bluuebunny/crossref_metadata_2025 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

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(Industrial Electrochemistry and Electrochemical Engineering Division H. H. Dow Memorial Student Achievement Award) Mechanistic Analysis of Interface Stability in Solid-State Batteries
Authors: Vishnugopi Bairav Sabarish , Mukherjee Partha P.
Published: September 2023

Solid-state batteries (SSBs) utilizing lithium metal anodes are promising next-generation energy storage systems, capable of offering enhanced energy density and power density when compared to conventional lithium-ion batteries. However, the morphological instability of the lithium anode continues to be a major challenge, resulting in filamentous lithium growth and internal short circuit across a wide range of inorganic solid electrolytes. In addition, the formation and growth of interfacial voids during stripping is a critical mechanism that limits the rate performance of SSBs. A coupled set of electrochemical-transport-mechanics processes governs the dynamic evolution and stability of the solid electrolyte/lithium interface. This interaction is affected by various factors including the mechanical properties and microstructure of the solid electrolyte and lithium metal, external pressure, operating temperature, and interfacial heterogeneities. In this presentation, the competing nature of interfacial mechanisms including electrodissolution, lithium mechanics and lithium diffusion kinetics on the origin of voids during stripping will be discussed. The coupled electrochemical-mechanical processes governing the evolution of lithium filaments, especially driven by microstructural heterogeneities such as grain boundaries will be delineated. An analysis pertaining to the dependence of such failure mechanisms on the external temperature, temperature and current density will be presented. Lastly, the role of underlying electrochemical interactions at the solid-solid interface on the onset of thermal instability in SSBs will be evaluated.
MgSc2Se4 Solid Electrolyte for Rechargeable Mg Batteries
Authors: Kundu Sumana , Kraytsberg Alexander , Ein-Eli Yair
Published: September 2023

MgSc2Se4 is among the most promising magnesium-ion solid electrolyte, as it possesses a high room temperature Mg+2 conductivity (~ 10-4 S/cm). However, MgSc2Se4 is also demonstrating a considerably high electronic conductivity (10-5 to 10-8 S/cm). Such high electronic conductivity restricts the applications of the material in all solid-state Mg-ion batteries. Efforts to lower the electronic conductivity via the enrichment of the material with selenium aliovalent doping, were not successful thus far. This suggests that the electronic conductivity may follow a model, which is different from a common model of charge transfer by electrons in a conduction band of the wide band gap semiconductor MgSc2Se4. Here, we will discuss and present data showing that the electronic transport in the Mg-Sc-Se ceramic is facilitated via the Berthelot-type conductivity mechanism. This suggests an electronic transport through a low-conducting matrix stuffed with nano-scaled free electron-containing regions. These inclusions are well-distributed across the Mg-Sc-Se, and the electronic transport takes place via electron tunneling between these conductive regions, through low-conducting matrix spacers. It is shown that these conductive zones, being comprised of elemental metallic Sc and ScSe mix, behave as a metallic-type electronic conductor. The nature of these conductive inclusions and the synthetic parameters controlling the appearance of such conductive areas will be discussed, as well as routes to minimize their formation.
Glass Electrolyte Infiltrated Cathode in an All Solid State Lithium Cell
Authors: Rauch William , Allie Lazbourne , Grant Adrian
Published: September 2023

Ion conducting glasses have been known for more than half a century, but their effective application in batteries is limited. Johnson Energy Storage is demonstrating a novel all solid state lithium battery construction which utilizes a lithium ion conducting glass to transport ions from deep within a structured cathode network. The unique application of the glass electrolyte is dependent upon a networked cathode structure, infiltration of the glass into the cathode and developing a glass with both sufficient ionic transport and a large voltage stability window. The advantages provided include continuity of transport channels and large contact surfaces between the active cathode material and the glass electrolyte. Both are required for effective transport and low impedance. Cells are shown with the potential for long cycle life and stability cycling from 3.0-4.3 volts utilizing a metallic lithium anode.
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.

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Investigation of the Reaction Mechanism of All-Solid-State Lithium-Sulfur Batteries by Operando in Situ Raman Spectroscopy
Authors: Venkatesan Savunthari Kirankumar , Dai Huidong , Maxwell Derrick , Mukerjee Sanjeev
Published: September 2023

In recent years, all-solid-state lithium-sulfur batteries (ASSLSBs) with sulfide-based solid electrolytes have become a leading energy storage system due to their high ionic conductivity, ultra-high energy density, high safety, and low cost. There have been many challenges with the practical applications of Li-S batteries, however, as a result of the sluggish redox kinetics of lithium polysulfide (LPS) and its shuttling effects. Single-atom catalysts (SACs) with atomically dispersed metal-based sites have proven to be promising electrocatalysts in Li-S batteries. To construct the ASSLSBs, we design and develop MoS2/SnS2 and Fe SACs with MoS2/SnS2 cathodes, Li5.4PS4.4Cl1.6 sulfide-based solid electrolytes, and Li-In anode. In the current study, in situ Raman spectroscopy is used to determine the LPS species in the sulfur cathode with SACs and without SACs during the ASSLSBs cycling. The aim is to understand the charge-discharge mechanism and the influence of SACs on the dissolution of sulfur and poly-sulfides. As compared to the MoS2/SnS2 cathode, the Fe@MoS2/SnS2 cathode exhibit the highest catalytic LPS conversion. In addition, the Fe@MoS2/SnS2 cathode delivers a high discharge capacity and long-cycling performance with high coulombic efficiency in ASSLSBs. In operando in situ Raman studies, SACs provide important new insights into the charge-discharge reaction mechanism for the next generation of ASSLSBs.
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.
Detection, Analysis, and Behavior of Soft-Shorts in Solid-State Batteries
Authors: Counihan Michael J. , Chavan Kanchan , Barai Pallab , Powers Devon J. , Hu Shiyu , Zhang Yuepeng , Srinivasan Venkat , Tepavcevic Sanja
Published: September 2023

Lithium metal batteries face numerous challenges before being employed in practical energy storage systems. Chief among these is the suppression of lithium dendrites, which lead to cell shorting and thermal runaway. In the field of solid-state batteries, there is often talk of “soft-shorts”, where small lithium dendrites form, short, then disappear. However, there is no clear consensus on the definition of soft-shorts, how they behave, and what their presence means for solid electrolyte development. Here, we use composite polymer electrolytes as exemplary solid electrolytes to detect, analyze, and thoroughly describe the varied behavior of soft-shorts. We define soft-shorts and show quantitatively that both ionic and electronic current flow simultaneously in a soft-shorted cell. The amount of each current depends on dendrite size, which dictates the resistance to the electronic pathway as well as Joule heating of the thin metal filaments. This heating leads to the “burning out” of the dendrites, which is responsible for the rapid un-shorting of soft-shorted cells. We use computational modeling to quantify the dendrite properties and explain how this leads to the observed transient behavior. More persistent soft-shorts are analyzed with temperature-dependent, quantitative electrochemical impedance fitting, where it is shown that parallel ionic and electronic current paths present impedance data that can be misinterpreted without rigorous analysis. The advantages and disadvantages of several soft-short characterization techniques are discussed. In the end, we show that soft-shorts are diverse in nature and thus require diverse tools and keen eyes from researchers to avoid the over-selling of flawed materials for lithium metal batteries.
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)
Lithium Dendrite Growth, Healing Strategies and Microstructural Imparity in Solid Electrolyte of All Solid-State Batteries
Authors: Amin Ruhul , Dixit Marm , Parejiya Anand , Essehli Rachid , Muralidharan Nitin , Balasubramanian Mahalingam , Belharouak Ilias
Published: September 2023

The major challenges for the development of all solid-state batteries (ASSBs) are stable solid electrolytes and robust interfacial design that enables to charge and discharge ASSBs faster for a practical application at ambient conditions. However, ASSBs have several interfaces such as anode | solid electrolyte (SE), cathode | SE, catholyte | active material, etc. These interface properties vary depending on the contact condition, energy states, type defects and chemical/electrochemical stability. The life and performance of ASSB relies largely on these interfaces since Li-depleted space-charge layer generation, and spatial variation in interfacial adhesion originates at the interfaces and results inhomogeneous current distribution which ultimately leads to dendrite formation and battery failure. Our group has developed an electrochemical approach to healing the dendrite from the solid electrolyte [1] that would revive the battery from the failure state. This presentation will focus on the deliberately dendrite growth inside into the sintered dense Li6.25Al0.25La3Zr2O12 (LALZO) plate, removal strategy of the growth dendrite from the LALZO by developed electrochemical technique and characterize its microstructural imparity after dendrite healing. Noting that after the dendrite healing the microstructure of solid electrolyte LALZO is assumed to be different from the original state. Here we performed the neutron tomography of the LALZO solid electrolyte to understand the microstructural integrity after the healing of dendrite from the LALZO solid electrolyte. The obtained results and developed process provide the pathway to revive the battery not only in cell level but also a module or a system level.

Figure 1
In Operando Neutron Image Characterizations of Li Metal in All Solid State Batteries
Authors: Zhu Hongli
Published: September 2023

Neutron imaging has a high sensitivity to Li, strong penetrability to the cell framework, and quick data collection, allowing the spatiotemporal observation of Li evolution. In addition, neutron imaging can reconstruct the 3D structure of all-solid-state Li metal batteries through neutron computed tomography. In comparison, the reported X-ray computed tomography cannot directly observe Li metal. Lithium (Li) metal can significantly boost the energy density of all-solid-state batteries. In the past years, great efforts have been paid to develop high-performance all-solid-state Li metal batteries; however, the cycling life is not satisfactory due to the severe dendrite issue. It has been reported that Li can propagate inside the solid-state electrolytes to cause the battery short circuit. The mechano-electrochemical behavior of Li plays a key but lacks deep understanding. Meanwhile, there is a widely observed phenomenon that the voltage dynamically maintains stability but not increasing during battery charging (named "soft short") in all-solid-state Li batteries. In comparison to the “hard short” that the battery was permanently in short, the discussion on the "soft short" is scarce. Powerful operando characterization can provide chances to investigate the mechano-electrochemical behavior and the "soft short" fundamentally.Herein, for the first time, we successfully visualize the Li deformation and the "soft short" in all-solid-state Li metal batteries using operando neutron imaging. Our work can give direct evidence for researchers to a better understanding of the Li creeping and the "soft short" through neutron imagings and inspire more strategies in stabilizing Li metal anode to achieve high-performance all-solid-state Li metal batteries.
Inelastic Deformation Mechanisms in Ceramic and Glass Electrolytes & Dendrites
Authors: Athanasiou Christos E. , Liu Xing , Gao Huajian , Sheldon Brian W.
Published: September 2023

Ceramic and glass electrolytes are a promising replacement for the liquid electrolytes that are commonly used in Li-ion batteries. Their mechanical properties are known to play a critical role not only in practical issues related to safe cell assembly, but also in the battery cell performance. In this talk, inelastic deformation mechanisms in ceramic and sulfide glass electrolytes will be presented and their implication in battery performance will be discussed. Such mechanisms can be either introduced by additive materials in the electrolyte matrix or can even be inherently present in the electrolytes. In the first part of the talk, a methodology for toughening ceramic oxide electrolytes via the use of nanoscale reinforcement will be shown. Then, measurements showing viscoplastic deformation of amorphous sulfide electrolytes will be presented. Finally, strategies for implementing mechanically robust and high performance solid-state batteries will be discussed.
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.
In-Situ Polymerization in 3D Ceramic Frameworks for High-Performance Composite Solid Electrolytes
Authors: Nguyen An-Giang , Park Chan-Jin
Published: September 2023

In the Battery of Things era, lithium-ion batteries (LIBs) act as the heart of any electronic device, from tiny devices such as earphones and smart pens to electric vehicles (EVs). Unfortunately, current safety issue associated with conventional LIBs originates from the use of flammable liquid electrolytes. Therefore, solid-state batteries (SSBs) using solid-state electrolytes (SSEs) as a potential candidate can address the safety concerns and revive the lithium metal to further increase the energy density of batteries. Among several types of SSEs such as ceramic electrolytes, solid polymer electrolytes, and composite solid electrolytes (CSEs), CSEs are more attractive by combining the advantages of both ceramic and polymer electrolytes. However, CSEs still suffer from insufficient ionic conductivity at room temperature to meet the requirement for high-performance electrolytes. In this study, 3D ceramic porous framework as a continuous lithium-ion conduction pathway as well as a backbone for in-situ polymer penetration was prepared to overcome the challenge. The synergistic effect of the 3D continuous framework, well-organized polymer, and their interphase enabled high-performance SSEs. A solid-state lithium-ion cell composed of 3D-Li6.4La3Zr1.4Ta0.6O12 containing CSE, LiNi0.8Co0.1Mn0.1O2 cathode, and Li metal anode, could operate for 230 cycles by maintaining a high capacity of 118.8 mAh g-1, and showed good rate capability up to 5 C at 30 °C. In addition, a solid-state sodium ion cell composed of 3D-Na3.3Zr1.7La0.3(SiO4)2(PO4) containing CSE, Na3Mg0.05V1.95(PO4)3@C cathode, and Na metal anode achieved a long lifespan of 3000 cycles at 2 C with zero fading and excellent rate capability up to 10 C at 30 °C.
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.
Enhancing Cycling Stability and Capacity Retention of High-Capacity-High-Voltage Cathodes by Reengineering Interfaces Via Electrochemical Fluorination
Authors: Prasad Thapaliya Bishnu , Borisevich Albina Y , Meyer Harry M , Dai Sheng
Published: September 2023

High-capacity high voltage cathodes (NMC811, LNMO) are promising cathodes for electromobility due to high energy densities. However, several factors (extensive oxidation of electrolytes, growth of thick cathode electrolyte interphase (CEI), irreversible capacity loss, low coulombic efficiency) related to high energy density materials inhibit their practical application. Herein, we report the formation of the conformal LiF interfaces on NMC811/LNMO cathodes via novel electrochemical fluorination. An electrochemically induced LiF layer stabilized the interfaces and reduces the leakage of the electrons allowing lithium-ion conduction. Because of such robust CEI composed of LiF, electrochemically fluorinated cathodes demonstrated significantly improved cycling stability and enhanced capacity.
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.
Investigating Intercalation of Chloroaluminate Anions in Graphene-Based Materials for Rechargeable Aluminum-Ion Batteries
Authors: Yoon Hana , Rezaee Mehdi , Lee Yeong A , Yim Kanghoon , Tamarany Rizcky , Lee Chan-Woo , McGraw Valerie S. , Taniguchi Takashi , Watanabe Kenji , Kim Philip , Yoo Chung-Yul , Bediako Daniel Kwabena
Published: September 2023

Development of energy storage systems with high energy and power density, high safety, long cycle life, and low cost is crucial for various applications, including portable electronics and grid storage of renewable energies. Among various battery technologies, rechargeable aluminum ion batteries are particularly attractive due to the abundance, low cost, and safety of aluminum. However, unlike lithium ion batteries, many aspects of the fundamental intercalation processes and dynamics in these aluminum-based battery systems remain unresolved.

In this study, we investigate the intercalation of chloroaluminate ions in atomically thin carbon cathodes using mesoscopic devices for charge transport and operando optical microscopy. These measurements provide insights into the energetics and dynamics of intercalation processes in atomically thin samples. We compare the atomically thin single crystal measurements to the cycling response of a high-performance rechargeable aluminum ion battery consisting of a few-layer graphene–multiwall carbon nanotube composite cathode. Our findings show that these nano-composites exhibit a high specific capacity and cyclic stability at high current densities, with a ~3-fold improvement in overall ion diffusivity in the aluminum ion battery. However, the battery cells still exhibit chloroaluminate diffusivities less than ~1% of those in mesoscopic single crystals. Our results highlight the distinction between intrinsic and ensemble electrochemical behavior in aluminum-based batteries and demonstrate that engineering ion transport to enhance diffusivity in these devices can lead to significant improvements in battery performance.
Carbonate-Based Localized High Concentrated Electrolyte for Long-Cycle-Life Lithium Metal Batteries
Authors: Le Linh , Liao Meng , Nguyen Au , Kou Rong , Wang Donghai
Published: September 2023

Rechargeable Lithium Metal Batteries (LMBs) using high-voltage cathodes can deliver the highest possible energy densities among all electro-chemistries. However, the notorious reactivity of metallic lithium as well as the catalytic nature of the cathode materials largely prevent their practical application. Here, we demonstrate a formulated carbonate-based high concentrated electrolyte with LiPF6 that supports the most commercial aggressive and high-voltage cathode to realize a highly stable Li metal full-cell with limited metallic Li. The formation of stable Li2O/LiF-rich solid electrolyte interface (SEI) layers afforded stable operations of resultant LMBs under practical working conditions. Our electrolyte contributes to both high efficiency of 99.5% for Li||Cu half cell and ~100% for lithium full cells based on 4.3 V Ni-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes. Notably, at a loading of 4.0 mAh.cm−2, our full cells showed a capacity retention of ~80% over 280 cycles at lean electrolyte condition of 5 μL.mAh-1. The effective stabilization that inhibited the aggressive chemistries at extreme potentials in LMBs upon practical conditions by our electrolyte was determined to be the formation of the dense, inorganic-rich interphase.
Lithium-Ion Battery Cathode-Electrolyte Interface
Authors: Luo Hongmei
Published: September 2023

The global energy crisis, consumption of fossil fuels, and the associated environmental issues have stimulated extensive interest in searching for sustainable energy storage and conversion systems. Rechargeable lithium-ion batteries (LIBs) are widely used in mobile devices, hybrid, and electric vehicles. Electrode-electrolyte interface has a strong impact on battery capacity decrease and long-term cycling stability. In order to improve fundamental understanding of the involved phenomena to accelerate the rational design of cathode materials and stable interface, Li(Ni,Co,Mn)O2 (NCM) is a cathode material for rechargeable LIB and also a promising electrocatalyst for oxygen evolution reaction (OER). Their battery performance and catalytic activity are highly correlated to their structures. Multiple processes occurring at the cathode/electrolyte interface led to overall performance degradation. One failure mechanism is the dissolution of transition metals from the cathode. Our efforts employ thin film as a model cathode to monitor the Mn dissolution. Using LiMn2O4 and NCM as cathode materials, we will focus on electrochemical characterization, cation mixing, oxygen evolution, and thin film deposition with controlled crystal structures and composition. We will further introduce our work employing the scanning electrochemical microscope to study LIBs degradation and cathode-electrolyte interface in situ and in real-time.
How Cyclic Aging at Different Temperatures Affects Safety of Li-Ion Pouch Cells
Authors: Feinauer Max , Abdellatif Abdelaziz , Sichler Peter , Wohlfahrt-Mehrens Margret , Waldmann Thomas
Published: September 2023

Li-ion battery safety behavior is critical and should be examined carefully. However, safety testing is typically performed only on pristine cells. This neglects the significant effect of aging conditions, such as ambient temperature, on safety behavior. For example, aging at low temperatures results in Li plating and thus drastically reduces safety [1–3]. Cells aged at higher temperatures with a pronounced solid-electrolyte-interface (SEI) layer on the anode show an increased onset of self-heating leading to improved safety [3,4].

The temperature dependent cyclic aging behavior of commercial Li-ion pouch cells is evaluated using an Arrhenius plot. Further Post-Mortem analyses of aged cells from both branches of the V-shaped Arrhenius plot confirm two dominant aging mechanisms: Li plating and SEI growth for the low and high temperature ranges, respectively.

Heat-wait-seek (HWS) tests under quasi-adiabatic conditions in an accelerated rate calorimeter (ARC) are used to evaluate safety behavior and identify critical temperatures such as the onset of self-heating. Multiple sensors (voltage, resistance, temperature, strain, and ultrasonic transmission) are placed on the pouch cell to provide a better understanding of the processes taking place during HWS tests. These sensors show that some critical events, such as the onset of swelling, venting, or separator melting, are only slightly affected by aging. In contrast, the onset of self-heating depends on the aging mechanism and state of health (SOH) of the cell, as a more pronounced aging has a greater impact on the change in safety. This knowledge can be used, for example, by cell manufacturers to estimate the minimum safety of aged cells based on tests of new cells.

References

[1] T. Waldmann, M. Wohlfahrt-Mehrens, Electrochimica Acta 230 (2017) 454–460. https://doi.org/10.1016/j.electacta.2017.02.036.

[2] A.A. Abd‐El‐Latif, P. Sichler, M. Kasper, T. Waldmann, M. Wohlfahrt‐Mehrens, Batteries & Supercaps 4 (2021) 1135–1144. https://doi.org/10.1002/batt.202100023.

[3] M. Feinauer, A.A. Abd-El-Latif, P. Sichler, A. Aracil Regalado, M. Wohlfahrt-Mehrens, T. Waldmann, Journal of Power Sources 570 (2023) 233046. https://doi.org/10.1016/j.jpowsour.2023.233046.

[4] M. Börner, A. Friesen, M. Grützke, Y.P. Stenzel, G. Brunklaus, J. Haetge, S. Nowak, F.M. Schappacher, M. Winter, Journal of Power Sources 342 (2017) 382–392. https://doi.org/10.1016/j.jpowsour.2016.12.041.

Figure 1