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74
result(s) for
"Mukherjee, Partha P"
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Linking void and interphase evolution to electrochemistry in solid-state batteries using operando X-ray tomography
by
Shevchenko, Pavel
,
Cortes, Francisco Javier Quintero
,
De Carlo, Francesco
in
639/301/299/891
,
639/301/930/2735
,
639/638/161/891
2021
Despite progress in solid-state battery engineering, our understanding of the chemo-mechanical phenomena that govern electrochemical behaviour and stability at solid–solid interfaces remains limited compared to at solid–liquid interfaces. Here, we use operando synchrotron X-ray computed microtomography to investigate the evolution of lithium/solid-state electrolyte interfaces during battery cycling, revealing how the complex interplay among void formation, interphase growth and volumetric changes determines cell behaviour. Void formation during lithium stripping is directly visualized in symmetric cells, and the loss of contact that drives current constriction at the interface between lithium and the solid-state electrolyte (Li
10
SnP
2
S
12
) is quantified and found to be the primary cause of cell failure. The interphase is found to be redox-active upon charge, and global volume changes occur owing to partial molar volume mismatches at either electrode. These results provide insight into how chemo-mechanical phenomena can affect cell performance, thus facilitating the development of solid-state batteries.
Understanding electrochemical behaviour and stability at solid–solid interfaces remains challenging. Operando synchrotron X-ray computed microtomography loss reveals that reconfiguration of interfacial contact is critical to explain cell failure during solid-state battery cycling.
Journal Article
Quantifying the unknown impact of segmentation uncertainty on image-based simulations
by
Martinez, Carianne
,
Mukherjee, Partha P.
,
Sharma, Krish
in
631/114/2397
,
639/301/1034/1037
,
639/705/1042
2021
Image-based simulation, the use of 3D images to calculate physical quantities, relies on image segmentation for geometry creation. However, this process introduces image segmentation uncertainty because different segmentation tools (both manual and machine-learning-based) will each produce a unique and valid segmentation. First, we demonstrate that these variations propagate into the physics simulations, compromising the resulting physics quantities. Second, we propose a general framework for rapidly quantifying segmentation uncertainty. Through the creation and sampling of segmentation uncertainty probability maps, we systematically and objectively create uncertainty distributions of the physics quantities. We show that physics quantity uncertainty distributions can follow a Normal distribution, but, in more complicated physics simulations, the resulting uncertainty distribution can be surprisingly nontrivial. We establish that bounding segmentation uncertainty can fail in these nontrivial situations. While our work does not eliminate segmentation uncertainty, it improves simulation credibility by making visible the previously unrecognized segmentation uncertainty plaguing image-based simulation.
Image-based simulation for obtaining physical quantities is limited by the uncertainty in the underlying image segmentation. Here, the authors introduce a workflow for efficiently quantifying segmentation uncertainty and creating uncertainty distributions of the resulting physics quantities.
Journal Article
Modeling of Mesoscale Variability in Biofilm Shear Behavior
by
Kumar, Aloke
,
Mukherjee, Partha P.
,
Barai, Pallab
in
Bacteria
,
Bacterial Adhesion
,
Bacterial Physiological Phenomena
2016
Formation of bacterial colonies as biofilm on the surface/interface of various objects has the potential to impact not only human health and disease but also energy and environmental considerations. Biofilms can be regarded as soft materials, and comprehension of their shear response to external forces is a key element to the fundamental understanding. A mesoscale model has been presented in this article based on digitization of a biofilm microstructure. Its response under externally applied shear load is analyzed. Strain stiffening type behavior is readily observed under high strain loads due to the unfolding of chains within soft polymeric substrate. Sustained shear loading of the biofilm network results in strain localization along the diagonal direction. Rupture of the soft polymeric matrix can potentially reduce the intercellular interaction between the bacterial cells. Evolution of stiffness within the biofilm network under shear reveals two regimes: a) initial increase in stiffness due to strain stiffening of polymer matrix, and b) eventual reduction in stiffness because of tear in polymeric substrate.
Journal Article
Heterogeneous Solid Electrolyte Interphase Interactions Dictate Interface Instability in Sodium Metal Electrodes
by
Naik, Kaustubh G.
,
Vishnugopi, Bairav S.
,
Mukherjee, Partha P.
in
electro-chemo-mechanical heterogeneities
,
Electrodes
,
Electrolytes
2024
Sodium (Na) metal batteries have attracted recent attention due to their low cost and high abundance of Na. However, the advancement of Na metal batteries is impeded due to key challenges such as dendrite growth, solid electrolyte interphase (SEI) fracture, and low Coulombic efficiency. This study examines the coupled electro‐chemo‐mechanical interactions governing the electrodeposition stability and morphological evolution at the Na/electrolyte interface. The SEI heterogeneities influence transport and reaction kinetics leading to the formation of current and stress hotspots during Na plating. Further, it is demonstrated that the heterogeneity‐induced Na metal evolution and its influence on the stress distribution critically affect the mechanical overpotential, contributing to a faster SEI failure. The analysis reveals three distinct failure mechanisms—mechanical, transport, and kinetic—that govern the onset of instabilities at the interface. Finally, a comprehensive comparative study of SEI failure in Na and lithium (Li) metal anodes illustrates that the electrochemical and mechanical characteristics of the SEI are crucial in tailoring the anode morphology and interface stability. This work delineates mechanistic stability regimes cognizant of the SEI attributes and underlying failure modes and offers important guidelines for the design of artificial SEI layers for stable Na metal electrodes. The electrochemical and structural heterogeneities in the solid electrolyte interphase (SEI) influence the reaction kinetics of Na metal electrodes, resulting in current focusing and stress hotspots during electrodeposition. This work delineates mechanistic stability regimes cognizant of the SEI attributes and underlying failure modes and offers important guidelines for the design of artificial SEI layers for stable Na metal electrodes.
Journal Article
Probing the Impact of Vacancy Diffusion on Void Dynamics at the Lithium Metal–Solid Electrolyte Interface
by
Vishnugopi, Bairav S.
,
Mukherjee, Partha P.
,
Banerjee, Sourim
in
Batteries
,
Electrodes
,
Electrolytes
2026
Lithium (Li) metal‐based solid‐state batteries (SSBs) are considered promising candidates for next‐generation energy storage due to their superior energy density and enhanced safety compared to conventional Li‐ion systems. However, their practical application is limited by challenges such as void formation at the Li‐solid electrolyte (SE) interface, which disrupts ion transport and accelerates interfacial degradation. This work investigates how the coupled effects of electro‐dissolution kinetics and surface diffusion at the Li metal surface govern the evolution of interfacial morphology during stripping. This work examines the influence of three distinct surface diffusion modes, which are terrace diffusion, step diffusion, and interlayer diffusion, on maintaining interfacial stability. In addition, how the dominant surface diffusion mechanism can overcome the contact loss due to high reaction kinetics is explored. Furthermore, the roughness of the Li metal anode surface is quantified, and the influence of different diffusion mechanisms on the evolution of the dynamic solid–solid interface is examined. The critical role of temperature in enhancing Li surface diffusivity and expanding the regime of stable contact is highlighted. By identifying distinct regimes of interface stability, this study analyzes how non‐uniform electrochemical dynamics dictate void morphology evolution and interfacial contact. These insights offer guiding principles for engineering robust Li–SE interfaces in SSBs. Understanding void formation at the lithium(Li) metal–solid electrolyte (SE) interface is crucial to improving interfacial stability in solid‐state batteries(SSBs). In this work, the competing electrochemical interactions, including surface diffusion modes are studied in dictating interface evolution during electro‐dissolution. A distinct surface diffusion mode for stable contact is identified, and the role of temperature and overpotential is explored.
Journal Article
Electrodeposition Stability Landscape for Solid–Solid Interfaces
by
Naik, Kaustubh G.
,
Vishnugopi, Bairav S.
,
Mukherjee, Partha P.
in
Butler–Volmer kinetics
,
electrodeposition stability
,
electro‐chemo‐mechanical coupling
2024
As solid‐state batteries (SSBs) with lithium (Li) metal anodes gain increasing traction as promising next‐generation energy storage systems, a fundamental understanding of coupled electro‐chemo‐mechanical interactions is essential to design stable solid‐solid interfaces. Notably, uneven electrodeposition at the Li metal/solid electrolyte (SE) interface arising from intrinsic electrochemical and mechanical heterogeneities remains a significant challenge. In this work, the thermodynamic origins of mechanics‐coupled reaction kinetics at the Li/SE interface are investigated and its implications on electrodeposition stability are unveiled. It is established that the mechanics‐driven energetic contribution to the free energy landscape of the Li deposition/dissolution redox reaction has a critical influence on the interface stability. The study presents the competing effects of mechanical and electrical overpotential on the reaction distribution, and demarcates the regimes under which stress interactions can be tailored to enable stable electrodeposition. It is revealed that different degrees of mechanics contribution to the forward (dissolution) and backward (deposition) reaction rates result in widely varying stability regimes, and the mechanics‐coupled kinetics scenario exhibited by the Li/SE interface is shown to depend strongly on the thermodynamic and mechanical properties of the SE. This work highlights the importance of discerning the underpinning nature of electro‐chemo‐mechanical coupling toward achieving stable solid/solid interfaces in SSBs. This work explores the thermodynamic foundations of mechanics‐coupled reaction kinetics and reveals its implications on electrodeposition stability in solid‐state batteries. Depending on the material properties of the solid electrolyte (SE), lithium (Li) metal/SE interfaces can exhibit distinct mechanics‐driven energetic contributions to the free energy landscape of the reaction, resulting in different scenarios of mechanics‐reaction kinetics coupling and electrodeposition stability regimes.
Journal Article
The BRAVO Clinical Study Protocol: Oral Varespladib for Inhibition of Secretory Phospholipase A2 in the Treatment of Snakebite Envenoming
by
Samuel, Stephen P.
,
Manikath, Neeraj
,
Gerardo, Charles J.
in
BRAVO
,
clinical trial
,
Clinical trials
2022
Introduction: Snakebite is an urgent, unmet global medical need causing significant morbidity and mortality worldwide. Varespladib is a potent inhibitor of venom secretory phospholipase A2 (sPLA2) that can be administered orally via its prodrug, varespladib-methyl. Extensive preclinical data support clinical evaluation of varespladib as a treatment for snakebite envenoming (SBE). The protocol reported here was designed to evaluate varespladib-methyl for SBE from any snake species in multiple geographies. Methods and Analysis: BRAVO (Broad-spectrum Rapid Antidote: Varespladib Oral for snakebite) is a multicenter, randomized, double-blind, placebo-controlled, phase 2 study to evaluate the safety, tolerability, and efficacy of oral varespladib-methyl plus standard of care (SoC) vs. SoC plus placebo in patients presenting with acute SBE by any venomous snake species. Male and female patients 5 years of age and older who meet eligibility criteria will be randomly assigned 1:1 to varespladib-methyl or placebo. The primary outcome is the Snakebite Severity Score (SSS) that has been modified for international use. This composite outcome is based on the sum of the pulmonary, cardiovascular, nervous, hematologic, and renal systems components of the updated SSS. Ethics and Dissemination: This protocol was submitted to regulatory authorities in India and the US. A Clinical Trial No Objection Certificate from the India Central Drugs Standard Control Organisation, Drug Controller General-India, and a Notice to Proceed from the US Food and Drug Administration have been obtained. The study protocol was approved by properly constituted, valid institutional review boards or ethics committees at each study site. This study is being conducted in compliance with the April 1996 ICH Guidance for Industry GCP E6, the Integrated Addendum to ICH E6 (R2) of November 2016, and the applicable regulations of the country in which the study is conducted. The trial is registered on Clinical trials.gov, NCT#04996264 and Clinical Trials Registry-India, 2021/07/045079 000062.
Journal Article
Thermal Modulation of Electrodeposition Stability in Sodium Metal Electrodes
by
Chatterjee, Deep
,
Vishnugopi, Bairav S.
,
Mukherjee, Partha P.
in
Batteries
,
dendrite growth
,
electrodeposition stability
2026
Sodium metal batteries (SMBs) have gained interest due to the high natural abundance and lower cost of sodium (Na) compared to lithium (Li), making them a promising alternative to conventional Li‐based battery systems. However, a key challenge toward the commercial viability of SMBs lies in mitigating uneven electrodeposition and dendrite growth, stemming from inherent interfacial instabilities during Na plating. This work explores how electrodeposition stability in SMBs is governed by thermal conditions, which directly affect ionic transport and interfacial reaction kinetics. A range of thermal environments are explored using a phase‐field modeling (PFM) framework, with a particular emphasis on the influence of temperature gradient‐induced thermodiffusion (Soret effect) on deposition dynamics. A quantitative analysis of dendrite growth under varying thermal conditions is conducted to identify regimes that promote stable plating behavior. It is found that operational temperature serves as a strong modulator of plating instability by simultaneously influencing reaction kinetics and ion transport, and thermodiffusion under imposed temperature gradients further redistributes ionic flux and alters deposition morphology. This work provides new insights into the role of thermal landscapes in dictating interface evolution during Na metal plating and offers design guidelines for leveraging thermal conditions to enhance deposition stability in Na metal electrodes. Unstable electrodeposition in sodium metal electrodes during plating gives rise to dendritic morphologies. A comprehensive analysis of how various thermal profiles, including uniform and non‐uniform temperature distributions and thermodiffusion can affect electrodeposition instability has been performed. Mechanistic interface instability descriptors have been introduced to quantify dendritic growth.
Journal Article
Surface energy-driven electrodeposition stability in sodium metal electrodes
by
Chatterjee, Deep
,
Vishnugopi, Bairav S
,
Singla, Aditya
in
Anodes
,
Commercialization
,
dendrite growth
2025
Dendrite growth arising from interfacial instability remains a major obstacle to the advancement and commercialization of metal anode-based batteries. Sodium metal batteries (SMBs), a promising alternative to lithium (Li)-based systems due to the broad availability and lower cost of sodium (Na), suffer from pronounced interfacial instabilities during plating. A principal modulating factor influencing the propensity for dendritic growth in metal anodes is the interfacial surface energy at the active metal-electrolyte interface. This work explores the role of surface energy-induced interfacial instability in SMBs employing liquid electrolytes. It is shown that higher interfacial energies promote a more uniform deposition front, thereby reducing the tendency for uneven electrodeposition. For low interfacial energies, the reduced energetic penalty for creating new surfaces promotes rapid tip growth and branching, leading to highly unstable deposition morphologies with pronounced dendritic features. Furthermore, a comparative analysis between Li and Na metal anodes reveals that intrinsic differences in the material properties significantly influence electrodeposition stability. Through a combination of qualitative visualization and quantitative analysis, this study provides a comprehensive understanding of the role of surface energy in dictating interface evolution in SMBs, offering insights for the rational design of stable metal anode systems.
Journal Article
Electro-chemo-mechanics of anode-free solid-state batteries
by
Sandoval, Stephanie Elizabeth
,
Liao, Daniel W.
,
Vishnugopi, Bairav S.
in
639/166/988
,
639/301/299/891
,
Batteries
2025
Anode-free solid-state batteries contain no active material at the negative electrode in the as-manufactured state, yielding high energy densities for use in long-range electric vehicles. The mechanisms governing charge–discharge cycling of anode-free batteries are largely controlled by electro-chemo-mechanical phenomena at solid–solid interfaces, and there are important mechanistic differences when compared with conventional lithium-excess batteries. This Perspective provides an overview of the factors governing lithium nucleation, growth, stripping and cycling in anode-free solid-state batteries, including mechanical deformation of lithium, the chemical and mechanical properties of the current collector, microstructural effects, and stripping dynamics. Pathways for engineering interfaces to maximize performance and extend battery lifetime are discussed. We end with critical research questions to pursue, including understanding behaviour at low stack pressure, tailoring interphase growth, and engineering current collectors and interlayers.
Anode-free batteries contain no active material at the negative electrode when manufactured, and this can enable them to have high energy density. This Perspective presents a critical overview of the mechanisms governing the behaviour of anode-free solid-state batteries and provides guidance to improve this type of battery.
Journal Article