Unraveling the Role of Li and Mg Substitution in Layered Sodium Oxide Cathodes for Sodium-Ion Batteries.

Substituting electrochemically active elements such as Li and Mg in P2-type layered sodium oxide is an effective strategy for developing competitive cathode materials for sodium-ion batteries. However, the lack of atomic-level understanding regarding the distribution of substitution positions complicates the comprehension of the roles of substituting atoms and the mechanism of sodium-ion intercalation. In this study, we identified the stable configurations of Na in Na0.75Ni0.3Mn0.7O2 and Na0.75Li0.15Mg0.05Ni0.1Mn0.7O2 materials using the site exclusion method. Through simulating the complete charging process for both materials, the structure evolution of the cathodes during the cycling and the impact of the partial substitution of Ni elements by Li and Mg atoms were comprehensively elucidated. Our findings revealed that Mg atoms effectively regulate the distribution of forces within the materials, essentially serving as supportive pillars within the cathode. Meanwhile, Li atoms efficiently mitigated electron localization, consequently diminishing volume fluctuations during the charging process. More importantly, the substitution with Li and Mg atoms could synergistically reduce the interaction between transition metals and sodium ions, thereby reducing the diffusion energy barrier of Na ions. This study not only enhances the comprehension of substituted metal atoms in P2 layered oxides but also offers new insights for the development of sodium-ion cathode materials.

Enabling an Excellent Ordering-Enhanced Electrochemistry and a Highly Reversible Whole-Voltage-Range Oxygen Anionic Chemistry for Sodium-Ion Batteries.

Though considerable Mg-doped layered cathodes have been exploited, some new differences relative to previous reports can be concluded by doping a heavy dose of Mg via two rational strategies. Unlike the common unit cell of the P63/mmc group by X-ray diffraction, neutron diffraction reveals a large supercell of the P63 group and enhanced ordering for Na11/18Mg1/18[Ni1/4Mg1/9Mn11/18]O2 with Mg occupying both the Na and Mn sites. Compared with only one obvious voltage plateau of Na0.5[Ni0.25Mn0.75]O2 (NNM), Na11/18Mg1/18[Ni1/4Mg1/9Mn11/18]O2 (NMNMM) shows more severe voltage plateaus but with excellent electrochemical performance. Na0.5[Mg0.25Mn0.75]O2 (NMM) with Mg only occupying the Ni site displays a highly reversible whole-voltage-range oxygen redox chemistry and smooth voltage curves without any voltage hysteresis. Cationic Ni2+/Ni4+ couples are responsible for the charge compensations of NNM and NMNMM, while only the oxygen anionic reaction accounts for the capacity of NMM between 2.5 and 4.3 V. Interestingly, the Mn3+/Mn4+ pair contributes all capacity for all cathodes between 1.5 and 2.5 V. All cathodes undergo a double-phase mechanism: an irreversible P2-O2 phase transition for NNM, an enhanced reversible P2-O2 phase transition for NMNMM, and a highly reversible P2-OP4 phase transition for NMM. In addition, the designed cathodes display excellent rate capability and long-term cycling stability but with a large difference in the various voltage ranges of 2.5-4.3 and 1.5-2.5 V, respectively. This work provides a good understanding of ion doping and some new insights into exploiting high-performance materials.

The Mutual Incorporation of Mg2+ and CO32- into Hydroxyapatite: A DFT Study.

Hydroxyapatite (HA) with a stoichiometry composition of Ca10(PO4)6(OH)2 is widely applied for various biomedical issues, first of all for bone defect substitution, as a catalyst, and as an adsorbent for soil and water purification. The incorporation of foreign ions changes the acid-base relation, microstructure, porosity, and other properties of the HA materials. Here, we report the results of calculations of the density functional theory and analyze the possibility of two foreign ions, CO32- and Mg2+, to be co-localized in the HA structure. The Na+ was taken into account for charge balance preservation. The analysis revealed the favorable incorporation of CO32- and Mg2+ as a complex when they interact with each other. The energy gain over the sole ion incorporation was pronounced when CO32- occupied the A position and Mg2+ was in the Ca(2) position and amounted to -0.31 eV. In the most energy-favorable complex, the distance between Mg2+ and the O atom of carbonate ion decreased compared to Mg…O distances to the surrounding phosphate or hydroxide ions, and amounted to 1.98 Å. The theoretical calculations agree well with the experimental data reported earlier. Understating the structure-properties relationship in HA materials varying in terms of composition, stoichiometry, and morphology paves the way to rational designs of efficient bio-based catalytic systems.

Boosting Reversibility of Mn-Based Tunnel-Structured Cathode Materials for Sodium-Ion Batteries by Magnesium Substitution.

Electrochemical irreversibility and sluggish mobility of Na+ in the cathode materials result in poor cycle stability and rate capability for sodium-ion batteries. Herein, a new strategy of introducing Mg ions into the hinging sites of Mn-based tunnel-structured cathode material is designed. Highly reversible electrochemical reaction and phase transition in this cathode are realized. The resulted Na0.44Mn0.95Mg0.05O2 with Mg2+ in the hinging Mn-O5 square pyramidal exhibits promising cycle stability and rate capability. At a current density of 2 C, 67% of the initial discharge capacity is retained after 800 cycles (70% at 20 C), much improved than the undoped Na0.44MnO2. The improvement is attribute to the enhanced Na+ diffusion kinetics and the lowered desodiation energy after Mg doping. Highly reversible charge compensation and structure evolution are proved by synchrotron-based X-ray techniques. Differential charge density and atom population analysis of the average electron number of Mn indicate that Na0.44Mn0.95Mg0.05O2 is more electron-abundant in Mn 3d orbits near the Fermi level than that in Na0.44MnO2, leading to higher redox participation of Mn ions.

Whole-Voltage-Range Oxygen Redox in P2-Layered Cathode Materials for Sodium-Ion Batteries.

Oxygen-redox of layer-structured metal-oxide cathodes has drawn great attention as an effective approach to break through the bottleneck of their capacity limit. However, reversible oxygen-redox can only be obtained in the high-voltage region (usually over 3.5 V) in current metal-oxide cathodes. Here, we realize reversible oxygen-redox in a wide voltage range of 1.5-4.5 V in a P2-layered Na0.7 Mg0.2 [Fe0.2 Mn0.6 □0.2 ]O2 cathode material, where intrinsic vacancies are located in transition-metal (TM) sites and Mg-ions are located in Na sites. Mg-ions in the Na layer serve as "pillars" to stabilize the layered structure during electrochemical cycling, especially in the high-voltage region. Intrinsic vacancies in the TM layer create the local configurations of "□-O-□", "Na-O-□" and "Mg-O-□" to trigger oxygen-redox in the whole voltage range of charge-discharge. Time-resolved techniques demonstrate that the P2 phase is well maintained in a wide potential window range of 1.5-4.5 V even at 10 C. It is revealed that charge compensation from Mn- and O-ions contributes to the whole voltage range of 1.5-4.5 V, while the redox of Fe-ions only contributes to the high-voltage region of 3.0-4.5 V. The orphaned electrons in the nonbonding 2p orbitals of O that point toward TM-vacancy sites are responsible for reversible oxygen-redox, and Mg-ions in Na sites suppress oxygen release effectively.

Partial substitution of magnesium in lanthanum manganite perovskite for nitric oxide oxidation: The effect of substitution sites.

Lanthanum manganite (LaMnO3) with magnesium (Mg) substituted the A- and B-sites were reported for the first time in this work. The Mg substituted LaMnO3 catalysts were prepared by means of citric acid sol-gel method. The impact of partial substitution of Mg and its substitution site on the catalytic performance of LaMnO3 in nitric oxide (NO) oxidation was investigated. Through series of characterizations, it was found that Mg substitution at both A- and B-sites improves the specific surface area, Mn4+ content, reactivity of surface oxygen species, redox property and NO adsorption capacity of LaMnO3. However, Mg substitution at the A-site of LaMnO3 can cause the total charge imbalance of B-site, which significantly improves the amount and reactivity of surface active oxygen species. Therefore, the catalytic activity of the samples decreases in the order: La0.9Mg0.1MnO3 > LaMn0.9Mg0.1O3 > LaMnO3. This study will shed more light on the fundamental understanding and designing of perovskite catalyst.

Effects of Mg and Sb Substitution on the Magnetic Properties of Magnetic Field Annealed MnBi Alloys.

Rare-earth-free permanent magnets have attracted considerable attention due to their favorable properties and applicability for cost-effective, high-efficiency, and sustainable energy devices. However, the magnetic field annealing process, which enhances the performance of permanent magnets, needs to be optimized for different magnetic fields and phases. Therefore, we investigated the effect of composition on the crystallization of amorphous MnBi to the ferromagnetic low-temperature phase (LTP). The optimal compositions and conditions were applied to magnetic field annealing under 2.5 T for elemental Mg- and Sb/Mg pair-substituted MnBi. The optimum MnBi composition for the highest purity LTP was determined to be Mn56Bi44, and its maximum energy product, (BH)max, was 5.62 MGOe. The Mg-substituted MnBi exhibited enhanced squareness (Mr/Ms), coercivity (Hc), and (BH)max values up to 0.8, 9659 Oe, and 5.64 MGOe, respectively, whereas the same values for the Sb/Mg pair-substituted MnBi were 0.76, 7038 Oe, and 5.60 MGOe, respectively. The substitution effects were also investigated using first-principles calculations. The density of states and total magnetic moments of Mn16Bi15Mg and Mn16Bi15Sb were similar to those of pure Mn16Bi16. Conversely, the Sb-substituted MnBi resulted in a dramatic enhancement in the anisotropy constant (K) from a small negative value (-0.85 MJ/m3) to a large positive value (6.042 MJ/m3).

Structural Stabilization of P2-type Sodium Iron Manganese Oxides by Electrochemically Inactive Mg Substitution: Insights of Redox Behavior and Voltage Decay.

Layered P2-type Na0.8 Mn0.5 Fe0.5 O2 cathode material is a promising candidate for next-generation sodium-ion batteries due to the economical and environmentally benign characteristics of Mn and Fe. The poor cycling stability of the material, however, is still a problem that must be solved. To address the problem, electrochemically inactive Mg2+ was introduced into the structure by substituting some of the Fe ions. It was shown that Mg substitution led to a smoother voltage profile with improved cycling performance and rate capability. These observations were attributed to the suppressed structural changes during electrochemical processes. Detailed redox mechanisms, associated local structural changes, and phase transitions were investigated by X-ray absorption spectroscopy and X-ray diffraction. From the detailed analysis of electrochemical behaviors, it was also identified how the redox reactions and structural disordering occurred in the high- and low-voltage regions and how Mg substitution stabilized the structure.

Bimetallic Sulfide with Controllable Mg Substitution Anchored on CNTs as Hierarchical Bifunctional Catalyst toward Oxygen Catalytic Reactions for Rechargeable Zinc-Air Batteries.

The exploitation of high-efficiency and cheap bifunctional cathode electrocatalyst is of significant importance to rechargeable zinc-air batteries. In this paper, a bimetallic sulfide coupled with a CNT ((Co, Mg)S2@CNTs) hybrid catalyst is developed via a proposed vulcanization process. The (Co, Mg)S2@CNTs) with controllable Mg substitution has a tailored crystal structure (amorphous and crystalline), which catalyzes the oxygen reduction/evolution reaction (ORR/OER). The active sites of CoS2@CNTs are activated by doping Mg ions, which accelerates the kinetics of the oxygen adsorption for ORR and oxygen desorption for OER. Meanwhile, the hybrid catalyst exhibits a unique hierarchal morphology and a "catalytic buffer", which further accelerate the mass transfer of catalytic processes. In addition, the outer wall of CNTs as substrate effectively avoid the agglomeration of (Co, Mg)S2 particles by reasonably providing adsorption sites. The inner and outer walls of CNTs form a high-speed conduction pathway, quickly transferring the electrons produced by oxygen catalytic reactions. As a result, the (Co, Mg)S2@CNTs exhibit an ORR performance comparable with commercial catalyst Pt/C-RuO2 and remarkable OER performance (Ej=10 = 1.59 V). The high power density of 268 mW cm-2 and long-term charge/discharge stability of the zinc-air battery proves the feasibility of (Co, Mg)S2@CNTs application in high-power devices.

Cadmium ion-chlorophyll interaction - Examination of spectral properties and structure of the cadmium-chlorophyll complex and their relevance to photosynthesis inhibition.

Chlorophyll was shown to spontaneously form a complex with cadmium, which is incorporated at the central position of the chlorophyll molecule porphyrin ring, where it replaces magnesium. The rate of complex formation depended on the ratio of Cd2+ ions to chlorophyll concentration in the solution. In solutions with chlorophyll concentration of C = 1 × 10-5 M and Cd2+ concentrations of C = 1 × 10-5 M, C = 1 × 10-3 M and C = 9 × 10-3 M, Cd-Chl complex formation was completed after 200 h, 50 h and 33 h, respectively. The formation of Cd-Chl complex followed the second order over all substrates reaction order, first order over Cd2+ concentration and first over Chl concentration. The pseudo second order reaction rate constant k, when Cd2+ concentration was equal Chl concentration have been obtained as k = 1.510 ± 0.023 × 10-4 M-1min-1. Quantum chemistry computations showed that Cd-chlorophyll complex existed in two conformations in the methanol solution with cadmium ion placed either below or above the coordination plane. Two times smaller overlap integral of the Chl fluorescence spectrum with the Cd-Chl absorption spectrum IChl,Cd-Chl= 2.4223 × 10-13 cm3/M in comparison with the overlap integral of the Chl fluorescence spectrum with the Chl absorption spectrum IChl,Chl= 4.6210 × 10-13 cm3/M (twice lower probability of energy transfer Chl∗ → Cd-Chl than Chl∗ → Chl) and lower Förster critical distance for resonance energy transfer: RoChl→Cd-Chl= 46.773 Å, RoChl→Chl= 52.086 Å, indicated that in plants intoxicated with cadmium, taken up from the contaminated soil, the energy transfer between Chl and Cd-Chl in antennas will be disturbed, which may be one of the reasons for the inhibition of photosynthesis.