Protective Coating of Single-Crystalline Ni-Rich Cathode Enables Fast Charging in All-Solid-State Batteries

Wengao Zhao; Ruizhuo Zhang; Fucheng Ren; Leonhard Karger; Sören L. Dreyer; Jing Lin; Yuan Ma; Yong Cheng; Avnish Singh Pal; Martin Velazquez-Rizo; Ali Ahmadian; Ziyan Zhang; Philipp Müller; Jürgen Janek; Yong Yang; Aleksandr Kondrakov; Torsten Brezesinski

doi:10.1021/acsnano.4c14322

Protective Coating of Single-Crystalline Ni-Rich Cathode Enables Fast Charging in All-Solid-State Batteries

Wengao Zhao
, Ruizhuo Zhang
, Fucheng Ren
, Leonhard Karger
, Sören L. Dreyer
, Jing Lin
, Yuan Ma
, Yong Cheng
, Avnish Singh Pal
, Martin Velazquez-Rizo
, Ali Ahmadian
, Ziyan Zhang
, Philipp Müller
, Jürgen Janek
, Yong Yang
, Aleksandr Kondrakov
, Torsten Brezesinski

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Research output: Contribution to journal › Article › peer-review

37 Scopus citations

Abstract

Improving interfacial stability between cathode active material (CAM) and solid electrolyte (SE) is vital for developing high-performance all-solid-state batteries (ASSBs), with compatibility issues among the cell components representing a major challenge. CAM surface coating with a chemically inert ion conductor is a promising approach to suppress side reactions occurring at the cathode interfaces. Another strategy to mitigate mechanical degradation involves utilizing single-crystalline particle morphologies. Their more robust bulk structure and lower tortuosity for charge transport, compared to polycrystalline (PC) CAMs, can significantly enhance cyclability in ASSBs. Herein, we coated a LiNbO₃ protective layer onto the free surface of quasi single-crystalline LiNi_0.83Co_0.12Mn_0.05O₂ (SC83) particles. Pellet-stack ASSB cells using the LiNbO₃@SC83 CAM and argyrodite Li₆PS₅Cl as SE showed a capacity retention of 88% after 1000 cycles at the 1 C rate, compared to only 71% for the uncoated counterpart and far superior to that of LiNbO₃@PC83 (30%). The effectiveness of LiNbO₃ coating and the SC-NCM nature in mitigating electro-chemo-mechanical degradation was studied by combining modeling and physical/electrochemical characterizations. We demonstrate that the capacity decay at fast charge is due primarily to the mechanical degradation of CAM particles, while it is strongly determined by CAM|SE interfacial reactions under slow-charging conditions.

Original language	English
Pages (from-to)	8595-8607
Number of pages	13
Journal	ACS nano
Volume	19
Issue number	9
DOIs	https://doi.org/10.1021/acsnano.4c14322
State	Published - Mar 11 2025

Funding

This work was supported by BASF SE. The authors acknowledge the support from the Karlsruhe Nano Micro Facility (KNMFi, www.knmf.kit.edu), a Helmholtz research infrastructure at Karlsruhe Institute of Technology (KIT, www.kit.edu). The authors also thank the electron microscopy team at BASF SE as well as Thomas Bergfeldt and colleagues for conducting the ICP-OES analysis. Y.Y. acknowledges financial support from the National Natural Science Foundation of China (grant nos. 22261160570 and 21935009).

Keywords

electro-chemo-mechanical degradation
interfacial stability
Ni-rich layered oxide cathode
protective coating
thiophosphate solid electrolyte

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10.1021/acsnano.4c14322

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Zhao, W., Zhang, R., Ren, F., Karger, L., Dreyer, S. L., Lin, J., Ma, Y., Cheng, Y., Pal, A. S., Velazquez-Rizo, M., Ahmadian, A., Zhang, Z., Müller, P., Janek, J., Yang, Y., Kondrakov, A., & Brezesinski, T. (2025). Protective Coating of Single-Crystalline Ni-Rich Cathode Enables Fast Charging in All-Solid-State Batteries. ACS nano, 19(9), 8595-8607. https://doi.org/10.1021/acsnano.4c14322

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title = "Protective Coating of Single-Crystalline Ni-Rich Cathode Enables Fast Charging in All-Solid-State Batteries",

abstract = "Improving interfacial stability between cathode active material (CAM) and solid electrolyte (SE) is vital for developing high-performance all-solid-state batteries (ASSBs), with compatibility issues among the cell components representing a major challenge. CAM surface coating with a chemically inert ion conductor is a promising approach to suppress side reactions occurring at the cathode interfaces. Another strategy to mitigate mechanical degradation involves utilizing single-crystalline particle morphologies. Their more robust bulk structure and lower tortuosity for charge transport, compared to polycrystalline (PC) CAMs, can significantly enhance cyclability in ASSBs. Herein, we coated a LiNbO3 protective layer onto the free surface of quasi single-crystalline LiNi0.83Co0.12Mn0.05O2 (SC83) particles. Pellet-stack ASSB cells using the LiNbO3@SC83 CAM and argyrodite Li6PS5Cl as SE showed a capacity retention of 88\% after 1000 cycles at the 1 C rate, compared to only 71\% for the uncoated counterpart and far superior to that of LiNbO3@PC83 (30\%). The effectiveness of LiNbO3 coating and the SC-NCM nature in mitigating electro-chemo-mechanical degradation was studied by combining modeling and physical/electrochemical characterizations. We demonstrate that the capacity decay at fast charge is due primarily to the mechanical degradation of CAM particles, while it is strongly determined by CAM|SE interfacial reactions under slow-charging conditions.",

keywords = "electro-chemo-mechanical degradation, interfacial stability, Ni-rich layered oxide cathode, protective coating, thiophosphate solid electrolyte",

author = "Wengao Zhao and Ruizhuo Zhang and Fucheng Ren and Leonhard Karger and Dreyer, \{S{\"o}ren L.\} and Jing Lin and Yuan Ma and Yong Cheng and Pal, \{Avnish Singh\} and Martin Velazquez-Rizo and Ali Ahmadian and Ziyan Zhang and Philipp M{\"u}ller and J{\"u}rgen Janek and Yong Yang and Aleksandr Kondrakov and Torsten Brezesinski",

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Zhao, W, Zhang, R, Ren, F, Karger, L, Dreyer, SL, Lin, J, Ma, Y, Cheng, Y, Pal, AS, Velazquez-Rizo, M, Ahmadian, A, Zhang, Z, Müller, P, Janek, J, Yang, Y, Kondrakov, A & Brezesinski, T 2025, 'Protective Coating of Single-Crystalline Ni-Rich Cathode Enables Fast Charging in All-Solid-State Batteries', ACS nano, vol. 19, no. 9, pp. 8595-8607. https://doi.org/10.1021/acsnano.4c14322

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T1 - Protective Coating of Single-Crystalline Ni-Rich Cathode Enables Fast Charging in All-Solid-State Batteries

AU - Zhao, Wengao

AU - Zhang, Ruizhuo

AU - Ren, Fucheng

AU - Karger, Leonhard

AU - Dreyer, Sören L.

AU - Lin, Jing

AU - Ma, Yuan

AU - Cheng, Yong

AU - Pal, Avnish Singh

AU - Velazquez-Rizo, Martin

AU - Ahmadian, Ali

AU - Zhang, Ziyan

AU - Müller, Philipp

AU - Janek, Jürgen

AU - Yang, Yong

AU - Kondrakov, Aleksandr

AU - Brezesinski, Torsten

PY - 2025/3/11

Y1 - 2025/3/11

N2 - Improving interfacial stability between cathode active material (CAM) and solid electrolyte (SE) is vital for developing high-performance all-solid-state batteries (ASSBs), with compatibility issues among the cell components representing a major challenge. CAM surface coating with a chemically inert ion conductor is a promising approach to suppress side reactions occurring at the cathode interfaces. Another strategy to mitigate mechanical degradation involves utilizing single-crystalline particle morphologies. Their more robust bulk structure and lower tortuosity for charge transport, compared to polycrystalline (PC) CAMs, can significantly enhance cyclability in ASSBs. Herein, we coated a LiNbO3 protective layer onto the free surface of quasi single-crystalline LiNi0.83Co0.12Mn0.05O2 (SC83) particles. Pellet-stack ASSB cells using the LiNbO3@SC83 CAM and argyrodite Li6PS5Cl as SE showed a capacity retention of 88% after 1000 cycles at the 1 C rate, compared to only 71% for the uncoated counterpart and far superior to that of LiNbO3@PC83 (30%). The effectiveness of LiNbO3 coating and the SC-NCM nature in mitigating electro-chemo-mechanical degradation was studied by combining modeling and physical/electrochemical characterizations. We demonstrate that the capacity decay at fast charge is due primarily to the mechanical degradation of CAM particles, while it is strongly determined by CAM|SE interfacial reactions under slow-charging conditions.

AB - Improving interfacial stability between cathode active material (CAM) and solid electrolyte (SE) is vital for developing high-performance all-solid-state batteries (ASSBs), with compatibility issues among the cell components representing a major challenge. CAM surface coating with a chemically inert ion conductor is a promising approach to suppress side reactions occurring at the cathode interfaces. Another strategy to mitigate mechanical degradation involves utilizing single-crystalline particle morphologies. Their more robust bulk structure and lower tortuosity for charge transport, compared to polycrystalline (PC) CAMs, can significantly enhance cyclability in ASSBs. Herein, we coated a LiNbO3 protective layer onto the free surface of quasi single-crystalline LiNi0.83Co0.12Mn0.05O2 (SC83) particles. Pellet-stack ASSB cells using the LiNbO3@SC83 CAM and argyrodite Li6PS5Cl as SE showed a capacity retention of 88% after 1000 cycles at the 1 C rate, compared to only 71% for the uncoated counterpart and far superior to that of LiNbO3@PC83 (30%). The effectiveness of LiNbO3 coating and the SC-NCM nature in mitigating electro-chemo-mechanical degradation was studied by combining modeling and physical/electrochemical characterizations. We demonstrate that the capacity decay at fast charge is due primarily to the mechanical degradation of CAM particles, while it is strongly determined by CAM|SE interfacial reactions under slow-charging conditions.

KW - electro-chemo-mechanical degradation

KW - interfacial stability

KW - Ni-rich layered oxide cathode

KW - protective coating

KW - thiophosphate solid electrolyte

UR - https://www.scopus.com/pages/publications/86000434730

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DO - 10.1021/acsnano.4c14322

M3 - Article

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AN - SCOPUS:86000434730

SN - 1936-0851

VL - 19

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EP - 8607

JO - ACS nano

JF - ACS nano

IS - 9

ER -

Protective Coating of Single-Crystalline Ni-Rich Cathode Enables Fast Charging in All-Solid-State Batteries

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