bluuebunny/crossref_metadata_2025_split huggingface dataset:
Interfacial Coatings to Enable the High Temperature Co-Sintering of All Ceramic Solid State NMC/LLZO Li Metal Batteries
Authors: Hoft Richard Mariano , Wachsman Eric D 
Published: December 2024

Solid-state batteries based on lithium-stuffed oxides ceramics promise to improve the safety and energy density over commercial Li ion batteries. Li7La3Zr2O12 (LLZO) is one of the most promising of these solid electrolytes as it has high ionic conductivity and low reactivity with Li metal. The major challenge of this material is its high interfacial resistance with commonly used cathodes such as LiCoO2 (LCO) and particularly Li2NixMnyCozO2 (NMC) due to the solid-solid nature of the contact and the thermochemical instability of these materials when mixed at high temperatures.
Previous experiments elucidated the nature of the thermochemical instability between LLZO and NMC by exploring various parameters such as sintering atmosphere, Li content of the LLZO, Ni content of the NMC, and processing temperature. This work expands this understanding by introducing an interfacial coating on the NMC to ameliorate the reaction between LLZO and NMC. The coatings explored were lithium metal oxides predicted to be stable with both LLZO and NMC. These interfacial coatings will minimize the interfacial resistance between LLZO and NMC to provide a pathway for producing a solid-state ceramic Li metal battery that can achieve theoretical capacities at commercially applicable charge rates at room temperature.
Preliminary results identified lithium aluminates and lithium silicates as prime interfacial coatings for minimizing the as-assembled interfacial area-specific resistance (ASR) as determined by Electrochemical Impedance Spectroscopy (EIS) of symmetric cells. Furthermore, increasing the Li content of the coatings was shown to further improve the interfacial ASR, confirming computational studies performed by collaborators. These coated NMCs were then fabricated into Li metal full cells using conventional tapecasting, lamination, and sintering processes. These cells were cycled using a constant current and constant voltage cycling procedure with EIS run before and after each charge cycle. These EIS results suggest that delamination caused by the volume change of NMC during electrochemical cycling is the cause for observed capacity fade.
Mixed Conductive Materials to Improve the Conductive Path of All-Solid-State Battery Composite Electrodes
Authors: Jeon Young-Gyu , Lim Chang-Hun , Kim Hyun-Kyung 
Published: December 2024

Lithium-ion Batteries (LIBs) function as energy-storage devices in various electronic applications. However, the use of flammable liquid electrolytes raises significant safety concerns, including the risk of fire or explosion. To mitigate these safety issues, all-solid-state batteries (ASSBs) have emerged as a promising alternative as they are composed of solid electrolytes instead of liquid ones. Li7La3Zr2O12 (LLZO) stand out as a highly promising garnet-type solid electrolyte, known for its chemically and electrochemically stable characteristics, making it suitable for ASSBs. However, LLZO suffers from high interfacial resistance, leading to decreased ion conductivity. In particular, the formation of voids during composite electrode fabrication interrupts ion conduction paths, resulting in a significantly increased resistance. Consequently, the high interfacial resistance arising from solid-state contacts can significantly impair the electrochemical performance and hinder practical cell operation. For these reasons, ASSBs typically use an excess of 10 wt.% or more solid electrolytes during electrode manufacturing, leading to a decrease in the active material fraction. Therefore, conducting research on electrode design aimed at optimizing the content of inactive components, such as the use of conductive additives and solid electrolytes, is necessary to improve the performance of ASSBs. In addition, novel approaches are needed to address the above-mentioned issues by reducing the interfacial resistance within composite electrodes containing solid electrolytes and maximizing electrochemical reactions.
This study aims to improve the performance of ASSBs by incorporating carbon nanotubes (CNTs) as a conductive additive with the solid electrolyte LLZO to establish an efficient charge transport pathway and improve interfacial resistance. When using CNT@LLZO as a conductive additive, the internal voids within the electrode are minimized, and an effective Li-ion conduction pathway is formed, resulting in improved electrochemical performance. Further details will be presented in the meeting.
Properties of Li1.3Al0.7Ti1.3(PO4)3 Ceramic Solid Electrolyte Densified by Cold Sintering Process
Authors: Inada Ryoji , Oizumi Kanta , Kurahashi Kaito , Tojo Tomohiro 
Published: December 2024

Replacing a flammable organic liquid electrolyte with a non-flammable solid electrolyte is the most promising way to improve the safety of Li-ion batteries. Oxide-based solid electrolytes have the advantages of good chemical stability and ease of handling, but for many of them, the high temperature sintering is required for densification and reduction of grain-boundary resistance for Li-ion conduction. However, co-sintering with electrode active materials at high temperature for fabrication of solid state batteries may cause side reactions and increase the internal resistance.1

Cold sintering (CS) is an attractive process for lowering the densification temperature of various ceramic materials.2
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7 In this study, we applied CS for the densification of Li-ion conductive Li1.3Al0.7Ti1.3(PO4)3 (LATP) ceramic electrolyte. LATP powder was mixed with proper amount of deionized water or LiOH solution with various concentration as a transient liquid phase (TLP) and densified by CS at 200-250 °C for 0.5 h under uni-axial pressure of 600 MPa. After CS, the relative density of LATP pellet was increased to 85-90 %, and LiOH addition to TLP is effective for increasing the density. Grain size of LATP in the pellet is 0.5-1 µm and nanoparticle precipitation was observed near the grain-boundary area. Similar microstructure is confirmed in previous works.2
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7 XRD measurements reveal the formation of LiTiOPO4 phase after CS. The amount of LiTiOPO4 phase tends to increase with LiOH concentration. It is thought that this heterogeneous phase precipitate during CS process and plays a role in bonding between LATP particles.
From impedance measurement, we obtained ionic conductivity of 4 × 10-5 S/cm at room temperature in LATP densified at 250 °C by CS with TLP with an optimum LiOH concentration, which is higher than LATP densified by CS with TLP without LiOH (1.7 × 10-5 S/cm) and pressed LATP powder without adding TLP (3.6 × 10-7 S/cm). However, the conductivity of LATP by CS is lower than LATP sintered at 1000 ºC (= 2.3 × 10-4 S/cm). To improve ionic conducting property further, controlling the amount of precipitation phases after CS is necessary.
This work was supported by Grant-in-Aid for Scientific Research (JSPS KAKENHI) Grant Number 22K18793 from the Japan Society for the promotion of Science (JSPS), and Innovative Elemental Technology Research in Green Technologies for Excellence (GteX) Program Grant Number JPMJGX23S7 of the Japan Science and Technology Agency (JST).
References

P. Jiang et al., Energy Technol. 11, 2201288 (2023).

J. Guo et al., Angew. Chem., Int. Ed. 55, 11457-11461 (2016).

J-H. Seo et al., Ceram. Internat. 43, 15370-15374 (2017).

J-H. Seo et al., Jpn. J. Appl. Phys. 60, 037001 (2021).

N. Hamao et al., Materials 14, 4737 (2021).

N. Hamao et al., Chem. Lett. 50, 1784-1786 (2021).

A. Mormeneo-Segarra et al., Ceram. Internat. 49, 36497-36506 (2023).
Scalable Surface Micro-Texturing of LLZO Solid Electrolytes for Battery Applications
Authors: Go Wooseok , Parkinson Dilworth Y. , Oropeza Dayana , Zorba Vassilia , Murali Sriram S. , Doeff Marca M. , Tucker Mike C 
Published: December 2024

A challenge for lithium lanthanum zirconate (LLZO)-based solid-state batteries is to increase the critical current density (CCD) to enable high current cycling. A promising strategy is to modify the LLZO surface morphology to provide a larger contact area with Li metal. Examples of such modifying surface morphology include surface patterning through laser cutting [1] and roughening by shot peening [2]. However, these techniques still have challenges in scale-up and application to thin electrolyte layers. Surface patterning using a laser cutter leads to surface contamination requiring post-heat treatment in an inert atmosphere, and shot-peening has a potential risk of mechanical failure caused by impact stress, making it especially difficult to use for thin electrolytes.
Here, we present an easily scalable process to prepare surface-textured thin LLZO electrolytes. The texturing process is a simple pressing of green LLZO tapes between micro-textured substrates. A variety of textures can be produced depending on the type of substrate, and texturing can be on either one side or both sides. For this work, after pressing and sintering, several micro-patterns are formed on thin LLZO (~118 μm thick). The properties of the various samples were characterized to investigate the impact of the surface texturing, and the most promising ones were selected for electrochemical testing in symmetrical lithium cells and full cells. Li symmetric cells using a coarse ridge-textured LLZO exhibit ~2.5 times increased CCD compared to planar non-textured LLZO, and a solid-state full cell shows stable cycling and improved rate performance. We believe this process offers a favorable tradeoff of processing complexity vs. structural optimization to maximize CCD.
[1] Xu R, et al Adv. Mater., e2104009, 33(49), (2021)
[2] Kodama M, et al J. Power Sources, 231556, 537 (2022)
Advantageous Li3PO4 Coating on Conductive Agents for Sulfide-Based All-Solid-State-Batteries
Authors: Jo Younghoon , Moon Janghyuk , Ha Chaeyeon , Chang Hongjun , Kim Young-Jun 
Published: December 2024

Sulfide-based all-solid-state-batteries (ASSBs) are garnering attentions as a next-generation battery system due to their high ionic conductivity and the ductility-derived processability. However, it is imperative to address the issue of side reactions between carbon additive-based conductive agents and solid electrolytes. Irreversible reactions of solid electrolytes, stemming from narrow electrochemical stability window, lead to capacity fading of ASSBs. Previous research has explored conductive agents in the form of fibers with a smaller specific surface area or reducing the proportion of conductive agents. Nevertheless, these approaches have not provided a fundamental solution.
Herein, we apply an oxide coating to the surface of carbon nanofiber conductive agents to prevent interfacial side reactions between the electrolyte and the conductive agent. Through computational screening among various oxide-based coating candidates, Li3PO4 is identified as possessing the highest chemical interfacial stability and superior ionic conductivity when interfaced with cathode active materials and solid electrolytes. This approach not only preserves the electronic percolation pathway essential for high-rate capability but also effectively suppress the decomposition of solid electrolytes through a stable ceramic layer. The efficacy of the Li3PO4 coating is demonstrated through enhanced ionic conductivity by up to 150% and improved rate capability and cycle performance in ASSBs, without significant loss of electronic conductivity in the composite cathode. This work introduces a novel concept in conductive agent modification, offering significant advantages in both ionic and electronic conductivity aspects.
Investigating Electro-Chemo-Mechanical Properties of Conversion Cathodes for Solid-State Batteries
Authors: Alsac Elif Pinar , Nelson Douglas Lars , Yoon Sun Geun , Wang Congcheng , Thomas Talia A. , Eze Udochukwu D , Harris John M , Liu Yuhgene , McDowell Matthew Todd 
Published: December 2024

Solid-state batteries (SSBs) could offer higher energy density and improved safety compared to traditional Li-ion batteries. Challenges remain, however, including contact loss/fracture and the effective design of high-conductivity cathode composites. Intercalation-type oxides such as LiNixMnyCo1-x-yO2 (NMC) are widely used in SSB cells. However, these materials have limited capacity and are expensive. Conversion materials such as sulfur, sulfides, and fluorides, on the other hand, show much higher capacity and have been widely investigated for batteries with liquid electrolytes. While their use in conventional Li-ion batteries is challenging due to detrimental interactions with the liquid electrolyte, solid-state batteries (SSBs) offer a potential solution due to improved stability with solid electrolytes. However, conversion cathodes undergo relatively large volume changes during charging and discharging reactions. This volume expansion and contraction is of particular concern for SSBs, since such changes in the all-solid-state environment may lead to interfacial contact loss, cracks within the composite cathode, and degradation of performance.
Here, we investigate the electro-chemo-mechanical evolution of various high-capacity conversion-type solid-state cathode composites (sulfur and other transition metal sulfides). X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) reveal redox reactions at transition metal sites in the composite cathodes, and electron microscopy is correlated to these measurements to determine how cracks evolve within the composite electrodes throughout cycling. The combined electrochemical and spectroscopic measurements reveal that while sulfur has a single conversion step, transition metal sulfides have a more complex, multi-step conversion mechanism. Real-time stack-pressure monitoring is used to provide insight into how stack pressure changes are linked to the diverse reaction pathways during charge and discharge of different conversion cathode materials. We show that there is different pressure evolution behavior for various conversion materials, and the electrode microstructure is also shown to influence stack pressure evolution. Overall, this study gives insight into material evolution and degradation mechanisms, guiding the design of superior cathodes for SSBs.
(Invited) Ionic Liquids As Multifunctional Electrolytes for Sodium Secondary Batteries
Authors: Matsumoto Kazuhiko , Qiu Jie , Wang Di , Liu Huazhen , Zhang Shaoning , Murakami Keisuke , Araya Kousei , Wu Shengan , Hwang Jinkwang 
Published: December 2024

To sustain the fast-growing energy demand, high-performance electrolytes and electrode materials are required for secondary batteries. Sodium secondary batteries have emerged as expedient lithium-ion battery alternatives due to the low costs and high abundance of sodium resources. Ionic liquids (ILs) with low vapor pressure and low flammability are fascinating electrolytes for sodium secondary batteries owing to their intrinsic high safety and thermal stability.[1,2] In this talk, multifunctionalities of ionic liquid electrolytes for sodium secondary batteries will be comprehensively presented, especially targeting the performance of a range of negative and positive electrode materials and dual electrolyte system combined with beta-alumina. Intermediate temperature operation is also possible with the aid of thermally stable ionic liquids. Advantages of operation at intermediate temperature will be also discussed based on the results of electrochemical analysis.
References
[1] K. Matsumoto, J. Hwang, S. Kaushik, C.-Y. Chen, R. Hagiwara, Energy Environ. Sci. 12, 3247 (2019).
[2] A. Basile, M. Hilder, F. Makhlooghiazad, C. Pozo-Gonzalo, D. R. MacFarlane, P. C. Howlett, M. Forsyth, Adv. Energy Mater., 8, 1703491 (2018).
(Invited) Challenges and Advances in High-Energy Magnesium Batteries
Authors: Setiawan Dedy , Hwang Jiwon , Choi Jin , Park Yewon , Lee Yeon Woo , Lee Hyungjin , Lee Hochun , Hong Seung-Tae 
Published: December 2024

Despite the widespread use of Li-ion batteries, their limited energy density poses a significant challenge. Magnesium (Mg) batteries present a promising alternative due to their higher energy density and lower cost. However, existing Mg battery technologies encounter obstacles, particularly regarding electrode-electrolyte compatibility. The initial Mg battery prototype, employing the Mg/Mo6S8 system, exhibited a mere ~60 Wh/kgcell, significantly lower than Li-ion batteries (~300 Wh/kgcell). Despite efforts over the past two decades to develop new cathodes, electrolytes, and Mg anodes, most reported Mg battery systems have struggled with low energy densities and reproducibility issues.
In this presentation, we highlight recent breakthroughs in Mg batteries, achieving energy densities comparable to Li-ion batteries. Our approach incorporates novel cathode materials developed in our research group, surface-modified Mg anodes, and conventional nonaqueous electrolytes. Through our work, we aim to shed light on the development of advanced Mg battery systems capable of surpassing the energy density limitations of Li-ion batteries while maintaining cost-effectiveness.
Scalable and Cost-Effective Approaches to Rechargeable Zinc Sponge Anodes
Authors: DeBlock Ryan H. , Rolison Debra R. , Long Jeffrey W. 
Published: December 2024

Historic metallic zinc (Zn) anodes suffer from catastrophic dendritic growth and limited charge-discharge reversibility in alkaline electrolyte. To combat these issues, the Naval Research Laboratory pioneered a 3D-architected zinc “sponge” anode that distributes the electrochemical reaction thus decreasing local current density and suppressing shape change [1]. Fabrication methods to Zn sponges have evolved from lab-scale protocols with specialized materials to those that are scalable, rapid, and cost-effective. The latest generation of zinc sponge fabrication methods employ common pore-forming agents such as sodium chloride and calcium carbonate combined with chemical sintering and a simplified thermal treatment. These methods are adaptable to various form factors, including plates, cylinders, and discs and can be scaled to hundreds of square centimeters. We evaluate these new Zn sponges in electrochemical configurations including zinc–air, nickel–zinc, and silver–zinc to demonstrate their cycle life and specific power capabilities.
[1] J. F. Parker, C. N. Chervin, E. S. Nelson, D. R. Rolison, and J.W. Long. Energy Environ. Sci. 7 (2014) 1117–1124.
Microstructure Analysis and Performance Study of Wood Lignin-Derived Carbon Foam Electrode for Sodium-Ion Batteries
Authors: Biswas Diprajit , Yan Qiangu , Cai Zhiyong , Kazyak Eric 
Published: December 2024

Carbon foams (CF) offer a promising avenue for advancing energy storage systems due to their unique structure characterized by interconnected open-cell pores and surface-residing carbon nanofibers [1,2]. This structure provides tunability to the porosity, pore structure and size, which makes them ideal for high-energy dense electrodes for energy storage devices. Lignin-derived foams are particularly noteworthy as they utilize an abundant waste stream from paper products, offering a sustainable alternative to fossil-fuel-derived carbons often used in batteries. CFs can serve as electrodes or hosts for energy storage devices based on porosity, pore structure and size, and degree of graphitization, which significantly influences battery capacity, reversibility, and electrochemical reactions [3]. Utilizing natural CF from kraft lignin not only minimizes impacts compared to fossil-fuel-derived carbon sources [4] but also cuts production costs [2], making them an attractive option for large-scale energy storage systems.
In this investigation, we examined lignin-derived CFs with differing porosity and pore structures, carbonized across a temperature range of 800°C to 1300°C. Various characterization techniques corroborated the transition from disordered to ordered carbon structure, escalating the graphitization with the increased carbonization temperatures. Pouch cells are assembled using a standard sodium-based electrolyte. Half-cells demonstrated reversible capacities surpassing 200 mAh/g at C/10, affirming the potential of lignin-derived CF-based Na-ion batteries for large-scale energy storage applications. The performance is studied as a function of CF microstructure, porosity, pore structure and size, particle size, and degree of graphitization for a fundamental understanding of the CF electrode. In conclusion, utilizing sodium and lignin, both abundant and low-cost materials, presents a promising avenue for the energy storage industry on a large scale.

REFERENCES

[1] F. Xu, Y. Gui, S. Zuo, J. Li, S. Wang, Preparation of lignin-based carbon foam monoliths with high strength and developed micrometer-sized cell/nano-sized porous structures using a self-bubbling method, J Anal Appl Pyrolysis 163 (2022).
[2] Q. Yan, R. Arango, J. Li, Z. Cai, Fabrication and characterization of carbon foams using 100% Kraft lignin, Mater Des 201 (2021).
[3] X.Y. Cui, Y.J. Wang, H.D. Wu, X.D. Lin, S. Tang, P. Xu, H.G. Liao, M. Sen Zheng, Q.F. Dong, A Carbon Foam with Sodiophilic Surface for Highly Reversible, Ultra-Long Cycle Sodium Metal Anode, Advanced Science 8 (2021).
[4] S.F. Schneider, C. Bauer, P. Novák, E.J. Berg, A modeling framework to assess specific energy, costs and environmental impacts of Li-ion and Na-ion batteries, Sustain Energy Fuels 3 (2019) 3061–3070.