Solid Electrolyte–Cathode Interface Dictates Reaction Heterogeneity and Anode Stability

Naik, Kaustubh G.; Chatterjee, Debanjali; Mukherjee, Partha P.

doi:10.1021/acsami.2c11339

Cited by 19 publications

(11 citation statements)

References 62 publications

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“…This implies that the synergistic effect from our composite separator and CNT host anode would be a potential solution for utilizing Li metal as an anode. One of the previous studies revealed that the microstructural heterogeneity of the cathode, which is induced by the compositional ratio and particle sizes of the active material, has a significant effect on spatially uneven current and Li + transport during charging/discharging . Therefore, it is anticipated that further Li + flux delocalization could be obtained when the cathode design is configured along with our proposed separator/anode pair.…”

Section: Resultsmentioning

confidence: 97%

Delocalized Lithium Ion Flux by Solid-State Electrolyte Composites Coupled with 3D Porous Nanostructures for Highly Stable Lithium Metal Batteries

Lee,

Park,

Hwang

et al. 2023

ACS Nano

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This work investigates the root cause of failure with the ultimate anode, Li metal, when employing conventional/composite separators and/or porous anodes. Then a feasible route of utilizing Li metal is presented. Our operando and microscopy studies have unveiled that Li + flux passing through the conventional separator is not uniform, resulting in preferential Li plating/stripping. Porous anodes alone are subject to clogging with moderate-or high-loading cathodes. Here we discovered it is necessary to seek synergy from our separator and anode pair to deliver delocalized Li + to the anode and then uniformly plate Li metal over the large surface areas of the porous anode. Our polymer composite separator containing a solid-state electrolyte (SE) can provide numerous Li + passages through the percolated SE and pore networks. Our finite element analysis and comparative tests disclosed the synergy between the homogeneous Li + flux and current density reduction on the anode. Our composite separators have induced compact and uniform Li plating with robust inorganic-rich solid electrolyte interphase layers. The porous anode decreased the nucleation overpotential and interfacial contact impedance during Li plating. Full cell tests with LiFePO 4 and Li[Ni 0.8 Mn 0.1 Co 0.1 ]O 2 (NMC811) exhibited remarkable cycling behaviors: ∼80% capacity retention at the 750th and 235th cycle, respectively. A high-loading NMC811 (4 mAh cm −2 ) full cell displayed maximum cell-level energy densities of 334 Wh kg −1 and 783 Wh L −1 . This work proposes a solution for raising energy density by adopting Li metal, which could be a viable option considering only incremental advancement in conventional cathodes lately.

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Section: Resultsmentioning

confidence: 97%

Delocalized Lithium Ion Flux by Solid-State Electrolyte Composites Coupled with 3D Porous Nanostructures for Highly Stable Lithium Metal Batteries

Lee,

Park,

Hwang

et al. 2023

ACS Nano

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“…As confirmed in the low‐stack‐pressure experiment, the relatively high uniformity of the pore size can lead to a homogeneous cathode reaction within the electrode, and it may have helped to maintain a uniform ionic transport pathway at the CA|CA interface during long‐term cycling. In addition, because the non‐uniformity of the reaction in the cathode can lead to reaction heterogeneity at the anode/SE interface according to a recent report, [ 63 ] the larger anode/SE interfacial resistance of the bare NCM may be the result of cross‐talk caused by the reaction heterogeneity at the cathode side.…”

Section: Resultsmentioning

confidence: 99%

Organic‐Additive‐Derived Cathode Electrolyte Interphase Layer Mitigating Intertwined Chemical and Mechanical Degradation for Sulfide‐Based Solid‐State Batteries

Park

Lee

et al. 2023

Advanced Energy Materials

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terms of safety and the ability to use highcapacity anodes, such as lithium metal, thereby attracting interest in the realization of high-energy density solid-state batteries (SSBs). [3][4][5][6][7][8] Sulfide solid electrolytes are especially promising and advanced systems for industrial application owing to their high ionic conductivity (exceeding that of liquid electrolytes), high mechanical deformability, and low gravimetric density. [9][10][11][12] However, sulfide SEs suffer from chronic interfacial issues at the cathode-SE interfaces such as chemical degradation caused by side reactions due to the low oxidation stability of the S 2− anion [13][14][15] and a common issue of the mechanical contact loss between the cathode and SE due to the volume change of the cathode during galvanostatic cycling. [16][17][18] Conventionally, oxide-based inorganic compounds with electronic-insulating and ionic-conducting character have been mainly proposed as the cathode coating layer to solely resolve cathode-SE chemical degradation. [19,20] Representatively, LiNbO 3 and Li 2 ZrO 3 and their derivatives have been widely used and studied, with mitigated chemical degradation verified, suggesting improved cycle stability. However, the chemical-degradation-induced increase in the electronic resistance or diffusion of the cation in the cathode (i.e., Co for LiCoO 2 ) to the solid electrolyte is still not fully suppressed. [21][22][23] To design a coating material with better compatibility in both the oxide-based cathode and sulfide-based solid electrolyte, material screening with density functional theory (DFT) calculation has been attempted, considering further phase stability and electrochemical stability. [10,24] A few materials have been suggested within the set criteria; however, achieving uniform coverage of the materials with target composition and structure on the cathode is unexpectedly difficult given the monotonous application process of solid-state reaction at moderate temperature (300-500 °C) after solution-based precursor mixing and drying on the cathode surface. [25][26][27] Limiting the reaction temperature to exclude side reactions with the cathode material can instead induce discrepancies in the structure and composition from the target material; thus, it is difficult to achieve the original properties predicted from the DFT calculation. In addition, although the mechanical properties of the cathode coating layer have rarely been considered in the field of SSBs thus far, the high stiffness of oxide-based inorganic compounds could result in vulnerability to chemical degradation due to crack formation Keeping both the chemical and physical state of the electrode-electrolyte interface intact is one of the greatest challenges in achieving solid-state batteries (SSBs) with longer cycle lives. Herein, the use of organic electrolyte additives in the cathode electrolyte interphase (CEI) layer to mitigate the intertwined chemical and mechanical degradation in sulfide-based SSBs is demonstrated. Lithium difluorobis(oxala...

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“…The role of electric energy storage technologies, i.e., batteries, is ever-increasing. Recently, the concept of the solid-state battery (SSB) has been attracting strong interest as it has the potential to further advance lithium-ion battery technology. − The ultimate target for the anode material is lithium metal due to its low redox potential of E H = −3.04 V and high theoretical capacity of q th = 3861 mAh/g. , The successful implementation of the reversible lithium metal anode concept, however, is hampered especially by morphological instabilities at the metal anode interface and dendrite formation due to inhomogeneous metal dissolution and deposition. − This places high demands on potential solid electrolyte (SE) separator materials. These demands include, e.g., ensuring homogeneous current flow, compensating for volume changes at the interface, and providing high mechanical resistance to dendrite growth.…”

Section: Introductionmentioning

confidence: 99%

Influence of Microstructure on the Material Properties of LLZO Ceramics Derived by Impedance Spectroscopy and Brick Layer Model Analysis

Eckhardt,

Kremer,

Fuchs

et al. 2023

ACS Appl. Mater. Interfaces

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Variants of garnet-type Li 7 La 3 Zr 2 O 12 are being intensively studied as separator materials in solid-state battery research. The material-specific transport properties, such as bulk and grain boundary conductivity, are of prime interest and are mostly investigated by impedance spectroscopy. Data evaluation is usually based on the one-dimensional (1D) brick layer model, which assumes a homogeneous microstructure of identical grains. Real samples show microstructural inhomogeneities in grain size and porosity due to the complex behavior of grain growth in garnets that is very sensitive to the sintering protocol. However, the true microstructure is often omitted in impedance data analysis, hindering the interlaboratory reproducibility and comparability of results reported in the literature. Here, we use a combinatorial approach of structural analysis and three-dimensional (3D) transport modeling to explore the effects of microstructure on the derived material-specific properties of garnet-type ceramics. For this purpose, Al-doped Li 7 La 3 Zr 2 O 12 pellets with different microstructures are fabricated and electrochemically characterized. A machine learning-assisted image segmentation approach is used for statistical analysis and quantification of the microstructural changes during sintering. A detailed analysis of transport through statistically modeled twin microstructures demonstrates that the transport parameters derived from a 1D brick layer model approach show uncertainties up to 150%, only due to variations in grain size. These uncertainties can be even larger in the presence of porosity. This study helps to better understand the role of the microstructure of polycrystalline electroceramics and its influence on experimental results.

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Solid Electrolyte–Cathode Interface Dictates Reaction Heterogeneity and Anode Stability

Cited by 19 publications

References 62 publications

Delocalized Lithium Ion Flux by Solid-State Electrolyte Composites Coupled with 3D Porous Nanostructures for Highly Stable Lithium Metal Batteries

Delocalized Lithium Ion Flux by Solid-State Electrolyte Composites Coupled with 3D Porous Nanostructures for Highly Stable Lithium Metal Batteries

Organic‐Additive‐Derived Cathode Electrolyte Interphase Layer Mitigating Intertwined Chemical and Mechanical Degradation for Sulfide‐Based Solid‐State Batteries

Influence of Microstructure on the Material Properties of LLZO Ceramics Derived by Impedance Spectroscopy and Brick Layer Model Analysis

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