bluuebunny/crossref_metadata_2025_split huggingface dataset:
How Low Temperature Heat Transfer Fluids Improve Localized High-Concentration Electrolytes for Lithium-Metal Batteries
Authors: Weintz Dominik , Woelke Christian , Winter Martin , Cekic-Laskovic Isidora 
Published: December 2024

The rising deployment of portable devices and electric vehicles has accelerated the development of high energy-dense batteries and revived interest in lithium metal as an anode material in recent years. However, by employing the widely-used organic carbonate-based electrolyte formulations in lithium-metal batteries (LMBs), whisker-like Li deposits emerge during galvanostatic cycling, precipitating a rapid active material degradation.1 Consequently, researchers have shifted their focus towards novel electrolyte formulations aimed at facilitating a dense Li deposition and prolonging the cycle life of LMBs. A promising approach is the application of localized high-concentration electrolytes (LHCEs) due to their unique solvation structure, causing the formation of an effective anion-derived Solid Electrolyte Interphase (SEI) and a dense Li deposition morphology.2–5 One of the remaining challenges for this novel electrolyte concept is the low ionic conductivity and the resulting declining galvanostatic cycling performance at higher current densities (> 1 mA cm-2), thus making the increase of the ion mobility crucial to enable LHCEs to become viable electrolyte solutions for LMBs.
In our study, we investigated inexpensive heat transfer fluids as effective co-diluents for LHCEs employed in LMBs. Incorporating these low-cost fluids into the electrolyte formulation results in lower viscosity and enhances molecular diversity, thereby improving transport properties and causing superior fast-charging capabilities of the resulting LMB chemistry. While the introduction of these novel co-diluents appears to have no discernible effect on the composition of the interphase layer formation, their presence promotes a more uniform lithium deposition morphology, particularly under higher charging rates. Additionally, the non-flammable nature of these components enhances the safety profile of the LMBs, rendering the novel components as multifunctional co-diluents for LHCEs and concurrently improving several crucial properties of the resulting electrolyte formulation.

References:

Horstmann, B. et al. Strategies towards enabling lithium metal in batteries: interphases and electrodes. Energy Environ. Sci.
14, 5289–5314 (2021).

Cao, X., Jia, H., Xu, W. & Zhang, J.-G. Review—Localized High-Concentration Electrolytes for Lithium Batteries. J. Electrochem. Soc.
168, 010522 (2021).

Ren, X. et al. Enabling High-Voltage Lithium-Metal Batteries under Practical Conditions. Joule
3, 1662–1676 (2019).

Ren, F. et al. Solvent–Diluent Interaction-Mediated Solvation Structure of Localized High-Concentration Electrolytes. ACS Appl. Mater. Interfaces
14, 4211–4219 (2022).

Angarita-Gomez, S. & Balbuena, P. B. Ion mobility and solvation complexes at liquid–solid interfaces in dilute, high concentration, and localized high concentration electrolytes. Mater. Adv.
3, 6352–6363 (2022).
Influence of Oxygen Defects on Electrochemical Performance of Ni-Rich Layered Oxides for Future Lithium-Ion Batteries
Authors: Henseler David , Vettori Kilian , Schröder Steffen , Nakamura Takashi , Henss Anja , Janek Jürgen 
Published: December 2024

Ni-rich layered cathode active materials (CAMs) are promising candidates for application in lithium-ion batteries due to their high reversible capacity. To further improve the performance of lithium-ion batteries, changing the transition metal composition in CAMs is a good approach to gain a higher capacity, better capacity retention as well as higher rate capability and safety. The oxygen lattice has been considered and widely accepted to be electrochemically inactive, even though it plays a key role in the phase transformations that occur at high degrees of delithiation, as oxygen is released during these high delithiation states. In addition, released oxygen can cause thermal runaway, by exothermic reaction with electrolyte 1,2. However, the effect of oxygen defects and vacancies on the electrochemical performance of cathode active materials in lithium-ion batteries has been scarcely investigated. Research has mainly focused on lithium-rich layered materials, where oxygen vacancies have led to improved battery performance in terms of rate capability, higher discharge capacity and reduced oxygen evolution 3. However, many of these publications suffer from an unprecise content of oxygen deficiencies within the cathode active material with large errors. In this work, a solid-state reactor for electrochemical extraction of oxygen is used to obtain an accurate oxygen deficiency with low error for Ni-rich layered NCM 811 4. Using this process, 1 mol%, 2 mol% and 5 mol% oxygen deficient NCM 811 are produced and (electro)chemically characterized. The effect of oxygen defect concentration on discharge capacity, capacity retention, rate capability and structural stability is investigated in liquid cells. In addition, electrochemical impedance spectroscopy (EIS) is used to reveal changes in electrode resistances. To obtain the cathode impedance only, a three-electrode setup is used, which utilizes a μ-reference electrode made of gold wire.
References

1 R. Jung, M. Metzger, F. Maglia, C. Stinner and H. A. Gasteiger, J. Electrochem. Soc., 164, A1361 (2017).

2 R. Jung, P. Strobl, F. Maglia, C. Stinner and H. A. Gasteiger, J. Electrochem. Soc., 165, A2869 (2018).

3 B. Qiu, M. Zhang, L. Wu, J. Wang, Y. Xia, D. Qian, H. Liu, S. Hy, Y. Chen, K. An, Y. Zhu, Z. Liu, and Y. S. Meng, Nat. Commun., 7, 12108 (2016).

4 T. Nakamura, H. Gao, K. Ohta, Y. Kimura, Y. Tamenori, K. Nitta, T. Ina, M. Oishi and K. Amezawa, J. Mater. Chem. A, 7, 5009 (2019).
Ethereal Based Electrolytes for Ultrastable LiNi0.8Mn0.1Co0.1O2 (NMC811)||Si Full Cells
Authors: Wu Xianyang , Li Xinlin , Amine Khalil , Wu Dezhen , Li Tianyi , Su Chi Cheung , Yang Zhenzhen , Ingram Brian J. 
Published: December 2024

With its impressive specific capacity of 3579 mAh/g (when alloyed into Li15Si4 at room temperature), Silicon (Si) anode is widely regarded as an ideal alternative to graphite anodes. However, its commercial viability is still hampered by rapid capacity degradation. Liquid electrolytes based on ethereal solvents such as dimethoxyethane (DME) and diglyme (DG) have demonstrated excellent long-term cycling performance in Li||Si half cells. However, their utilization in full cells like LiNi0.8Mn0.1Co0.1O2 (NMC811)||Si remains limited due to their relatively low oxidation stability at the NMC811 side.
In this investigation, innovative electrolyte systems employing Lithium bis(fluorosulfonyl)imide (LiFSI) salt were developed. Various ethereal solvents including DME, DG, 2,2-dimethyl-3,6,9,12-tetraoxa-2-silatridecane (1NM3), and self-synthesized 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG) were methodically examined. Initially, density functional theory (DFT) calculations were utilized to compare the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels of these solvents, revealing that 1NM3 and FDG exhibited lowered HOMO levels, suggesting enhanced oxidative stability on the NMC811 cathode side compared to DME and DG. Subsequently, the solvation structure of the prepared electrolyte systems was investigated via Fourier Transform Infrared Spectroscopy (FTIR). The addition of a -CF3 functional group and the weaker dissociation capacity of FDG resulted in significant cation-anion aggregates (AGGs) within the FDG-based electrolytes, while no such AGGs were observed in the DME, DG, and 1NM3-based electrolytes. Electrochemical properties and performances were further evaluated through systematic tests on Li||Al, Li||Si half cells, and LiNi0.8Mn0.1Co0.1O2 (NMC811)||Si full cells. Differential capacity (dQ/dv) profiles from Si||Li half cells revealed their distinct reduction behavior on the Si anode. Potentiostatic hold tests on NMC811||Li half cells demonstrated the superior oxidative stability of FDG-based electrolytes up to 4.5 V vs. Li/Li+. Long-term cycling results confirmed significant improvements with 1NM3 and FDG solvents in NMC811||Si full cells, maintaining a high specific capacity of 900 mAh/g after 500 cycles for the FDG-based electrolytes. Further analysis of the interphases formed on electrodes via depth-profiling X-ray photoelectron spectroscopy (XPS) indicated enhanced oxidative stability on the NMC811 cathode and improved solid electrolyte interphase (SEI) on Si anodes, leading to enhanced electrochemical performance. Thus, our exploration of these ethereal electrolytes has paved the way for strategic advancements in crafting novel electrolytes specifically designed for Si anodes, highlighting their remarkable long-term cycling capabilities within NMC811||Si full cells.
Understanding and Controlling Stack Pressure Inhomogeneity in Anode-Free Solid-State Batteries
Authors: Thorpe Micah , Zhang Mengyao , Liao Daniel W. , Kim Younggyu , Sandoval Stephanie Elizabeth , Nelson Douglas Lars , Shevchenko Pavel , McDowell Matthew Todd , Thouless M.D. , Dasgupta Neil P. 
Published: December 2024

Lithium (Li) metal anodes are widely studied as replacements for current graphite anodes as they have projected higher energy density. However, Li-metal batteries face issues with dendrite propagation and the eventual formation of dead Li. Solid-state batteries (SSBs) are a promising pathway to realize Li-metal batteries, which is attributed to their ability to improve safety and stability through the use of solid-state electrolytes. In particular, “anode-free” SSBs can enable high energy densities by forming a Li metal anode in situ. The initial Li nucleation, plating, and stripping behaviors in anode-free SSBs is influenced not only by the interfacial electrochemistry, but also by the mechanical stresses present along the current collector interface. Mechanical stress also plays a key role in Li metal anode deformation, where creep is the dominant deformation mechanism. However, to date, stack pressure is typically reported as a singular value, rather than considering the temporal and spatial variations in interfacial stress as the battery cycles.
This work investigates the role of inhomogeneous stack pressure on Li anode formation and dissolution against a sulfide solid electrolyte. To compensate for this inhomogeneous stack pressure, elastomeric interlayers are used to increase the uniformity of stress along the interface, and thus improve electrochemical cyclability. To analyze the impact of elastomeric interlayers on areal Li plating coverage, post-mortem optical microscopy images of the current collector are captured, showing an improvement in areal coverage from 49% to 70%. The reversible capacity also increases from 89% to 94% with inclusion of an elastomer layer. To confirm the trends in an elastomer layer on increasing stack pressure homogeneity, the mechanical stress at the anode-free interface is modeled using finite-element simulations under different stack pressure geometries. System-level simulations illustrate tradeoffs with respect to the uniformity of mechanical stress and energy density. This work demonstrates the importance of studying external auxiliary components and packaging in SSBs to optimize anode-free SSB performance.
Relating Capacity Loss to Crack Propagation in All-Solid-State Batteries - a 3D Imaging Study
Authors: Lindner Adrian , Kiyek Vivien , Mail Matthias , Menesklou Wolfgang , Finsterbusch Martin , Scherer Torsten , Kübel Christian , Fattakhova-Rohlfing Dina , Guillon Olivier , Krewer Ulrike 
Published: December 2024

In an attempt to find energy storage systems able to overcome the challenges of traditional lithium-ion-batteries, solid-state batteries are one of the most sought-after technologies in recent years. The possibility to eliminate safety concerns of organic electrolytes as well as the utilization of lithium metal as a high energy anode material have pushed their development in academia and industry alike. Garnet type oxides like Li7La3Zr2O12 (LLZO) are promising candidates due to their relatively high ionic conductivity and electrochemical stability. However, LLZO can be susceptible to the formation of secondary phases and cracks during operation, leading to severe capacity loss. Therefore, present work tackles the challenge of crack formation through high-resolution 3D-imaging. FIB-SEM tomography of LCO-LLZO composite cathodes reveals the spatial and temporal distribution of cracks during electrochemical cycling. Additionally, quantitative image analysis reveals a connection between crack formation and electrode properties, e.g., impeding three-dimensional electronic and ionic transport. Based on structural simulations (GeoDict), ionic transport in the electrolyte drops by 50 % after crack formation. In summary, we show how high-resolution FIB-SEM tomography can be applied to solid-state battery research.

Acknowledgements

This work was funded by the German Ministry for Education and Research (BMBF) in the project CatSE2 under the reference number 03XP0510C. This work was carried out with the support of the Karlsruhe Nano Micro Facility (KNMF) a Helmholtz Research Infrastructure at Karlsruhe Institute of Technology (KIT).
Figure 1: Development of pore size distribution (PSD) in garnet type solid state composite cathodes during cycling. Initially (0 cycles), pores are distributed homogeneously throughout the cathode. After cycling (EoL), we find that cracks form close to the separator, leading to an accumulation of inactive regions.

Figure 1
Elucidating Ion Transport Phenomena in Sulfide/Polymer Composite Electrolytes for Practical Solid-State Batteries
Authors: Oh Kyeong-Seok , Lee Ji Eun , Lee Yong-Hyeok , Jeong Yi-Su , Kristanto Imanuel , Min Hong-Seok , Kwak Sang Kyu , Lee Sang-Young 
Published: December 2024

Solid-state batteries (SSBs) are emerging as a safer, higher-energy alternative to traditional lithium-ion batteries, driven by the demand for advanced energy storage solutions. Despite the potential of inorganic/polymer composite solid-state electrolytes (CSEs) to enhance SSB performance, the mechanisms of ion transport in these systems remain poorly understood. This study aims to elucidate these mechanisms by exploring the formation of bi-percolating ion channels and ion conduction at the interfaces between inorganic and polymer electrolytes in CSEs.
We selected a model CSE composed of argyrodite-type Li6PS5Cl (LPSCl) and a gel polymer electrolyte (GPE) containing a Li+-glyme complex for ion conduction and a crosslinked ethoxylated trimethylolpropane triacrylate (ETPTA) polymer for structural support. Our findings reveal that the percolation threshold of the LPSCl phase within the CSE is significantly influenced by the elasticity of the GPE phase. Moreover, by modulating the solvation/desolvation dynamics of the Li+-glyme complex within the GPE, we achieved enhanced ion conduction across the LPSCl-GPE interface.
The optimized CSE, incorporating a balance of material chemistry and composition, was integrated with an aramid nonwoven porous substrate to achieve scalability and flexibility in manufacturing. The resultant CSE, with dimensions of 8 × 6 (cm × cm) and a thickness of approximately 40 μm, was paired with a high-mass-loading LiNi0.7Co0.15Mn0.15O2 cathode and a graphite anode to construct an SSB full cell. This assembly, characterized by a bi-cell configuration and a negative (N)/positive (P) capacity ratio of 1.1, exhibited a remarkable volumetric energy density of 480 Wh Lcell
-1 and stable cyclability at 25 °C.
This study not only advances our understanding of ion transport phenomena in CSEs but also presents a pragmatic approach to the design and fabrication of SSBs with superior performance metrics. By integrating insights into ion channel formation and interfacial conduction with innovative materials engineering, we present a scalable and effective strategy for the development of high-performance SSBs. This research underscores the critical role of CSE design in overcoming the limitations associated with both inorganic and polymer electrolytes, paving the way for the next generation of energy storage technologies.

Figure 1
(Invited) Towards Automated Materials Discovery for Next-Generation Batteries with Solid-State Electrolytes
Authors: Wang Yan 
Published: December 2024

Solid-state batteries are increasingly seen as essential for next-generation energy applications in consumer electronics and electric vehicles. The key component of solid-state batteries is the solid-state electrolytes with high ionic conductivity and great interfacial stability against battery electrodes. Traditional discovery of solid-state electrolyte materials for high ionic conductivity often proceeds based on trial-and-error without an understanding of underlying structure-composition-property relationships, and so far only a handful of lithium and sodium conductors have been discovered with desired conductivity.
Computational modeling based on density functional theory has become a cornerstone of materials design, by providing insights into fundamental processes that are not easily accessible in experiments, and enabling fast and efficient prediction even before material synthesis [1-2]. Such predictive power has made computational modeling a critical tool to design new solid-state ionic conducting materials with desired properties and accelerate the development of next-generation batteries with solid-state electrolytes.
In this talk, I will present our recent findings in the physical and chemical design principles for solid-state materials with high ionic conductivity and stability [3]. More specifically, I will discuss crystallographic features which would enable fast ionic transport in inorganic solids, such as body-centered-cubic in sulfides [1] and corner-shared-polyhedron frameworks in oxides [4], and demonstrate how high-throughput calculations can be applied with such features in the design and discovery of new ionic conductors. I will also discuss our most recent efforts at Samsung Advanced Materials Lab, where we are developing an automation platform for inorganic battery materials discovery by combining high-throughput computation and robotic synthesis [5].
[1] Y. Wang et al., “Design principles for solid-state lithium superionic conductors,” Nature Materials, 14, 1026-1031, (2015).
[2] G. Ceder, S. Ong, Y. Wang, “Predictive modeling and design rules for solid electrolytes.” MRS Bulletin, 43(10), 746-751 (2018).
[3] Y. Xiao, Y. Wang, G. Ceder, et. al., “Understanding interface stability in solid-state batteries”, Nature Review Materials, 5, 105 (2020).
[4] K. Jun, Y. Wang, G. Ceder, et. al., “Lithium superionic conductors with corner-sharing frameworks”, Nature Materials 21, 924 (2022)
[5] J. Chen, S. R. Cross, Y. Wang, W. Sun, et. al., “Navigating phase diagram complexity to guide robotic inorganic materials synthesis”, Nature Synthesis, 1-9, 2024
Strategies for Mixed Ionic-Electronic Conductivity in Co-Doped Li-Garnet Based Electrolytes
Authors: Pachulska Klaudia , Cuper Aleksandra , Winkowska-Struzik Magdalena , Michalski Przemyslaw , Struzik Michal 
Published: December 2024

Solid-state electrolytes based on lithium garnet frameworks, such as Li7La3Zr2O12 (LLZO), brings a promise for enhanced safety and performance of next-generation lithium-ion batteries. Despite the promise of higher energy and power density than liquid electrolyte-based cells, superiority of their solid-state counterparts has not yet been demonstrated in working systems. One of the explanations can be attributed to the mismatch of the design and composition of the currently used battery electrodes to work with the solid electrolyte. One possible scenario for improving the electrochemical performance of solid-state electrolyte cells could be the use of composite electrodes, one component of which would be LLZO-based material modified to conduct both lithium ions and electrons to serve as a medium between the solid electrolyte and the electrochemically active material.
In this study, we explore impact of the simultaneous doping with transition metals on the garnet framework of LLZO with perspective to introduce mixed ionic-electronic conductivity with enhanced overall conductivity. We investigate the crystal structure using X-ray diffraction (XRD) and elucidate the local structural changes through Raman spectroscopy. The electric transport properties, crucial for battery performance, are thoroughly characterized via impedance spectroscopy and DC measurements.
Our results reveal a systematic enhancement in the electronic contribution to total conductivity. These findings not only advance the fundamental understanding of LLZO doping mechanisms but also offer practical insights into tailoring solid electrolytes for high-performance lithium-ion batteries.
This work has been financed by National Science Centre, UMO-2019/33/B/ST5/02134.
Design of Composite Cathode Electrodes for All-Solid-State Batteries
Authors: Kim Dong-Gyu , Kim Hyun-Kyung 
Published: December 2024

Li-ion batteries (LIBs) have high energy density and long-cycle energy storage; hence, they are widely used as power sources in electric devices. However, safety remains a major issue. Conventional LIBs developed using organic, liquid electrolytes may exhibit issues such as combustion and explosion. To address these issues, all-solid-state batteries (ASSBs) are considered promising candidates for advanced LIBs, offering high electrochemical stability and excellent safety owing to the non-flammability of the intrinsic inorganic solid electrolyte used1. The deployment of solid-state electrolytes (SSEs) into all-solid-state Li batteries is a promising approach due to the non-flammability and compatibility of SSEs with Li metal; thus, they have the potential to meet the increasing demands for high energy density and enhanced safety. Among the various SSEs, Li7La3Zr2O12 (LLZO) can be doped with Al, Ga, Ta, etc., to stabilize its cubic structure. LLZO exhibits high ionic conductivities (in the range of 10−4–10−3 S·cm−1), a wide operating voltage window, and excellent elastic and shear moduli. However, all ASSBs have solid-state electrode structures consisting solely of solid materials. As a result, Li-ion diffusion primarily occurs at the interfaces between the cathode-active material and solid electrolyte. Composite cathodes within ASSBs often exhibit numerous voids and high interfacial resistance. The limited ion conduction paths have constrained the electrochemical performance of ASSBs because of the inadequate contact areas between the active materials and solid electrolytes in the composite cathode2. To improve the electrochemical performance of ASSBs, some design issues of the composite cathode electrode need to be solved.
The aim of this study is to enhance the performance of ASSBs using a bimodal garnet-type solid electrolyte, Li7La3Zr2O12 (LLZO), composed of electrolytes of two different sizes. The bimodal electrolyte composite cathode exhibits a higher density and fewer voids compared to the monomodal electrolyte, as the small powder particles fill the voids between the large ones.3 Finally, ASSBs prepared using the bimodal electrolyte achieve a low interface resistance and a large contact area between the solid electrolyte and the cathode material, resulting in enhanced electrochemical performance. Further details regarding the electrochemical and structural properties will be presented in the meeting.