Highly-solvating Electrolyte Enables Mechanically Stable and Inorganic-rich Cathode Electrolyte Interphase for High-performing Potassium-ion Batteries.

Cathode-electrolyte interphase (CEI) is crucial for the reversibility of rechargeable batteries, yet receives less attention compared to solid-electrolyte interphase (SEI). The prevalent weakly-solvating electrolyte is usually proposed from the standing point of obtaining robust SEI, however, the resultant weak ion-solvent interaction gives rise to excessive free solvents and forms thick CEI with high kinetic barriers, which is disadvantageous for interfacial stability at the high working voltage. Herein, we report a highly-solvating electrolyte to immobilize free solvents by generating stable ternary complexes and facilitate the growth of homogeneous and ultrathin CEI to boost the electrochemical performances of potassium-ion batteries (PIBs). Through time-of-flight secondary ion mass spectrometry and cryogenic transmission electron microscopy, we reveal that the deliberately coordinated complexes are the key to forming mechanically stable and inorganic-rich CEI with superior diffusion kinetics for high-performing PIBs. Coupling with a K0.5MnO2 cathode and a soft carbon (SC) anode, we achieve a high energy density (202.3 Wh kg-1) with an exceptional cycle lifespan (92.5% capacity retention after 500 cycles) in a SC||K0.5MnO2 full cell, setting new performance benchmarks for PIBs. This article is protected by copyright. All rights reserved.

Strong d-π Orbital Coupling of Co-C4 Atomic Sites on Graphdiyne Boosts Potassium-Sulfur Battery Electrocatalysis.

Potassium-sulfur (K-S) batteries are severely limited by the sluggish kinetics of the solid-phase conversion of K2S3/K2S2 to K2S, the rate-determining and performance-governing step, which urgently requires a cathode with facilitated sulfur accommodation and improved catalytic efficiency. To this end, we leverage the orbital-coupling approach and herein report a strong d-π coupling catalytic configuration of single-atom Co anchored between two alkynyls of graphdiyne (Co-GDY). The d-π orbital coupling of the Co-C4 moiety fully redistributes electrons two-dimensionally across the GDY, and as a result, drastically accelerates the solid-phase K2S3/K2S2 to K2S conversion and enhances the adsorption of sulfur species. Applied as the cathode, the S/Co-GDY delivered a record-high rate performance of 496.0 mAh g-1 at 5 A g-1 in K-S batteries. In situ and ex situ characterizations coupling density functional theory (DFT) calculations rationalize how the strong d-π orbital coupling of Co-C4 configuration promotes the reversible solid-state transformation kinetics of potassium polysulfide for high-performance K-S batteries.

Dual-Salt Electrolyte Additive Enables High Moisture Tolerance and Favorable Electric Double Layer for Lithium Metal Battery.

The carbonate electrolyte chemistry is a primary determinant for the development of high-voltage lithium metal batteries (LMBs). Unfortunately, their implementation is greatly plagued by sluggish electrode interfacial dynamics and insufficient electrolyte thermodynamic stability. Herein, lithium trifluoroacetate-lithium nitrate (LiTFA-LiNO3 ) dual-salt additive-reinforced carbonate electrolyte (LTFAN) is proposed for stabilizing high-voltage LMBs. We reveal that 1) the in situ generated inorganic-rich electrode-electrolyte interphase (EEI) enables rapid interfacial dynamics, 2) TFA- preferentially interacts with moisture over PF6 - to strengthen the moisture tolerance of designed electrolyte, and 3) NO3 - is found to be noticeably enriched at the cathode interface on charging, thus constructing Li+ -enriched, solvent-coordinated, thermodynamically favorable electric double layer (EDL). The superior moisture tolerance of LTFAN and the thermodynamically stable EDL constructed at cathode interface play a decisive role in upgrading the compatibility of carbonate electrolyte with high-voltage cathode. The LMBs with LTFAN realize 4.3 V-NCM523/4.4 V-NCM622 superior cycling reversibility and excellent rate capability, which is the leading level of documented records for carbonate electrode.

Fluorination of Covalent Organic Framework Reinforcing the Confinement of Pd Nanoclusters Enhances Hydrogen Peroxide Photosynthesis.

Metal-isolated clusters (MICs) physically confined on photoactive materials are of great interest in the field of photosynthesis of hydrogen peroxide (H2O2). Despite recent important endeavors, weak confinement of MICs in the reported photocatalytic systems leads to their low catalytic activity and stability. Herein, we report a new strategy of fluorinated covalent organic frameworks (COFs) to strongly confine Pd ICs for greatly boosting the photocatalytic activity and stability of H2O2 photosynthesis. Both experimental and theoretical results reveal that strong electronegative fluorine can increase the metal-support interaction and optimize the d-band center of Pd ICs, thus significantly enhancing the stability and activity of photocatalytic H2O2. An optimal TAPT-TFPA COFs@Pd ICs photocatalyst delivers a stable H2O2 yield rate of 2143 µmol h-1 g-1. Most importantly, the as-made TAPT-TFPA COFs@Pd ICs exhibit high catalytic stability over 100 h, which is the best among the reported materials.

Cu2O/2D COFs Core/Shell Nanocubes with Antiphotocorrosion Ability for Efficient Photocatalytic Hydrogen Evolution.

Photocorrosion of highly active photocatalysts is an urgent problem to be solved in the field of photocatalysis; however, searching for effective strategies for inhibiting photocorrosion of photocatalysts is still a grand challenge. Herein, we design and construct a class of Cu2O/2D PyTTA-TPA COFs (PyTTA: 1,3,6,8-Tetrakis(4-aminophenyl)pyrene, TPA: p-benzaldehyde) core/shell nanocubes to greatly boost the performance of photocatalytic hydrogen evolution and significantly inhibit the photocorrosion. The optimal Cu2O/PyTTA-TPA COFs core/shell nanocubes exhibit an excellent photocatalytic H2 evolution rate of 12.5 mmol h-1 g-1, which is ∼8.0-fold and ∼20.0-fold higher than those of PyTTA-TPA COFs and Cu2O nanocube, respectively, and also is the best in all the reported metal oxides catalytic materials. The mechanism studies demonstrate that the appropriate matching band gaps and tight integration of PyTTA-TPA COFs and Cu2O nanocubes can significantly facilitate the separation of photogenerated electron-hole pairs in the Cu2O/PyTTA-TPA COFs core/shell nanocube during the photocatalytic process, which ameliorates the photocatalytic H2 evolution activity. Most importantly, the 2D PyTTA-TPA COFs shell with outstanding intrinsic stability protects Cu2O nanocubes core from photocorrosion by showing no morphology and crystal structure change after 1000 times of photoexcitation.

Achieving High-Performance 3D K+ -Pre-intercalated Ti3 C2 Tx MXene for Potassium-Ion Hybrid Capacitors via Regulating Electrolyte Solvation Structure.

The development of high-performance anode materials for potassium-based energy storage devices with long-term cyclability requires combined innovations from rational material design to electrolyte optimization. A three-dimensional K+ -pre-intercalated Ti3 C2 Tx MXene with enlarged interlayer distance was constructed for efficient electrochemical potassium-ion storage. We found that the optimized solvation structure of the concentrated ether-based electrolyte leads to the formation of a thin and inorganic-rich solid electrolyte interphase (SEI) on the K+ -pre-intercalated Ti3 C2 Tx electrode, which is beneficial for interfacial stability and reaction kinetics. As a proof of concept, 3D K+ -Ti3 C2 Tx //activated carbon (AC) potassium-ion hybrid capacitors (PIHCs) were assembled, which exhibited promising electrochemical performances. These results highlight the significant roles of both rational structure design and electrolyte optimization for highly reactive MXene-based anode materials in energy storage devices.

Nanoengineering of Advanced Carbon Materials for Sodium-Ion Batteries.

Recent research shows that the continuing importance of carbon anode materials plays an important role in the development of sodium-ion batteries. Nevertheless, the practical deployment of sodium-ion batteries still faces many challenges such as mediocre sodium storage capability and short cycle life. Therefore, it is imperative to explore improvement methods to boost their competitiveness. Herein, various nanoengineering strategies, including nanostructure design, defect and heteroatom doping, and nanocomposite optimization, are proposed as reliable and effective approaches to improve electrochemical performances and structural stability of carbon-based anode materials for sodium-ion batteries (SIBs). The feasibility of nanoengineering is highlighted as a promising approach to develop next-generation carbon materials for sodium-ion batteries.

Reaction Mechanisms of Layered Lithium-Rich Cathode Materials for High-Energy Lithium-Ion Batteries.

Layered lithium-rich cathode materials have attracted extensive interest owing to their high theoretical specific capacity (320-350 mA h g-1 ). However, poor cycling stability and sluggish reaction kinetics inhibit their practical applications. After many years of quiescence, interest in layered lithium-rich cathode materials is expected to revive in answer to our increasing dependence on high-energy-density lithium-ion batteries. Herein, we review recent research progress and in-depth descriptions of the structure characterization and reaction mechanisms of layered lithium-rich manganese-based cathode materials. In particular, we comprehensively summarize the proposed reaction mechanisms of both the cationic redox reaction of transition-metal ions and the anionic redox reaction of oxygen species. Finally, we discuss opportunities and challenges facing the future development of lithium-rich cathode materials for next-generation lithium-ion batteries.

Dendrite-Free Sodium Metal Batteries Enabled by the Release of Contact Strain on Flexible and Sodiophilic Matrix.

The formation of sodium (Na) dendrites during cycling has impeded the practical application of Na metal anodes. Herein, we developed a flexible graphene-based matrix, e.g., a porous reduced graphene oxide (PRGO) film, to support dendrite-free Na nucleation and plating, contributing to high-performance Na metal batteries. The PRGO film possessed outstanding merits of sodiophilicity and flexibility. The sodiophilic PRGO film enabled uniform Na nucleation in the initial electroplating stage. Furthermore, the flexible PRGO film with a small Young's modulus effectively alleviated the texture deformation of electrodeposited Na, leading to a compact and dendrite-free Na deposition layer. The well-maintained Na metal anodes on the PRGO film exhibited superior cyclability, high Coulombic efficiency, and improved energy density in both half-cell and full-cell testing. This work illustrates the great significance of mechanical properties of the supporting matrix for the Na electroplating, which provides a new strategy to develop high-performance dendrite-free Na metal batteries.

K2 Ti2 O5 @C Microspheres with Enhanced K+ Intercalation Pseudocapacitance Ensuring Fast Potassium Storage and Long-Term Cycling Stability.

Benefiting from the natural abundance and low standard redox potential of potassium, potassium-ion batteries (PIBs) are regarded as one of the most promising alternatives to lithium-ion batteries for low-cost energy storage. However, most PIB electrode materials suffer from sluggish thermodynamic kinetics and dramatic volume expansion during K+ (de)intercalation. Herein, it is reported on carbon-coated K2 Ti2 O5 microspheres (S-KTO@C) synthesized through a facile spray drying method. Taking advantage of both the porous microstructure and carbon coating, S-KTO@C shows excellent rate capability and cycling stability as an anode material for PIBs. Furthermore, the intimate integration of carbon coating through chemical vapor deposition technology significantly enhances the K+ intercalation pseudocapacitive behavior. As a proof of concept, a potassium-ion hybrid capacitor is constructed with the S-KTO@C (battery-type anode material) and the activated carbon (capacitor-type cathode material). The assembled device shows a high energy density, high power density, and excellent capacity retention. This work can pave the way for the development of high-performance potassium-based energy storage devices.

Temperature-Dependent Nucleation and Growth of Dendrite-Free Lithium Metal Anodes.

It is essential to develop a facile and effective method to enhance the electrochemical performance of lithium metal anodes for building high-energy-density Li-metal based batteries. Herein, we explored the temperature-dependent Li nucleation and growth behavior and constructed a dendrite-free Li metal anode by elevating temperature from room temperature (20 °C) to 60 °C. A series of ex situ and in situ microscopy investigations demonstrate that increasing Li deposition temperature results in large nuclei size, low nucleation density, and compact growth of Li metal. We reveal that the enhanced lithiophilicity and the increased Li-ion diffusion coefficient in aprotic electrolytes at high temperature are essential factors contributing to the dendrite-free Li growth behavior. As anodes in both half cells and full cells, the compact deposited Li with minimized specific surface area delivered high Coulombic efficiencies and long cycling stability at 60 °C.

Aegis of Lithium-Rich Cathode Materials via Heterostructured LiAlF4 Coating for High-Performance Lithium-Ion Batteries.

Lithium-rich oxides have been regarded as one of the most competitive cathode materials for next-generation lithium-ion batteries due to their high theoretical specific capacity and high discharge voltage. However, they are still far from being commercialized due to low rate capability and poor cycling stability. In this study, we propose a heterostructured LiAlF4 coating strategy to overcome those obstacles. The as-developed lithium-rich cathode material shows outstanding performance including a high reversible capacity (246 mA h g-1 at 0.1C), excellent rate capability (133 mA h g-1 at 5C), and ultralong cycling stability (3000 cycles). Comparing with those of pristine and AlF3-coated lithium-rich cathode materials, the enhanced performances can be attributed to the introduction of the lithium-ion-conductive nanolayer and the generation of nonbonding O n- species in the active material lattice, which enable rapid and effective lithium ion transport and diffusion. Our work provides a new strategy to develop high-performance lithium-rich cathode materials for high-energy-density lithium-ion batteries.