ABSTRACT
This paper presents the relationship between the chemical composition and size of steel balls, the parameters of the nitriding process, and their magnetic properties, defined in this study by ferromagnetic resonance (FMR) and SQUID. Balls made from AISI 1010 and AISI 52100 steels, with diameters of 2.5 and 3 mm, respectively, were investigated. On samples made of AISI 1010 and AISI 52100 steel, single-phase layers of iron nitrides γ' with a thickness of gmp = 50 and 37 µm, respectively, were produced. Then, the samples were annealed at a temperature of 520 °C for 4 h in an inert atmosphere (N2/Ar) at a pressure of 200 Pa. After the nitriding processes, steel balls were subjected to standard physical metallurgy and X-ray examinations. During annealing of nitrided layers with a two-phase layer of iron nitrides, at first, the transformation of the ε phase into the γ' phase with the release of nitrogen into the atmosphere takes place. The FMR signals did not originate from isolated ions, but from more magnetically complex systems, e.g., Fe-Fe pairs or iron clusters, while the observed FMR line position is normally even lower and occurs for a magnetic induction below 200 mT. The fact that the magnetic centers did not contain mainly isolated Fe ions, additionally confirmed the abnormal increase in resonance signal intensity as a function of temperature, which is a behavior inconsistent with the Curie-Weiss law. The results obtained from measurements by the SQUID method, recording variations in magnetization as a function of temperature, confirm the untypical reinforcement of the magnetic conditions of the samples with the increase in temperature. For the samples tested, the magnetization was relatively weaker when the tests were conducted in a stronger magnetic field.
ABSTRACT
The development of reliable and safe high-energy-density lithium-ion batteries is hindered by the structural instability of cathode materials during cycling, arising as a result of detrimental phase transformations occurring at high operating voltages alongside the loss of active materials induced by transition metal dissolution. Originating from the fundamental structure/function relation of battery materials, the authors purposefully perform crystallographic-site-specific structural engineering on electrode material structure, using the high-voltage LiNi0.5 Mn1.5 O4 (LNMO) cathode as a representative, which directly addresses the root source of structural instability of the Fd 3 ¯ m structure. By employing Sb as a dopant to modify the specific issue-involved 16c and 16d sites simultaneously, the authors successfully transform the detrimental two-phase reaction occurring at high-voltage into a preferential solid-solution reaction and significantly suppress the loss of Mn from the LNMO structure. The modified LNMO material delivers an impressive 99% of its theoretical specific capacity at 1 C, and maintains 87.6% and 72.4% of initial capacity after 1500 and 3000 cycles, respectively. The issue-tracing site-specific structural tailoring demonstrated for this material will facilitate the rapid development of high-energy-density materials for lithium-ion batteries.
ABSTRACT
Spinel LiNi0.5 Mn1.5 O4 (LNMO) is a promising cathode candidate for the next-generation high energy-density lithium-ion batteries (LIBs). Unfortunately, the application of LNMO is hindered by its poor cycle stability. Now, site-selectively doped LNMO electrode is prepared with exceptional durability. In this work, Mg is selectively doped onto both tetrahedral (8a) and octahedral (16c) sites in the Fd 3 â¾ m structure. This site-selective doping not only suppresses unfavorable two-phase reactions and stabilizes the LNMO structure against structural deformation, but also mitigates the dissolution of Mn during cycling. Mg-doped LNMOs exhibit extraordinarily stable electrochemical performance in both half-cells and prototype full-batteries with novel TiNb2 O7 counter-electrodes. This work pioneers an atomic-doping engineering strategy for electrode materials that could be extended to other energy materials to create high-performance devices.
