Transition Metal Dissolution Mechanisms and Impacts on Electronic Conductivity in Composite LiNi0.5Mn1.5O4 Cathode Films

Hestenes, Julia C.; Sadowski, Jerzy T.; May, Richard; Marbella, Lauren E.

doi:10.1021/acsmaterialsau.2c00060

Transition Metal Dissolution Mechanisms and Impacts on Electronic Conductivity in Composite LiNi_0.5Mn_1.5O₄ Cathode Films

Journal Article · Thu Nov 10 00:00:00 EST 2022 · ACS Materials Au

DOI:https://doi.org/10.1021/acsmaterialsau.2c00060· OSTI ID:1907829

Hestenes, Julia C. ^[1]; ^[2]; May, Richard ^[1]; ^[1]

Columbia Univ., New York, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

The high-voltage LiNi_0.5Mn_1.5O₄ (LNMO) spinel cathode material offers high energy density storage capabilities without the use of costly Co that is prevalent in other Li-ion battery chemistries (e.g., LiNi_xMn_yCo_zO₂ (NMC)). Unfortunately, LNMO-containing batteries suffer from poor cycling performance because of the intrinsically coupled processes of electrolyte oxidation and transition metal dissolution that occurs at high voltage. In this work, we use operando electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies to demonstrate that transition metal dissolution in LNMO is tightly coupled to HF formation (and thus, electrolyte oxidation reactions as detected with operando and in situ solution NMR), indicative of an acid-driven disproportionation reaction that occurs during delithiation (i.e., battery charging). Leveraging the temporal resolution (s-min) of magnetic resonance, we find that the LNMO particles accelerate the rate of LiPF₆ decomposition and subsequent Mn²⁺ dissolution, possibly due to the acidic nature of terminal Mn-OH groups. X-ray photoemission electron microscopy (XPEEM) provides surface-sensitive and localized X-ray absorption spectroscopy (XAS) measurements, in addition to X-ray photoelectron spectroscopy (XPS), that indicate disproportionation is enabled by surface reconstruction upon charging, which leads to surface Mn³⁺ sites on the LNMO particle surface that can disproportionate into Mn²⁺_(dissolved) and Mn⁴⁺_(s). During discharge of the battery, we observe high quantities of metal fluorides (in particular, MnF₂) in the cathode electrolyte interphase (CEI) on LNMO as well as the conductive carbon additives in the composite. Electronic conductivity measurements indicate that the MnF₂ decreases film conductivity by threefold compared to LiF, suggesting that this CEI component may impede both the ionic and electronic properties of the cathode. Ultimately, to prevent transition metal dissolution and the associated side reactions in spinel-type cathodes (particularly those that operate at high voltages like LNMO), the use of electrolytes that offer improved anodic stability and prevent acid byproducts will likely be necessary.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOD; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1907829

Report Number(s):: BNL--223842-2023-JAAM

Journal Information:: ACS Materials Au, Journal Name: ACS Materials Au Journal Issue: 2 Vol. 3; ISSN 2694-2461

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Transition Metal Dissolution Mechanisms and Impacts on Electronic Conductivity in Composite LiNi0.5Mn1.5O4 Cathode Films

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