bluuebunny/crossref_metadata_2025 huggingface dataset:
Navigating the Minefield of Battery Literature
Authors: Xu Kang
Published: November 2022

Battery research has been very hot.

With more than 600 publications each week, “breakthroughs” reported each month in high-impact journals, and new journals popping up each year, how can one effectively follow the literature?

To make things more difficult, a substantial fraction of the literatures are not straightforward to comprehend.

The early career scientists and engineers may be struggling with complicated jargon system that is already established, accepted, and taken for granted by the battery research community, or being puzzled by the many seemingly conflicting results from various, or even sometimes the same, sources.

In this context, the battery literature itself may have become a key hurdle to progress in battery research.

This talk will highlight a few recurring misconceptions and inaccuracies often encountered in battery research literature, so that students and junior researchers new to the field could circumvent these traps and better equipped to handle the inundation of battery research papers.
Physics-Based Simulation of Electrochemical Impedance Spectroscopy of Complex Electrode Microstructures
Authors: Qu Danqi , Malik Affan , Yu Hui-Chia
Published: November 2022

Electrochemical impedance spectroscopy (EIS) is a widely used technique to measure macroscopic properties of electrodes. However, the underlying connections between the obtained macroscopic properties and electrode microstructures are not well understood because of the complexity of coupled electrochemical mechanisms and microstructure morphology. In this work, we present a smoothed-boundary-method (SBM) electrochemical simulation framework to directly simulate the electrochemical dynamics with explicit consideration of electrode microstructures and extract EIS curves from the electrochemical simulations. This method uses continuous domain parameters to define the complex geometries of electrode particles and electrolyte phase in the interparticle space, thus circumventing the requirement of mesh conforming to the complex electrode microstructures in the simulations. The SBM is also utilized to calculate the double-layer capacitance that is required in the physics-based EIS simulations. The effects of the state of charge, salt concentration in electrolyte, and particle size distribution in electrode on the resulting EIS curves are examined using the SBM simulations. This simulation tool allows us to accessibly reveal the underlying connections between intrinsic material properties, microstructures, and macroscopic EIS measurements of battery electrodes.
A Battery Cycling Optimization Framework Coupling Prediction Models and Bayesian Optimization
Authors: Deng Changyu , Lu Wei
Published: November 2022

Energy storage is widely used in many fields, for instance, electrical grid, electric vehicles, portable devices and so forth. Rechargeable batteries such as lithium-ion, lithium-oxygen, sodium-ion, lead acid, and more broadly, supercapacitors, are highly needed to achieve high capacity and long duration while maintaining low cost. An essential task of battery research and development, in both industry and academia, and for both simulation and experiment, is to optimize the parameters for best performance. A special property of battery cycling optimization is that we evaluate the performance as a function of cycles when calculating the score of the objective function. A huge challenge is the difficulty to query the objective function due to the cost to obtain the performance, i.e., long cycling time (in both simulation and experiment) causes battery optimization to be a time-consuming task. What is worse, the space of parameter is often large and thus a great number of queries are necessary. To shorten computation time in simulation, or reduce cost in experiment, we require powerful optimization algorithms. We aim for an asynchronously parallel algorithm which considers early stopping and is flexible to incorporate prior knowledge of the batteries. Our optimization algorithm consists of two major components, a predictor and a sampler. For battery cycling, some information is revealed before finishing all cycles, thus the predictor can predict the final outcome with uncertainty based on existing information. The uncertainty of the prediction is described by a probability distribution. The sampler determines new query points based on existing observations; the observations include finished cycles and predictions from the predictor. The next searching points are those with highest expected improvement over existing query points. We compare our algorithm with current optimization methods to show significant reduction of optimization time.
(Digital Presentation) Potential Application of Plasma Pyrolysis in Dairy Industries
Authors: Fasihi Morteza , Mohammadhosseini Babak , Ostovarpour Farzaneh , Abbassi Shanbehbazari Mohammad Sadegh , Khani Mohammad Reza , Shokri Babak
Published: November 2022

The objective of the current study is to examine plasma pyrolysis as a suitable method for producing value-added products from dairy waste. With the use of this technique, hazardous materials of various kinds could be changed into non-hazardous products that complied with the majority of emission requirements. The creation of high-quality syngas is another advantage of using the suggested disposal strategy. As can be seen in figure 1, the outcomes of the trials showed that not only is it feasible to dispose of dairy waste using a plasma incinerator, but the resulting products and synthetic gases are also highly desirable. These gases that arise are frequently safe for the environment. They can be employed directly or indirectly in the energy generation sectors, which is another excellence.

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(Invited) Battery Challenges for Energy Storage and Electric Vehicles
Authors: Liu Jun
Published: November 2022

Batteries play a critical role in modern society. The electrification of transportation and deep decarbonization of the energy infrastructure require the development and deployment of high energy, low-cost battery materials and technologies, but energy storage and electric vehicles have very different requirements and challenges. For energy storage, the challenge is to reduce cost and achieve exceptionally long cycle life (>>10,000 deep charge/discharge cycles) in order to reduce the life cycle cost by three to five times to less than $0.03 kWh-1. Lithium iron phosphate and redox flow batteries remain the most attractive approaches. Fundamental understanding of the degradation mechanisms over very long cycling is the key to further improve the cycle life of such technologies. Sodium ion batteries are also attractive for energy storage, but the electrode and cell level performances are still behind of what can be achieved with lithium-ion batteries. For electric vehicle applications, lithium metal anodes provide the opportunity for next generation high energy and lost cost batteries. Despite great progresses made in the last few years, controlling system level reaction and failure mechanisms remain a large challenge.
A Reachable Sodium-Oxygen Battery Based on Sodium Superoxide Chemistry
Authors: Kondori Alireza , Esmaeilirad Mohammadreza , mosen Harzandi Ahmad , Asadi Mohammad
Published: November 2022

Sodium-oxygen (Na-O2) batteries offer a great potential to provide high energy density storage systems needed for small-sized and inexpensive electric vehicles owing to the abundance of sodium compared with lithium. Yet, their development is hindered by the low cycle life and poor energy efficiencies due to (i) the formation of singlet oxygen, resulting in parasitic reactions with the air cathode and the organic electrolyte, (ii) the formation of unstable SEI layers and dendrites associated with the metallic sodium anode, and (iii) lack of an active, stable cathode catalyst to reduce the overpotentials and improve the cycle stability.

Here, we have developed a Na-O2 battery cell composed of a highly active cathode catalyst that works well in synergy with an ether-based ionic-liquid electrolyte with specific redox mediators to act as co-catalysts to reversibly form and decompose sodium superoxide (NaO2) via surface-mediated pathway at a low polarization gap of about 40 mV at a capacity of 1000 mAh/g. Different electrochemical and physicochemical characterization techniques, i.e., Raman spectroscopy, XRD, XPS, DEMS, SEM, and TEM were used to understand the cell chemistry. Moreover, a chemically synthesized Na anode protection layer implemented in this battery cell enabled a long cycle life of 900 with all-time energy efficiencies more than 80%, exceeding state-of-art Na-O2 and Na-air batteries. The outcome of our study reveals the significance of the proper cell components design in Na-O2 battery technologies as a promising venue in energy conversion and storage systems.
Numerical Simulation of Primary Zn/MnO2 Batteries Under Continuous and Intermittent Discharge
Authors: Chadderdon Xiaotong
Published: November 2022

In this work, a multiphase continuum model is developed to simulate discharge behavior of primary Zn/MnO2 alkaline batteries. Both macroscopic and microscopic phenomena are integrated to describe the species diffusion in cell length and particle length scales. The predicted battery performance is validated against experiments under different rates of continuous and intermittent discharge. The model is applied to better understand evolution of internal gradients and local conditions, polarization sources and sensitivity to design parameters. Although accurate point prediction is challenging for small (less than 2%) design changes due to the complexities in reaction chemistries and limitations imposed by model assumptions, predictive modeling has shown to be useful for larger design and experimental changes. For example, the amounts of ZnO precipitation in the separator are predicted through simulation under different discharge protocols to evaluate the risk of internal shorting, and are in good agreement with experimental testing.
Surface Treatments of Metal Hydride Anode Material for Next-Generation Nickel-Metal Hydride Battery
Authors: Liu Nian , Chen Zhitao
Published: November 2022

The development of the emergency call system (eCall system) was promoted by increasingly harsh and strict policies in many countries to enhance safety of drivers and passengers. A reliable battery technology with advantages of wide operating temperature range, long shelf life, ease of maintenance, and safety is essential to power and implement the eCall system. Nickel metal hydride (NiMH) battery and lithium-ion battery (LIB) are two of the most mature rechargeable battery technologies and candidates for eCall system. Compared to LIB, NiMH battery is a safer choice due to the intrinsic non-flammability of aqueous electrolyte. Moreover, NiMH battery has better low temperature performance than LIB because ions are more mobile in aqueous electrolytes than in organic electrolytes. Hence, NiMH battery is a promising alternative for safety-sensitive application. A limitation of today’s NiMH technology is that anode materials capable of discharging at low temperature (-40°C) have short cycle and calendar life. This is due to the fracture and dissolution of active materials during cycling. In this work being presented, we have coated the metal hydride anode material with lanthanum trifluoride (LaF3), which is insoluble in alkaline electrolyte and inert at anode operating potential window, to encapsulate the particle and improve capacity retention. The coated particle achieved stable cycling over 200 cycles at room temperature. Moreover, the LaF3 coating is electrically conductive and does not affect the kinetics. The coated particle still achieved more than 150 mAh/g at extremely low operating temperature (-40°C). Thorough material characterization has been carried out to investigate the structure of the coating and correlate to the performance enhancement.
Achieving Enhanced Mobility of Ions in Ionic Liquid-Based Gel Polymer Electrolytes By Incorporating Inorganic Nanofibers for Li-Ion Battery
Authors: Garaga Mounesha N , Bhattacharyya Sahana , Greenbaum Steve G
Published: November 2022

Polymer electrolytes have received much attention in Li-ion battery research because of their unique properties, such as, high ionic conductivity, high mechanical strength including good electrode-electrolyte contact. A major research has been focused on improving the conductivity while retaining the mechanical stability of polymer electrolytes. In this context, ionic liquid-based gel polymer electrolytes are an excellent candidate. A detailed NMR investigation of PMMA-ILs gels electrolytes probing the structure and dynamics of ions was recently reported.[1] The presence of ILs in polymer matrix not only improves the conductivity but also enhances the self-healing capability. In another study, self-healing capability that reduces the dendrite formation at the interface has been discovered, for example, in PVDF-HFP-ILs electrolyte.[2] In this regard, this work reports the possible ways to enhance the ionic conductivity of such polymer electrolyte further by adding Al2O3 nanofibers. A series of PVDF-HFP-ILs with 1M LiTFSI in EMIMTFSI at different ratios of Al2O3nanofibers were prepared through solution cast technique. The dynamics of ions confined within polymer-Al2O3 matrix was explored through Impedence and PFG NMR spectroscopy. The amorphocity and the distribution of Al2O3 nanofibers are studied through XRD and SEM-EDX analyses. Lastly, the local structure of ions and their interaction with polymer and Al2O3 nanofibers were established through a detailed solid-state NMR analyses detecting 1H, 27Al, 13C, 19F, 7Li nuclei including 2D 13C{1H} HETCOR experiments. A reasonable enhancement in terms of ionic conductivity was observed with the addition of Al2O3 nanofibers, which improves the conducting pathways within the polymer network.

[1] M. N. Garaga, N. Jayakody, C. C. Fraenza, B. Itin, and S. Greenbaum, Journal of Molecular Liquids 329, 115454 (2021).

[2] T. Chen, W. Kong, Z. Zhang, L. Wang, Y. Hu, G. Zhu, R. Chen, L. Ma, W. Yan, Y. Wang, J. Liu, and Z. Jin, Nano Energy 54, 17 (2018).
Transfer Learning Enabled Deep Learning Model for the Prediction of Battery Performance from Electrolyte Formulations
Authors: Sharma Vidushi , Giammona Maxwell , Zubarev Dmitry , Erdmann Tim , Tek Andy , Nugyuen Khanh , Na Young-Hye
Published: November 2022

Next generation batteries utilizing lithium (Li) metal anode could represent a 10x improvement in anode specific capacity compared to currently used graphite anodes however they still face major challenges associated with their evenness of plating and interfacial stability with the electrolyte. The capability to quickly evaluate and optimize liquid electrolyte formulations that can form stable solid-electrolyte interface (SEI) layers and bring out the best battery performance across a range of relevant performance outcomes will be critical to the realization of these next generation batteries. Integrating AI into battery research and development workflows has the potential to significantly increase the rate of new materials discovery, however, while machine learning models can successfully predict expected specific capacity or cycle life of the battery based on electrode designs, the complexity of liquid electrolytes used in batteries needs more contextual information than a machine or deep learning models can capture from simple structure-performance correlations. The lithium metal anode SEI layer is a formed out of the complex physio-chemical interactions between the lithium metal and the electrolyte and models will likely need to be able to capture those molecular attributes within the electrolyte composition that are decisive in electrolyte-Li interfacial chemistry. For this purpose, we will discuss the scope of two AI approaches that can predict battery performance based on electrolyte composition. The first approach showcases the capability of a deep learning model that is designed specially to represent electrolyte formulation based on structure-to-performance relationship. The second approach improves upon the first by incorporating transfer learning of quantum chemical attributes of electrolyte molecules and building a property-to-performance correlation. We will also discuss how transfer learning of ‘selective’ quantum chemical properties of electrolyte molecules to the capacity predicting deep learning model broadens the scope of the model towards recognizing new beneficial additives to the electrolyte formulation. Using this approach, the model retains impressive predictive accuracies despite limited experimental training data and predictions are validated and improved with experimental feedback for new electrolyte formulations in coin cell tests.
The Electrochemical Growth of 2D Metals on Insulators Using a Graphene Interface
Authors: Medina Arturo , Drexler Matthew N , Lee Dong-Chan , Boruta Michael , Boruta Nicholas , Alamgir Faisal M.
Published: November 2022

2D confined metals (2D-M) under heteroepitaxial relations with graphene (Gr) allow for the potential control of chemical properties of the 2D-M by an external electric field. If this external electric field is supplied by an insulating substrate (such as a dielectric or a ferroelectric), then it can enable a non-Faradaic manipulation of electrocatalytic reactions via the M-Gr electrocatalyst system. In this work, we will explore the architecture of a 2D metal-graphene (2D M-Gr), where the substrate is supplying an electric field as well as fulfilling the role of the insulating substrate (dielectric) in the system. The insulating substrate will carry an embedded electron charge at the interface between two dielectric (DE) layers, close to the surface of the metal, allowing for electronic influence on the metal. In this system, graphene acts as an imperfect screener of electric fields allowing the dielectric/ferroelectric-generated field to influence the metal. We find that providing an approximate potential of 0.1 V yields a significant increase in the hydrogen evolution current within a 2D platinum/graphene (2D Pt/Gr) system. Extended X-ray absorption fine structure (EXAFS) studies are used to examine 2D M-Gr epitaxy. EXAFS results indicate a strain condition imposed by Gr on the metal grown, where Gr is constraining nearest-neighbor distances through epitaxial directions. Experimental research on the strain induced in graphene-templated Pt monolayers by Alamgir et al. found that a single graphene layer induces a 3.5% compressive strain on the Pt adlayer deposited onto it, increasing the catalytic activity of the system In the 2D M-Gr system, our strained, epitaxially grown metal on Gr will be demonstrated on an Au/Gr/DE and Pd/Gr/DE system.

References:

Abdelhafiz, Ali, et al. “Layer-by-Layer Evolution of Structure, Strain, and Activity for the Oxygen Evolution Reaction in Graphene-Templated PT Monolayers.” ACS Applied Materials & Interfaces, vol. 7, no. 11, 2015, pp. 6180–6188., https://doi.org/10.1021/acsami.5b00182.

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(Digital Presentation) Crack-Free Ni-P Film for Power Devices
Authors: Fujimori Yuji , Shimizu Masahiro , Kurashina Tadashi , Arai Susumu
Published: November 2022

Demands for power devices are expanding with the electrification of automobiles. Power devices are soldered using Ni-P films prepared by an electrochemical method to withstand required high currents. However, cracks are inevitably induced in Ni-P films during high mounting temperatures. Ni-P films play an important role as a solder joint material and the P concentration is a critical factor that affects the mechanical properties of Ni-P films. Therefore, in this work, we focused on the P concentration and tried to prepare Ni-P films without cracks induced by high heat treatments. Ni-P films with different P concentration were formed on an Al substrate by an electroplating using a Watt bath and then investigated the relationship between the P concentration and the generation of cracks by X-ray diffraction and thermal expansion analyses. By the heat treatment at 300 °C or higher, Ni-P compounds mainly composed of Ni3P was formed in the Ni-P film with P concentration of 8 wt.% or more and the film shrank by 0.11%. In contrast, the 2 wt.% or less P- Ni film did not cause the formation of Ni3P and little shrinkage was observed even after the high treatment at 400 °C. The obtained results indicate that the phase transition to Ni-P compounds by the heat treatment is responsible for the mechanical disintegration, that is, the P concentration in the film is closely related to the generation of cracks. We propose the method for suppressing cracks by controlling the P concentration in the Ni film.

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Recent Advances in Electrodeposition of Copper Ultrathin Films on Cobalt Substrate
Authors: Guo Lian , Han Jianwen , Yakobson Eric , Shao Wenbo , Whitten Kyle , Najjar Elie
Published: November 2022

As the miniaturization trend in integrated circuits fabrication continues, alternative liner materials in copper interconnects have been actively explored. Cobalt has been widely investigated and employed due to its low resistance at nanoscales, integration compatibility, as well as benefit of improving copper electromigration resistance. However, direct electrodeposition of copper onto cobalt remains less explored due to the stability issue of cobalt in acidic copper damascene process. Subsequent processes of copper seeding and copper electroplating face increasing technical difficulties when widths and aspect ratios of electro-fill features become more challenging.

Direct electrodeposition of copper on cobalt has been explored in acidic and alkaline chemistries, both of which were formulated by MacDermid Alpha Semiconductor Solutions. In both cases, well-adherent, nearly-pinhole-free, and ultrathin Cu has been successfully electrodeposited onto cobalt substrate with less than 10% cobalt loss. SEM images in Figure 1 imply uniform dispersion of copper on cobalt. XRF and ICP analysis confirm that the thinnest copper films deposited could be no thicker than 2 nm. Corrosion test in acidic copper plating bath shows that an ultrathin copper layer of thickness less than 2 nm can effectively suppress cobalt dissolution by a factor of three in comparison to non-coated bare cobalt.

This work could pave the avenue towards direct copper electrodeposition onto cobalt liner in semiconductor manufacturing for advanced technology nodes.

Figure 1. Top-down SEM images. (left) As-received cobalt substrate; (center) Cu of 2 nm nominal thickness electrodeposited on cobalt from an acidic solution; (right) Cu of 2 nm nominal thickness electrodeposited on cobalt from an alkaline solution. All three images have the same scale and scale bars are 200 nm.

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Fast and One-Pot Reductive Deposition of Continuous Uio-66 Films
Authors: Xie Sijie , Zhang Xuan , Fransaer Jan
Published: November 2022

UiO-66 (UiO stands for the University of Olso) film membrane is promising for molecular/ion separations owing to its sub-nano-sized pore apertures and superior chemical stability among the metal-organic framework (MOF) family, but the preparation of it remains difficult and challenging up to now. Here we report a fast and one-pot reductive deposition approach to the high-quality UiO-66 film coatings. In the deposition, the nitrate anions are introduced as pro-bases to accelerate the deprotonation of the ditopic linker-H2BDC (1,4-benzenedicarboxylic acid), which renders the continuous UiO-66 films coating in an hour. Importantly, the morphology of the deposited UiO-66 films can be well-tuned by the molar ratio of the ditopic linker to monotopic modulator because of their completing deprotonation process. The continuous, intergrown, and crystalline UiO-66 films can be obtained at optimized conditions (i.e., deposition temperature at 120 ℃, and the molar ratio of the linker to the modulator of 1:120). Besides, the proposed reductive deposition is also feasible for the fabrication of the analogues of UiO-66 with distinct ligands, like the Zr-fumaric films and Zr-naph (naph is the 1,4-naphthalenedicarboxylic acid) films. These deposited films can be prospective separation mediums for molecular sieving.

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Development of a Quantitative and Predictive Model for Electrodeposition of Metals and Alloys with Experimental Verifications
Authors: Ma Yifan , Pepas Jakub , Kang Minju , Carsley John , Chen Hailong
Published: November 2022

Electrodeposition is widely used in the refinery, manufacture, and coating of metals and alloys. Electrodeposition is a complicated process with many factors, such as deposition potential, current density, electrolyte composition and concentration, convection, additives, and temperature, can have significant impacts on the phase composition, morphology, and particle size of the deposited metals/alloys, thus consequentially impacting the physical and chemical properties of the deposited parts. In the past, a recipe for a particular metal/alloy electrodeposition is commonly established through trial-and-error tests, which is very time consuming. Here we report our recent efforts trying to build a quantitative and predictive model based on ex situ and in situ experimental characterizations of electrodeposition processes.

To build the model, we chose copper as the model material for electrodeposition. A few electrochemical cells which have different geometries and dimensions and provide non-uniform current density distributions were designed and used. Through variation of the electrode placement and cell geometry, the current density distribution on the working electrode in the electrodeposition process can be tuned. The amount and growth rate of the deposited Cu layer in various electrochemical cells and under different deposition conditions (such as different potential, electrolyte concentration or physical location) were experimentally measured with using carefully calibrated and normalized X-ray diffraction (XRD) data. A multi-physics multi-scale model was developed to quantify the distribution of the current density and the growth rate of deposited Cu at different locations. The experimentally measured data was used to verify and improve the model. The results showed that the model can accurately predict the distribution of the current density with given nominal deposition potential or current, and thus predict the growth rate of the deposited Cu phase.

The success of this model offers hopes to rationally design the deposition of metals and alloys to replace conventional trial-and-error method. The impact of different deposition substrates, additives, electrolyte concentrations will also be discussed. Proof-of-concept experiments also demonstrated that this rational design method can be applied to the design of electrodeposition of alloys, offering a much broader range of potential applications.
Pulsed Electrophoretic Deposition of Nanocarbons and Their Optical, Thermal, and Electrical Applications
Authors: Wang Dan , Hall Timothy , Snyder Stephen , Radhakrishnan Rajeswaran , Liu Danny , Le Huong , Inman Maria , Taylor E. Jennings
Published: November 2022

Electrophoretic deposition (EPD) is a well-established, scalable industrial manufacturing technology for depositing a wide variety of coatings across a broad range of substrates, geometries and sizes. Conventional electrophoretic deposition (EPD) is the migration of small, suspended particles in a liquid driven by a constant electrical potential difference. As a subset of electrodeposition, EPD has been used to deposit layers on various conducting and semiconducting surfaces from polar, aqueous, and non-polar suspensions. On the other hand, state of the art developments within nanoscience and nanotechnology has opened a new vista for the field of nanocarbon materials. Nanostructured carbon materials, such as carbon nanotubes, graphene, carbon quantum dots, etc., exhibit excellent physical and chemical properties, and have been gaining attention in both fundamental research and technological applications.

In this invited presentation, Faraday Technology will discuss an innovative electrophoretic deposition (EPD) manufacturing process, based on the use of pulsed electric fields, for controlled, reproducible, scalable deposition of a wide variety of nanocarbon based coatings across a broad range of substrates, geometries and sizes (Figure 1). The effects of waveforms, electrolytes, substrates, etc. on the formation of robust and uniform coating will be discussed in this talk. The optical and electrical properties, and environmental survivability of nanocarbon coatings will be demonstrated via a variety of testing or characterizations. Faraday will also introduce their applications ranging from low-reflective coatings, solar absorber, high emissivity coatings, to thin film electrodes for energy storage.

In summary, a scalable EPD manufacturing process for fabricating nanocarbon based coatings have been developed at Faraday for various applications ranging from optical, thermal, to electrical fields.

Acknowledgements: The financial support from NASA SBIR program through contracts No. 80NNSC18P2062 & 80NSSC19C0177, DOD DMEA STTR program through grant No. HQ0727-21-P-0029, DARPA SBIR program through grant No. W31P4Q-22-C-0014, DOD MDA STTR program through grant No. HQ0147-19-C-7065, DOD Air Force SBIR program through grant No. FA9453-19-P-0573, NASA SBIR program through contracts No. 80NSSC20C0287 are acknowledged.

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Electro-Codeposition of Composite Materials for Enhanced Thermal and Electrical Properties
Authors: Hall Timothy , Wang Dan , Le Huong , Garich Holly , Minary Majid
Published: November 2022

State of the art cryocoolers, high powered electronic systems, and space platforms require next generation high conductivity composite materials that can reduce product weight while improving performance. To meet this need, Faraday Technology with the help of Universities, National Labs, and industrial partners is developing a scalable electro-codeposition method to produce high conductivity hybrid graphene/copper composite materials.

Specifically, this talk will highlight two activities ongoing at Faraday and demonstrate the feasibility of fabricating either composite or laminated graphene-copper hybrid foils or direct printed composite nanowires via a pulse electro-codeposition approach. These activities indicated these composite materials can achieve a greater than 50% reduction in sheet resistance and a ~50% increase in mechanical strain compared to Cu foils. Additionally, we identified a strong dependance of material surface roughness on the measurement of thermal conductivity when using the 3-ω technique in a Closed Cycle He Cryostat. We will also discuss the opportunity to produce a wide range of material shapes by enabling a direct print apparatus that combines x,y,z control methods with an electro-codeposition printhead. If successful we envision that method to print next generation composite materials like ‘covetics’ that have the potential to meet many of the electronics and space community’s needs by enabling in space structural repairs, fabrication of new electronic components or sensors, or be utilized as heat exchanger composite materials. Finally, this activity also identified commercial partners interested in integrating these next generation into high powered electronics like laser diodes or invertors for electric vehicles.
Exchange Coupled SmCo5/FeCo Core/Shell Nanocomposites Fabricated By Ultrasound Assisted Electroless Deposition
Authors: Kim Jaehun , Lee Gyutae , Kim In Yea , Kim Chae Yoon , Lim Gi hwan , Lee Min-Jeong , Kim Dong Hyun , Kim Jong-ryoul , Lim Jae-Hong
Published: November 2022

Owing to high Saturation Magnetization (Ms) and high Remanence Magnetization (Mr), Rare Earth (RE) based Permanent Magnet (PM) has been widely used in various applications such as motor in Electric Vehicle (EV) and generator. With increasing concerns about climate change, EV is considered as a next generation vehicle because EV did not emit pollutants such as CO2, NOx and SOx. Over the past years, Nd2Fe14B is mainly used as PM in EV due to excellent maximum energy product (BHmax) around room temperature. However, The Nd2Fe14B has relatively low operating temperature (<200℃), which limits high speed operation. On the other hand, SmCo5 possesses high thermal, chemical stability and coercivity (Hc), making it a suitable magnetic material for high speed operation in harsh environment. However, unfortunately SmCo5 PM was only used in limited areas due to the lower Ms, Mr, BHmax than Nd2Fe14B. Therefore, interest in research to improve magnetic properties of SmCo5 is increasing. In particular, exchange coupling in core/shell structure between hard magnetic core and soft magnetic shell has attracted much attention because it can increase Ms, Mr, BHmax simultaneously while reducing high price RE element. In our work, we utilized electroless deposition on SmCo5 Nanoparticles (NPs) to fabricate exchange coupled SmCo5/FeCo hard/soft nanocomposites because of low cost and easy to control the soft phase thickness by modulating electrolyte bath parameters such as pH, temperature and additives. However, prior research clarified that the exchange coupling in 0-Dimensional NPs via electroless deposition was difficult because of inevitable particle aggregation caused by magnetic dipoles. Thus, inhibition of particle aggregation would be significant breakthrough. Accordingly, we prevented particle aggregation through ultrasound during the electroless deposition process.

The SmCo5 NPs were fabricated through Sn-sensitization, Pd-activation, and ultrasound assisted FeCo-electroless deposition, successively. Figure 1 shows that the schematic illustration of the effects of ultrasound. The magnetic properties of SmCo5/FeCo NPs were measured by Vibrating-Sample Magnetometer (VSM). When ultrasound was not applied, the hard magnetic properties reduced due to agglomerated NPs. On the other hand, in case ultrasound was applied exhibits exchange coupled hysteresis loop. Figure 2 shows that minor hysteresis loops of exchange coupled SmCo5/FeCo NPs fabricated by ultrasound assisted electroless deposition. We successfully fabricated exchange coupled SmCo5/FeCo NPs and the Ms, Mr, theoretical BHmax increased about 11%, 10.7%, 24.3%, respectively.

As a result, SmCo5/FeCo which fabricated by ultrasound assisted electroless deposition showed the increase in magnetic properties while maintaining Mr/Ms, which might broaden the future application fields.

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Perspectives and Impact of the Hull Cell for the Electrodeposition of Alloys and Metal Matrix Composites
Authors: Podlaha Elizabeth J.
Published: November 2022

Alloy and metal matrix composite electrodeposited materials are of interest due to their unique and often superior properties compared to their elemental counterparts. However, the deposit composition is not always known a priori due to coupled kinetic behavior of different reduction reactions and the influence of second phase particles. Models can enable predicting deposit composition from different electrolytes, and to validate such models data is needed. While a Hull cell and a rotating Hull cell are convenient tools to survey resulting deposit compositions with current density, it can also be used to provide information to better understand the deposition mechanisms and kinetic-transport behavior. In this talk, the history of the use of a Hull cell and rotating Hull cell will be discussed in the context of the underlying theory in current distribution, and the cautionary tale of when a Hull cell design is not always useful. Today, integrating scanning compositional tools with linear sweep voltammetry, the rotating Hull cell can be used to swiftly determine the partial current densities of metal ion reduction in the study of alloy systems that exhibit anomalous and induced codeposition. It can also aid in the study of composite electrodeposition to incorporate second phase particles into a growing metal matrix alloys. Extracting kinetic and mass transport data from this approach can help to develop better models for the electrodeposition process itself that governs the resulting deposit composition. Furthermore, new directions in the use of a Hull cell cell to assess electrodeposits for gas evolving reactions, such as the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in water splitting will be discussed.
Transformation in the Industry Leads to Future Challenges of Electrodeposition
Authors: Venz Rainer
Published: November 2022

Abstract:

Industries are developing permanently and therefore are in a constant change. In the last couple of years, some fundamental changes started and will lead to significant challenges of electrodeposition technologies.

What are the drivers for such changes? There are two main drivers, one is the legislation, with the REACh as a prominent example, that requires to replace many substances. For the plating industry, the main three substance are hexavalent chrome, Cobalt and PFOS, but also many others.

The other driver is the transition of vehicles from internal combustion engines (ICE) to alternative drive train concepts, mainly e-mobility. This transformation gives a new focus on the requirements. The classical requirements, like corrosion- or wear resistance and decorative finishes, will be advanced to multi-functional layers with a strategic focus to electronics and functionalization of components. Electro-deposited layers will play a key role to fulfil such requirements in the future.

As a consequence, the requirements to the end product changes and the electroplating industry has new challenges to meet this new requirements.

Quick summary and benefit for the audience:

The presentation will show examples for global changes in our industry, highlight the resulting technology trends and give examples for potential solutions.
Molten Hydroxide Electrodeposition of Transition Metal Oxide Cathodes for Electrochemical Energy Storage
Authors: Patra Arghya , Braun Paul V.
Published: November 2022

State-of-the-art synthesis for layered oxide cathodes for Li and Na-ion battery involves prolonged high temperature (>700°C) multistep processing for long reaction times (~24 hours) under high oxygen pressure, followed by slurry casting after mixing with binders and additives. Here, we demonstrate an intermediate temperature (250-350°C) molten hydroxide-based electrodeposition process to grow alkali ion (Li+, Na+) intercalated transition metal oxides across multiple transition metal chemistries of the Li system (from layered LiCoO2 to cobalt-less orthorhombic LiMnO2, layered Li2MnO3, spinel LiNixMn1-xO4, LiMn2O4,) and Na system (O3 and P2 NaxCoO2, O’3 NaxMnO2) in thick film form factors. The highly textured ([110]||ND), dense (>95%) electroplated LiCoO2 cathodes can perform at ultrahigh thickness of ~200 µm (areal capacity ~13.6 mAh/cm2) in comparison to 40-60 µm for state-of-the-art slurry cast cathodes (areal capacity ~3-4 mAh/cm2 with a porosity of ~20%), a fivefold increase in areal capacity and volumetric energy density. We discuss the interplay of bulk crystallographic orientation of the electro-active material (LiCoO2), surface terminating planes interacting with the electrolyte, and electrochemically grown conformal surface protective layers on the electrochemical-chemo-mechanical degradation mechanisms during intercalation and deintercalation for high voltage operation (>4.2 V vs. Li). We also demonstrate electrochemically controllable isovalent transition metal doping and substitution in ceramic oxides (LiCoxMn1-xO2) by electrodeposition. Our findings highlight the influence of the unique molten hydroxide-based solution chemistry platform and electrochemical processing parameters, on regulating the phase assemblage, designing the microstructure, and controlling crystallographic orientation during electrocrystallization.
Electrodeposition of Molybdenum from Water-in-Salt Electrolytes
Authors: Liu Quanhong , Huang Qiang
Published: November 2022

Molybdenum is attractive to the manufacturing industry due to its high melting point and extremely low thermal expansion. Generally, Mo can be produced by thermal spraying, sintering, and pressing at high temperatures. Electrodeposition has been used widely as low-temperature method to prepare metals and alloys as coatings or films. However, it is well-known that metallic molybdenum is difficult to deposit from aqueous solution due to its highly negative reversible potential. More recently, a few studies have successfully deposited metallic molybdenum from highly concentrated acetate solutions1,2 as a thick coating on metallic objects. In this work, we report a systematic study on Mo deposition using this electrolyte system under the umbrella of water-in-salt concept. Aqueous electrolytes with an extremely high concentration of salt, known as water-in-salt electrolytes, offer a special electrolyte environment for electrodeposition where free water molecules are reduced by the hydration of salt.

This report focuses on the effects of substrate and electrolyte chemistry on the Mo deposition process as well as the film properties. In this study, Cu electrode is fabricated by depositing Cu layer on Pt electrode. The electrochemical behavior is studied using cyclic voltammetry on Pt and Cu disc electrodes, as shown in Figure 1. Mo deposition starts at about -2.0 V on both Pt and Cu. In the anodic scan, the deposited Mo film begins to dissolve at -0.7V. X-ray fluorescence is used to measure film thickness, which is consistent with the stripping charge according to Faraday’s laws. However, the amount of Mo deposited on Cu, represented by the anodic stripping charge excluding the charge for Cu stripping, is much higher than that on Pt electrode. On the other hand, the presence of CH3COOK is found extremely critical for Mo deposition despite of a high total concentration of acetate. It is believed to relate to a suppressed proton reduction in presence of alkaline metal cations in a super highly concentrated acetate electrolyte. This correlation between hydrogen evolution reaction and Mo deposition is also consistent with the promoted deposition rate on Cu than on Pt surface. DC deposition studies are carried out to further verify these observations and to allow characterization of deposited Mo. Details will be further discussed in the poster presentation.

1 Morley, T. J. et al., "The deposition of smooth metallic molybdenum from aqueous electrolytes containing molybdate ions," Electrochemistry Communications
15, 78-80 (2012).

2 Syed, R. et al., "Electrodeposition of thick metallic amorphous molybdenum coating from aqueous electrolyte," Surface & Coatings Technology
261, 15-20 (2015).

Figure 1
An Application Based Introduction to the Brush Plating Technique
Authors: Thomas Joshua , Milosevic Danijela
Published: November 2022

Selective or brush plating is an application method for electrodeposition which can be used for depositing an array of pure metals, alloys, and composite materials onto conductive surfaces. Brush plating has seen its most advantageous use in plating smaller areas of larger parts because the amount of masking used can be reduced, and smaller volumes of solution can be utilized compared to traditional tank plating methods. These same characteristics make brush plating portable and repair operations can be conducted in the field, at times without even disassembling equipment. Brush plating is currently used across a multitude of industrial applications in the fields of aerospace, oil and gas, marine environments, semiconductors, and other manufacturing.

‘Brush’ plating is often considered a manual technique where a technician directly applies the anode (wrapped in the ‘brush’ material) to the surface to be plated. The brush material must be a porous, non-conductive, flexible material which electrically separates the anode from the surface to be plated. The plating solution is absorbed into the brush material around the anode prior to plating by dipping it into a vessel containing the solution. Alternatively, solution can be pumped directly through the anode to the surface to be plated. As a result, smaller volumes of solution can be used because the entire part is not immersed in a large tank containing the plating solution. Masking can be placed around the area to be plated without needing to mask off every surface that isn’t receiving a deposit.

The current density used for brush plating is often high (0.2 to 1.5 A/cm2) relative to other electrochemical plating techniques. Brush plating solutions are typically highly concentrated and the brushing action against the surface where deposition is occurring allows for replenishment of the ion to be plated very close to the interface with the cathode. This allows for high plating rates (Up to 500 µm/hr) depending on the solution and other plating parameters utilized.

This presentation will introduce the audience to the brush plating technique through the use of current and classical applications with multiple deposits. Pros and cons of the technique for different circumstances will be discussed. The influence of the brush material on the electrochemical interface during plating and the resulting deposit will be highlighted. Current research includes the development of deposits for chrome alternatives, alloys for corrosion resistance, and applying deposits to challenging substrates.
Numerical Model of an Enzymatic Glucose Sensor with a Blocking Layer on the Electrode
Authors: Jacobs Samuel , Miller Michael , Batmanghelich Farhad , Orazem Mark E.
Published: November 2022

Glucose oxidase-based biosensors are a primary method for continuous glucose monitoring. b-glucose reacts with immobilized glucose oxidase to form gluconic acid and hydrogen peroxide. Hydrogen peroxide is oxidized on an adjacent electrode. The resulting anodic current is proportional to the concentration of glucose. The measured current may be influenced by oxidation of secondary species, such as ascorbic acid and acetaminophen, or fouling of the sensor via foreign body response.[1-3] A blocking layer, placed between the electrode and the immobilized enzyme layer, may act to prevent diffusion of secondary species to the electrode, and reduce the influence of the foreign body response.[3]

The influence of a blocking layer on the steady and transient operation of the sensor was evaluated numerically. A blocking layer was added to the steady and transient glucose sensor model outlined in previous work [4] to address the potential influence of acetaminophen. Sensor performance was evaluated for multiple blocking layer thicknesses, reacting species diffusion coefficients, and oxygen concentration. The polarization behavior of the sensor was modeled. Selectivity to glucose was improved by addition of a blocking layer, but sensitivity to oxygen was increased with increasing blocking layer thickness.

Numerical simulations of the transient response to a step change in glucose for a sensor with the blocking layer had a response time comparable to the response without the blocking layer, except when the hydrogen peroxide diffusion was greatly reduced in the blocking layer. A step change in acetaminophen yielded time constants comparable to that of the glucose step change in the absence of a blocking layer. The results are sensitive to the thickness of the blocking layer and to the diffusivity of the interfering species in the blocking layer.

References

Basu, A., & Veettil, S. (2016). Direct Evidence of Acetaminophen Interference with Subcutaneous Glucose Sensing in Humans: A Pilot Study. Diabetes Technology & Therapeutics, 18(S2), 43-47.

Surani, S., & Sharma, M. (2021). Interaction between vitamin C and point of care glucose monitoring. Are we overly wary of it or is it a valid concern? Current Medical Research and Opinion, 37(7), 1111-1113.

Yang, Y., Zhang, S., & Kingston, M. (2000). Glucose sensor with improved haemocompatibility. Biosensors and Bioelectronics, 15, 221-227.

Jacobs and M. E. Orazem, ``Transient Response of a Continuous Glucose Monitor," presented at the 240th Meeting of the Electrochemical Society, Orlando, Florida, October 10-14, 2021.

Acknowledgement

The support of Medtronic Diabetes (Northridge, CA) is gratefully acknowledged.