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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}
}
  • Core–shell materials have attracted a great deal of interest since core–shell particles have superior physical and chemical properties compared to their single-component counterparts. The cathode material Li(Ni{sub 0.8}Co{sub 0.15}Al{sub 0.05}){sub 0.8}(Ni{sub 0.5}Mn{sub 0.5}){sub 0.2}O{sub 2} (LNCANMO) with a core–shell structure was synthesized via a co-precipitation method and investigated as the cathode material for lithium ion batteries. The core–shell particle consisted of LiNi{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2} (LNCAO) as the core and LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} as the shell. The cycling behavior between 2.8 and 4.3 V at a current of 0.1 C-rate showed a reversible capacity of ∼195 mAh g{supmore » −1} with little capacity loss after 50 cycles. Extensive assessment of the electronic structures of the LNCAO and LNCANMO cathode materials was carried out using X-ray absorption spectroscopy (XAS). XAS has been used for structure refinement on the transition metal ion of the cathode. In particular, XAS studies of electrochemical reactions have been done from the viewpoint of the transition metal ion. In this study, Ni K-edge XAS spectra of the charge and discharge processes of LNCAO and LNCANMO were investigated.« less
  • Thermal stability of charged LiNi xMn yCo zO 2 (NMC, with x + y + z = 1, x:y:z = 4:3:3 (NMC433), 5:3:2 (NMC532), 6:2:2 (NMC622), and 8:1:1 (NMC811)) cathode materials is systematically studied using combined in situ time- resolved X-ray diffraction and mass spectroscopy (TR-XRD/MS) techniques upon heating up to 600 °C. The TR-XRD/MS results indicate that the content of Ni, Co, and Mn significantly affects both the structural changes and the oxygen release features during heating: the more Ni and less Co and Mn, the lower the onset temperature of the phase transition (i.e., thermal decomposition) and themore » larger amount of oxygen release. Interestingly, the NMC532 seems to be the optimized composition to maintain a reasonably good thermal stability, comparable to the low-nickel-content materials (e.g., NMC333 and NMC433), while having a high capacity close to the high-nickel-content materials (e.g., NMC811 and NMC622). The origin of the thermal decomposition of NMC cathode materials was elucidated by the changes in the oxidation states of each transition metal (TM) cations (i.e., Ni, Co, and Mn) and their site preferences during thermal decomposition. It is revealed that Mn ions mainly occupy the 3a octahedral sites of a layered structure (R3¯m) but Co ions prefer to migrate to the 8a tetrahedral sites of a spinel structure (Fd3¯m) during the thermal decomposition. Such element-dependent cation migration plays a very important role in the thermal stability of NMC cathode materials. The reasonably good thermal stability and high capacity characteristics of the NMC532 composition is originated from the well-balanced ratio of nickel content to manganese and cobalt contents. As a result, this systematic study provides insight into the rational design of NMC-based cathode materials with a desired balance between thermal stability and high energy density.« less
  • Single-phase LiNi 0.45Mn 0.45Co 0.1-yAl yO 2 layered oxide materials with 0 ≤ y ≤ 0.10 were prepared using the glycine-nitrate combustion method. Al-substitution has a minimal effect on the defect concentration and rate capability of the materials, but raises the operating voltage and reduces the capacity fade of the materials during prolonged cycling compared to the unsubstituted system. In situ X-ray diffraction suggests the presence of Al has a significant structural impact during battery operation. It acts to limit the changes in lattice parameters observed during electrochemical charging and cycling of the materials. High-resolution X-ray diffraction reveals structural distortionsmore » in the transition metal layers of as-synthesized powders with high Al-contents, as well as a structural evolution seen in all materials after cycling.« less
  • Using ab initio calculations combined with experiments, we clarified how the kinetics of Li-ion diffusion can be tuned in LiNixMnyCozO2 (NMC, x + y + z = 1) materials. It is found that Li-ions tend to choose oxygen dumbbell hopping (ODH) at the early stage of charging (delithiation), and tetrahedral site hopping (TSH) begins to dominate when more than 1/3 Li-ions are extracted. In both ODH and TSH, the Li-ions surrounded by nickel (especially with low valence state) are more likely to diffuse with low activation energy and form an advantageous path. The Li slab space, which also contributes tomore » the effective diffusion barriers, is found to be closely associated with the delithiation process (Ni oxidation) and the contents of Ni, Co, and Mn.« less
  • The capacity degradation mechanism in lithium nickel–manganese–cobalt oxide (NMC) cathodes (LiNi 1/3Mn 1/3Co 1/3O 2 (NMC 333) and LiNi 0.4Mn 0.4Co 0.2O 2 (NMC 442)) during high-voltage (cut-off of 4.8 V) operation has been investigated. In contrast to NMC 442, NMC 333 exhibits rapid structural changes including severe micro-crack formation and phase transformation from a layered to a disordered rock-salt structure, as well as interfacial degradation during high-voltage cycling, leading to a rapid increase of the electrode resistance and fast capacity decline. The fundamental reason behind the poor structural and interfacial stability of NMC 333 was found to be correlatedmore » to its high Co content and the significant overlap between the Co 3+/4+ t 2g and O 2- 2p bands, resulting in oxygen removal and consequent structural changes at high voltages. In addition, oxidation of the electrolyte solvents by the extracted oxygen species generates acidic species, which then attack the electrode surface and form highly resistive LiF. These findings highlight that both the structural and interfacial stability should be taken into account when tailoring cathode materials for high voltage battery systems.« less