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Title: Surface Structural and Chemical Evolution of Layered LiNi0.8Co 0.15Al 0.05O2 (NCA) under High Voltage and Elevated Temperature Conditions

Abstract

This work reports new insights into structural and chemical evolution of surface phases of LiNi0.8Co0.15Al0.05O2 (NCA) held at constant high voltages (up to 4.75 V) as well as high temperatures (60 °C) by correlating crystal structure using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) imaging with chemistry using electron energy loss spectroscopy (EELS). We also followed the Al distribution within individual NCA particles by X-ray energy dispersive spectroscopy (EDS). The progression of these phases as a function of distance from the edge shows simultaneous evolution of crystal structures and chemistry from rocksalt to layered, forming a complete solid solution. We have also observed an extended disordered phase with rocksalt (Fm3m) symmetry in which quantitative electron energy loss spectroscopy reveals it to be an oxygen deficient cation disordered phase with chemical characteristics, as determined by EELS, similar to spinel. The formation of these disordered phases with cation and oxygen vacancies has been driven by surface oxygen loss caused by reactions with the electrolyte followed by cation migration from the octahedral 3a M (M = Ni, Co, Al) layer to the octahedral 3b Li layer. These surface rocksalt phases are not fully dense as they contain Al and Limore » as well as a high concentration of cation and oxygen vacancies. After discharge, Li is detected within these phases indicative that Li transport has occurred through these rocksalt phases. At 60 °C and 4.75 V a very large impedance rise is observed leading to complete cell irreversibility which is caused by significant metal dissolution from the cathode and formation of surface porosity. In the near surface region of some particles, a phase transformation from R3m (O3) to P3m1 (O1) is also observed which has become thermodynamically stable from complete delithiation as well as from local Al surface depletion.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [1];  [1]
+ Show Author Affiliations
  1. Rutgers Univ., Piscataway, NJ (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Binghamton Univ., NY (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1599787
Grant/Contract Number:  
AC02-05CH11231; SC0012583; SC0012704; NSF MRI 1429232
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 23; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; spinel; electron energy loss spectroscopy; chemical structure; oxygen phase transitions

Citation Formats

Mukherjee, Pinaki, Faenza, Nicholas V., Pereira, Nathalie, Ciston, Jim, Piper, Louis F. J., Amatucci, Glenn G., and Cosandey, Frederic. Surface Structural and Chemical Evolution of Layered LiNi0.8Co 0.15Al 0.05O2 (NCA) under High Voltage and Elevated Temperature Conditions. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.7b05305.
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Mukherjee, Pinaki, Faenza, Nicholas V., Pereira, Nathalie, Ciston, Jim, Piper, Louis F. J., Amatucci, Glenn G., & Cosandey, Frederic. Surface Structural and Chemical Evolution of Layered LiNi0.8Co 0.15Al 0.05O2 (NCA) under High Voltage and Elevated Temperature Conditions. United States. https://doi.org/10.1021/acs.chemmater.7b05305
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Mukherjee, Pinaki, Faenza, Nicholas V., Pereira, Nathalie, Ciston, Jim, Piper, Louis F. J., Amatucci, Glenn G., and Cosandey, Frederic. Mon . "Surface Structural and Chemical Evolution of Layered LiNi0.8Co 0.15Al 0.05O2 (NCA) under High Voltage and Elevated Temperature Conditions". United States. https://doi.org/10.1021/acs.chemmater.7b05305. https://www.osti.gov/servlets/purl/1599787.
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@article{osti_1599787,
title = {Surface Structural and Chemical Evolution of Layered LiNi0.8Co 0.15Al 0.05O2 (NCA) under High Voltage and Elevated Temperature Conditions},
author = {Mukherjee, Pinaki and Faenza, Nicholas V. and Pereira, Nathalie and Ciston, Jim and Piper, Louis F. J. and Amatucci, Glenn G. and Cosandey, Frederic},
abstractNote = {This work reports new insights into structural and chemical evolution of surface phases of LiNi0.8Co0.15Al0.05O2 (NCA) held at constant high voltages (up to 4.75 V) as well as high temperatures (60 °C) by correlating crystal structure using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) imaging with chemistry using electron energy loss spectroscopy (EELS). We also followed the Al distribution within individual NCA particles by X-ray energy dispersive spectroscopy (EDS). The progression of these phases as a function of distance from the edge shows simultaneous evolution of crystal structures and chemistry from rocksalt to layered, forming a complete solid solution. We have also observed an extended disordered phase with rocksalt (Fm3m) symmetry in which quantitative electron energy loss spectroscopy reveals it to be an oxygen deficient cation disordered phase with chemical characteristics, as determined by EELS, similar to spinel. The formation of these disordered phases with cation and oxygen vacancies has been driven by surface oxygen loss caused by reactions with the electrolyte followed by cation migration from the octahedral 3a M (M = Ni, Co, Al) layer to the octahedral 3b Li layer. These surface rocksalt phases are not fully dense as they contain Al and Li as well as a high concentration of cation and oxygen vacancies. After discharge, Li is detected within these phases indicative that Li transport has occurred through these rocksalt phases. At 60 °C and 4.75 V a very large impedance rise is observed leading to complete cell irreversibility which is caused by significant metal dissolution from the cathode and formation of surface porosity. In the near surface region of some particles, a phase transformation from R3m (O3) to P3m1 (O1) is also observed which has become thermodynamically stable from complete delithiation as well as from local Al surface depletion.},
doi = {10.1021/acs.chemmater.7b05305},
journal = {Chemistry of Materials},
number = 23,
volume = 30,
place = {United States},
year = {Mon Nov 05 00:00:00 EST 2018},
month = {Mon Nov 05 00:00:00 EST 2018}
}
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