bluuebunny/crossref_metadata_2025 huggingface dataset:
Interrelations between Dendrite Growth and Electrolyte's Microstructure in Garnet Type Solid Electrolyte
Authors: Raj Vikalp , Mitlin David , Aetukuri Naga Phani B.
Published: December 2024

Solid state lithium metal batteries incorporating ceramic solid electrolytes are visioned as a promising alternative for future energy storage. However much has to be investigated regarding the electro-chemo-mechanical stability of these electrolytes. Herein we investigate the role of microstructure of garnet type ceramic solid electrolyte in lithium dendrite propagation. Clear evidence of dendrite favoring the growth along the grain boundaries is observed which suggests the role both mechanical and electronic properties of solid electrolyte plays in dendrite propagation. Furthermore, in our present study, tantalum-doped LLZTO with a nominal composition of Li6.4La3Zr1.4Ta0.6O12 was fabricated using two approaches: one involving conventional powder processing followed by reactive sintering, and the other incorporating an intermediate-stage high-energy milling step. These fabrication routes resulted in distinct microstructures, influencing their electrochemical behavior during extended cycling. The relation between the two was then analyzed in detail using surface science and bulk techniques, as well as quantitative stereology. Notably, our findings demonstrate for the first time that compact grain size distribution critically affects short-circuit failure. Lithium metal dendrites propagate intergranularly along "weak-links" in the microstructure, characterized by percolating arrays of LLZTO grains significantly smaller than the average. Additionally, lithium metal accumulates inside the pores along the dendrite's path through the compact. These observations underscore the role of enhanced electrical conductivity—specifically, electron accumulation—in the dendrite-driven failure phenomenology. Complementing the experimental findings, mechanistic modeling was employed to provide a comprehensive understanding of the interrelations between microstructure, chemo-mechanical stress, and electrochemical stability in garnet-based solid-state electrolytes.

Figure 1
Lithium Dendrite Deflection in Solid Electrolytes through Mixed Ionic-Electronic Conducting Interlayers
Authors: Yu Zikang , Gan Chenjie , Mijailovic Aleksandar S , Stone Aidan , Hurt Robert , Shi Changmin , Sheldon Brian W.
Published: December 2024

Solid state lithium metal batteries using garnet solid electrolytes such as LLZTO (Li6.4La3Zr1.7Ta0.3O12) can enable substantial improvements in energy density and safety. However, lithium dendrite penetration at high current densities in LLZTO limits its practical development. In this work, we propose a laminated composite architecture consisting of reduced graphene oxide embedded between LLZTO discs to form a mixed ion-electron conducting interlayer that provides electro-chemo-mechanical synergistic advantages for suppressing dendritic penetration. The critical current density using a single-sided Li plating testing protocol was increased from 0.55 to 3.8 mA·cm-2 at room temperature. In addition, Li-Li symmetric tests showed stable cycling at 0.5 mA·cm-2 for over 500 hours. A finite element simulation of these multi-layered structures also provides additional insight into the design of multilayered structures. The overall results provide a promising proof-of-concept demonstration along with important design guidelines for multilayered architecture that can potentially enable high performance solid-state batteries.
Solid State Gradients: One Step Aqueous Spray Deposition of Novel Graduated Cathode/Solid Electrolyte Interfaces for Improved Solid State Batteries.
Authors: Tudball Matthew , Miller Thomas Samuel
Published: December 2024

Lithium ion batteries are a necessity of daily life, being used more than ever in increasing size and power for applications like handheld devices, large scale energy storage and transport. They also offer huge potential in our shift towards renewable energy, therefore the production and use of these batteries is set to increase dramatically.

Solid state batteries (SSB’s) replace the liquid electrolyte with a solid. This offers more stability against lithium dendrite formation which is the main cause of battery short-circuiting and failure. Because of this, solid state electrolytes (SSE’s) may be the answer to the challenge of pure lithium anodes, which are the highest theoretical capacity anode, but are hampered by rapid dendrite formation. SSE’s can have higher gravimetric and volumetric capacity due to the reduced electrolyte content and also make for safer batteries, particularly under stress, as the flammable liquid electrolyte has been removed.

This work demonstrates a new manufacturing method for SSB’s, that allows for the formation of a novel design of the electrode/electrolyte interface. Ultrasonic spray coating is the process of spraying a material layer by layer to form thin films. By graduating between two or more different materials a gradient can be manufactured.

Current SSB’s are formed by separately manufacturing a cathode film and a solid electrolyte film, then assembling these on top of each other to make the battery. This can cause interface issues between the cathode and the SSE, particularly, areas of poor contact, poor solid electrolyte interface (SEI) formation and degradation of the cathode. All of these issues lead to higher resistance, lower capacity and higher degradation.

This work shows that a spray deposited graduated combined cathode/SSE removes the interfacial issues seen in the literature to create a battery that has 10x lower resistance, longer cycle life, lower capacity loss and performs substantially better under high rate conditions. All of which are necessary to help solid state batteries become more real world applicable.

This new manufacturing technique is the only known way to produce this structure in a cheap, industrially relevant way, and is easily expandable to a larger scale. On top of this, unlike standard manufacturing methods, the methodology is almost entirely water based, which removes costs of solvent recapture and increases safety.

This layer by layer gradient deposition technique is also applicable to other areas of materials research and has been used on silicon anodes and lithium sulfur batteries, as well as membranes for direct air capture and fuel cells.

Figure 1
An All-Solid-State Lithium Metal Battery Integrating LiNiO2 Cathode with Halide Solid Electrolyte
Authors: Chen Hsi , Wu Nae-Lih (Nick)
Published: December 2024

LiNiO2 (LNO) stands as the pinnacle in the advancement of Ni-rich cathode materials (LiNixCoyMn1-x-yO2 or LiNixCoyAl1-x-yO2), leveraging maximal nickel utilization and cobalt elimination to achieve the highest energy density at a reduced cost. Nevertheless, the commercialization of LNO is impeded by safety concerns and limited cycle life when employed in liquid electrolytes. To address them, we report an all-solid-state lithium metal battery (ASSLMB) integrating LNO cathode with a halide solid electrolyte (Li3InCl6, LIC). Apart from enhancing safety, the ASSLMB demonstrates remarkable improvement in cycle stability under low applied pressure, while maintaining the specific capacity. Through systematic synchrotron operando x-ray characterizations (including absorption, diffraction and microscopy) and post-mortem analyses, we unveil crucial insights into the electrochemical dynamics of the ASSLMB and identify the dominant factors contributing to capacity degradation over cycling.
Sulfide Solid Electrolyte Coated Cathode in All-Solid-State Batteries
Authors: Kim Jun tae , Shin Hyeon-ji , Jung Hun-Gi
Published: December 2024

Using a sulfide solid electrolyte, the all-solid-state batteries emerge as a promising candidate for next generation batteries, having significant advantages such as high lithium ionic conductivity and wide electrochemical stability window. These characteristics pave the way for the realization of elevated power and energy densities. Nonetheless, this cutting-edge technology is not without its hurdles; indeed, there are pressing issues that demand attention and refinement.

In contrast to conventional lithium-ion batteries, which rely on organic liquid electrolytes with high wettability having uniform lithium ion transfer pathways within electrodes, the ASSBs encounter constraints in establishing solid-solid interfaces owing to its intrinsic solid nature. This limitation becomes particularly apparent during the cycling, wherein the fluctuating volume of the active material, prompted by the (de)intercalation of lithium ions, precipitates the degradation of the interface between active material and solid electrolyte within the composite electrode. This phenomenon leads up to loss of the lithium ionic pathway, precipitating a deterioration in cell performance

The key point of this study lies in the endeavor to enhance battery performance through the application of a solid electrolyte coating onto the surface of the active material. By doing so, the aim is to preserve a uniform pathway for lithium ion transfer within the composite electrode. It is noteworthy that the solid electrolyte coating layer exerts profound influence on the electrochemical dynamics of the cell, important in adapting the formation of homogeneous lithium ionic pathway and the mitigation of void formation within the composite electrode. Thus, the main thrust of this research is to validate the formation of meticulously uniform solid electrolyte coating layer, depend upon the size of the solid electrolyte particles.

In pursuit of this objective, a multifaceted approach was adopted. Through the utilization of liquid-phase process and a dispersant, the particle size of the solid electrolyte was deliberately manipulated, thereafter subjecting it to a dispersion process for the application of solid electrolyte coating. Intriguingly, it was observed that as the particle size of the solid electrolyte diminished, a more uniform solid electrolyte coating layer ensured, thereby engendering better electrochemical performance. Furthermore, it was corroborated that the lithium ionic pathway persevered even after long cycling, attributable to the presence of the solid electrolyte coating layer. Concomitantly, the incidence of undesirable side reactions was appreciably mitigated, with the homogeneous electrochemical reactions within composite electrode.
Electrochemical Properties of Prelithated Silicon-Graphite Mixtures As an Anode Material for Quasi-Solid-State Battery
Authors: Jang Boyun , Kim Daeil , Han Byol , Park Yeonjin , Kim Joon-soo
Published: December 2024

To guarantee the minimum safety of Li-ion battery, quasi-solid electrolyte such as gel polymer is one of potential candidates by retarding the fire. With the safety issue, the requirement of higher energy density is still main issue for the next generation Li-ion battery. To enhance the energy density, Silicon (Si) is well known as potential anode due to its much higher theoretical specific capacity than that of graphite. Nevertheless, Si’s large volumetric changes during cycles hinder its application for the next generation Li-ion battery. Here, specially designed process to prelithiate Si nanoparticles with size of several hundred nanometers were developed, and physical mixture of Si and graphite was applied to coin-type full cell with quasi-solid electrolyte. Specifically, Si nanoparticles were annealed with Li-sources such as Li2CO3 or LiOH in reduction atmosphere. Simultaneously, Carbon (C) sources such as Toluene or ethylene was injected to Si nanoparticles to form C- layer to gain electrical conductivity of Si. Prelithiated Si and graphite were mixed with various composition from 0:100 to 50:50 (in wt.%), and the mixture was applied as anode material with Ni-rich cathode and gel electrolyte for assembly of coin-type cell. Specific capacity of prelithiated Si exhibited around 1,300 mAh/g with extremely high initial capacity of 88%. Microstructure of the Si nanoparticles were studied by using XRD, SEM and HR-TEM analysis. Various gel electrolyte was applied not only for separator but also for inside of cathode and anode. Effect of types and compositions of gel electrolytes on electrochemical properties such as cycle performance of quasi-solid-state Li-ion battery was investigated. Also, interface properties especially between anode materials and gel electrolyte were precisely investigated through the EIS (Electrochemical Impedance Spectroscopy) measurements to enhance the cycle performances. This quasi-solid-state Li-ion battery can solve the safety problem as well as low energy density at the same time.
Aging Property of Halide Solid Electrolyte at the Cathode Interface
Authors: Kim Wonju , Noh Joohyeon , Kang Kisuk
Published: December 2024

Halide solid electrolytes have recently emerged as a promising option for cathode-compatible catholytes in solid-state batteries, owing to their superior oxidation stability at high voltage and their interfacial stability. However, their day-to-month-scale aging at the cathode interface has remained unexplored until now, while its elucidation is indispensable for practical deployment. Herein, we investigate the stability of halide solid electrolytes (e.g., Li3InCl6) when used with conventional layered oxide cathodes during extended calendar aging. We find that, contrary to their well-known oxidation stability, halide solid electrolytes can be vulnerable to reductive side reactions with oxide cathodes (e.g., LiNi0.8Co0.1Mn0.1O2) in the long term. More importantly, the calendar aging at a low state of charge or as-fabricated state causes more significant degradation than at a high state of charge, in contrast to typical lithium-ion batteries, which are more susceptible to high-state-of-charge calendar aging. This unique characteristic of halide-based solid-state batteries is related to the reduction propensity of metal ions in halide solid electrolytes and is correlated to the formation of an interphase due to the reductive decomposition triggered by the oxide cathode in a lithiated state. This understanding of the long-term aging properties provides new guidelines for the development of cathode-compatible halide solid electrolytes.
Cellulose Nanofiber-Based Separators for Durable Zn Ion Batteries
Authors: Qin Jiaqian
Published: December 2024

Aqueous zinc-ion batteries (ZIBs) are promising as the next-generation energy storage system due to their inherent safety and low cost, but challenges relating to H2O-induced side reactions and dendrite growth of the zinc anode are restricting its practical application. Generally, the zinc dendrites are generated by the inhomogeneous and uneven zinc deposition, which can affect the plating/stripping efficiency and even induce short circuit, thus greatly shortening the cycle lifespan and decreasing the electrochemical performance. And the side reactions are ascribed the active H2O molecules derived from the solvated Zn2+ ions, which can easily decompose into H+ and OH−, thus inducing a series of parasitic reactions and resulting in a sluggish interface kinetics. To alleviate these issues, strenuous efforts have been devoted, such as designing three-dimensional zinc anode, constructing alloyed anodes, modifying the anode-electrolyte interface, employing the “water-in-salt” electrolyte, introducing electrolyte additive, utilizing hydrogel electrolytes, and controlling exposed basal planes for zinc plating. As a key component of ZIBs, separator plays a vital role in transferring Zn2+ ions and physically separating cathode and anode, whereas the studies on separators are in infancy, implying their research value and application potential can be further explored. Herein, we develop a series of cellulose nanofiber (CNF)-based separators (CNF/GO composite separator (CG), CNF-ZrO2 composite (ZC) separator, WC-CNF (WCCNF) separator, and CNF-lithium magnesium silicate (LMS) separator (CNF+LMS)) for stable aqueous ZIBs.
Enhancing the Viability of Zinc-Polyiodide Flow Batteries: A Study on Innovative Composite Polyamide-Porous Separators for Optimized Ionic Conductivity and Ion Permeability
Authors: Somwangthanaroj Anongnat , Yoopensuk Warunyoo , Kao-ian Wathanyu , Pakawanit Phakkhananan , Kheawhom Soorathep
Published: December 2024

Zinc-polyiodide flow batteries (ZIFBs) are recognized for their superior theoretical energy capacity and are considered prominent energy storage devices. The viability of ZIFBs relies on the development of cost-effective separators demonstrating excellent ionic conductivity and selective ion permeability. In this study, an economical polymer blend comprising poly(ether sulfone) (PES) and sulfonated poly(ether ether ketone) (sPEEK) was fabricated using a phase inversion technique. The resulting sponge-like structure of the porous substrate exhibits high ionic conductivity. Additionally, the selected porous substrate was topped with a thin-film polyamide synthesized from m-phenylenediamine (MPD) and 1,3,5-benzene tricarbonyl trichloride (TMC) through interfacial polymerization (IP). This polyamide layer effectively mitigates undesired triiodide ion migration while maintaining high ionic conductivity. The innovative approach allows for a composite separator with a finely tunable structure. Employing such a separator enables ZIFBs to operate stably with a high coulombic efficiency (CE) of 91% over 100 cycles at a current density of 10 mAh cm-2. This study explores the trade-off between ionic conductivity and ion permeability, demonstrating that adjusting the morphology of composite separators enhances their physical characteristics, ensuring the stable and efficient operation of ZIFBs.
Sustainable Organophosphorus Anolyte for Non-Aqueous Redox Flow Battery
Authors: Mahoney Emily , Malapit Christian
Published: December 2024

Recent advances in redox flow batteries (RFB) have made them a viable option for grid-scale energy storage. Vanadium redox flow batteries (VRFB) are the most prominent and commercially viable, however, when compared to lithium-ion batteries they have low energy density due to low cell potentials (U = 1.5 V in VRFB). To boost cell potentials, researchers have begun exploring organic platforms. These can be engineered to exhibit extreme potentials while offering high tunability, earth abundance, and cost-effectiveness. Here, we investigated the viability of phosphorus containing organic molecules as anolytes in RFB. Through molecular engineering, we developed a series of novel, sustainably derived, organic anolytes with highly negative redox potentials (–2.0 to –2.5 V vs. Fc/Fc+) that operate in acetonitrile and dimethylformamide, allowing for a wide cell potential. Through electrochemical studies using cyclic voltammetry, charge/discharge cycling, and various mechanistic studies (decomposition studies, EPR analysis, X-ray crystallography), we found an excellent candidate. Guided by this discovery, we tuned our system to create a long-lived anolyte which exhibited no capacity fade over 350 cycles with an average coulombic efficiency of 99.3%. When paired with an appropriate catholyte (e.g. E1/2 ≥ 0.5 V), an organophosphorus-based RFB could double the cell potential (U ~ 3V) and energy density found in VRFB. This performance establishes our anolyte as one of the most negative and stable reported in non-aqueous RFB.

Figure 1
Influence of Interlayer Cation Ordering on Na+ Transport in P2-Type Electrodesfor Sodium-Ion Batteries
Authors: Gabriel Eric , Wang Zishen , Singh Vibhu Vardhan , Graff Kincaid , LIU Jue , Koroni Cyrus , Hou Dewen , Schwartz Darin , Li Cheng , Liu Juejing , Guo Xiaofeng , Osti Naresh , Ong Shyue Ping , Xiong Claire
Published: December 2024

P2-typeNa2/3Ni1/3Mn2/3O2 (PNNMO) has been extensively studied because of itsdesirable electrochemical properties as a positive electrode for sodium ion batteries. PNNMO exhibits intralayer transition metal ordering of Ni and Mn and intralayer Na+/vacancy ordering. The Na+/vacancy ordering is often considered a major impediment to fast Na+ transport and can be affected by the transition metal ordering. We show by neutron/X-ray diffraction and density functional theory (DFT) calculations that Li doping (Na2/3Li0.05Ni1/3Mn2/3O2, LFN5) promotes ABC-type interplanar Ni/Mn ordering without disrupting the Na+/vacancy ordering and creates low-energy Li-Mn coordinated diffusion pathways. A structure model is developed to quantitatively identify both the intralayer cation mixing and interlayer cationic stacking fault densities. Quasielastic neutron scattering reveals that the Na+ diffusivity in LFN5 is enhanced by an order of magnitude over PNNMO, increasing its capacity at high current. Na2/3Ni1/4Mn3/4O2 (NM13) lacks Na+/vacancy ordering but has comparable diffusivity to LFN5. However, NM13 has the smallest capacity at a high current. The high site energy of Mn-Mn coordinated Na compared to Ni-Mn, and higher density of Mn-Mn coordinated Na+ sites in NM13 disrupts the connectivity of low-energy Ni-Mn coordinated diffusion pathways. These results suggest that the interlayer ordering can be tuned through the control of composition, which has an equal or greater impact on Na+ diffusion than the Na+/ vacancy ordering.
Design of Spherical Hard Carbon Secondary Particles for Na-Ion Battery Anode Application
Authors: Hong Seong Ung , Lee Byoung-Sun
Published: December 2024

Recently, Na-ion rechargeable batteries have been successfully developed and launched as the main power sources of a few novel electric vehicles in China. An energy density of the mass-produced Farasis Energy Na-ion batteries have been announced as between 140 Wh/kg and 160 Wh/kg with the layered oxide cathode and hard carbon anode combination. Though the commercialization of the Na-ion batteries is highly remarkable owing to the cost-effectiveness and long lifespan, the energy density of the Na-ion batteries needs to be improved even further considering the current state-of-art advanced practical Li-ion batteries of ca. 300 Wh/kg.

Development of a novel anode material can contribute to the energy density improvement. Hard carbons with random shapes, which have been employed as the main anode materials in the commercial Na-ion batteries, have demonstrated the specific capacity of 200 to 300 mAh/g based on the carbonized biomasses. To improve energy density, shape and microstructure of the hard carbons need to be carefully designed. On the one hand, random shapes are not highly desired to achieve high tap density. Instead, spherical shapes with uniform particle sizes are beneficial to increase tap density as well as the energy density [1]. On the other hand, the carbonaceous microstructure needs to be optimized because the Na is stored through various mechanisms with combinations of i) adsorption at the surface of open pores, ii) adsorption at defect sites of graphene sheets, iii) insertion between graphene layers, and iv) pore filling [2]. As such, design of spherical hard carbon with well-established microstructure can provide high energy density. In this work, spherical hard carbon in Figure 1 was prepared using carbon precursor material (polyacrylonitrile) and sacrificial polymer (poly(styrene-co-acrylonitrile)) dissolved in the cosolvent (N,N-dimethylformamide). Carbonaceous microstructures were modified using the chemical and physical approaches. The morphological, structural, and electrochemical characterizations will be presented at the conference.

[1] Oh, H. J. et al., Chem. Eng. J. 454, 140252 (2023)

[2] Chen, C. et al., Carbon Energy 4, 1133-1150 (2022)

Figure 1. SEM image of spherical hard carbon

Figure 1
Hybrid Electrolyte Strategies for High-Energy Sodium-Based Batteries
Authors: Lee Wang-Geun
Published: December 2024

Sodium-based batteries are emerging as a promising and crucial technology for sustainable energy storage due to the abundance and cost-effectiveness of sodium compared to lithium. While these batteries offer an attractive option for large-scale applications, they face challenges such as lower voltage and energy density. To overcome these limitations and enhance high-energy sodium-based battery performance, researchers are exploring innovative hybrid electrolyte strategies. Hybrid electrolytes, which combine solid and liquid systems, provide improvements in safety, efficiency, and performance.

This study explores various hybrid approaches, including organic-solid-aqueous hybrids, quasi-solid anolytes, and over-saturated catholytes. These methods aim to address the limitations of sodium-ion batteries and pave the way for high-performance energy storage solutions. For instance, an organic-solid-aqueous hybrid system lets different non-aqueous and aqueous materials adapt, which leads to wider voltage ranges. Additionally, using non-aqueous sodium metal anodes and aqueous ferrocyanide redox cathodes in these hybrid electrolyte systems demonstrates viable voltage ranges and reversible performance. Research on quasi-solid electrolytes showed potential in developing thicker anodes, while over-saturated catholyte research explored the use of solid cathode materials.The diverse hybrid electrolyte approaches have revealed promising possibilities for both aqueous and non-aqueous sodium-based batteries. These advancements enhance battery stability and durability, leading to higher voltage and energy density across various applications. Recent advancements in sodium anode and aqueous cathode designs have enabled the application of sodium-based batteries in different types, including seawater and sodium-flow batteries. One significant innovation is the use of NASICON ceramic electrolytes, which offer improved ionic conductivity and stability, allowing for further material adaptations and optimization of battery performance.

In conclusion, the exploration of hybrid electrolyte strategies for sodium-based batteries represents a novel approach towards realizing the full potential of this technology. As research and development progress, sodium-based batteries with hybrid electrolytes could become foundational for sustainable energy storage, contributing to a cleaner and more efficient energy future.
Understanding Benzophenone Degradation Pathways to Improve Non-Aqueous Redox Flow Battery Performance
Authors: Barros Romo Adolfo I. , Maurya Sandip , Davis Benjamin L
Published: December 2024

The growing energy demand forces us to look for alternative sources of energy such as wind or solar. However, this type of intermittent energy must be stored for later use. In this sense, redox flow batteries (RFBs) are presented as an interesting tool for energy storage. Non-aqueous RFBs allow a wide electrochemical window for organic solvents such as acetonitrile, propylene carbonate or dimethylformamide. These solvents allow us to reach very positive and negative potentials, opening an electrochemical window greater than 5 V before observing degradation of the solvents.

In the design of electrolytes for RFBs it is essential to address aspects such as charge density, stability, price, and the voltage that the redox couple allows us to achieve. In this sense, organic molecules have been widely used as anolytes due to their high charge density, great solubility and the possibility of reaching very negative and positive potentials that would provide RFBs with efficient performance. In our search for organic molecules with E1/2 potentials equal or more negative than -2.0 V, we begun investigating benzophenone and derivatives. The BP family of derivatives have attracted the attention of the anolyte development community due to their extremely negative reduction potentials. In these molecules it is possible to achieve the first reduction at E1/2 -2.25 V vs Ag/Ag+ and the second reduction process at E1/2 -2.8 V vs Ag/Ag+. Although this molecule presents very negative reduction potentials, our initial evaluations show that they are not stable for sufficient time to be used in RFBs. Herein, we detail the degradation mechanism of benzophenones, using product characterization obtained after cycling the anolytes in redox flow batteries. We observed the generation of benzocarbinol and benzopinacol after water and support electrolyte (TBAPF6) addition respectively to a dianion (BP-●●) chemically reduced. Based on the degradation mechanism, we propose a mitigation pathway to improve the performance of these carriers, including modification of ortho position with bulky groups to protect the carbonyl group.
Long Durable Prussian-Blue Analogous Cathode for Aqueous Sodium-Ion Batteries
Authors: Feng Zhenxing
Published: December 2024

Aqueous sodium-ion batteries are attractive battery alternatives for stationary energy storage due to their inherently low cost and high safety. The development of advanced electrode materials with excellent performance and low cost is crucial for the success of aqueous Na-ion batteries. We recently have studied Prussian-blue analogous based electrodes as promising cathodes for aqueous Na-ion batteries. We found that Na1.88Fe[Fe(CN)6]·0.7H2O exhibited fast ionic diffusion that enables the fast charging rate (> 100C), super long cycle life (> 17,000 cycles), high capacity retention and rate capability. In combination of electrochemical characterization and multimodal synchrotron X-ray scattering and spectroscopy methods, we attributed the superior performance to the sodium deficiency and new phase induced through the ball-milling processes. Our work also underlines the importance of fabricating aqueous batteries on the basis of the Earth-abundant, cost- effective, and non-toxic elements.
Modulating the Electrochemical Potential and Zn2+ Diffusion Kinetics in Hydrated Vanadate
Authors: Liu Chaofeng
Published: December 2024

Hydrated vanadate (V2O5·nH2O) is regarded as one of the promising cathodes for aqueous zinc ion batteries owing to their high specific capacity and low cost, however, their relatively low operating voltage and sluggish kinetics limit their practical applications. Compared to preinserted metal cations, we develop a series of organic cations, with similar molecular structure but distinct functional terminal-groups, are pre-intercalated into the lattice of hydrated vanadate to regulate the local chemical coordination and the electronic structure of the redox cation. The stronger polarity or larger size causes larger local distortion of VO6 octahedron and V t
2g orbitals splitting, leading to a higher open circuit voltage (>1.60 V) and higher mid-point voltage (>0.75 V) in comparison with unmodified sample. In addition, the modified samples present higher ion diffusion coefficient of 10-8~-7 cm2/s compared with 10-9~-8 cm2/s, resulting in a better rate performance. The understanding on the correlation among local chemical coordination, electrochemical potentials, and ion diffusion could serves as a guide for designing and developing higher energy and power densities in next generation rechargeable batteries.
Porous Carbons for Positive Electrode of Zn-Carbon Rechargeable Battery
Authors: Yoshikawa Masaaki , Fujimoto Hiroyuki , Ogumi Zempachi , Abe Takeshi
Published: December 2024

Zinc is widely applied in multivalent energy storage systems because it is a safe, inexpensive, abundant resource, and attractive high capacities (820 mAhg−1) and low redox potential (−0.76 V vs standard hydrogen electrode). Carbon materials have long been used in various batteries, and are known to most effectively increase the capacity of the EDLC. Therefore, we are working on the development of a novel Zinc-Carbon rechargeable battery. Porous carbon materials prepared with different activation methods were evaluated as positive electrodes for Zinc-Carbon rechargeable battery. Higher capacities were obtained with chemically activated carbons than with steam-activated carbons. KOH-activated carbon which has BET surface area over 3,000m2/g showed the highest capacity of over 400mAh/g-carbon. Furthermore, the dependence of charge–discharge characteristics on electrolyte was explored using different electrolyte such as KOH, NH4Cl, ZnSO4 and ZnCl2. Gas evolution was observed during the charging reaction in alkaline electrolytes such as KOH, but no gas evolution was observed in acidic electrolytes such as ZnCl2. The cycle performances were measured when KOH-activated carbon was used as the positive electrode and ZnCl2 was used as the electrolyte, 33% decrease in capacity was observed after 100 cycles. It is thought that the reason of this is not the carbon of the positive electrode but the deterioration of the zinc of the negative electrode. In addition, the discharge capacity tended to be higher for chlorine- ion-containing electrolytes such as ZnCl2 and NH4Cl. The discharge capacity of Zinc-Carbon rechargeable batteries tended to be proportional to the mesopore volume and the surface acidic functional groups of activated carbon. KOH-activated carbon has higher mesopore volume and surface acidic functional groups than other activated carbons, therefore it seemed to provide high capacity in combination with as acidic electrolyte.

Figure 1
Inkjet Printed Ti3C2Tx MXene Electrodes for Zn-Ion Storage
Authors: Viviani Prisca , Gibertini Eugenio , Bussetti Gianlorenzo , Magagnin Luca
Published: December 2024

The exploration of non-lithium chemistries in electrochemical energy storage, as an alternative to conventional lithium-ion batteries, is gaining attention. Zinc-ion chemistry, in particular, poses great promises in transforming the energy storage field, because of its higher energy density, quicker charging capabilities and enhanced safety features, making this technology a compelling option for various applications [1]. During the charging step in zinc ion batteries (ZIBs) or hybrid zinc ion supercapacitors (ZISCs), zinc ions are reduced to metallic zinc. However, the uneven distribution and nucleation of zinc on the anodic surface represents a critical issue, as a dendritic growth of zinc will follow, leading to the battery failure. This effect, however, can be smoothened and regulated by treating the surface to improve a “zincophilic” character to the surface [2]. In this context, MXene and, in particular, Ti3C2Tx MXenes (MX) are emerging as candidate material suitable both as interfacial regulator for highly reversible and smooth Zn plating / stripping [3]. However, despite some studies pointed out the lattice matching between Zn and Ti3C2Tx as the main reason for the smooth and [002] oriented Zn growth during plating, a deep understanding of the electrochemistry of Zn2+ at the MX interface is still lacking.

In this work, we investigate the behaviour of Ti3C2Tx MXene thin film produced by inkjet printing in ZnSO4 electrolyte. In particular, we paid attention to two aspects: the mechanism of Zn ions storage both in the overpotential deposition (OPD) and underpotential deposition (UPD) regions. When the OPD region is considered, electrochemical analyses combined with morphological and microstructural characterization suggested that Zn deposition is mostly solution-controlled rather than surface tuned. On the other hand, we investigate the effect of MX flakes size on the Zn crystal growth, as smaller flakes may affect negatively the growth of hexagonal Zn crystals. In particular, in-situ analyses as Raman and electrochemical atomic force microscope (EC-AFM) as well chemical analyses by x-ray photoelectron spectroscopy (XPS) suggested that a phenomenon of underpotential deposition of metallic Zn occurs in the narrow potential region preceding Zn plating potential.

Bibliography

[1] Y. Lv, L. Zhang, X. Wei, B. Qiu, W. Zhang, Q. Qin, D. Jia, X. He, Z. Liu, F. Wei, The emerging of zinc-ion hybrid supercapacitors: Advances, challenges, and future perspectives, Sustainable Materials and Technologies 35 (2023) e00536. https://doi.org/10.1016/j.susmat.2022.e00536.

[2] P. He, Q. Chen, M. Yan, X. Xu, L. Zhou, L. Mai, C.-W. Nan, Building better zinc-ion batteries: A materials perspective, EnergyChem 1 (2019) 100022. https://doi.org/10.1016/j.enchem.2019.100022.

[3] Y. Shen, H. Lv, L. Chen, Recent advances in two-dimensional MXenes for zinc-ion batteries, Materials Chemistry Frontiers 7 (2023) 2373–2404. https://doi.org/10.1039/D3QM00003F.
Exploring Binderless Tin and Hard Carbon Anodes Via Electrospray Deposition for Sodium-Ion Batteries
Authors: Gordon Kenneth , Burnell Collin , Usie Griffin , Liu Zhi , Fei Ling
Published: December 2024

For decades, lithium-ion batteries have seen widespread usage in a variety of applications from consumer electronics such as smartphones to the more recent developments of electric vehicles. As the usage of lithium for batteries increases, one growing concern is the finite amount that could be found within the Earth’s crust. An alternative that is being considered is sodium-ion batteries due to how plentiful sodium is in the Earth’s crust and similar chemical properties to lithium. One of the main challenges of sodium-ion batteries is the development of anode materials because sodium does not intercalate well with graphite, which is one of the most used materials in lithium-ion batteries. One promising development for anode materials is the use of hard carbon derived from the pyrolysis of polymers such as polyacrylonitrile (PAN) which can have various morphologies and potential for adding other high-capacity components to boost the performance. One material that has received attention is tin which has been previously added into electrospun carbon nanofibers with applications in both lithium and sodium ion batteries. They often include sacrificial materials such as polymethyl methacrylate (PMMA) to produce tin and porous carbon composite nanofibers. While tin on electrospun carbon nanofibers have been studied, there is little work that has been done with the structures that can be produced through electrospray deposition. Thus, our work seeks to explore the development of tin and hard carbon anodes via electrospray deposition with and without air assistance. This will allow for an increased loading of tin as well as exploration of the performance of hard carbon anodes with different structures in sodium ion batteries. Through the use of electrospray deposition, with and without air assistance, the performance of different morphologies such as microdisks, nanospheres, and thin films can be tested with a greater variation in tin concentrations that can exceed the mass of the precursor polymer. Further variation can be introduced by varying the porosity of the structures by introducing PMMA into the spray solutions at different concentrations. The use of electrospray deposition also allows for the production of binderless anodes by coating directly onto the current collector, promising for light-weight batteries development.
Zn-Sn Alloy Seed Layer-Coated Cu Current Collector for Anode-Free Aqueous Zn Ion Batteries
Authors: Jang YoungSeok , Shin Jigang , Go Busung , You Soobum , Kim Seungju , Sattar Tahir , Doo Seokgwang
Published: December 2024

Zn ion batteries (ZIB) stand at the forefront of alternative advanced energy storage technologies due to the intrinsic properties of Zn, including its low reduction potential (-0.76 V vs. SHE), and high theoretical specific capacity (820 mAh g-1) acquired by its multi-electron redox processes. Nonetheless, the utilization of current thick Zn foil anode remains a big challenge to commercialization, caused by the dendrite growth, severe surface side reaction, and high N/P ratio, which leads to the limitation of cell energy density. Herein, we report anode-free technology based on ultra-thin Zn-Sn alloy seed layer-coated Cu foil (ASL@Cu), to break through the limit of cell energy density. Incorporating Sn and carbon in the seed layer results in a strong affinity towards Zn, inhibiting the irreversible surface reactions, and eventually offering efficient electron transport routes. The resulting ASL showed rapid kinetics for Zn2+ deposition (lower nucleation overpotential) and exhibited an extended cycle life at a current density of 4 mA cm-2. This work sheds light on the strategic design of anode-free to achieve outstanding performance with a constrained amount of Zn on the Cu current collector.
Structurally Robust Cu-Doped P3- Na0.62Mn1-XCuxO2 Cathodes for High-Capacity Sodium-Ion Batteries
Authors: Rakhymbay Lunara , Konarov Aishuak
Published: December 2024

Nowadays sodium-ion batteries (SIBs) are attracting significant interest due to environmentally abundant and cost-effective sodium sources and are projected as an alternative to Li-ion batteries [1]. Getting from lithium-ion batteries to sodium-ion batteries presents many obstacles with regards to material advancement and comprehension of the underlying mechanisms. Certainly, during the last decade research focused on the study and development of SIB materials, particularly cathode materials [2]. Among the all reported cathode materials layered transition metal oxides (NaxTMO2, where TM = Mn, Co, Cr, Fe etc) has been found to be appealing owing to its simple synthesis, high energy density and high capacity [3]. The structure of NaxTMO2 can be described as P2, P3 and O3 where the letters P, O represent the prismatic and octahedral Na+ coordination environment and a number indicates TMO2 layer [4]. Mn-based P3-type materials are seen as more renewable due to their ability to synthesize at lower temperatures than P2-type materials. These materials have the ability to provide high capacities but suffer from several phase transitions which leads to poor electrochemical performance. In order to enhance the cycling performance of layered cathodes, it has been demonstrated that employing doping in the structure [5].

In this work, we investigated the Cu-doping effect on Na0.62Mn1-xCuxO2
( x=0.09, 0.19 and 0.28) material properties. The Na0.62Mn1-xCuxO2 materials are synthesized via solid-state method in the oxygen atmosphere, whose crystal structure and atomic compositions are confirmed by XRD and ICP-AAS. The HR-TEM, XPS, XANES, operando-XRD and in-situ DEMS analysis were employed to systematically examine surface morphology and structure evolution during cycling.

Acknowledgment

This work was supported by the grant funding of young scientists for scientific and technical projects for 2024-2026 (Ministry of Science and Higher Education of the Republic of Kazakhstan) (AP22788427) " Advancing the Frontiers: High-performance anode-free lithium-sulfur batteries".

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K. Wang, Prof. P. Yan, J. Fu, Prof. M. Su, Adv. Energy Mater. 2019, 31, 1904816.
Addressing Hurdles to Decadal Operation of Next-Generation Flow Battery Chemistries
Authors: Saraidaridis James D
Published: December 2024

In recent years, the excitement and promise of active materials designed specifically for Flow Battery applications manifested chemistries that deliver on core performance requirements such as stability, voltage, solubility, and cost. Stable organic and organometallic chemistries have a path to deliver improved performance compared to established elemental actives (e.g. V, Fe, Cr, S, Br).[1], [2], [3] As researchers and businesses seek to commercialize these new flow battery chemistries, system level performance requirements are equally vital to real-world success and need to be addressed: active crossover management, water crossover management, side reaction mitigation, SOC matching and balancing, pH management, and more.

The ligand-modified chromium-iron chemistry identified by Robb, Farrell, and Marshak showed promise in initial reports describing high performance over the span of a day of cycling.[1] RTX Technology Research Center, in collaboration with Robb and Marshak over the subsequent years, has examined performance of KCr(PDTA)|K4Fe(CN)6 over longer durations and at larger scales. In striving for longer-lived systems, the team has introduced new components and sub-systems that range from commercial membrane selection,[4] to recombination cells,[5] to reactor performance retention strategies.[6]

Acknowledgements:

The work presented herein was funded in part by the Advanced Research Projects Agency-Energy (ARPA-E) and the Advanced Materials & Manufacturing Technology Office, U.S. Department of Energy, under Award Number DE-AR000994 and DE-EE0009794. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

References

Robb, B.H., J.M. Farrell, and M.P. Marshak, Chelated Chromium Electrolyte Enabling High-Voltage Aqueous Flow Batteries. Joule, 2019. 3(10): p. 2503-2512.

Kwabi, D.G., et al., Alkaline Quinone Flow Battery with Long Lifetime at pH 12. Joule, 2018. 2(9): p. 1894-1906.

Goulet, M.-A., et al., Stability of Flow Battery Organic and Organometallic Reactant Molecules. Meeting Abstracts, 2017. MA2017-01(3): p. 240.

Saraidaridis, J.D., et al., Transport of Ligand Coordinated Iron and Chromium through Cation-Exchange Membranes. Journal of The Electrochemical Society, 2022.

Selverston, S., R.F. Savinell, and J.S. Wainright, In-tank hydrogen-ferric ion recombination. Journal of Power Sources, 2016. 324: p. 674-678.

Saraidaridis, J. and Z. Yang, Electrolyte Takeover Strategy for Performance Recovery in Polysulfide-Permanganate Flow Batteries. Journal of The Electrochemical Society, 2021. 168(11): p. 110556.
Electrochemical Performance of Zinc in Potassium Acetate-Based Electrolytes at Industrially Relevant Currents and Utilizations
Authors: Dutta Debayon , Turney Damon E. , Lambert Timothy N. , Banerjee Sanjoy
Published: December 2024

Batteries for long-duration, grid-scale energy storage need to be inexpensive to manufacture, safe to operate, environmentally friendly and have high energy density for successful integration into the electric grid. To this effect, aqueous zinc rechargeable batteries are ideal candidates due to the low cost and well-established supply chain of zinc, its compatibility and benignity in ambient environmental conditions and water-based electrochemistry and high theoretical gravimetric and volumetric capacity of the zinc anode material (820 mAh/g and 5850 mAh/mL respectively). However, good cycle life and utilization of the zinc has proven difficult due to various zinc failure mechanisms that exist. Zinc-ion batteries are of particular interest in comparison to their alkaline counterparts due to the absence of electrochemically inactive materials being formed during zinc discharge which affects cycle life performance. Most zinc-ion research done has employed low utilizations of the zinc active material at low to modest current densities (i.e. <1 mA/cm2). In this work, we investigate the electrochemical stability window of potassium acetate (KOAc) electrolytes in comparison to 25 wt.% potassium hydroxide (KOH) solution and as a function of concentration on various current collector surfaces. As the acetate concentration is varied from 1 m to 27 m, the largest electrochemical window is measured at 3.3 V for 27 m KOAc on a gold surface. Additionally, the zinc utilization and reversibility at a current density of 25 mA/g (~4.5 mA/cm2) during cycling is examined in select concentrations of these KOAc electrolytes. Zinc//zinc symmetric single-discharge experiments concluded that whilst 27 m KOAc was unsuccessful in electrostripping even ~1% of the zinc mass, lowering the concentration to 5 m KOAc provides an effective strategy for utilizing a practical amount of zinc mass. Furthermore, adding a small amount of acetic acid to this KOAc concentration allows to circumvent the formation of zinc oxide completely. Overall, the studies are fruitful in understanding the relationship between zinc anode, the electrolyte system and their synergistic electrochemical performance at industrially relevant parameters in pursuit of the scale-up of zinc-ion battery devices.