bluuebunny/crossref_metadata_2025_split huggingface dataset:
Zinc Anodes with Electrodeposited Ionomer Protection Layer for Rechargeable Zinc-Air Batteries
Authors: Vacandio Florence , Knauth Philippe , Kwarteng Papa-kwakye , Pasquini Luca , Syahputra Suanto 
Published: September 2023

Metal air batteries are assembled from a metal anode and a porous cathode in a suitable electrolyte. They combine the design of fuel cells and conventional batteries and have been demonstrated to have large theoretical energy densities higher compared to devices based on Li-ion chemistry, due to the ability to use air at the cathode and to exchange two electrons per zinc atom. ZAB represent a safe, environmentally benign, affordable and simple way to store and deliver electrical energy for a wide variety of devices. However, research efforts are necessary to increase the efficiency of rechargeable ZAB and mitigate obnoxious occurrences that decrease the number of charge-discharge cycles such as zinc dendrite formation, cathode degradation and alkaline electrolyte carbonation.
The protection of zinc metal anodes in zinc-air batteries (ZAB) is an efficient way to reduce corrosion and Zn dendrite formation and improve cyclability and overall battery efficiency. The extent of improvement depends on the type and thickness of the protective layer.
In this work, we explore an advanced coating of the zinc anode by anion-conducting poly(N-vinylbenzyl, N,N,N trimethylammonium) chloride (PVBTMA) that is electropolymerized directly on the zinc metal. The Zn deposition in presence of quaternary ammonium salts and polyelectrolytes was recently studied to improve the cyclability. The major advances foreseen by this approach are excellent qualities of the metal/ionomer interface, due to the in-situ deposition process, improving the corrosion protection and the selective anion permeability; furthermore, the chosen ionomer presents a high stiffness and strength to resist the formation of zinc dendrites, due to the stiff polystyrene backbone. Moreover, the presence of a polyelectrolyte separator facilitates device miniaturization. The zinc anode protection layer was observed by optical microscopy and scanning electron microscopy (Figure : SEM micrographs of Zn pellet with PVBTMA layer: a) from 0.01 M precursor solution, b) and c) from 0.1 M precursor solution) .and the wettability of the ionomer-coated zinc surface was investigated by contact angle measurements.
The resulting ZAB battery with PVBTMA anode coating is analyzed in terms of cyclability in alkaline electrolyte and solid-state configuration using a Whatman paper separator.
The goal is to pair metal-free electrode materials with appreciable catalytic activity for oxygen reduction and evolution with a zinc anode that has a protection layer against dendrite formation to maximize efficiency.

Figure 1
In Situ Mechanical Measurements in Vanadium Pentoxide Cathodes for Aqueous Zinc-Ion Batteries during Battery Cycling
Authors: Marckx Bret A , Capraz Omer Ozgur Özgür 
Published: September 2023

Aqueous rechargeable zinc-ion batteries (AZIBs) are currently gaining traction as a potential successor to lithium-ion batteries for use in large-scale, stationary energy storage applications due to their inherent safety, low environmental impact, and low-cost. Recent advances have made breakthroughs in these anode and electrolyte stability; however, cathode development still lags preventing the commercial use of AZIBs. Vanadium pentoxide (V2O5) shows promise as a cathode material due to its low cost, environmental friendliness, and high specific capacity versus zinc (in excess of 400 mAh/g)1. V2O5 exhibits a single layer crystal structure which provides a large number of theoretical storage sites2. However, charge storage mechanisms and driving force behind the capacity fade in V2O5 are not well known yet. The lack of understanding surrounding insertion and storage mechanisms of zinc ions into V2O5 cathodes must be addressed to progress toward commercial viability.
In this study, we aim to conduct in-operando stress and stress measurements in V2O5 during battery cycling. Curvature interferometry and digital image correlation techniques will be employed for in operando stress and strain measurements, respectively the composite V2O5 cathode will consist of a 7:2:1 ratio of active material, super P, and PVDF binder. By combining stress and strain measurements, coupled with spectroscopy studies, our goal is to identify the how interfacial stress and structural strains play a role on the charge storage mechanisms in V2O5.
References:

Xu, X. et al. Enhanced charge transfer and reaction kinetics of vanadium pentoxide for zinc storage via nitrogen interstitial doping. CEJ, vol. 451, p. 3, (2023). DOI: 10.1016/j.cej.2022.138770

Tang, B. et al. Issues and opportunities facing aqueous zinc-ion batteries. Energy Environ. Sci., Issue 11, pp. 3288-3304 (2019). DOI: 10.1039/C9EE02526J
High Performance Zinc-Based Anodes for Aqueous Zinc Batteries
Authors: Fayette Matthew , Li Xiaolin , Reed David 
Published: September 2023

In the past thirty years, there has been significant development in the search for alternative energy sources such as secondary battery systems. Zinc (fourth-most mined material) has attracted much attention due to its abundance, low-cost, and recyclability. Moreover, as zinc-based batteries can be manufactured with aqueous-based electrolytes that benefits from many advantages of Zn anode, such as low redox protentional (-0.76V vs SHE), high theoretical capacity (820mAh/g), and enhanced safety. These features allow for high applicability in large-scale stationary energy storage system. Zinc-based batteries (MnO2/Zinc) have been previously commercialized and are one of the dominant technologies in the primary battery market. However, the alkaline MnO2/Zn battery is not currently considered re-chargeable due to the formation of zinc-dendrites, passivation of Zn metal, and cathode poisoning. In contrast to the alkaline system, the mild acidic system does not suffer from zinc passivation as there is negligible generation of zinc oxide/zinc hydroxide.
In this work, we report a proof-of concept work where electrodeposited zinc-based anodes (zinc and zinc-alloys) are used in mild acidic aqueous electrolyte. The study provides a comparison of commercial zinc foil, and electrodeposited zinc/zinc-alloy. The anodes are further analyzed structurally through X-ray diffraction and scanning electron microscopy. To evaluate the feasibility of each anode. further electrochemical characterization was carried out in coin cells as symmetric and full cells. The electrodeposited zinc-based anodes exhibit low electrode polarization (~0.030-0.045V), and more stable cycling performance at 10 mA cm-2 compared to commercial zinc foil. Furthermore, full cells with an electrodeposited zinc or zinc-alloy anode, DTT cathode, in 2M ZnSO4 delivered comparable capacities but higher stability compared to commercial zinc. Consequently, this work points toward a further development for anode materials in rechargeable aqueous zinc batteries for scalable applications.
Flash Pyrolyzed Coal Char for Sodium Ion Battery Anodes
Authors: Moon Jaron V , Karimi Zahra , Prlina Alex , Ginkel Chanel Van , Eddings Eric , Warren Roseanne 
Published: September 2023

Present day lithium ion batteries face challenges regarding the sustainability, cost, and natural resource availability of their components. Sodium has been shown to be a complementary energy storage material, providing usable volumetric energy density. In designing sodium ion batteries (SIBs), hard carbon is used at the anode in place of graphite, due to the necessary micro domain structure needed to store sodium ions. Coal char is a low cost material and viable source of hard carbon. The use of coal char in SIBs also provides a high value, secondary use pathway for the abundant char component of coal.
In this work, flash pyrolyzation is explored as a novel approach for coal char synthesis for SIB anodes using a Utah local bituminous coal. During flash pyrolyzation, char is heated in a drop-tube furnace at 1000 oC/s vs. the traditional slow pyrolyzation approach where char is heated at 20 oC/min. Flash pyrolyzed (FP) char has a surface structure that is vastly different in comparison to the slow pyrolyzed (SP) char (Figure 1.), larger d-spacing (FP d-spacing = 0.379 nm, SP d-spacing = 0.364 nm) and a smaller closed micropore diameter (FP micropore = 1.52 nm, SP micropore = 1.91 nm), as concluded from X-ray diffraction (XRD) and small angle X-ray scattering (SAXS) analysis, respectively.
The SIB performance of FP char vs. SP char is tested and compared in ether-based and ester-based electrolytes. FP char performs better as a SIB anode than SP char in both electrolytes. Additionally, both char anodes achieve higher reversible capacity and better initial coulombic efficiencies (ICE) in an ether-based vs. ester-based electrolyte. When FP char is combined with an ether-based electrolyte, a 10th cycle reversible capacity of 109.4 mAh/g is achieved, whereas a SP char with an ester-based electrolyte cell has a 10th cycle reversible capacity of 72.5 mAh/g, when both cells are cycled at 50 mA/g (sodium metal half-cells). FP ether cells also perform with an initial coulombic efficiency (ICE) of 64%, but SP ester cells only show an ICE value of 52%. The enhanced electrochemical performance of the FP cells is attributed to differences in surface/bulk structure due to the high heating rate. The improvement in char anode performance in ether-based cells is likely due to the formation of a thinner solid-electrolyte interphase and/or improved sodiation due to an ether-based electrolyte.

Figure 1
Interface Controls Large-Volume Change Anodes Pulverization
Authors: Kim Namhyung , Xu Yaobin , Gwalani Bharat , Cai Jiyu , Fayette Matthew , Omenya Fredrick , Li Guosheng , Gao Peiyuan , Reed David , Chen Zonghai , Wang Chongmin , Li Xiaolin 
Published: September 2023

Micron sized alloys have been considered as the most attractive candidates for advanced lithium or sodium ion battery anodes due to their high capacity, cost effectiveness, and ease of mass production. However, their large volume variation during (de)alloying reaction with Li or Na ions causes severe mechanical degradation of anode materials, resulting in particle pulverization and loss of electrical interparticle contact. In addition, this substantial volumetric fluctuation leads to newly exposed anode surface to electrolyte and instability of solid-electrolyte interphase (SEI), which can bring about continuously formation of SEI layers. To mitigate the large volume change issues of micron sized alloys, various approaches have been studied such as introducing various electrolytes and additives for stabilizing the SEI layers. However, these modified SEI layers are still not enough to suppress the large volume fluctuation of micron sized alloys.
Here, we demonstrate that the effect of interface between electrolyte and anode surface on anode pulverization. With micron sized alloying anodes for sodium-ion batteries (Bi and Sn), we observed substantially different pulverization behavior as a choice of electrolyte solvents leading to different anode-electrolyte interface. This different interface reactivity between solvents has a big impact on not only pulverization behavior of alloying anodes but also formation and growth of SEI layers on the surface of anode. Thus, the electrochemical performances of the alloying anodes also can be influenced by its interface characteristics. We thoroughly analyzed the effect of interface of alloying anode from electrode-level to nanoscale by various characterization tools such as Scanning electron microscopy (SEM), X-ray computed tomography (X-ray CT), X-ray photoelectron spectroscopy (XPS), Atom probe tomography (APT), and cryo-transmission electron microscopy (TEM). Moreover, we clarified the mechanism of the interface reaction and pulverization pathway by theoretical simulations. We believe this study can help researchers to understand the degradation behavior of large volume change alloy anodes.
Transition Metal-Doped SnO2 As Versatile Battery Electrode Material
Authors: Birrozzi Adele , Lenzer Anja , Asenbauer Jakob , Mullaliu Angelo , Bresser Dominic 
Published: September 2023

Tin oxide-based materials have been intensively investigated as alternative anodes for lithium-ion batteries due to their high specific capacity, environmental friendliness, non-toxicity, and ease of handling. However, the initial formation of Li2O upon lithiation is essentially irreversible, which has a severe effect on the first cycle Coulombic efficiency and the reversibly achievable capacity in general.[1]It has been shown that the incorporation of transition metal dopants can address this issue, as it enables the reversible formation and reformation of Li2O.[2] The choice of the dopant, however, plays a critical role for the long-term cycling stability, rate capability, and eventual energy density of the resulting lithium-ion cells.[3]

While there have been intensive studies published already on the effect of different dopants for Li-ion battery applications, targeting an optimized combination for achieving enhanced cycling performance[3] and an in-depth understanding of the reaction mechanism,[4,5] the investigation as Na-ion battery active material has not been reported so far. In fact, our results show that the reaction mechanism is fundamentally different, while the incorporation of transition metal dopants is still favorable for the eventual charge storage via sodium cations. The resulting insights into the de-/sodiation mechanism are anticipated to enable the development of further enhanced electrode active materials for sodium-ion batteries and, thus, support the recent success of this alternative battery technology.

Reference
s

[1] D. Bresser, S. Passerini, B. Scrosati, Energy Environ. Sci.
2016, 9, 3348.
[2] Y. Ma, Y. Ma, G. Giuli, T. Diemant, R. J. Behm, D. Geiger, U. Kaiser, U. Ulissi, S. Passerini, D. Bresser, Sustain. Energy Fuels
2018, 2, 2601.
[3] A. Birrozzi, J. Asenbauer, T. E. Ashton, A. R. Groves, D. Geiger, U. Kaiser, J. A. Darr, D. Bresser, Batter. Supercaps
2020, 3, 284.
[4] J. Asenbauer, A. Wirsching, M. Lang, S. Indris, T. Eisenmann, A. Mullaliu, A. Birrozzi, A. Hoefling, D. Geiger, U. Kaiser, R. Schuster, D. Bresser, Adv. Sustain. Syst.
2022, 6, 2200102.
[5] A. Birrozzi, A. Mullaliu, T. Eisenmann, J. Asenbauer, T. Diemant, D. Geiger, U. Kaiser, D. Oliveira de Souza, T. E. Ashton, A. R. Groves, J. A. Darr, S. Passerini, D. Bresser, Inorganics
2022, 10, 46.
(Best Student Presentation) Extending the NaCl-AlCl3 Phase Diagram to Enable Low-Cost, Long-Duration Na-Al Batteries for the Grid
Authors: Weller Jon Mark , Li Minyuan Miller , Polikarpov Eugenia , Han Kee Sung , Li Guosheng , Kidner Neil , Patel Anant , Jung Keeyoung 
Published: September 2023

Achieving deep grid decarbonization via intermittent renewable power sources requires extensive grid-scale energy storage technologies to deliver stable power during periods of low generation. Doing so at scale and at low cost further adds to this challenge, as current solutions generally rely on geographically limited solutions such as pumped hydro storage, or costly battery chemistries focusing primarily on Li-ion technologies. As an alternative, battery systems based on lower cost materials such as sodium offer an attractive alternative for low-cost, scalable, and non-geographically limited electrochemical energy storage.
This work combines an abundant and inexpensive molten sodium metal anode with a cost-effective aluminum cathode to provide a proof-of-concept alternative for grid-scale energy storage. Building on prior work utilizing the high reversibility of the neutral sodium chloroaluminate (NaAlCl4) molten salt electrolyte commonly used for classic molten sodium batteries, this work demonstrates greater capacity utilization of the NaCl-AlCl3 binary system by ‘overcharging’ this Na-Al battery to form an acidic chloroaluminate catholyte, NaAl2Cl7. Leveraging the reaction between NaAlCl4 and NaAl2Cl7 in conjunction with that between Al/NaCl and NaAlCl4 advantageously utilizes the majority of Na available in the cathode for capacity, in addition to providing a higher discharge voltage (~ 2 V compared to ~ 1.6 V for the NaAlCl4 reaction), thereby adding ~ 119 Wh kg-1 additional specific energy, on top of the 493 Wh kg-1 theoretical specific energy of the neutral Na-Al battery reaction between Al/NaCl and NaAlCl4.
Fundamental aspects of the acidic chloroaluminate reaction are investigated, showing that cells using only the acidic reaction are able to cycle for hundreds of cycles. The acidic reaction between NaAlCl4 and NaAl2Cl7 occurs via a solution-phase reaction, unlike the two-phase neutral reaction between NaCl/Al and NaAlCl4, and we confirm via Raman and NMR spectroscopies that complete conversion to NaAl2Cl7 occurs at end of charge. Na-Al batteries utilizing both reactions demonstrate high areal capacity (~ 46 mAh cm-2) and excellent reversibility. Enabled by the rapid mass transfer and solid-liquid reaction mechanism of the chloroaluminate catholyte, a higher areal capacity cell with ~ 132 mAh cm-2 is demonstrated, allowing a discharge duration of 28.2 h, implying that this Na-Al battery chemistry may be suitable for long-duration energy storage for grid applications. Finally, the raw active materials cost of this battery is estimated to be only ~ $7 kWh-1, which is promising for enabling low-cost renewable power utilization for the grid.

Figure 1
Development and Characterization of New Cathode Materials for Sodium-Metal Chloride Batteries
Authors: D'Urso Claudia , Frusteri Leone , Samperi Mario , Leonardi Gianluca 
Published: September 2023

Solid metal halides are used as active cathode ingredients in the case of Na-NiCl2 batteries that require a fused secondary electrolyte, sodium tetrachloraluminate (NaAlCl4), to facilitate the movement of the Na+ ion into the cathode. The sodium-nickel chloride (Na - NiCl2) battery has been extensively investigated as a promising system for large-scale energy storage applications. The growth of Ni and NaCl particles in the cathodes is one of the most important factors that degrade the performance of the Na-NiCl2 battery. The larger the particles of active ingredients contained in the cathode, the smaller the active surface available for the electrochemical reaction. Therefore, the growth of Ni and NaCl particles can lead to an increase in cell polarization resulting from the reduced active area. A higher current density, a higher state of charge (SOC) at the end of the charge (EOC) and a lower Ni / NaCl ratio are the main parameters that result in the rapid growth of Ni particles.
In light of these problems, cathode and chemistry Nano-materials with recognized and well-documented electrochemical functions have been studied and manufactured to simultaneously improve battery performance and develop less expensive and more performing, sustainable and environmentally friendly materials. Starting from the well-known cathodic material (Na-NiCl2), the new electrolytic materials have been prepared on the replacement of nickel with iron (10-90%substitution of Nichel with Iron), to obtain a new material with potential advantages compared to current battery technologies; for example, (1) lower cost of cathode material compared to the state of the art as well as (2) choices of cheaper materials (stainless steels could be used for cell components, including cathode current collectors and cell housings).
The study on the particle size of the cathode and the physico-chemical characterization of the cathode was carried out in the test cell using, where possible, the GITT method (galvanostatic technique of intermittent titration). Furthermore, the impact of temperature on the different cathode compositions of the positive electrode was being studied. Especially the optimum operating temperature is an important parameter of the active material.
A Multiscale Hollow Spherical LATP Active Filler Improves Conductivity and Mechanical Strength in Composite Solid Electrolytes
Authors: Howell Benjamin R , Patil Bebi H , Gallaway Joshua W 
Published: September 2023

The performance of composite solid electrolytes (CSEs) composed of poly(ethylene oxide) and ceramic oxide-type solid electrolyte fillers has been shown to be highly dependent on the available surface area of filler inside of the composite. This is due to the formation of new transport pathways in the polymer-ceramic interphase, a region some tens of nanometers between the bulk polymer and ceramic surface. The small volume of this interphase relative to the size of traditional particles presents a design problem: Using micron-scale filler particles, a nm-thick interphase can never occupy a meaningful volume fraction of the composite. Thus, nanoparticles are often used in CSEs. However, the inevitable agglomeration of nanoparticles prevents a continuous interphase from forming even in the best dispersion conditions. Therefore, efforts to explore and exploit this synergistic transport mechanism have so far relied on careful, slow, and expensive methods designed to yield a continuous polymer-ceramic interphase between electrodes, e.g., cast nanowires, infiltrated 3D-structures, or templating.
In this work we report a ceramic solid electrolyte, Li1.3Al0.3Ti1.7(PO4)3 or LATP, with a multiscale hollow spherical microstructure, designed to maximize the available continuous interphase volume in the composite. The hollow spherical structure is achieved by synthesizing LATP particles onto 10-15 μm carbon spheres, then subsequently pyrolyzing the carbon to achieve micron-scale hollow spheres composed of nano-scale LATP particles. This structure effectively prevents the bulk agglomeration of individual LATP particles, while still allowing for long, continuous interphase pathways. Importantly, the non-directionality of the filler means that the manufacture of the films remains simple.
The hollow spherical microstructure of the filler had significantly enhanced the room temperature conductivity of the composite solid electrolyte, to 1.64 x 10-4 S/cm – the highest reported for an LATP-containing CSE with micron-scale filler particles. The mechanical properties, thermal stability, and electrochemical stability of the composite solid electrolyte were also significantly enhanced. This approach is a promising method to exploiting the synergistic transport in composite solid electrolytes while maintaining their excellent manufacturability.
Study of Li-Si Alloy Composition for Anode Materials in Sulfide-Based All-Solid-State-Batteries
Authors: Kim Min Ju , Kang Sung , Lim Hyung-Tae 
Published: September 2023

Lithium alloys are promising anode materials with high specific capacity for all-solid-state-batteries (ASSBs). In this study, ASSBs were fabricated by consisting of Li-Si alloy anode, sulfide electrolytes and sulfur composite cathode.
During discharge-charge cycles, changes in polarization resistance in the anode and cathode were separately traced using three-electrode system of an embedded Indium reference electrode in ASSBs. As de-alloying and alloying in Li-Si anode, Li distribution and phase changes were investigated using x-ray diffraction, optical microscopy and Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMs). A half-cell was fabricated by using Indium foil as a counter electrode to study the Li ion diffusion coefficient in Galvanostatic Intermittent Titration Technique(GITT). It is observed that Li composition (22:5 ~ 1:1) in Li-Si alloy anode affected the chemo-mechanical stability and volume expansion behavior in ASSBs, which were associated with the redox behavior of sulfide solid electrolyte.