bluuebunny/crossref_metadata_2025 huggingface dataset:
Advanced Analytical System with Standardized Data Analysis for Electrochemical CO2 Reduction
Authors: Senocrate Alessandro , Kraus Peter , Bernasconi Francesco , Battaglia Corsin
Published: February 2024

Electrochemical CO2 reduction (CO2RR) is a promising way to convert CO2 emissions into sustainable fuels and chemicals, approaching a circular carbon economy.
1 Depending on catalyst type and reaction conditions, different gaseous and liquid products can be obtained from the CO2RR, and their production rates vary with reaction time. Thus, assessing the product distribution online during CO2RR is a key component of any catalytic performance analysis.
2,3 However, while gaseous products are readily analyzed online, liquid products are assessed typically only at the end of the reaction due to the lack of suitable automated liquid sampling and analysis methods. In addition, electrolyzer parameters such as gas flow rates, temperatures and pressures are seldom recorded, causing the loss of significant information on catalysts, electrodes, and electrolyzers behavior.

To overcome these issues, we assemble a comprehensive analytical system coupling online gas and liquid product analysis by chromatography (leveraging a special automated liquid sampling valve) with electrochemical protocols to assess CO2RR performance, electrolyzer cell resistance and electrode surface area. In addition, we record CO2 gas flow rates, electrolyzer temperatures, and gas and liquid pressures.
4 To rapidly and reproducibly handle the large and heterogeneous data volume obtained we implement a standardized data pipeline based on our own open-source software,5 which automatically parses the numerous different raw data files, composes a data set following FAIR practices,6 and post-processes and plots the data in a standardized way (see example in Fig. 1 below). We validate the analytical system by carrying out CO2RR at 200 mA/cm2 on Cu gas diffusion electrodes, following the changes in selectivity with reaction time for > 10 gaseous and liquid products, and recording mass flow rates, electrolyzer temperatures and pressures. The modular nature of our analytical system, combined with the standardized data pipeline, allows us to freely increase the number and type of sensors used with minimal impact on the data analysis time, as well as to multiplex our analysis to parallel electrolyzer cells, paving the way for a much deeper and faster understanding of the function of CO2RR catalysts, electrodes, and electrolyzers.

References

[1] Senocrate, Battaglia, J. Energy Storage
2021, 36, 102373.

[2] Wang, de Araújo, Ju, Bagger, Schmies, Kühl, Rossmeisl, Strasser, Nat.
Nanotechnol.
2019, 14, 1063. [3] Löffler, Khanipour, Kulyk, Mayrhofer, Katsounaros ACS Catal.
202
0, 10, 6735.

[4] Senocrate, Kraus, Bernasconi, Battaglia, in preparation
2023.

[5] https://dgbowl.github.io

[5] Kraus, Vetsch, Battaglia, Journal of Open Source Software
2022, 7, 4166.

Figure 1
(Invited) Hybrid Bonding from Hype to Reality: How Will Hybrid Bonding Dtw Pave the Way to Large Set of Applications?
Authors: Gallezot Martin
Published: February 2024

Packaging and 3D integration have grown in importance as one of the key technology enablers to compensate for the slowing of two-dimensional scaling. Today, advanced 3D SoC are calling for fine interconnect where microbumps are hitting manufacturing limitation at 10µm pitch and beyond. Hybrid bonding technology is a good candidate for high interconnect density and connects dies in packages using tiny copper-to-copper connections, as opposed to bumps. This technology is already mature for wafer to wafer hybrid bonding and is expected to open new opportunities for die to wafer hybrid bonding, providing the same downscaling in pitch as well as additional flexibility and heterogeneity. This derived technology is of great interest for many applications such as chiplet, memory stacking, photonics with imagers, displays, optic transceivers and RF. However, there are still some hurdles to overcome to get this technology in full production. CEA-Leti has been involved in hybrid bonding process development for more than 20 years with industrial partners in wafer to wafer and today in die to wafer. This presentation will discuss about:

Limitations of the technology: specific process challenges, interconnect alignment, design and architecture,...

What needs to be developed to pass the hurdle: known good die, throughput & yield,...

Key achievements / performances and roadmap at CEA-Leti on this promising technology
Unraveling the Slurry/Substrate Interfacial Reaction Mechanism for Wide Band Gap (WBG) Chemical Mechanical Planarization (CMP)
Authors: Powell Joseph L. , Philipossian Ara , Sampurno Yasa , Keleher Jason J.
Published: February 2024

Wide band gap (WBG) semiconductors have become of great interest to extend Moore’s Law beyond the limitations of current Si IC technology. More specifically, WBG materials (i.e., Silicon Carbide and Gallium Nitride) have been shown to increase performance due to their intrinsic properties (i.e., high capacitance, thermal stability, and wear resistance) associated with these materials. Current CMP processing of these WBG materials utilizes aggressive chemical conditions (i.e., abrasive nanoparticles and harsh oxidizers) and increasing shear forces to obtain the desired material removal rates (MRR) and surface planarity. Unfortunately, these processing conditions can cause defectivity (i.e., organic residue, pad debris, scratches, etc.) during the polishing process, leading to increasingly complex post-CMP cleaning steps. This work focuses on the strategic design of chemically activated, peroxide-based CMP slurries for emergent materials that target redox activation at the slurry-substrate surface interface to achieve improved CMP performance (i.e., enhanced material removal rates, superior surface quality, and low defects). More specifically, the catalytic generation of reactive oxygen species (ROS) (i.e., hydroxyl radical (*OH) and singlet oxygen (1O2)) at the substrate interface via surface complexation during the polishing process is exploited. The generated ROS can weaken the Si-C bonds within the surface of the substrate, allowing the particles to remove the surface more readily. This work explored organometallic complexes and non-metal catalysts, such as boron-based additives, as surface-active redox modulators. Initial results show that lower-stability complexes result in equally low MRR ranges below 400 nm/hr, while highly stable complexes increase the MRR as high as 1600 nm/hr. This complex stability/MRR trend has been further correlated to changes in the electron-poor areas of the complexes and ROS generation via radical trapping. The surface roughness analysis has shown improved surface quality between 0.8-1.0 nm across the substrate; however, organic residues from the complexes remain. Transitioning to non-metal boron electrophiles has shown similar MRR results (1000-1400 nm/hr) but can alleviate surface contamination. This implementation of Araca. Inc.’s patent-pending Flucto-CMP® technology employs megasonic energy to promote enhanced ROS generation, thus accelerating removal and significantly improving surface defectivity.
(Invited) Comparison of Empirical Models for Broadband Insertion Losses in TSV-Interconnects
Authors: Coakley Kevin J , Kabos Pavel , Moreau Stephane , Obeng Yaw
Published: February 2024

The reliability of through silicon via (TSV)-interconnects depends on various factors including integration schemes, manufacturing process (construction materials, wafer-scale homogeneity, thermal budget) and operating conditions. The magnitude of the frequency-dependent $S_{21}$ microwave scattering parameter quantifies insertion losses in TSV-interconnects. The insertion loss depends on the instantaneous electrical characteristics of the device under test. We attribute insertion loss (which affects device reliability) to reorientation of electrically active defects, cracks, voids, dielectric constant variation, and water molecules affected by heat. We model insertion losses with equivalent circuit models of varying complexity. We compare results determined with global and local models fit to low-frequency and high-frequency subsets of the full spectrum. We estimate model parameters with a stochastic optimization implementation of the Levenberg-Marquadt method. To illustrate the relevance of this methodology, for TSV-interconnects from two different providers, we quantify how estimated model parameters vary with thermal cycles for TSV-interconnects fabricated at particular wafer locations.
(Invited, Digital Presentation) 2-D Van Der Waal Materials for Advanced Interconnect Applications
Authors: Obeng Yaw , Perez Jesus
Published: February 2024

Advanced interconnects require new materials to minimize high frequency signal loss and manage high temperature excursions due Joule heating. In this talk, we will review our on-going material selection modeling, and the thermo-mechanical reliability testing of interconnect prototypes that incorporate 2-D van der Waal thin films. Specifically, we will discuss our use of broadband microwave spectroscopy, that enables the accurate in-operando analysis of the electrical and magnetic properties without compromising the kinetic conditions of the experiment, to investigate high speed signal loss in 3-D integrated test circuits. The BDS method is sensitive to the actual electronic structure of the constituent materials and interfacial processes in the test structures. Using BDS, we have studied and characterized the 2-D van Der Wall, and other chalcogenide thin films in purposely built prototypical 3-D integrated circuit (3D-IC) during cycled high-temperature storage. We show that the microwave signal loss in these devices is attributable to the energy dissipation through the signal’s interactions with the copper barrier / cladding materials.
(Invited, Digital Presentation) Integration of 2D Material Characterization and Reliability into Device Manufacturing
Authors: Mansfield Elisabeth , Holm Jason , Keller Robert
Published: February 2024

After the unique properties of graphene were realized, scientists began seeking other types of atomically thin materials that exhibited similar attractive and exciting properties. There is now a range of materials including single element (e.g. phosphorene) and compounds (e.g, transitional metal dichalcogenides and MXenes) that show promise for electronic, quantum, superconducting and optoelectronic applications. As with any new material, understanding structure and inherent defects is an important part to optimizing performance in these materials for their intended applications.

Manufacturing optimized devices that incorporate newly-emerging materials requires predictable performance throughout device lifetimes. Unexpected degradation in device performance, sometimes leading to failure, is often traceable to poor material reliability. Reliability is rooted in the stability of the atoms making up a material, and is determined by geometry, microstructure, chemistry, dimensional scale, proximity to other materials, and exposure to external stressors. Integration of powerful characterization techniques and reliability tests of materials under operational conditions improves fundamental understanding and accelerates development of highly-reliable materials and devices.

This talk will cover recent work on 2D materials characterization and reliability testing of these materials with the ultimate goal of manufacturability. Characterization of defects, primarily with transmission-SEM, to characterize diverse 2D materials (e.g., topological insulators, transition metal dichalcogenides, semiconductors) will be demonstrated. Initial measurement results to understand the impact of reliability challenges (e.g. electrical, thermal) the material may experience during manufacturing will be discussed. The advancement of this work to identify potential device configurations, material interfaces and use conditions that will be problematic will be presented.
(Invited) Development of Interfacial Materials for High-Performance Battery Materials
Authors: Wang Donghai
Published: February 2024

Metal and alloy anode materials are the most promising anode for next-generation batteries. The interfacial instability in the electrochemical energy storage devices has been the primary issue hindering their practical application. In this talk, I will present approaches on de novo designing and architecting stable interphases on electrode materials using chemically and electrochemically active materials. The strategy works by introducing multiple functional components into the polymer composite which can bond to the Li-based material surface to participate in the formation of the SEI. The reinforced SEI shows much better stability than the SEI generated by the electrolyte additive strategy. The functional-material-derived interfaces/interphases present desirable ionic conductivity, density, homogeneity, and mechanical strength. The interfaces/interphases reinforced by the interfacial materials show much better stability than that reinforced by conventional strategies such as using electrolyte additive-commercially used solution to interface stability issues. Our findings open a new way to design stable electrochemically stable interfaces in electrode materials for next-generation electrochemical energy storage.
(Invited) Lithium Phosphorus Sulfide Chloride-Polymer Composite Via Solution-Precipitation Process for Improving Stability Toward Dendrite Formation of Li-Ion Solid Electrolyte
Authors: Liu Gao
Published: February 2024

Improving the mechanical strength of ceramic solid electrolytes such as lithium phosphorus sulfide families for pressure-driven dendrite blocking as well as reducing the electronic conductivity to prevent a dendrite formation inside the electrolytes are very important to extend the lifespan of all-solid-state lithium-metal batteries. Here, we propose a low-temperature solution−precipitation process to prepare polymer−solid electrolyte composites for a highly uniform polymer distribution in the electrolyte to enhance their mechanical strength and reduce their electronic conduction. The composites with up to 12 wt % of polymer are prepared, and the composites exhibit high ionic conductivities of up to 0.3 mS/cm. Furthermore, the electrochemical stability of the electrolyte composites on Li striping/plating cycles is investigated. We confirm that the proposed solution precipitation process makes the composite much more stable than the bare solid electrolyte and causes them to outperform similar composites from the other existing preparation methods, such as mechanical mixing and solution dispersion.
(Invited) Designing Sustainable Battery Technologies
Authors: Kendrick Emma
Published: February 2024

Sustainability in battery technologies needs to be considered from the outset, however sustainability means many things, and needs to be considered holistically from materials, manufacturing, life-time and recyclability. Three different aspects of sustainable considerations within lithium-ion and sodium-ion technology development are discussed; materials developments, cell lifetime and optimisations, and design for recycling.

The cell is comprised of a nickel based layered oxide material cathode with hard carbon anode. To maximise energy density and life-time degradation of the bulk and surface of the O3-type oxides require stabilisation.1 We discuss the optimisation of a facile method for manufacturing a stabilised O3- type layered oxide via simultaneous doping and surface coating. A higher average voltage is obtained, which stabilised the high voltage phase transition to higher voltages, and results in longer-cycle life.2

To understand the sodium-ion cell in more detail, we have performed a detailed electrochemical analysis of a hard-carbon and layered oxide cathode and extracted parameters for multi-physics models. The kinetics and thermodynamics have been studied at different temperatures, and the limitations of the cell elucidated.

Finally design for remanufacture is also discussed, utilising water-based binder systems we show differences in delamination and material recovery. Utilising different recycling schemes through shredding and physical processing through to disassembly processes improvements in recovery rates are required. Particularly for low value materials, where the techno-economics of the processes do not currently work. Direct recycling of materials reclaimed from the batteries, wherever possible allows value within the material design to be maintained, rather than relying directly upon elemental value. Aspects of direct loop recycling and short loop recycling are discussed with respect to current lithium-ion technologies, and the ability to directly translate this to sodium-ion.3

In conclusion three aspects for sustainability considerations are discussed with respect to the materials life-cycle; active material optimisation, longevity and life-time when in use and electrode developments for recycling.4

1 T. Song and E. Kendrick, J. Phys. Mater., 2021, 4, 32004.

2 T. Song, L. Chen, D. Gastol, B. Dong, J. F. Marco, F. Berry, P. Slater, D. Reed and E. Kendrick, Chem. Mater., 2022, 34, 4153–4165.

3 G. D. J. Harper, E. Kendrick, et al. J. Phys. Energy, 2023, 5, 021501.

4 Picture created by DALL-E 2 algorithm with Nightcafe

Figure 1
3D Printed Stamps for Transfer Printing of Flexible and Wearable Supercapacitors
Authors: Gupta Khushal , Sekhar Nath Sudhansu , Sundriyal Poonam
Published: February 2024

In recent times, there has been an increasing demand for portable, lightweight, and flexible electronic devices. These electronic devices are required in healthcare, robotics, sports, defence, and other applications. Energy storage unit is one of the key requirements of these electronics and solid-state micro-supercapacitors (MSCs) are preferred for flexible and wearable electronics.[1,2] However, conventional methods of manufacturing MSCs are complex, time-consuming, and costly. This work aims to explore an alternative approach to developing MSCs by transferring electronic inks onto paper, textiles, and other flexible substrates using 3D-printed stamps. Different in-plane MSCs with varying finger widths and interspace gaps were fabricated to find the optimum electrochemical properties. The developed devices exhibit excellent electrochemical performance including high power density, high energy density, excellent lifetime, and excellent flexibility under different mechanical deformation conditions (such as bending, rolling, folding, etc.). This approach has a huge potential for fabrication of next-generation electronics for flexible and wearable electronic applications.

References:

Zhang, C., Kremer, M. P., Seral‐Ascaso, A., Park, S. H., McEvoy, N., Anasori, B., ... & Nicolosi, V. (2018). Stamping of flexible, coplanar micro‐supercapacitors using MXene inks. Advanced Functional Materials, 28(9), 1705506.

Sundriyal, P., & Bhattacharya, S. (2019). Scalable micro-fabrication of flexible, solid-state, inexpensive, and high-performance planar micro-supercapacitors through inkjet printing. ACS Applied Energy Materials, 2(3), 1876-1890.
(Invited) Science and Technology Endeavors in Lithium Ion Battery Recycling
Authors: Belharouak Ilias , Bai Yaocai , Yu Lu , Essehli Rachid , Muralidharan Nitin
Published: February 2024

The dominance of lithium-ion batteries in expanding markets such as electric vehicles is driving enormous interests in battery recycling. The growing demand is generating a huge number of spent lithium-ion batteries, thereby urging the development of cost-effective and environmentally sustainable recycling technologies to manage electrode scraps and end-of-life batteries. Currently, liuthium ion battery recycling of end-of-life batteries is still in its infancy, with many fundamental and technological hurdles to overcome. The recycling rate of waste LIBs is projected to be much behind the rapid growth of LIB market because of the complexity of the technology and its use cases. Several recycling strategies, including pyrometallurgical process, hydrometallurgical process, and direct recycling approach, are being adopted on market and under further development by researchers. Here, we provide an overview of the current state of battery recycling by outlining and evaluating the incentives, key issues, and recycling strategies. A direct recycling strategy, which is developed under the US. Advanced Battery Recycling Consortium (ReCell), will be highlighted through discussion of its benefits, processes, and challenges. Perspectives on the future energy and environmental science of this important field will also be discussed.
Using Cell Motility and Particle Tracking to Deduce Mechanisms and Kinetics Underlying Photocatalytic Water Disinfection in Real Time
Authors: Vidwans Niraj Ashutosh , Y Bhupesh Pydiraju , Sandhu Eshan , Lele Pushkar P. , Vaddiraju Sreeram
Published: February 2024

Photocatalysis is a promising water disinfection method that has the potential to complement traditional approaches to water remediation. Large-scale implementation of photocatalysis for water remediation requires a two-fold improvement to the current state-of-the-art: understanding of the mechanisms underlying photocatalyst-pathogen interaction and pathogen inactivation during photocatalysis, and a process for rapid catalyst discovery that provides for evaluating photocatalyst efficacies in a reliable manner. Toward this goal, we will discuss the use of novel tools developed in our laboratory to track the viability loss of bacterial cells inactivated by photocatalytic treatment in real time. Using optical microscopy and particle-tracking algorithms, we observed that, when exposed to titanium dioxide (TiO2) nanowire-assisted photocatalytic stressors, the change in the motility of Escherichia coli (E. coli) cells tracks viability loss precisely. Furthermore, using phase and fluorescence optical microscopy, real-time observations of the interactions between the cells and the photocatalyst nanowires were also performed. Our findings suggest that these interactions occur through collisions between the nanowires and bacteria. Based on these observations, we developed a phenomenological model explaining the pseudo-first-order kinetics of E. coli inactivation. Through the use of fluorescence-based microscopy, we observed that the motility loss (and hence viability loss) was due to the dissipation of the proton motive force that powers motility, caused by cell membrane integrity loss. Our experiments show a good match between the kinetics of motility loss and viability loss for various operating conditions, showing that the methods presented here are versatile in applicability. Overall, our results indicate that these in situ methods offer significant time-savings for characterizing viability loss of pathogens over the traditional ex-situ methods. As indicated above, these methods will also help accelerate the evaluation of novel antibacterial agents, including, but not limited to novel photocatalysts, against emerging treatment-resistant pathogens, for applications ranging from water disinfection to equipment decontamination in healthcare facilities.
Exploring the Use of Static Mixers for Enhanced Flow-Electrode Capacitive Deionization
Authors: Ceron Maira Raquel , Overland Alexandra E. L. , Hawks Steven A.
Published: February 2024

Water desalination plays a major role in alleviating water scarcity issues, but it faces major barriers due to high energy use, low water utilization, and significant environmental impacts. Flow electrode capacitive deionization (FCDI) is a new ultra-efficient electrochemical water treatment technology capable of desalinating saline streams (e.g., brackish water, seawater) with less than 10% of the feed water rejected as waste. Here we use a structured flow plate design to maximize charge transfer while incurring a negligible pressure drop penalty. Different 3D printed flow plate structures were characterized individually in a flow capacitor arrangement to quantify their relative merits in terms of the tradeoff between conductivity and flow characteristics with carbon slurries containing 5-9 wt% activated carbon and 0-1 wt% carbon black.

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 #LLNL-ABS-846456
Experimental Challenges in the Electrocatalytic Benchmarking of Multicomponent Alloys
Authors: Colic Viktor , Martinez Hincapie Ricardo Alonso
Published: February 2024

Multicomponent alloys, especially complex solid solutions (CSS), and more specifically high entropy alloys (HEA) have emerged as promising new types of electrocatalysts [1] for numerous reactions of significance for energy conversion. Their exceptional properties and the large number of degrees of freedom available for tuning their properties make CSSs promising candidates for overcoming the limitations of traditional catalysts: activity limitations imposed by the scaling, as well as stability issues.

Despite the large interest they have garnered, their potential still remains to be understood and harnessed, as their electrochemical behavior still needs to be understood. Significant experimental challenges need to be addressed and widely applied standards need to be implemented in order to understand and correctly asses the electrocatalytic behavior of such catalysts. The electrochemical surface area (ECSA) determination, identification of active sites, understanding their operando behavior, effects of crystallinity [2] as well as basic experimental challenges, such as careful Ohmic drop correction, are some of the most important experimental challenges in the electrocatalytic assessment of CSSs.

Here, an overview of CSS catalysts for the oxygen reduction reaction to date will be given (Figure 1A) [1]. Traditional methods used to evaluate the ECSA of well-known systems (e.g. noble metal electrodes) are discussed in relation to their use in CSS evaluation. For instance, the application of double layer charging current techniques, surface limited reactions and surface science techniques all have their advantages and drawbacks for the determination of the electrochemical surface area in terms of ease of application, size of errors introduced and reliability. Additionally, crystallinity (more generally, the effects of long- and short-range order, Figure 1B), phase separations, oxide layer growth and other caveats during electrocatalytic benchmarking of CSSs will be discussed.

Figure 1
In-Situ Liquid-State NMR Investigations of Lithium-Ion Battery Electrolyte Decomposition
Authors: Wahyudi Wandi , Mindemark Jonas , Edström Kristina
Published: February 2024

Liquid electrolytes play important roles in the lithium-ion batteries (LIBs). In particular, an amount of the electrolyte decomposes to form solid-electrolyte interphase (SEI) that stabilizes the electrolyte-electrode interfaces, while the remining bulk solution transports the cation between the electrodes.[1] In order to develop better electrolytes such as with improved safety and chemical stability, efforts have been devoted to understanding the electrolyte decomposition process, which are mainly performed by studying the solid products that precipitate in the SEI and gases that are released during the decomposition.[2, 3] However, the liquid products or species that are soluble in the electrolyte remain as a mystery. Here, we employ in-situ liquid-state nuclear magnetic resonance (NMR) spectroscopy to study the evolution of LIB electrolyte composition caused by the degradation process. Using the 1D and 2D NMR techniques, we confirm that some degradation products are indeed soluble in the electrolyte. The identification of these compounds gives insights into the degradation processes, which also has implications on how the long-term function of the electrolyte will be affected. Besides the new insights into electrolyte decomposition process in the LIBs, the presented techniques can be extended for studying electrolytes in a broad range of battery systems.

REFERENCES

[1] W. Wahyudi, X. Guo, V. Ladelta, L. Tsetseris, M.I. Nugraha, Y. Lin, V. Tung, N. Hadjichristidis, Q. Li, K. Xu, J. Ming, T.D. Anthopoulos, Adv. Sci.
2022, 9, 2202405.

[2] W. Wahyudi, V. Ladelta, L. Tsetseris, M.M. Alsabban, X. Guo, E. Yengel, H. Faber, B. Adilbekova, A. Seitkhan, A.H. Emwas, M.N. Hedhili, L.J. Li, V. Tung, N. Hadjichristidis, T.D. Anthopoulos, J. Ming, Adv. Funct. Mater.
2021, 31, 2101593.

[3] C. Misiewicz, R. Lundström, I. Ahmed, M.J. Lacey, W.R. Brant, E.J. Berg, J. Power Sources
2023, 554, 232318.
Introducing a Novel Light Scattering Technique for Visualising Operando State-of-Charge Changes Within Individual Active Particles and Across the Electrode
Authors: Merryweather Alice Jane , Schnedermann Christoph , Langley Cathryn Elinor
Published: February 2024

In our presentation we will demonstrate the application of a recently developed operando optical microscopy technique to mechanistic studies of lithium-ion battery electrodes and active material characterisation. Our technique probes state-of-charge (SoC) changes in the active particles within the electrode during battery operation, based on the intensity variation of scattered light across each active particle. This enables detailed spatially resolved data on an individual particle level to be utilised for furthering mechanistic understanding of battery capability and degradation, and it also allows global statistics to be established for the optimisation and screening of new electrode materials. The technique is agnostic to the underlying battery chemistry, so in principle can be applied to study any battery electrode.

In this talk, we will demonstrate how our technique can be used in the study of two key dynamic processes, solid-state ion transport and mechanical degradation. The ability to quantify ion transport during battery operation helps to provide insights into how lithium-ion dynamics affect the (de)lithiation mechanisms and degradation mechanisms of battery electrodes, which is crucial to improving their electrochemical performance. Using lithium cobalt oxide (LCO) as a case study, we will show how ion-transport mechanisms can be deduced by observing moving phase boundaries within particles during cycling.

We will then demonstrate how local SoC changes within Ni-rich nickel manganese cobalt oxide (NMC) active particles can be visualised during operation, and how the intra-particle ion gradients identified can be used to determine the mechanistic origins of first-cycle capacity losses. Building on this, we will highlight how variation in the rates of (dis)charge between a population of active particles could be used to characterise the performance of new electrode compositions.

In addition, we will highlight how lithium-ion concentration gradients can also be identified in high-rate niobium tungsten oxide (NWO) anode materials during initial lithiation and under initial rapid delithiation conditions and demonstrate how this can lead to particle cracking. Expanding on this, we illustrate how the proportion of cracked particles within an electrode can be quantified and then monitored over successive cycles as a potential metric for screening the stability of new electrode materials.
Thin-Film Electrodes Based on Conjugated Polyelectrolytes for High-Performance Pseudocapacitance in Aqueous Media
Authors: Yip Benjamin Rui Peng , Vazquez Ricardo J. , McCuskey Samantha R. , Quek Glenn , Jiang Yan , Ohayon David , Wang Xuehang , Bazan Guillermo C.
Published: February 2024

Conjugated polyelectrolytes (CPEs) are an emerging class of materials that exhibits competitive pseudocapacitive performances in their hydrogel form due to their mixed electronic/ionic conductive nature. Interest in developing solid-state electrodes based on CPEs for practical applications is needed. However, the water-soluble nature of the CPEs hinders their thin-film stability in aqueous media. Herein, we report that the slow-dried drop-casted CPE-K thin films formed a solid-state electrode insoluble in aqueous electrolyte solutions when the salt concentration is higher than 0.1 M. XRD measurements revealed that slow-dried, drop-casted CPE-K film possesses a more ordered macromolecular structure when compared to its pre-deposited powder form. DLS measurements revealed that the extent of CPE-K aggregation increases as a function of salt concentration, which enhances the stability of the films in the electrolyte solutions. In addition, AFM imaging suggests well-ordered and uniform nanostructures. As a result, it is possible to use CPE-K thin-film as a pseudocapacitive electrodes capable to maintain 85% (71 F g-1 ) of its original capacitance (84 F g-1) at a specific current of 500 A g-1. In addition, CPE-K film electrodes exhibit good cycling stability where a capacitance retention of 93% after 100,000 cycles at a current density of 35 A g-1 was obtained. To our knowledge, such high charge/discharge rates and stabilities are greater than those reported for state-of-the-art CP in any form. Further electrochemical characterization revealed that surface-controlled pseudocapacitive behavior dominates the charge-storing mechanism of the CPE-K electrodes. In addition, our electrochemical analysis suggests that facile ionic diffusion attributed to the presence of an ionic lattice in the ordered structure of the CPE-K films is responsible for the unprecedented charging and cycling performances. These findings provide a new strategy to obtain solid-state electrodes based on CPEs without the need for binders or additives. Additional advantages such as water processability, low cost, and bio-compatibility may allow CPE-K to be a sustainable solution for the future of electrochemical energy storage.
Impacts of E-Beam Irradiation on Polycrystalline Metals in Both Bulk and Thin Film Forms
Authors: Sultana Najmin Ara , Ojha Manish , Al-Allaq Aiman H , Mohammed Yousuf S , Pendleton Tilda , Baumgart Helmut , Elmustafa Abdelmageed
Published: February 2024

This study aims to explore the impact of e-beam irradiation on the mechanical and structural characteristics of four different polycrystalline metals (Ni, Cr, V, and Ti), in both bulk and thin film forms. Thin metal films are fabricated using magnetron sputtering. The primary goal is to identify suitable metal candidates for growing thin films, which could serve as exit windows for e-beam accelerators. This selection is based on their properties, power dissipation capabilities, and the effects of irradiation on mechanical attributes such as hardness, ductility, defect density, and strength.

For the bulk polycrystalline metal samples, a series of nanoindentation tests has been conducted before and after e-beam irradiation to investigate changes in hardness and elastic modulus. Additionally, to compare performance with the bulk samples, thin metal films are subjected to the same procedure before and after irradiation, allowing for the evaluation of film hardness, moduli, and creep properties. Results indicate that irradiated bulk samples of Ni, Cr, and V become harder, whereas Ti experiences softening. There is no significant irradiation effect on modulus for all for polycrystalline metal samples. To understand the underlying reasons behind these effects, both the fabricated metal films and bulk metal samples undergo comprehensive characterization tests for their microstructural properties, elastic behavior, and chemical composition. This involves the utilization of SEM with EDS, FESEM and AFM to analyze microstructure and surface attributes of the films, followed by X-ray diffraction to gain insight into film morphology and lattice orientation.
Interfacial Electrochemical Polymerization of PEDOT@Polyoxometalates Thin Films As Electroactive Material for Energy Storage Devices
Authors: Quintero Jaime Andrés , Holzinger Angelika , Cywinski Kamil , Freund Michael S , Scanlon Micheal D.
Published: February 2024

The urgent need for a decarbonized power sector has been one of the most important motivations to get a full transition from the fossil-fuel energy sources to a sustainable energy future based on renewable energy alternatives. In this regard, energy conversion and storage devices, such as batteries, fuel cells and supercapacitors, play a key role in supplying steady power and energy densities in order to guarantee the current energy demand [1]. Among the different alternatives, the design and synthesis of advanced functional nanostructured materials provide an important route to obtain efficient energy devices with high power densities, stability and remarkable energy densities [2].

Conducting polymers (CP) have been extensively exploited in a wide application range as result of their remarkable charge-mobility, electrical conductivity, and the scalable synthesis processes. Additionally, the storage of charge, which occurs by a doping process, has been ideal for application as electrochemical supercapacitors [3]. In addition, the CPs network have provided an interesting electrode material in which other active materials (i.e., graphene, MOF) and redox species can be incorporated to induce additional pseudocapacitive processes in the electrode, enhancing the charge stored. The polyoxometalates (POMs), inorganic heteropolyanions received great attention due to their multielectron redox processes in aqueous media [4].

Herein, we have explored the electrosynthesis of composite materials based on PEDOT and polyoxometalates (POMs) employing the electrochemical polymerization at a polarized organic | aqueous liquid | liquid interface (L|L), in which the POM acts as oxidizing agent of EDOT and electroactive specie incorporated in the polymer chain network as dopant. The polymerization process was based on the ion migration-controlled by the potential biasing of the water-oil interface. The resulting thin films show the presence of Mo and W within the polymer as well as the presence of different redox processes associated with the POM incorporated in the PEDOT. The induced pseudocapacitive processes in the composite materials have shown high stability in acid media, making it a good candidate as an electrode material in symmetric supercapacitors.

References

[1] F. Béguin et al, Adv. Mater. 2014, 26, 2219-2251.

[2] M. Li et al., 30 years of Lithium-Ion Batteries, Adv. Mater. 2018, 30, 1800561.

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Multi-Parameter Optimization of Siloxene-PANI Composites for High-Performance and Flexible Energy Storage Application
Authors: Deepak Nav , Kumar Arun , Shukla Shobha , Saxena Sumit
Published: February 2024

The development of high-performance energy storage devices is crucial for various applications, such as electric vehicles, portable electronics, and renewable energy systems. Supercapacitors have emerged as a promising technology due to their high power density and long cycle life. However, their low energy density has limited their widespread application. To address this limitation, researchers have been exploring various strategies, including the use of new electrode materials and optimized electrode design. In this study, a high-energy-density energy storage device was developed using a composite material composed of siloxene and polyaniline (PANI) for flexible supercapacitor designs. Here, optimized material's surface area, pore distribution, and electronic transition, achieving a specific capacitance of 483 F/g at 1A/g in a three-electrode system using a 1 M H2SO4 electrolyte. The optimized material also exhibited a retention rate of 92.6% at 5A/g. The optimized siloxene-PANI composite material was then used to fabricate a flexible asymmetrical supercapacitor (SiP4//AC). The supercapacitor exhibited a high energy density of 19.7 Wh/kg at a power density of 248 W/kg, with a cyclic stability of 90.26% and a coulombic efficiency of 97%. The flexible design of the supercapacitor using the siloxene-PANI composite material allowed for its use in wearable electronics and other applications requiring high-performance, flexible energy storage devices. The study provides valuable insights into the development of energy storage devices with high energy density and high power density, which will pave the way for the practical application of supercapacitors in various fields.
Electro-Codeposition of Composite Materials for Enhanced Thermal and Electrical Properties
Authors: Hall Timothy , Wang Dan , Le Huong , Garich Holly , Roberts Nick
Published: February 2024

State of the art cryocoolers, high powered electronic systems, semiconductor backplanes, 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, a ~50% increase in mechanical strain, and a 100% increase in thermal conductivity compared to Cu foils.

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.

Acknowledgements: Faraday Technology acknowledges the Department of Energy and NASA SBIR activities under Contract No. DE-SC0021676 (DOE Phase II) and 80NSSC22CA099 (NASA Phase II).
Effect of the Reinforcement Phase on the Electrical and Mechanical Properties of Cu-SWCNTs Nanocomposites for Potential Application on Conductors Wires
Authors: Castellanos Edgar Leonardo , Arizmendi-Morquecho Ana María , Martinez Guerra Eduardo
Published: February 2024

In this research a pre-treatment of single-walled carbon nanotubes (SWCNTs) was performed to obtain Cu-SWCNTs composites by combination of electroless deposition and powder metallurgy technique. Previously, the SWCNTs were subjected to a chemical functionalization in acid medium and coated with metallic copper to improve their incorporation into the metal matrix. The results revealed a suitable inclusion of carboxyl, carbonyl and hydroxyl groups in the nanotubes, maintaining their structural integrity. On the other hand, electroless process allowed a complete reduction of copper sulfate to a metallic copper and then a suitable carbon nanotubes incorporation into the matrix. Microhardness measurements presented an improvement of 13% compared with pure copper and, a good wear resistance (2.1x10-4 mm3/Nm) in the sample that reached the best hardness performance was observed. An increase of the wear rate with the concentration of nanotubes can also be seen, which could be related to the high porosity in this samples. Finally, the maximum electrical conductivity reached was 96% IACS in the samples with the least amount of SWCNTs which confirms their excellent dispersion into the copper matrix. Furthermore, the decrease of conductivity with high content of nanotubes (>0.1 weight%) could also be attributed to increase of nanocarbon agglomeration and porosity which acting as insulation barriers.

Figure 1
Activation Processes for Electrodeposition on Passive Nickel Surfaces
Authors: Akbarova Khavar , Leimbach Martin , Bund Andreas
Published: February 2024

Electrodeposited layer systems consisting of nickel and chromium are commonly used for decorative applications and to protect components against corrosion. Sometimes, already deposited chromium layers have to stripped again to do rework on technical parts. As a result passive layers can form at the surface of the nickel layer. This often leads to poor adhesion of subsequent layers. To prevent such adhesion problems nickel layers have to be activated to allow subsequent deposition of chromium. The thickness of the passive layers depends on the current density and treatment time during chromium stripping, as well as on the properties of the chromium layer to be removed. In summary, process fluctuations in all steps lead to an impairment of the activation effect and thus to adhesion problems.

This work will discuss recent results from a project within the framework of the Central Innovation Program for SMEs (ZIM) of the AiF. The aim of the project is to optimize the electrolyte composition and the individual treatment stages. Furthermore, the focus is on establishing measuring techniques for the various process parameters and developing a process model for the implementation of a controlled activation process in a large-scale plant. To achieve these ambitious goals, different parameter settings such as current density and treatment time were studied during the activation process and the effect of these parameters on the subsequent nickel and chromium deposition was evaluated.