Substituting inert phosphate with redox-active silicate towards advanced polyanion-type cathode materials for sodium-ion batteries

Sun, Ruimin; Dou, Mingyue; Zhang, Yuxiang; Chen, Jingyu; Chen, Yuhao; Han, Bo; Xia, Kaisheng; Gao, Qiang; Liu, Huan; Cai, Zhao; Zhou, Chenggang

doi:10.1039/d2nr06602e

Cited by 15 publications

(3 citation statements)

References 50 publications

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“…The data implies that the electrolyte is effective at a low N/P ratio and obtains a relatively high rate and power density. At last, the electrochemical performance of SMBs in this study is compared with the reported work (Figure f); remarkably, this work demonstrates exceptional rate and cycle performance. – …”

Section: Resultsmentioning

confidence: 55%

Reductive Competition Effect-Derived Solid Electrolyte Interphase with Evenly Scattered Inorganics Enabling Ultrahigh Rate and Long-Life Span Sodium Metal Batteries

Wan,

Song,

Chen

et al. 2023

J. Am. Chem. Soc.

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Constructing an inorganic-rich and robust solid electrolyte interphase (SEI) is one of the crucial approaches to improving the electrochemical performance of sodium metal batteries (SMBs). However, the low conductivity and distribution of common inorganics in SEI disturb Na + diffusion and induce nonuniform sodium deposition. Here, we construct a unique SEI with evenly scattered high-conductivity inorganics by introducing a self-sacrifice LiTFSI into the sodium salt-base carbonate electrolyte. The reductive competition effect between LiTFSI and FEC facilitates the formation of the SEI with evenly scattered inorganics. In which the high-conductive Li 3 N and inorganics provide fast ions transport domains and high-flux nucleation sites for Na + , thus conducive to rapid sodium deposition at a high rate. Therefore, the SEI derived from LiTFSI and FEC enables the Na∥Na 3 V 2 (PO 4 ) 3 cell to show 89.15% capacity retention (87.62 mA h g −1 ) at an ultrahigh rate of 60 C after 10,000 cycles, while the cell without LiTFSI delivers only 48.44% capacity retention even after 8000 cycles. Moreover, the Na∥Na 3 V 2 (PO 4 ) 3 pouch cell with the special SEI presents a stable capacity retention of 92.05% at 10 C after 2000 cycles. This unique SEI design elucidates a new strategy to propel SMBs to operate under extreme high-rate conditions.

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Section: Resultsmentioning

confidence: 55%

Reductive Competition Effect-Derived Solid Electrolyte Interphase with Evenly Scattered Inorganics Enabling Ultrahigh Rate and Long-Life Span Sodium Metal Batteries

Wan,

Song,

Chen

et al. 2023

J. Am. Chem. Soc.

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“…Since inert PO 4 3− adds dead weight and limits the discharge capacity of phosphate based polyanions, so replacing it with some redox active anions (e.g., SiO 4 4− ) can be great strategy to improve the electrochemical properties. Sun et al [155] systematically replaced inert PO 4 3− with redox active silicate SiO 4…”

Section: Element Dopingmentioning

confidence: 99%

“…Sun et al. [ 155 ] systematically replaced inert PO 4 3− with redox active silicate SiO 4 4− , as it regulates the crystal structure and electrochemical performance by enabling additional redox‐active sites of Si for improved Na‐storage capacity and reducing bandgap of fabricated Na 3 V 2 (PO 4 ) 2.9 (SiO 4 ) 0.1 . The introduction of Si in small amount is beneficial for the improvement of electrochemical performance, but the addition of too much Si > 0.1 can destroy the crystal structure of Na 3 V 2 (PO 4 ) 3 and deteriorate the performance.…”

Section: Strategies For Improving High‐performance Phosphate‐based Po...mentioning

confidence: 99%

Recent Development of Phosphate Based Polyanion Cathode Materials for Sodium‐Ion Batteries

Ahsan,

Cai,

Wang

et al. 2024

Advanced Energy Materials

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Sodium‐ion batteries (SIBs) are regarded as next‐generation secondary batteries and complement to lithium‐ion batteries (LIBs) for large‐scale electrochemical energy storage applications due to the abundant availability, even distribution, and cost‐effectiveness of raw sodium resources. The phosphate‐based polyanions stand out of various cathode material owing to their high operation voltage, stable structure, superior safety, and excellent sodium‐storage properties. The undesirable electric conductivities and specific capacities limit their large‐scale industrialization. Herein, a recent research development of phosphate‐based polyanion cathodes including orthophosphate, oxyphosphate, pyrophosphate, and mixed phosphates is thoroughly reviewed. Subsequently, the effect of modification strategies including element doping, surface coating, morphology control, and electrode design toward high‐performance cathode materials for SIBs are systematically explored. Finally, the future research directions of phosphate‐based polyanion cathodes based on electrochemical performance including reversible capacity, voltage, energy density, rate capacity, cycling stability, and commercial applications are comprehensively concluded. It is believed that current review will present instructive perspectives into developing practicable phosphate‐based polyanion cathode materials for SIBs.

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From Lab to Application: Challenges and Opportunities in Achieving Fast Charging with Polyanionic Cathodes for Sodium‐Ion Batteries

Lu,

Li,

et al. 2024

Advanced Materials

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Sodium‐ion batteries (SIBs), recognized for balanced energy density and cost‐effectiveness, are positioned as a promising complement to lithium‐ion batteries (LIBs) and a substitute for lead–acid batteries, particularly in low‐speed electric vehicles and large‐scale energy storage. Despite their extensive potential, concerns about range anxiety due to lower energy density underscore the importance of fast‐charging technologies, which drives the exploration of high‐rate electrode materials. Polyanionic cathode materials are emerging as promising candidates in this regard. However, their intrinsic limitation in electronic conductivity poses challenges for synchronized electron and ion transport, hindering their suitability for fast‐charging applications. This review provides a comprehensive analysis of sodium ion migration during charging/discharging, highlighting it as a critical rate‐limiting step for fast charging. By delving into intrinsic dynamics, key factors that constrain fast‐charging characteristics are identified and summarized. Innovative modification routes are then introduced, with a focus on shortening migration paths and increasing diffusion coefficients, providing detailed insights into feasible strategies. Moreover, the discussion extends beyond half cells to full cells, addressing challenges and opportunities in transitioning polyanionic materials from the laboratory to practical applications. This review aims to offer valuable insights into the development of high‐rate polyanionic cathodes, acknowledging their pivotal role in advancing fast‐charging SIBs.

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Substituting inert phosphate with redox-active silicate towards advanced polyanion-type cathode materials for sodium-ion batteries

Abstract: Polyanion-type phosphate materials with Na-super-ionic conductor structures are promising for next-generation sodium-ion battery cathodes, however, the intrinsically low electroconductivity and limited energy density have restricted their practical applications. In this...

Cited by 15 publications

References 50 publications

Reductive Competition Effect-Derived Solid Electrolyte Interphase with Evenly Scattered Inorganics Enabling Ultrahigh Rate and Long-Life Span Sodium Metal Batteries

Reductive Competition Effect-Derived Solid Electrolyte Interphase with Evenly Scattered Inorganics Enabling Ultrahigh Rate and Long-Life Span Sodium Metal Batteries

Recent Development of Phosphate Based Polyanion Cathode Materials for Sodium‐Ion Batteries

From Lab to Application: Challenges and Opportunities in Achieving Fast Charging with Polyanionic Cathodes for Sodium‐Ion Batteries

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