Prussian blue analogs (PBAs) are promising cathode materials for sodium‐ion batteries (SIBs) due to their low‐cost, similar energy density comparable with that of LiFePO4 in lithium‐ion batteries, and long cycle life. Nevertheless, crystal water (≈10 wt%) in PBAs from aqueous synthesis environments can bring significant side effects in real SIBs, especially for calendar life and high temperature storage performance. Therefore, it is of great importance to eliminate crystal water in PBAs for future commercial applications. Herein, a facile heat‐treatment method is reported in order to remove water from Fe‐based PBAs. Although the heat‐treated sample can be easily rehydrated in air, it still exhibits a stable cycling performance over 2000 times under controlled charge cut‐off voltage. In situ synchrotron high‐temperature powder X‐ray diffraction demonstrates that the as‐prepared sample is maintained at a new trigonal phase after dehydration. Moreover, the redox reaction of low‐spin Fe2+/Fe3+ is activated and the high‐temperature storage performance of as‐prepared sample is significantly improved after removal of water.
great significance to develop electrochemical energy-storage technique and take advantage of sustainable and renewable energy. [1][2][3][4][5][6][7] Owing to natural abundance, wide availability, and low cost of sodium resources, sodium-ion batteries (SIBs) have been considered as one of most fascinating alternatives to the well-commercialized lithium-ion batteries for future large-scale stationary energy-storage systems with high adaptability and energy efficiency. [8][9][10][11][12][13] To develop satisfactory electrode materials in the future development of SIBs, continued research efforts have been devoted to screen new cathodes over the past few years. [14][15][16][17][18][19] Among a wide variety of cathode candidates including layered oxides, polyanion compounds, and Prussian blue analogues, layered oxide cathode materials have received significant attention because of the high voltage, low cost, and simple synthesis. Recently, research has made dramatic progress especially on manganese-based layered oxides such as zinc-doped Na 0.833 [Li 0.25 Mn 0.75 ]O 2 , Na 0.7 Mg 0.05 [Mn 0.6 Ni 0.2 Mg 0.15 ]O 2 , and Na 2.3 Cu 1.1 Mn 2 O 7−δ , which open new opportunities for developing high-performance cathode materials. [20][21][22][23][24] However, typical P2-type Na 2/3 Ni 1/3 Mn 2/3 O 2 cathode material As one of the most promising cathode candidates for room-temperature sodium-ion batteries (SIBs), P2-type layered oxides face the challenge of simultaneously realizing high-rate performance while achieving long cycle life. Here, a stable Na 2/3 Ni 1/6 Mn 2/3 Cu 1/9 Mg 1/18 O 2 cathode material is proposed that consists of multiple-layer oriented stacking nanoflakes, in which the nickel sites are partially substituted by copper and magnesium, a characteristic of the material that is confirmed by multiscale scanning transmission electron microscopy and electron energy loss spectroscopy techniques. Owing to the optimal morphology structure modulation and chemical element substitution strategy, the electrode displays remarkable rate performance (73% capacity retention at 30C compared to 0.5C) and outstanding cycling stability in Na half-cell system couple with unprecedented full battery performance. The underlying thermal stability, phase stability, and Na + storage mechanisms are clearly elucidated through the systematical characterizations of electrochemical behaviors, in situ X-ray diffraction at different temperatures, and operando X-ray diffraction upon Na + deintercalation/intercalation. Surprisingly, a quasi-solid-solution reaction is switched to an absolute solid-solution reaction and a capacitive Na + storage mechanism is demonstrated via quantitative electrochemical kinetics calculation during charge/discharge process. Such a simple and effective strategy might reveal a new avenue into the rational design of excellent rate capability and long cycle stability cathode materials for practical SIBs.
Considering the ever‐growing climatic degeneration, sustainable and renewable energy sources are needed to be effectively integrated into the grid through large‐scale electrochemical energy storage and conversion (EESC) technologies. With regard to their competent benefit in cost and sustainable supply of resource, room‐temperature sodium‐ion batteries (SIBs) have shown great promise in EESC, triumphing over other battery systems on the market. As one of the most fascinating cathode materials due to the simple synthesis process, large specific capacity, and high ionic conductivity, Na‐based layered transition metal oxide cathodes commonly suffer from the sluggish kinetics, multiphase evolution, poor air stability, and insufficient comprehensive performance, restricting their commercialization application. Here, this review summarizes the recent advances in layered oxide cathode materials for SIBs through different optimal structure modulation technologies, with an emphasis placed on strategies to boost Na+ kinetics and reduce the irreversible phase transition as well as enhance the store stability. Meanwhile, a thorough and in‐depth systematical investigation of the structure–function–property relationship is also discussed, and the challenges as well as opportunities for practical application electrode materials are sketched. The insights brought forward in this review can be considered as a guide for SIBs in next‐generation EESC.
As one of the most promising cathodes for rechargeable sodium-ion batteries (SIBs), O3-type layered transition metal oxides commonly suffer from inevitably complicated phase transitions and sluggish kinetics. Here, a Na[Li Ni Mn Cu Mg ]O cathode material with the exposed {010} active facets by multiple-layer oriented stacking nanosheets is presented. Owing to reasonable geometrical structure design and chemical substitution, the electrode delivers outstanding rate performance (71.8 mAh g and 16.9 kW kg at 50C), remarkable cycling stability (91.9% capacity retention after 600 cycles at 5C), and excellent compatibility with hard carbon anode. Based on the combined analyses of cyclic voltammograms, ex situ X-ray absorption spectroscopy, and operando X-ray diffraction, the reaction mechanisms behind the superior electrochemical performance are clearly articulated. Surprisingly, Ni /Ni and Cu /Cu redox couples are simultaneously involved in the charge compensation with a highly reversible O3-P3 phase transition during charge/discharge process and the Na storage is governed by a capacitive mechanism via quantitative kinetics analysis. This optimal bifunctional regulation strategy may offer new insights into the rational design of high-performance cathode materials for SIBs.
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.
Delivery of high‐energy density with long cycle life is facing a severe challenge in developing cathode materials for rechargeable sodium‐ion batteries (SIBs). Here a composite Na0.6MnO2 with layered–tunnel structure combining intergrowth morphology of nanoplates and nanorods for SIBs, which is clearly confirmed by micro scanning electron microscopy, high‐resolution transmission electron microscopy as well as scanning transmission electron microscopy with atomic resolution is presented. Owing to the integrated advantages of P2 layered structure with high capacity and that of the tunnel structure with excellent cycling stability and superior rate performance, the composite electrode delivers a reversible discharge capacity of 198.2 mAh g−1 at 0.2C rate, leading to a high‐energy density of 520.4 Wh kg−1. This intergrowth integration engineering strategy may modulate the physical and chemical properties in oxide cathodes and provide new perspectives on the optimal design of high‐energy density and high‐stable materials for SIBs.
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