Calcium-Pillar Boosting Smooth Phase Transition in Potassium Vanadate Nanobelts toward Superior Cycling Performance in Potassium-Ion Batteries.

The depletion of lithium resources has prompted exploration into alternative rechargeable energy storage systems, and potassium-ion batteries (PIBs) have emerged as promising candidates. As an active cathode material for PIBs, potassium vanadate (KxV2O5) usually suffers from structural damage during electrochemical K-ion insertion/extraction and hence leading to unsatisfactory cycling performance. Here, we introduce Ca2+ ions as pillars into the potassium vanadate to enhance its structural stability and smooth its phase transition behavior. The additional Ca2+ not only stabilizes the layered structure but also promotes the rearrangement of interlayer ions and leads to a smooth solid-solution phase transition. The optimal composition K0.36Ca0.05V2O5 (KCVO) exhibits outstanding cyclic stability, delivering a capacity of ∼90 mA h g-1 at 20 mA g-1 with negligible capacity decay even after 700 cycles at 500 mA g-1. Theoretical calculations indicate lower energy barriers for K+ diffusion, promoting rapid reaction kinetics. The excellent performances and detailed investigations offer insights into the structural regulation of layered vanadium cathodes.

Zero-Strain Sodium Lanthanum Titanate Perovskite Embedded in Flexible Carbon Fibers as a Long-Span Anode for Lithium-Ion Batteries.

"High-capacity" graphite and "zero-strain" spinel Li4Ti5O12 (LTO) occupy the majority market of anode materials for Li+ storage in commercial applications. Nevertheless, their intrinsic drawbacks including the unsafe potential of graphite and unsatisfactory capacity of LTO limit the further development of lithium-ion batteries (LIBs), which is unable to satisfy the ever-increasing demands. Here, a novel Na0.35La0.55TiO3 perovskite embedded in multichannel carbon fibers (NLTO-NF) is rationally designed and synthesized through an electrospinning method. It not only has the advantages of a respectable specific capacity of 265 mAh g-1 at 0.1 A g-1 and superb rate capability, but it also possesses the zero-strain characteristic. Impressively, an ultralong cycling life with 96.3% capacity retention after 9000 cycles at 2 A g-1 is achieved in the half cell, and 90.3% of capacity retention ratio is obtained after even 2500 cycles at 1 A g-1 in the coupled LiFePO4/NLTO-NF full cell. This study introduces a new member with excellent performance to the zero-strain materials family for next-generation LIBs.

Effects of electrode materials on the performance of Zr0.75Hf0.25O2-based ferroelectric thin films via post deposition annealing.

In this work, the effects of top electrode (TE) and bottom electrode (BE) on the ferroelectric properties of zirconia-based Zr0.75Hf0.25O2(ZHO) thin films annealed by post-deposition annealing (PDA) are investigated in detail. Among W/ZHO/BE capacitors (BE = W, Cr or TiN), W/ZHO/W delivered the highest ferroelectric remanent polarization and the best endurance performance, revealing that the BE with a smaller coefficient of thermal expansion (CTE) plays a vital role in enhancing the ferroelectricity of fluorite-structure ZHO. For TE/ZHO/W structures (TE = W, Pt, Ni, TaN or TiN), the stability of TE metals seems to have a larger impact on the performance over their CTE values. This work provides a guideline to modulate and optimize the ferroelectric performance of PDA-treated ZHO-based thin films.

Feather-like few-layer WSe2 nanosheets grown on W substrates: an excellent electrocatalyst for the hydrogen evolution reaction.

Thin films of few-layer WS2 nanosheets and WSe2 nanosheets were directly grown on W substrates via a scalable infrared-heating CVD method. The WSe2 nanosheets are in a unique feather-like assembly, and mainly composed of the 2H phase, while the presence of a metallic 1T phase was confirmed through atomic resolution TEM observation. Feather-like WSe2 nanosheets delivered excellent electrocatalytic performances for the HER in acid, including a low overpotential of 141 mV to yield a current at 10 mA cm-2, and superb long-term stability at high currents. The highly efficient electrocatalysis is mainly attributed to the unique feather-like morphology of the WSe2 nanosheets with numerous sharp barbules to help maximize the exposed edge sites, along with other beneficial factors including the presence of a 1T phase and slight O-doping.

Introducing a Pseudocapacitive Lithium Storage Mechanism into Graphite by Defect Engineering for Fast-Charging Lithium-Ion Batteries.

The extreme fast-charging capability of lithium-ion batteries (LIBs) is very essential for electric vehicles (EVs). However, currently used graphite anode materials cannot satisfy the requirements of fast charging. Herein, we demonstrate that intrinsic lattice defect engineering based on a thermal treatment of graphite in CO2 is an effective method to improve the fast-charging capability of the graphite anode. The activated graphite (AG) exhibits a superior rate capability of 209 mAh g-1 at 10 C (in comparison to 15 mAh g-1 for the pristine graphite), which is attributed to a pseudocapacitive lithium storage behavior. Furthermore, the full cell LiFePO4||AG can achieve SOCs of 82% and 96% within 6 and 15 min, respectively. The intrinsic carbon defect introduced by the CO2 treatment succeeds in improving the kinetics of lithium ion intercalation at the rate-determining step during lithiation, which is identified by the distribution of relaxation times (DRT) and density functional theory (DFT) calculations. Therefore, this study provides a novel strategy for fast-charging LIBs. Moreover, this facile method is also suitable for activating other carbon-based materials.

Ultra-stable potassium storage and hybrid mechanism of perovskite fluoride KFeF3/rGO.

Potassium-ion batteries (PIBs) are promising for large-scale energy storage due to the abundant reserves of the element potassium yet few satisfactory cathode materials have been developed due to the limitation of the large ionic radius of the potassium ion. Cubic perovskite fluorides have three-dimensional diffusion channels and a robust structure, which are favorable for ion transfer, but their poor electronic conductivity needs to be compensated. Here, we synthesized cubic KFeF3 powder by a solvothermal procedure. After the combination with reduced graphene oxide (rGO) and carbon coating, its electronic conductivity is greatly improved. In the optimal sample KFeF3/rGO-PVA-500, KFeF3 nano-particles (smaller than 50 nm) distribute on the rGO surface evenly. Owing to the special structure, KFeF3/rGO-PVA-500 provides an excellent rate performance and cycling stability. In particular, a high capacity retention of 94% is obtained after 1000 cycles at 200 mA g-1. In addition, a hybrid reaction mechanism combining mainly solid solution and partly conversion processes is revealed by employing in situ and ex situ characterization.

Active-Site-Specific Structural Engineering Enabled Ultrahigh Rate Performance of the NaLi3Fe3(PO4)2(P2O7) Cathode for Lithium-Ion Batteries.

Iron-based mixed-polyanionic cathode Na4Fe3(PO4)2(P2O7) (NFPP) has advantages of environmental benignity, easy synthesis, high theoretical capacity, and remarkable stability. From NFPP, a novel Li-replaced material NaLi3Fe3(PO4)2(P2O7) (NLFPP) is synthesized through active Na-site structural engineering by an electrochemical ion exchange approach. The NLFPP cathode can show high reversible capacities of 103.2 and 90.3 mA h g-1 at 0.5 and 5C, respectively. It also displays an impressive discharge capacity of 81.5 mA h g-1 at an ultrahigh rate of 30C. Density functional theory (DFT) calculation demonstrates that the formation energy of NLFPP is the lowest among NLFPP, NFPP, and NaFe3(PO4)2(P2O7), indicating that NLFPP is the easiest to form and the conversion from NFPP to NLFPP is thermodynamically favorable. The Li substitution for Na in the NFPP lattice causes an increase in the unit cell parameter c and decreases in a, b, and V, which are revealed by both DFT calculations and in situ X-ray powder diffraction (XRD) analysis. With hard carbon (HC) as the anode, the NLFPP//HC full cell shows a high reversible capacity of 91.1 mA h g-1 at 2C and retains 82.4% after 200 cycles. The proposed active-site-specific structural tailoring via electrochemical ion exchange will give new insights into the design of high-performance cathodes for lithium-ion batteries.

High ICE Hard Carbon Anodes for Lithium-Ion Batteries Enabled by a High Work Function.

Hard carbons (HC) derived from biomass material are most promising anodes for lithium-ion batteries (LIBs) because of their cost effectiveness and environmental friendliness. However, the low initial Coulombic efficiency (ICE) of HC anodes reduces the energy density of full cells, which seriously impedes their practical applications. Herein, we demonstrate that the ICE of HC anodes can be significantly improved by modulating the work function of a model HC derived from cotton and deliberately treated to form C-Cl bonds on its surface. By X-ray absorption near-edge structure and density functional theory (DFT) calculation studies, it is verified that the introduction of the C-Cl bond leads to the electron transfer from C to Cl and enhances the work function of the system. In addition, this Cl-doped HC anode can inhibit the reduction of solvent molecules in the electrolyte and reduce the formation of a solid electrolyte interface (SEI) film. Consequently, the ICE is improved from 64.8 to 78.1%. This study provides an effective route to reduce the formation of the SEI film and improve the ICE of hard carbon anodes for LIBs.