancing Ammonia Production Rates from Electrochemical Nitrogen Reduction by Engineering Three-Phase Boundary with Phosphorus-Activated Cu Catalysts, J. Energy Chem., 84 (2023) 394-401.
[4] J.H. Jang, S.Y. Park, D.H. Youn, Y.J. Jang. Recent Advances in Electrocatalysts for Ammonia Oxidation Reaction.Catalysts., 13 (2023) 803.
Refining Mn(III) Active Sites in MnO2-Based Self-Assembled Electrodes Via Oxygen Vacancy Induction to Enhance Oxygen Reaction Performance in Zinc-Air Batteries
Authors: He Zizhou , Xu Nengneng , Wang Yudong , Zhou Xiao-Dong 
Published: August 2024

Rechargeable zinc-air batteries are considered as a promising candidate for next-generation electrochemical energy conversion devices due to their safety, low cost, and high theoretical capacity/ energy density. Over the past few decades, α-MnO2-based electrodes have demonstrated their excellent performance and competitiveness in oxygen catalytic reactions. (1) According to eg filling theory, Mn(III) (t2g3eg1) sites in [MnO6] octahedral unit deliver superior bifunctional activity compared to Mn(II) (t2g3eg2) and Mn(IV) (t2g3eg0) sites.(2) However, the presence of unpaired single electrons of the Mn(III) site leads to low thermodynamic stability. Introducing oxygen vacancies to promote the electron rearrangement of the [MnO6] unit is a promising approach for enhancing the durability of Mn(III) active sites. Herein, we construct an oxygen-vacancy-enhanced MnO2-based electrode via a self-assembly process (NiCo2O4-MnO2@Ni foam). The intrinsic oxygen catalytic activity of NiCo2O4-MnO2@Ni foam is significantly improved by forming abundant highly stable Mn(III) active sites, which accelerate the mass transfer ability. As expected, the NiCo2O4-MnO2@Ni foam shows good bifunctional activity with a low overpotential of 0.69 V. The zinc-air battery assembled by NiCo2O4-MnO2@Ni foam exhibits a high peak power density of 576 mW cm-2, surpassing that of the Pt/C-Ir/C electrode. Additionally, benefiting from its stable flower-shaped hierarchical structure, the self-assembled electrode demonstrates long-term charge-discharge cycling stability, which lasts over 800 hours. This work provides innovative insights into enhancing MnO2-based electrodes by oxygen vacancy introduction.
References

N. Xu, Q. Nie, L. Luo, C. Z. Yao, Q. Gong, Y. Liu, X. Zhou, and J. Qiao, ACS applied materials & interfaces (2018).

Z. Yin, R. He, H. Xue, J.-M. Chen, Y. Wang, X. Ye, N. Xu, J. Qiao and H. Huang, Energy Materials (2022).
Novel Electrocatalytic Hydrogenation Using a Solid Polymer Electrolyte (SPE) Reactor
Authors: Atobe Mahito , Shida Naoki 
Published: August 2024

Organic electrosynthetic reactions, which are driven by electricity, can generally be carried out under mild conditions (room temperature and ambient pressure). In addition, they do not require any hazardous reagents and produce less waste than other conventional chemical syntheses. Therefore, electrosynthesis is known to be a mild and clean method for organic synthesis and there has recently been renewed interest in its development. However, electrosynthesis also has some disadvantages. Ordinary chemical reactions are homogeneous, while the reaction field of electrolysis is a heterogeneous interface, therefore electrosynthesis has a productive drawback. In addition, a large amount of supporting electrolyte is usually required. Therefore, the availability of solvents is limited by the necessity for dissolution of a supporting electrolyte. The presence of the supporting electrolyte might also cause separation problems in the reaction workup. Moreover, in an ordinary electrolysis system, solution resistance is generated between the working and counter electrodes, resulting in a decrease in energy efficiency. To overcome these problems, we focused on a solid polymer electrolyte (SPE) reactor which was originally developed for fuel cell technologies and demonstrated various electrocatalytic hydrogenations in a SPE reactor (Figure 1) [1-5].
As shown in Figure 1, a SPE membrane such as a proton exchange membrane (PEM) is integrated into the central part of the reactor, and is sandwiched between a pair of catalyst layers on the anode and cathode sides. For this reason, the substrate solution does not require a supporting electrolyte and the cell resistance can be minimized. The anode and cathode have highly porous 3D structures in order to conduct an efficient electrochemical reaction. Moreover, the reaction can be carried out in a flow operation. Thus, the SPE reactor system possesses many characteristics designed to overcome the disadvantages of conventional electrosynthetic processes.
In a series of studies we have conducted, in this presentation, we will discuss two topics such as diastereoselective reduction of cyclic ketones and electrocatalytic hydrogenation of pyridines.
The authors gratefully acknowledged support by JST CREST Grant No. 18070940, Japan.
[1] A. Fukazawa, M. Atobe, et al. ACS Susutain. Chem. Eng.
2019, 7, 11050.
[2] S. Nogami, M. Atobe, et al. J. Electrochem. Soc.
2020, 167, 155506.
[3] A. Fukazawa, M. Atobe, et al. Org. Biomol. Chem.
2021, 19,7363.
[4] S. Nogami, M. Atobe, et al. ACS Catalysis,
2022, 12, 5430.
[5] Y. Shimizu, M. Atobe, et al. ACS Energy Lett.,
2023, 8, 1010.

Figure 1
Electroauxiliary-Assisted C-C Bond Formations in Lithium Perchlorate / Nitromethane Solution
Authors: Akahane Shinnosuke , Kitano Yoshikazu , Okada Yohei 
Published: August 2024

C-nucleosides have C-C bonds between ribosyl moiety and nucleobase at anomeric carbon. This substitution of covalent bond gives hydrolysis resistance to C-nucleosides. Therefore, C-nucleosides are good candidates for antiviral or antitumor drugs as mimic building blocks of oligonucleotide.
To synthesize nucleosides, cation intermediate is used for installing nucleobase on ribosyl moiety. When it comes to generation of cation intermediate, electrochemical methodology is one of the useful tools. In electrochemical method, 1’-arylthioriboses are used as glycosyl donors. They have thioether group as electroauxiliary at anomeric carbon forging O,S-acetal that are activated with anodic oxidation to generate corresponding cation intermediate. Since electrochemically generated cation intermediates have high reactivity enough to react with carbon nucleophiles, this method can be adopted to C-nucleoside synthesis.
Previously, electrochemical nucleoside synthesis was reported using cation pool method in combination with electroauxiliary. To avoid undesired oxidation of nucleophile, it is important to pool the cation and/or to lower the oxidation potential of ribose. The low temperature condition such as -78 ~ -50 oC is necessary to pool cation intermediates.
In this research, we aimed to achieve electrochemical C-C bond formation at anomeric carbon with ambient temperature condition. In this strategy, we use glycosyl donors with lowered oxidation potential to avoid competitive oxidation with carbon nucleophiles. We also adapt lithium perchlorate/nitromethane system for electrolysis.

Figure 1
New Electrochemical Channel Flow Cell Design for Electrochemical Studies at Elevated Temperatures and Pressures
Authors: Abdulaziz Muna , Petruk Ariel , Sciaini German , Trevani Liliana 
Published: August 2024

Temperature exerts a considerable influence on the efficiency of chemical and electrochemical processes, and it is expected that studies under wide temperature and pressure (T and p) conditions can significantly impact fields of technological interest such as energy storage and conversion, water treatment, waste conversion, metal recovery, and electrosynthesis, among others.1 The electrochemical studies conducted by Bard’s group in near-critical and supercritical aqueous solutions,2 as well as the contributions made by MacDonald’s and Lvov’s3,4 groups on corrosion and pH determination in hydrothermal systems, offer valuable insights into the effects of temperature and pressure on electrochemical reactions under extreme conditions and construction materials and electrode designs. Other studies in the field, though they did not reach such harsh conditions, made valuable contributions by proposing innovative hydrodynamic electrode systems, from channel cells for studies up to 110 oC,5 a rotating disc electrode for temperatures up to 150 oC,6 and even an imping jet electrode able to reach 210 oC.7 Unfortunately, these studies were rarely expanded to more than one or two systems.
In this work, various hydrodynamic electrode configurations have been examined to conclude that the channel flow cell design presents several advantages over other systems for high T and P applications. These cells can provide consistent and reproducible mass transport conditions across a broad range of flow rates and allow channel dimension adjustments to tackle diverse technological challenges. Furthermore, this configuration aligns well with spectroscopic techniques like Raman/SERS (surface-enhanced Raman spectroscopy). COMSOL Multiphysics was used when designing the cell prototype, and validation of the model was carried out using data from previous studies.8 The high T,p cell uses disposable thin-film electrodes (TFEs) patterned onto sapphire wafers through nanofabrication methods; a significant amount of time has been invested in testing the performance of the TFEs up to at least 150°C. These results will also be presented along with experiments conducted with the new channel cell under ambient conditions.

References

(1) Giovanelli, D.; Lawrence, N. S.; Compton, R. G., Electroanalysis (New York, N.Y.)
2004, 16 (10), 789-810.
(2) Liu, C.-y.; Snyder, S. R.; Bard, A. J. J. Phys. Chem.B
1997, 101 (7), 1180-1185.
(3) Macdonald, D. D. Corrosion
2013, 34 (3), 75-84.
(4) Balashov, V. N.; Fedkin, M. V.; Lvov, S. N., J. Electrochem. Soc.
2009, 156 (7), C209.
(5) Wang, H.; Jusys, Z.; Behm, R. J.; Abruña, H. D., J. Electroanal. Chem.
2021, 896, 115251.
(6) Fleige, M. J.; Wiberg, G. K.; Arenz, M., Rev Sci Instrum
2015, 86 (6), 064101.
(7) Trevani, L. N.; Calvo, E.; Corti, H. R., Electrochem. Commun
2000, 2 (5), 312-316.
(8) Moorcroft, M. J.; Lawrence, N. S.; Coles, B. A.; Compton, R. G.; Trevani, L. J. Electroanal. Chem.
2001, 506 (1), 28-33.
Noise Interrogation during an Induced Faradaic Reaction
Authors: Wheeler Kaden , Kajal Kajal , Roehrich Brian , Chung Julia , Gott Joseph , Sepunaru Lior 
Published: August 2024

Single-entity electrochemistry has emerged as a potent method that allows for examination of individual responses within a system to comprehend a bulk response. For example, utilizing electrodes on the micrometer scale or smaller provides the requisite sensitivity to discern the impact of a nanoparticle contacting the electrode surface which catalyzes a reaction. Nevertheless, the detection of nanoimpacts is limited by the presence of noise which stems from the inherent non-inert nature of electrodes.
Understanding the noise level under a continuous Faradaic reaction becomes crucial for detecting catalysis at the sub-micron scale. In this presentation, I will describe how we understand and quantify the level of noise under diverse conditions. We measured noise while varying electrode size, sampling frequency, and redox-probe concentration. These results allowed us to formulate a model to predict noise at an electrode. Commonly, noise is thought to scale with the square root of current. However, our measurements reveal that the background noise level shifts from a square root dependence at the macroscale to a linear dependence at the microscale. Moreover, a chemically-coupled reaction (EC’) produces lower noise in comparison with a purely electrochemical reaction that produces the same steady-state current. In combination, these results suggest that diffusion partially dictates the amount of noise, along with the amount of redox-active species exchanging charge with the electrode. By understanding these noise sources, we may begin to control them, yielding more accurate and precise single-entity results.
Toward Sustainable Olefins: Electroreduction of CO2 to Multi-Carbon Olefins Using Trimetallic Cu-Rich Catalysts
Authors: Amouzesh Seyed Parsa , Asadi Mohammad 
Published: August 2024

The sustainable conversion of carbon monoxide (CO2) into value-added chemicals via electrochemical methods, powered by renewable electricity, is considered as a promising approach to meet the global energy demand and close the anthropogenic carbon cycle. However, this technology is in the early stage of development, particularly in the production of multi-carbon (C2+) hydrocarbons due to well-studied thermodynamic and kinetic barriers. To overcome these challenges, developing a catalyst with high activity and selectivity is crucial to minimize energy input and maximize the effectiveness of C2+ products formation.
In this work, we will present our recent advancement on developing non-precious tri-metallic catalysts with copper-rich surface synthesized by our developed atomically controllable and environmentally friendly synthesis method. The developed nanostructured tri-metallic electrocatalysts by this method show remarkable selectivity and activity in the electrochemical conversion of CO2 to olefins. In particular, our electrochemical results show an overall C2+ olefine Faradaic efficiency (FE%) of 69% more specifically 58% ethylene and 11% propylene at a current density of -112 mA/cm² under applied potential of -2.8 V in an anion exchange membrane (AEM) electrolyzer. To gain a better understanding of the catalytic performance and find a structural-performance relationships for the developed materials, we performed several physicochemical and electrochemical characterization experiments, including X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), and X-ray photoelectron spectroscopy (XPS). We will discuss morphology and atomic structure changes of the developed materials under realistic conditions, with a specific focus on understanding how different trimetallic interfaces influence selectivity and activity in the electrochemical CO2 reduction reaction (eCO2RR).