bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemical Properties of Garnet-Type Ta and Ga Co-Doped Li7La3Zr2O12 for Solid-State Li Batteries
Authors: Inada Ryoji , Hori Akio , Muramoto Yuta , Tojo Tomohiro 
Published: December 2024

Li-stuffed garnet-type oxide Li7La3Zr2O12 (LLZ) has attracted much attention because of the high ionic conductivity at room temperature, excellent thermal performance, and good chemical stability against Li metal.1,2 However, poor interfacial connection causes non-uniform Li plating and intergranular penetration of Li dendrite in polycrystalline LLZ when the cell is cycled particularly at high current densities, resulting in internal short-circuit failure.3,4 The tolerance for Li dendrite growth into LLZ is influenced by many factors such as the interfacial resistance between LLZ and Li anode, cell stacking pressure and microstructure (density and grain size) of LLZ. In this study, we fabricated Ga and Ta co-doped LLZ (Li6.55-3xGaxLa3Zr1.55Ta0.45O12, LGLZT) ceramic electrolyte and investigated the effects on the Ga amounts on the microstructure, ionic conductivity, and the tolerance for Li dendrite growth.
LGLZT with Ga amounts x = 0.025, 0.05 and 0.10 were synthesized via a conventional solid-state reaction process. Sintering condition was set to 1150 °C for 2 hours in air. Relative densities for all sintered samples were ranged from 93-95 %. From XRD analysis, each sintered sample has a cubic garnet phase and diffraction peaks from other phases were not detected. Calculated lattice parameter was decreased with increasing Ga amounts x, due to the Ga3+ incorporation in the crystal lattice. In SEM observation, microstructure of sintered LGLZT was strongly influenced by x, because the amounts of liquid Li-Ga-O phase formed during high temperature sintering is also changed by x.5,6 When x increases, grain growth in sintered LGLZT is promoted and the segregation for Ga and O elements becomes more remarkable. Ionic conductivity of LGLZT at room temperature also enhanced with x, and maximum value of 0.84 mS/cm, which is much superior to the value for the sample without Ga (= 0.64 mS/cm). The effect of Ga amounts in LGLZT on the tolerance for Li dendrite growth will be discussed in the presentation.
This work was supported by Grant-in-Aid for Scientific Research (JSPS KAKENHI) Grant Number 22H01468 from the Japan Society for the promotion of Science (JSPS).
References

R. Murugan et al., Angew. Chem., Int. Ed. 46, 7778−7781 (2007).

A.J. Samson et al., Energy Environ. Sci. 12, 2957−2975 (2019).

R. Inada et al., Batteries 4, 26 (2018).

Y. Matsuki et al., J. Electrochem. Soc. 166, A5470−A5473 (2019)

Y. Matsuda et al., Solid State Ionics 311, 69−74 (2017).

Y. Yamazaki et al., Batteries 8, 158 (2022).
A Comparative Safety Analysis of Lithium-Ion and Solid-State Lithium-Metal Pouch Cells
Authors: Fakkema Jonathan , Sapra Harsh , Kazyak Eric 
Published: December 2024

Solid-state batteries (SSBs) have become a promising candidate for the next step in lithium battery evolution. SSBs have the potential to provide larger gravimetric and volumetric energy densities, while many researchers believe they will also have an intrinsically higher safety profile. SSBs may not pose the same fire risk as conventional lithium-ion batteries (LiBs) since they lack a flammable liquid electrolyte [1]. However, recent developments have called this common belief into question. Not only do solid-state electrolytes (SSEs) fail to prevent lithium filaments from propagating and causing short-circuit events, but the higher energy density and presence of metallic lithium in SSBs create unique avenues for thermal runaway compared to LiBs [2-3]. Furthermore, there exists no comprehensive assessment of the overall safety of SSBs relative to current LiB technology.
This work presents an analysis of the comparative safety profiles of LiBs and SSBs. Thermal and mechanical testing is performed on full pouch cells with an industry-relevant combination of Li7La3Zr2O12 garnet-type SSE and gel-polymer catholyte. Time-synchronized captures of open-circuit voltage, surface and gas temperatures, gas species compositions, and high-speed imaging provide quantifiable metrics to compare the safety of SSBs against LiBs under identical conditions. Parameters such as heat generation rate, maximum temperature, and gas evolution are reported.
References:
[1] A. Manthiram, X. Yu, S. Wang, Lithium Battery Chemistries Enabled by Solid-State Electrolytes, Nature Reviews Materials, 2 (2017) 16103.
[2] J. Sastre et al., Blocking Lithium Dendrite Growth in Solid-State Batteries with an Ultrathin Amorphous Li-La-Zr-O Solid Electrolyte, Communications Materials, 2 (2021) 76.
[3] T. Inoue, K. Mukai, Are All-Solid-State Lithium-Ion Batteries Really Safe? – Verification by Differential Scanning Calorimetry with an All-Inclusive Microcell, ACS Appl. Mater. Interfaces, 9, 2 (2017) 1507-1515.
Fluoride-Ion Migration Mechanism in Fluoride Battery Electrolyte Material Cs2RbBiF6 with Double-Perovskite Structure
Authors: Moriwake Hiroki , Ogawa Takafumi , Kuwabara Akihide , Ikuhara Yuichi , Niwa Eiki , Sakakibara Kou , Mori Daisuke 
Published: December 2024

Recently, fluoride-ion batteries have been extensively studied for next-generation rechargeable batteries. In this battery system, fluoride-ion electrolyte material with high fluoride-ion conduction is strongly desired. A limited number of the fluoride-ion electrolyte material were reported. Most of them have Fluorite structure or Tysonite structure and their related crystal structures. If we have new fluoride-ion electrolyte material in another crystal structure, we can expand our choice of material. In this study, we carried out theoretical studies using first-principles static and dynamic calculations for fluoride battery electrolyte material Cs2RbBiF6 with double-perovskite structure. first-principles static and dynamic calculations in this study were performed by projector augmented wave (PAW) methods based on density functional theory (DFT). The generalized gradient approximations parameterized for the solid system (GGA-PBE_sol) were used. Our calculations revealed this material, Cs2RbBiF6 consists of strong covalent bonding BiF6 octahedron and ionic Cs-F bonding. Phonon calculations showed instability of BiF6 octahedron rotations. This indicates that BiF6 octahedron rotations can occur in elevated temperature regions. The fluoride-ion conduction behavior was studied by first-principles molecular dynamics calculations. The fluoride-ion conduction trajectory recorded at 600 K is shown in Fig. 1. In this figure, fluoride-ion mainly migrates around the BiF6 octahedron. On the other hand, fluoride-ion mainly migrations between BiF6 octahedrons were not so often observed. Migration energies were determined using the nudged elastic band (NEB) method and were evaluated to be 0.089 eV for the path within the BiF6 octahedron and 0.212 eV for the path between BiF6 octahedron. Our calculation results indicate the potential of high fluoride-ion conduction of these materials.
Acknowledgments: This work was supported by the RISING3 (JPNP21006) projects from the New Energy and Industrial Technology Development Organization (NEDO), Japan.

Figure 1
State-of-the-Art Na-Ion Batteries: Electrolyte Approach to Address the Issues of Cycle-Life
Authors: LE Phung M-L , Tran Thanh-Nhan , Le Minh-Kha 
Published: December 2024

With a worldwide trend towards the efficient use of renewable energies, the electricity supply sector has a pressing need for inexpensive energy storage. Sodium-ion batteries (NIBs) are an emerging battery technology with promising cost, safety, sustainability, and performance advantages over current commercialized lithium-ion batteries. Therefore, NIBs are attractive prospects for stationary storage application (utility scale and behind-the-meter), and transportation applications where energy density is less critical, and lifetime operational cost is the overriding factor.
Sodium-ion batteries have similar architecture/construction as state-of-the-art Li-ion batteries and can be a drop-in to the existing manufacturing infrastructure. The abundance of sodium alleviates some of the critical materials supply chains issues associated with lithium. Gravimetric energy densities are reported in the range of 100-200 Wh/kg making them a potential complementary/substitutional technology to lithium iron phosphate-based batteries. Sodium-ion batteries operate in a similar temperature regime as lithium-ion technologies but can be shipped uncharged (0% state of charge) for improved safety. However, before commercializing NIBs, R&D activities must be focusing on cost reduce by: (1) improving technical performance (increasing cycle life and energy density); (2) Establishing supply chains; (3) achieving economies of scales. Recently, some commercialization efforts have been demonstrating in pouch cells, 18650 cells, and/or modules showing very promising data, such as: Natron (US/Prussian blue), Faradion (UK/Layered Oxide), TIAMAT(FR/polyanionic), CATL (CN/Layered Oxide), and HiNa (CN/Layered Oxide).
Improving the lifespan as well as energy density of the NIB is one of main targets to support for the deployment if NIBs at scale in various market. In PNNL, we have been developing some advanced electrolytes which are nonflammable and help to resolve the issue of battery cycle life through enhancing/stabilizing the interfacial reaction and preventing the materials failure during long-term operation. In addition, the fundamental aspects and deep exploring on reaction kinetic helps to unveiling the mysteries of the battery degradation and operation failure.
Analysis of Commercial Na-Ion 18650 Cell Performance: Cell-to-Cell Variation and Long-Term Cycling
Authors: Wittman Reed M , Dubarry Matthieu , Rich Chaz , Langendorf Jill , Bates Alex Martin 
Published: December 2024

The development of commercial Na-ion battery cells for various energy storage applications has ramped up rapidly in the last three years. Currently, 18650 format cells from several manufacturers have been released for purchase through wholesalers, indicating that Na-ion cells may soon be ready for adoption into the grid, electric vehicles, and various consumer electronics. The promise of Na-ion is lower cost and only moderately reduced power and energy density compared to Li-ion cells. Thus, they may work as a drop-in replacement for Li-ion technologies depending on the use case.
To be adopted for a wide range of energy storage applications, the commercial cell performance needs to be evaluated under a variety of conditions. Sandia National Labs has embarked on a long-term cycling study of Na-ion cells from two different manufacturers to help fill the gaps in performance evaluation. This study covers variations in performance based on temperature, state of charge, cycling rate, and various simulated duty cycles. Initial results from the first few months of testing of these new cells will be presented.
In addition to the long-term cycling study, we conducted materials characterization and cell-to-cell cycling variance analysis. This is to understand the fundamentals of the battery mechanics, operation, and manufacturing quality. Initial results showed that the two manufacturers are using similar electrode chemistries, with a positive electrode active material that is likely a sodium iron manganese nickel oxide (Na(FexMnyNiz)O) and a negative electrode that is composed of hard carbon. During initial cell variance analysis, we observed that the different manufacturers are producing cells with similar performance, with incremental capacity curves that match each other in feature location and amplitude. Manufacturer A’s cells have about 10% more capacity than manufacturer B’s cells, which is likely a product of cycling to a voltage limit 100 mV higher than manufacturer B’s. Both manufacturers have cell-to-cell variance of capacity of less than 1% which matches what is observed in Li-ion cell production. We will also detail more analysis of cell variations like temperature and rate-based capacity variations as well as internal resistance values, electrochemical impedance spectrums and voltage relaxation times.

SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525.
Polysaccharide-Based Hydrogel Electrolyte Membranes for Quasi-Solid-State Rechargeable Alkaline Zinc Batteries
Authors: Inoue Hiroshi , Chiku Masanobu , Higuchi Eiji , Zhen Cheng 
Published: December 2024

Introduction

Rechargeable zinc battery is a promising energy device because of its advantages such as high safety, low cost, environmental friendliness etc. However, the reduction in discharge capacity due to hydrogen evolution reaction and short circuits caused by dendrite growth during charging hinder the practical application of rechargeable zinc battery. We have demonstrated the effectiveness of crosslinked polyacrylate-based hydrogel electrolytes (HEs) as an alternative to aqueous alkaline solutions to improve these issues.1 We have recently become interested in physical gels in which the host polymer is cross-linked by intermolecular interactions such as hydrogen bonding and ionic bonding, and prepared new HEs by mixing xanthan gum (XG), one of polysaccharides, as host polymer and aqueous KOH solutions. The XG-based HEs showed ionic conductivity comparable to the corresponding alkaline aqueous solutions. However, we have not succeeded in producing self-standing XG-based HE membranes under alkaline conditions yet. In this study, we have used another polysaccharide, starch, to prepare and characterize self-standing HE membranes under alkaline conditions. Moreover, we fabricated quasi-solid-state Zn/HE/positive electrode cell and evaluated charge-discharge performances.

Experimental

Commercial starch powder was mixed with (4 M KOH-0.3 M ZnO) aqueous solution with stirring to obtain a homogeneous sol, and then dried to prepare starch-based HE. The prepared starch-based HE membrane was soaked in the electrolyte solution before fabricating cells.

Results and Discussion

The photos of prepared starch-based HE membrane are shown in Fig. 1. As can be seen from these figures, the HE membrane was able to stretch and contract without tearing, suggesting that it exhibited high physical strength. The ionic conductivity of the HE membrane was a little lower than that of electrolyte solution. Using a Cu/HE membrane/Zn cell, the redox waves due to Zn deposition/dissolution at a Cu electrode were observed by cyclic voltammetry. Charge-discharge measurements using a Zn/HE membrane/Zn symmetrical cell showed an overpotential of about 50 mV for Zn deposition/dissolution, which was almost the same as a cell using a (4 M KOH-0.3 M ZnO) aqueous solution. In charge-discharge test using a γ-MnO2/HE membrane/Zn cell at 2 C-rate between 0.8 and 1.8 V, the initial discharge capacity was 253 mAh g-1, which was ca. 82 % of the theoretical capacity. However, the discharge capacity decreased to ca. 70 mAh g-1 by the 50th cycle.
This work is based on results obtained from a project, JPNP21006, commissioned by the New Energy and Industrial Technology Development Organization (NEDO).

Reference

C. Iwakura, H. Murakami, S. Nohara, N. Furukawa, H. Inoue, J. Power Sources, 152, 291 (2005).

Figure 1
Ultrasmall α-MnO2 Cathodes for Multivalent Rechargeable Batteries
Authors: Iimura Reona , Kobayashi Hiroaki , Kawasaki Shiori , Mandai Toshihiko , Kisu Kazuaki , Orimo Shin-ichi , Yamaguchi Kazuya , Ichitsubo Tetsu , Honma Itaru 
Published: December 2024

The energy density of lithium-ion batteries (LIBs), widely used today, is nearing its theoretical limits. This situation calls for a significant advancement in battery performance to meet the demands of an increasingly electrified society, which includes applications like electric vehicles and smart grids. Moreover, given the unstable global conditions, there is a growing demand for the creation of batteries with minimal susceptibility to price fluctuations. Multivalent rechargeable batteries, utilizing elements such as Mg, Ca, and Zn, emerge as promising alternatives to LIBs due to their cost-effectiveness, enhanced safety features, and higher volumetric energy density. However, despite their potential, designing cathode materials that balance high energy and high-rate capabilities remains challenging. Oxide-based cathodes have garnered attention for their ability to offer higher voltage operational capacities. Nevertheless, many cathodes materials face room-temperature capability issues, particularly in Mg and Ca battery cells, owing to sluggish multivalent cation diffusion rates.
In this work, we successfully synthesized ultrasmall α-MnO2 ( < 10 nm ) by newly developed alcohol reflux process as a common cathode material. Compared with α-MnO2 cathode synthesized by conventional hydrothermal method, the incorporation of ultrasmall α-MnO2 significantly enhanced the performance of all battery systems such as rate capabilities and reversibility. These findings open new avenues for the development of next-generation rechargeable battery cathode.
Promoting Homogeneous Zinc-Ion Transfer through Preferential Ion Coordination Effect in Gel Electrolyte for Stable Zinc Metal Batteries
Authors: Lee Sangyeop , Han Im Kyung , Kim Youn Soo , Park Soojin 
Published: December 2024

In an era increasingly defined by climate change, the shift towards sustainable energy solutions has become a critical global imperative. This shift underscores the importance of developing eco-friendly electricity sources as viable alternatives to fossil fuels, addressing both environmental concerns and the issues of intermittency and instability that plague renewable energy sources. Electrochemical energy storage, exemplified by rechargeable batteries, has emerged as a key technology in this context, offering a means to store renewable energy efficiently. Notably, lithium-ion batteries (LIBs) have dominated the field due to their high energy density and application versatility. However, the safety risks associated with LIBs, particularly those related to thermal runaway, have prompted the search for safer alternatives.
Water-based aqueous batteries, and specifically aqueous zinc (Zn) metal batteries (AZMBs), have been identified as promising candidates in this regard. AZMBs, leveraging the advantages of zinc as an anode material and Zn2+ ions for charge transfer, offer a blend of high energy density, low environmental impact, and inherent safety. Yet, the commercial adoption of AZMBs faces challenges, notably the dendritic growth on zinc anodes during charge/discharge cycles, which undermines battery performance and safety.
Addressing this challenge, our research focuses on sulfobetaine methacrylate (SBMA) as a repeating unit for the zwitterionic polymer matrix and examine the improvement of anode reversibility through preferential ion coordination behavior. The abundant polar groups in SBMA interact favorably with internal ions and influence charge carrier migration during cell operation. Using two-dimensional (2D) correlation spectroscopy in conjunction with Raman spectroscopy, it has been found that the interaction priority order of SO3
- functional groups increases when the concentration of ZnSO4 salt in the gel electrolyte rises from 2 m (mol·kg-1) to 5 m. Preferential coordination stimulates the uniform distribution of Zn2+ ions within the structure and alleviate the tip effect, contributing to improved stability during electrodeposition. Additionally, the combined effect of a zwitterionic gel and an electrostatic interaction hinders the 2D diffusion of Zn atoms on the anode surface and enables a dendrite-free electrode morphology accordingly. As a result, a zwitterionic gel polymer electrolyte (ZGPE) with 5 m ZnSO4 supports durable aqueous zinc metal batteries through uniform Zn plating/stripping behavior, as demonstrated by long-term symmetrical cell results (>3600 h cycle life at an areal capacity of 0.5 mAh·cm-2 and a current density of 0.5 mA·cm-2). The feasibility of the proposed system was further validated by Zn|Zn0.25V2O5 full cells, which exhibited excellent cyclability as preferential ion coordination retains the anode sustainability and prevents performance degradation.
Water Content Gradient Electrolyte for Highly Stable Aqueous Zinc Metal Batteries
Authors: Wang Ziqing , Mullins Charles Buddie 
Published: December 2024

Recent interest focuses on aqueous zinc metal batteries (AZMBs) for large-scale energy storage systems due to their affordability and safety.1 However, the dendrite growth and parasitic reactions on the Zn anode and the dissolution on the cathode harm the sustainability of AZMBs.2 Several strategies have been proposed to stabilize zinc anode and protect oxide-based cathodes by decreasing the water content in the electrolytes.3-5 However, the actual performance of these low water-content electrolytes is unsatisfactory because of their high viscosity and low ionic conductivity. In contrast, high water-content electrolytes (i.e., conventional aqueous electrolytes) provide promising physicochemical properties, whereas water decomposition on the electrode surface is inevitable, further negatively impacting electrochemical performance. In this study, we design a unique gradient electrolyte where a water content gradient is achieved from electrode to separator. Specifically, a molecular crowding electrolyte with less water content and suppressed water activity is coated on the electrode surface, and a conventional aqueous electrolyte with high water content is dropped on the separator. By assembling the battery, the MCE on both electrodes and the AqE on the separator form a sandwich-like gradient electrolyte (GE). Due to the AqE in between, the ionic conductivity within GE is significantly improved than MCE. Meanwhile, the MCE on the electrode surface regulates uniform zinc deposition and reduces parasitic reactions related to water decomposition. As a result, the highly reversible zinc plating/stripping occurs in Zn/Cu asymmetric cells with an average Coulombic efficiency of 99.1% for over 1000 cycles. Moreover, the Zn/Zn symmetric cells can stably cycle with reduced overpotential than MCE for over 1000 hours at different current densities. Full cell batteries employing MnO2 exhibit excellent capacity retention after 1000 cycles at 2 A g–1 due to the suppressed cathodic dissolution. This gradient electrolyte offers a facile strategy to protect electrodes and prevent side reactions without sacrificing ionic conductivity and viscosity.
References:
1. F. Wan et al. ACS Energy Lett.
2020, 5 (11), 3569-3590.
2. M. Zhang et al. Adv. Energy Mater.
2024, 14 (9), 2303737.
3. H. Ren et al. Adv. Mater.
2023, 35 (1), 2208237.
4. L. Qian et al. Adv. Funct. Mater.
2023, 33 (23), 2301118.
5. Y. Zhong et al. Angew. Chem. Int. Ed.
2023, 62 (40), e202310577.

Figure 1