Exploring 3D microstructural evolution in Li-Sulfur battery electrodes using in-situ X-ray tomography

Yermukhambetova, Assiya; Tan, C. S.; Daemi, Sohrab R.; Bakenov, Zhumabay; Darr, Jawwad A.; Brett, Daniel; Shearing, Paul R.

doi:10.1038/srep35291

Cited by 75 publications

(70 citation statements)

References 36 publications

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“…One of the more compelling advantages of X-ray tomography compared to other techniques such as FIB-SEM is the nondestructive nature of the imaging process, which allows in situ and operando characterization to be carried out in specialized cells as previously reported by our group. 44 In particular for sulfur electrodes, tortuosity and effective electrical conductivity are a strong function of state of charge and cycle life. Cycling data for the elemental sulfur electrode has been included in ESI, † that we propose can be validated in future work with cell simulation models, such as those presented by Danner et al 7 and Thangavel et al, 8 with the inclusion of the image-based workflow presented here.…”

Section: Discussionmentioning

confidence: 99%

Three-dimensional image based modelling of transport parameters in lithium–sulfur batteries

Tan

Kok

Daemi

et al. 2019

Phys. Chem. Chem. Phys.

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Section: Discussionmentioning

confidence: 99%

Three-dimensional image based modelling of transport parameters in lithium–sulfur batteries

Tan

Kok

Daemi

et al. 2019

Phys. Chem. Chem. Phys.

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“…The lithium-sulfur battery has been studied intensively as a next generation electrochemical energy storage device because of its superior theoretical energy density of 2600 Wh kg −1 , which surpasses that of current state-of-the-art Li-ion batteries with energy density of 300–600 Wh kg −1 , depending upon intercalation chemistries 1 – 4 . However, the nature of the chemical species and reactions in a functional Li-S battery lead to several critical challenges 3 – 5 .…”

Section: Introductionmentioning

confidence: 99%

Operando Multi-modal Synchrotron Investigation for Structural and Chemical Evolution of Cupric Sulfide (CuS) Additive in Li-S battery

Sun

Zhao

Lin

et al. 2017

Sci Rep

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Conductive metal sulfides are promising multi-functional additives for future lithium-sulfur (Li-S) batteries. These can increase the sulfur cathode’s electrical conductivity to improve the battery’s power capability, as well as contribute to the overall cell-discharge capacity. This multi-functional electrode design showed initial promise; however, complicated interactions at the system level are accompanied by some detrimental side effects. The metal sulfide additives with a chemical conversion as the reaction mechanism, e.g., CuS and FeS2, can increase the theoretical capacity of the Li-S system. However, these additives may cause undesired parasitic reactions, such as the dissolution of the additive in the electrolyte. Studying such complex reactions presents a challenge because it requires experimental methods that can track the chemical and structural evolution of the system during an electrochemical process. To address the fundamental mechanisms in these systems, we employed an operando multimodal x-ray characterization approach to study the structural and chemical evolution of the metal sulfide—utilizing powder diffraction and fluorescence imaging to resolve the former and absorption spectroscopy the latter—during lithiation and de-lithiation of a Li-S battery with CuS as the multi-functional cathode additive. The resulting elucidation of the structural and chemical evolution of the system leads to a new description of the reaction mechanism.

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“…X-ray diffraction [32][33][34] and X-ray absorption spectroscopy (XAS) [35][36][37][38][39] have been used for operando experiments that focus on polysulfides, giving bulk, non-spatially resolved information. Transmission X-ray microscopy 33,40 provides spatiallyresolved microstructural information but lacks the ability to provide chemical information at the sulfur K-edge due to the hard X-ray energies needed for imaging. Methods such as first principles have been used to generate "standard" polysulfide X-ray spectra to isolate individual species before disproportionation 41,42 as a complement to operando studies and verification of experimental data.…”

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Operando Spectromicroscopy of Sulfur Species in Lithium-Sulfur Batteries

Miller

Kasse

Heath

et al. 2017

J. Electrochem. Soc.

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In this study, a novel cross-sectional battery cell was developed to characterize lithium-sulfur batteries using X-ray spectromicroscopy. Chemically sensitive X-ray maps were collected operando at energies relevant to the expected sulfur species and were used to correlate changes in sulfur species with electrochemistry. Significant changes in the sulfur/carbon composite electrode were observed from cycle to cycle including rearrangement of the elemental sulfur matrix and PEO 10 LiTFSI binder. Polysulfide concentration and area of spatial diffusion increased with cycling, indicating that some polysulfide dissolution is irreversible, leading to polysulfide shuttle. Fitting of the maps using standard sulfur and polysulfide XANES spectra indicated that upon subsequent discharge/charge cycles, the initial sulfur concentration was not fully recovered; polysulfides and lithium sulfide remained at the cathodes with higher order polysulfides as the primary species in the region of interest. Quantification of the polysulfide concentration across the electrolyte and electrode interfaces shows that the polysulfide concentration before the first discharge and after the third charge is constant within the electrolyte, but while cycling, a significant increase in polysulfides and a gradient toward the lithium metal anode forms. This chemically and spatially sensitive characterization and analysis provides a foundation for further operando spectromicroscopy of lithium-sulfur batteries. New "beyond lithium-ion" battery chemistries are essential to meet the increasing demand for long-lasting, high capacity energy storage in portable electronics and electric vehicles. Lithium-sulfur (Li-S) batteries are an attractive Li-ion alternative that provides large capacity (1672 mAh g −1 ) and energy density (2500 Wh kg −1 ) while also being low cost, earth-abundant, and lightweight.1-3 Li-S batteries have a unique chemistry that achieves high capacity via chemical transformation rather than Li intercalation. Elemental sulfur (S 8 ) is reduced through a series of soluble Li polysulfides (Li 2 S x , 2 ≤ x ≤ 8) to a final solid discharge product (Li 2 S), and the process is reversed upon charging. [4][5][6] However, Li-S suffers from unrealized theoretical capacity and rapid capacity fade due to loss processes that are not well-understood. 2,7 While many advances in electrode and electrolyte engineering have been made in an attempt mitigate these performance issues, 8-14 a gap remains in the mechanistic understanding of Li-S battery operation. Several mechanisms for reduced capacity and capacity fade have been proposed. Lithium polysulfides, which are necessary for operation, dissolve into the liquid electrolyte, remain dissolved, and "shuttle" between the electrodes rather than participating in the electrochemical reactions, decreasing the amount of active material available. 3,[15][16][17][18] Low sulfur utilization results in initially low capacity that then continues to decrease with subsequent cycles. [19][20][21] Batteries are spatiall...

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Exploring 3D microstructural evolution in Li-Sulfur battery electrodes using in-situ X-ray tomography

Cited by 75 publications

References 36 publications

Three-dimensional image based modelling of transport parameters in lithium–sulfur batteries

Three-dimensional image based modelling of transport parameters in lithium–sulfur batteries

Operando Multi-modal Synchrotron Investigation for Structural and Chemical Evolution of Cupric Sulfide (CuS) Additive in Li-S battery

Operando Spectromicroscopy of Sulfur Species in Lithium-Sulfur Batteries

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