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Epitaxial growth of an atom-thin layer on a LiNi_0.5Mn_1.5O₄ cathode for stable Li-ion battery cycling.

ABSTRACT: Transition metal dissolution in cathode active material for Li-based batteries is a critical aspect that limits the cycle life of these devices. Although several approaches have been proposed to tackle this issue, this detrimental process is not yet overcome. Here, benefitting from the knowledge developed in the semiconductor research field, we apply an epitaxial method to construct an atomic wetting layer of LaTMO₃ (TM = Ni, Mn) on a LiNi_0.5Mn_1.5O₄ cathode material. Experimental measurements and theoretical analyses confirm a Stranski-Krastanov growth, where the strained wetting layer forms under thermodynamic equilibrium, and it is self-limited to monoatomic thickness due to the competition between the surface energy and the elastic energy. Being atomically thin and crystallographically connected to the spinel host lattices, the LaTMO₃ wetting layer offers long-term suppression of the transition metal dissolution from the cathode without impacting its dynamics. As a result, the epitaxially-engineered cathode material enables improved cycling stability (a capacity retention of about 77% after 1000 cycles at 290 mA g^-1) when tested in combination with a graphitic carbon anode and a LiPF₆-based non-aqueous electrolyte solution.

SUBMITTER: Zhu X

PROVIDER: S-EPMC8943144 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

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Epitaxial growth of an atom-thin layer on a LiNi0.5Mn1.5O4 cathode for stable Li-ion battery cycling.

Zhu Xiaobo X Schülli Tobias U TU Yang Xiaowei X Lin Tongen T Hu Yuxiang Y Cheng Ningyan N Fujii Hiroki H Ozawa Kiyoshi K Cowie Bruce B Gu Qinfen Q Zhou Si S Cheng Zhenxiang Z Du Yi Y Wang Lianzhou L

Nature communications 20220323 1

Transition metal dissolution in cathode active material for Li-based batteries is a critical aspect that limits the cycle life of these devices. Although several approaches have been proposed to tackle this issue, this detrimental process is not yet overcome. Here, benefitting from the knowledge developed in the semiconductor research field, we apply an epitaxial method to construct an atomic wetting layer of LaTMO3 (TM = Ni, Mn) on a LiNi0.5Mn1.5O4 ca ...[more]

PMID: 35322022

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Project description:The high-voltage LiNi0.5Mn1.5O4 (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., LiNixMnyCozO2 (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.

Dataset Information

Epitaxial growth of an atom-thin layer on a LiNi_0.5Mn_1.5O₄ cathode for stable Li-ion battery cycling.

Publications

Epitaxial growth of an atom-thin layer on a LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> cathode for stable Li-ion battery cycling.

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