Passivation Layers in Lithium and Sodium Batteries: Potential Profiles, Stabilities, and Voltage Drops

Xiao, Chuanlian; Usiskin, Robert; Maier, Joachim

doi:10.1002/adfm.202100938

Cited by 15 publications

(20 citation statements)

References 50 publications

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“…It was assumed that there is no electric field in the SEI; the SEI components are charge-neutral; the bands are flat; and the liquid electrolyte does not contribute to the potentials in the SEI. A more rigorous approach is to align the Fermi Level of the electrode with the charged point defect states in the SEI while considering the defect formation under the influence of the electrostatic potential on the electrode. − In a recent paper by Swift et al, the band alignments with such a rigorous approach for single-crystalline LiF and Li 2 O interlayers on the Li-metal surface have been calculated. Comparing the results in ref with the simple band alignment approach (the results for bulk structures in Figure ), the energy difference between the Li E F to the CBM is slightly underestimated (less than ∼0.4 eV).…”

Section: Methodsmentioning

confidence: 99%

Impact of Electronic Properties of Grain Boundaries on the Solid Electrolyte Interphases (SEIs) in Li-ion Batteries

Feng

Pan

2021

J. Phys. Chem. C

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Electron leakage through the solid-state electrolyte interphase (SEI) in Li-ion batteries causes the reduction of the electrolyte and the consumption of Li-ions, decreasing the battery capacity and performance. Given the multicomponents and mosaic structures of SEI, the extended defects such as grain boundaries (GBs) and interfaces in SEI are likely to serve as the electron conduction pathways, as the individual SEI components are wide-bandgap insulators in their single-crystalline forms. In this work, the electronic properties of representative GBs of the main SEI components (LiF, Li 2 O, and Li 2 S) on the Li-metal in various electrolytes were investigated via density functional theory (DFT) calculations. It was found that all the GB structures have smaller bandgaps than their corresponding single crystals, with an order of amorphous GBs < Tilt GBs < Twist GBs < single crystals. Some GBs, such as the symmetric Li 2 S Tilt ∑3 (1̅ 21̅ )/[111] GB and the amorphous LiF GB, showed empty electronic states lower than the standard Li + /Li 0 depositing potential. These GB states can trap electrons from the Li-metal, contributing to Li-dendrite growth and electron leakage through SEI. Structural analysis revealed that more under-coordinated atoms in the GBs led to smaller bandgaps and more excess electron localization in the less dense GB regions. These insights suggested that dense SEI structures such as sharp interfaces and well-ordered GBs are preferred to design a fully electronically passivating SEI.

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Section: Methodsmentioning

confidence: 99%

Impact of Electronic Properties of Grain Boundaries on the Solid Electrolyte Interphases (SEIs) in Li-ion Batteries

Feng

Pan

2021

J. Phys. Chem. C

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“…Second, the chemically driven interphase formation may be governed by the diffusion‐controlled Reaction 3 since its growth rate decreases as a function of reaction time. [ 44 ] This may be fundamentally different from the electrochemically driven growth mode during electrochemical cycling.…”

Section: Resultsmentioning

confidence: 99%

Clarifying the Electro‐Chemo‐Mechanical Coupling in Li₁₀SnP₂S₁₂ based All‐Solid‐State Batteries

Sun

Wang

Osenberg

et al. 2022

Advanced Energy Materials

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on the fundamental understanding of the electrochemical reaction mechanisms and the synchronously occurred degradation causes. [1,2] In this respect, considerable efforts using various probing techniques, such as optical microscopy, [3] scanning electron microscopy (SEM), [4][5][6][7] transmission electron microscopy (TEM), [8,9] time-of-flight secondary-ion mass spectrometry (TOF-SIMS), [10] X-ray photoelectron spectroscopy (XPS), [11] magnetic resonance imaging, [12,13] neutron depth profiling, [14] and (synchrotron) X-ray computed tomography (CT) [15,16] have been devoted to characterize the physical, chemical, and mechanical transformation at the solid-solid interfaces where both the electrochemical and degradation reactions occur. These dedicated endeavors have to some extent revealed how the compositional, structural, and mechanical change evolve at the solidsolid interfaces. [17][18][19] With that being said, the precise coupling mechanism by which these factors interact with each other remains elusive due to the incomplete understanding of the deeply-buried and dynamically-evolving solid-solid interface. [20,21] A potential pathway toward addressing the aforementioned challenge is to combine noninvasive probing tools and theoretical modeling. Nevertheless, accurate experimental characterization and advanced modeling that can fundamentally clarify the underlying electro-chemo-mechanical coupling at the solid-solid interfaces in ASSBs are still missing.A fundamental clarification of the electro-chemo-mechanical coupling at the solid-solid electrode|electrolyte interface in all-solid-state batteries (ASSBs) is of crucial significance but has proven challenging. Herein, (synchrotron) X-ray tomography, electrochemical impedance spectroscopy (EIS), time-of-flight secondary-ion mass spectrometry (TOF-SIMS), and finite element analysis (FEA) modeling are jointly used to decouple the electro-chemo-mechanical coupling in Li 10 SnP 2 S 12 -based ASSBs. Non-destructive (synchrotron) X-ray tomography results visually disclose unexpected mechanical deformation of the solid electrolyte and electrode as well as an unanticipated evolving behavior of the (electro)chemically generated interphase. The EIS and TOF-SIMS probing results provide additional information that links the interphase/electrode properties to the overall battery performance. The modeling results complete the picture by providing the detailed distribution of the mechanical stress/strain and the potential/ionic flux within the electrolyte. Collectively, these results suggest that 1) the interfacial volume changes induced by the (electro)chemical reactions can trigger the mechanical deformation of the solid electrode and electrolyte; 2) the overall electrochemical process can accelerate the interfacial chemical reactions; 3) the reconfigured interfaces in turn influence the electric potential distribution as well as charge transportation within the SE. These fundamental discoveries that remain unreported until now significantly improve the understanding of ...

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“…This is expected from the gradient of the chemical potential of Na and is analogous to the metal-to-oxygen ratio in oxides ( e.g., in oxides on Fe). 55 , 56 …”

Section: Resultsmentioning

confidence: 99%

Influence of Porosity of Sulfide-Based Artificial Solid Electrolyte Interphases on Their Performance with Liquid and Solid Electrolytes in Li and Na Metal Batteries

Lim

Fenk

Küster

et al. 2022

ACS Appl. Mater. Interfaces

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Realization of all-solid-state batteries combined with metallic Li/Na is still hindered due to the unstable interface between the alkali metal and solid electrolytes, especially for highly promising thiophosphate materials. Artificial and uniform solid-electrolyte interphases (SEIs), serving as thin ion-conducting films, have been considered as a strategy to overcome the issues of such reactive interfaces. Here, we synthesized sulfide-based artificial SEIs (Li x S y and Na x S y ) on Li and Na by solid/gas reaction between the alkali metal and S vapor. The synthesized films are carefully characterized with various chemical/electrochemical techniques. We show that these artificial SEIs are not beneficial from an application point of view since they either contribute to additional resistances (Li) or do not prevent reactions at the alkali metal/electrolyte interface (Na). We show that Na x S y is more porous than Li x S y , supported by (i) its rough morphology observed by focused ion beam-scanning electron microscopy, (ii) the rapid decrease of R interface (interfacial resistance) in Na x S y -covered-Na symmetric cells with liquid electrolyte upon aging under open-circuit potential, and (iii) the increase of R interface in Na x S y -covered-Na solid-state symmetric cells with Na 3 PS 4 electrolyte. The porous SEI allows the penetration of liquid electrolyte or alkali metal creep through its pores, resulting in a continuous chemical reaction. Hence, porosity of SEIs in general should be carefully taken into account in the application of batteries containing both liquid electrolyte and solid electrolyte.

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Passivation Layers in Lithium and Sodium Batteries: Potential Profiles, Stabilities, and Voltage Drops

Cited by 15 publications

References 50 publications

Impact of Electronic Properties of Grain Boundaries on the Solid Electrolyte Interphases (SEIs) in Li-ion Batteries

Impact of Electronic Properties of Grain Boundaries on the Solid Electrolyte Interphases (SEIs) in Li-ion Batteries

Clarifying the Electro‐Chemo‐Mechanical Coupling in Li₁₀SnP₂S₁₂ based All‐Solid‐State Batteries

Influence of Porosity of Sulfide-Based Artificial Solid Electrolyte Interphases on Their Performance with Liquid and Solid Electrolytes in Li and Na Metal Batteries

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Passivation Layers in Lithium and Sodium Batteries: Potential Profiles, Stabilities, and Voltage Drops

Cited by 15 publications

References 50 publications

Impact of Electronic Properties of Grain Boundaries on the Solid Electrolyte Interphases (SEIs) in Li-ion Batteries

Impact of Electronic Properties of Grain Boundaries on the Solid Electrolyte Interphases (SEIs) in Li-ion Batteries

Clarifying the Electro‐Chemo‐Mechanical Coupling in Li10SnP2S12 based All‐Solid‐State Batteries

Influence of Porosity of Sulfide-Based Artificial Solid Electrolyte Interphases on Their Performance with Liquid and Solid Electrolytes in Li and Na Metal Batteries

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Clarifying the Electro‐Chemo‐Mechanical Coupling in Li₁₀SnP₂S₁₂ based All‐Solid‐State Batteries