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Structural Origins of Voltage Hysteresis in the Na-Ion Cathode P2-Na_0.67[Mg_0.28Mn_0.72]O₂: A Combined Spectroscopic and Density Functional Theory Study.

ABSTRACT: P2-layered sodium-ion battery (NIB) cathodes are a promising class of Na-ion electrode materials with high Na⁺ mobility and relatively high capacities. In this work, we report the structural changes that take place in P2-Na_0.67[Mg_0.28Mn_0.72]O₂. Using ex situ X-ray diffraction, Mn K-edge extended X-ray absorption fine structure, and ²³Na NMR spectroscopy, we identify the bulk phase changes along the first electrochemical charge-discharge cycle-including the formation of a high-voltage "Z phase", an intergrowth of the OP4 and O2 phases. Our ab initio transition state searches reveal that reversible Mg²⁺ migration in the Z phase is both kinetically and thermodynamically favorable at high voltages. We propose that Mg²⁺ migration is a significant contributor to the observed voltage hysteresis in Na_0.67[Mg_0.28Mn_0.72]O₂ and identify qualitative changes in the Na⁺ ion mobility.

SUBMITTER: Bassey EN

PROVIDER: S-EPMC8280737 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The Mg(II) and heterometallic Mn(II)/Na(I) complexes of isoferulic acid (3-hydroxy-4-methoxycinnamic acid, IFA) were synthesized and characterized by infrared spectroscopy FT-IR, FT-Raman, electronic absorption spectroscopy UV/VIS, and single-crystal X-ray diffraction. The reaction of MgCl2 with isoferulic acid in the aqueous solutions of NaOH resulted in synthesis of the complex salt of the general formula of [Mg(H2O)6]⋅(C10H9O4)2⋅6H2O. The crystal structure of this compound consists of discrete octahedral [Mg(H2O)6]2+ cations, isoferulic acid anions and solvent water molecules. The hydrated metal cations are arranged among the organic layers. The multiple hydrogen-bonding interactions established between the coordinated and lattice water molecules and the functional groups of the ligand stabilize the 3D architecture of the crystal. The use of MnCl2 instead of MgCl2 led to the formation of the Mn(II)/Na(I) complex of the general formula [Mn3Na2(C10H7O4)8(H2O)8]. The compound is a 3D coordination polymer composed of centrosymmetric pentanuclear subunits. The antioxidant activity of these compounds was evaluated by assays based on different antioxidant mechanisms of action, i.e., with •OH, DPPH• and ABTS•+ radicals as well as CUPRAC (cupric ions reducing power) and lipid peroxidation inhibition assays. The pro-oxidant property of compounds was measured as the rate of oxidation of Trolox. The Mg(II) and Mn(II)/Na(I) complexes with isoferulic acid showed higher antioxidant activity than ligand alone in DPPH (IFA, IC50 = 365.27 μM, Mg(II) IFA IC50 = 153.50 μM, Mn(II)/Na(I) IFA IC50 = 149.00 μM) and CUPRAC assays (IFA 40.92 μM of Trolox, Mg(II) IFA 87.93 μM and Mn(II)/Na(I) IFA 105.85 μM of Trolox; for compounds' concentration 10 μM). Mg(II) IFA is a better scavenger of •OH than IFA and Mn(II)/Na(I) IFA complex. There was no distinct difference in ABTS•+ and lipid peroxidation assays between isoferulic acid and its Mg(II) complex, while Mn(II)/Na(I) complex showed lower activity than these compounds. The tested complexes displayed only slight antiproliferative activity tested in HaCaT human immortalized keratinocyte cell line within the solubility range. The Mn(II)/Na(I) IFA (16 μM in medium) caused an 87% (±5%) decrease in cell viability, the Mg salt caused a comparable, i.e., 87% (±4%) viability decrease in a concentration of 45 μM, while IFA caused this level of cell activity attenuation (87% ± 5%) at the concentration of 1582 μM (significant at α = 0.05).

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Structural Origins of Voltage Hysteresis in the Na-Ion Cathode P2-Na_0.67[Mg_0.28Mn_0.72]O₂: A Combined Spectroscopic and Density Functional Theory Study.

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Structural Origins of Voltage Hysteresis in the Na-Ion Cathode P2-Na0.67[Mg0.28Mn0.72]O2: A Combined Spectroscopic and Density Functional Theory Study.

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Structural Origins of Voltage Hysteresis in the Na-Ion Cathode P2-Na_0.67[Mg_0.28Mn_0.72]O₂: A Combined Spectroscopic and Density Functional Theory Study.