bluuebunny/crossref_metadata_2025_split huggingface dataset:
Platinum Catalyst Degradation: Unusual Nucleation and Growth of Nanoislands
Authors: Valls Mascaró Francesc , Koper Marc T. M. , Rost Marcel J. 
Published: July 2022

The longevity of a catalyst plays a crucial role for many industrial scale applications. Platinum is the best candidate to be used in electrochemical energy conversion systems due to its high activity. However, platinum catalysts degrade during fuel cell operation. The origin of this degradation, the loss of material, is very likely rooted in the roughening of the surface: the nucleation and growth of nanoislands [1, 2, 3, 4]. It is known that the extend of this roughening can be tuned by additives, change of the electrolyte pH, or operation within different potential windows [5, 6, 7]. In this work, we study the degradation of different platinum stepped surfaces under potential cycling to oxidative potentials. Interestingly, we quantify significantly less degradation on surfaces with narrower terraces: Ra(Pt(111)) > Ra(Pt(15 15 14)) > Ra(Pt(554)) > Ra(Pt(553)) > Ra(Pt(533)). We present here a model that explains this trend, in which steps act like sinks for both adatoms and vacancies, slowing down the nucleation and growth of the above mentioned nanoislands. We support our results, which were derived until now solely on electrochemical measurements, with in-operando Electrochemical Scanning Tunneling Microscopy (EC-STM) images.

References:

[1] Jacobse, L. et al., Nat. Mater. 17, 277 (2018)
[2] Jacobse, L. et al., ACS Cent. Sci. 5 (12), 1920 (2019)
[3] Rost, M.J. et al., Nat. Commun. 10, 5233 (2019)
[4] Hanselman, S. et al., Phys. Chem. Chem. Phys. 22, 10634 (2019)
[5] Lopes, P.P. et al., ACS Catal. 6, 2536 (2016)
[6] Topalov, A. et al., Chem. Sci., 5, 631 (2014)
[7] Ruge, M. et al., J. Am. Chem. Soc., 139, 4532 (2017)
Thick Copper Layer Growth By Dynamic Hydrogen Bubble Template Using Continuous and Pulse Currents
Authors: Schoenleber Jonathan , Gigandet Marie-Pierre , Fedi Baptiste , Hihn Jean-Yves 
Published: July 2022

Copper is the most widely used materials for microelectronics applications due to their electrical and thermal conduction properties, and in several appplications, thick and porous layers are requested.
Different possibilities still exists such as copper-zinc or copper-manganese electrodeposition followed by an anodic dissolution, but the faster and simpler way resides in electroforming deposition made by Dynamic Hydrogen Bubble Template (DHBT) [1]. This process works in unusual potentials and current densities where the competition between hydrogen discharge (commonly avoided) and copper reduction is very high. In this case, this method achieves thick deposits in very short time (few seconds) with high currents allowing a very fast growth of copper around hydrogen bubbles. Pores and ligaments sizes can be controlled by several operating parameters i.e. current densities, temperature, deposit time as well as by chemical additives [2].
With the use of a copper sulphate acid bath at various concentrations, with or without additives (acetic or hydrochloric acids) and by applying current densities between 100 and 400 A.dm-2, it is possible to obtain thick and porous coatings, with pores diameters between 10 and 500 µm and ligaments length between 10 and 200 µm. An example of a SEM image shows the morphology of the deposits obtained in top view and in cross section (Figure 1). Another possibility to control the 3D growth resides in the use of pulsed currents, with an effect on bubbles size. Furthermore, reverse pulses are useful for edge effects limitation.
[1] Abdel-Karim, R.; El-Raghy, S. Chap 4 in Advanced materials and their applications - micro to nano scale. One Central Press, United Kingdom, pp 69–91, 2017
[2] Shin, H.-C.; Liu, M. Chem. Mater. 2004, 16, 25, 5460–5464 doi.org/10.1021/cm048887b
Figure 1 : SEM images of a) top view and b) cross section of a DHBT copper deposit

Figure 1
(Invited) 3-D Visualization of Li Metal Plating and Stripping with Operando Video Microscopy
Authors: Dasgupta Neil P. 
Published: July 2022

In recent years, there has been an explosion of research into Li metal anodes for high-energy-density batteries. However, despite tremendous progress in the field, the reversible plating and stripping of Li has been hindered by the complex interplay between electrode morphology, surface chemistry, and mechanics. This has led to many empirical observations of improved performance, but our ability to rationally design solutions to solve the challenges of reversibility remain limited by our fundamental understanding of the complex electrodeposition and dissolution processes involved [1]. In an analogous example, Li plating on graphite anodes during fast-charging also plagues the Li-ion community [2], but fundamental studies of the complex nature of Li plating on intercalation electrodes is equally lacking.
To address these challenges, in situ/operando analyses are of paramount importance to the community. However, given the dynamic nature of Li plating and stripping, challenges arise with respect to tradeoffs in spatial and temporal resolution. To address these challenges, we have recently integrated our optical visualization cells with a digital microscope capable of focus variation microscopy. This enables 3-D visualization of the electrode morphology with high temporal resolution, allowing for video capture of Li plating and stripping [2-3].
In this talk, I will discuss the application of operando 3-D microscopy for visualization of both Li metal anodes and Li plating on graphite surfaces during fast-charging of Li-ion batteries. In the case of Li metal anodes, we observe significant anisotropy in the geometric shape of individual pits during stripping [3]. The nucleation density and anisotropy are shown to be strongly influenced by the surface microstructure and underlying crystallographic texture of the Li metal surface. As a results, pits can exhibit strong faceting, which influences the nature of nucleation at pit edges in subsequent cycles [4]. As a parallel example, we demonstrate 3-D visualization of Li plating on graphite electrodes during fast-charge, which illustrates the coupling between nucleation of Li plating and local heterogeneity in state-of-charge [2]. Overall, these results highlight the importance of both spatial and temporal heterogeneity in the nature of nucleation, growth, dissolution, pitting, and dead Li formation
References
[1] K. N. Wood, M. Noked, N. P. Dasgupta, ACS Energy Lett.
2, 664 (2017).
[2] Y. Chen, K.-H. Chen, A. J. Sanchez, E. Kazyak, V. Goel, Y. Gorlin, J. Christensen, K. Thornton, N. P. Dasgupta, J. Mater Chem. A
9, 23522 (2021).
[3] A. J. Sanchez, E. Kazyak, Y. Chen, J. Lasso, N. P. Dasgupta, J. Mater Chem. A.
9, 21013 (2021).
[4] A. J. Sanchez, E. Kazyak, Y. Chen, K.-H. Chen, E. R. Pattison, N. P. Dasgupta,
ACS Energy Lett.
5, 994 (2020).
Diversity Matters: Influence of Surface Heterogeneities in the Electrochemical Nucleation and Dissolution of Au Nanoparticles
Authors: Bernal Lopez Miguel , Torres Daniel , Semsari Parapari Sorour , Čeh Miran , Žužek Rožman Kristina , Šturm Sašo , Ustarroz Jon 
Published: July 2022

The investigation of the nucleation and dissolution of gold nanoparticles on a glassy carbon substrate with Scanning Electrochemical Cell Microscopy (SECCM) combined with in-situ electrochemical TEM (EC-TEM) revealed the subtle influence of the local properties of the substrate on the electrochemical processes. Conducting hundreds of locally-resolved voltammograms at the micro-scale resulted in the observation of a diversity of responses for nucleation, allowing to address experimentally the statistical nature of the nucleation and growth process. Moreover, during the electrochemical dissolution of previously electrodeposited nanoparticles (NPs), the confinement conditions of the SECCM-cell allowed the resolution of a multitude of events characterized as current spikes. Such current events are not observable in the macro-scale since the electrochemical response over the large electrode area is the convolution of the activity all over the electrode surface. The EC-TEM experiments demonstrated that such current spikes were generated by the dissolution of individual NPs distributed over a time range. Combining SECCM and EC-TEM unmasked information previously not seen from the electrochemical nucleation, growth, and dissolution of supported metal nanoparticles [1]. This approach could accelerate the discovery of novel functional electrode materials by facilitating the rational design of protocols for electrodeposition of nanostructured materials and the evaluation of their stability under electrochemical conditions. The possibility to consider the heterogeneous nature of the supports and the differences within nanomaterial ensembles opens the opportunity to consider the diversity of electrochemical parameters as descriptors to understand and describe the relationships between activity, stability, and structure.
[1] M. Bernal, D. Torres, S. Semsari, M. Čeh, K. Žužek Rožman, S. Šturm, J. Ustarroz, Diversity matters: Influence of surface heterogeneities in the electrochemical nucleation and dissolution of Au nanoparticles, under revision
(Invited) Effect of Additive Species on the Nucleation and Growth Process on Zn Negative Electrode Surface
Authors: Homma Takayuki , Onabuta Yusuke , Otani Tomohiro , Kunimoto Masahiro , Fukunaka Yasuhiro 
Published: July 2022

Zn is one of the promising candidates as negative electrode materials for next-generation secondary batteries, especially those for large capacity applications such as grid-scale energy storage. While the Zn has numbers of attracting features such as crustal abundance, applicability of aqueous system, etc., which enable to realize the secondary batteries with high performance and safety with lower cost, the major drawback is evolution of irregular morphology called mossy structure with highly filamentous features at the electrode surface during charge-discharge cycles. Unlike the conventional dendritic growth which proceeds under diffusion-limited conditions, formation of the mossy structure takes place without such a condition. At the same time, it has been reported that the growth of these irregular structures could be suppressed by applying metallic species as additives to form uniform electrodeposition [1]. We have investigated formation process of the mossy structure on the Zn anode surface, focusing on its initial stage in combination with the additive effects such as Pb and Sn [2]. In this presentation, we will introduce the results of our research on the nucleation and growth process of the mossy structure through experimental analysis and computational modeling. For the theoretical calculation, we attempted to develop multi-scale simulation model by employing density functional theory (DFT) and kinetic Monte Carlo (KMC) approaches [3], and the results will be described focusing on the effects of the metallic additives.
This work is financially supported in part by MEXT/JSPS Grant-in-Aid for Scientific Research No. 21H01642.
[1] For example, F. Mansfeld, S. Gilman, J. Electrochem. Soc. 117, 1328 (1970); Y. Ito, M. Nyce, R. Plivelich, M. Klein, D. Steingart, S. Banerjee, J. Power Sources, 196, 2340 (2011).
[2] For example, T. Otani, M. Nagata, Y. Fukunaka, T. Homma, Electrochim. Acta, 206, 366 (2016); T. Otani, Y. Fukunaka, T. Homma, Electrochim. Acta, 242, 364 (2017).
[3] Y. Onabuta, M. Kunimoto, S. Wang, Y. Fukunaka, H. Nakai, T. Homma, J. Phys. Chem.C, submitted.
(Digital Presentation) Mechanistic Understanding of Rhenium Electrodeposition
Authors: McBride Michael , Dervishi Enkeleda , Edwards Randy , Stull Jamie A , Clark Courtney L , Hooks Daniel E 
Published: July 2022

The electrodeposition of rhenium (Re) has received renewed attention in the past decade for a wide range of applications in aerospace, nuclear, catalysis, biomedical and electrical fields. Rhenium has unique and superior properties when compared with other refractory metals, making it attractive as an engineering material. It has a very high modulus of elasticity and superior tensile strength and creep-rupture strength over a wide temperature range. Re also is very resistant to highly corrosive environments, possesses a very high melting point, and enhanced wear resistance properties. However, Re is difficult to deposit by electrolysis of their aqueous solutions due to its very low over potential for hydrogen evolution.
The electrodeposition of rhenium has been demonstrated in the literature with approaches ranging from simple acidic solutions, induced codepostion with iron group metals, and water-in-salt electrolytes. However, these coatings are generally deposited at low Faradaic efficiency, are brittle, and limited in the obtainable thickness (sub-micron) due to absorbed hydrogen and formation of oxide phases.
Herein, we present systematic studies progressing towards the development of stable and efficient electrolytes to enable the electrodeposition of thick (100+ microns) Re coatings. Examples from both simple acidic solutions and water-in-salt electrolytes will be presented. Specifically, we correlate nucleation and growth mechanisms of Re with the ability to produce thick coatings. Pulse/pulse reverse electroplating was applied to manipulate the obtained grain structure. Correlations between electrolyte composition and pulse parameters with observed morphology will be discussed.
The ultimate goal of this project is the electrodeposition of rhenium-cobalt (Re-Co) graded density samples of millimeter thickness. Thus, understanding how to transition from a coating of pure metallic rhenium to a graded composition of Re-Co as a function of dynamic processing conditions will be presented. Towards this end, we are using a combination of electrochemical techniques with in situ measurements (atomic force microscopy, Raman, optical microscopy) to isolate variables controlling nucleation and growth which lead to the grain structure of the deposit.
LA-UR-21-31694
Elucidating and Mitigating High-Voltage Interfacial Chemomechanical Degradation of Nickel-Rich Lithium-Ion Battery Cathodes Via Conformal Graphene Coating
Authors: Luu Norman , Lim Jin-Myoung , Torres Castanedo Carlos Gerardo , Park Kyu-Young , Moazzen Elahe , He Kun , Meza Patricia E. , Li Wenyun , Downing Julia , Hu Xiaobing , Dravid Vinayak , Barnett Scott A , Bedzyk Michael , Hersam Mark C 
Published: July 2022

Layered-type, nickel-rich lithium nickel manganese cobalt oxides (NMCs) are well-established cathode materials for high-performance lithium-ion batteries. These materials exhibit stable cycling within mild voltage windows (up to 4.3 V vs. Li/Li+) but can be charged to higher potentials (4.8 V vs. Li/Li+) to access additional capacity. However, high-voltage operation is generally avoided due to severe interfacial and chemomechanical degradation, such as electrolyte decomposition reactions and non-uniform buildup of chemomechanical strains that can result in particle fracture and compromised cyclability.
In this work, we find that a conformal graphene coating enables significant enhancements in the cycle life and coulombic efficiency of NMC cathodes during high voltage electrochemical cycling. Postmortem surface chemical analysis reveals that graphene-coated NMC electrodes exhibit reduced spectral intensities corresponding to electrolyte decomposition products, suggesting that the interfacial graphene layer limits parasitic electrode-electrolyte interactions. Furthermore, global and local structural analysis shows that the graphene coating mitigates mechanical degradation, which was evidenced by reduced microstrain, particle fracture, and electrochemical creep. Based on these observations, we propose a mechanistic relationship between the spatial uniformity of lithium flux and primary particle-level mechanical degradation, and show that a conformal graphene coating is well-suited to address these issues associated with high voltage chemomechanical degradation. Overall, these results delineate a pathway for rationally mitigating high-voltage chemomechanical degradation of nickel-rich cathodes that can be applied to existing and emerging classes of battery materials.
https://doi.org/10.1021/acsaem.1c01995
Polysiloxane-Based Single-Ion Conducting Polymer Electrolyte for High-Performance Li‖NMC811 Batteries
Authors: Liang Hai-Peng , Zarrabeitia Maider , Chen Zhen , Jovanovic Sven , Merz Steffen , Granwehr Josef , Passerini Stefano , Bresser Dominic 
Published: July 2022

The ongoing electrification of the transportation sector is triggering a continuous search for batteries with higher energy density. One approach to achieve this goal is the transition to lithium-metal anodes. However, the practical implementation brings about severe safety issues such as the dendritic deposition and growth of metallic lithium and the consequent risk of accidental short circuiting of the cell, resulting in a thermal runaway.1 Solid-state electrolytes such as polymers are considered a viable strategy to overcome this issue, especially single-ion conducting polymers, owing to the absence of the detrimental reversed cell polarization, the uniform Li+ flux, and frequently higher limiting current densities.2,3 In fact, the latter is of utmost importance for the fast charging of battery cells as well as the eventual power density. So far, however, the cycling performance at high dis-/charge rates and high current densities for battery cells comprising a polymer electrolyte remained little investigated and commonly non-satisfactory.
Here, we report the development of a polysiloxane-based single-ion conducting polymer electrolyte (PSiOM) with a Li+ conductivity exceeding 10−4 S cm−1 at ambient temperature and excellent stability towards both lithium metal and high-energy LiNi0.8Co0.1Mn0.1O2 (NMC811) as the active material for the positive electrode. This new polymer electrolyte enables dendrite-free lithium deposition, thanks to the formation of a suitable electrode|electrolyte interface and interphase and the uniform Li+ flux. Moreover, PSiOM allows for an outstanding capacity retention of, e.g., 90% at 1C and 86% at 2C after 300 cycles and rapid charging and discharging at C rates as high as 5C. It is important to note that we used reasonable active material mass loadings for these tests (>7 mg cm-2), which means that the current densities applied were up to 7.20 mA cm−2 at 40 °C and 2.88 mA cm−2 at 20 °C. To the best of our knowledge, these current densities are among the highest reported so far for polymer-based electrolytes.

References

(1) Kalhoff, J.; Eshetu, G. G.; Bresser, D.; Passerini, S. Safer Electrolytes for Lithium-Ion Batteries: State of the Art and Perspectives. ChemSusChem
2015, 8 (13), 2154–2175.
(2) Zhang, H.; Li, C.; Piszcz, M.; Coya, E.; Rojo, T.; Rodriguez-Martinez, L. M.; Armand, M.; Zhou, Z. Single Lithium-Ion Conducting Solid Polymer Electrolytes: Advances and Perspectives. Chemical Society Reviews
2017, 46 (3), 797–815.
(3) Nguyen, H.-D.; Kim, G.-T.; Shi, J.; Paillard, E.; Judeinstein, P.; Lyonnard, S.; Bresser, D.; Iojoiu, C. Nanostructured Multi-Block Copolymer Single-Ion Conductors for Safer High-Performance Lithium Batteries. Energy & Environmental Science
2018, 11 (11), 3298–3309.
(Invited) Enabling Fast Charging of Lithium-Ion Batteries without Lithium Plating
Authors: Dasgupta Neil P. 
Published: July 2022

Today’s Li-ion technology is highly optimized for performance at relatively slow charging operation. However, significant challenges still present for fast charging conditions (> 4C). In state-of-the-art Li-ion batteries (LIBs) with high energy densities, the electrodes are relatively thick (> 100 μm), which leads to a tradeoff between energy density and high-power performance. In addition, the electrochemical potential of the anode can easily become more negative than Li/Li+ during fast charging, resulting in Li plating [1]. Therefore, new approaches are needed to overcome these energy/power tradeoffs in LIBs
In this talk, I will introduce three strategies to enable fast charging LIBs, using industrially-relevant pouch cells with thick (>3 mAh/cm2) electrode loadings. In the first strategy, vertical channels are introduced into post-calendared electrodes using laser ablation patterning [2]. The resulting 3-D anode architecture consists of a hexagonal close-packed array of vertical channels that serve as linear pathways for rapid ionic diffusion through the electrode thickness. This allows for a more homogeneous flux of Li throughout the volume of the electrode. As a result, the accessible capacity of the electrode during fast charging increases, and Li plating is eliminated.
In the second strategy, the energy/power tradeoffs in carbonaceous anode materials are overcome by forming hybrid blends of graphite and hard carbon [3]. This allows for a balance between the higher energy density of graphite with the faster rate performance of hard carbon. By controlling the graphite/hard carbon ratio, we identify an optimal blend for fast charging.
In the third strategy, we demonstrate the potential to eliminate Li plating and enabling 4C fast charging purely through interfacial control. This is achieved by coating the surface of graphite with a solid-state electrolyte material using Atomic Layer Deposition (ALD) [4]. These coatings eliminate electrolyte decomposition during the formation cycle, resulting in an “artificial SEI” with a resistance that is 75% lower than the natural SEI that forms in carbonate electrolytes. This challenges the fundamental assumption that fast charging of thick graphite anodes must be solved by improving mass transport, highlighting the critical role of the SEI on fast-charge performance.
[1] Y. Chen, K.-H. Chen, A. J. Sanchez, E. Kazyak, V. Goel, Y. Gorlin, J. Christensen, K. Thornton, N. P. Dasgupta, J. Mater Chem. A
9, 23522 (2021).
[2] K.-H. Chen, M. Namkoong, V. Goel, C. Yang, S. Kazemiabnavi, S. M. Mortuza, E. Kazyak, J. Mazumder, K. Thornton, J. Sakamoto, N. P. Dasgupta, J. Power Sources
471, 228475 (2020).
[3] K.-H. Chen, V. Goel, M. J. Namkoong, M. Wied, S. Müller, V. Wood, J. Sakamoto, K. Thornton, N. P. Dasgupta, Adv. Energy Mater.
11, 2003336 (2020).
[4] E. Kazyak, K.-H. Chen, Y. Chen, T. H. Cho, N. P. Dasgupta, Adv. Energy Mater, In Press (2021).