Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Sandwich-like Catalyst–Carbon–Catalyst Trilayer Structure as a Compact 2D Host for Highly Stable Lithium–Sulfur Batteries

Herein, we propose the construction of a sandwich-structured host filled with continuous 2D catalysis–conduction interfaces. This MoN-C-MoN trilayer architecture causes the strong conformal adsorption of S/Li₂S_x and its high-efficiency conversion on the two-sided nitride polar surfaces, which are supplied with high-flux electron transfer from the buried carbon interlayer. The 3D self-assembly of these 2D sandwich structures further reinforces the interconnection of conductive and catalytic networks. The maximized exposure of adsorptive/catalytic planes endows the MoN-C@S electrode with excellent cycling stability and high rate performance even under high S loading and low host surface area. The high conductivity of this trilayer texture does not compromise the capacity retention after the S content is increased. Such a job-synergistic mode between catalytic and conductive functions guarantees the homogeneous deposition of S/Li₂S_x, and avoids thick and devitalized accumulation (electrode passivation) even after high-rate and long-term cycling.     

Achieving Rich and Active Alkaline Hydrogen Evolution Heterostructures via Interface Engineering on 2D 1T‐MoS2 Quantum Sheets

Large‐scale production of hydrogen from water‐alkali electrolyzers is impeded by the sluggish kinetics of hydrogen evolution reaction (HER) electrocatalysts. The hybridization of an acid‐active HER catalyst with a cocatalyst at the nanoscale helps boost HER kinetics in alkaline media. Here, it is demonstrated that 1T–MoS₂ nanosheet edges (instead of basal planes) decorated by metal hydroxides form highly active ${\text{edge}}_{{\text{1T‐MoS}}_{\text{2}}}$/ ${\text{edge}}_{\text{Ni}{(\text{OH})}_{\text{2}}}$ heterostructures, which significantly enhance HER performance in alkaline media. Featured with rich ${\text{edge}}_{{\text{1T‐MoS}}_{\text{2}}}$/ ${\text{edge}}_{\text{Ni}{(\text{OH})}_{\text{2}}}$ sites, the fabricated 1T–MoS₂ QS/Ni(OH)₂ hybrid (quantum sized 1T–MoS₂ sheets decorated with Ni(OH)₂ via interface engineering) only requires overpotentials of 57 and 112 mV to drive HER current densities of 10 and 100 mA cm^?2, respectively, and has a low Tafel slope of 30 mV dec^?1 in 1 m KOH. So far, this is the best performance for MoS₂‐based electrocatalysts and the 1T–MoS₂ QS/Ni(OH)₂ hybrid is among the best‐performing non‐Pt alkaline HER electrocatalysts known. The HER process is durable for 100 h at current densities up to 500 mA cm^?2. This work not only provides an active, cost‐effective, and robust alkaline HER electrocatalyst, but also demonstrates a design strategy for preparing high‐performance catalysts based on edge‐rich 2D quantum sheets for other catalytic reactions.     

Interlayer Engineering of Molybdenum Trioxide toward High‐Capacity and Stable Sodium Ion Half/Full Batteries

Orthorhombic molybdenum trioxide (MoO₃) is one of the most promising anode materials for sodium‐ion batteries because of its rich chemistry associated with multiple valence states and intriguing layered structure. However, MoO₃ still suffers from the low rate capability and poor cycle induced by pulverization during de/sodiation. An ingenious two‐step synthesis strategy to fine tune the layer structure of MoO₃ targeting stable and fast sodium ionic diffusion channels is reported here. By integrating partially reduction and organic molecule intercalation methodologies, the interlayer spacing of MoO₃ is remarkably enlarged to 10.40 Å and the layer structural integration are reinforced by dimercapto groups of bismuththiol molecules. Comprehensive characterizations and density functional theory calculations prove that the intercalated bismuththiol (DMcT) molecules substantially enhanced electronic conductivity and effectively shield the electrostatic interaction between Na⁺ and the MoO₃ host by conjugated double bond, resulting in improved Na⁺ insertion/extraction kinetics. Benefiting from these features, the newly devised layered MoO₃ electrode achieves excellent long‐term cycling stability and outstanding rate performance. These achievements are of vital significance for the preparation of sodium‐ion battery anode materials with high‐rate capability and long cycling life using intercalation chemistry.     

A Complexing Agent to Enable a Wide-Temperature Range Bromine-Based Flow Battery for Stationary Energy Storage

Bromine-based flow batteries (Br-FBs) are considered one of the most promising energy storage systems due to their features of high energy density and low cost. However, they generally suffer from uncontrolled diffusion of corrosive bromine particularly at high temperatures. That is because the interaction between polybromide anions and the commonly used complexing agent (N–methyl–N–ethyl–pyrrolidinium bromide [MEP]) decreases with increasing temperatures, which causes serious self-discharge and capacity fade. Herein, a novel bromine complexing agent, 1–ethyl–2–methyl–pyridinium bromide (BCA), is introduced in Br-FBs to solve the above problems. It is proven that BCA can combine with polybromide anions very well even at a high temperature of 60 °C. Moreover, the BCA contributes to decreasing the electrochemical polarization of Br⁻/Br₂ couple, which in turn improves their power density. As a result, a zinc–bromine flow battery with BCA as the complexing agent can achieve a high energy efficiency of 84% at 40 mA cm⁻², even at high temperature of 60 °C and it can stably run for more than 400 cycles without obvious performance decay. This paper provides an effective complexing agent to enable a wide temperature range Br-FB.     

Rational Designs for Lithium-Sulfur Batteries with Low Electrolyte/Sulfur Ratio

Lithium-sulfur batteries (LSBs) are considered a promising next-generation energy storage device owing to their high theoretical energy density. However, their overall performance is limited by several critical issues such as lithium polysulfide (PS) shuttles, low sulfur utilization, and unstable Li metal anodes. Despite recent huge progress, the electrolyte/sulfur ratio (E/S) used is usually very high (≥20 µL mg⁻¹), which greatly reduces the practical energy density of devices. To push forward LSBs from the lab to the industry, considerable attention is devoted to reducing E/S while ensuring the electrochemical performance. To date, however, few reviews have comprehensively elucidated the possible strategies to achieve that purpose. In this review, recent advances in low E/S cathodes and anodes based on the issues resulting from low E/S and the corresponding solutions are summarized. These will be beneficial for a systematic understanding of the rational design ideas and research trends of low E/S LSBs. In particular, three strategies are proposed for cathodes: preventing PS formation/aggregation to avoid inadequate dissolution, designing multifunctional macroporous networks to address incomplete infiltration, and utilizing an imprison strategy to relieve the adsorption dependence on specific surface area. Finally, the challenges and future prospects for low E/S LSBs are discussed.     

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

Functionalized Silver-Ion-Mediated α-dC/β-dC Hybrid Base Pairs with Exceptional Stability: α-d-5-Iodo-2′-Deoxycytidine and Its Octadiynyl Derivative in Metal DNA

Silver-mediated α-dC–Ag⁺–β-dC hybrid base pairs decorated with 5-iodo- or 5-octadiynyl residues are well accommodated in duplex DNA. A strong T_m increase and favorable thermodynamic data for duplex DNA were observed after addition of silver ions. The phenomenon is particularly obvious when both nucleobases of the base pairs are functionalized. Neither the position of the base pair, nor the type of 5-substituent had a negative influence. On the contrary, functionalization of conventional silver-mediated β-dC–Ag⁺–β-dC homo base pairs showed a negative impact induced by the bulky substituents. To this end, cytosine modified 12-mer oligodeoxynucleotides were prepared by solid-phase synthesis employing new α-anomeric 2′-deoxycytidine phosphoramidites. A multigram scale synthesis was developed for 5-iodo-α-d -2′-deoxycytidine ( 1 ) employing the direct glycosylation of cytosine with Hoffer's α-d -halogenose followed by separation of anomeric DMT nucleosides. Regarding base-pair stability and functionalization silver-mediated α/β-dC hybrid base pairs were found to be superior to β/β-dC homo pairs. According to their extraordinary properties, they might find applications in DNA diagnostics, material science, or nanotechnology.     

Single-Crystalline TiO2(B) Nanobelts with Unusual Large Exposed {100} Facets and Enhanced Li-Storage Capacity

The {100} facet of single-crystalline TiO₂(B) is an ideal platform for inserting Li ions, but it is hard to be obtained due to its high surface energy. Here, the single-crystalline TiO₂(B) nanobelts from H₂Ti₃O₇ with nearly 70% {100} facets exposed are synthesized, which significantly enhances Li-storage capacity. The first-principle calculations demonstrate an ab in-plane 2D diffusion through the exposed {100} facets. As a consequence, the nanobelts can significantly accommodate Li ions in LiTiO₂ formula with specific capacity up to 335 mAh g⁻¹, which is in good agreement with the electrochemical characterizations. Coating with conductive and protective poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate), the cut-off discharge voltage is as low as 0.5 V, leading to a capacity of 160.7 mAh g⁻¹ after 1500 cycles with a retention rate of 66% at 1C. This work provides a practical strategy to increase the Li-ion capacity and cycle stability by tailoring the crystal orientation and nanostructures.