Manipulating Layered P2@P3 Integrated Spinel Structure Evolution for High‐Performance Sodium‐Ion Batteries

Abstract

Structural evolution of the cathode during cycling plays a vital role in the electrochemical performance of sodium‐ion batteries. A strategy based on engineering the crystal structure coupled with chemical substitution led to the design of the layered P2@P3 integrated spinel oxide cathode Na0.5Ni0.1Co0.15Mn0.65Mg0.1O2, which shows excellent sodium‐ion half/full battery performance. Combined analyses involving scanning transmission electron microscopy with atomic resolution as well as in situ synchrotron‐based X‐ray absorption spectra and in situ synchrotron‐based X‐ray diffraction patterns led to visualization of the inherent layered P2@P3 integrated spinel structure, charge compensation mechanism, structural evolution, and phase transition. This study provides an in‐depth understanding of the structure‐performance relationship in this structure and opens up a novel field based on manipulating structural evolution for the design of high‐performance battery cathodes.

Tailoring P2/P3 Biphases of Layered NaxMnO2 by Co Substitution for High‐Performance Sodium‐Ion Battery

“…Recently, engineering P2/P3 biphases in layered oxides has been reported as an effective strategy for improving the electrochemical performance due to the synergistic effect between phases. [ 12,16–23 ] For example, Guo and co‐workers [ 16 ] demonstrated that the crystalline structure of P2/P3–Na 0.7 Li 0.06 Mg 0.06 Ni 0.22 Mn 0.67 O 2 cathode combines the respective advantages of P2 and P3 phases, and thus exhibits enhanced long‐term cycling performance over 100 cycles and rate capability (≈102 mA h g −1 at 5 C) compared with the pure P2 or P3 phase. Ionic substitution is a feasible method to manipulate the phase composition of Na x MnO 2 layered oxides.…”

“…[ 12,20,22 ] Dou and co‐workers [ 12 ] employed Zn substitution to synthesize P2/P3 intergrowth composite, which exhibits improved structural stability and humidity resistance. Chou and co‐workers [ 22 ] demonstrated that Mg can manipulate the phase components and designed P2/P3 integrated spinel Na 0.5 Ni 0.1 Co 0.15 Mn 0.65 Mg 0.1 O 2 cathode for advanced SIBs. To the best of our knowledge, utilization of Co substitution to tune the phase composition in Na x MnO 2 has been scarcely explored so far.…”

“…The details are summarized in Table S4 (Supporting Information). [ 12,16,18,20–22,42–44 ] Specific capacities of the MCA samples decrease with increasing P3 content accompanied by improving of cycling stability. However, the P3 cathode (MCA‐4) shows poor electrochemical performance.…”

Recent Advances on Mixed Metal Sulfides for Advanced Sodium‐Ion Batteries

“…[1][2][3][4] However, because of the larger ionic radius, higher reduction potential, and slower reaction kinetics of Na + ions compared to Li + ions, exploring electrodes with high reversible capacities and facile reaction processes remains challenging. [5][6][7][8] In the past few years, a wide range of promising materials has been developed as efficient electrode materials for SIBs, including cathode materials (e.g., polyanions, [9][10][11][12] transition metal oxides, [13][14][15][16][17] hexacyanoferrates [18,19] ) and anode materials (e.g., alloys, [20][21][22][23][24][25][26] metal chalcogenides, [27][28][29][30][31][32] carbonaceous materials [33][34][35] ). It is noteworthy that the electrodes with two/multiple-electron reactions are more favored because of the high theoretical capacity for energy storage.…”

微纳结构过渡金属化合物能源转化电催化剂研究进展

“…As a result, the P sites prefer to attract the protons in the electrolyte, contributing to a suitable bonding between the catalytic sites and the intermediates/products. In addition, researches about phosphides for electrocatalytic oxygen reactions have been also reported recently, extending the applications of phosphides in energy conversion [96][97][98][99][100]. Tuning the crystal structure via the strain effect has been proved to be an effective way to improve the activity.…”