Enhanced Electrochemical Performance of Disordered Rocksalt Cathodes Enabled by a Graphite Conductive Additive

Shripad Patil; Krishna Prasad Koirala; Matthew J. Crafton; Guang Yang; Wan Yu Tsai; Bryan D. McCloskey; Chongmin Wang; Jagjit Nanda; Ethan C. Self

doi:10.1021/acsami.3c05619

Enhanced Electrochemical Performance of Disordered Rocksalt Cathodes Enabled by a Graphite Conductive Additive

Shripad Patil, Krishna Prasad Koirala, Matthew J. Crafton, Guang Yang, Wan Yu Tsai, Bryan D. McCloskey, Chongmin Wang, Jagjit Nanda, Ethan C. Self

Energy Storage & Conversion

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

2 Scopus citations

Abstract

Cobalt-free cation-disordered rocksalt (DRX) cathodes are a promising class of materials for next-generation Li-ion batteries. Although they have high theoretical specific capacities (>300 mA h/g) and moderate operating voltages (∼3.5 V vs Li/Li⁺), DRX cathodes typically require a high carbon content (up to 30 wt %) to fully utilize the active material which has a detrimental impact on cell-level energy density. To assess pathways to reduce the electrode’s carbon content, the present study investigates how the carbon’s microstructure and loading (10-20 wt %) influence the performance of DRX cathodes with the nominal composition Li_1.2Mn_0.5Ti_0.3O_1.9F_0.1. While electrodes prepared with conventional disordered carbon additives (C65 and ketjenblack) exhibit rapid capacity fade due to an unstable cathode/electrolyte interface, DRX cathodes containing 10 wt % graphite show superior cycling performance (e.g., reversible capacities ∼260 mA h/g with 85% capacity retention after 50 cycles) and rate capability (∼135 mA h/g at 1000 mA/g). A suite of characterization tools was employed to evaluate the performance differences among these composite electrodes. Overall, these results indicate that the superior performance of the graphite-based cathodes is largely attributed to the: (i) formation of a uniform graphitic coating on DRX particles which protects the surface from parasitic reactions at high states of charge and (ii) homogeneous dispersion of the active material and carbon throughout the composite cathode which provides a robust electronically conductive network that can withstand repeated charge-discharge cycles. Overall, this study provides key scientific insights on how the carbon microstructure and electrode processing influence the performance of DRX cathodes. Based on these results, exploration of alternative routes to apply graphitic coatings is recommended to further optimize the material performance.

Original language	English
Pages (from-to)	39253-39264
Number of pages	12
Journal	ACS Applied Materials and Interfaces
Volume	15
Issue number	33
DOIs	https://doi.org/10.1021/acsami.3c05619
State	Published - Aug 23 2023

Funding

Research conducted at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) was sponsored by the Vehicle Technologies Office (VTO) under the Office of Energy Efficiency and Renewable Energy (EERE). Some scanning electron microscopy measurements were conducted at the Center for Nanophase Materials Sciences (CNMS), which is a DOE Office of Science User Facility. The STEM/EDX experimental work reported here was performed under the support of the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, of the U.S. Department of Energy under Contract No. DE-LC-000L053 under the program of Next-Generation Cathode and made use of the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by U.S. Department of Energy, Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for the U.S. Department of Energy under Contract DE-AC05-76RLO1830. The DEMS experimental work was supported through the Disordered Rocksalt Program, funded by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the U.S. Department of Energy (DOE). The publisher, by accepting the article for publication, acknowledges that the U.S. 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 U.S. 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/doepublic-accessplan).

Funders	Funder number
DOE Public Access Plan
Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office	DE-LC-000L053
U.S. Government
William R. Wiley Environmental Molecular Sciences Laboratory
U.S. Department of Energy
Office of Science
Office of Energy Efficiency and Renewable Energy
Biological and Environmental Research
Pacific Northwest National Laboratory	DE-AC05-76RLO1830
Vehicle Technologies Office	DE-AC05-00OR22725, DE-AC02-05CH11231
UT-Battelle

Keywords

carbon additives
cation-disordered rocksalt (DRX)
coating
high capacity
lithium-ion battery cathodes

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1021/acsami.3c05619

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title = "Enhanced Electrochemical Performance of Disordered Rocksalt Cathodes Enabled by a Graphite Conductive Additive",

abstract = "Cobalt-free cation-disordered rocksalt (DRX) cathodes are a promising class of materials for next-generation Li-ion batteries. Although they have high theoretical specific capacities (>300 mA h/g) and moderate operating voltages (∼3.5 V vs Li/Li+), DRX cathodes typically require a high carbon content (up to 30 wt %) to fully utilize the active material which has a detrimental impact on cell-level energy density. To assess pathways to reduce the electrode{\textquoteright}s carbon content, the present study investigates how the carbon{\textquoteright}s microstructure and loading (10-20 wt %) influence the performance of DRX cathodes with the nominal composition Li1.2Mn0.5Ti0.3O1.9F0.1. While electrodes prepared with conventional disordered carbon additives (C65 and ketjenblack) exhibit rapid capacity fade due to an unstable cathode/electrolyte interface, DRX cathodes containing 10 wt % graphite show superior cycling performance (e.g., reversible capacities ∼260 mA h/g with 85% capacity retention after 50 cycles) and rate capability (∼135 mA h/g at 1000 mA/g). A suite of characterization tools was employed to evaluate the performance differences among these composite electrodes. Overall, these results indicate that the superior performance of the graphite-based cathodes is largely attributed to the: (i) formation of a uniform graphitic coating on DRX particles which protects the surface from parasitic reactions at high states of charge and (ii) homogeneous dispersion of the active material and carbon throughout the composite cathode which provides a robust electronically conductive network that can withstand repeated charge-discharge cycles. Overall, this study provides key scientific insights on how the carbon microstructure and electrode processing influence the performance of DRX cathodes. Based on these results, exploration of alternative routes to apply graphitic coatings is recommended to further optimize the material performance.",

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author = "Shripad Patil and Koirala, {Krishna Prasad} and Crafton, {Matthew J.} and Guang Yang and Tsai, {Wan Yu} and McCloskey, {Bryan D.} and Chongmin Wang and Jagjit Nanda and Self, {Ethan C.}",

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AU - Patil, Shripad

AU - Koirala, Krishna Prasad

AU - Crafton, Matthew J.

AU - Yang, Guang

AU - Tsai, Wan Yu

AU - McCloskey, Bryan D.

AU - Wang, Chongmin

AU - Nanda, Jagjit

AU - Self, Ethan C.

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Y1 - 2023/8/23

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AB - Cobalt-free cation-disordered rocksalt (DRX) cathodes are a promising class of materials for next-generation Li-ion batteries. Although they have high theoretical specific capacities (>300 mA h/g) and moderate operating voltages (∼3.5 V vs Li/Li+), DRX cathodes typically require a high carbon content (up to 30 wt %) to fully utilize the active material which has a detrimental impact on cell-level energy density. To assess pathways to reduce the electrode’s carbon content, the present study investigates how the carbon’s microstructure and loading (10-20 wt %) influence the performance of DRX cathodes with the nominal composition Li1.2Mn0.5Ti0.3O1.9F0.1. While electrodes prepared with conventional disordered carbon additives (C65 and ketjenblack) exhibit rapid capacity fade due to an unstable cathode/electrolyte interface, DRX cathodes containing 10 wt % graphite show superior cycling performance (e.g., reversible capacities ∼260 mA h/g with 85% capacity retention after 50 cycles) and rate capability (∼135 mA h/g at 1000 mA/g). A suite of characterization tools was employed to evaluate the performance differences among these composite electrodes. Overall, these results indicate that the superior performance of the graphite-based cathodes is largely attributed to the: (i) formation of a uniform graphitic coating on DRX particles which protects the surface from parasitic reactions at high states of charge and (ii) homogeneous dispersion of the active material and carbon throughout the composite cathode which provides a robust electronically conductive network that can withstand repeated charge-discharge cycles. Overall, this study provides key scientific insights on how the carbon microstructure and electrode processing influence the performance of DRX cathodes. Based on these results, exploration of alternative routes to apply graphitic coatings is recommended to further optimize the material performance.

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Enhanced Electrochemical Performance of Disordered Rocksalt Cathodes Enabled by a Graphite Conductive Additive

Abstract

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Keywords

UN SDGs

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