bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Transition Metal Oxides and Sulfides for Supercapacitor Applications
Authors: Singhal Rahul 
Published: November 2022

Energy produced by renewable energy sources need to be stored till required. Therefore, the development of high energy density energy storage systems is required to fulfil the energy needs around the world without any significant environmental impact. Recently, energy storage devices such as rechargeable batteries, fuel cells, and supercapacitors have attracted significant attention owing to their diverse applications in hybrid electric vehicles, energy management, and smart portable electronic devices. Rechargeable batteries such as lithium-ion batteries have been widely employed for various commercial application ranging from consumer electronics to hybrid electric vehicles. However, rechargeable batteries possess high energy density but often suffers from slow charging/discharging, limited cycle life, high cost of Li metal, low power density, poor cycle life, and environmental issues. Currently, supercapacitors are becoming more popular to overcome the issues raised by Li on rechargeable batteries such as low power density and limited cycle life.
Various transition metal-based materials such as oxides, sulfide, selenides, nitrides, phosphide are being used for supercapacitor applications due to their high theoretical specific capacitance abundant sources, and low cost. Transition metal oxides have attracted great attention of the researchers for supercapacitor applications because of their multiple oxidation states due to which multiple electrons transfer exists and discharge time extends, resulting in improving energy density in rapid Faraday redox reactions.
Our group is actively engaged in studying supercapacitor behavior of various transition metal oxides, sulfides, and their composites with carbonaceous materials such as carbon nanotube, graphene oxide (GO), reduced graphene oxide(rGO), and carbon nanotubes (CNT). We have synthesized pure MnO2 and CuS along with their composites with graphene oxide and multiwall carbon nanotube (MWCNT). It was reported that the specific capacitance of CuS and CuS-GO nanocomposite was found to be 158 F/g and 250 F/g, respectively, at a current density of 0.5A/g. The specific capacitance of MnO2 and MnO2/MWCNT nanocomposite was found to be as 124 F/g and 145 F/g, respectively, at a current density of 0.5A/g. The detailed studies on electrochemical performances of various transition metal oxide/sulfides and their composite with carbonaceous materials will be presented at 242nd ECS Meeting.
Multichannel Electrochemical Impedance Spectroscopy and Equivalentcircuit Synthesis of a Kw-Scale Vanadium Redox Flow Battery
Authors: Trovo Andrea , Zamboni Walter , Guarnieri Massimo 
Published: November 2022

An original multichannel Electrochemical Impedance Spectroscopy (EIS) system operating at high bias current and suitable for kW-class Vanadium Redox Flow Batteries (VRFBs) is presented. Power and signal connections, whose stray parameters affected measurements, required a careful optimization and calibration in the implementation of the measurement chain. In any cases, electromagnetic interferences set an upper limit to the applied stimulus frequency that limited the set of measurement data at each bias point. The work provides early results obtained with this EIS system, which were used to identify an equivalent circuit of the whole stack in which each cell is represented with a dynamic Thévenin equivalent, i.e. the series of a voltage source, a variable resistor and a variable RC loop. The dependence of the equivalent parameters on the operating conditions has been experimentally analyzed, confirming that only the RC-loop resistance is strongly affected by mass transport. In addition, more complex equivalent circuits have been proposed, i.e. a Randles cell modified with CPE, a Randles cell modified with CPE and Warburg element and a two-loop model of ZARC elements. The inclusion of the constant phase element constitutes a substantial improvement in the fit, Fig. 1. Conversely, the addition of the Warburg element, which aims to model the mass transfer in the electrochemical process, does not produce significant effects for the frequencies at which we have experimental data. To our knowledge, this is the first dynamic equivalent circuit of a whole stack that has been validated against EIS measurements taken on a real industrial-scale VRFB. Building on the measurement methodology here presented, advanced online state of health of industrial flow batteries can be developed and implemented.

References

[1] Trovò A, Zamboni W, Guarnieri M. “Multichannel Electrochemical Impedance Spectroscopy and equivalent circuit synthesis of a large-scale vanadium redox flow battery.” J Power Sources (2021) 493: 229703.
[2] Trovò A, Di Noto V, Epoupa M. J, Gamabaro C, Guarnieri M. “Fast Response of kW-Class Vanadium Redox Flow Batteries," in IEEE Trans Sustain Energy (2021), vol. 12, no. 4, pp. 2413-2422
[3] Sanchez-Diez E, Ventosa E, Guarnieri M, Trovò A, Flox C, Marcilla R, Soavi F, Mazur P, Aranzabe E, Ferreta R. “Redox flow batteries: status and perspective towards sustainable stationary energy storage.” J Power Sources (2021), 481: 228804.
[4] Guarnieri M, Trovò A, Picano F. “Enhancing the efficiency of kW-class vanadium redox flow batteries by flow factor modulation: An experimental method”, Appl Energy (2020), 262: 114532.
[5] Trovò A, Guarnieri M. “Standby thermal management system for a kW-class vanadium redox flow battery”. Energ Conv Manag (2021), 226: 113510.

Figure 1
Vanadium/Water Electrolyser for Recharge of Vanadium Oxygen Fuel Cells
Authors: Noack Jens , Roznyatovskaya Nataliya , Menictas Chris , Skyllas-Kazacos Maria , Tübke Jens 
Published: November 2022

The vanadium/oxygen fuel cell (VOFC) has evolved from developments to vanadium redox flow batteries (VRFB) for storage of renewable energy and perhaps for mobile applications. In VOFCs, oxygen is used to oxidise divalent vanadium ions to trivalent ions instead of the redox reactions of V(IV)/V(V) to achieve potentially higher energy densities and eliminate temperature stability problems associated with the energy storage medium compared to VRFBs. To charge a VOFC as an energy storage system, the discharge reactions have to be reversed with as few side reactions as possible. This process involves reducing trivalent vanadium ions to divalent vanadium ions through the application of electrical energy. The cathodic water generated during the discharge is used as the reductant. The water itself is oxidised to oxygen to keep the cycle between the charge and discharge processes as short and efficient as possible. This process is also exactly the reversal of the process which happens in VRFBs when atmospheric oxygen oxidizes divalent vanadium ions in vanadium electrolytes. As a synergistic effect, vanadium/water electrolysis can be also used to regenerate oxidized electrolytes and increase the life time of the batteries.
Using a cell with a commercial and iridium-based catalyst coated membrane, it was possible to fully reduce V3.5+ and V3+ solutions to V2+ with the formation of oxygen and with coulomb efficiencies of over 96%. The process was followed by introduction of an additional reference electrode to measure the redox potential of the electrolyte, the negative electrode potential and to calculate the positive redox potential. The cell achieved a maximum current density of 75 mA/cm2 during this process and was limited by the proximity of the V(III) reduction to the hydrogen evolution reaction. Due to the specific reaction mechanisms of V(IV) and V(III) ions, V(III) solutions were reduced with an energy efficiency of 61%, making this process nearly twice as energy efficient as the reduction of V(IV) to V(III). Polarisation curves and electrochemical impedance spectroscopy were used to further investigate the losses of halfcell reactions and to find ways of further increasing efficiency and performance levels.

Figure 1
(Edward G. Acheson Award) Exploration of Amorphous Thin Film Electronics
Authors: Kuo Yue 
Published: November 2022

Thin films are critical elements in modern semiconductor devices. They are often prepared in the amorphous phase due to practical reasons, such as the reliability and manufacturability concerns. For example, the amorphous high-k gate dielectric is less prone to current leakage than the polycrystalline dielectric in the MOS device (1). The utilization of amorphous silicon (a-Si:H) or metal oxide semiconductor layer enables the commercial production of thin film transistor (TFT) arrays for flat panel displays (2). Requirements for amorphous thin films are related to the products. For advanced MOSFETs, the nanometer EOT gate dielectric is necessary (3). For LCD or OLED TVs or monitors, the fabrication process has to be low temperature, large area capability, and high throughput (4). In addition, the fabricated device has to be highly reliable, i.e., resistant to damages from subsequent process steps and environmental exposure.
In this talk, examples on amorphous thin films conducted in my group will be given and discussed. The doped metal oxide high-k thin film, which has a crystallization temperature higher than that of the undoped film (5), will be examined with respect to fundamental material and electrical properties. Novel devices made from this kind of film, e.g., nanocrystals embedded nonvolatile memories (6) and nano-resistor solid state incandescent LEDs (SSI-LEDs) (7), will be shown and the principles will be deliberated. Separately, PECVD process condition affects the a-Si:H TFT performance as well as the uniformity of the large-area material properties (8), which can be explained with the generalized deposition-etching mechanism (9). Applications of a-Si:H TFTs in nonvolatile memories, e.g., using the floating-gate structure (10), and protein/DNA analysis, e.g., attached with the microchannel device (11), will also be examined.
In order to achieve the best device performance with high reliability, both the bulk film and the interface properties of the amorphous thin film have to be tightly controlled, which requires the multidisciplinary approach. This is the early stage of the field. Many new and unique applications of the amorphous thin films can be expected in the near future.

Y. Kuo, ECS Trans., 54(1), 273-281 (2013).

Y. Kuo, Amorphous Silicon Thin Film Transistors, Kluwer, Norwell, MA, 2004.

J. Yan, Y. Kuo, and J. Lu, Electrochem. Solid-State Lett., 10(7), H199-H202 (2007).

Y. Kuo, ECS Interface, 22(1), 55-60 (2013).

J.-Y. Tewg, Y. Kuo, and J. Lu, Electrochem. Solid-State Lett., 8(1), G27-G29 (2005).

Y. Kuo, ECS Trans., 3(3), 253-263 (2006).

Y. Kuo and C.-C. Lin, Appl. Phys. Letts., 102(3), 031117 (2013).

Y. Kuo, J. Electrochem. Soc., 142, 186-190 (1995).

Y. Kuo, Appl. Phys. Lett., 63(2), 144-146 (1993).

Y. Kuo and H. Nominanda, Appl. Phys. Letts.,
89, 173503 (2006).

H. Lee and Y. Kuo, Electrochem. Solid-State Letts., 9, J21-J23 (2006).
(Invited) Status of Room-Temperature Mass-Production Capability Plasma-Based Copper Etch Process
Authors: Kuo Yue 
Published: November 2022

Copper (Cu) dominate interconnect applications in advanced ICs, large-area flat panel displays, and other microelectronics for its high conductivity, long lifetime, and plenty of raw material supply at the low cost. It is preferable that Cu arrow lines are prepared with the plasma etching method. However, due to the low volatility of the Cu halide or organic compound in the plasma reaction, there is lack of practical manufacturable etching process that satisfies requirements on large-area, high-throughput, room-temperature, simple, and low cost.
Since IBM introduced the CMP Cu etching method (1), it has been widely adopted in IC production. This a tedious process that involves sputter and electroplating depositions, dielectric etching, mechanical polishing, and environmental unfriendly slurry solutions. There are challenges in endpoint detection, dishing, and preparing very fine lines.
We first reported a 2-step plasm-based Cu etch process that could be conducted at room temperature under the typical plasm etching condition without requiring high-density plasma or extra power source (2,3). Instead of spontaneously removing the plasma-Cu reaction product, the Cu film is converted into a compound at a high rate, which is then dissolved in an acid or alkaline solution. Being described as a disruptive technology, this process has been successfully demonstrated in the fabrication of CMOS hips, TFT LCD panels, and sub 0.5 μ lines (4,5).
Recently, we published a new process that replaces the corrosive chlorine- or bromine-containing feed gas with oxygen (6). The new process can reduce the production cost, e.g., no need of corrosion-resistant tubes, valves, flow controllers, and pumps. The large-area and high throughput advantages are maintained in the new process.
In this talk, the principle of the oxygen or halogen plasma-based Cu etch process will be discussed with respect to the reaction mechanism, material properties, and limitations. Possible future development of this technology will be examined.

https://www.chiphistory.org/ibm-s-development-of-copper-interconnect-for-ics

Kuo and S. Lee, ECS Proc.
99–30, 328 (1999).

Kuo and S. Lee, Jpn. J. Appl. Phys.
39, L188 (2000).

Kuo, Proc. 16th Intl. Workshop AM-FPD Dev, 211 (2009).

Kuo, ECS Trans.
66, 139 (2015).

Y. Kuo and J. Q. Su, Jpn. J. Appl. Phys.
61, 030902 (2022).
Additive Manufacture of Graphene Electrodes for Supercapacitor Applications
Authors: Reale Batista Mariana Desiree , Chandrasekaran Swetha , Moran Bryan , Salazar de Troya Miguel A , Carleton Adam , Roy Thomas , Zeng Manhao , Pinongcos Anica , Lin Dun , Wang Zhen , Hensleigh Ryan , Kuntz Joshua , Beck Victor A , Tortorelli Daniel , Stadermann Michael , Li Yat , Zheng Rayne , Zheng Rayne , Worsley Marcus Andre 
Published: November 2022

Electrochemical energy storage devices, such as supercapacitors, are essential contributors to the implementation of sustainable energy. Supercapacitors exhibit fast charging/discharging ability and have attracted considerable attention within the automotive, aerospace, and telecommunication industries. Although these devices show great potential to meet power density metrics, they lack in terms of their energy density. To overcome this challenge, we are investigating better materials, architectures, and additive manufacturing techniques to print electrodes that increase the energy density while maintaining their high-power densities. Topology optimization was used to design an electrode with optimum performance. These electrodes were printed by projection micro stereolithography (PµSL) using PR48, a commercially available polymer resin. The printed electrodes were converted to carbon electrodes through pyrolysis at 1050 ֯C and characterized by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrical impedance spectroscopy. The performance of the PR48 optimized electrodes were compared against PR48 electrodes printed as a simple cubic lattice structure previously shown to improve capacitance and rate capability. The results show that our optimized electrodes have higher areal capacitances for all the current densities tested and they perform better in GCD and CV tests. Lastly, to increase the surface area of the electrodes and increase the capacitance further, we developed a resin formulation by combining graphene oxide (GO) into TMPTA polymer. Electrodes printed with 3%GO/TMPTA have improved electrochemical performance compared to PR48 as evidenced by their higher capacitances and their better GCD and CV curves. This work demonstrates the benefits of using topology optimization to design electrodes and materials development to improve the functional properties of 3D printable resins.
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under contract DE-AC52-07NA27344. Lawrence Livermore National Security, LLC

Figure 1
(Digital Presentation) Selective Lead Recovery from a Mixture of Lead and Tin for Silicon Solar Module Recycling
Authors: Click Natalie , Tao Meng 
Published: November 2022

During the recycling of solar modules, it is imperative to recover all the toxic lead used in solder. In this experiment, acetic acid is investigated for lead leaching and electrowinning from a mixture of lead and tin. 0.0636 g of tin powder (Alfa Aesar, 325 mesh, 99.8%) and 0.0372 g of lead powder (Alfa Aesar, 100 mesh, 99.95%, atomized) were combined with 30 mL of 0.01 M acetic acid (Sigma Aldrich) and 100 μL hydrogen peroxide (Alfa Aesar, ACS, 29-33% w/w). The solution was allowed to sit for 48 hours before electrowinning to allow the hydrogen peroxide to decompose. A copper working electrode, graphite counter electrode, and silver/silver chloride reference electrode were used in a three-electrode system.
A cyclic voltammogram shows lead reduction around –0.4 V vs Ag/AgCl, and a large stripping peak around –0.05 V. There is only one set of redox peaks in the graph, indicating only lead is reduced and oxidized. EDX confirms the presence of metallic lead on the working electrode after electrowinning at –0.6 V vs Ag/AgCl for 90 minutes. Only lead is present on the working electrode surface, no tin. These results show acetic acid to be a promising leachate for the electrowinning of metallic lead from silicon solar module solder waste.

Figure 1
Fabrication and Characterization of Conductive FeCo@Au Nanowire Alloys for Semiconductor Connector
Authors: Kim In Yea , Lim Gi hwan , Kim Chae Yoon , Lee Min-Jeong , Kim Jaehun , Kim Dong Hyun , Lim Jae-Hong 
Published: November 2022

A semiconductor test socket is one of the essential components for final electrical and performance testing of semiconductors. Due to the miniaturization of semiconductors, fine pinching of test sockets is required, so research on connectors for semiconductor inspection capable of fine processing is being actively conducted. The connector for semiconductor inspection consists of a powder coated with conductive powder on a magnetic material and rubber, and an electrical signal is transmitted through the conductive powder. A finer pitch rubber test socket shall maintain the electrical characteristics (resistance) at the same level, even though a smaller conductive path is formed as the gap between conductive paths narrows to respond to the increase in demand for fine pitch products.
Therefore, in this study, a technique for forming a conductive pathway between conductive powders to maintain the electrical properties of a semiconductor socket for fine pitch is introduced. In order to effectively improve a thin conductive path, a conductive nanowire was prepared to form a conductive pathway between conductive powders. Fig. 1 shows the schematic diagram for the fabrication of FeCo nanowires. FeCo nanowires were synthesized through electroplating using AAO (Anodic Aluminum Oxide) as a template, and Au as a conductive material was coated on the surface of FeCo wires through an electrochemical method to synthesize FeCo@Au. To uniformly coat Au on the surface of the FeCo wire during the coating process, sonication, vortex, and stay three methods were compared, as shown in Fig. 2. As a result of confirming the surface shape by SEM, the most uniform method was confirmed by the vortex method. In addition, the magnetic properties of FeCo@Au synthesized with a smooth surface were analyzed through VMS (Vibrating Sample Magnetometer). As a result, it can be confirmed that alignment through magnetism is possible. From these results, it was confirmed that the method of increasing the electrical conductivity by adding a wire to reduce resistance of semiconductor connector.

Figure 1
Initiated Chemical Vapor Deposited Anion-Conducting Solid-State Polymeric Electrolytes for All Solid-State Batteries: Impacts of Deposition Conditions and Polymer Composition on Performance Metrics
Authors: Ford Hunter , Chaloux Brian , Miller Joel , Klug Christopher , Long Jeffrey W. , Kim Youngchan , Jugdersuren Battogtokh , Liu Xiao , DeBlock Ryan H. , Johannes Michelle D. , Rolison Debra R. , Sassin Megan B. 
Published: November 2022

Achieving both high energy and power density, two traditionally opposed battery metrics, requires moving away from the 200+ years-old 2D layered battery configuration to a three-dimensional all solid-state battery (3D SSB) configuration. The enhanced power and energy benefits bestowed by a 3D SSB design have been demonstrated in the Li-ion 3D SSB literature.1 However, due to limitations in thermal and electronic conductivity of Li-Ion active materials, 3D Li-ion SSBs are limited to microscale dimensions. A potential means around this limitation is to switch to conductive metal electrodes such as Zn and Ag, for which 3D architectures have been demonstrated.2 In such a case, the remaining roadblock to a macroscale 3D SSB is the submicron-thick solid-state electrolyte, which requires a non-line-of-sight deposition method for incorporation into the complex 3D base electrode. Initiated chemical vapor deposition (iCVD) is a non–line-of-sight method that is ideal for generating conformal polymer coatings on complex 3D architectures. We focus on polymers amenable to iCVD protocols that can be modified post-deposition to introduce anion conduction pathways that can facilitate Ag and Zn redox. Submicron-thick coatings of poly-dimethylaminomethylstyrene (pDMAMS) that are pinhole-free and electronically insulating on both 2D planar and complex 3D electrode architectures are prepared via iCVD. The pDMAMS coatings are rendered anion-conducting through a vapor-phase methylation process and subsequent ion exchange to yield desirable anion species (e.g., OH–, Br–, or HCO3
–). X-ray photoelectron spectroscopy, ATR-IR spectroscopy, and solid-state magic-angle spinning NMR spectroscopy confirm the structure of the pDMAMS film before and after quaternization, while atomic force microscopy and cyclic voltammetry with redox probes confirm conformality and absence of pinholes in the submicron film. With the use of cyclic voltammetry and AC electrochemical impedance spectroscopy, the electronic and ionic conductivities of the polymer films are measured before and after quaternization. Molecular dynamics simulations of pDMAMS as a function of anion and H2O content in the film are used to generate computational results (e.g., glass-transition temperature Tg, anion conductivity) for comparison to experimental results.
1. Long, J.W.; Dunn, B.; Rolison, D.R.; White, H.S. Chem. Rev. 2004, 104, 10, 4463–4492.
2. Parker, J.F.; Chervin, C.N.; Nelson, E.S.; Rolison, D.R.; Long, J.W. Energy Environ Sci. 2014, 7, 1117-1124.