bluuebunny/crossref_metadata_2025_split huggingface dataset:
High Throughput Studies of Doped Li-La-Zr-O Garnet Solid Electrolytes
Authors: Anderson Ethan , Jonderian Antranik , McCalla Eric 
Published: September 2023

Lithium lanthanum zirconium oxide (LLZO) is a leading candidate for solid Li-batteries due to its high lithium-ion conductivity, stability in air and against Li metal, and compatibility with high-voltage cathodes.1,2 Despite significant research being done, our understanding of LLZO is limited by the relatively small number of compositions which have been studied; both in the larger Li-La-Zr-O system and in the doped cubic LLZO system, which can accommodate an extremely wide range of dopants.3To study this large number of compositions, we have applied a high-throughput methodology for synthesizing, characterizing, and testing sets of 64 LLZO electrolytes at the mg-scale. We employ a citrate sol-gel synthesis method whereby reagent solutions are dispensed across a well-plate to give a composition gradient. After drying and calcining the gels, the resulting powders are pelleted and then sintered at the desired temperature. High-throughput characterization techniques utilized include powder X-ray diffraction, impedance spectroscopy, DC polarization, and electrochemical stability window testing.
Using our methodology, we have recently studied over 700 samples to produce a full phase stability diagram for the Li-La-Zr-O pseudoternary system.4 We found there is significant solubility of Li in the La2Zr2O7 pyrochlore structure, and that both cubic and tetragonal undoped LLZO appearing throughout the system have similarly poor bulk conductivities. This previous study again emphasizes the key role dopants play in LLZO. Herein, our methodology is applied to a comprehensive doping study where 60 different dopants are evaluated under identical synthesis conditions to allow for a thorough understanding of dopant effects on structure, ionic conductivity, electronic conductivity, and electrochemical stability window. Our samples achieve high conductivities over 1 mS/cm and relative densities above 90% with our combinatorial synthesis. Dopant content is optimized for each promising dopant to compare best-case results and correlate performance with structural properties like lattice parameters and density. Since comparing dopants in the literature is often difficult due to varying synthesis methods, this systematic work is essential in rational design of these electrolytes.
1.Q. Liu, et al., J. Power Sources
2018, 389, 120-134.
2.T. Thompson, et al., ACS Energy Letters
2017, 2, 462-468.
3.F. Zheng, et al., J. Power Sources
2018, 389, 198-213.
4.E. Anderson et al., DOI:10.1016/j.ssi.2022.116087.
(Invited) All-Solid Battery Interfaces and Research in the Toyota-ECS Young Investigator Fellowship
Authors: Arthur Timothy Sean 
Published: September 2023

Advances in hybrid and electric vehicle technologies combined with a demand for green initiatives have motivated necessary diversification in energy storage research. To achieve customer expectations for hybrid and electric vehicles, new battery systems with higher energy densities, power densities and cycle life than the current state-of-art are needed. Post Li-ion battery systems, such as solid-state batteries, are at the forefront of research and development for the future of mobility.
ECS and the Toyota Research Institute of North America (TRINA), have partnered to create the ECS Toyota Young Investigator Fellowship since 2014. The fellowship supports young faculty members conducting electrochemical research in green energy technology. The purpose of this fellowship is to encourage young professors and scholars to pursue innovative research in sustainability including next generation solid-state batteries.
Here, we will show the progress of fundamental research of all-solid-state battery (ASSB) interfaces at TRINA. In addition, we will take a look at the history and relationship of TRINA and the ECS in the Toyota-ECS Young Investigator Fellowship. Throughout the years, the knowledge and relationships built through the Fellowship immensely supports the progress of post lithium-ion batteries. Finally, we show deep appreciation and will highlight key technical achievements of Toyota-ECS Young Investigator Fellowship winners in battery technology.

Figure 1
Multiscale Modeling of Heterogeneous Interfaces in All Solid-State Batteries
Authors: Wan Liwen , Kim Kwangnam , Dive Aniruddha Mukund , Wang Bo , Heo Tae Wook , Wood Marissa , Wood Brandon C. 
Published: September 2023

Ion transport and degradation at the solid-electorlyte/cathode interfaces dictate the performance of all solid-state batteries. For example, it has been routinely observed that in many superionic oxide conductors, Li-ion transport kinetics are orders of magnitude slower at the interfaces, such as grain boundaries or interfaces with common electrode materials, compared to the bulk phases. Upon electrochemical cycling, interdiffusion and/or electrolyte/cathode decomposition at these interfaces can further deteriorate Li-ion transport kinetics. Therefore, the ability to understand, predict and precisely control ion transport kinetics and the degree of interfacial degradation are critical and would have a transformative impact on the development of solid-state battery technologies for practical applications. Here I will address the need of a multiscale and multiphysics modeling framework to understand Li-ion transport mechanisms at complex interfaces and predict the kinetics of Li-ion transport in solid-electrolyte/cathode composite architectures that are relevant for all solid-state Li batteries. I will also emphasize the importance of using a closely coupled theory-experiment approach to reveal the atomic details of the interfaces and unravel the degradation mechanisms of interfaces and its impact on Li-ion transport. I will use the garnet-type solid-state electrotype and lithium cobalt oxide cathode as an example to demonstrate the predictive power of such a multiscale, multiphysics modeling framework towards establishing the correlations between ion transport and local atomic structure, chemical environment, and mesoscopic microstructure features in the cathode/electrolyte composites.
This work was sponsored by the Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office and was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. An award of computer time was provided by the Innovative and Novel Computational Impact on Theory and Experiment (INCITE) program. This research used resources of the Argonne Leadership Computing Facility, which is a DOE Office of Science User Facility supported under Contract DE-AC02-06CH11357.
Cycling Efficiency Improvement of Solid-State Batteries-Laser Textured Interfaces
Authors: Yan Shuo , Guo Deliang , Yim Chae-Ho , Merati Ali , Baranova Elena A. , Weck Arnaud , Abu-Lebdeh Yaser 
Published: September 2023

Solid-state lithium metal batteries (SS-LMBs) with ceramic electrolytes have attracted significant interest towards their potential to produce safe and powerful storage devices. Among ceramic electrolyte materials utilized in SS-LMBs, non-flammable perovskites (La2/3-xLi3xTiO3, LLTO) are cost-effective and have a wider electrochemical window than conventional liquid electrolytes (> 5V). However, the high interfacial resistance at the LLTO/cathode interface restricts the reversible capacity and the cycling efficiency of SSLMBs. Herein, a novel approach of laser texturing at the interface was investigated as a solution to these two challenges.
In this study, the laser-texturing technique was first used to produce micro-patterns on the side of the LLTO against the cathode. This increased surface contact area provided more pathways for Li-ion migration at the interface, leading to decreased interfacial resistance and an improved battery energy density. A few drops of liquid electrolyte were added to fill the void spaces between the laser-textured LLTO and the cathode.
Overall, this study conceptually proved the effectiveness of using laser texturing to improve the interfacial contact. Further efforts are needed to optimize the pattern design and establish a more stable interface that could enable long-term cycling of the SS-LMBs.
Application of Artificial Interphase on Ni-Rich Cathode Materials Via Hybrid Ceramic-Polymer Electrolyte in All Solid State Batteries
Authors: Liao Cheng Hung , Chen Chia-Chin , Jeng Ru-Jong , Wu Nae-Lih (Nick) 
Published: September 2023

Among many cathode materials, nickel-rich LiNi0.83Co0.12Mn0.05O2 (NCM 831205) has been spotlighted as one of the most feasible candidates for next-generation LIBs because of its high discharge capacity (~200 mAh/g). However, NCM 831205 shows significant performance degradation, which is mostly attributed to cation mixing, surface side reactions, and intrinsic structural instability originating from the large volume changes during repeated cycling.
Conventional lithium ion batteries (LIB) normally use flammable nonaqueous liquid electrolytes, resulting in a serious safety issue in use. In this respect, all-solid-state batteries (ASSB) are regarded as a fundamental solution to address the safety issue by using a solid state electrolyte in place of the conventional liquid one.
This work employed lithium sulfonate (SO3Li) tethered polymer, obtained from sulfonation of commercial polymer, to serve as the artificial protective coating on the active NCM831205 of the cathode for ASSB based on hybrid PEO-ceramic solid electrolyte.
The coating layer should prevent direct contact of electrolyte with the cathode, thus avoid the negative effects such as microcracks of NCM831205 and undesired CEI formation. The preparation of hybrid ceramic-polymer electrolyte through a solvent-free process. The hybrid electrolytes exhibit good flexibility and processability with respect to pure ceramic and pure PEO polymer electrolyte.
It is demonstrated that the hybrid electrolytes can penetrate into cathode under 60°C, providing a good Li+ transfer channel inside the battery. Moreover, the sulfone based polymer protective coating could effectively improve the electrochemical stability of the NCM831205 without sacrificing the battery performance.

Keywords: NCM831205, Artificial Polymer Coating, All-Solid-State Batteries
Optimizing Sulfur Utilization in High Loading Cathode for All-Solid-State Lithium-Sulfur Battery
Authors: Kindle Michael , Yu Zhaoxin , Marty Daniel , Xu Yaobin , Zeng Chao , Wang Chongmin , Bao Jie , Xu Zhijie , Lu Dongping 
Published: September 2023

All Solid-state Lithium-Sulfur battery (ASSLSB) possesses a great promise in providing a safe, high energy density, and low cost battery technology for vehicle electrification and grid energy storage. To achieve practically high specific energy in ASSLSB (e.g., >400 Wh/Kg), sulfur cathodes with high areal capacity (>6 mAh cm-2) are essentially needed to offset the relatively low working voltage of elemental sulfur cathode (1.9 V vs. Li). This requires high mass loading sulfur cathodes by maximizing both sulfur content in the whole electrode and sulfur utilization rate to reduce the parasitic weights. An optimal electrode architecture featuring sufficiently connected sulfur/solid electrolyte/carbon triple interfaces is desired to enable sulfur’s fast accessibility to electron and Li-ion simultaneously. Due to the non-flowability of those three solid components, however, it is very hard to maximize the contact of trip solid phases, which need new insights of the materials design and processing technology.
This work looks at carbon microstructures and their impact on triple-point contact between electrochemically active sulfur, carbon, and the solid-state electrolyte (SSE) that comprises most composite cathodes in ASSLSB systems. While significant work has gone into understanding and developing novel carbon host structures for liquid Li-S cells for improving sulfur utilization, polysulfide trapping, better understanding is needed for ASSLSBs. Specifically, how sulfur infiltration, loading, and spatial distribution within the porous carbon host impacts sulfur utilization. Understanding how the infiltrated sulfur that resides in the porous carbon host connects with both carbon and solid electrolyte networks across the whole electrode structure and maintains its robustness during the repeated cell cycling is needed to achieve full utilization in high sulfur loading electrodes. The solid sulfur cathode system examined in the present study is a composite of porous carbon, sulfur, and a sulfide-based solid electrolyte. A combination of porous carbon hosts is investigated and correlated to the cell performance at practical conditions. Advanced characterization and computational tools are used to further elucidate the key parameters for high sulfur utilization in ASSLSBs with high sulfur loading cathodes. Details of the study will be presented and discussed at the meeting.
Reference:
(1) Nagata, H. and Y. Chikusa (2016). "All-Solid-State Lithium–Sulfur Battery with High Energy and Power Densities at the Cell Level." Energy Technology 4(4): 484-489
(2) Banerjee, A., et al. (2020). "Interfaces and Interphases in All-Solid-State Batteries with Inorganic Solid Electrolytes." Chemical Reviews 120(14): 6878-6933.
(Invited) Addressing Energy/Power Tradeoffs in Composite Solid-State Battery Electrodes
Authors: Dasgupta Neil P. 
Published: September 2023

Solid-state batteries (SSBs) have seen a dramatic increase in research in recent years because of their ability to address safety challenges associated with flammable liquid electrolytes, and the potential to enable Li metal anodes. However, SSBs present unique challenges, including high interfacial impedances, accommodation of mechanical stresses due to solid-solid interfacial contact, and (electro)chemical instabilities that can evolve during dynamic cycling conditions. Furthermore, a significant challenge facing the scale-up of SSBs is to improve our understanding of processing science needed to enable manufacturing.
While a significant amount of attention has been paid recently to the Li metal anode/electrolyte interface, there has been significantly less work on the cathode side of the SSB. In SSBs, the cathodes are typically composites of the active material and solid electrolyte (SE) phases, which experience rate limitations. Analogous to porous electrodes with liquid electrolytes, the rate capability of these composite solid-state electrodes is strongly dependent on electrode thickness (electrode capacity) and electrode composition/microstructure. These results in tradeoffs between energy and power density, which are exacerbated at high charging rates.
To address these challenges, we have recently applied operando optical microscopy to directly observe state-of-charge (SoC) gradients in composite solid-state electrodes, using graphite as a model active material [1]. To describe mass transport in these composite electrodes, continuum-scale modeling was performed, which illustrates the critical role of the electrode microstructure and tortuosity on rate capability. These in situ observations are consistent with ex situ measurements of Li-graphite half-cells, where we quantify the rate capability as a function of areal capacity.
To overcome these limitations, we engineered composite SSB electrodes with controlled microstructure and 3-D architectures. These electrodes showed improved homogeneity in the local SOCs throughout the electrode thickness, enabling high-rate cycling capabilities. Overall, the insights presented here will enable new strategies to overcome power/energy tradeoffs in SSBs with composite electrodes.
[1] A. L. Davis, V. Goel, D. W. Liao, M. N. Main, E. Kazyak, J. Lee, K. Thornton, N. P. Dasgupta, ACS Energy Lett. 6, 2993 (2021)
(Invited) Multi-Scale Implications of Material Heterogeneity on Solid State Battery Performance
Authors: Hatzell Kelsey 
Published: September 2023

Solid state batteries are comprised of an ensemble of materials with varying structural, mechanical, chemical, and transport properties1,2. Orchestrating these materials to act synergistically and enable high power and high energy densities requires understanding how solid state electrodes and electrolytes can be engineered to enable: (1) efficient ion and electron transport and (2) maintain uniform contact between components during electrochemical cycling. Bulk processing approaching (e.g. coating, sintering, densification, etc.) do not lead to much control over material properties across various length scales (nano-to-meso). Material heterogenities exist within the cathode, solid electrolyte, and anode. In the cathode, the solid electrolyte and active material can be non-uniformly distributed leading to bottlenecks for transport and non-uniform active material utilization. In the solid electrolyte, active and passive heterogenities can influence how the ion moves between the anode and cathode and cause deleterious current focusing dynamics3,4. Finally, at the anode voiding and contact loss can occur in alkali metal anodes. This talk discusses our recent work combining operando synchrotron studies, electrochemical characterization, and advanced material characterization to unravel the implications of heterogenity on performance and degradation mechanism in solid state batteries.
[1] Zaman, Wahid, and Kelsey B. Hatzell. "Processing and manufacturing of next generation lithium-based all solid-state batteries." Current Opinion in Solid State and Materials Science 26.4 (2022): 101003.
[2] Ren, Yuxun, and Kelsey B. Hatzell. "Elasticity-oriented design of solid-state batteries: challenges and perspectives." Journal of Materials Chemistry A 9.24 (2021): 13804-13821.
[3]Dixit, Marm B., et al. "Polymorphism of garnet solid electrolytes and its implications for grain-level chemo-mechanics." Nature Materials 21.11 (2022): 1298-1305.
[4]Ren, Yuxun, Nicholas Hortance, and Kelsey B. Hatzell. "Mitigating Chemo-Mechanical Failure in Li-S Solid State Batteries with Compliant Cathodes." Journal of The Electrochemical Society 169.6 (2022): 060503.
Enabling the High-Temperature Co-Sintering of NMC and Li-Stuffed Garnets through Thermochemical Stability Studies
Authors: Hoft Richard Mariano , Ivanov Daniel , Wachsman Eric 
Published: September 2023

Solid-state batteries based on lithium-stuffed oxides ceramics promise to improve the safety and energy density over current commercial 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.
This work experimentally elucidates the nature of the thermochemical instability between LLZO and NMC by providing experimental validation of computational work performed by collaborators and exploring various parameters such as sintering atmosphere, Li content, and processing temperature. Improving our understanding of these two compounds in sintering environments will allow for minimizing 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 have already determined several trends in NMC/LLZO thermochemical instability. XRD and TGA/DSC results have shown a heavy dependence on the composition of NMC used. Namely, the higher the nickel content of the NMC, the more it will react with LLZO at high temperature. However, the theoretical capacity of NMC increases with increasing nickel content such that NMC622 appears to be the optimal composition because of its higher theoretical capacity compared to NMC111 while reacting less than NMC811. The atmosphere during sintering has been shown to also be important with pure O2 gas providing better stability at temperatures above 1000°C compared to argon gas. Furthermore, increasing the Li concentration in the LLZO has been shown to increase the decomposition reaction of NMC and LLZO, leading to the formation of new phases.
(Digital Presentation) Electrochemical Properties of Ta-Doped Li7La3Zr2O12 Ceramic Electrolyte Sintered with Ga2O3 Additive
Authors: Inada Ryoji , Akimoto Keigo , Yamazaki Yusuke 
Published: September 2023

A garnet-type oxide with the formula of Li7La3Zr2O12 (LLZO) has attracted much attention because of its high Li ion conductivity at room temperature, excellent thermal performance, and high stability against Li metal.1,2) However, poor interfacial connection causes non-uniform Li plating and intergranular penetration of Li dendrite in polycrystalline LLZO when the cell is cycled particularly at high current densities, resulting in internal short-circuit failure.3,4) It has been pointed out that the tolerance for Li dendrite growth into LLZO is influenced by many factors such as the interfacial resistance between LLZO and Li anode, cell stacking pressure and microstructure (density and grain size) of LLZO. In this study, we fabricated Ta-doped LLZO (Li6.55La3Zr1.55Ta0.45O12) solid electrolytes with Ga2O3 additive and investigated the effects on the microstructure and electrochemical properties.
Ta-doped LLZO with Ga2O3 additive were synthesized via a conventional solid-state reaction process. 1-7 mol % Ga2O3 powder was mixed with calcined Ta-doped LLZO powder. The mixture was pelletized and then sintered at different temperatures with an Al-free crucible. In XRD analysis, each sintered sample has a cubic garnet phase and diffraction peaks from other phases were not detected. In SEM observation, microstructure of sintered sample was strongly influenced by sintering temperature and Ga2O3 addition, due to the sintering with liquid Li-Ga-O phase during high temperature sintering.5, 6) The high total (bulk + grain-boundary) ionic conductivity above 1 mS cm-1 at room temperature was obtained in samples composed of large grains with the size of several 10 to 100 µm. However, the tolerance for Li dendrite growth characterized in a symmetric cell is improved remarkably in the samples with uniform microstructure composed of fine grains with the size of below 5 µm. Since the interfacial resistance between Li and solid electrolyte was adjusted to the same level, the difference in tolerance for Li dendrite growth is mainly attributed to the difference in microstructure depending on both the sintering condition and the amounts of Ga2O3 addition.
References
[1] R. Murugan, V. Thangadurai, W. Weppner, Angew. Chem., Int. Ed. 46, 7778−7781 (2007).
[2] A.J. Samson, K. Hofstetter, S. Bag, V. Thangadurai, Energy Environ. Sci. 12, 2957−2975 (2019).
[3] E.J. Cheng, A. Sharafi, J. Sakamoto, Electrochimica Acta 223, 85−91 (2017).
[4] R. Inada, S. Yasuda, H. Hosokawa, M. Saito, T. Tojo, Y. Sakurai, Batteries 4, 26 (2018).
[5] Y. Matsuda, A. Sakaida, K. Sugimoto, D. Mori, Y. Takeda, O. Yamamoto, N. Imanishi, Solid State Ionics 311 (2017) 69−74.
[6] Y. Yamazaki, S. Miyake, K. Akimoto, R. Inada, Batteries 8, 158 (2022).