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Title: Direct Observation of Lattice Aluminum Environments in Li Ion Cathodes LiNi 1–yz Co y Al z O 2 and Al-Doped LiNi x Mn y Co z O 2 via 27 Al MAS NMR Spectroscopy

Abstract

Direct observations of local lattice aluminum environments have been a major challenge for aluminum -bearing Li ion battery materials, such as LiNi1-y-zCoyAlzO2 Al(NCA) and aluminum-doped LiNixMnyCozO2 (NMC). Al-27 magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy is the only structural probe currently available that can qualitatively and quantitatively characterize lattice and nonlattice (i.e., surface, coatings, segregation, secondary phase etc.) aluminum coordination and provide information that helps discern its effect in the lattice. In the present study, we use NMR to gain new insights into transition metal (TM)-O-Al coordination and evolution of lattice aluminum sites upon cycling. With the aid of first-principles DFT calculations, we show direct evidence of lattice Al sites, nonpreferential Ni/Co-O-Al ordering in NCA, and the lack of bulk lattice aluminum in aluminum -"doped" NMC. Aluminum coordination of the paramagnetic (lattice) and diamagnetic (nonlattice) nature is investigated for Al-doped NMC and NCA. For the latter, the evolution of the lattice site(s) upon cycling is also studied. A clear reordering of lattice aluminum environments due to nickel migration is observed in NCA upon extended cycling.

Authors:
; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1346729
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Applied Materials and Interfaces; Journal Volume: 8; Journal Issue: 26
Country of Publication:
United States
Language:
English
Subject:
27Al MAS NMR; Al segregation; DFT; NCA; NCA, NMC, lattice Al, Al segregation, transition metal migration, 27Al MAS NMR, DFT; NMC; lattice Al; transition metal migration

Citation Formats

Dogan, Fulya, Vaughey, John T., Iddir, Hakim, and Key, Baris. Direct Observation of Lattice Aluminum Environments in Li Ion Cathodes LiNi 1–y–z Co y Al z O 2 and Al-Doped LiNi x Mn y Co z O 2 via 27 Al MAS NMR Spectroscopy. United States: N. p., 2016. Web. doi:10.1021/acsami.6b04516.
Dogan, Fulya, Vaughey, John T., Iddir, Hakim, & Key, Baris. Direct Observation of Lattice Aluminum Environments in Li Ion Cathodes LiNi 1–y–z Co y Al z O 2 and Al-Doped LiNi x Mn y Co z O 2 via 27 Al MAS NMR Spectroscopy. United States. doi:10.1021/acsami.6b04516.
Dogan, Fulya, Vaughey, John T., Iddir, Hakim, and Key, Baris. Wed . "Direct Observation of Lattice Aluminum Environments in Li Ion Cathodes LiNi 1–y–z Co y Al z O 2 and Al-Doped LiNi x Mn y Co z O 2 via 27 Al MAS NMR Spectroscopy". United States. doi:10.1021/acsami.6b04516.
@article{osti_1346729,
title = {Direct Observation of Lattice Aluminum Environments in Li Ion Cathodes LiNi 1–y–z Co y Al z O 2 and Al-Doped LiNi x Mn y Co z O 2 via 27 Al MAS NMR Spectroscopy},
author = {Dogan, Fulya and Vaughey, John T. and Iddir, Hakim and Key, Baris},
abstractNote = {Direct observations of local lattice aluminum environments have been a major challenge for aluminum -bearing Li ion battery materials, such as LiNi1-y-zCoyAlzO2 Al(NCA) and aluminum-doped LiNixMnyCozO2 (NMC). Al-27 magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy is the only structural probe currently available that can qualitatively and quantitatively characterize lattice and nonlattice (i.e., surface, coatings, segregation, secondary phase etc.) aluminum coordination and provide information that helps discern its effect in the lattice. In the present study, we use NMR to gain new insights into transition metal (TM)-O-Al coordination and evolution of lattice aluminum sites upon cycling. With the aid of first-principles DFT calculations, we show direct evidence of lattice Al sites, nonpreferential Ni/Co-O-Al ordering in NCA, and the lack of bulk lattice aluminum in aluminum -"doped" NMC. Aluminum coordination of the paramagnetic (lattice) and diamagnetic (nonlattice) nature is investigated for Al-doped NMC and NCA. For the latter, the evolution of the lattice site(s) upon cycling is also studied. A clear reordering of lattice aluminum environments due to nickel migration is observed in NCA upon extended cycling.},
doi = {10.1021/acsami.6b04516},
journal = {ACS Applied Materials and Interfaces},
number = 26,
volume = 8,
place = {United States},
year = {Wed Jul 06 00:00:00 EDT 2016},
month = {Wed Jul 06 00:00:00 EDT 2016}
}