A Layered–Tunnel Intergrowth Structure for High‐Performance Sodium‐Ion Oxide Cathode

Xiao, Yao; Wang, Pengfei; Yin, Ya‐Xia; Zhu, Yanfang; Yang, Xinan; Zhang, Xudong; Wang, Yue-Sheng; Guo, Xiaodong; Zhong, Benhe; Guo, Yu‐Guo

doi:10.1002/aenm.201800492

Cited by 125 publications

(62 citation statements)

References 37 publications

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“…In all the cases, however, a complex phases' stabilization can be supposed. This behaviour was expected [19,20], and also desired: in fact, for similar cathode materials, small deviations from sodium stoichiometry as well as the cation substitution can produce mixtures of phases, which can be beneficial for the electrochemical application [1,3].…”

Section: Xrpdmentioning

confidence: 74%

From tunnel NMO to layered polymorphs oxides for sodium ion batteries

et al. 2020

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The search for highly performing cathode materials for sodium batteries is a fascinating topic. Unfortunately, Na0.44MnO2 (NMO), the well-known cathode material with good electrochemical performances, suffers from structural degradation due to reduction of Mn4+ to the Jahn–Teller Mn3+ ion, limiting the long-term cyclability. The cation substitution can be a useful way to mitigate the problem, thanks to the possible stabilization of mixtures of different polymorphs. In this paper, NMO was first substituted with Fe ions, obtaining Na0.44Mn0.5Fe0.5O2, with layered structure, then Al, Si and Cu (10% atom) were substituted on both Mn and Fe ions. Mixtures of P3 type phases, in different amount depending on dopant, were obtained and quantified by Rietveld refinements, and relationships between chemical composition, polymorph type and morphology were proposed. Cyclic voltammetry showed broad peaks, due to the complex structural transitions consequent to the intercalation/deintercalation of sodium. Charge discharge cycles disclosed the superior performances of Cu doped sample, which also benefits from improved air stability, a well-known issue of layered compounds. Discharge capacity values of about 63 mAh/g were detected at 1C, and after 50 cycles at C/2, capacities of about 80 mAh/g are obtained, with a capacity retention of 86%.

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Section: Xrpdmentioning

confidence: 74%

From tunnel NMO to layered polymorphs oxides for sodium ion batteries

et al. 2020

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“…Later, Gao et al prepared interface‐rich P2–tunnel Na x Co 0.1 Mn 0.9 O 2 composite (0.44 < x < 0.7) with Co substitution to address the Jahn–Teller distortion ( Figure a,b) . With merits of the phase interface that provides extra channels for rapid Na + diffusion and active sites for charge storage, the hybrid cathode demonstrates a discharge capacity of 219 mAh g −1 at 0.1 C and 117 mAh g −1 at 5 C. Moreover, Guo and co‐workers prepared layered‐tunnel intergrowth Na 0.6 MnO 2 by thermal polymerization and subsequent solid‐state reaction (Figure c) . In situ XRD results suggest that the hybrid material achieves highly reversible structural evolution between P2–tunnel and OP4‐tunnel phases over a wide voltage range, which leads to remarkable performances in energy density of 520.4 Wh kg −1 , discharge capacity of 198.2 mAh g −1 , and capacity retention of 85.1% after 100 cycles at 1 C (Figure d).…”

Section: Sibsmentioning

confidence: 99%

“…Copyright 2018, Royal Society of Chemistry. c) XRD pattern and Rietveld refinement plots of layered–tunnel intergrowth sample; inset: HRTEM image of the layered–tunnel intergrowth sample; d) cyclic performance of layered–tunnel intergrowth electrode at 1 C. Reproduced with permission . Copyright 2018, Wiley‐VCH.…”

Section: Sibsmentioning

confidence: 99%

Layer‐Based Heterostructured Cathodes for Lithium‐Ion and Sodium‐Ion Batteries

Deng

Liang

et al. 2019

Adv Funct Materials

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A critical bottleneck that hinders major performance improvement in lithium-ion and sodium-ion batteries is the inferior electrochemical activity of their cathode materials. While significant research progresses have been made, conventional single-phase cathodes are still limited by intrinsic deficiencies such as low reversible capacity, enormous initial capacity loss, rapid capacity decay, and poor rate capability. In the past decade, layer-based heterostructured cathodes acquired by combining multiple crystalline phases have emerged as candidates with a huge potential to realize performance breakthrough. Herein, recent studies on the structural properties, electrochemical behaviors, and synthesis route optimizations of these heterostructured cathodes are summarized for in-depth discussions. Particular attention is paid to the latest mechanism discoveries and performance achievements. This review thus aims to promote a deeper understanding of the correlation between the crystal structure of cathodes and their electrochemical behavior, and offers guidance to design advance cathode materials from the aspect of crystal structure engineering.

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“…Na x MnO 2 is a promising material because tunnel‐type Na 0.44 MnO 2 , P2‐type Na 0.67 MnO 2 , and O3‐type NaMnO 2 have been extensively studied with similar synthesis conditions. Thus, a Mn‐based CSM cathode material, Na 0.6 MnO 2 , with a synergistic layered–tunnel structure was synthesized by coprecipitation with a subsequent heat treatment . The layered and tunnel structures in this CSM were characterized by Rietveld refinement (Figure g,h) and high‐resolution transmission electron microscopy, and the CSM exhibited an enhanced comprehensive electrochemical performance during cycling with a high initial capacity of 193.6 mAh g −1 (Figure g).…”

Section: Classification Of Csmsmentioning

confidence: 99%

Composite‐Structure Materials for Na‐Ion Batteries

2018

Small Methods

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structure materials, [25][26][27][28][29][30][31][32][33] polyanion-based materials, [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50] alloying materials, [9,[51][52][53][54][55][56] and Prussian blue analogs. [57][58][59][60][61] However, most of these developed materials are classified as single crystalline structures and exhibit limited electrochemical performances. Thus, scientists have started to think about developing a new material system that possesses the advantages of multiple materials in one material. An attractive strategy to accomplish this goal is the composite-structure material system, which has received much attention recently. [62][63][64] Compared with single-structure materials, compositestructure materials (CSMs) always exhibit better comprehensive electrochemical performance, e.g., larger reversible capacities and better cycling or rate performance. [65,66] The best example of a CSM has been studied in LIBs for many years, i.e., lithium-manganese-rich layered oxides (LLOs), [67][68][69][70] which possess both layered rhombohedral structures and mono clinic Li 2 MnO 3 -like structures. These CSMs deliver a high discharge capacity of ≈300 mAh g −1 and a high energy density of ≈1000 Wh kg −1 , which are almost two times larger than those of conventional cathode materials for LIBs.Electrode materials for NIBs are mostly derived from LIBs. Recently, some CSMs have been proposed to create NIBs with high electrochemical performance, exhibiting great potential in high-energy-density devices. However, most published CSMs are identified after the synthesis process, and few studies have been conducted on designing CSMs because of the complexity of their crystalline structure. In addition, characterizing all the structures in CSMs is more difficult than characterizing singlestructure materials. Currently, adjusting structural proportions and further balancing the electrochemical performance of CSMs still remain major challenges. Examining the literature, a detailed review of CSMs used in NIBs is lacking. In this work, research development of CSMs for NIBs is conducted based on the crystalline structure, including structure design, identification, and adjustment. Some important work and recent achievements on CSMs with a future outlook based on a mechanism analysis are also reviewed. By reviewing previous important studies on CSMs, a new electrode-material structure system for NIBs is established in this work. Structures in CSMsMost NIB electrode materials are developed based on LIB materials because the batteries have similar mechanisms. [1,3,4] Due to the growing concern of aggravated environmental problems (air pollution, global warming, etc.) and Li resources, Na-ion batteries have received significant attention as a promising alternative. Many electrode materials for Na-ion batteries have been reported in the past, especially over the past five years. However, most of these materials have a single crystalline structure and exhibit a limited electrochemical performance. Recently,...

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A Layered–Tunnel Intergrowth Structure for High‐Performance Sodium‐Ion Oxide Cathode

Cited by 125 publications

References 37 publications

From tunnel NMO to layered polymorphs oxides for sodium ion batteries

From tunnel NMO to layered polymorphs oxides for sodium ion batteries

Layer‐Based Heterostructured Cathodes for Lithium‐Ion and Sodium‐Ion Batteries

Composite‐Structure Materials for Na‐Ion Batteries

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