Properties of the Space Charge Layers Formed in Li-Ion Conducting Glass Ceramics

Katzenmeier, Leon; Helmer, Simon; Braxmeier, Stephan; Knobbe, Edwin; Bandarenka, Aliaksandr S.

doi:10.1021/acsami.0c21304

Cited by 32 publications

(36 citation statements)

References 35 publications

(50 reference statements)

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“…In previous studies, we explored the formation of SCL under blocking conditions experimentally using electrochemical impedance spectroscopy (EIS) and spectroscopic ellipsometry on a model material system, a Li + -ion-conducting glass-ceramic by Ohara Inc. The SCL width was found to range up to 200 nm into the SSE at a bias potential of 1.5 V with spectroscopic ellipsometry, which is in reasonable agreement with the capacitance of such a layer measured with impedance spectroscopy.…”

Section: Introductionsupporting

confidence: 66%

Modeling of Space-Charge Layers in Solid-State Electrolytes: A Kinetic Monte Carlo Approach and Its Validation

et al. 2022

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The space-charge layer (SCL) phenomenon in Li +ion-conducting solid-state electrolytes (SSEs) is gaining much interest in different fields of solid-state ionics. Not only do SCLs influence charge-transfer resistance in all-solid-state batteries but also are analogous to their electronic counterpart in semiconductors; they could be used for Li + -ionic devices. However, the rather "elusive" nature of these layers, which occur on the nanometer scale and with only small changes in concentrations, makes them hard to fully characterize experimentally. Theoretical considerations based on either electrochemical or thermodynamic models are limited due to missing physical, chemical, and electrochemical parameters. In this work, we use kinetic Monte Carlo (kMC) simulations with a small set of input parameters to model the spatial extent of the SCLs. The predictive power of the kMC model is demonstrated by finding a critical range for each parameter in which the space-charge layer growth is significant and must be considered in electrochemical and ionic devices. The time evolution of the charge redistribution is investigated, showing that the SCLs form within 500 ms after applying a bias potential.

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Section: Introductionsupporting

confidence: 66%

Modeling of Space-Charge Layers in Solid-State Electrolytes: A Kinetic Monte Carlo Approach and Its Validation

et al. 2022

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“…The restriction of TFSI − can release the space charge at the interface, strengthening the uniform lithium deposition as well. [35][36][37] The synergistic coupling of the PEGMA polymers with LAGP promotes the rapid transport of Li + and high t Li+ of the PEGMA-LAGP system (Details are shown in Figure S4, Supporting Information). The thermal decomposition temperature of PEGMA-LAGP is 333.4 °C (Figure S4d, Supporting Information), which is comparable to that of bare commercial polypropylene (312.6 °C).…”

Section: Resultsmentioning

confidence: 99%

8.5 µm‐Thick Flexible‐Rigid Hybrid Solid–Electrolyte/Lithium Integration for Air‐Stable and Interface‐Compatible All‐Solid‐State Lithium Metal Batteries

Zhang

Wang

et al. 2022

Advanced Energy Materials

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batteries (LIBs) have no longer satisfied such requirements due to the insufficient specific capacity offered by intercalationbased electrode materials. [1][2] In pursuit of energy-dense battery systems, lithiummetal batteries (LMBs) are revived as the most promising alternatives because of the high specific capacity (3860 mA h g −1 ), lowest reduction potentials (−3.04 V vs standard hydrogen electrode) and lowest metal density (0.534 g cm −3 ). [3] The wide interests in LMBs also arise from the possibility to afford high-voltage, high-capacity yet lithium-free cathodes, and boost the energy density of the cell by at least twofold (such as Li−V 2 O 5 ≈2118 W h kg −1 and Li−S ≈2600 W h kg −1 ). [4] Unfortunately, comprising lithium into the liquid-electrolyte system is not as effective as desired. Conventional organic electrolytes that are highly flammable and inherently incompatible with lithium generally lead to unfavorable solid-electrolyte interface (SEI), uncontrollable formation of lithium dendrite, cascade thermal runaways, and severe safety concerns. [5,6] Apart from interface defects, multiple limitations generate consequently and become challenging, e.g., high Li + diffusion barriers, accelerated side reactions, infinite volume changes, and "dead lithium" formation. [7] These drawbacks further exaggerate the inhomogeneity All-solid-state lithium batteries (ASSLBs), as the next-generation energy storage system, potentially bridge the gap between high energy density and operational safety. However, the application of ASSLBs is technically handicapped by the extremely weak interfacial contact and dendrite growth that is prone to unstabilize solid electrolyte interphase (SEI) with limited electrochemical performance. In this contribution, air-stable and interfacecompatible solid electrolyte/lithium integration is proposed by in situ copolymerization of poly(ethylene glycol methacrylate)-Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3lithium (PEGMA-LAGP-Li). The first-of-this-kind hierarchy provides a promising synergy of flexibility-rigidity (Young's modulus 3 GPa), high ionic conductivity (2.37 × 10 −4 S cm −1 ), high lithium-ion transfer number (t Li+ = 0.87), and LiF-rich SEI, all contributing to homogenized lithium-ion flux, significantly prolonged cycle stability (>3500 h) and obvious dendrite suppression for high-performance ASSLBs. Furthermore, the integration protects lithium from air corrosion, providing insights into a novel interfaceenhancement paradigm and realizing the first ASSLBs assembly in ambient conditions without any loss of specific capacity.

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“…The calculated n‐SCL thickness is in good agreement with the order of magnitude found using impedance spectroscopy in earlier work. [ 15 ]…”

Section: Resultsmentioning

confidence: 99%

“…The same layer structure was found when investigating the electrochemical nature of these SCLs in blocking conditions, with no interfacial Li + transfer, as elucidated in previous work. [ 15 ] Upon applying a bias potential to the SSE under blocking conditions, the bulk of the electrolyte will be shielded by two oppositely charged layers formed at the interfaces between electrodes and electrolyte. Adjacent to the negatively biased electrode, the only mobile species (Li + ) will accumulate on vacant lattice sites to form an accumulation layer.…”

Section: Introductionmentioning

confidence: 99%

“…The in situ approach allows comparison of these findings to previously published work. [ 15 ] Furthermore, the exact concentration changes in and the thickness of these layers are determined with fits using an effective medium approximation (EMA). Similar to the eye visible, optical changes of Li‐intercalation into a graphite anode, [ 21 ] we assumed that the presence and absence of Lithium do change the optical properties in a way detectable by the ellipsometer.…”

Section: Introductionmentioning

confidence: 99%

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Characterization and Quantification of Depletion and Accumulation Layers in Solid‐State Li⁺‐Conducting Electrolytes Using In Situ Spectroscopic Ellipsometry

et al. 2021

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The future of mobility depends on the development of next‐generation battery technologies, such as all‐solid‐state batteries. As the ionic conductivity of solid Li+‐conductors can, in some cases, approach that of liquid electrolytes, a significant remaining barrier faced by solid‐state electrolytes (SSEs) is the interface formed at the anode and cathode materials, with chemical instability and physical resistances arising. The physical properties of space charge layers (SCLs), a widely discussed phenomenon in SSEs, are still unclear. In this work, spectroscopic ellipsometry is used to characterize the accumulation and depletion layers. An optical model is developed to quantify their thicknesses and corresponding concentration changes. It is shown that the Li+‐depleted layer (≈190 nm at 1 V) is thinner than the accumulation layer (≈320 nm at 1 V) in a glassy lithium‐ion‐conducting glass ceramic electrolyte (a trademark of Ohara Corporation). The in situ approach combining electrochemistry and optics resolves the ambiguities around SCL formation. It opens up a wide field of optical measurements on SSEs, allowing various experimental studies in the future.

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Properties of the Space Charge Layers Formed in Li-Ion Conducting Glass Ceramics

Cited by 32 publications

References 35 publications

Modeling of Space-Charge Layers in Solid-State Electrolytes: A Kinetic Monte Carlo Approach and Its Validation

Modeling of Space-Charge Layers in Solid-State Electrolytes: A Kinetic Monte Carlo Approach and Its Validation

8.5 µm‐Thick Flexible‐Rigid Hybrid Solid–Electrolyte/Lithium Integration for Air‐Stable and Interface‐Compatible All‐Solid‐State Lithium Metal Batteries

Characterization and Quantification of Depletion and Accumulation Layers in Solid‐State Li⁺‐Conducting Electrolytes Using In Situ Spectroscopic Ellipsometry

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Properties of the Space Charge Layers Formed in Li-Ion Conducting Glass Ceramics

Cited by 32 publications

References 35 publications

Modeling of Space-Charge Layers in Solid-State Electrolytes: A Kinetic Monte Carlo Approach and Its Validation

Modeling of Space-Charge Layers in Solid-State Electrolytes: A Kinetic Monte Carlo Approach and Its Validation

8.5 µm‐Thick Flexible‐Rigid Hybrid Solid–Electrolyte/Lithium Integration for Air‐Stable and Interface‐Compatible All‐Solid‐State Lithium Metal Batteries

Characterization and Quantification of Depletion and Accumulation Layers in Solid‐State Li+‐Conducting Electrolytes Using In Situ Spectroscopic Ellipsometry

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Product

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Characterization and Quantification of Depletion and Accumulation Layers in Solid‐State Li⁺‐Conducting Electrolytes Using In Situ Spectroscopic Ellipsometry