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Lithium nickel manganese cobalt oxide (Li x Ni y Mn z Co 1−y−z O 2 , 0 < x , y , z < 1, also known as NMC) is a class of cathode materials used in lithium ion batteries. Despite the increasing use of NMC in nanoparticle form for next-generation energy storage applications, the potential environmental impact of released nanoscale NMC is not well characterized. Previously, we showed that the released nickel and cobalt ions from nanoscale Li 1/3 Ni 1/3 Mn 1/3 Co 1/3 O 2 were largely responsible for impacting the growth and survival of the Gram-negative bacterium Shewanella oneidensis MR-1 (M. N. Hang et al. , Chem. Mater. , 2016, 28 , 1092). Here, we show the first steps toward material redesign of NMC to mitigate its biological impact and to determine how the chemical composition of NMC can significantly alter the biological impact on S. oneidensis . We first synthesized NMC with various stoichiometries, with an aim to reduce the Ni and Co content: Li 0.68 Ni 0.31 Mn 0.39 Co 0.30 O 2 , Li 0.61 Ni 0.23 Mn 0.55 Co 0.22 O 2 , and Li 0.52 Ni 0.14 Mn 0.72 Co 0.14 O 2 . Then, S. oneidensis were exposed to 5 mg L −1 of these NMC formulations, and the impact on bacterial oxygen consumption was analyzed. Measurements of the NMC composition, by X-ray photoelectron spectroscopy, and composition of the nanoparticle suspension aqueous phase, by inductively coupled plasma-optical emission spectroscopy, showed the release of Li, Ni, Mn, and Co ions. Bacterial inhibition due to redesigned NMC exposure can be ascribed largely to the impact of ionic metal species released from the NMC, most notably Ni and Co. Tuning the NMC stoichiometry to have increased Mn at the expense of Ni and Co showed lowered, but not completely mitigated, biological impact. This study reveals that the chemical composition of NMC nanomaterials is an important parameter to consider in sustainable material design and usage.
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Understanding the Mechanism of Secondary Cation Release from the (001) Surface of Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 : Insights from First-Principles
The transformations of complex metal oxides in aqueous settings must be studied to form a chemical understanding of how technologically relevant nanomaterials impact the environment upon disposal. Owing to the inherent heterogeneity and structural complexity of the ternary intercalation material Li(NixMnyCo1-x-y)O2 (NMC), the mechanisms of chemical processes at the solid–water interface are challenging to model. Here, density functional theory (DFT) + solvent ion methodology is used to study the energetics of stepwise release of two surface metals following unique pathways. The study spans different combinations of metal removal and also considers unique patterns of defects formed by modeling the NMC surface in supercells. The approach here also considers the equilibration of the surface with the surroundings between successive metal removals. A key finding is that a second metal removal prefers to proceed at a metal lattice site adjacent to the initial defect, and this is attributed in part to how the resulting slab with two metal vacancies maintains the most antiferromagnetic couplings between the remaining Ni/Mn.
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- Award ID(s):
- 2001611
- PAR ID:
- 10473342
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry C
- Volume:
- 127
- Issue:
- 43
- ISSN:
- 1932-7447
- Page Range / eLocation ID:
- 21022 to 21032
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.jpcc.3c02764
