Formation of LiF Surface Layer during Direct Fluorination of High-Capacity Co-Free Disordered Rocksalt Cathodes

Yiman Zhang; Ethan C. Self; Bishnu P. Thapaliya; Raynald Giovine; Harry M. Meyer; Linze Li; Yuan Yue; Dongchang Chen; Wei Tong; Guoying Chen; Chongmin Wang; Raphaële Clément; Sheng Dai; Jagjit Nanda

doi:10.1021/acsami.1c07882

Formation of LiF Surface Layer during Direct Fluorination of High-Capacity Co-Free Disordered Rocksalt Cathodes

Yiman Zhang, Ethan C. Self, Bishnu P. Thapaliya, Raynald Giovine, Harry M. Meyer, Linze Li, Yuan Yue, Dongchang Chen, Wei Tong, Guoying Chen, Chongmin Wang, Raphaële Clément, Sheng Dai, Jagjit Nanda

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Abstract

Disordered rocksalt (DRX) cathodes have attracted interest due to their high capacity and compositional flexibility (e.g., Co-free chemistries). However, the sloping voltage profile and gradual capacity fade during cycling have hindered the widespread adoption of these materials. Simulations predict that fluorine substitution in DRX cathodes will improve their capacity, rate performance, and cyclability. In this study, we use a fluidized bed reactor to fluorinate a model Li-rich DRX composition (Li1.15Ni0.375Ti0.375Mo0.1O2, NTMO) to investigate how fluorine content impacts the cathode's structure and electrochemical performance. Instead of substituting O with F to form oxyfluoride phases, direct fluorination of DRX cathodes leads to the formation of LiF surface films, which improves the specific energy and capacity retention. This study demonstrates the feasibility of direct fluorination to improve the electrochemical performance of high-voltage cathodes by tuning the material's surface chemistry.

Original language	English
Pages (from-to)	38221-38228
Number of pages	8
Journal	ACS Applied Materials and Interfaces
Volume	13
Issue number	32
DOIs	https://doi.org/10.1021/acsami.1c07882
State	Published - Aug 18 2021

Funding

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, under the Applied Battery Materials Program, of the U.S. Department of Energy under contract no. DE-AC05-00OR22725. B.P.T. and S.D. were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under contract number DE-AC05-00OR22725. The NMR results reported here made use of shared facilities of the UCSB MRSEC (NSF DMR #1720256), a member of the Materials Research Facilities Network ( www.mfn.org ). Electron microscopy work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at PNNL. This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). Acknowledgments

Keywords

Co-free disordered rocksalt cathode
LiF formation
direct fluorination
interfacial stability
oxyfluoride compounds

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Zhang, Y., Self, E. C., Thapaliya, B. P., Giovine, R., Meyer, H. M., Li, L., Yue, Y., Chen, D., Tong, W., Chen, G., Wang, C., Clément, R., Dai, S., & Nanda, J. (2021). Formation of LiF Surface Layer during Direct Fluorination of High-Capacity Co-Free Disordered Rocksalt Cathodes. ACS Applied Materials and Interfaces, 13(32), 38221-38228. https://doi.org/10.1021/acsami.1c07882

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title = "Formation of LiF Surface Layer during Direct Fluorination of High-Capacity Co-Free Disordered Rocksalt Cathodes",

abstract = "Disordered rocksalt (DRX) cathodes have attracted interest due to their high capacity and compositional flexibility (e.g., Co-free chemistries). However, the sloping voltage profile and gradual capacity fade during cycling have hindered the widespread adoption of these materials. Simulations predict that fluorine substitution in DRX cathodes will improve their capacity, rate performance, and cyclability. In this study, we use a fluidized bed reactor to fluorinate a model Li-rich DRX composition (Li1.15Ni0.375Ti0.375Mo0.1O2, NTMO) to investigate how fluorine content impacts the cathode's structure and electrochemical performance. Instead of substituting O with F to form oxyfluoride phases, direct fluorination of DRX cathodes leads to the formation of LiF surface films, which improves the specific energy and capacity retention. This study demonstrates the feasibility of direct fluorination to improve the electrochemical performance of high-voltage cathodes by tuning the material's surface chemistry.",

keywords = "Co-free disordered rocksalt cathode, LiF formation, direct fluorination, interfacial stability, oxyfluoride compounds",

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Zhang, Y, Self, EC , Thapaliya, BP, Giovine, R, Meyer, HM, Li, L, Yue, Y, Chen, D, Tong, W, Chen, G, Wang, C, Clément, R, Dai, S & Nanda, J 2021, 'Formation of LiF Surface Layer during Direct Fluorination of High-Capacity Co-Free Disordered Rocksalt Cathodes', ACS Applied Materials and Interfaces, vol. 13, no. 32, pp. 38221-38228. https://doi.org/10.1021/acsami.1c07882

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AU - Zhang, Yiman

AU - Self, Ethan C.

AU - Thapaliya, Bishnu P.

AU - Giovine, Raynald

AU - Meyer, Harry M.

AU - Li, Linze

AU - Yue, Yuan

AU - Chen, Dongchang

AU - Tong, Wei

AU - Chen, Guoying

AU - Wang, Chongmin

AU - Clément, Raphaële

AU - Dai, Sheng

AU - Nanda, Jagjit

PY - 2021/8/18

Y1 - 2021/8/18

N2 - Disordered rocksalt (DRX) cathodes have attracted interest due to their high capacity and compositional flexibility (e.g., Co-free chemistries). However, the sloping voltage profile and gradual capacity fade during cycling have hindered the widespread adoption of these materials. Simulations predict that fluorine substitution in DRX cathodes will improve their capacity, rate performance, and cyclability. In this study, we use a fluidized bed reactor to fluorinate a model Li-rich DRX composition (Li1.15Ni0.375Ti0.375Mo0.1O2, NTMO) to investigate how fluorine content impacts the cathode's structure and electrochemical performance. Instead of substituting O with F to form oxyfluoride phases, direct fluorination of DRX cathodes leads to the formation of LiF surface films, which improves the specific energy and capacity retention. This study demonstrates the feasibility of direct fluorination to improve the electrochemical performance of high-voltage cathodes by tuning the material's surface chemistry.

AB - Disordered rocksalt (DRX) cathodes have attracted interest due to their high capacity and compositional flexibility (e.g., Co-free chemistries). However, the sloping voltage profile and gradual capacity fade during cycling have hindered the widespread adoption of these materials. Simulations predict that fluorine substitution in DRX cathodes will improve their capacity, rate performance, and cyclability. In this study, we use a fluidized bed reactor to fluorinate a model Li-rich DRX composition (Li1.15Ni0.375Ti0.375Mo0.1O2, NTMO) to investigate how fluorine content impacts the cathode's structure and electrochemical performance. Instead of substituting O with F to form oxyfluoride phases, direct fluorination of DRX cathodes leads to the formation of LiF surface films, which improves the specific energy and capacity retention. This study demonstrates the feasibility of direct fluorination to improve the electrochemical performance of high-voltage cathodes by tuning the material's surface chemistry.

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Formation of LiF Surface Layer during Direct Fluorination of High-Capacity Co-Free Disordered Rocksalt Cathodes

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