Three Birds with One Stone: Multifunctional TiN-MXene-Co@CNTs Network as Sulfur/Lithium Host for High-Areal-Capacity Lithium-Sulfur Batteries.

The inevitable shuttling and slow redox kinetics of lithium polysulfides (LiPSs) as well as the uncontrolled growth of Li dendrites have strongly limited the practical applications of lithium-sulfur batteries (LSBs). To address these issues, we have innovatively constructed the carbon nanotubes (CNTs) encapsulated Co nanoparticles in situ grown on TiN-MXene nanosheets, denoted as TiN-MXene-Co@CNTs, which could serve simultaneously as both sulfur/Li host to kill "three birds with one stone" to (1) efficiently capture soluble LiPSs and expedite their redox conversion, (2) accelerate nucleation/decomposition of solid Li2S, and (3) induce homogeneous Li deposition. Benefiting from the synergistic effects, the TiN-MXene-Co@CNTs/S cathode with a sulfur loading of 2.5 mg cm-2 could show a high reversible specific capacity of 1129.1 mAh g-1 after 100 cycles at 0.1 C, and ultralong cycle life over 1000 cycles at 1.0 C. More importantly, it even achieves a high areal capacity of 6.3 mAh cm-2 after 50 cycles under a sulfur loading as high as 8.9 mg cm-2 and a low E/S ratio of 5.0 µL mg-1. Besides, TiN-MXene-Co@CNTs as Li host could deliver a stable Li plating/striping behavior over 1000 h.

Dynamic Modulation of Li2O2 Growth in Li-O2 Batteries through Regulating Oxygen Reduction Kinetics with Photo-Assisted Cathodes.

Widely acknowledged that the capacity of Li-O2 batteries (LOBs) should be strongly determined by growth behaviors of the discharge product of lithium peroxide (Li2O2) that follows both coexisting surface and solution pathways. However until now, it remains still challenging to achieve dynamic modulation on Li2O2 morphologies. Herein, the photo-responsive Au nanoparticles (NPs) supported on reduced oxide graphene (Au/rGO) have been utilized as cathode to manipulate oxygen reduction reaction (ORR) kinetics by aid of surface plasmon resonance (SPR) effects. Thus, we can experimentally reveal the importance of matching ORR kinetics with Li+ migration towards battery performance. Moreover, it is found that Li+ concentration polarization caused "sudden death" of LOBs is supposed to be just a form of suspended animation that could timely recover under irradiation. This work provides us an in-depth explanation on the working mechanism of LOBs from a kinetic perspective, offering valuable insights for the future battery design.

Controllable Crystallization of Two-Dimensional Bi Nanocrystals with Morphology-Boosted CO2 Electroreduction in Wide pH Environments.

Two-dimensional low-melting-point (LMP) metal nanocrystals are attracting increasing attention with broad and irreplaceable applications due to their unique surface and topological structures. However, the chemical synthesis, especially the fine control over the nucleation (reduction) and growth (crystallization), of such LMP metal nanocrystals remains elusive as limited by the challenges of low standard redox potential, low melting point, poor crystalline symmetry, etc. Here, a controllable reduction-melting-crystallization (RMC) protocol to synthesize free-standing and surfactant-free bismuth nanocrystals with tunable dimensions, morphologies, and surface structures is presented. Especially, ultrathin bismuth nanosheets with flat or jagged surfaces/edges can be prepared with high selectivity. The jagged bismuth nanosheets, with abundant surface steps and defects, exhibit boosted electrocatalytic CO2 reduction performances in acidic, neutral, and alkaline aqueous solutions, achieving the maximum selectivity of near unity at the current density of 210 mA cm-2 for formate evolution under ambient conditions. This work creates the RMC pathway for the synthesis of free-standing two-dimensional LMP metal nanomaterials and may find broader applicability in more interdisciplinary applications.

Identification of Dynamic Active Sites Among Cu Species Derived from MOFs@CuPc for Electrocatalytic Nitrate Reduction Reaction to Ammonia.

Direct electrochemical nitrate reduction reaction (NITRR) is a promising strategy to alleviate the unbalanced nitrogen cycle while achieving the electrosynthesis of ammonia. However, the restructuration of the high-activity Cu-based electrocatalysts in the NITRR process has hindered the identification of dynamical active sites and in-depth investigation of the catalytic mechanism. Herein, Cu species (single-atom, clusters, and nanoparticles) with tunable loading supported on N-doped TiO2/C are successfully manufactured with MOFs@CuPc precursors via the pre-anchor and post-pyrolysis strategy. Restructuration behavior among Cu species is co-dependent on the Cu loading and reaction potential, as evidenced by the advanced operando X-ray absorption spectroscopy, and there exists an incompletely reversible transformation of the restructured structure to the initial state. Notably, restructured CuN4&Cu4 deliver the high NH3 yield of 88.2 mmol h-1 gcata-1 and FE (~ 94.3%) at - 0.75 V, resulting from the optimal adsorption of NO3- as well as the rapid conversion of *NH2OH to *NH2 intermediates originated from the modulation of charge distribution and d-band center for Cu site. This work not only uncovers CuN4&Cu4 have the promising NITRR but also identifies the dynamic Cu species active sites that play a critical role in the efficient electrocatalytic reduction in nitrate to ammonia.

In Situ Fabrication of Porous Cox P Hierarchical Nanostructures on Carbon Fiber Cloth with Exceptional Performance for Sodium Storage.

Superior high-rate performance and ultralong cycling life have been constantly pursued for rechargeable sodium-ion batteries (SIBs). In this work, a facile strategy is employed to successfully synthesize porous Cox P hierarchical nanostructures supported on a flexible carbon fiber cloth (Cox P@CFC), constructing a robust architecture of ordered nanoarrays. Via such a unique design, porous and bare structures can thoroughly expose the electroactive surfaces to the electrolyte, which is favorable for ultrafast sodium-ion storage. In addition, the CFC provides an interconnected 3D conductive network to ensure firm electrical connection of the electrode materials. Besides the inherent flexibility of the CFC, the integration of the hierarchical structures of Cox P with the CFC, as well as the strong synergistic effect between them, effectively help to buffer the mechanical stress caused by repeated sodiation/desodiation, thereby guaranteeing the structural integrity of the overall electrode. Consequently, Cox P@CFC as an anode shows a record-high capacity of 279 mAh g-1 at 5.0 A g-1 with almost no capacity attenuation after 9000 cycles.

Insight into the effects of dislocations in nanoscale titanium niobium oxide (Ti2Nb14O39) anode for boosting lithium-ion storage.

Defect engineering through induction of dislocations is an efficient strategy to design and develop an electrode material with enhanced electrochemical performance in energy storage technology. Yet, synthesis, comprehension, identification, and effect of dislocation in electrode materials for lithium-ion batteries (LIBs) are still elusive. Herein, we propose an ethanol-thermal method mediated with surfactant-template and subsequent annealing under air atmosphere to induce dislocation into titanium niobium oxide (Ti2Nb14O39), resultant nanoscale-dislocated-Ti2Nb14O39 (Nano-dl-TNO). High-resolution transmission electron microscope (HRTEM), fast Fourier transform (FFT), and Geometrical phase analysis (GPA) denote that the high dislocation density engraved with stacking faults forms into the Ti2Nb14O39 lattice. The presence of dislocation could offer an additional active site for lithium-ion storage and tune the electrical and ionic properties of the Ti2Nb14O39. The resultant Nano-dl-TNO delivers superior rate capability, high specific capacity, better cycling stability, and making Ti2Nb14O39 a suitable candidate among fast-charging anode materials for lithium-ion batteries. Moreover, In-situ High-resolution transmission electron microscope (HRTEM) and Geometrical phase analysis (GPA) evinces that the removal of the dislocated area in the Nano-dl-TNO leads to the contraction of the lattice, alleviation of the total volume expansion, causing the symmetrization and preserves structural stability. The present findings and designed approach reveal the rose-colored perspective of dislocation engineering into mixed transition metal oxides as next-generation anodes for advanced lithium-ion batteries and all-solid-state lithium-ion batteries.

Graphdiyne/Graphene/Graphdiyne Sandwiched Carbonaceous Anode for Potassium-Ion Batteries.

Graphdiyne (GDY) has been considered as an appealing anode candidate for K-ion storage since its triangular pore channel, alkyne-rich structure, and large interlayer spacing would endow it with abundant active sites and ideal diffusion paths for K-ions. Nevertheless, the low surface area and disordered structure of bulk GDY typically lead to unsatisfied K storage performance. Herein, we have designed a GDY/graphene/GDY (GDY/Gr/GDY) sandwiched architecture affording a high surface area and fine quality throughout a van der Waals epitaxy strategy. As tested in a half-cell configuration, the GDY/Gr/GDY electrode exhibits better capacity output, rate capability, and cyclic stability as compared to the bare GDY counterpart. In situ electrochemical impedance spectroscopy/Raman spectroscopy/transmission electron microscopy are further applied to probe the K-ion storage feature and disclose the favorable reversibility of GDY/Gr/GDY electrode during repeated potassiation/depotassiation. A full-cell device comprising a GDY/Gr/GDY anode and a potassium Prussian blue cathode enables a high cycling stability, demonstrative of the promising potential of the GDY/Gr/GDY anode for K-ion batteries.

Novel Bake-in-Salt Method for the Synthesis of Mesoporous Mn3O4@C Networks with Superior Cycling Stability and Rate Performance.

The commercial applications of Mn3O4 in lithium ion batteries (LIBs) are greatly restricted because of the low electrical conductivity and poor cycling stability at high current density. To overcome these drawbacks, mesoporous Mn3O4@C networks were designed and synthesized via an improved bake-in-salt method using NaCl as the assistant salt, and without the protection of inert gas. The added NaCl plays a versatile role during the synthetic process, including the heat conducting medium, removable hard template and protective layer. Because of the homogeneous distribution of Mn3O4 nanoparticles within the carbon matrix, the as-prepared Mn3O4@C networks show excellent cycling stability in LIBs. After cycling for 950 times at a current density of 1 A g-1, the discharge capacity of the as-prepared Mn3O4@C networks is determined to be 754.4 mA h g-1, showing superior cycling stability as compared to its counterparts. The valuable and promising method, simple synthetic procedure and excellent cycling stability of the as-prepared Mn3O4@C networks makes it a promising candidate as the potential anode material for LIBs.