MXenes, as an emerging family of conductive two-dimensional materials, hold promise for late-model electrode materials in Li-ion batteries. A primary challenge hindering the development of MXenes as electrode materials is that a complete understanding of the intrinsic storage mechanism underlying the charge/discharge behavior remains elusive. This article presents two key discoveries: first, the characteristics of the Ti 3 C 2 T x structure can be modified systematically by calcination in various atmospheres, and second, these structural changes greatly affect Li-ion storage behavior, which reveals the mechanism for lithium storage in Ti 3 C 2 T x MXene. Specifically, via ammonization, the interlayer spacing gets dilated and uniform, giving rise to only one redox couple. In stark contrast, there are two well-recognized redox couples corresponding to two interlayer spacings in pristine Ti 3 C 2 T x MXene, in which Li-ion (de)intercalation occurs between interlayers in a sequential manner as evidenced by ex situ X-ray diffraction (XRD). Notably, the XRD diffraction peaks shift hardly in the whole range of charge/discharge voltage, indicating a zero-strain feature upon Li-ion (de)intercalation. Moreover, the diffusion-controlled contribution percentage to capacity inversely depends on the scan rate. The understanding suggests a new design principle of the MXene anode: reduced lateral size to shorten the diffusion path and dilated interlayer spacing.

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.

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.