bluuebunny/crossref_metadata_2025 huggingface dataset:
Highly Porous Copper Catalysts for Electrochemical Ammonia Production from Nitrate-Containing Waste Water
Authors: Su Jenn Fang
Published: February 2024

Nitrate from agricultural runoff and industrial waste streams is one of the major impurities in water. As high level of nitrate in drinking water may cause methemoglobinemia in infants and gastrointestinal cancer in adults, previous efforts on electrochemical wastewater treatment have aimed to solve this problem by converting nitrates to environmentally benign nitrogen gas. In the present study, we adjust this approach and propose an opportunity to transform nitrates to ammonia, which can serve as a key chemical used in fertilizer and fuel. Additionally, the electrochemical reduction of nitrate to ammonia can also offer an appealing alternative to the energy- and resource-intensive Haber-Bosch process. In this work, we explore the structure-activity relationship of copper catalysts using Cu foil, Cu particle, and porous Cu in terms of their performances in electrochemical nitrate reduction toward ammonia. Under the optimal conditions, the synthesized porous Cu exhibits a nitrate conversion of 84% with an ammonia selectivity of 85% and a Faraday efficiency of 58% at an applied potential of -0.75 V. Further investigations on surface structural effects reveal that the electrochemical surface area and the fraction of (111) crystal facet on porous Cu are significantly larger than other Cu materials, impacting their catalytic activity for electrochemical ammonia production.

Figure 1
Designing a Stable and Electrically Conductive Colloidal Suspension for Improved Flow Electrode Capacitive Deionization
Authors: Overland Alexandra E. L. , Ceron Maira Raquel , Hawks Steven A.
Published: February 2024

With increasing effects from major droughts and water shortages, water desalination has garnered significant technological interest. Like many technologies, desalination suffers from high energy consumption, capital cost, process inefficiencies, and material degradation. Flow electrode capacitive deionization (FCDI) is a relatively new water desalination technology that combines aspects of electrodialysis and capacitive deionization to deliver a device which can achieve >90% water recovery at high productivity and thermodynamic efficiency. A fundamental challenge in FCDI, though, is engineering an electrically conductive slurry with excellent colloidal stability. Here, we explore the tradeoff between electrical conductivity and sedimentation rate using commercially available surfactants. We find that the optimal surfactant is non-intuitive and strongly depends on the type of carbon used in the slurry (e.g., activated carbon, carbon black, etc.).

This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. Funding was provided by Lawrence Livermore National Laboratory Directed Research and Development (LDRD) Grant #22-DR-011. IM release number: LLNL-ABS-846651.
Comparing the Evolution of Lithium-Ion Cells across Energy, Power, Lifetime, and Temperature with the Enpolite Plot
Authors: Dechent Philipp , Jöst Dominik , Barbers Elias
Published: February 2024

In the field of solar technologies, NREL has tracked the evolution of various technologies on the Best Research Cell Efficiency Chart for decades. This allows for a "sanity check" of a new technology, as there is a clear guideline for the entire solar field when a new technology has a significant advantage, even if it is small. In the battery field, however, many "wonder batteries" are presented that focus on only one indicator of battery performance, such as fast charging capability, while neglecting others such as energy density, cycle life, or operating temperature. This makes it difficult for even experts to evaluate new technologies.

On the other hand, with new efforts by the battery community to create an open and shared battery data ecosystem, a whole new set of data can be leveraged to create better and more holistic comparisons of new technologies to the state of the art. In addition to the previous publication of the ENPOLITE plot (doi.org/10.1021/acsenergylett.1c00743) and on the website https://enpolite.org/, in this paper we show our extension of the work on the plot to include a time scale.

The ENPOLITE plot is a highly informative tool for comparing the evolution of battery technology. At a glance, it provides crucial details such as capacity, cell format, cell chemistry, aging test duration, measurement temperature, specific power, energy density and achieved lifetime for each cell. In addition, the battery life coefficient derived from this plot allows comparison of lithium-ion batteries of different weights or volumes, capacities and cell chemistries.

The ENPOLITE Plot combines multiple parameters to facilitate a thorough comparison of various battery degradations, making it an incredibly useful tool for battery researchers and developers. It not only displays cell-specific parameters during cycling, but also includes information on specific stored energy and storage temperature in a calendar format. This comprehensive approach allows researchers to identify trends and patterns in battery performance, helping to develop more efficient and durable battery technology.

We hope to provide the battery community with a better tool for evaluating and ranking new technologies and improvements to existing battery types.

Figure 1
Silver-Alloys Electrodeposition for Electrical Conductivities
Authors: Orecchioni Quentin , Gigandet Marie-Pierre , Tardelli Joffrey , Hihn Jean-Yves
Published: February 2024

The needs of the ecological transition are based on a larger use of electricity in several processes and access to new resources in large quantities such as hydrogen. The production of the latest by electrolysis as well as the electrification of the means of land transport and the anticipation of the needs of the aeronautics relies on higher capacities in current transmission. The specifications of the connectors and power transmission devices are increasingly stringent, requiring high-quality coatings when intended for contact current transmission. Silver and silver alloys appears to be an excellent choice for such application [1].

The standard electrochemical potential of silver being among the highest, the stability range of its oxides, in aqueous solution, is all the more reduced. In order to maintain these oxidized forms in solution and thus be able to reduce them to the cathode, formulations mixing complex, pH buffer system and other additives have been developed. The electroplating of hard silver in cyanide environments remains the most widely used industrial process, but the specifications can only be obtained by the use of chemical species whose mechanism of action is often poorly known. Moreover, nature and concentrations of additives used in the bath have a direct impact on the coatings properties. An alternative exists in the complexation of other metals with silver, to form an alloy with properties which depends strongly on the electrolysis parameters. To work properly, the working potential must be shifted from the thermodynamic equilibrium [2]. The present study is part of the SILAHPERF project, led by IRT-M2P and UTINAM Institute, which try to investigate the codeposition mechanism of various silver-based alloys of interest with a particular focus on silver-tungsten while seeking for environmental-friendly solution, focused on electrolysis parameters. Indeed, an alternative to cyanides as complexing agent is expected, face to the raising number of regulations. Therefore, a large number of complexing agent are evaluated, with their electrochemical behavior in i=f(E) curves, and with the deposition yield as well as the alloying element content as a function of the deposition potential. As an example for silver-tungsten alloys, complexing agents may be a combination of a carboxylic acid and an amino compound. The most popular couple is the citrate-thiourea system, however tartrate, oxalate, ammonia and urea are also good candidates. Finally, coating properties are evaluated by several technics (SEM – XRD, GDOES ...)

[1] M. Myers, ‘Overview of the Use of Silver in Connector Applications (503-1016), p. 14.

[2] A. Kola, X. Geng, and E. J. Podlaha, ‘Ag–W electrodeposits with high W content from thiourea–citrate electrolytes’, Journal of Electroanalytical Chemistry, vol. 761, pp. 125–130, Jan. 2016, doi: 10.1016/j.jelechem.2015.12.002.
Cu Foil Modification By Ag Inkjet Printing for Improved Li Plating in Anode-Free Li Batteries
Authors: Gibertini Eugenio , Mirbagheri Seyedalireza , Magagnin Luca
Published: February 2024

The rush in the development of new generation of lithium-ion batteries (LIB) is focused on enhancing the specific energy of batteries by employing innovative materials and manufacturing techniques. Anode-free lithium metal batteries (AFLBs) are an emerging technology that can almost double the specific energy of LIBs by eliminating the conventional graphite negative electrode or excess lithium metal 1. However, AFLBs are well-known to suffer of fast capacity decay due to the poor lithium plating and stripping efficiency process associated to the typical porous growth of Li during charge 2. Tuning the interfacial electrochemistry was widely demonstrated to be one the most performing key to enable efficient and smooth Li deposition. In this regards, functional coatings of metals as Sn, Al, Zn and Ag have been widely demonstrated to dramatically improve the quality of Li plating process respect to the neat Cu foil substrate, by forming lithium-rich alloys that provide minimum Li nucleation overpotentials 3. Inkjet printing (IJP) could be a viable technique for electrode fabrication in LIBs manufacturing, being a quick, easy and scalable technology able to deposit both thin film and patterned structures 4. However, very poor attention has been paid so far to the potentiality of IJP for Cu modification for improved Li plating in AFLBs.

In this work, we employed a Fujifilm Dimatix inkjet printer to achieve “lithiophilic” coatings of Ag nanoparticles deposited on a Cu foil. In particular, potenziodynamic and galvanostatic electrochemical test were employed to investigate the effect of the Ag printed structures on the Li nucleation overpotential. Ex-situ morphological analysis by electron scanning microscopy (SEM) were usefully employed to investigate the surface evolution of the printed electrodes during lithium alloying and plating. In particular, the effect pf patterned Ag structured rather than fully coated Cu was investigated, revealing that patterning can provide more mechanically robust electrode and efficient catalytic sites for Li electrodeposition respect to fully coated inkjet printed electrodes.

Bibliography

L. Lin et al., Advanced Materials, 34, 2110323 (2022).

L. Su and A. Manthiram, Small Structures, 3, 2200114 (2022).

X. Gu, J. Dong, and C. Lai, Engineering Reports, 3, e12339 (2021).

P. Viviani, E. Gibertini, F. Iervolino, M. Levi, and L. Magagnin, Journal of Manufacturing Processes, 72, 411–418 (2021).
Preparation and Characterization of Tin-Nickel Coatings for Corrosion Protection of PEM Electrolyzer Components
Authors: Leimbach Martin , Kurniawan Mario , Aziz Carlos , Hoess Christian Elieser , Fritz Mathias , Bund Andreas
Published: February 2024

Hydrogen production by electrolysis offers significant advantages over established and more common processes such as steam reforming with regard to carbon dioxide emissions, in particular through the use of electrical energy from renewable sources and the establishment of a decentralized supply structure. The advantages of PEM (proton exchange membrane) electrolysis include high power density, scalability, and the high purity of the produced hydrogen. However, so far the manufacturing of PEM electrolyzers is time consuming, which makes the widespread use difficult and is a significant cost driver for this technology.

In the framework of the publically funded flagship project H2Giga, a series of manufacturing processes are developed for industrial scale-up production of PEM electrolyzer components, in particular the bipolar plates (BPP) and the porous transport layers (PTL). Base materials like stainless steel are used that can be processed at a low cost, but need protective coatings to withstand the highly corrosive conditions during electrolysis, especially at the anode side.

A novel approach is focusing on nickel-based alloy coatings, in particular tin-nickel, which emerged as a promising alternative to precious metal coatings. These alloys show a wide stability range under strong anodic polarization in an acidic electrolyte due to the formation of a passive layer. However, the long-term stability does not yet meet the industrial requirements in preliminary tests. A post-treatment of the coating can improve the stability by the formation of a homogenous oxide film with several tens of nanometers in thickness. Physical, chemical and electrochemical methods for post-treatment were compared in terms of oxide morphology and corrosion behavior under anodic polarization. Eventually, both high corrosion resistance and low contact resistance have to be ensured for the application in PEM electrolyzers.
Electrochemical Strategies to Control Dendritic Growth in Sodium-Metal Batteries
Authors: Hosseinzadegan Meghdad , Nyholm Leif , Hernández Guiomar , Rehnlund David
Published: February 2024

Sustainable development can be pursued through electrification in all sectors, and energy storage devices -mainly batteries- play a crucial role in this process. This leads to an ever-increasing demand for rechargeable batteries. However, the current generation of the rechargeable batteries, namely lithium-ion batteries, is produced using elements such as Li, Ni, and Co which have limited resources. Sodium-ion batteries (SIBs) on the other hand are considered as a good alternative due to the abundance of Na resources and fundamental similarities of Na and Li. While the cathode material for SIBs has reached a commercial level of reliability, the identification of a high energy anode material still remains a challenge. Although Na metal as an anode material offers high energy density, the main issue is that Na metal has a tendency for dendritic growth during electrodeposition.

In this work, different electrochemical strategies are used to mitigate dendritic Na growth. High overpotential nucleation pulses during stripping and/or plating steps are applied in order to induce two-dimensional growth. The impact of these strategies is studied using three-electrode symmetrical cells with Na metal as the working, counter, and reference electrodes, in an electrolyte composed of NaPF6 in EC/PC with FEC as an additive. Chronopotentiograms recorded during extended cycling (with and without Na pre-nucleation) are examined with special attention being paid to the overpotentials occurring on each cycle. Ex-situ SEM images are used to relate the different potential profiles during extended galvanostatic cycling to the different surface morphologies.

The results show that a combination of oxidative (stripping) and reductive (plating) pulses has an obvious effect on inhibiting dendritic growth during electrodeposition of Na metal. The results encourage the deployment of electrochemical strategies to prevent dendritic growth in Na metal anodes and paves the way for experiments with new electrolyte compositions to further help overcoming the challenges associated with Na deposition.
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.
Control of Crystallographic Growth Orientation and Twinning Structure in Copper Nanowires by Template-Assisted Electrodeposition
Authors: Huang Hao-Che , Chen Hsin-Yu
Published: February 2024

Synthesis and characterization of noble metal nanowires have been a popular topic in the field of microelectronic devices and catalysts. Nanotwinned copper nanowires (nt-CuNWs) possess high mechanical strength, excellent electromigration resistance and low electrical resistivity, which have been considered as a promising interconnect material in ultra-large scale integrated circuits (ICs). Here, we deposited nt-CuNWs in two different anodic aluminum oxide (AAO) templates with respective pore sizes of 70 nm and 35 nm pore by pulse electrodeposition. The influence of thermal treatment on the Cu seed layer deposited on AAO membranes prior to electrodeposition is investigated. Both coarse and thin nt-CuNWs mainly grew in <111> crystallographic direction with (111) texture coefficients (TC(111)) > 2.5, and an aspect ratio (AR) > 100 according to x-ray diffraction analysis. An addition of gelatin (14 ppm) in the copper sulfate electrolyte is found to suppress the growth of (220)-oriented Cu grains in the AAO by forming copper nanowires with large TC(111) > 2.65 and high-density nanotwin structure. This study provides a simple route to tailoring microstructure and physical properties of nanoscale copper wires, which is beneficial for the interconnect technology development in semiconductor IC devices.
(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).
Effect of Pulse Parameters on Early Stage Nucleation Phenomena
Authors: Dhara Trina , Chakraborty Soukhin , Mukherjee Partha P. , DasGupta Sunando
Published: February 2024

Pulse electrodeposition has garnered significant attention from decades to control important parameters of the growing electrodeposits such as grain size, crystal orientation, and microhardness. Recently, pulse charging has become a major research focus due to its ability to suppress dendritic growth during the charging process for metal-anode based rechargeable batteries. In this work, we have comprehensively studied the effect of pulse duty cycle, D (D = tON/(tON+tOFF)) and frequency on the nucleation phenomena using an in-situ visualization technique (Figure 1). The nuclei density of copper electrodeposits on Indium Tin Oxide (ITO) coated glass substrate is evaluated microscopically and quantified using image processing. The pulse parameters are made equivalent to the corresponding DC voltage (VDC) by two possible ways, i) increasing the peak voltage (VPeak) based on the duty cycle applied (VPeak = VDC/D) , and ii) expanding the total deposition time, or in other words equating the cumulative reaction time (tON) in pulses to the total DC time (tDC = ∑tON). Interestingly, exactly opposite trends are observed for the two aforementioned methods. A sharp increase (∼75%) and decrease (∼80%) in nuclei density as compared to DC are observed while reducing the duty cycle till D = 1/4 for the two methods respectively. However, a decline in nuclei density is noticed while increasing in frequency in both methods. The associated pulse time scales, and the coalescence of the evolving nuclei due to merging of the diffusion zones surrounding a growing nucleus are likely to play the leading role behind this observation. The results add insights to the governing process, and will be useful in designing efficient pulse parameters to control dendritic growth.

Figure 1
(Invited) Bottom-up Gold Filling for Manufacture of X-Ray Gratings: Mechanism and Implications
Authors: Josell Daniel , Moffat Thomas P
Published: February 2024

Over the past four years a process for extreme superconformal deposition of gold has been demonstrated and explored for void-free filling of recessed features on patterned substrates for application in X-ray imaging. Uniform and complete void-free filling was detailed on 100 mm silicon wafers patterned with micrometer pitch vias of aspect ratio (height/diameter) 23 and trenches of aspect ratio (height/width) exceeding 60 as well as trenches more than 300 μm deep and fractal patterns of spatially varying depth. This talk discusses a proposed mechanism and model for the observed behavior. Simulations capture key features of the experimental processes, including not only the bottom-up filling itself but also an extended incubation period of conformal deposition that precedes its start as well as self-passivation of the active deposition that accompanies the completion of filling. Feature filling results with relevant electrochemistry are discussed in the context of predicted behavior for different deposition conditions. Cross-sectioned 60 μm deep trenches Au filled at fixed potentials, the associated current transients, a Au filled grating and a simulation of filling in 50 μm deep trenches are all shown in the figure.

Figure 1
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
Local pH Change during CoMo-TiO2 Composite Electrodeposition and Alkaline HER Electrolysis
Authors: Wang Cheng , Podlaha Elizabeth J
Published: February 2024

Alloys of Co-Mo and Co-Mo-P are of interest for their ability to enhance the hydrogen evolution reaction (HER)1-2 and adding TiO2 to the alloy surface can further enhance HER.3-5 To better understand the influence of TiO2 particles on the electrodeposition of Co-Mo and Co-Mo-P alloys and the resulting HER kinetics, electrodeposition was conducted on a copper mesh electrode in close proximity to a pH probe to measure the local change of pH. The deposit composition and the HER characterized. There was a significant enhancement in the HER exchange current density when TiO2 particles were present in the alloy, taking into account any changes in the surface area. The enhancement was associated with a local pH change. Without TiO2 particles present in the solid state, the local pH change follows an expected increase with time as hydrogen is evolved and the hydroxide ion is generated at the electrode surface. In contrast, when TiO2 particles were present at the surface and in the metal alloy matrix, the local pH initially decreases slightly and remains constant (Fig 1). The results suggest that the enhanced HER performance with TiO2 in the alloy composite electrocatalyst is a consequence of the buffering of the local pH. In contrast, during electrodeposition there is little change in the pH transient with and without having TiO2 particles in the electrolyte.

C. C. McCrory, A. Jung, I.M. Ferrer, S.M. Chatman, J.C. Peters, T.F. Jaramillo, J Am Chem Soc, 137 (13) 4347 (2015).

A. C. Thenuwara, L. Dheer, N. H. Attanayake, Q. Yan, U. V. Waghmare, D. R. Strongin, ChemCatChem.
10 4832-4837 (2018).

A.R. Shetty, A.C. Hegde, Mater. Sci. Energy Technol. 1 (2) 97 (2018).

C. Wang, Hubert K. Bilan, E. J. Podlaha, J. Electrochem. Soc.
166 (10) F661 (2019).

C. Wang and E. J. Podlaha, J. Electrochem. Soc.
167 (13) 132502 (2020).

Figure 1. Change of pH during HER on a Co-Mo electrodeposit at different HER electrolysis current densities.

Figure 1
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
Reduction of the Calcination Temperature for Improvement of Ni-Rich Single-Crystal Cathode
Authors: Lee Soo-Been , Lim Hyung-Woo , Sun Yang-Kook
Published: February 2024

Synthesizing a high-performance single-crystal cathode with a Ni-rich composition for use in Li-ion batteries is a difficult task. This is because sintering of particles requires calcination at high temperatures, but performing calcination at very high temperatures can damage Ni-rich layered cathode materials. Therefore, finding ways to reduce the calcination temperature required for the synthesis of single-crystal cathodes can improve the cathode's performance. In this research, a Ce dopant was introduced to successfully synthesize a Ni-rich single-crystal cathode with the composition Li[Ni0.9Co0.05Mn0.05]O2 (NCM90) at a calcination temperature that was 50°C lower than its optimal temperature. Dopants affect the growth and sintering behavior of cathode materials during calcination depending on their properties. For example, W retards the growth and sintering of grains, preventing the formation of single-crystal particles, while Ce promotes the formation of single-crystal particles. Taking advantage of Ce's ability to promote single-crystal particle formation, a Ce-doped NCM90 cathode was synthesized at a calcination temperature of 800°C, while the undoped NCM90 cathode remained polycrystalline at this temperature. The Ce-doped NCM90 cathode showed an initial capacity of 199.7 mAh g−1 at 0.1 C, and after 100 cycles at 0.5 C, it retained 80.5% of its initial capacity, demonstrating better cycling stability than the undoped NCM90 cathode. The Ce dopant protracted the detrimental H2-H3 phase transition, which reduced capacity loss as revealed by differential capacity analysis. Additionally, the presence of Ce in the cathode improved its thermal stability.
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.
Oxygen Hole Formation Controls Stability in LiNiO2 Cathodes: DFT Studies of Oxygen Loss and Singlet Oxygen Formation in Li-Ion Batteries
Authors: Genreith-Schriever Annalena R. , Banerjee Hrishit , Menon Ashok S. , Bassey Euan N. , Piper Louis F. , Grey Clare P. , Morris Andrew J.
Published: February 2024

Ni-rich cathode materials achieve both high voltages and capacities in Li-ion batteries but are prone to structural instabilities and oxygen loss via the formation of singlet oxygen. Using ab initio molecular dynamics simulations, we observe spontaneous O2 loss from the (012) surface of delithiated LiNiO2, singlet oxygen forming in the process. We find that the origin of the instability lies in the pronounced oxidation of O during delithiation, i.e., O plays a central role in Ni-O redox in LiNiO2. For LiNiO2, NiO2, and the prototype rock salt NiO, density-functional theory and dynamical mean-field theory calculations based on maximally localised Wannier functions yield a Ni charge state of ca. +2, with O varying between –2 (NiO), –1.5 (LiNiO2) and –1 (NiO2). Predicted XAS Ni K and O K-edge spectra are in excellent agreement with experimental XAS spectra, confirming the predicted charge states. The calculations also show that a high-voltage O K-edge feature at 531 eV previously assigned to lattice O-redox processes could alternatively arise from O-redox induced water intercalation and O–O dimer formation with lattice O at high states of charge. The O2 surface loss route observed here consists of 2 surface O•– radicals combining to form a peroxide ion, which is oxidised to O2, leaving behind 2 O vacancies and 2 O2– ions: effectively 4 O•– radicals disproportionate to O2 and 2 O2– ions. The reaction liberates ca. 3 eV per O2 molecule. Singlet oxygen formation is caused by the singlet ground state of the peroxide ion, with spin conservation dictating the preferential release of 1O2, the strongly exergonic reaction providing the free energy required for the formation of 1O2 in its excited state.
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).