Stability of FeF3‑Based Sodium-Ion Batteries in Nonflammable Ionic Liquid Electrolytes at Room and Elevated Temperatures

Zifei Sun; Baichuan Wang; Matthew G. Boebinger; Alexandre Magasinski; Samik Jhulki; Yawei Zhang; Wenbin Fu; Matthew T. McDowell; Gleb Yushin

doi:10.1021/acsami.2c10851

Stability of FeF₃‑Based Sodium-Ion Batteries in Nonflammable Ionic Liquid Electrolytes at Room and Elevated Temperatures

Zifei Sun, Baichuan Wang, Matthew G. Boebinger, Alexandre Magasinski, Samik Jhulki, Yawei Zhang, Wenbin Fu, Matthew T. McDowell, Gleb Yushin

Materials MicroAnalysis

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

12 Scopus citations

Abstract

Iron trifluoride (FeF₃), a conversion-type cathode for sodium-ion batteries (SIBs), is based on cheap and abundant Fe and provides high theoretical capacity. However, the applications of FeF₃-based SIBs have been hindered by their low-capacity utilization and poor cycling stability. Herein, we report greatly enhanced performance of FeF₃ in multiple types of ionic liquid (IL) electrolytes at both room temperature (RT) and elevated temperatures. The Pyr_1,4FSI electrolyte demonstrated the best cycling stability with an unprecedented decay rate of only ∼0.023% per cycle after the initial stabilization and an average coulombic efficiency of ∼99.5% for over 1000 cycles at RT. The Pyr_1,3FSI electrolyte demonstrated the best cycling stability with a capacity decay rate of only ∼0.25% per cycle at 60 °C. Cells using Pyr_1,3FSI and EMIMFSI electrolytes also showed promising cycling stability with capacity decay rates of ∼0.039% and ∼0.030% per cycle over 1000 cycles, respectively. A protective and ionically conductive cathode electrolyte interphase (CEI) layer is formed during cycling in ILs, diminishing side reactions that commonly lead to gassing and excessive CEI growth in organic electrolytes, especially at elevated temperatures. Furthermore, the increased ionic conductivity and decreased viscosity of ILs at elevated temperatures help attain higher accessible capacity. The application of ILs sheds light on designing a protective CEI for its use in stable SIBs.

Original language	English
Pages (from-to)	33447-33456
Number of pages	10
Journal	ACS Applied Materials and Interfaces
Volume	14
Issue number	29
DOIs	https://doi.org/10.1021/acsami.2c10851
State	Published - 2022

Funding

This work was supported, in part, by the Army Research Office (Grant No. W911NF-17-1-0053) and the National Aeronautics and Space Administration (Grant No. 80NSSC20M0249). M.G.B. acknowledges support from the DOE Office of Science Graduate Student Research Program for research performed at Oak Ridge National Laboratory. A portion of the TEM studies was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. The characterization work was also performed, in part, at the Georgia Tech Institute for Electronics and Nanotechnology, a member of the National Nanotechnology Coordinated Infrastructure (NNCI), which is supported by the National Science Foundation (ECCS-2025462).

Keywords

battery
in situ TEM
ionic liquid
iron fluoride
sodium ion

Access to Document

10.1021/acsami.2c10851

Cite this

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title = "Stability of FeF3‑Based Sodium-Ion Batteries in Nonflammable Ionic Liquid Electrolytes at Room and Elevated Temperatures",

abstract = "Iron trifluoride (FeF3), a conversion-type cathode for sodium-ion batteries (SIBs), is based on cheap and abundant Fe and provides high theoretical capacity. However, the applications of FeF3-based SIBs have been hindered by their low-capacity utilization and poor cycling stability. Herein, we report greatly enhanced performance of FeF3 in multiple types of ionic liquid (IL) electrolytes at both room temperature (RT) and elevated temperatures. The Pyr1,4FSI electrolyte demonstrated the best cycling stability with an unprecedented decay rate of only ∼0.023% per cycle after the initial stabilization and an average coulombic efficiency of ∼99.5% for over 1000 cycles at RT. The Pyr1,3FSI electrolyte demonstrated the best cycling stability with a capacity decay rate of only ∼0.25% per cycle at 60 °C. Cells using Pyr1,3FSI and EMIMFSI electrolytes also showed promising cycling stability with capacity decay rates of ∼0.039% and ∼0.030% per cycle over 1000 cycles, respectively. A protective and ionically conductive cathode electrolyte interphase (CEI) layer is formed during cycling in ILs, diminishing side reactions that commonly lead to gassing and excessive CEI growth in organic electrolytes, especially at elevated temperatures. Furthermore, the increased ionic conductivity and decreased viscosity of ILs at elevated temperatures help attain higher accessible capacity. The application of ILs sheds light on designing a protective CEI for its use in stable SIBs.",

keywords = "battery, in situ TEM, ionic liquid, iron fluoride, sodium ion",

author = "Zifei Sun and Baichuan Wang and Boebinger, {Matthew G.} and Alexandre Magasinski and Samik Jhulki and Yawei Zhang and Wenbin Fu and McDowell, {Matthew T.} and Gleb Yushin",

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AU - Sun, Zifei

AU - Wang, Baichuan

AU - Boebinger, Matthew G.

AU - Magasinski, Alexandre

AU - Jhulki, Samik

AU - Zhang, Yawei

AU - Fu, Wenbin

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AU - Yushin, Gleb

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N2 - Iron trifluoride (FeF3), a conversion-type cathode for sodium-ion batteries (SIBs), is based on cheap and abundant Fe and provides high theoretical capacity. However, the applications of FeF3-based SIBs have been hindered by their low-capacity utilization and poor cycling stability. Herein, we report greatly enhanced performance of FeF3 in multiple types of ionic liquid (IL) electrolytes at both room temperature (RT) and elevated temperatures. The Pyr1,4FSI electrolyte demonstrated the best cycling stability with an unprecedented decay rate of only ∼0.023% per cycle after the initial stabilization and an average coulombic efficiency of ∼99.5% for over 1000 cycles at RT. The Pyr1,3FSI electrolyte demonstrated the best cycling stability with a capacity decay rate of only ∼0.25% per cycle at 60 °C. Cells using Pyr1,3FSI and EMIMFSI electrolytes also showed promising cycling stability with capacity decay rates of ∼0.039% and ∼0.030% per cycle over 1000 cycles, respectively. A protective and ionically conductive cathode electrolyte interphase (CEI) layer is formed during cycling in ILs, diminishing side reactions that commonly lead to gassing and excessive CEI growth in organic electrolytes, especially at elevated temperatures. Furthermore, the increased ionic conductivity and decreased viscosity of ILs at elevated temperatures help attain higher accessible capacity. The application of ILs sheds light on designing a protective CEI for its use in stable SIBs.

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