LiMgPO4 -Coating-Induced Phosphate Shell and Bulk Mg-Doping Enables Stable Ultra-High-Voltage Cycling of LiCoO2 Cathode.

Stable cycling of LiCoO2 (LCO) cathode at high voltage is extremely challenging due to the notable structural instability in deeply delithiated states. Here, using the sol-gel coating method, LCO materials (LMP-LCO) are obtained with bulk Mg-doping and surface LiMgPO4 /Li3 PO4 (LMP/LPO) coating. The experimental results suggest that the simultaneous modification in the bulk and at the surface is demonstrated to be highly effective in improving the high-voltage performance of LCO. LMP-LCO cathodes deliver 149.8 mAh g-1 @4.60 V and 146.1 mAh g-1 @4.65 V after 200 cycles at 1 C. For higher cut-off voltages, 4.70 and 4.80 V, LMP-LCO cathodes still achieve 144.9 mAh g-1 after 150 cycles and 136.8 mAh g-1 after 100 cycles at 1 C, respectively. Bulk Mg-dopants enhance the ionicity of CoO bond by tailoring the band centers of Co 3d and O 2p, promoting stable redox on O2- , and thus enhancing stable cycling at high cut-off voltages. Meanwhile, LMP/LPO surface coating suppresses detrimental surface side reactions while allowing facile Li-ion diffusion. The mechanism of high-voltage cycling stability is investigated by combining experimental characterizations and theoretical calculations. This study proposes a strategy of surface-to-bulk simultaneous modification to achieve superior structural stability at high voltages.

Enhanced Hydrogen Detection Based on Mg-Doped InN Epilayer.

It is a fact that surface electron accumulation layer with sheet electron density in the magnitude of ~1013 cm−2 on InN, either as-grown or Mg-doped, makes InN an excellent candidate for sensing application. In this paper, the response of hydrogen sensors based on Mg-doped InN films (InN:Mg) grown by molecular beam epitaxy has been investigated. The sensor exhibits a resistance variation ratio of 16.8% with response/recovery times of less than 2 min under exposure to 2000 ppm H2/air at 125 °C, which is 60% higher in the magnitude of response than the one based on the as-grown InN film. Hall-effect measurement shows that the InN:Mg with suitable Mg doping level exhibits larger sheet resistance, which accords with buried p-type conduction in the InN bulk. This work shows the advantage of InN:Mg and signifies its potential for sensing application.

p-Type Doping of GaN Nanowires Characterized by Photoelectrochemical Measurements.

GaN nanowires (NWs) doped with Mg as a p-type impurity were grown on Si(111) substrates by plasma-assisted molecular beam epitaxy. In a systematic series of experiments, the amount of Mg supplied during NW growth was varied. The incorporation of Mg into the NWs was confirmed by the observation of donor-acceptor pairs and acceptor-bound excitons in low-temperature photoluminescence spectroscopy. Quantitative information about the Mg concentrations was deduced from Raman scattering by local vibrational modes related to Mg. In order to study the type and density of charge carriers present in the NWs, we employed two photoelectrochemical techniques, open-circuit potential and Mott-Schottky measurements. Both methods showed the expected transition from n-type to p-type conductivity with increasing Mg doping level, and the latter characterization technique allowed us to quantify the charge carrier concentration. Beyond the quantitative information obtained for Mg doping of GaN NWs, our systematic and comprehensive investigation demonstrates the benefit of photoelectrochemical methods for the analysis of doping in semiconductor NWs in general.

Poultry manure and sugarcane straw biochars modified with MgCl2 for phosphorus adsorption.

Increases in agricultural productivity associated to the crescent use of finite reserves of phosphorus improved the demand for ways to recycle and reuse this nutrient. Biochars, after doping processes, seem to be an alternative to mitigate the large use of P reserves. Sugarcane straw and poultry manure were submerged in an MgCl2 solution in a 1:10 solid/liquid ratio and subsequently pyrolyzed at 350 and 650 °C producing biochar. Increasing concentrations of P were agitated with biochars in order to obtain the maximum adsorption capacity of P with the aid of Langmuir and Freudelich isotherm. MPAC was extracted, successively, with H2SO4 (0.5 mol L-1), NaHCO3 (0.5 mol l-1 a pH 8.5) and H2O, until no P was detected in the solution. Biochars without the addition of Mg did not have the ability to adsorb P but had this property developed after the doping process. The poultry manure biochar presented higher MPAC (250.8 and 163.6 mg g-1 of P at 350 and 650 °C, respectively) than that of sugarcane straw (17.7 and 17.6 mg g-1 of P at 350 and 650 °C, respectively). The pyrolysis temperature changed significantly the MPAC values for the poultry manure biochar, with an increase in the adsorbed P binding energy for both biochars. H2SO4 showed the best extraction power, desorbing, with a lower number of extractions, the greater amount of the adsorbed P. These materials doped with Mg and subjected to pyrolysis have characteristics that allow their use in P adsorption from eutrophic and wastewaters and therefore its use as a slow release phosphate fertilizer, indicating to be competitive in quality and quantity with available soluble chemical sources in the market.

Magnesium-promoted rapid self-reconstruction of NiFe-based electrocatalysts toward efficient oxygen evolution.

The acceleration of active sites formation through surface reconstruction is widely acknowledged as the crucial factor in developing high-performance oxygen evolution reaction (OER) catalysts for water splitting. Herein, a simple one-step corrosion method and magnesium (Mg)-promoted strategy are reported to develop the NiFe-based catalyst with enhanced OER performance. The Mg is introduced in NiFe materials to preparate a "pre-catalyst" Mg-Ni/Fe2O3. In-situ Raman shows that Mg doping would accelerate the self-reconstruction of Ni/Fe2O3 to form active NiOOH species during OER. In-situ infrared indicates that Mg doping benefits the formation of *OOH intermediate. Theoretical analysis further confirms that Mg doping can optimize the adsorption of oxygen intermediates, accelerating the OER kinetics. Accordingly, the Mg-Ni/Fe2O3 catalyst exhibits excellent OER performance with overpotential of 168 mV at 10 mA cm-2. The anion exchange membrane water electrolyzer achieved 200 mA cm-2 at voltage of 1.53 V, showing excellent stability over 500 h as well. This work demonstrates the potential of Mg-promoted strategy in regulating the activity of transition metal-based OER electrocatalysts.

Green synthesis and characterization of polyphenol-coated magnesium-substituted manganese ferrite nanoparticles: Antibacterial and antioxidant properties.

Magnesium-substituted manganese ferrite (Mn0.9Mg0.1Fe2O4) nanoparticles were obtained through a wet chemical method and coated with green-extracted polyphenol from Punica granatum peel. The obtained spinel nanocomposite was fully characterized. The X-ray diffraction pattern revealed a single phase with an average crystalline size of 3.33-8.74 nm, confirming the cubic-spinel structure. The FESEM micrograph showed a quasi-spherical shape with nearly uniform particles, indicating mild agglomeration. The mean size of the Mn0.9Mg0.1Fe2O4 was 13.66 nm with a standard deviation of 2.05. The BET isotherms indicated a surface area of 85.45 m2/g. The basic groups attached to the external surface of Mg-doped spinel ferrite were discovered. The resulted superparamagnetic modified doped-nanoferrite particles showed antibacterial activity as well as antioxidant efficiency through studying Catalase (CAT), Glutathione (GSH), and Glutathione Peroxidase (GSH-Px) parameters. The outcomes highlight the promising potential of polyphenol-functionalized Mn0.9Mg0.1Fe2O4 magnetite nanosized particles for the development of novel anti-biofilm agents.

Li-Site Defects Induce Formation of Li-Rich Impurity Phases: Implications for Charge Distribution and Performance of LiNi0.5- xMxMn1.5O4 Cathodes (M = Fe and Mg; x = 0.05-0.2).

An understanding of the structural properties that allow for optimal cathode performance, and their origin, is necessary for devising advanced cathode design strategies and accelerating the commercialization of next-generation cathodes. High-voltage, Fe- and Mg-substituted LiNi0.5Mn1.5O4 cathodes offer a low-cost, cobalt-free, yet energy-dense alternative to commercial cathodes. In this work, the effect of substitution on several important structure properties is explored, including Ni/Mn ordering, charge distribution, and extrinsic defects. In the cation-disordered samples studied, a correlation is observed between increased Fe/Mg substitution, Li-site defects, and Li-rich impurity phase formation-the concentrations of which are greater for Mg-substituted samples. This is attributed to the lower formation energy of MgLi defects when compared to FeLi defects. Li-site defect-induced impurity phases consequently alter the charge distribution of the system, resulting in increased [Mn3+] with Fe/Mg substitution. In addition to impurity phases, other charge compensators are also investigated to explain the origin of Mn3+ (extrinsic defects, [Ni3+], oxygen vacancies and intrinsic off-stoichiometry), although their effects are found to be negligible.

Competing Mechanisms Determine Oxygen Redox in Doped Ni-Mn Based Layered Oxides for Na-Ion Batteries.

Cation doping is an effective strategy for improving the cyclability of layered oxide cathode materials through suppression of phase transitions in the high voltage region. In this study, Mg and Sc are chosen as dopants in P2-Na0.67Ni0.33Mn0.67O2, and both have found to positively impact the cycling stability, but influence the high voltage regime in different ways. Through a combination of synchrotron-based methods and theoretical calculations it is shown that it is more than just suppression of the P2 to O2 phase transition that is critical for promoting the favorable properties, and that the interplay between Ni and O activity is also a critical aspect that dictates the performance. With Mg doping, the Ni activity can be enhanced while simultaneously suppressing the O activity. This is surprising because it is in contrast to what has been reported in other Mn-based layered oxides where Mg is known to trigger oxygen redox. This contradiction is addressed by proposing a competing mechanism between Ni and Mg that impacts differences in O activity in Na0.67MgxNi0.33- xMn0.67O2 (x < 0 < 0.33). These findings provide a new direction in understanding the effects of cation doping on the electrochemical behavior of layered oxides.

P2/O3 Biphasic Cathode Material through Magnesium Substitution for Sodium-Ion Batteries.

P2-type Fe-Mn-based oxides offer excellent discharge specific capacity and are as affordable as typical layered oxide cathode materials for sodium-ion batteries (SIBs). After Cu modification, though they can improve the cycling performance and air stability, the discharge specific capacity will be reduced. Considering the complementary nature of biphasic phases in electrochemistry, hybridizing P2/O3 hybrid phases can enhance both the storage performance of the battery and specific capacity. Herein, a hybrid phase composite with high capacity and good cycle performance is deliberately designed and successfully prepared by controlling the amount of Mg doping in the layered oxide. It has been found that the introduction of Mg can activate anion redox in the oxide layer, resulting in a significant increase in the specific discharge capacity of the material. Meanwhile, the dual-phase structure can produce an interlocking effect, thus effectively alleviating structure strain. The degradation of cycling performance caused by structural damage during the high-voltage charging and discharging process is clearly mitigated. The results show that the specific discharge capacity of Na0.67Cu0.2Mg0.1Fe0.2Mn0.5O2 is as high as 212.0 mAh g-1 at 0.1C rate and 186.2 mAh g-1 at 0.2C rate. After 80 cycles, the capacity can still maintain 88.1%. Moreover, the capacity and cycle performance as well as the stability can still remain stable even in the high-voltage window. Therefore, this work offers an insightful exploration for the development of composite cathode materials for SIBs.

Enhanced Thermoelectric Performance of Mg-Doped AgSbTe2 by Inhibiting the Formation of Ag2Te.

The existence of Ag2Te has always been an obstacle for p-type thermoelectric material AgSbTe2 to improve its thermoelectric performance. In this work, AgSb1-xMgxTe2 samples are synthesized by melting-slow-cooling and then spark plasma sintering (SPS). Through increasing the solubility of Ag2Te in the AgSbTe2 matrix by Mg doping, the formation of Ag2Te is inhibited. Density functional theory calculations confirm more valence bands are involved in electrical transport due to Mg doping. Therefore, the electrical conductivity of AgSb1-xMgxTe2 samples has been greatly improved due to the reduction of Ag2Te with n-type electrical conductivity. Moreover, the downward trend of ZT, which is caused by the structural transition of Ag2Te at about 418 K, disappears. Meanwhile, lattice defects form in the AgSb0.98Mg0.02Te2 sample, and Mg doping improves the configurational entropy change, resulting in a decrease in lattice thermal conductivity over the entire temperature range of measurement. Finally, a high ZT value of 1.31 at 523 K is achieved for the AgSb0.98Mg0.02Te2 sample. This study demonstrates that Mg doping can effectively improve AgSbTe2 thermoelectric performance by inhibiting the formation of the Ag2Te impurity phase.

Increasing the Performance of {[(1-x-y) LiCo0.3Cu0.7] (Al and Mg doped)] O2}, xLi2MnO3, yLiCoO2 Composites as Cathode Material in Lithium-Ion Battery: Synthesis and Characterization.

Twenty-eight samples of {[(1-x-y) LiCo0.3Cu0.7](Al and Mg doped)]O2}, xLi2MnO3, and yLiCoO2 composites were synthesized using the sol-gel method. Stoichiometric weights of LiNO3, Mn(Ac)2⋅4H2O, Co(Ac)2⋅4H2O, Al(NO3)3.H2o, Mg(NO3)2⋅6H2O, and Cu(NO3)2.H2O for the preparation of these samples were applied. From this work, we confirmed the high performance of two samples, namely, Sample 18, including Al doped with structure "Li1.5Cu0.117Co0.366Al0.017Mn0.5O2" and Sample 17, including Mg doped with structure "Li1.667Cu0.1Mg0.017Co0.217Mn0.667O2", compared with other compositions. Evidently, the used weight of cobalt in these two samples were lower compared with LiCoO2, resulting in advantages in the viewpoint of cost and toxicity problems. Charge and discharge characteristics of the mentioned cathode materials were investigated by performing cycle tests in the range of 2.2-4.5 V. These types of systems can help to reduce the disadvantages of cobalt arising from its high cost and toxic properties. Our results confirmed that the performance of such systems is similar to that of pure LiCoO2 cathode material, or greater in some cases. The biggest disadvantages of LiCoO2 are its cost and toxic properties, typically making it cost around five times more to manufacture than when using copper.

Effects of Mg Doping to a LiCoO2 Channel on the Synaptic Plasticity of Li Ion-Gated Transistors.

Artificial synapses with ideal functionalities are essential in hardware neural networks to allow for energy-efficient analog computing. However, the realization of linear and symmetric weight updates in real synaptic devices has proven challenging and ultimately limits the online training capabilities of neural network systems. Herein, we investigate the effect of Mg doping on a LiCoO2 (LCO) channel in a Li ion-gated synaptic transistor, so as to improve long-term and short-term plasticity. Two transistor structures, based on a lithium phosphorus oxynitride electrolyte, were examined by using undoped LCO and Mg-doped LCO as the channel material between the source and drain electrodes. It was found that Mg doping increased the initial channel conductance by 3 orders of magnitude, which is probably due to the substitution of Co3+ by Mg2+ and the compensation of hole creation. It was further found that the doped channel transistor showed good retention characteristics and better linearity of long-term potentiation and depression when voltage pulses were applied to the gate electrode. The improved retention and linearity are attributed to an extended range of the insulator-to-conductor transition by Mg doping and Li-ion extraction/insertion cooperated in the LCO channel. Using the obtained synaptic weight update, artificial neural network simulations demonstrated that the doped channel transistor shows an image recognition accuracy of ∼80% for handwritten digits, which is higher than ∼65% exhibited by the undoped channel transistor. Mg doping also improved short-term plasticity such as paired-pulse facilitation/depression and Hebbian spike timing-dependent plasticity. These results indicate that elemental doping to the channel of Li ion-gated synaptic transistors could be a useful procedure for realizing robust neuromorphic systems based on analog computing.

Structural Evolution of Mg-Doped Single-Crystal LiCoO2 Cathodes: Importance of Morphology and Mg-Doping Sites.

Layered lithium cobalt oxide (LiCoO2, LCO), which serves as a structural motif for the widely adopted layered cathodes in lithium-ion batteries, has a long history, and its unstable phase transition during high-voltage operation (∼4.5 V) remains an intractable problem. Many research strategies, such as surface coating and immobile ion doping, have been proposed to address this issue, but a clear understanding of the effects has not been demonstrated because of various potential parameters (e.g., particle size, shape, and dopant content). Herein, we report a molten salt synthesis method that produces sphere-like single-crystal magnesium (Mg)-doped LCO. In situ X-ray diffraction and X-ray absorption fine structure analyses confirmed that the lattice strain was effectively alleviated by the effects of both the particle shape and Mg doping compared to the plate-like and sphere-like single-crystal LCO samples. Furthermore, the preference for Mg doping in the Co site (3b) rather than in the Li site (3a) in the LCO framework is systematically revealed, and a clear understanding of Mg doping that suppresses the monoclinic phase transition is discussed in detail.

Effect of Mg Doping on the Physical Properties of Fe2O3 Thin Films for Photocatalytic Devices.

Undoped and Mg-doped (y = [Mg2+]/[Fe3+] = 1, 2, 3, and 4 at.%) Fe2O3 thin films were synthesized by a simple spray pyrolysis technique. The thin films were extensively characterized. X-ray diffraction (XRD) and energy-dispersive spectroscopy (EDS) analysis confirmed the successful insertion of Mg in the rhombohedral structure of Fe2O3. In addition, scanning electronic microscope (SEM) and confocal microscope (CM) images showed a homogenous texture of the film, which was free of defects. The rough surface of the film obtained by spray pyrolysis is an important feature for photocatalysis and gas sensor applications. The direct band gap of the doped Fe2O3 films obtained for [Mg2+]/[Fe3+] = 3 at.% was Edir = 2.20 eV, which recommends the Mg-doped iron oxide as an optical window or buffer layer in solar cell devices. The photodegradation performance of Mg-doped Fe2O3 was assessed by studying the removal of methylene blue (MB) under sunlight irradiation, with an effective removal efficiency of 90% within 180 min. The excellent photodegradation activity was attributed to the strong absorption of Mg-doped Fe2O3 in the UV and most of the visible light, and to the effective separation of photogenerated charge carriers.

Uptake of arsenic(V) using iron and magnesium functionalized highly ordered mesoporous MCM-41 (Fe/Mg-MCM-41) as an effective adsorbent.

Mesoporous silica (MCM-41) is widely used as a supporting material due to its large specific surface area and good stability, but it cannot remove heavy metals due to the lack of adsorption active sites. In this study, the MCM-41 (a mesoporous SiO2 material) decorated with iron and magnesium oxide (Fe/Mg-MCM-41) was found to be an excellent adsorbent to remove arsenic(V) from water. FTIR, BET, TEM-EDS, XRD, XPS, etc. were applied for characterization analysis. Adsorption isotherms were fitted well by the Langmuir model and the experimental maximum adsorption capacity of Fe/Mg4-MCM-41 (magnesium accounts for 4%) was 71.53 mg/g at pH = 3. Thermodynamics analysis suggested exothermic nature of adsorption behavior. Kinetic process was well described by the pseudo-second-order model and adsorption rate was controlled by intraparticle diffusion and film diffusion. Moreover, the adsorption behavior of As(V) onto Fe/Mg4-MCM-41 was investigated under different reaction conditions, such as pH, temperature, Mg-doping and competing ions. The results showed that loading a certain amount of magnesium can significantly improve arsenic removal efficiency. Additionally, Fe/Mg4-MCM-41 exhibits high arsenic(V) removal in the wide pH range of 3-10. The Fe/Mg4-MCM-41 can be regenerated and used after four consecutive cycles. The high arsenic(V) sorption capacity, wide range of pH applications, ability to regenerate, and reusability of Fe/Mg4-MCM-41 confirmed that this adsorbent is promising for treating As-contaminated wastewater.

Multifractal analysis of Mg-doped ZnO thin films deposited by sol-gel spin coating method.

A multifractal analysis has been performed on the 3D (three-dimensional) surface microtexture of magnesium-doped zinc oxide (ZnO:Mg) thin films with doping concentration of 0, 2, 4, and 5%. Thin films were deposited onto the glass substrates via the sol-gel spin coating method. The effect of magnesium doping, on the crystal structure, morphology, and band gap for ZnO:Mg thin films has been analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and UV-Vis spectroscopy. It has been observed that the surface of ZnO thin films is multifractal in nature. However, multifractality and complexity observed to decrease with increasing content of Mg in ZnO thin films due to formation of islands on the surface in accordance with Volmer-Weber growth mechanism. The investigations revealed that crystallinity, microtexture, morphology, and optical properties of the thin films can be tuned by controlling the Mg content within the ZnO lattice. In particular, their optical band gap energies were 3.27, 3.31, 3.34, and 3.33 eV at 0, 2, 4, and 5%, respectively. The prepared thin films of ZnO:Mg with tuned characteristics would have promising applications in optoelectronic devices.

Transport Mechanisms and Dielectric Features of Mg-Doped ZnO Nanocrystals for Device Applications.

Magnesium-doped zinc oxide "ZnO:Mg" nanocrystals (NCs) were fabricated using a sol gel method. The Mg concentration impact on the structural, morphological, electrical, and dielectric characteristics of ZnO:Mg NCs were inspected. X-ray diffraction (XRD) patterns display the hexagonal wurtzite structure without any additional phase. TEM images revealed the nanometric size of the particles with a spherical-like shape. The electrical conductivity of the ZnO NCs, thermally activated, was found to be dependent on the Mg content. The impedance spectra were represented via a corresponding circuit formed by a resistor and constant phase element (CPE). A non-Debye type relaxation was located through the analyses of the complex impedance. The conductivity diminished with the incorporation of the Mg element. The AC conductivity is reduced by raising the temperature. Its plot obeys the Arrhenius law demonstrating a single activation energy during the conduction process. The complex impedance highlighted the existence of a Debye-type dielectric dispersion. The various ZnO:Mg samples demonstrate high values of dielectric constant with small dielectric losses for both medium and high-frequency regions. Interestingly, the Mg doping with 3% content exhibits colossal dielectric constant (more than 2 × 104) over wide temperature and frequency ranges, with Debye-like relaxation. The study of the electrical modulus versus the frequency and at different temperatures confirms the non-Debye relaxation. The obtained results reveal the importance of the ZnO:Mg NCs for device applications. This encourages their application in energy storage.

Effects of Mg Doping at Different Positions in Li-Rich Mn-Based Cathode Material on Electrochemical Performance.

Li-rich Mn-based layered oxides are among the most promising cathode materials for next-generation lithium-ion batteries, yet they suffer from capacity fading and voltage decay during cycling. The electrochemical performance of the material can be improved by doping with Mg. However, the effect of Mg doping at different positions (lithium or transition metals) remains unclear. Li1.2Mn0.54Ni0.13Co0.13O2 (LR) was synthesized by coprecipitation followed by a solid-state reaction. The coprecipitation stage was used to introduce Mg in TM layers (sample LR-Mg), and the solid-state reaction (st) was used to dope Mg in Li layers (LR-Mg(st)). The presence of magnesium at different positions was confirmed by XRD, XPS, and electrochemical studies. The investigations have shown that the introduction of Mg in TM layers is preferable in terms of the electrochemical performance. The sample doped with Mg at the TM positions shows better cyclability and higher discharge capacity than the undoped sample. The poor electrochemical properties of the sample doped with Mg at Li positions are due to the kinetic hindrance of oxidation of the manganese-containing species formed after activation of the Li2MnO3 component of the composite oxide. The oxide LR-Mg(st) demonstrates the lowest lithium-ion diffusion coefficient and the greatest polarization resistance compared to LR and LR-Mg.

Combining Surface Holistic Ge Coating and Subsurface Mg Doping to Enhance the Electrochemical Performance of LiNi0.8Co0.1Mn0.1O2 Cathodes.

Nickel-rich layered cathode LiNi0.8Co0.1Mn0.1O2 (NCM811) is the most promising cathode material due to its high specific capacity and lower cost than lithium cobalt oxides. However, NCM811 suffers from structural instability and capacity degradation during charge-discharge cycles. Herein, we report a strategy to construct a conductive network by employing a holistic Ge coating, which interconnects Mg-doped NCM811 particles. Dopant Mg ions, serving as a "pillar" in the Li slab of NCM811, substantially enhance the structural reversibility. The Ge particles are not only coated on the electrode surface but also enter into the electrode pores to form a multidimensional conductive structure, which improves the conductivity of the electrode and slows down the interface side reaction, thus minimizing the irreversible loss of NCM811 upon long cycling. The modified NCM811 electrode delivers a high discharge capacity (∼204 mAh g-1 at 0.1C), excellent rate performance (∼155 mAh g-1 at 10C), and high capacity retention (83% after 200 cycles) even at 4.4 V. Additionally, a cylindrical full battery with graphite/modified NCM811 undergoes 1000 cycles with 86% capacity retention at 2C.

Unraveling the Synergistic Effect of Mg and Ti Codoping to Realize an Ordered Structure and Excellent Performance for Sodium-Ion Batteries.

Layered cathodes have been recognized as potential advanced candidates for sodium-ion batteries (SIBs), but the poor electrochemical performance has seriously hindered their further development. Herein, an ordered Na2/3[Ni2/9Mg1/9Mn5/9Ti1/9]O2 (NMMT) is designed and investigated as a high-performance cathode for SIBs through the synergistic effect of Mg and Ti codoping. Compared to the single Mg- or Ti-doped materials, NMMT clearly exhibits superstructure ordering diffraction peaks, and neutron diffraction further confirms that the diffraction peaks can be well indexed by a larger supercell P63, rather than the common unit cell P63/mmc by X-ray diffraction (XRD). High-resolution transmission electron microscopy also approves the ordering arrangement. This material shows an obvious capacity activation process during the first cycles, thus delivering 113 mA h g-1 specific capacity at 0.1 C (close to the theoretical value). Excellent rate capability even at 15 C and cycling stability after 500 cycles between 2.0 and 4.3 V can also be achieved, indicating that an ordered cathode is still promising. Besides, a single-phase reaction mechanism is revealed by ex situ/in situ XRD experiments. This study offers some insights into the material design and characterization of layered oxide cathodes for high-performance SIBs in the future.