Dataset Information

Cycling Stability of Lithium-Ion Batteries Based on Fe-Ti-Doped LiNi_0.5 Mn_1.5 O₄ Cathodes, Graphite Anodes, and the Cathode-Additive Li₃ PO₄.

ABSTRACT: This study addresses the improved cycling stability of Li-ion batteries based on Fe-Ti-doped LiNi_0.5 Mn_1.5 O₄ (LNMO) high-voltage cathode active material and graphite anodes. By using 1 wt% Li₃ PO₄ as cathode additive, over 90% capacity retention for 1000 charge-discharge cycles and remaining capacities of 109 mAh g^-1 are reached in a cell with an areal capacity of 2.3 mAh cm^- ² (potential range: 3.5-4.9 V). Cells without the additive, in contrast, suffer from accelerated capacity loss and increase polarization, resulting in capacity retention of only 78% over 1000 cycles. An electrolyte consisting of ethylene carbonate, dimethyl carbonate, and LiPF₆ is used without additional additives. The significantly improved cycling stability of the full cells is mainly due to two factors, namely, the low Mn^III content of the Fe-Ti-doped LNMO active material and the use of the cathode-additive Li₃ PO₄ . Crystalline Li₃ PO₄ yields a drastic reduction of transition metal deposition on the graphite anode and prevents Li loss and the propagation of cell polarization. Li₃ PO₄ is added to the cathode slurry that makes it a very simple and scalable process, first reported herein. The positive effects of crystalline Li₃ PO₄ as electrode additive, however, should apply to other cell chemistries as well.

SUBMITTER: Stuble P

PROVIDER: S-EPMC10460850 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature

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Publications

Cycling Stability of Lithium-Ion Batteries Based on Fe-Ti-Doped LiNi0.5 Mn1.5 O4 Cathodes, Graphite Anodes, and the Cathode-Additive Li3 PO4.

Stüble Pirmin P Müller Marcus M Bergfeldt Thomas T Binder Joachim R JR Hofmann Andreas A

Advanced science (Weinheim, Baden-Wurttemberg, Germany) 20230622 24

This study addresses the improved cycling stability of Li-ion batteries based on Fe-Ti-doped LiNi0.5 Mn1.5 O4 (LNMO) high-voltage cathode active material and graphite anodes. By using 1 wt% Li3 PO4 as cathode additive, over 90% capacity retention for 1000 charge-discharge cycles and remaining capacities of 109 mAh g-1 are reached in a cell with an areal capacity of 2.3 mAh cm- 2 (potential range: 3.5-4.9 V). ...[more]

PMID: 37348083

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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

Cycling Stability of Lithium-Ion Batteries Based on Fe-Ti-Doped LiNi_0.5 Mn_1.5 O₄ Cathodes, Graphite Anodes, and the Cathode-Additive Li₃ PO₄.

Publications

Cycling Stability of Lithium-Ion Batteries Based on Fe-Ti-Doped LiNi<sub>0.5</sub> Mn<sub>1.5</sub> O<sub>4</sub> Cathodes, Graphite Anodes, and the Cathode-Additive Li<sub>3</sub> PO<sub>4</sub>.

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