Zero Lithium Miscibility Gap Enables High-Rate Equimolar Li(Mn,Fe)PO4 Solid Solution.

Forming olivine-structured Li(Mn,Fe)PO4 solid solution is theoretically a feasible way to improve the energy density of the solid solutions for lithium ion batteries. However, the Jahn-Teller active Mn3+ in the solid solution restricts their energy density and rate performance. Here, as demonstrated by operando X-ray diffraction, we show that equimolar LiMn0.5Fe0.5PO4 solid solution nanocrystals undergo a single-phase transition during the whole (de)lithiation process, with a feature of zero lithium miscibility gap, which endows the nanocrystals with excellent electrochemical properties. Specifically, the energy density of LiMn0.5Fe0.5PO4 reaches 625 Wh kg-1, which is 16% higher than that of LiFePO4. Moreover, the high-performance LiMn0.5Fe0.5PO4 nanocrystals are prepared by a microwave-assisted hydrothermal synthesis in pure water.

Controlled Hydrothermal/Solvothermal Synthesis of High-Performance LiFePO4 for Li-Ion Batteries.

The sluggish Li-ion diffusivity in LiFePO4 , a famous cathode material, relies heavily on the employment of a broad spectrum of modifications to accelerate the slow kinetics, including size and orientation control, coating with electron-conducting layer, aliovalent ion doping, and defect control. These strategies are generally implemented by employing the hydrothermal/solvothermal synthesis, as reflected by the hundreds of publications on hydrothermal/solvothermal synthesis in recent years. However, LiFePO4 is far from the level of controllable preparation, due to the lack of the understanding of the relations between the synthesis condition and the nucleation-and-growth of LiFePO4 . In this paper, the recent progress in controlled hydrothermal/solvothermal synthesis of LiFePO4 is first summarized, before an insight into the relations between the synthesis condition and the nucleation-and-growth of LiFePO4 is obtained. Thereafter, a review over surface decoration, lattice substitution, and defect control is provided. Moreover, new research directions and future trends are also discussed.

High-Energy-Density Hydrogen-Ion-Rocking-Chair Hybrid Supercapacitors Based on Ti3C2 T x MXene and Carbon Nanotubes Mediated by Redox Active Molecule.

MXenes have emerged as promising high-volumetric-capacitance supercapacitor electrode materials, whereas their voltage windows are not wide. This disadvantage prevents MXenes from being made into aqueous symmetric supercapacitors with high energy density. To attain high energy density, constructing asymmetric supercapacitors is a reliable design choice. Here, we propose a strategy to achieve high energy density of hydrogen ion aqueous-based hybrid supercapacitors by integrating a negative electrode of Ti3C2 T x MXene and a positive electrode of redox-active hydroquinone (HQ)/carbon nanotubes. The two electrodes are separated by a Nafion film that is proton permeable in H2SO4 electrolyte. Upon charging/discharging, hydrogen ions shuttle back and forth between the cathode and anode for charge compensation. The proton-induced high capacitance of MXene and HQ, along with complementary working voltage windows, simultaneously enhance the electrochemical performance of the device. Specifically, the hybrid supercapacitors operate in a 1.6 V voltage window and deliver a high energy density of 62 Wh kg-1, which substantially exceeds those of the state-of-the-art aqueous asymmetric supercapacitors reported so far. Additionally, the device exhibits excellent cycling stability and the all-solid-state planar hybrid supercapacitor displays exceptional flexibility and integration for bipolar cells to boost the capacitance and voltage output. These encouraging results provide the possibility of designing high-energy-density noble-metal-free asymmetric supercapacitors for practical applications.