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Title: From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes

Abstract

Surface alumina coatings have been shown to be an effective way to improve the stability and cyclability of cathode materials. However, a detailed understanding of the relationship between the surface coatings and the bulk layered oxides is needed to better define the critical cathode–electrolyte interface. In this work, we systematically studied the effect of the composition of Ni-rich LiNi xMn yCo 1–x–yO 2 (NMC) on the surface alumina coatings. Changing cathode composition from LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532) to LiNi 0.6Mn 0.2Co 0.2O 2 (NMC622) and LiNi 0.8Mn 0.1Co 0.1O 2 (NMC811) was found to facilitate the diffusion of surface alumina into the bulk after high-temperature annealing. By use of a variety of spectroscopic techniques, Al was seen to have a high bulk compatibility with higher Ni/Co content, and low bulk compatibility was associated with Mn in the transition metal layer. It was also noted that the cathode composition affected the observed morphology and surface chemistry of the coated material, which has an effect on electrochemical cycling. The presence of a high surface Li concentration and strong alumina diffusion into the bulk led to a smoother surface coating on NMC811 with no excess alumina aggregated on the surface. Structuralmore » characterization of pristine NMC particles also suggests surface Co segregation, which may act to mediate the diffusion of the Al from the surface to the bulk. The diffusion of Al into the bulk was found to be detrimental to the protection function of surface coatings leading to poor overall cyclability, indicating the importance of compatibility between surface coatings and bulk oxides on the electrochemical performance of coated cathode materials.In conclusion, these results are important in developing a better coating method for synthesis of next-generation cathode materials for lithium-ion batteries.« less

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [3];  [3]; ORCiD logo [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Sciences Division
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1417024
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 9; Journal Issue: 47; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; MAS NMR; NMC; TEM; alumina coating; aluminum doping; aluminum insertion; cathode materials; compositional effect

Citation Formats

Han, Binghong, Key, Baris, Lapidus, Saul H., Garcia, Juan C., Iddir, Haim, Vaughey, John T., and Dogan, Fulya. From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes. United States: N. p., 2017. Web. doi:10.1021/acsami.7b13597.
Han, Binghong, Key, Baris, Lapidus, Saul H., Garcia, Juan C., Iddir, Haim, Vaughey, John T., & Dogan, Fulya. From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes. United States. doi:10.1021/acsami.7b13597.
Han, Binghong, Key, Baris, Lapidus, Saul H., Garcia, Juan C., Iddir, Haim, Vaughey, John T., and Dogan, Fulya. Wed . "From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes". United States. doi:10.1021/acsami.7b13597.
@article{osti_1417024,
title = {From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes},
author = {Han, Binghong and Key, Baris and Lapidus, Saul H. and Garcia, Juan C. and Iddir, Haim and Vaughey, John T. and Dogan, Fulya},
abstractNote = {Surface alumina coatings have been shown to be an effective way to improve the stability and cyclability of cathode materials. However, a detailed understanding of the relationship between the surface coatings and the bulk layered oxides is needed to better define the critical cathode–electrolyte interface. In this work, we systematically studied the effect of the composition of Ni-rich LiNixMnyCo1–x–yO2 (NMC) on the surface alumina coatings. Changing cathode composition from LiNi0.5Mn0.3Co0.2O2 (NMC532) to LiNi0.6Mn0.2Co0.2O2 (NMC622) and LiNi0.8Mn0.1Co0.1O2 (NMC811) was found to facilitate the diffusion of surface alumina into the bulk after high-temperature annealing. By use of a variety of spectroscopic techniques, Al was seen to have a high bulk compatibility with higher Ni/Co content, and low bulk compatibility was associated with Mn in the transition metal layer. It was also noted that the cathode composition affected the observed morphology and surface chemistry of the coated material, which has an effect on electrochemical cycling. The presence of a high surface Li concentration and strong alumina diffusion into the bulk led to a smoother surface coating on NMC811 with no excess alumina aggregated on the surface. Structural characterization of pristine NMC particles also suggests surface Co segregation, which may act to mediate the diffusion of the Al from the surface to the bulk. The diffusion of Al into the bulk was found to be detrimental to the protection function of surface coatings leading to poor overall cyclability, indicating the importance of compatibility between surface coatings and bulk oxides on the electrochemical performance of coated cathode materials.In conclusion, these results are important in developing a better coating method for synthesis of next-generation cathode materials for lithium-ion batteries.},
doi = {10.1021/acsami.7b13597},
journal = {ACS Applied Materials and Interfaces},
number = 47,
volume = 9,
place = {United States},
year = {Wed Nov 01 00:00:00 EDT 2017},
month = {Wed Nov 01 00:00:00 EDT 2017}
}

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