bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis of Aptes-Capped Self-Adsorption Pd Nanoparticles and Application in Metallization on Glass Substrate with High Adhesion
Authors: Yang Pei-Qing , Wei Tzu Chien 
Published: February 2024

Palladium is the most used catalysts in the electroless deposition process. The technology that use the amino silane compound (3-Aminopropyl) Triethoxysilane (APTES) as surface modifier is quite mature. Therefore, an innovative idea that one step palladium catalyst APTES-Pd with APTES as capping agent and surface modifier appeared. APTES-Pd is capable to adsorb on surface of glass substrate by forming Si-O covalent bond. Comparing to commercial palladium catalysts, the process is complex and need to work at high concentration, APTES-Pd has easier process and able to work at low concentration. The particle size of APTES-Pd is characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The configuration of APTES-Pd as well as the effect of modification on glass substrate is explained by X-ray photoelectron spectroscopy (XPS).
Glass substrate is a good option as an interposer substrate. It has serval advantages, such as low k, high resistivity, high stability, low coefficient of thermal expansion (CTE) mismatch with copper material and good mechanical properties. However, because glass substrate (SiO2) is stable and surface is smooth, it’s hard to electroless deposit Cu layer with high adhesion on it. The adhesion that using commercial palladium catalysts Sn/Pd for electroless copper deposition is too low to pass tape test. Because interaction between Sn/Pd and substrate is electrostatic adsorption which is lower than covalent bond. Using APTES-Pd for electroless copper deposition is capable to improve the interaction between glass and Cu layer. APTES-Pd can pass tape test on glass substrate. But its adhesion is still too low to be measured by T-Peel. To enhance the adhesion of the metal films on glass substrates, we coat titanium dioxide (TiO2) as adhesion promoter. TiO2 can not only bond to glass substrate but increase surface roughness. After coating TiO2 film, the adhesion of metal film increases to 122 gf/cm.
(Invited) Electroless Cu, Pb and Ag Monolayer Deposition – Generality of an Electroless Monolayer Deposition Phenomenon
Authors: Dalgamouni Mariam , Brankovic Stanko 
Published: February 2024

Recent progress in fuel cell catalysis has been enabled in great part by facile methods for catalyst monolayer synthesis based on surface limited redox replacement (SLRR) of underpotentially deposited (UPD) monolayers. Although this approach has been very effective, it has shown a limited applications in majority of heterogeneous gas phase catalysis problems where substrates are oxide based materials with very limited conductivity. In this talk we point out a new possibility for catalyst monolayer synthesis via SLRR on metal surfaces which are not part of a broadly conductive substrates such as metal nanoparticles imbedded in various oxide or zeolite supports. This is enabled by discovery of an electroless (E-less) Pb, Cu and Ag monolayer deposition phenomenon. Fundamentals of the E-less monolayer deposition are reviewed, and new data illustrating Cu and Ag monolayer deposition are presented. The focus is on emphasizing generality of the E-less monolayer deposition phenomenon, its self-termination and surface selectivity towards substrates at which Cu, Ag and Pb form UPD monolayer. Examples of the thin films and catalyst monolayer deposition via SLRR of E-less Cu, Ag and Pb monolayer are presented under the auspices of a newly developed two-step electroless atomic layer deposition protocol (E-less ALD)1.
1) Electroless Pb Monolayer Deposition – Prelude for Further Advances in Catalyst Monolayer Synthesis via Surface Limited Redox Replacement Reaction”, K. Ahmadi, N. Dole, D. Wu, T. Salavati‐Fard, L. C. Grabow, F. C. Robles Hernandez, and S. R. Brankovic, ACS Catalysis, 11, 4650 (2021).
Porous Silicon and Silicon Nanotubes with Embedded FePt Nanoparticles Investigated by High Temperature Magnetic Measurements
Authors: Rumpf Klemens , Granitzer Petra , Gonzalez-Rodriguez Roberto , Coffer Jeffery 
Published: February 2024

Porous silicon (PSi) and silicon nanotubes (SiNTs) are presented as a platform for filling with FePt nanostructures. The difference of the magnetic characteristics between the two systems is figured out. Furthermore, the FePt filled templates are compared with the same template materials filled with Ni/Co by electrodeposition.
The porous silicon is produced by anodization of a highly doped n-type silicon wafer in a 10 wt% HF solution. The produced morphology offers separated pores of about 50 nm and a mean distance between the pores of 50 nm. The SiNTs are fabricated in using an array of ZO wires as template, subsequent silicon deposition and finally etching off the ZO. The inner diameter of the tubes and also the wall thickness can be tuned by the fabrication process. In this work SiNTs with comparable inner diameter to the PSi structure and a wall of about 10 nm are used (1). FePt nanoparticles (NPs) are deposited electroless inside the pores and the tubes, respectively whereat the molar ratio of Fe is varied. For this purpose a 3 component solution consisting of H2PtCl6, Fe(NO3)3 and citric acid is used, whereas the ratio of the components is modified.
The varying magnetic response of the different composite systems, porous silicon and silicon nanotubes is investigated. PSi/FePt shows a higher coercivity and remanence than SiNTs/FePt and thus a higher hard magnetic performance. The variation of the coercivities between SiNTs/FePt and PSi/FePt is about 57%.
Considering the FePt deposits with different molar ratio of Fe the coercivities vary in a range of 5% in the case of both template types. Comparing FePt loaded samples with Co loaded samples in all cases an increase of the coercivity and of the remanence is observed for FePt, whereat in the case of PSi as template material the increase is significantly stronger than in the case of SiNTs samples. Figure 1 shows the comparison of the hysteresis of PSi and SiNTs filled with FePt NPs.
The influence of high temperatures on the nanocomposite samples is of interest, as well as the high temperature magnetic behavior. Therefore, beside low temperature and room temperature magnetic measurements, the magnetic behavior of the samples is investigated at high temperatures up to 1273 K.
(1) K. Rumpf, et.al, ECS Transactions 98 (2020) 37
Electrochemical Additive Manufacturing of Binary and Ternary Alloys at the Mircon Scale by Electrohydrodynamic Redox 3D Printing
Authors: Porenta Nikolaus , Nydegger Mirco , Menétrey Maxence , Hammadi Souzan , Reiser Alain , Spolenak Ralph 
Published: February 2024

The need for miniaturisation throughout many different industries brings classical subtractive manufacturing techniques to their limits. Additive manufacturing is able to overcome these limits which has made it a topic of interest in many scientific fields. This additional geometric freedom becomes increasingly important if feature sizes on the micron- or even nano-scale are desired. Multiple different techniques to fabricate device-grade metals at such length-scales have been reported [1]. As one of these techniques, electrohydrodynamic redox printing (EHD-RP) has shown promise to be a versatile fabrication tool [2, 3, 4] depositing dense, pure metallic structures at high deposition rates.
In this contribution, we present our work on additively manufactured alloys. First, we introduce a novel EHD-RP approach using aqueous metal salt electrolytes instead of sacrificial anodes as ion sources. The use of metal salts not only expands the range of manufacturable metals, but also enables the fabrication of metal alloys with precise compositional control without the need for additives or a surplus of the less noble metal. We demonstrate this control by fabricating binary and ternary Cu-Ag, Cu-Zn and Cu-Ag-Zn alloys. The composition of the fabricated alloy exactly mirrors the composition of the aqueous metal salt solutions. These systems were chosen as a representative immiscible and miscible system, in order to study different growth mechanisms. Microstructural analysis of Cu-Ag alloys reveals the formation of a metastable mixed phase. Cu-Ag alloys were successively dealloyed to produce nano-porous Ag structures. The compositional control over the Cu-Ag alloy enables precise control of porosity in the dealloyed structures. These nano-porous Ag structures have also been tested as substrates for surface enhanced Raman spectroscopy.
(1) L. Hirt, A. Reiser, R. Spolenak & T. Zambelli, Adv. Mater
2017, 29, 1604211
(2) A. Reiser, M. Lindén, P. Rohner, A. Marchand, H. Galinski, A. S. Sologubenko, J. M. Wheeler, R. Zenobi, D. Poulikakos & R. Spolenak, Nat. Comm.
2019, 10, 1853
(3) M. Nydegger, A. Pruška, H. Galinski, R. Zenobi, A. Reiser & R. Spolenak, Nanoscale
2022, 14, 17418
(4) M. Menétrey, L. Koch, A. Sologubenko, S. Gerstl, R. Spolenak & A. Reiser, Small
2022, 18, 2205302
Localized Electrochemical Deposition Using Copper Pyrophosphate-Based Electrolyte
Authors: Song Yunha , Lee Jinhyun , Kim Youjung , Seo Jinmyeong , Hwang Inseong , Yoon Sanghwa , Yoo Bongyoung 
Published: February 2024

Additive manufacturing (AM) has gained popularity across various industries due to its cost-effectiveness, low material consumption, and minimal environmental impact. Localized electrochemical deposition (LECD), as one of the AM methods, has the capability to produce microcomponents or structures at an microscale in a specific position as designed, without the need for any mask or support material[1]. By reducing copper ions in the local area according to the position of the micro-wire, 3D structures could be produced. This electrochemical deposition process has a significant advantage in that it is a low-temperature process and has lower costs compared to other processes[2].
Using the LECD process, the micrometer of copper columns was conventionally deposited in copper sulfate-based electrolyte[3]. However, this electrolyte has the possibility to cause damage to the metal substrate used as the cathode due to its low pH, resulting in metal dissolution. The utilization of copper pyrophosphate-based electrolyte, which is a solution with a pH close to neutral, can solve this problem. Also, copper pyrophosphate-based electrolyte offers an advantage over conventional alkaline-based electrolytes in that it removes cyanide pollution of the environment and hazards to human health.[4]
In this study, the microanode was employed using a platinum wire(100 μm in diameter), while a copper substrate was employed as the cathode in the electrochemical deposition process. The micrometer copper columns were deposited using copper pyrophosphate-based electrolyte by varying the main electrochemical deposition factors, such as applied potential and pulse duty cycle. In addition The surface morphology of the deposited micrometer-scale copper columns was observed through scanning electron microscopy.
REFERENCES
[1] Suryavanshi, Abhijit P., and Min-Feng Yu. "Probe-based electrochemical fabrication of freestanding Cu nanowire array." Applied Physics Letters 88.8 (2006): 083103.
[2] Madden, John D., and Ian W. Hunter. "Three-dimensional microfabrication by localized electrochemical deposition." Journal of microelectromechanical systems 5.1 (1996): 24-32.
[3] Lin, J. C., et al. "Localized electrochemical deposition of micrometer copper columns by pulse plating." Electrochimica Acta 55.6 (2010): 1888-1894.
[4] Chen, C-C. "A New Process for Cyanide-Free Copper Plating."Electroplating and Pollution Control 23.4 (2003): 10-11.
Uniformity of Electrodeposited Coatings Onto Additively Manufactured Graphite Lattice Electrodes
Authors: Clemens Auston L. , Jung Kyle , Ivanovskaya Anna N. , Davis Jonathan T. , Orme Christine , Jayathilake Buddhinie Srimali , Akolkar Rohan , Dudukovic Nikola A. 
Published: February 2024

The ability to uniformly electrodeposit metallic coatings onto geometrically complex substrates plays a significant role in developing specialized applications from coating detailed RF components to depositing catalytic coatings onto ordered foams electrodes for electrochemical flow reactors. However, there presently lacks guidelines for electrodeposition in porous media due to the problem’s multi-scale complexity. We present a framework for deconvoluting this process through continuum-level modeling and experimental validation of electrodeposited copper onto additively manufactured conductive lattice structures. Through numerical simulations we can predict thickness profiles and validate the model prediction and coating quality through micro-computed tomography. We further devise scaling laws with the aim of facilitating control over deposition uniformities on different lattice architectures and dimensions under fluid flow. In extension, the manufacturing platform for functionalized electrodes is extended to battery applications as use in novel electrode geometries within rechargeable secondary batteries as well as plating thickness evolution in custom redox flow battery cathodes for grid scale energy storage.
This work is performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 within the LDRD program 20-ERD-056. LLNL-ABS-847849.
Coupling Metal Oxides and Dendritic Gold Current Collectors for High-Performance Hybrid Supercapacitors on Silicon Wafer
Authors: Arcoraci Davide , Reina Marco , Zaccagnini Pietro , Baudino Luisa , Serrapede Mara , Lamberti Andrea 
Published: February 2024

Hybrid supercapacitors have gained significant attention in recent years due to their potential to combine the advantages of both batteries and capacitors. In this study, we investigate the use of metal oxides materials in a hybrid supercapacitor using a dendritic gold current collector, the device was implanted on a silicon wafer. Metal oxide materials, such as iron Oxide (Fe2O3) and manganese oxide (Mn2O3), are known for their high pseudo-capacitance and excellent electrochemical performance in water based electrolyte.
By integrating dendritic gold current collectors with these materials, we aim to enhance its energy storage capacity and cycling stability. The silicon substrate provides mechanical support and pave the way for on-chip application, while the dendritic gold current collector offers a high surface area for efficient ion adsorption and desorption along the electrode-electrolyte interface. The metal oxide is coated onto the porous gold electrode using a simple and low cost-effective method, the electroplating, by mean of a solution based on FeSO4. The performance of the hybrid supercapacitor is evaluated through various electrochemical tests, including cyclic voltammetry, galvanostatic charge-discharge cycling, and electrochemical impedance spectroscopy, adopting neutral water based electrolyte. The results show that the enhanced hybrid supercapacitor with metal oxide materials exhibits significantly improved electrochemical performance compared to the device with a flat metal oxide electrode. The Fe-coated dendritic electrode exhibits a high specific capacitance over 20 mF cm-2, while the MnO2-coated flat electrode demonstrates similar specific capacitance over 25 mF cm-2. Additionally, the hybrid supercapacitor shows excellent cycling stability with negligible capacitance loss after 1000 cycles.
In conclusion,the results suggest that mixing micro-structured current collectors with metal oxides can lead to simplified area's balancing technique for planar electrochemical cells, destinated to the development of on-chip devices with large operating voltage window, high energy storage capability and efficiency.

Figure 1
Modeling, Model Calibration, and Characterization of Graphite Anodes from Coal Derived Carbon for Battery Applications
Authors: Paul Abigail , Magee Regan , Wilczewski Warren , Wolfe Kody D , Wichert Nathan , Wang Fengkun , Mollah Rafid , Jones Matthew , Trembly Jason , Staser John A. , Garrick Taylor R. 
Published: February 2024

Most current production electric vehicles (EVs) contain cells with a battery pack or module in order to maintain electrical conductivity, prevent fatigue due to vibrations, and provide efficient cooling. Various module hardware has to be designed in order to facilitate the efficient rejection of heat and contain volume change due to operation and battery cell aging. As we see a shift towards EVs both globally and domestically, the time from concept development to vehicle production needs to rapidly decrease. The use of model-based engineering is critical to driving rapid design and virtual prototyping of electric vehicles to ensure that battery module components meet EV requirements.
Currently, empirical data is used to characterize and parameterize battery models that are used to drive design decisions at the battery cell and battery module level. Typical vehicle level use profiles such as the Hybrid Pulse Power Characterization (HPPC) profile, constant rate discharge, constant rate charging, and US06 drive cycles are traditionally used to parameterize battery models. In this work, we discuss select cell level testing profiles, evaluate the electrochemical transport and reaction parameters that are estimated using a porous electrode model, and provide insight and recommendations based on data from coal derived graphite for battery applications.
References

Garrick, T. R., Gao, J., Yang, X., & Koch, B. J. (2021). “Modeling Electrochemical Transport within a Three-Electrode System.” Journal of The Electrochemical Society, 168(1), 010530.

Lopata, J. S., Garrick, T. R., Wang, F., Zhang, H., Zeng, Y., & Shimpalee, S. (2023). “Dynamic Multi-Dimensional Numerical Transport Study of Lithium-Ion Battery Active Material Microstructures for Automotive Applications.” Journal of The Electrochemical Society, 170(2), 020530.
Quantifying Volume Change in Battery Electrode Microstructures
Authors: Teel Hunter , Lopata Joseph Steven , Garrick Taylor R. , Wang Fengkun , Zhang Han , Zeng Yangbing , Shimpalee Sirivatch 
Published: February 2024

A three-dimensional microstructure-based modeling method (3DMS) is developed [1, 2] to predict the mechanical behaviors of porous electrode that includes both active material (AM) and binders inside lithium-ion battery during compression, reversible expansion (intercalation dependent), and irreversible expansion (aging dependent). The geometry of both AM and binder is generated stochastically to create microstructures by using a modified MATBOX opensource program with our in-house code. The advanced technique of volume element generation is also established to overcome the interfacial error due to complexity of binder distribution. The Finite Element Analysis (FEA) based solid-stress model is applied to predict local mechanical activities including stress-strain relationship and microstructure evolution during compression, intercalation, and aging.
The predictions of behavior in the porous electrode under compressive loads will be presented and the insights into the microstructure deformation will be discussed. Further, the analysis results will be validated using experimental testing results acquired at various length scales. This work can be used for the model-based FEA platform to predict the impact of volume change under charge/discharge cycles, volume change of a jelly-roll during formation, and the response of the active material in typical pouch cells during battery module assembly.
The predictions of reversible expansion in the porous electrode during cycling will be presented and the insights into the microstructure expansion as compared to continuum porous electrode models from previous work [3-8] will be discussed.
Finally, insights into the linkage between irreversible volume expansion in the porous electrode during aging cycling will be discussed and compared to testing acquired for automotive-relevant large format [9] pouch cells.
References

J. S. Lopata, T. R. Garrick, F. Wang, H. Zhang, Y. Zeng and S. Shimpalee, ECSarXiv (2022).

J. S. Lopata, T. R. Garrick, F. Wang, H. Zhang, Y. Zeng and S. Shimpalee, J Electrochem Soc, 170, 020530 (2023).

D. J. Pereira, J. W. Weidner and T. R. Garrick, J Electrochem Soc, 166, A1251 (2019).

D. J. Pereira, M. A. Fernandez, K. C. Streng, X. X. Hou, X. Gao, J. W. Weidner and T. R. Garrick, J Electrochem Soc, 167, 080515 (2020).

D. J. Pereira, A. M. Aleman, J. W. Weidner and T. R. Garrick, J Electrochem Soc, 169, 020577 (2022).

T. R. Garrick, K. Kanneganti, X. Y. Huang and J. W. Weidner, J Electrochem Soc, 161, E3297 (2014).

T. R. Garrick, K. Higa, S.-L. Wu, Y. Dai, X. Huang, V. Srinivasan and J. W. Weidner, J Electrochem Soc, 164, E3592 (2017).

T. R. Garrick, X. Huang, V. Srinivasan and J. W. Weidner, J Electrochem Soc, 164, E3552 (2017).

T. R. Garrick and J. W. Weidner, in Electrochemical Society Meeting Abstracts 233, p. 1345 (2018).
Ni-Rich Cathode Active Materials Surface Degradation in Ambient Air with Stabilisation Treatment Proposal
Authors: Galantowicz Joanna Maria , Coulbeck Elliot , Tallant Neil , Simmons Mark , Kendrick Emma 
Published: February 2024

Ni-rich cathode active materials, such as NMC811 (Li[Ni0.8Mn0.1Co0.1]O2), are promising cathode materials due to their higher theoretical capacity of 200mAh/g, lower cobalt ratio, and overall decreased material expenses. However, the material undergoes a phase transition from layered ( ) through spinel ( ) to rock salt ( ) at high state of charge with oxygen release, and formation of rock salt structures on the surface with lithium carbonates and lithium hydroxides (Residual Lithium Compound (RLC)) while material is exposed to ambient air, all of which is followed by an increase in surface impedance and a decrease in final battery performance.
Here, we explore the chemical and electrochemical evaluation of the Ni-rich cathode active material surfaces when exposed to ambient air for fourteen days (RH~40%). The combination of Fourier-transform infrared spectroscopy (FT-IR) and electrochemical impedance spectroscopy (EIS) will be investigated. These complementary non-destructive approaches will be utilised to characterise the decomposition of the original layered surface and formation of RLC. In addition, the research will be evaluated using STA, XRD, formation, diffusion coefficient, and cycle life in a half-cell using lithium-ion discs as counter electrodes. Furthermore, we show a technique for stabilising the material in air using Experimental ElectroRite®1 Additive provided by Lubrizol Ltd. which reduces the formation of the RLC and the corresponding surface phase changes, often attributed to the presence of Ni2+ ions. This work contributes to a greater understanding of the surface stabilisation through chemical treatment required and suggests routes to create stable water-based Ni-rich cathode inks.