Homeostatic Solid Solution Reaction in Phosphate Cathode: Breaking High‐Voltage Barrier to Achieve High Energy Density and Long Life of Sodium‐Ion Batteries

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(23)

Published: Feb. 19, 2024

Abstract The stable phase transformation during electrochemical progress drives extensive research on vanadium‐based polyanions in sodium‐ion batteries (SIBs), especially Na 3 V 2 (PO 4 ) (NVP). And the electron transfer between 3+/4+ redox couple NVP could be generally achieved, owing to confined crystal variation battery service. However, more favorable 4+/5+ is still hard‐to‐access situation due high barrier and further brings about corresponding inefficiency energy densities. In this work, multilevel frame (MLNP) alters reaction pathway undergo homeostatic solid solution process breaks of at voltage, taking by progressive transition metal (V, Fe, Ti, Cr) couple. diversified paths across diffusion barriers realized distinctive release/uptake inactive Na1 site, confirmed calculations density functional theory. Thereby its volume change merely 1.73% multielectron‐transfer (≈2.77 electrons). MLNP cathode achieve an impressive 440 Wh kg −1 , driving leading development among other NASICON structure SIBs. integration multiple couples with low strain modulates effectively will open a new avenue for fabricating high‐performance cathodes

Language: Английский

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

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: June 27, 2024

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

Language: Английский

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Unlocking Quasi‐Monophase Behavior in NASICON Cathode to Drive Fast‐Charging Toward Durable Sodium‐Ion Batteries

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(37)

Published: March 19, 2024

Abstract The NASICON cathode, Na 3 V 2 (PO 4 ) , has garnered significant attention due to its robust framework with fast + migration. To expand application scenarios by diversified electronic reaction, the substitution of vanadium cost‐effective and abundant redox elements is a special research topic. Nevertheless, in terms reducing toxicity, increasing content widening voltage range, 4+/5+ couple FeV(PO often accompanies asymmetric irreversible electrochemical reactions that pose dilemma for capacity structural stability, especially at high currents. Herein, this work, FeV 1/3 Ti 2/3 (NFVT) achieved highly reactive multiple electron transfer (Ti 2+/3+ Fe 2+ / 3+ 3+/4+ 5+ utilizing reaction quasi‐monophase behavior, it can reserve great retention after 3,000 cycles. More competitively, boosting kinetics makes fast‐charging characteristic, just requiring only 3.63 min reach 80% state charge C. rapid ion/electron transport dynamics achieve decay 0.043% per cycle unlocking behavior NFVT full cells. present study provides fresh perspective on designing cathode materials capabilities sodium‐ion batteries.

Language: Английский

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

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(27)

Published: May 22, 2024

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

Language: Английский

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Medium- and high-entropy materials as positive electrodes for sodium-ion batteries: Quo Vadis?

Energy storage materials, Journal Year: 2024, Volume and Issue: 67, P. 103213 - 103213

Published: Feb. 6, 2024

Language: Английский

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A Medium‐Entropy NASICON Cathode for Sodium‐Ion Batteries Achieving High Energy Density Through Dual Enhancement of Voltage and Capacity

Advanced Energy Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 17, 2025

Abstract Na 3 V 2 (PO 4 ) (NVP) is recognized for its promising commercialization potential as a sodium‐ion battery (SIB) cathode, due to thermodynamic stability and open structure. However, the limited energy density remains major obstacle further advancement of NVP. Herein, medium‐entropy NASICON 3.3 1.4 Al 0.3 (MgCoNiCuZn) 0.06 (NVAMP‐0.3) designed by introducing 3+ , Mg 2+ Co Ni Cu Zn regulate configurational entropy. These NVAMP‐0.3 achieve an elevated average operating voltage (3.33 V) high capacity (138.1 mAh g −1 based on 2.3 + through /V 4+ 5+ multi‐electron reactions. By simultaneously enhancing voltage, exhibits impressive 460 Wh kg . Furthermore, demonstrates excellent low‐temperature tolerance with retention rate 94.6% after 300 cycles at −40 °C. In situ XRD unveils underlying cause unique phenomenon where solid‐solution reaction accounts faster electrochemical kinetics compared redox. DFT calculations indicate that possesses superior electronic conductivity reduced migration barriers. A pouch cell assembled cathode hard carbon anode highly stable cycling (89.3% 200 1 C). This study provides valuable insights into developing NASICON‐type cathodes densities SIBs.

Language: Английский

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Rational Design of Prussian Blue Analogues for Ultralong and Wide-Temperature-Range Sodium-Ion Batteries

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 14, 2025

Architecting Prussian blue analogue (PBA) cathodes with optimized synergistic bimetallic reaction centers is a paradigmatic strategy for devising high-energy sodium-ion batteries (SIBs); however, these usually suffer from fast capacity fading and sluggish kinetics. To alleviate the above problems, herein, series of early transition metal (ETM)-late (LTM)-based PBA (Fe-VO, Fe-TiO, Fe-ZrO, Co-VO, Fe-Co-VO) cathode materials have been conveniently fabricated via an "acid-assisted synthesis" strategy. As paradigm, FeVO-PBA (FV) delivers superb rate capability (148.9 56.1 mAh/g under 0.5 100 C, respectively), remarkable cycling stability over 30,000 cycles, high energy density (259.7 Wh/kg full cell), wide operation-temperature range (-60-80 °C). In situ/ex situ techniques functional theory calculations reveal quasi-zero-strain multielectron redox mechanisms during cycling, supporting its higher specific stable cycling. It considered that d-d electron compensation effect between Fe V enhanced reversibility kinetics reactions simultaneously improved electronic conductivity structural cathode. This work may pave new way rational design high-performance SIBs.

Language: Английский

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Double-pinning effect assisting Na4VMn(PO4)3 with superior structural and electrochemical stabilization for sodium-ion batteries

Nano Energy, Journal Year: 2023, Volume and Issue: 119, P. 109002 - 109002

Published: Oct. 17, 2023

Language: Английский

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Achieving Rapid Sodiation/Desodiation Kinetics in NASICON-Structured Na3MnTi(PO4)3 via Cr Doping

Energy storage materials, Journal Year: 2024, Volume and Issue: 68, P. 103371 - 103371

Published: March 27, 2024

Language: Английский

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Emerging high voltage V⁴⁺/V⁵⁺ redox reactions in Na₃V₂(PO₄)₃-based cathodes for sodium-ion batteries

Chemical Science, Journal Year: 2024, Volume and Issue: 15(23), P. 8651 - 8663

Published: Jan. 1, 2024

In this review, we will focus on NVP-based cathodes which achieve reversible activation of the V 4+ /V 5+ redox couple and improve energy density SIBs.

Language: Английский

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