Conformal three-dimensional interphase of Li metal anode revealed by low-dose cryoelectron microscopy

Han, Bing; Li, Xiangyan; Bai, Shuang; Zou, Ye; Lu, Bingyu; Zhang, Minghao; Ma, Xiaomin; Chang, Zhi; Meng, Ying Shirley; Gu, Meng

doi:10.1016/j.matt.2021.09.019

Cited by 45 publications

(32 citation statements)

References 36 publications

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“…direct electron detection cameras can cool down the sample to ≈−193 °C, which allows us to probe the fine details of Li Metal and SEI at the atomic scale. [10][11][12][13][14][15][16][17][18][19][20] The reductive decomposition of electrolyte was believed to result in surficial passivation layer (SEI exoskeleton) on the anode. [21][22][23] Here, we observe that some components of the SEI exoskeleton can be found on the surface of plated inner crystalline Li BCC as well.…”

Section: Introductionmentioning

confidence: 99%

Cryo‐Electron Tomography of Highly Deformable and Adherent Solid‐Electrolyte Interphase Exoskeleton in Li‐Metal Batteries with Ether‐Based Electrolyte

Han

Wang

et al. 2022

Advanced Materials

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The 3D nanocomposite structure of plated lithium (LiMetal) and solid electrolyte interphases (SEI), including a polymer‐rich surficial passivation layer (SEI exoskeleton) and inorganic SEI “fossils” buried inside amorphous Li matrix, is resolved using cryogenic transmission electron microscopy. With ether‐based DOLDME‐LiTFSI electrolyte, LiF and Li2O nanocrystals are formed and embedded in a thin but tough amorphous polymer in the SEI exoskeleton. The fast Li‐stripping directions are along [1¯10] or [121¯], which produces eight exposed {111} planes at halfway charging. Full Li stripping produces completely sagging, empty SEI husks that can sustain large bending and buckling, with the smallest bending radius of curvature observed approaching tens of nanometers without apparent damage. In the 2nd round of Li plating, a thin LiBCC sheet first nucleates at the current collector, extends to the top end of the deflated SEI husk, and then expands its thickness. The apparent zero wetting angle between LiBCC and the SEI interior means that the heterogeneous nucleation energy barrier is zero. Due to its complete‐wetting property and chemo‐mechanical stability, the SEI largely prevents further reactions between the Li metal and the electrolyte, which explains the superior performance of Li‐metal batteries with ether‐based electrolytes. However, uneven refilling of the SEI husks results in dendrite protrusions and some new SEI formation during the 2nd plating. A strategy to form bigger SEI capsules during the initial cycle with higher energy density than the following cycles enables further enhanced Coulombic efficiency to above 99%.

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Section: Introductionmentioning

confidence: 99%

Cryo‐Electron Tomography of Highly Deformable and Adherent Solid‐Electrolyte Interphase Exoskeleton in Li‐Metal Batteries with Ether‐Based Electrolyte

Han

Wang

et al. 2022

Advanced Materials

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“…In 2021, Han et al. [ 19 ] have employed cryo‐STEM tomography mapping to reveal 3D morphology and distribution of SEI as well as “dead” Li, which provides insights into the working mechanism of SEI in Li metal anodes. In addition, synchrotron X‐ray computed tomography (SXCT) [ 7c,20 ] is proved to be a highly suitable technique to 3D unravel and track the Li microstructure evolution, particularly at the interface after or during electrochemical deposition.…”

Section: Metal Anodes: Promises Challenges and Recent Advances In Fun...mentioning

confidence: 99%

“…[ 30 ] Copyright 2020, Springer Nature), NMR [ 31 ] (Reproduced with permission. [ 31 ] Copyright 2020, Springer Nature), and cryo‐STEM tomography [ 19 ] (Reproduced with permission. [ 19 ] Copyright 2021, Elsevier).…”

Section: Metal Anodes: Promises Challenges and Recent Advances In Fun...mentioning

confidence: 99%

“…[ 31 ] Copyright 2020, Springer Nature), and cryo‐STEM tomography [ 19 ] (Reproduced with permission. [ 19 ] Copyright 2021, Elsevier). c) Theoretical modelling methods include MC/MD [ 32 ] (Reproduced with permission.…”

Section: Metal Anodes: Promises Challenges and Recent Advances In Fun...mentioning

confidence: 99%

“…In 2018, Zachman et al [17] have employed cryo-FIB tomography to reveal 3D and local structures of different types of Li dendrites on the nanoscale, and combined with cryo-STEM EELS mapping to identify the composition of intact SEI in LMBs. In 2021, Han et al [19] have employed cryo-STEM tomography mapping to reveal 3D morphology and distribution of SEI as well as "dead" Li, which provides insights into the working mechanism of SEI in Li metal anodes. In addition, synchrotron X-ray computed tomography (SXCT) [7c,20] is proved to be a highly suitable technique to 3D unravel and track the Li microstructure evolution, particularly at the interface after or during electrochemical deposition.…”

Section: Metal Anodes: Promises Challenges and Recent Advances In Fun...mentioning

confidence: 99%

See 2 more Smart Citations

Promoting Mechanistic Understanding of Lithium Deposition and Solid‐Electrolyte Interphase (SEI) Formation Using Advanced Characterization and Simulation Methods: Recent Progress, Limitations, and Future Perspectives

Dong

Jie

et al. 2022

Advanced Energy Materials

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In recent years, due to its great promise in boosting the energy density of lithium batteries for future energy storage, research on the Li metal anode, as an alternative to the graphite anode in Li‐ion batteries, has gained significant momentum. However, the practical use of Li metal anodes has been plagued by unstable Li (re)deposition and poor cyclability. Although tremendous efforts have been devoted to the stabilization of Li metal anodes, the mechanisms of electrochemical (re‐)deposition/dissolution of Li and solid‐electrolyte‐interphase (SEI) formation remain elusive. This article highlights the recent mechanistic understandings and observations of Li deposition/dissolution and SEI formation achieved from advanced characterization techniques and simulation methods, and discusses major limitations and open questions in these processes. In particular, the authors provide their perspectives on advanced and emerging/potential methods for obtaining new insights into these questions. In addition, they give an outlook into cutting‐edge interdisciplinary research topics for Li metal anodes. It pushes beyond the current knowledge and is expected to accelerate development toward a more in‐depth and comprehensive understanding, in order to guide future research on Li metal anodes toward practical application.

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Pre‐Lithiation of Silicon Anodes by Thermal Evaporation of Lithium for Boosting the Energy Density of Lithium Ion Cells

Adhitama

Brandao

Dienwiebel

et al. 2022

Adv Funct Materials

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Silicon (Si) is one of the most promising anode candidates to further push the energy density of lithium ion batteries. However, its practical usage is still hindered by parasitic side reactions including electrolyte decomposition and continuous breakage and (re‐)formation of the solid electrolyte interphase (SEI), leading to consumption of active lithium. Pre‐lithiation is considered a highly appealing technique to compensate for active lithium losses. A critical parameter for a successful pre‐lithiation strategy by means of Li metal is to achieve lithiation of the active material/composite anode at the most uniform lateral and in‐depth distribution possible. Despite extensive exploration of various pre‐lithiation techniques, controlling the lithium amount precisely while keeping a homogeneous lithium distribution remains challenging. Here, the thermal evaporation of Li metal as a novel pre‐lithiation technique for pure Si anodes that allows both, that is, precise control of the degree of pre‐lithiation and a homogeneous Li deposition at the surface is reported. Li nucleation, mechanical cracking, and the ongoing phase changes are thoroughly evaluated. The terms dry‐state and wet‐state pre‐lithiation (without/with electrolyte) are revisited. Finally, a series of electrochemical methods are performed to allow a direct correlation of pre‐SEI formation with the electrochemical performance of pre‐lithiated Si.

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Conformal three-dimensional interphase of Li metal anode revealed by low-dose cryoelectron microscopy

Cited by 45 publications

References 36 publications

Cryo‐Electron Tomography of Highly Deformable and Adherent Solid‐Electrolyte Interphase Exoskeleton in Li‐Metal Batteries with Ether‐Based Electrolyte

Cryo‐Electron Tomography of Highly Deformable and Adherent Solid‐Electrolyte Interphase Exoskeleton in Li‐Metal Batteries with Ether‐Based Electrolyte

Promoting Mechanistic Understanding of Lithium Deposition and Solid‐Electrolyte Interphase (SEI) Formation Using Advanced Characterization and Simulation Methods: Recent Progress, Limitations, and Future Perspectives

Pre‐Lithiation of Silicon Anodes by Thermal Evaporation of Lithium for Boosting the Energy Density of Lithium Ion Cells

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