A three dimensional kinetic Monte Carlo model for simulating the carbon/sulfur mesostructural evolutions of discharging lithium sulfur batteries

Thangavel, Vigneshwaran; Guerrero, Oscar Xavier; Quiroga, Miguel; Mikala, Adelphe Matsiegui; Rucci, A.; Franco, Alejandro A.

doi:10.1016/j.ensm.2019.07.011

Cited by 41 publications

(36 citation statements)

References 45 publications

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“…It expands the accessible length scales of existing structure-sensitive methods, such as X-ray tomography (13), with a seamless resolution from sub-nanometers to sub-micrometers. The data analysis approach allows to directly validate the structural evolution obtained with modelling attempts (16,57,59) using in situ scattering data (54). The example of Li2O2 deposition serves to demonstrate that seamless structural information all the way from atomic to micrometric scales holds key to important mechanistic detail (here second etransfer versus disproportionation).…”

Section: Discussionmentioning

confidence: 99%

In situ small-angle X-ray scattering reveals solution phase discharge of Li–O ₂ batteries with weakly solvating electrolytes

Prehal

Samojlov

Nachtnebel

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

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Electrodepositing insulating lithium peroxide (Li2O2) is the key process during discharge of aprotic Li–O2 batteries and determines rate, capacity, and reversibility. Current understanding states that the partition between surface adsorbed and dissolved lithium superoxide governs whether Li2O2 grows as a conformal surface film or larger particles, leading to low or high capacities, respectively. However, better understanding governing factors for Li2O2 packing density and capacity requires structural sensitive in situ metrologies. Here, we establish in situ small- and wide-angle X-ray scattering (SAXS/WAXS) as a suitable method to record the Li2O2 phase evolution with atomic to submicrometer resolution during cycling a custom-built in situ Li–O2 cell. Combined with sophisticated data analysis, SAXS allows retrieving rich quantitative structural information from complex multiphase systems. Surprisingly, we find that features are absent that would point at a Li2O2 surface film formed via two consecutive electron transfers, even in poorly solvating electrolytes thought to be prototypical for surface growth. All scattering data can be modeled by stacks of thin Li2O2 platelets potentially forming large toroidal particles. Li2O2 solution growth is further justified by rotating ring-disk electrode measurements and electron microscopy. Higher discharge overpotentials lead to smaller Li2O2 particles, but there is no transition to an electronically passivating, conformal Li2O2 coating. Hence, mass transport of reactive species rather than electronic transport through a Li2O2 film limits the discharge capacity. Provided that species mobilities and carbon surface areas are high, this allows for high discharge capacities even in weakly solvating electrolytes. The currently accepted Li–O2 reaction mechanism ought to be reconsidered.

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Section: Discussionmentioning

confidence: 99%

In situ small-angle X-ray scattering reveals solution phase discharge of Li–O ₂ batteries with weakly solvating electrolytes

Prehal

Samojlov

Nachtnebel

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

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“…The representation of the evolution of the cathode mesostructures in the game follows a similar strategy as in The Great Li–Air Escapade VR : lookup tables are built based on calculations carried out by using simplified versions of models previously reported by us [56,64, 67] . In the LSB case, the (carbon‐based) cathode evolution representation is more complex (Figure 21).…”

Section: Battery Virtual Reality Serious Gamesmentioning

confidence: 99%

“…In the game, sulfur particles initially present in the cathode pores are represented as cubes in yellow color randomly localized, and the precipitates are represented as green spheres forming gradually and randomly locating on the carbon surface upon the LSB cell discharge. Pre‐calculated lookup tables using kMC simulations can be used to describe sulfur particles dissolution, polysulfides formation and Li 2 S precipitation [67] …”

Section: Battery Virtual Reality Serious Gamesmentioning

confidence: 99%

Entering the Augmented Era: Immersive and Interactive Virtual Reality for Battery Education and Research**

Franco

Chotard

Loup-Escande

et al. 2020

Batteries & Supercaps

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We present a series of innovative serious games we develop since four years using Virtual Reality (VR) technology to teach battery concepts at the University (from undergraduate to doctorate levels) and also to the general public in the context of science festivals and other events. These serious games allow interacting with battery materials, electrodes and cells in an immersive way. They allow experiencing impossible situations in real life, such as building with hands battery active material crystal structures at the nanometer scale, flying inside battery composite electrodes to calculate their geometrical tortuosities at the micrometer scale, experiencing the electrochemical behavior of different battery types by driving an electric vehicle and interacting with a virtual smart electrical grid impacted by 3D‐printed devices operated from the real world. Such serious games embed mathematical models with different levels of complexity representing the physical processes at different scales. We describe the technical characteristics of our VR serious games and their teaching goals, and we provide some discussion about their impact on the motivation, engagement and learning following four years of experimentation with them. Finally, we discuss why our VR serious games have also the potential to pave the way towards an augmented era in the battery field by supporting the R&D activities carried out by scientists and engineers.

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“…kinetic Monte Carlo to model crystal growth 56 ) would allow a more direct validation of mechanistic hypothesis. Such models could be either run independently, or if computationally feasible, synergistically combined with in situ SAXS, according to the algorithm presented in Fig.…”

Section: In Situ Small and Wide Angle X-ray Scattering Data Analysismentioning

confidence: 99%

Exclusive solution discharge in Li-O2 batteries

Prehal

Samojlov²,

Nachtnebel³

et al. 2020

Preprint

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<b>Electrodepositing insulating and insoluble Li2O2 is the key process during discharge of aprotic Li-O2 batteries and determines rate, capacity, and reversibility. Current understanding states that the partition between surface adsorbed and solvated LiO2 governs whether Li2O2 grows as surface film or particles, leading to low or high capacities, respectively. Here we show that Li2O2 forms exclusively as particles via solution mediated LiO2 disproportionation. We describe a unified O2 reduction mechanism that conclusively explains capacity limitations across the whole range of electrolytes. Low-donor-number electrolytes are shown to accelerate disproportionation rather than slowing it down. Deciding for particle morphology and achievable capacities are species mobilities, true areal rate and the rate at which associated LiO2 forms in solution. Provided that species mobilities and surface are high, this allows for high capacities even with low-donor-number electrolytes, previously considered prototypical for low capacity via surface growth. The tools for these insights include microscopy, hydrodynamic voltammetry, a numerical reaction model, and in situ small/wide angle X-ray scattering (SAXS/WAXS). Combined with sophisticated data analysis, SAXS allows retrieving rich quantitative information from complex multi-phase systems. On a wider perspective, this SAXS method is a powerful in situ metrology with atomic to sub-micron resolution to study mechanisms in complex electrochemical systems and beyond.<br></b>

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A three dimensional kinetic Monte Carlo model for simulating the carbon/sulfur mesostructural evolutions of discharging lithium sulfur batteries

Cited by 41 publications

References 45 publications

In situ small-angle X-ray scattering reveals solution phase discharge of Li–O ₂ batteries with weakly solvating electrolytes

In situ small-angle X-ray scattering reveals solution phase discharge of Li–O ₂ batteries with weakly solvating electrolytes

Entering the Augmented Era: Immersive and Interactive Virtual Reality for Battery Education and Research**

Exclusive solution discharge in Li-O2 batteries

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A three dimensional kinetic Monte Carlo model for simulating the carbon/sulfur mesostructural evolutions of discharging lithium sulfur batteries

Cited by 41 publications

References 45 publications

In situ small-angle X-ray scattering reveals solution phase discharge of Li–O 2 batteries with weakly solvating electrolytes

In situ small-angle X-ray scattering reveals solution phase discharge of Li–O 2 batteries with weakly solvating electrolytes

Entering the Augmented Era: Immersive and Interactive Virtual Reality for Battery Education and Research**

Exclusive solution discharge in Li-O2 batteries

Contact Info

Product

Resources

About

In situ small-angle X-ray scattering reveals solution phase discharge of Li–O ₂ batteries with weakly solvating electrolytes

In situ small-angle X-ray scattering reveals solution phase discharge of Li–O ₂ batteries with weakly solvating electrolytes