bluuebunny/crossref_metadata_2025 huggingface dataset:
Controlled Morphology Direct Iron Reduction from an Alkaline Slurry of Hematite for a Low-Cost Energy Storage Technology
Authors: Konovalova Anastasiia , Lapson Carinna , Kempler Paul A.
Published: February 2024

Iron-air batteries became a promising research direction for low-cost and long-duration energy storage. Moreover, extensive work on iron-related technologies can assist in the decarbonization of the steelmaking industry.1 To mitigate the issue of a parasitic hydrogen evolution reaction that significantly lowers the high theoretical specific capacity of the device, grafted Fe/C, as well as carbonyl-iron composite electrodes were studied.2 Despite the effectiveness of such methods and commercialization success, the complicated nature of a starting material makes it costly for plant-scale production. In this work, we are presenting the iron-plating method under alkaline conditions which is aimed to produce various morphology anodes for improved cycling in a pouch-cell with a perspective usage in the iron-air storage technology. This preparation approach of the battery component from abundant metal could replace the more emission-intensive technologies being used today. Additionally, a study on zinc monolithic anodes has proven to dramatically elevate the performance of the primary and secondary devices predicting a similar success for various metals.3 In the first cycle of the research, we discover how the faradaic efficiency and specific capacity of direct iron metal deposition from the iron (III) oxide slurry are impacted by varying temperatures of the process. Additionally, changes in the morphology and the porosity distribution are observed based on the initial controlled hematite particle size. The second cycle is dedicated to the cycling behavior of the prepared anodes. By performing a set of characterizations, we are able to account for the factors influencing the final performance of the prepared anodes. These findings allow us to better understand the feasibility of such a preparation method of the iron anode for an alternative energy storage scale-up.

Woodford, W. H.; Burger, S.; Ferrara, M.; Chiang, Y.-M., The iron-energy nexus: A new paradigm for long-duration energy storage at scale and clean steelmaking. One Earth
2022,
5 (3), 212-215.

Hang, B. T.; Eashira, M.; Watanabe, I.; Okada, S.; Yamaki, J.-I.; Yoon, S.-H.; Mochida, I., The effect of carbon species on the properties of Fe/C composite for metal–air battery anode. Journal of Power Sources
2005,
143 (1-2), 256-264.

Joseph F. Parker, C. N. C., Irina R. Pala, Meinrad Machler, Michael F. Burz, Jeffrey W. Long, Debra R. Rolison, Rechargeable nickel–3D zinc batteries: An energy-dense, safer alternative to lithium-ion. Science
2017,
356, 415–418.
Electrodeposition of Zn-Cr Alloys: A Comparison with Pure Zinc
Authors: Galeotti Francesca , Lissandrello Federico , Magagnin Luca
Published: February 2024

The electrodeposition of zinc coatings is one of the most common surface treatments for providing corrosion resistance to metallic components. From the thermodynamic point of view, zinc is located in a sweet spot, with its reduction potential being lower than most other common metals, while at the same time being not too susceptible to atmospheric corrosion; overall these features make zinc the ideal candidate for the electroplating of sacrificial coatings for corrosion protection. Owing it to its low cost and scalability, zinc electroplating has cemented itself as a cornerstone process in a variety of industrial sectors in the last decades. [1]

While zinc coatings corrosion resistance has proved to be satisfactory in most cases, it could still be improved to operate even in more aggressive environments. For this purpose, electrodeposition of zinc alloys with transition metals from the iron group (Ni, Co, Fe) has proven to be a successful method to enhance zinc coatings corrosion resistance. In particular, zinc-nickel alloys have found the greater success among them, due to improved corrosion resistance and mechanical properties. [2]

Zinc-chromium alloys also present a good opportunity to improve coatings performance, thanks to the passivating effect of Cr. In fact, electrodeposited ZnCr alloys with a Cr content up to 10.4% were found to exhibit a corrosion potential shifted by up 150 mV in the anodic direction with respect to the pure zinc counterpart. [3] This shift led to a significant decrease in the coating dissolution rate but was sufficiently small that the layers could still preserve their sacrificial nature towards the underlying steel.

In this work, ZnCr coatings are deposited on low carbon steel from an acidic sulfate formulation containing Cr(III) ions at various concentrations. The properties of ZnCr coatings are explored by varying the most common parameters such as current density, composition, and pH. Furthermore, the resulting coatings are characterized through conventional surface analysis techniques such as SEM, EDS, XRD and XRF. Finally, the corrosion resistance performance of the ZnCr coatings is compared to pure Zn coatings to highlight the benefits of the alloy.

Bibliography

[1] R. Winand, “Electrodeposition of Zinc and Zinc Alloys,” Mod. Electroplat. Fifth Ed., pp. 285–307, Feb. 2011.

[2] N. Lotfi, M. Aliofkhazraei, H. Rahmani, and G. B. Darband, “Zinc–Nickel Alloy Electrodeposition: Characterization, Properties, Multilayers and Composites,” Prot. Met. Phys. Chem. Surfaces, vol. 54, no. 6, pp. 1102–1140, Nov. 2018.

[3] V. Chakarova, T. Boiadjieva-Scherzer, D. Kovacheva, H. Kronberger, and M. Monev, “Corrosion behaviour of electrodeposited Zn-Cr alloy coatings,” Corros. Sci., vol. 140, pp. 73–78, Aug. 2018.
Silver-Rich Clusters Reveal the Initial Size of Nanoscale Network during Dealloying Via Kinetic Monte Carlo Simulation
Authors: Li Yong , Markmann Jürgen , Weissmuller Jorg
Published: February 2024

As residues of the master alloy that survived corrosion, the silver-rich clusters of nanoporous gold (NPG) fabricated by dealloying affect the functional properties of the material. Also, they are representative of the initial nanoscale network established at the beginning of dealloying. The evolution of silver-rich clusters during dealloying at different potentials is investigated via kinetic Monte Carlo simulations [1]. Our simulations show that the dealloying consists of two characteristic processes: (i) the primary process produces an initial three-dimensional bicontinuous network with silver-rich clusters embedded in the ligaments and pure gold covered on ligaments' surface. See Fig.1(a). (ii) the secondary process coarsens the ligaments and further dissolves silver from the ligaments. See Fig.1(b). The size of silver-rich clusters, L
Ag, scales with that of ligaments, L
lig, during primary dealloying for all studied potentials (Fig.1(c)). Both sizes decrease with increasing dealloying potential. The trends in size and potential are consistent with a Gibbs-Thompson-type relation (dash-dotted line in Fig.1(c)). Yet, the size of silver clusters remains invariant when the ligament size increases during secondary dealloying. Our simulations reveal that the survived clusters provided a way to measure the initial ligament size.

Fig.1. Renderings of slicing the NPG structure at different dealloying time (a-b) and the size evolution during primary dealloying (c) (Ref.[1]): (a) the primary dealloying establishes the initial 3D nanoscale network, (b) the secondary dealloying dissolves Ag clusters and coarsens ligaments, (c) inverse of Ag cluster size, L
Ag and of ligament size, L
lig, during primary dealloying as a function of dealloying potential, Φ.

Reference:

[1] Y. Li, B.-N. D. Ngô, J. Markmann, J. Weissmüller. Evolution of length scales and of chemical heterogeneity during primary and secondary dealloying, Acta Materialia, (2021) 117424.

Figure 1
Reactive Aerosol Jet Printing of 2D and 3D Ag Patterns
Authors: Gibertini Eugenio , Magagnin Luca
Published: February 2024

Printed electronics is a rapidly growing field that involves the use of printing technologies to create electronic devices such as sensors, displays, and solar cells 1. Unlike traditional electronics, which rely on rigid and bulky components, printed electronics can be obtained on flexible and lightweight substrates such as plastic and paper, allowing the development of novel applications such as wearable electronics, smart packaging, and medical sensors. Printing technologies uniquely feature miniaturization and patterning capability at low-cost and high-throughput production. Among them, screen-printing, inkjet printing (IJP) and aerosol jet printing (AJP) are the most employed to fabricate conductive metallic patterns of Ag, Au, Cu and other metal nanoparticles (NPs). These printing techniques typically requires concentrated ink of metal NPs. However, specially in the case of IJP and AJP the synthesis of very small NPs (d < 100 nm) as well as proper ink formulation and long-time stability are major limitations to printing conductive metallic patterns 2.

In this work, we propose an innovative method to produce 2D and 3D patterns and structures of Ag NPs by reactive Aerosol Jet Printing (r-AJP) on different substrates, using a custom-built aerosol jet printer. Ag NPs were in-situ reduced coupling two aerosol streams carrying the Ag precursor and a reducing agent, respectively. The process is fast, scalable and cheap. The electrical properties, in terms of both linear and areal electrical conductivity, of the r-AJP silver structures metallization patterns were investigated. Furthermore, the effect of both process parameters and precursor solution physical properties on printed Ag structure and morphology was assessed by x-ray diffraction (XRD) and scanning electron microscopy (SEM) in order to define the optimized condition for high definition 2d and 3D patterns by r-AJP.

Bibliography

P. Martins et al., Advanced Functional Materials, 33, 2213744 (2023).

Y. Sui and C. A. Zorman, J. Electrochem.
Soc., 167, 037571 (2020).
Ni-P Electroless Plating of Polyethylene Terephthalate Fibers with Various Twist Number Utilizing Supercritical CO2-Assisted Catalyzation
Authors: Kondo Hikaru , Kurioka Tomoyuki , Chiu Wan-Ting , Chen Chun-Yi , Chang Tso-Fu Mark , Ueno Roka , Jinno Arisa , Kurosu Hiromiti , Sone Masato
Published: February 2024

Weavable devices are multifunctional fabric-based devices prepared by weaving various functional fibers into a single piece of fabric. Metalized polymer fibers are promising electrical conductors for such weavable devices because of the decnet electrical conductivity derived from the metal coating and flexibility arising from the polymer fiber. However, ensuring both sufficient electrical conductivity and stability in these metalized polymer fibers for practical device application remains challenging because of the insufficent adhesion between the metal coating and polymer fiber. An electroless plating with the catalyzation step performed in supercritical carbon dioxide (sc-CO2)1 is developed to produce metallized polymers possessing high electrical conductivity and good adhesive properties between the metal coating and polymer fiber. In application, fibers are often twisted to enhance a specific property, such as the mechanical property, and the twist number (twist per meter, T/m) is expected to affect the electroless plating performance.

In this presentation, Ni-P electroless plating of polyethylene terephthalate (PET) fibers with a different twist number (twist per meter, T/m) is reported. The sc-CO2-assisted catalyzation was utilized to achieve electroless plating of Ni-P coatings on the PET fibers. The electrical resistance of the Ni-P/PET fibers was decreased following an increase in the twist number as listed in Table 1. Elemental analyses revealed that the Ni content in the Ni-P coating was higher for the PET fibers with a larger twist number. This tendency corresponded well the the electrical resistance results since Ni-P with a higher Ni content is expected to have a lower electrical resistance. Results obtained in this study indicate that PET fibers with a larger twist number is beneficial for the electroless Ni-P plating by decreasing of the electrical resistance in the fabricated Ni-P/PET fibers.

Reference

T.-F.M. Chang et al., Microelectron. Eng.
2020, 223, 111233.

Figure 1
Development of Electrodeposited Hierarchical Dendritic Wick Structure for Ultra-Thin Vapor Chamber Applications
Authors: Chiang Chao-yang , Yu Jui-Chen , Liu En-Chia , Liao Chien-Neng
Published: February 2024

Compact and light-weight electronic systems have posed stringent dimensional criteria for heat-dissipation components such as heat pipes and vapor chambers. An ultra-thin vapor chamber (UTVC) with an overall thickness below 1 mm requires an interior capillary wick structure less than 100 μm. The capillary wick layer provides a flow path for fluid circulation in an operational UTVC. The maximum UTVC heat transfer rate normally depends on liquid permeability (K) and capillary pressure (∆P) of the wick structure. Large K and ∆P values are rarely realized in typical homogeneous porous structure. In this study, a novel hierarchical dendritic copper wick was prepared to achieve large K and ∆P simultaneously by one-step electrodeposition and thermal sintering process. The effects of electrodeposition parameters, such as current density, deposition time, and solution conditions on the capillary performance of the dendritic copper wicks were investigated. The results indicate that the wicking capability is modulated by the dendritic morphology of Cu deposits. Moreover, a post-deposition sintering process can improve further the structural integrity of the Cu dendrites and the capillary performance of the electrodeposited wicks. An optimal dendritic copper wick of 30 μm in thickness possesses a promising capillary performance K/R

eff
of 0.811 μm, which is the thinnest wick reported in the literature.
Towards Extreme Fast Charging of 4.6 V LiCoO2 Viamitigating High-Voltage Kinetic Hindrance
Authors: Tang Yu , Tang Yu
Published: February 2024

High-voltage LiCoO2 (LCO) is an attractive cathode for ultra-high energy density lithium-ion batteries (LIBs) in the 3 C markets. However, the sluggish lithium-ion diffusion at high voltage significantly hampers its rate capability. Herein, combining experiments with density functional theory (DFT) calculations, we demonstrate that the kinetic limitations can be mitigated by a facial Mg2++Gd3+ co-doping method. The as-prepared LCO shows significantly enhanced Li-ion diffusion mobility at high voltage, making more homogenous Li-ion de/intercalation at a high-rate charge/discharge process. The homogeneity enables the structural stability of LCO at a high-rate current density, inhibiting stress accumulation and irreversible phase transition. When used in combination with a Li metal anode, the doped LCO shows an extreme fast charging (XFC) capability, with a superior high capacity of 193.1 mAh g−1 even at the current density of 20 C and high-rate capacity retention of 91.3% after 100 cycles at 5 C. This work provides a new insight to prepare XFC high-voltage LCO cathode materials.

Figure 1
Exploring the Electrochemical Properties of Ultrathin LiMn1.5Ni0.5O4 Films at High and Low Current Rates for Lithium-Ion Micro Battery Applications
Authors: Subash Sruthy , Karuppanan Kamala Bharathi , Lakshmanan Kumaresan , Vediappan Kumaran
Published: February 2024

The development in the miniaturized - smart electric and electronic gadgets with the advancement in technologies has dramatically enhanced the demand for cobalt free-high energy density batteries. Among various choice of high-performance cathode materials Ni substituted LiMn2O4 spinel of composition LiMn1.5Ni0.5O4 (LMNO) has proved to be one of the solutions to yield a high-performance high-energy density battery which can operate at a higher potential window. Ultra - thin films of LMNO fabricated by Pulsed laser deposition method at 600 °C substrate temperature using 2000 pulses. LMNO films fabricated on SrTiO3 (STO) and stainless steel (SS) substrates are employed for a detailed structural and electrochemical performance analysis. Disordered phase corresponding to fd3m space group of LMNO thin film exhibits better electrochemical performance compared to the ordered phase. Phase formation of LMNO thin films are studied employing X-ray diffraction and Raman spectroscopy methods. The morphology obtained for the film of thickness 41.63 nm identified from the scanning electron microscopy (SEM) images clearly reveals the effect of growth conditions such as substrate temperature and base pressure on the growth behavior of these films. Since the electrochemical data obtained for the films are area limited, the capacity of the ultra-thin film is significantly low and can be ameliorate by controlling the area. Kinetic study of LMNO film reveals that the lithium diffusion during the charge storage mechanism resembles to a diffusion-limited process similar to a faradic process. The cycling stability and rate capability at different current densities of LMNO thin film electrodes are further investigated. Charge discharge profile for both higher (25, 50, 75, 100 and 125 mA) and lower (5, 10, 15, 20, and 25 mA) current densities are obtained and subjected for 500 cycles. The thin film electrode shows a stable profile for 500 cycles. Areal discharge capacity of 1.3 μAh/cm2 is observed at a higher current density while at lower current density an areal discharge capacity obtained is 2.13 μAh/cm2 with a coulombic efficiency of around 80% and 96% respectively. Electrochemical impedance spectroscopy studies carried out on LMNO films before and after cycle shows a strong contribution of charge-transfer resistance along with film resistance and solution resistance and the equivalent circuit model for the same is evolved. Present studies indicates that LMNO ultra-thin films can be employed as a cathode layer for fabricating the all-solid thin film micro-batteries for energy applications.

Figure 1
Differences in the Ti4+/Ti3+ Redox Reactions between Li4Ti5O12 and LiTi2(PO4)3 Observed By Soft X-Ray Spectroscopy
Authors: Asakura Daisuke , Kitaura Hirokazu , Kiuchi Hisao , Miyawaki Jun , Harada Yoshihisa , Kobayashi Masaki , Amemiya Kenta , Yoshioka Satoru , Kobayashi Eiichi , Miseki Yugo , Hosono Eiji
Published: February 2024

Clarification of the redox reaction in electrode materials for Li-ion batteries is essential to obtain strategies to improve the performances such as charge-discharge capacity, voltage and cyclability. We focus on the difference in voltage, i.e., redox potential between Li4Ti5O12 (LTO) and LiTi2(PO4)3 (LTP). Spinel-type LTO with a redox potential around 1.5 V vs Li/Li+ is one of the anode materials [1], while the main redox potential of LTP (NASICON-type structure) is around 2.4 V vs Li/Li+ [2]. Although the difference in redox potential is as large as ~0.9 V, it has been thought to be that Ti4+/Ti3+ redox couple is identical for both LTO and LTP. Here, we demonstrate the electronic-structure analysis of LTO and LTP by using soft X-ray absorption spectroscopy (XAS) and soft X-ray photoemission spectroscopy (XPS). Operando Ti L
2,3-edge XAS by use of an all-solid-state cell [3,4] successfully revealed reversible Ti4+/Ti3+ redox reactions by discharge/charge for both materials, but the XAS line shapes were different. By analyzing the spectra using multiplet calculation [5], differences in the crystal-field splitting for the TiO6 octahedron and O 2p -> Ti 3d charge-transfer (CT) effect were found. The different CT effect was also confirmed by Ti 2p-3d resonant XPS measurements for the initial-state LTO and LTP samples. Moreover, the difference in redox potential is mostly explained by the energy levels of the pre-edge structures in the O K-edge XAS calibrated with the O 1s XPS spectra. In the presentation, the understandings of the spectroscopic results will be discussed in detail.

References

[1] K. M. Colbow et al., J. Power Sources
26 (1989) 397-402.

[2] C. Delmas et al., Solid State Ionics
28-30 (1988) 419-423.

[3] K. Akada et al., Sci. Rep.
9 (2019) 12452.

[4] K. Akada et al., J. Electron Spectrosc. Relat. Phenom.
233 (2019) 64-68.

[5] E. Stavitski and F. M. F. de Groot, Micron
41 (2010) 687-694.
Visualization of Lithium Plating Morphologies on Graphite Electrode By O
perando X-Ray Tomography
Authors: Klein Antoine , Sadd Matthew , Mozhzhukhina Nataliia , Olsson Martina , Xiong Shizhao , Matic Aleksandar
Published: February 2024

The plating of lithium metal on graphite electrodes in Li-ion batteries is a major factor limiting the fast charging of electric vehicles. Lithium metal plating leads to the growth of dendritic structures that can pierce through the battery’s separator resulting in an internal short circuit and catastrophic failure of the battery. Moreover, the plating of lithium metal on graphite is not reversible, manifesting in poor Coulombic efficiency, severe reduction of the battery’s life expectancy, and safety issues. Understanding how and when plating occurs in Li-ion batteries is crucial in the development of strategies to prevent plating under fast charging conditions. Thus, we have conducted an operando X-ray tomographic microscopy experiment to directly monitor the plating of lithium metal in a Li/Graphite cell when applying electrolytes with the additives vinylene carbonate (VC) and Lithium bis(fluorosulfonyl)imide (LiFSI). The experiment was performed at the ID19 beamline (ESRF, France) where tomographic scans, linked with the lithiation state of graphite, made it possible to gain a strong understanding of the mechanisms behind Li-deposition and stripping at high current rates in addition to understand the effect of the VC and LiFSI additives.
(Invited) Electrodeposition of In and Ga from Non-Aqueous Electrolytes
Authors: Fransaer Jan , Monnens Wouter
Published: February 2024

Indium and gallium are metals whose applications have increased during the last decades. Both metals are primarily used in the form of binary, tertiary or quaternary (semi)conductor compounds in integrated circuits, photovoltaics, liquid crystal display devices, lasers and light-emitting diodes.

In the past, the electrodeposition of indium and gallium has been investigated from both aqueous and non-aqueous electrolytes. Due to the negative standard reduction potentials of the two metals (E°In(III)/In(0) = −0.34 V and E°Ga(III)/Ga(0) = −0.53 V), their electrodeposition from aqueous electrolytes is hampered. This is especially true for gallium. In this talk, the electrodeposition of indium and gallium was investigated from several organic solvents. The investigated electrolytes are 1,2-dimethoxyethane (DME), polyethylene glycol (PEG), dimethyl sulfoxide (DMSO), and acetonitrile, containing chloride, bistriflimide, or methanesulfonate-based indium or gallium precursors.

The electrochemistry and the electrodeposition of indium and gallium was studied using various electrochemical methods in combination with quartz crystal microbalance (QCM) and rotating (ring) disk electrodes. DMSO-based electrolytes enabled the electrodeposition of indium at room temperature and above its melting point (159.6 °C), while DME electrolytes gave rise to gallium electrodeposits composed of small liquid gallium spheres (Fig 1). In all the investigated electrolytes, the formation of intermediate monovalent indium(I) or gallium(I) species during reduction and oxidation was demonstrated. These species are unstable and react away via disproportionation reactions. Yet, it was found that the extent of their formation and their stability depends on the nature of the electrolyte. In addition, the electrodeposition of indium antimonide (InSb) films and eutectic gallium indium (EGaIn) liquid metal lines and patterns will be discussed, as well as the electrochemical synthesis of spherical indium nanoparticles.
Influence of Cyclic Alkyl Carbonate Ring-Opening Processes on Electrode/Electrolyte Interphase Formation in Li-Ion Batteries
Authors: Gogoi Neeha , Berg Erik J.
Published: February 2024

Cyclic alkyl carbonates, such as ethylene and vinylene carbonate (EC and VC), form solid electrolyte interphases (SEI) suppressing continuous solvent reduction at the graphite anode. There is a consensus that the choice of carbonate clearly affects SEI performance. VC has been observed to polymerize, forming poly(VC), but also to release major amounts of CO2,1,2 which are two seemingly contradictory processes. In this work, we present a detailed study of reaction pathways of EC and VC in typical Li-ion battery electrolytes. The rate of the decomposition reactions of these carbonates in presence of hydroxide is monitored using an injection cell coupled mass spectrometer at varying temperatures ranging from 30°C to 60°C. The activation energies from the Arrhenius relationship between the CO2 evolution rate and the cell temperature confirms that VC hydrolysis is autocatalytic rather than stoichiometric. Direct quantifications and comparisons of the solubilized reaction products will be done over varying times and temperatures with the help of in-situ nuclear magnetic resonance (NMR) and Raman spectroscopy that will help in clarifying the individual steps in the reaction process. The kinetic studies of EC and VC hydrolysis in model systems like this is an important step towards improving our understanding towards carbonates as there is always some trace amounts of hydroxides present in the cells. The complex interconversions and equilibria of these organic alkyl carbonates and oxides investigated herein, will add to the knowledge of interphase formation processes, and support the tailoring of electrolyte formulations in order to enhance performance of future Li-ion batteries.

References:

(1) Sasaki, T.; Abe, T.; Iriyama, Y.; Inaba, M.; Ogumi, Z. Formation Mechanism of Alkyl Dicarbonates in Li-Ion Cells. J. Power Sources
2005, 150 (1–2), 208–215. https://doi.org/10.1016/j.jpowsour.2005.02.021.

(2) Ota, H.; Sakata, Y.; Inoue, A.; Yamaguchi, S. Analysis of Vinylene Carbonate Derived SEI Layers on Graphite Anode. J. Electrochem. Soc.
2004, 151 (10), A1659. https://doi.org/10.1149/1.1785795.

Figure 1
Pushing the Energy-Lifetime Frontier of Li-Ion Batteries with Optimized Ni-Rich, Co-Free NMA-W Cathodes
Authors: Hamam Ines , Omessi Roee , Dahn Jeff R.
Published: February 2024

Especially in the electric vehicle industry where both high energy density and long lifetime batteries are sought, Ni-based cathode materials such as LiNi1−x−yMnxCoyO2 (NMC) and LiNi1−x−yCoxAlyO2 (NCA) provide a fitting compromise in capacity and cyclability. In recent years, the high cost of cobalt in addition to the problematic geopolitics surrounding cobalt mining have motivated research efforts toward cobalt-free cathode materials.1 However, Ni-rich materials are subject to inevitable failure mechanisms such as microcracking and parasitic reactions with the electrolyte which are further aggravated with an increase in Ni-content and in the absence of Co.2 Many strategies have been proposed to overcome these challenges such as doping and/or coating the cathode particles,3 but there remains a need to further increase energy density with minimal compromise to lifetime.

In this work we present a cathode active material system designed to push Ni-rich and Co-free materials to the limit of their performance. This is done by choosing optimal polycrystalline particle size, a balance of Mn and Al content, and a sufficient amount of high-valence doping. Additionally, appropriate synthesis conditions are needed to obtain the desired morphology and infuse the intergranular boundaries with the W dopant. It is then important to choose an appropriate upper cutoff voltage during cycling to maximize energy while avoiding drastic crystal changes.4 This optimized NMA-W material system delivers specific capacity above 200 mAh/g while retaining 95% of its capacity without relying on any amount of Co.

The series of NMA-W materials presented in this work were characterized and tested. Scanning electron microscopy (SEM) images were used to observe morphology and crystallite growth after synthesis. X-ray diffraction (XRD) analysis was conducted to monitor the crystal parameters and accelerated rate calorimetry (ARC) was used to assess the thermal stability and safety of the material. Compression tests were also conducted to study the strength of the particles and their propensity to crack under stress.

Choi, J. U., Voronina, N., Sun, Y. K. & Myung, S. T. Recent Progress and Perspective of Advanced High-Energy Co-Less Ni-Rich Cathodes for Li-Ion Batteries: Yesterday, Today, and Tomorrow. Adv. Energy Mater.
10, 1–31 (2020).

Li, H. et al. An Unavoidable Challenge for Ni-Rich Positive Electrode Materials for Lithium-Ion Batteries. (2019) doi:10.1021/acs.chemmater.9b02372.

Yan, W., Yang, S., Huang, Y., Yang, Y. & Guohui Yuan. A review on doping/coating of nickel-rich cathode materials for lithium-ion batteries. J. Alloys Compd.
819, 153048 (2020).

Nam, G. W. et al. Capacity Fading of Ni-Rich NCA Cathodes: Effect of Microcracking Extent. ACS Energy Lett.
4, 2995–3001 (2019).
Extending Cycle Life of Li-Ion Batteries Via Gas-Phase Nanocoating of Cathode Active Materials
Authors: Behboudikhiavi Sepideh , Moitzheim Sébastien
Published: February 2024

The further penetration of the electric vehicles is dependent on the development of high-performance Li-ion batteries in terms of cost, cycle life, energy density, safety as well as sustainability. It is expected, in the short term, EVs will rely more on Li-ion technologies using active materials such as Ni-rich NMC cathode and Si anode for developing high specific energy and lower cost batteries1.

However, these active materials are facing multiple serious challenges which could hinder their targeted performance. Regarding this, Ni-rich NMC cathode active materials (CAM), in spite of their high energy density as a result of higher Ni content, tend to undergo dramatic capacity fade.

Since most degradation mechanisms are related to the surface of active materials, immense research and development efforts have been dedicated to surface modification techniques, and especially coating strategies2,3.

Examples of surface modification strategies include sol-gel, hydro/solvothermal deposition, and dry coating. A main drawback of these techniques is that they are not capable of precise control of the film thickness and uniformity. On the other hand, gas-phase coating techniques, such as atomic or molecular layer deposition, can address these shortcomings by offering a precise thickness control even in the range of angstroms and pinhole-free conformal coatings. As such, these coatings are better suited at mitigating interfacial degradation. Various nanocoating chemistries, such as oxides, fluorides, nitrides, phosphates and aluminates protect and stabilize the surface of Ni-rich cathode materials through the different pathways.

In this talk, we explore the benefits of gas-phase nanocoatings, and will show how we can produce surface modified Ni-rich CAM (e.g. NMC-811) in a continuous process that is ready for mass production.

References

M. S. E. Houache, C. H. Yim, Z. Karkar, and Y. Abu-Lebdeh, Batteries, 8 (2022).

D. Weber, Đ. Tripković, K. Kretschmer, M. Bianchini, and T. Brezesinski, Eur. J. Inorg. Chem., 2020, 3117–3130 (2020).

M. Lee et al., Chem. Mater., 34, 3539–3587 (2022).

Y. Zhao, K. Zheng, and X. Sun, Joule, 2, 2583–2604 (2018).
K0.5FeF3 as a New Zero-Strain Cathode Material for Lithium-Ion Batteries
Authors: Vogt Alexander , Geßwein Holger , Chable Johann , Baumann Aljoscha , Mutter Daniel , Urban Daniel F , Elsässer Christian , Lhoste Jérôme , Binder Joachim R.
Published: February 2024

The stability of the cathode is of crucial importance for the service life of lithium-ion batteries (LIB). In the cathode, the lattice parameter usually changes during (de-)insertion of lithium, which causes various signs of aging that have a negative effect on the capacity of the cell. This problem can be tackled using a specific type of materials called zero-strain (ZS) materials. These materials do not show any (de-)intercalation-induced structural changes and stresses. Such a zero-strain effect was already demonstrated with fluorine-containing materials [1] and even for the similar material K0.6FeF3
[2] for sodium-ion batteries (SIB). In this case, potassium ions are removed in the first cycle and the vacant lattice sites can be used for the incorporation of sodium ions, while keeping the structural integrity of the host material.

Complementary to experiments, theoretical atomistic simulations are powerful to develop design criteria for further ZS-materials. Combining experiments and simulations in this work, the structural behavior of the material K0.5FeF3 was investigated when used as a cathode material in a LIB. The synthesis of K0.5FeF3 was achieved by a Rapid Microwave-Enhanced Solvothermal Process, which allowed to obtain the material in a TTB-type (Tetragonal Tungsten Bronze) phase with a high degree of purity. The material was then processed into electrodes, which were galvanostatically cycled against lithium metal. It was shown that the material is suitable for LIB as a cathode material. X-ray diffraction experiments showed that the lattice parameter changed by less than 1% after the incorporation of Li-Ions, in good agreement with the theoretical calculations conducted in parallel.

Lattice Parameter

Charged

Discharged

a[Å]

12.74±0.024

12.73±0.006

c[Å]

3.99±0.008

4.00±0.002

Volume [Å3]

647.57±2.67

647.75±0.76

This work was supported by the German Research Foundation (DFG) BI 1636/7-1 and EL 155/29-1.

References

[1] De Biasi, L., et al. Journal of Power Sources, 2017, 362. Jg., S. 192-201.

[2] Han, Y., et al. Journal of Materials Chemistry A, 2016, 4. Jg., Nr. 19, S. 7382-7389.

Figure 1: Diffractograms of an electrode with K0.5FeF3, which was measured before use and an electrode after the first successful discharge, down to a voltage of 1.8 V.

Figure 1
Thermodynamic Stability of LixNiO2 and Polyvinylidene Difluoride Materials for Lithium+ Ion Batteries
Authors: Penrod Megan , Smith Benjamin , Coates Chloe , Rosner Maria , O'Keefe Christopher A. , Hall David S. , Grey Clare P.
Published: February 2024

LixNiO2 (LNO), a layered Li-ion battery cathode has been investigated for decades. LNO has been shown to proceed through multiple phase transitions at different states of lithiation as well as at different temperatures. However, in these experiments it has always been paired with additional materials typically found in the creation of cathodes, such as carbon black, aluminum foil and polyvinylidene difluoride binder. This paper investigates the thermal stability of LNO as a stand-alone material as well as a component of a traditional cathode through performing thermal gravimetric analysis (TGA), variable temperature powdered X-ray diffraction (VT-PXRD) and solid-state nuclear magnetic resonance (ss-NMR) at different states of lithiation and high temperatures. The reduction to nickel metal was found at temperatures exceeding 500 °C for the traditional cathodes at all states of charge due to the creation of lithium fluoride from hydrogen fluoride gas being released as polyvinylidene difluoride degrades. Nickel metal was also identified for the stand-alone LNO at lithium concentrations greater than x = 0.32 at temperatures of 600 °C as the system becomes depleted of oxygen and lithium due to the creation of lithium oxide. These finding indicate that the thermal stability of LNO at temperatures over 200 °C is sensitive to the presence of fluorine as well as the state of charge of the battery. Typical batteries do not reach these temperatures during cycling, but in the case of thermal runaway and recycling it is important to know the chemical reactions occurring at these temperatures and concentrations as toxic and corrosive hydrogen fluoride gas is released. An investigation into less fluorinated binder options is desirable to reduce the addressed issues.
In-Situ Formation of Low-Strain and Defect-Free Single Crystal NMC in Electrode Slurries
Authors: Carrier Laurie , Obrovac Mark
Published: February 2024

Synthesis of cathode materials for lithium-ion batteries usually results in agglomerations of single crystals.[1][2] Jet milling is commonly used in industry to deagglomerate cathode material powders.[3] However, dry grinding techniques can often lead to the introduction of defects, requiring a reheating step to reform pristine NMC. Wet milling in water has also been proposed, however, this results in lithium loss and crystal defects, again requiring additional drying and reheating steps are required to reform pristine NMC.[4][5]

Here we report a low-strain and defect-free NMC deagglomeration method that is performed in-situ during the electrode slurry dispersion process. In this method, cathode material, conductive additive and binder are planetary milled in N-methyl-2-pyrrolidone (NMP). This results in both the deagglomeration of cathode secondary particles and the formation of a well-dispersed electrode slurry. Figure 1(a-d) compares the SEM images of NMC samples deagglomerated by different dry grinding techniques and the in-situ slurry milling method. Figure 1(e) and (f) show lattice strains and the first cycle voltage curves of the same samples. In comparison to the dry grinding techniques, in-situ slurry milling was found to be more effective in secondary particle deagglomeration than dry methods and resulted in a single crystal NMC with the lowest lattice strain, lowest irreversible capacity, and highest coulombic efficiency. In fact, in-situ milling was found to reduce lattice strain compared to the original agglomerated cathode material, by relieving internal strains created at the grain boundaries of secondary particles. We believe that in-situ slurry milling is an effective method for NMC particle deagglomeration and improving NMC performance.

References:

[1] Zheng, L.; Bennett, J.C.; Obrovac, M.N. J. Electrochem. Soc.
2020, 167, 130536.

[2] Lee, S.-Y.; Park, G.-S.; Jung, C.; Ko, D.-S.; Park, S.-Y.; Goo Kim, H.; Hong, S.-H.; Zhu, Y.; Kim, M. Adv. Sci.
2019, 6, 1800843.

[3] Gommeren, H.J.C.; Heitzmann, D. A.; Molenaar, J. A. C.; Scarlett, B . Powder Technol.
2000, 18, 147-154.

[4] Kumakura, S.; Paulsen, J.; Yang, T.; Yang, H. Han, S.-Y. US 2020/0381727 A1, 2020.

[5] Paulsen, J.; Kumakura, S.; Yang, T.; Kim, D.-H.; Yang, H. US 2021/0143423 A1, 2021.

Figure 1
Dual Electrolyte Design for Lithium-Ion Batteries
Authors: Pechberty Clément , Reiner Sofia , Johansson Patrik
Published: February 2024

Lithium-ion batteries (LIBs) are today the most used energy storage for portable electronics and electric vehicles – but are laden with concerns of materials scarcity and availability. The development of high-voltage cobalt-free cathode active materials such as LiNi0.5Mn1.5O4 (LNMO) represents one promising route for next-generation LIBs due to their combination of high capacity and low cost. Combining LNMO with conventional LIB electrolytes based on carbonate solvents, however, typically leads to severe capacity fading due to a range of different degradation mechanisms1, not the least due to the wide electrochemical stability window (ESW) needed for a graphite//LNMO cell.

Here we use the rather novel route to design LIB cells by utilizing two different electrolytes to together cover the full ESW2. The separation of the two electrolytes is assured by designing them to be immiscible, either chemically or more mechanically, while for the functionality of the cell we also monitor the evolution of a stable solid electrolyte interphase (SEI) at the anode side and a stable cathode electrolyte interphase (CEI) at the cathode side. This proof-of-concept study allows us to shine light on the best ways to design a dual electrolyte cell.

References

K.
Guo et al.
,
“
High‐Voltage Electrolyte Chemistry for Lithium Batteries
”,
Small Science 2, 2100107 (2022).

S.
He et al.
,
“
Design of a Dual-Electrolyte Battery System Based on a High-Energy NCM811-Si/C Full Battery Electrode-Compatible Electrolyte
”,
ACS Appl Mater Interfaces 13, 54069–54078 (2021).
Fabrication of Si Anode for Enhancing Electrochemical Performance by Electrodeposition Method
Authors: Patel Yashkumar , Vanpariya Anjaliben , Mishra Atul
Published: February 2024

Silicon (Si) is one of the most abundant elements in the earth's crust and is important for the development of semiconductors, solar cells, and lithium ion battery (LIB)electrodes. silicon nanomaterials-based device production is currently hampered by high prices, high material consumption, and very sophisticated procedures of film deposition, including chemical vapour deposition (CVD) and plasma-enhanced chemical vapour deposition (PE-CVD).Future demand will need the development of cost-effective, simple, and high-throughput deposition techniques.moreover A large-scale use of Si anodes in LIB is hindered primarily by two factors: (a) a significant volume change (about 300%) during discharging and (b) the deterioration of silicon after several charging and discharging cycles. By covering silicon nanostructures with carbon nanomaterials that also improve the electrochemical performance of LIBs, these disadvantages may be eliminated. In order to meet all of these requirements, the electrodeposition approach may provide the means to create Si thin films in an aesthetic way. We studied We used water-contaminated BMImTf2N to electrolyze SiNPs on Graphene (Grn) -coated copper substrates at room temperature.SiNPs average 70-90 nanometres (nm). Grn layer on the Cu substrate enhances Si nucleation and prevents oxidation. At 0.5C, the charge capacity was 1350 mAh g-1 and the discharge capacity was 1588 mAh g-1. The columbic process's efficiency increased from 85% to 97% after 100 cycles. Grn's conductivity and volume expansion will boost Si's cycle life.

Figure 1
Electrochemical Performance of Dry Processed Graphite Electrode with PTFE Binder for Lithium-Ion Batteries
Authors: Hwang Jun Ho , Yoo Hyundong , Oh Seungeun , Kim Junho , Kim Seungeun , Kim Hansu
Published: February 2024

Both cathode and anode in Lithium-ion batteries (LIBs) are being manufactured by slurry coating process; however, currently used wet coating process has some drawbacks, including the difficulty in further increasing the electrode thickness as well as high fabrication cost mainly due to the use of facility for drying process. To address these issues, dry electrode fabrication process has been proposed and actively investigated as an alternative electrode manufacturing process. Dry electrode fabrication process with PTFE binder offers several advantages over conventionally used slurry coating process such as high manufacturing efficiency due to the non-solvent process and the ease of increasing the electrode thickness resulting from fibrillization of the PTFE binder. However, the instability of PTFE binder in dry processed graphite anodes remains a challenge, as the irreversible reaction of PTFE binder leads to the deterioration of the electrode. Furthermore, the properties of graphite materials including specific surface area, the particle size and shape can also affect the microstructure of the electrode and the electrochemical performance of graphite anode. In this work, the relationship between the properties of graphite and the electrochemical performance of dry processed graphite anode was investigated using various analytical techniques and the electrochemical characterization techniques. More detailed analyses results will be discussed in the presentation.
Thin-Film SiOx Coated Carbon Nanofibers As Stable Anodes for Lithium-Ion Batteries
Authors: Kim Na-Yeong , Jung Ji-Won
Published: February 2024

With the increase in the capacity of cathode materials in lithium-ion batteries(LIBs), the demand for novel anode materials with high theoretical energy density is following. Up to now, many candidates have been reported; silicon-based composites are considered a prospective alternative due to their abundant reserves and high energy density. However, The primary disadvantage of Si, electrochemical irreversibility during the charge/discharge process, hinder widespread use.

In this study, we adapted SiOx-coated carbon nanofibers (SiOx-CNFs) composite to the binder-free anode current collector for lithium-ion batteries. The composite has a structure where a thin amorphous SiOx (thickness ~100nm) is coated on the CNFs surface and is successfully synthesized by electrospinning and sputtering. This structure, surface SiOx-coated porous CNF, breaks through the significant drawback of Si-based composites, pulverization of Si element during the charge/discharge cycle. In addition to this, due to the structure of porous CNF, we achieved the curtail of electrode weight.

Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD) analyses are carried out to confirm the morphology and crystallinity. Furthermore, with cyclic voltammetry analysis, fast reaction kinetics and excellent electrochemical reversibility are verified. The cycle test is also conducted to prove excellent capacity and cyclic stability.
Highly Lithiophilic Oxidative Interfacial Layer for 3D Foam-Based Lithium Metal Anode: Lithium Impregnated Metal Foam Anode (LIMFA)
Authors: Choi Yusong , Lee Jaein , Ahn Tae-Young , Ha Sang-Hyeon
Published: February 2024

Numerous lithium-infused (or impregnated) lithium-metal anodes using pure Ni foams with excellent properties have been developed for use in Li batteries. However, pure Ni exhibits high reactivity with molten Li during infusion (e.g., coating, impregnation, etc.). Herein, a high-performance and ultra-stable (against molten Li) lithium-impregnated metal foam anode (LIMFA) is fabricated by a simple oxidation of nickel based alloy foam at 900 °C in air. A symmetric cell test employing the LIMFA anode showed stable stripping and plating performance. For thermal batteries without cup, LIMFA provided the highest reported specific capacity and first discharge of molten Li. After the cell discharge, the Ni based foam exhibited no Li leakage, surface damage, or structural collapse. Given these advantageous properties, in addition to its high specific capacity, LIMFA is expected to aid in the development of thermal batteries with enhanced performance.
High-Voltage Graphite//LiNi0.5Mn1.5O4 Full Cell with Bis(fluorosulfonyl)Imide and bis(trifluoromethyl)Sulfonylimide Ionic Liquid Electrolytes
Authors: Rath Purna Chandra , Chang Jeng-Kuei
Published: February 2024

Room-temperature ionic liquids (ILs) are a promising type of lithium-ion battery (LIB) electrolyte owing to their wide electrochemical stability windows, high thermal stability, non-volatility, and environmental friendliness. Particularly, bis(fluorosulfonyl)imide (FSI−)-based ILs are appealing due to their high ionic conductivity, low viscosity, and excellent anode compatibility. Nevertheless, the strong corrosivity of FSI− toward the Al current collector at high operating potential is a major concern and needs to be addressed. Three strategies have been adopted in this work to overcome this limitation. The effects of IL composition on the electrochemical properties of the LiNi0.5Mn1.5O4 (LNMO) cathode and graphite anode are investigated. First, Li+ fractions are modulated in the N-propyl-N-methylpyrrolidinium−FSI (PMP−FSI) IL. We find that simply increasing the LiFSI concentration (even to 3.2 m) in the PMP−FSI IL electrolyte cannot effectively inhibit Al corrosion, leading to a low charge-discharge Coulombic efficiency (CE) of the LNMO electrode. Second, increasing the bis(trifluoromethyl)sulfonylimide (TFSI−)/FSI− molar ratio leads to a reduced rate capability of the LNMO cathode and a unsatisfactory compatibility with the graphite anode. Finally, we propose a Li+/TFSI−/FSI− modulation concept to optimize the IL electrolyte. The optimal 2.4 m LiTFSI/PMP−FSI IL electrolyte minimizes the corrosion current of the Al substrate at 5 V. Moreover, the relatively high Li+ and FSI− content ensures superior charge-discharge properties of both the LNMO and graphite electrodes. A high reversible capacity of approximately 135 mAh g–1 at 0.1 C based on LNMO is verified for a graphite//LNMO full cell. This cell is able to retain ~85% of its initial capacity after 200 cycles. The obtained experimental results can guide the development of IL electrolytes for high-reliability LIBs.