The role of NaSICON surface chemistry in stabilizing fast-charging Na metal solid-state batteries

Edouard Quérel; Ieuan D. Seymour; Andrea Cavallaro; Qianli Ma; Frank Tietz; Ainara Aguadero

doi:10.1088/2515-7655/ac2fb3

The role of NaSICON surface chemistry in stabilizing fast-charging Na metal solid-state batteries

Edouard Quérel^*, Ieuan D. Seymour, Andrea Cavallaro, Qianli Ma^*, Frank Tietz, Ainara Aguadero^*

^*Corresponding author for this work

Chemistry

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

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Abstract

Solid-state batteries (SSBs) with alkali metal anodes hold great promise as energetically dense and safe alternatives to conventional Li-ion cells. Whilst, in principle, SSBs have the additional advantage of offering virtually unlimited plating current densities, fast charges have so far only been achieved through sophisticated interface engineering strategies. With a combination of surface sensitive analysis, we reveal that such sophisticated engineering is not necessary in NaSICON solid electrolytes (Na_3.4Zr₂Si_2.4P_0.6O₁₂) since optimised performances can be achieved by simple thermal treatments that allow the thermodynamic stabilization of a nanometric Na₃PO₄ protective surface layer. The optimized surface chemistry leads to stabilized Na|NZSP interfaces with exceptionally low interface resistances (down to 0.1 Ω cm² at room temperature) and high tolerance to large plating current densities (up to 10 mA cm⁻²) even for extended cycling periods of 30 min (corresponding to an areal capacity 5 mAh cm⁻²). The created Na|NZSP interfaces show great stability with increment of only up to 5 Ω cm² after four months of cell assembly.

Original language	English
Article number	044007
Journal	JPhys Energy
Volume	3
Issue number	4
DOIs	https://doi.org/10.1088/2515-7655/ac2fb3
Publication status	Published - 12 Nov 2021

Bibliographical note

Funding Information:
E Q and A A thank Dr Gwilherm Kerherve for his help with the XPS system, and Dr Peter A A Klusener, Dr Samuel J Cooper and Professor Nigel P. Brandon for fruitful discussions. I D S acknowledges the Imperial College Research Computing Service (10.14469/hpc/2232), and associated support services used during this work. This work has been funded by the Engineering and Physical Sciences Research Council (EPSRC/17100026 and EPSRC/R002010/1 Grants), the European Commission (Grant FETPROACT-2018-2020 ‘HARVERSTORE’ 824072) and Shell Global Solutions International B V.

Publisher Copyright:
© 2021 The Author(s). Published by IOP Publishing Ltd

Data Availability Statement

All data that support the findings of this study are included within the article (and any supplementary files).

Keywords

DFT
Interface resistance
Interfaces
LEIS
Na metal
NaSICON
Solid state batteries
Surface energy
XPS

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Cite this

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title = "The role of NaSICON surface chemistry in stabilizing fast-charging Na metal solid-state batteries",

abstract = "Solid-state batteries (SSBs) with alkali metal anodes hold great promise as energetically dense and safe alternatives to conventional Li-ion cells. Whilst, in principle, SSBs have the additional advantage of offering virtually unlimited plating current densities, fast charges have so far only been achieved through sophisticated interface engineering strategies. With a combination of surface sensitive analysis, we reveal that such sophisticated engineering is not necessary in NaSICON solid electrolytes (Na3.4Zr2Si2.4P0.6O12) since optimised performances can be achieved by simple thermal treatments that allow the thermodynamic stabilization of a nanometric Na3PO4 protective surface layer. The optimized surface chemistry leads to stabilized Na|NZSP interfaces with exceptionally low interface resistances (down to 0.1 Ω cm2 at room temperature) and high tolerance to large plating current densities (up to 10 mA cm−2) even for extended cycling periods of 30 min (corresponding to an areal capacity 5 mAh cm−2). The created Na|NZSP interfaces show great stability with increment of only up to 5 Ω cm2 after four months of cell assembly.",

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note = "Funding Information: E Q and A A thank Dr Gwilherm Kerherve for his help with the XPS system, and Dr Peter A A Klusener, Dr Samuel J Cooper and Professor Nigel P. Brandon for fruitful discussions. I D S acknowledges the Imperial College Research Computing Service (10.14469/hpc/2232), and associated support services used during this work. This work has been funded by the Engineering and Physical Sciences Research Council (EPSRC/17100026 and EPSRC/R002010/1 Grants), the European Commission (Grant FETPROACT-2018-2020 {\textquoteleft}HARVERSTORE{\textquoteright} 824072) and Shell Global Solutions International B V. Publisher Copyright: {\textcopyright} 2021 The Author(s). Published by IOP Publishing Ltd",

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AU - Ma, Qianli

AU - Tietz, Frank

AU - Aguadero, Ainara

N1 - Funding Information: E Q and A A thank Dr Gwilherm Kerherve for his help with the XPS system, and Dr Peter A A Klusener, Dr Samuel J Cooper and Professor Nigel P. Brandon for fruitful discussions. I D S acknowledges the Imperial College Research Computing Service (10.14469/hpc/2232), and associated support services used during this work. This work has been funded by the Engineering and Physical Sciences Research Council (EPSRC/17100026 and EPSRC/R002010/1 Grants), the European Commission (Grant FETPROACT-2018-2020 ‘HARVERSTORE’ 824072) and Shell Global Solutions International B V. Publisher Copyright: © 2021 The Author(s). Published by IOP Publishing Ltd

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N2 - Solid-state batteries (SSBs) with alkali metal anodes hold great promise as energetically dense and safe alternatives to conventional Li-ion cells. Whilst, in principle, SSBs have the additional advantage of offering virtually unlimited plating current densities, fast charges have so far only been achieved through sophisticated interface engineering strategies. With a combination of surface sensitive analysis, we reveal that such sophisticated engineering is not necessary in NaSICON solid electrolytes (Na3.4Zr2Si2.4P0.6O12) since optimised performances can be achieved by simple thermal treatments that allow the thermodynamic stabilization of a nanometric Na3PO4 protective surface layer. The optimized surface chemistry leads to stabilized Na|NZSP interfaces with exceptionally low interface resistances (down to 0.1 Ω cm2 at room temperature) and high tolerance to large plating current densities (up to 10 mA cm−2) even for extended cycling periods of 30 min (corresponding to an areal capacity 5 mAh cm−2). The created Na|NZSP interfaces show great stability with increment of only up to 5 Ω cm2 after four months of cell assembly.

AB - Solid-state batteries (SSBs) with alkali metal anodes hold great promise as energetically dense and safe alternatives to conventional Li-ion cells. Whilst, in principle, SSBs have the additional advantage of offering virtually unlimited plating current densities, fast charges have so far only been achieved through sophisticated interface engineering strategies. With a combination of surface sensitive analysis, we reveal that such sophisticated engineering is not necessary in NaSICON solid electrolytes (Na3.4Zr2Si2.4P0.6O12) since optimised performances can be achieved by simple thermal treatments that allow the thermodynamic stabilization of a nanometric Na3PO4 protective surface layer. The optimized surface chemistry leads to stabilized Na|NZSP interfaces with exceptionally low interface resistances (down to 0.1 Ω cm2 at room temperature) and high tolerance to large plating current densities (up to 10 mA cm−2) even for extended cycling periods of 30 min (corresponding to an areal capacity 5 mAh cm−2). The created Na|NZSP interfaces show great stability with increment of only up to 5 Ω cm2 after four months of cell assembly.

KW - DFT

KW - Interface resistance

KW - Interfaces

KW - LEIS

KW - Na metal

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KW - Surface energy

KW - XPS

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VL - 3

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ER -

The role of NaSICON surface chemistry in stabilizing fast-charging Na metal solid-state batteries

Abstract

Bibliographical note

Data Availability Statement

Keywords

Access to Document

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