bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Interfaces and Bulk: The Challenge of Heterogeneities in Solid Electrolytes
Authors: Dixit Marm , Amin Ruhul , Essehli Rachid , Muralidharan Nitin , Balasubramanian Mahalingam , Belharouak Ilias 
Published: September 2023

Solid electrolyte failure, its onset, and growth is largely discussed in terms of interfacial challenges. Heterogeneities at the interface lead to cascading issues that accelerate failure in solid electrolytes. However, similar observations are fewer and harder to obtain for the bulk of solid electrolyte materials. Herein, we discuss heterogeneities as they play a role at multiple length-scales : from the nanoscale local contacts of electrode | electrolyte, to more microscale roughness of the physical entities involved and at the bulk scale. We use atomic force microscopy, a custom built spatial electrochemical setup, and advanced characterization tools (synchrotron X-ray based) to investigate these heterogeneities. We will showcase that heterogeneities are indeed crucial in dictating the electrochemical performances of the solid electrolytes for a range of different material systems. We will conclude with a discussion of pathways that can help ameliorate these heterogenieties for high performance solid-state battery systems.
References:

Dixit, M. B., Vishugopi, B. S., Zaman, W., Kenesei, P., Park, J. S., Almer, J., Mukherjee, P. P., & Hatzell, K. B. (2022). Polymorphism of garnet solid electrolytes and its implications for grain-level chemo-mechanics. Nature Materials.(2022) 21, 1298–1305

Dixit, M., Beamer, C., Amin, R., Shipley, J., Eklund, R., Muralidharan, N., Lindqvist, L., Fritz, A., Essehli, R., Balasubramanian, M., & Belharouak, I. (2022). The Role of Isostatic Pressing in Large-Scale Production of Solid-State Batteries. ACS Energy Letters, 2022,11, 3936–3946.

Dixit, M., Muralidharan, N., Parejiya, A., Jafta, C., Du, Z., Neumayer, S., Essehli, R., Amin, R., Balasubramanian, M., & Belharouak, I. (2022). ACS Appl. Mater. Interfaces 2022, 14, 39, 44292–44302

Figure 1
CuS as Unique Cathode Material for Li Solid-State Batteries: Properties, Reaction Mechanism and Tomography
Authors: Adelhelm Philipp 
Published: September 2023

Copper sulfide (CuS) is a naturally occurring mineral that reacts with lithium via a conversion reaction to form Li2S and Cu. The theoretical energy density of the reaction is 961 Wh/kg, the theoretical cell voltage is 1.96 V. Among all the conversion reactions, copper sulfide shows a unique behavior as large, µm-sized copper crystallites are formed during discharge. Some years ago, it was shown that the reaction can proceed reversibly in suitable electrolytes.[1] This presentation will discuss the behavior of copper sulfide as a cathode material in solid state batteries. In this context, the low cell voltage allows the use of Li3PS4 as a solid electrolyte, which is a major advantage. Despite the large volume expansion (+74%), the material can be cycled in solid state batteries at high contents (70 wt%), again forming large copper crystallites.[2] The size of the crystallites allows the reaction to be studied by 3D X-ray tomography.[3] In addition to phase transformations, crack formation can also be observed. The latter is strongly pressure dependent and can be minimized by increasing the pressure.
[1] Birte Jache, Boris Mogwitz, Franziska Klein, Philipp Adelhelm (2014) Copper sulfides for rechargeable lithium batteries: Linking cycling stability to electrolyte composition Journal of Power Sources 247: 703-711.
[2] Aggunda L Santhosha, N Nazer, Raimund Koerver, Simon Randau, Felix H Richter, Dominik A Weber, Joern Kulisch, Torben Adermann, Jürgen Janek, Philipp Adelhelm (2020) Macroscopic displacement reaction of copper sulfide in lithium solid-state batteries Advanced Energy Materials 2002394: .
[3] Zhenggang Zhang, Kang Dong, Katherine A Mazzio, André Hilger, Henning Markötter, Fabian Wilde, Tobias Heinemann, Ingo Manke, Philipp Adelhelm (2022) Phase Transformation and Microstructural Evolution of CuS Electrodes in Solid-State Batteries Probed by in-situ 3D X-ray Tomography Advanced Energy Materials 2203143.

Figure 1
Two-Layer Structured Cathodes for Solid State Batteries
Authors: Kalnaus Sergiy , Polyzos Georgios , Chen Xi , Westover Andrew S , Muralidharan Nitin , Li Jianlin 
Published: September 2023

Designing a robust cathode is one of the major objectives in R&D of lithium-ion batteries. The challenges only get amplified in case of solid state battery cells as the methods for introduction of electrolyte into the cathode structure need to be developed. Ideally, a cathode should support high energy density of a cell which implies necessity for high thickness. This requirement is not trivial to fulfil, both from the standpoint of manufacturing and from the standpoint of overcoming transport limitations in thick cathodes. In this work, inspired by the previous effort on graded porosity cathode design [1], we present a two-layer cathode based on LiNi0.6Mn0.2Co0.2O2 (NMC622). The cathode is built using a densified “energy layer” as a support for the “power layer” in which high porosity and low tortuosity is achieved by the freeze tape casting technique. The distribution of the material in the two layers is guided by numerical simulations based on actual cathode microstructure. The performance of the structured cathodes containing Poly(ethylene oxide) (PEO) with lithium bis-trifluoromethanesulfonimide (LiTFSI) was experimentally investigated in cells containing metallic lithium counter electrode. The structured cathodes showed more than double capacity values and improved Coulombic efficiency compared to uniform cathodes of the same material loading.
[1] Kalnaus, S., Livingston, K., Hawley, W.B., Wang, H., Li, J., 2021, “Design and processing for high performance Li ion battery electrodes with double-layer structure J Energy Storage 44 (2021) 103582.

Acknowledgments: This research at Oak Ridge National Laboratory (ORNL), managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) under contract DE-AC05-00OR22725, was sponsored by Laboratory Directed Research and Development Program at ORNL.
(Invited) Understanding the Role of Mixed Ionic-Electronic Conductor Interlayer in All-Solid-State Lithium-Metal Batteries
Authors: Yao Yan 
Published: September 2023

All-solid-state lithium metal batteries are projected to offer one of the highest specific energy among rechargeable batteries. However, a major challenge in these batteries is the poor lithium-solid electrolyte contact and void formation at the interface during Li plating and stripping. To address this challenge, an interlayer strategy has been introduced between the solid electrolyte and the lithium metal to promote better interfacial contact, improve stripping/plating homogeneity, and therefore suppress lithium dendrite formation and propagation. In particular, a MIEC-type interlayer, composed of carbon-based materials that conduct both Li+ ions and electrons and have a certain lithium storage capacity, has been employed between the anode current collector and the electrolyte, allowing for over 1000 cycles at a high current density. While the use of a MIEC-type interlayer has only recently gained attention, many aspects of its working mechanism remain unclear. For example, where does lithium deposit in the interlayer, and what determines the deposition location? How does lithium transport in the interlayer? Is Li0 or Li+ transporting? In this talk, we will present our findings to better understand the interlayer physiochemical properties and lithium deposition behavior in order to achieve rational design of a MIEC-type interlayer.
Acknowledgement: This work was supported by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE) under the Vehicle Technologies Program under Contact DE-EE0008864.
Investigation and Improvement of the Pressure Control in Si Anode Based Solid-State Batteries
Authors: Lu Zijie , Loizzo Hannah 
Published: September 2023

Solid state batteries (SSBs) are promising next generation propulsion for electric vehicles due to their improved safety, high gravimetric and volumetric energy densities, and increased reliability. Silicon is one of the limited choices for the anode material for the SSBs due to its high applicable capacity, low operating potential and natural abundance. However, significant challenges remain for the commercialization of Si anode based SSBs, including the insufficient operational and calendar life, requirement of high stack pressure for operation, and inadequate fast charge capability.
Almost each of the technical challenges associated with Si anode is entangled with the volume change of Si during charging and discharging. Si possesses high lithium storage capacity because it can form various LixSiy compounds upon lithiation. For example, when 3.75 moles of Li+ is added to 1 mole of Si, the compound Li15Si4 is formed, which gives a capacity of 3578 mAh/gSi. What accompanies this is a considerable volume expansion (e.g., 280% increase for Li15Si4), resulting from the reorganization of the compound crystals. Assuming an anode that initially composes of perfectly compacted Si particles, this volume expansion translates to a 56% increase in the thickness of the Si anode. In a practical SSB, the real thickness variation in the Si anode is expected to be smaller because of the architecture design of the anode. Nonetheless, this volume change in Si creates many problems, including the Si particle pulverization, delamination of electrode from the current collector and electrolyte separator, loss of electronic and ion conductions in the electrode, among others. To maintain the electric contact in Si anode based SSBs, high stack pressures, from several MPa to several tens of MPa, are normally applied.
In this work, we carefully measure the real-time stack pressure in a specially designed setup. The stress-strain characteristics of Si anode based SSBs during operation, including the stack pressure spike and the degradation of the average stack pressure, is studied and correlated with the Si anode structure changes. Furthermore, different measures, including external and internal ones, are explored to improve the cell pressure control. The external measures include selecting an appropriate spring and using a mechanical buffer layer, while the internal measure refers to an elastic current collector design. As a result, a better SSB pressure control is obtained. More importantly, a reduction of the stack pressure significantly below 10 MPa without compromising the cell performance is achieved.
Interfacial Dynamics of Carbon Interlayers at Anode-Free Solid Electrolyte/Lithium Interfaces
Authors: Liao Daniel Wen , Cho Tae Ho , Sarna Shaurya , Kawakami Hiroki , Ikeda Nobuhisa , Kotaka Toshikazu , Aotani Koichiro , Dasgupta Neil P. 
Published: September 2023

Solid electrolytes (SEs) that incorporate lithium (Li) metal anodes provide a promising pathway to improve battery energy density and safety. However, Li metal anodes still suffer from multiple challenges, including 1) uniform Li deposition and dissolution, 2) continual formation of a solid-electrolyte interphase (SEI), and 3) limited rate capability. To control the interfaces, predefined interlayers such as gold, ZnO, carbon, and other coatings have been used tune the Li metal and SE interface. However, there is a need for improved fundamental understanding of the mechanistic role of these interlayers on performance and stability. In this work, we explore the application of an amorphous carbon interlayer in an argyrodite SE system, which is used for in situ Li metal formation in an “anode-free” configuration.
The incorporation of a carbon interlayer has been previously shown to act as a physical barrier between the SE and in situ formed Li metal, improve the uniform contact and current distribution across the SE/anode interface, and potentially suppress dendrite propagation [1]. However, the mechanism of this improved performance is not fully understood. Therefore, to study the influence of the carbon interlayer on interfacial performance, a detailed electrochemical analysis was performed.
First, the transition in reaction pathway from carbon lithiation to Li nucleation and growth was observed to change as a function of charging rates. To probe the lithiation effects of the carbon interlayer on subsequent Li deposition, incremental electrochemical impedance spectroscopy (EIS) and current-interrupt analysis was performed to study the dynamic changes of the carbon interlayer during the charging process prior to Li nucleation. To confirm the mode of metallic Li nucleation and growth, operando video microscopy and post-mortem focused ion-beam/scanning electron microscopy (FIB-SEM) was utilized. The preferential location of Li deposition and growth at the current collector and carbon interface confirms the transport of Li-ion through the lithiated carbon interlayer. Moreover, the Li metal deposition behavior was observed to depend on the electrochemical properties of the carbon interlayer during the lithiation process. These fundamental electrochemical studies will further our understanding of the design requirements for interlayers that can enable Li metal anodes in solid-state battery systems.
[1] Y.G. Lee, S. Fujiki, C. Jung, N. Suzuki, N. Yashiro, R. Omoda, D. S. Ko, T. Shiratsuchi, T. Sugimoto, S. Ryu, J. H. Ku, T. Watanabe, Y. Park, Y. Aihara, D. Im, I. T. Han, Nat. Ener.
5, 299-308 (2020)
Understanding the Interplay between Electrochemistry and Mechanics at Dendrite Tips in Sulfide and Oxide Electrolytes
Authors: Fincher Cole D. , Gilgenbach Colin , Carter W. Craig , Sheldon Brian W. , Chiang Yet-Ming 
Published: September 2023

Dendrite-induced short circuits threaten the deployment of solid-state batteries with metal anodes. Whether dendrites grow by internal chemical reduction of lithium or because of mechanical stresses has been a topic of debate. For both oxide and electrolyte electrolytes, we address this question by conducting operando microscopy to observe mechanical and electrochemical phenomena underlying dendrite growth. Here, we build upon the method from Athanasiou-Fincher et al. to observe stress-optic couplings around dendrite tips in thin oxide electrolytes[1]. Specifically, operando measurements of dendrite-induced stress fields are measured as a function of applied potential, and then the images are quantitatively analyzed to measure the mechanical driving forces underlying failure (i.e., the energy release rate). These operando measurements demonstrate a complex interplay between electrochemistry and mechanics. We develop a mechanistic framework to describe the observed behavior, discussed in juxtaposition with stress-corrosion cracking and linear elastic fracture mechanics. The resulting implications for electrolyte testing and design are discussed. Lastly, we assess whether mechanical stresses in electrolytes can be used to “steer” the dendrite growth directory. By dynamically applying mechanical loads to growing dendrites in LLZTO, we show that dendrite growth trajectory can be deflected to avoid short-circuit failures in oxide electrolytes[2]. Together, these results demonstrate a complex relationship between electrochemical and mechanical driving forces. Despite the observed complexity, processing-induced residual stresses can deflect dendrites and avert short circuits.
[1] CE Athanasiou=, CD Fincher=, C Gilgenbach, WC Carter, H Gao, YM Chiang, BW Sheldon. Manuscript in preparation. “On the Use of Photoelasticity for Operando Dendrite-Induced Stress Quantification in Ceramic Electrolytes,” 2022 Materials Research Society Fall Conference; manuscript in preparation.
[2] CD Fincher, CE Athansiou, C Gilgenbach, MJ Wang, BW Sheldon, WC Carter, YM Chiang, “Controlling dendrite propagation in solid-state batteries with engineered stress,” Joule, in press. DOIs: 10.1016/j.joule.2022.10.011
Enabling Stable Li Metal Anodes for Solid-State Batteries
Authors: Wood Marissa , Xiao Yiran , Freyman Megan C. , Zhu Cheng , Wang Bo , Li Sichi 
Published: September 2023

Solid-state batteries have the potential to transform energy storage by providing significantly higher energy densities and improved safety compared to conventional Li-ion batteries. However, robust high-capacity Li metal anodes are required to realize this technology. Current Li metal anode designs suffer from significant degradation over time due to non-uniform Li plating/stripping and loss of contact with the solid electrolyte during cycling. Carbon scaffold hosts have been shown to mitigate this problem in liquid electrolyte systems by creating a uniform electric field and providing abundant Li nucleation sites, but they have not been well explored in solid-state systems, which require the fabrication of more complicated mixed ion/electron conducting scaffolds to provide transport of both Li ions and electrons throughout the anode. We investigated the effect of scaffold architecture and chemistry on Li morphology and electrochemical performance using a combined experiment/theory approach. Scaffolds were characterized by SEM, Raman, and XPS before cycling in cells to evaluate their performance as hosts for Li plating/stripping. Atomistic and mesoscale modeling were used to help predict Li nucleation and current density hotspots and assist in guiding scaffold design. This work provides further insight into the relationship between anode design and Li metal cycling stability and will facilitate the development of safer, high-energy-density solid-state batteries.
Lawrence Livermore National Laboratory is operated by Lawrence Livermore National Security, LLC, for the U.S. Department of Energy, National Nuclear Security Administration under Contract DE-AC52-07NA27344.
Cross-Linked Anion Exchange Membranes for Non-Aqueous Redox Flow Battery
Authors: Mazumder MD Motiur Rahaman 
Published: September 2023

Abstract

The development of redox flow batteries (RFBs) has been one of the primary responses to the need to store harvested renewable energy for improving grid reliability and utilization.1–6 In this study, we synthesized and characterized different Bromobutyl Norbornene backbone-based anion-exchange membranes (AEM) with different Tetramethyl hexadiamine crosslinker amounts and explored the performance of AEMs in non-aqueous redox flow batteries under ideal conditions. Performance was compared based on high stability in a non-aqueous solvent, high permeability to the charge-carrying ion, low electric cell resistance, low cross-over of the redox-active molecules, high mechanical property, and low cost. 100 cycles battery data indicates that Bromobutyl Norbornene-based AEM performance is far better than the commercial best membrane Fuma-375. The best membrane will be found which will show no cross-over of redox-active electrolytes after 1000 battery cycle experiments and exhibit low resistance and high structural/chemical stability in MeCN solvent.

References

(1) Mazumder, Md. M. R.; Burton, A.; Richburg, C. S.; Saha, S.; Cronin, B.; Duin, E.; Farnum, B. H. Controlling One-Electron vs Two-Electron Pathways in the Multi-Electron Redox Cycle of Nickel Diethyldithiocarbamate. Inorg. Chem.
2021, 60 (17), 13388–13399. https://doi.org/10.1021/acs.inorgchem.1c01699.
(2) Mazumder, M. M. R.; Farnum, B. H. Two One Electron vs One Two-Electron Redox System of Nickel Diethyldithiocarbamate for Redox Flow Battery; ACS, 2021. https://doi.org/10.1021/scimeetings.1c00951.
(3) Mazumder, M. M. R. Ni(IV/II) Redox Couple 2e- Reversibility Improvement for Redox Flow Battery. ECS Meet. Abstr.
2021, MA2021-02 (5), 1855–1855. https://doi.org/10.1149/ma2021-0251855mtgabs.
(4) Islam, R.; Mazumder, M. M. R.; Farnum, B. H. Solvent Dependent Spectroscopic and Electrochemical Studies of Nickel (II) Diethyldithiocarbamate for Energy Storage. ECS Meet. Abstr.
2021, MA2021-01 (1), 54–54. https://doi.org/10.1149/ma2021-01154mtgabs.
(5) Rahaman Mazumder, M. M.; Islam, R.; Khan, M. A. R.; Anis‐Ul‐Haque, K. M.; Rahman, M. M. Efficient AcFc‐[Fe III (Acac) 3 ] Redox Couple for Non‐aqueous Redox Flow Battery at Low Temperature. Chem. – Asian J.
2023, 18 (1). https://doi.org/10.1002/asia.202201025.
(6) Mazumder, Md. M. R.; Dalpati, N.; Pokkuluri, P. R.; Farnum, B. H. Zinc-Catalyzed Two-Electron Nickel(IV/II) Redox Couple for Multi-Electron Storage in Redox Flow Batteries. Inorg. Chem.
2022, 61 (48), 19039–19048. https://doi.org/10.1021/acs.inorgchem.2c03124.
Grain Analysis of Ncm Cathode Materials By Astar Technique and Its Effect on Battery Performance
Authors: Jung Yongjo , Hong Kijoo , Kim Juseong , Lee Jiho , Kim Yong Il , Nam Sang Cheol 
Published: September 2023

Lithium-ion batteries (LIBs) are one of the most promising energy storage systems for portable electronic devices, electric vehicles, and renewable energy systems. Among the various cathode materials for LIBs, nickel cobalt manganese (NCM) oxide has attracted considerable attention due to its high specific capacity, good cycling stability, and appropriate cost for commercialization. However, Ni-rich NCM (Ni >80%) showed poor cyclability and huge gas evolution because of surface instability.
Single crystal NCM has been suggested as a solution to these issues due to its excellent properties. However, it is difficult to quantify the degree of single crystallinity because it is so far subjective. In this study, we employed ASTAR technique (transmission electron microscopy combined with electron backscatter diffraction) to investigate the microstructural features of NCM cathode materials. Our ASTAR analysis showed that NCM cathode materials consist of complex grain and grain boundary structures with varying orientations and sizes. By analyzing the grain size and its morphology, we were able to define the single crystallinity of NCM cathode materials, including the poly NCM and single crystal NCM particles.
Furthermore, we found that the grain size and its distribution significantly affects the battery performance and lifespan of NCM cathode materials. Specifically, the poly NCM particles exhibited a larger grain boundary and surface area compared to the single crystal NCM particles. The poly NCM particles also showed a faster DC-IR increase and a shorter lifespan than the single crystal NCM particles, indicating that the grain size has a critical influence on the battery performance and lifespan of NCM cathode materials.
Our results provide insights into the design and optimization of NCM cathode materials for next-generation LIBs. By controlling the grain size and its distribution of NCM cathode materials, it is possible to enhance the battery performance and lifespan. Therefore, our study highlights the importance of understanding the microstructural features of NCM cathode materials for developing high-performance and stable LIBs.