Stabilizing NASICON-type Na4MnCr(PO4)3 by Ti-substitution toward a high-voltage cathode material for sodium ion batteries.

The sodium superionic conductor Na4MnCr(PO4)3 gains increasing attention owing to its three-dimensional structure and the three-electron reaction. However, rapid structure degradation during cycling is the major challenge for its practical application. Herein, Ti4+ is utilized to replace a portion of Mn2+ in Na4MnCr(PO4)3. The low redox voltage and d0 electronic configuration of the Ti4+ ions are helpful to suppress the structure alteration and improve electronic conduction. Consequently, the as-prepared Na3.4Mn0.7Ti0.3Cr(PO4)3/C cathode exhibits a remarkable good 91.0% capacity retention after 500 cycles at 10C rate, with exceptional rate capacities of 99.5 mAh g-1 and 81.0 mAh g-1 at 5C and 10C rate, respectively. Furthermore, based on ≈2.86-electron reactions involving Mn2+/Mn3+ (3.5 V), Mn3+/Mn4+ (4.1 V), Cr3+/Cr4+ (4.3 V), and Ti3+/Ti4+ (2.1 V), the material can provide an energy density of approximately 541.6 Wh kg-1, slightly surpassing that of Na4MnCr(PO4)3. Ex-situ XRD investigation further elucidates that throughout the entire charge-discharge process, the Ti-substituted material experiences highly reversible solid-solution and two-phase reactions. Additionally, Ti substitution can greatly promote the interfacial charge transfer of the material and suppress the decomposition of the electrolyte during cycling. This work might open a new insight for designing sodium-ion battery cathode materials with good cycling stability and high energy density.

Microwave-Assisted Rapid Substitution of Ti for Zr to Produce Bimetallic (Zr/Ti)UiO-66-NH2 with Congenetic "Shell-Core" Structure for Enhancing Photocatalytic Removal of Nitric Oxide.

Efficient nitric oxide (NO) removal without nitrogen dioxide (NO2 ) emission is desired for the control of air pollution. Herein, a series of (Zr/Ti)UiO-66-NH2 with congenetic shell-core structure, denoted as Ti-UION, are rapidly synthesized by microwave-assisted post-synthetic modification for NO removal. The optimal Ti-UION (i.e., 2.5Ti-UION) exhibits the highest activity of 80.74% without NO2 emission with moisture, which is 21.65% greater than that of the UiO-66-NH2 . The NO removal efficiency of 2.5Ti-UION further increases to 95.92% without photocatalyst deactivation under an anhydrous condition. This is because selectively produced NO2 in photocatalysis is completely adsorbed into micropores, refreshing active sites for subsequent reaction. In addition, the enhanced photocatalytic activity after Ti substitution is due to the presence of Ti electron acceptor, the potential difference between the shell and core of Ti-UION crystal, and the high conductivity of TiO units. Additionally, the improved adsorption of gas molecules not only favors NO oxidation, but also avoids the emission of NO2 . This work provides a feasible strategy for rapid metal substitution in metal-organic frameworks and insights into enhanced NO photodegradation.

Ti-substituted O3-type layered oxide cathode material with high-voltage stability for sodium-ion batteries.

O3-type layered transition metal oxides (NaxTMO2) have attracted extensive attention as a promising cathode material for sodium-ion batteries because of their high capacity. However, the irreversible phase transition especially cycled under high voltage remains a concerning challenge for NaxTMO2. Herein, a Ti-substituted NaNi0.5Co0.2Mn0.3O2 cathode with strongly suppressed phase transition and enhanced storage stability is investigated. The Ti substitution effectively inhibits the irreversible phase transition and alleviates the structural change even charged to 4.3 V during the repeated Na+ deintercalation process. After storing in air or water, the original O3 phase structure of the material is integrally maintained without the generation of impurity phase. As a result, the as-prepared material shows excellent long-term cycle stability and rate performance when charged to a high voltage of 4.3 V.

Deciphering the Origin of High Electrochemical Performance in a Novel Ti-Substituted P2/O3 Biphasic Cathode for Sodium-Ion Batteries.

The layered Mn-based oxides (NaxMnO2), which is one of the most promising cathode families for rechargeable sodium-ion batteries, have received considerable attention because of their tunable electrochemical performances and low costs. Herein, a novel P2/O3 intergrown Li-containing Na0.8Li0.27Mn0.68Ti0.05O2 cathode material prepared by Ti-substitution into Mn-site is reported. Benefiting from the synergistic effects of the biphasic composite structure and inactive d0 element substitution, this P2/O3 electrode exhibits high initial charge/discharge capacity and excellent cycling performance. The combination of different characterization techniques including solid-state NMR, electron paramagnetic resonance, X-ray adsorption spectroscopy, and high-resolution transmission electron microscopy gives insights into the local electronic environment, the redox chemistry, and also the microstructure rigidity of these cathode materials upon cycling. On the basis of comprehensive comparison with the Ti-free P2/O3-Na0.8Li0.27Mn0.73O2, the observed improvement on the electrochemical performance is primarily attributed to the mitigation of notorious Mn3+/Mn4+ redox and the enhanced stability of the oxygen charge compensation behavior. From the viewpoint of structure evolution, Ti-substitution restrains the Li+ loss and irreversible structural degradation during cycling. This study provides an in-depth understanding of the electronic and crystal structure evolutions after inactive d0 element substitution and may shed light on the rational design of high-performance P2/O3 biphasic Mn-based layered cathodes.

Critical Role of Titanium in O3-Type Layered Cathode Materials for Sodium-Ion Batteries.

Recently, the substitution of inactive elements has been reported as a promising strategy for improving the structural stability and electrochemical performance of layered cathode materials for sodium-ion batteries (SIBs). In this regard, we investigated the positive effects of inactive Ti substitution into O3-type NaFe0.25Ni0.25Mn0.5O2 based on first-principles calculations and electrochemical experiments. After Ti substitution, Na[Ti0.03(Fe0.25Ni0.25Mn0.5)0.97]O2 exhibits improved capacity retention and rate capability compared with Ti-free NaFe0.25Ni0.25Mn0.5O2. Such an improvement is primarily attributed to the enhanced structural stability and lowered activation energy for Na+ migration, which is induced by Ti substitution in the host structure. Based on first-principles calculations of the average net charges and partial densities of states, we suggest that Ti substitution effectively enhances the binding between transition metals and oxygen by increasing the oxygen electron density, which in turn lowers the energy barrier of Na+ migration, leading to a notable enhancement in the rate capability of Na[Ti0.03(Fe0.25Ni0.25Mn0.5)0.97]O2. Compared with other inactive elements (e.g., Al and Mg), Ti is a more suitable substituent for improving the electrochemical properties of layered cathode materials because of its large total charge variation contributing to capacity. The results of this study provide practical guidelines for developing highly reliable layered cathode materials for SIBs.

Improving the Electrochemical Performance and Structural Stability of the LiNi0.8Co0.15Al0.05O2 Cathode Material at High-Voltage Charging through Ti Substitution.

LiNi0.8Co0.15Al0.05O2 (NCA) has been proven to be a good cathode material for lithium-ion batteries (LIBs), especially in electric vehicle applications. However, further elevating energy density of NCA is very challenging. Increasing the charging voltage of NCA is an effective method, but its structural instability remains a problem. In this work, we revealed that titanium substitution could improve cycle stability of NCA under high cutoff voltage significantly. Titanium ions with a relatively larger ion radius could modify the oxygen lattice and change the local coordination environment of NCA, leading to decreased cation migration, better kinetic and thermodynamic properties, and improved structural stability. As a result, the Ti-substituted NCA cathode exhibits impressive reversible capacity (198 mA h g-1 at 0.1C) with considerable cycle stability under a cutoff voltage up to 4.7 V. It is also revealed that Ti could suppress oxygen release in the high-voltage region, benefitting cycle and thermal stabilities. This work provides valuable insight into the design of high-voltage layered cathode materials for high-energy-density LIBs.

Improving the electrochemical performance of layered cathode oxide for sodium-ion batteries by optimizing the titanium content.

P2-type transition metal oxides are promising cathode materials for sodium-ion batteries. However, due to irreversible phase transition, these batteries exhibit low capacity and poor cycling stability. In this study, highly dense, spherical P2-type oxides Na0.67[Ni0.167Co0.167Mn0.67]1-xTixO2 (0 ≤ x ≤ 0.4) are synthesized by calcining a mixture of Na2CO3, spherical ternary precursor powder Ni0.167Co0.167Mn0.67O2, and different amounts of nanoscale TiO2. High-temperature X-ray diffraction results obtained during calcination reveal 850 °C as the optimum calcination temperature. All materials exhibit high crystallinity without any impurity phases. The initial reversible capacities of the as-prepared samples decrease with increasing Ti substitution; however, these samples attain better cycling stability. When x = 0.2, the sample delivers an initial discharge capacity of 138 mAh g-1 at 20 mA g-1 between 2 and 4.5 V. Even at 100 mA g-1, the sample delivers 101 mAh g-1 reversible capacity in the first cycle with capacity retention of 89.4% after 300 cycles. Moreover, the material shows sloping potential profiles, with the average voltages reaching up to ∼3.8 V. The ex-situ X-ray diffraction (XRD) results of the samples after cycling demonstrate that Ti substitution improves the structural stability. In general, Ti substitution is an effective approach for improving the electrochemical performance of ternary P2-type oxide Na0.67Ni0.167Co0.167Mn0.67O2.