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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Improving upon rechargeable battery technologies: On the role of high-entropy effects

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

An overview of high-entropy strategies for batteries is provided, emphasizing their unique structural/compositional attributes and positive effects on stability performance, alongside a discussion key challenges future research directions.

Language: Английский

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Synergistically Boosted Na⁺ Migration and Deep Desodiation Stability of NASICON Cathode via High Entropy Regulation

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

Abstract Mn‐containing sodium superionic conductor (NASICON) compounds have shown considerable potential as cathode for sodium‐ion batteries (SIBs) owing to higher working voltage (V 5+ /V 4+ : 3.9 V), lower cost, and toxicity compared full vanadium‐based NASICON Na 3 V 2 (PO 4 ) . Taking 3.3 1.7 Mn 0.3 (NVMP) an example, its practical application is still restricted by poor electronic conductivity, sluggish intrinsic + diffusion, high‐voltage stability. In this work, a high entropy strategy proposed develop 1.613 (Cr, Fe, Co, Ni, Zr) 0.1 (HE‐NVMP) not only enabling more rapid migration but also significantly improving deep desodiation Based on theoretical calculations experimental findings, such modification can efficiently alter the coordination environments of both V/Mn sites reducing diffusion energy barrier, increasing occupancy at Na(2) sites, consolidating structure Thus, obtained HE‐NVMP delivers superior high‐rate capability (91.7 mAh g −1 up 50 C excellent cycling performance (capacity retention: 81.2%) after 10 000 cycles 20 cutoff 4.1 V. More importantly, exhibits storage properties (4.5 V) with electrochemical polarization 75% reduction 1 capacity retention 80.3% 2000 pristine counterpart, indicating great rechargeable overcharge resistance capability.

Language: Английский

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Entropy Driving “Quasi‐Zero Strain” Stepwise Multicationic Redox Chemistry Toward a High‐Performance NASICON‐Cathode for Na‐Ion Batteries

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

Published: Feb. 14, 2025

Abstract Achieving multicationic redox reactions with low lattice strain accumulation upon repeated sodiation/desodiation processes is pivotal for developing high‐energy and long‐durability Na superionic conductor (NASICON)‐type cathodes but still a formidable task. Herein, novel NASICON‐structured high‐entropy 3.4 VMn 0.2 Fe Al 0.3 Cr (PO 4 ) 3 (HE‐NVMFACP) cathode delicately devised, where the entropy‐driving stepwise 2+ /Fe 3+ , V /V 4+ 5+ Mn /Mn /Cr couples not only trigger multielectron transfer chemistry, also alleviate accumulation. Consequently, HE‐NVMFACP exhibits high reversible capacity of 151.3 mAh g −1 an admirable energy density 520.5 Wh kg impressive “quasi‐zero strain” behavior (1.33% cell volume change) during whole charge‐discharge process. Meanwhile, excellent rate capability 90.4 at 50 C ultralong cycling life 91.9% retention after 5000 cycles are demonstrated. Advanced in situ/ex situ techniques reveal complete solid‐solution highly mechanism + uptake/release, rapid electrode process kinetics confirmed by systematic electrochemical measurements theoretical computations. Furthermore, HE‐NVMFACP||hard carbon Na‐ion full batteries assembled both coin pouch configurations, manifesting bright application prospects. The present strategy provides invaluable perspectives designing long‐life NASICON‐cathodes sodium‐ion batteries.

Language: Английский

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Advancing High-Voltage Cathodes for Sodium-Ion Batteries: Challenges, Material Innovations and Future Directions

Energy storage materials, Journal Year: 2025, Volume and Issue: 76, P. 104133 - 104133

Published: Feb. 19, 2025

Language: Английский

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Leveraging High-Entropy Substitution to Achieve V4+/V5+ Redox Couple and Superior Na+ Storage in Na3V2(PO4)3-based Cathodes for Sodium-Ion Battery

Energy storage materials, Journal Year: 2025, Volume and Issue: unknown, P. 104166 - 104166

Published: March 1, 2025

Language: Английский

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Tuning TM-O Bond Covalency to Boost Cationic Activity and Reversibility of Na₄Fe_1.5Mn_1.5(PO₄)₂P₂O₇

Nano Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 2, 2025

The pursuit of cost-effectiveness stimulates great interest in the Na4Fe1.5Mn1.5(PO4)2P2O7 (NMFPP) cathode. However, its cationic redox activity and reversibility are hardly up to expectation, accompanied by poor conductivity rapid structural degradation. These issues can be attributed high ionization degree TM-O bonds polyanion crystal field, which intensifies electronic localization degrades stability TMO6 octahedra under Jahn-Teller effect. Herein, a strategy is proposed enhance covalency bonds. Specifically, Ti4+ with strong electrophilicity introduced alter local structure bonds, including band bonding strength. Ultimately, both intrinsic lattice Ti modified Na4Mn1.3Fe1.5Ti0.1(PO4)2P2O7 (NMFTPP) well optimized, upgrading redox. This work reveals potential mechanism between bond conductivity/structural materials, opening feasible path for high-performance development sodium ion batteries.

Language: Английский

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Unlocking Advanced Sodium Storage Performance: High-Entropy Modulates Crystallographic Sites with Reversible Multi-Electron Reaction

Energy storage materials, Journal Year: 2024, Volume and Issue: unknown, P. 103920 - 103920

Published: Nov. 1, 2024

Language: Английский

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Mn-based tunnel-structured Na_0.44MnO₂ cathode materials for high-performance sodium-ion batteries: electrochemical mechanism, synthesis and modifications

Chemical Communications, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 11, 2024

Sodium-ion batteries (SIBs) have emerged as promising and mature alternatives to lithium-ion (LIBs) in the post-LIB era, necessitating development of cost-effective high-performance cathode materials. The unique crystal texture Mn-based tunnel-structured materials offers outstanding cycling stability, rate capability air making them a highly attractive option for sodium-ion storage applications. This comprehensive review summarizes recent advancements understanding mechanism, synthesis techniques, modification strategies materials, thereby significantly contributing advancement cathodes SIBs.

Language: Английский

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Surface-modified spinel high entropy oxide with hybrid coating-layer for enhanced cycle stability and lithium-ion storage performance

RSC Advances, Journal Year: 2024, Volume and Issue: 14(45), P. 33124 - 33132

Published: Jan. 1, 2024

This work demonstrates a method to enhance the electrochemical performance of spinel HEO (FeCoNiCrMn) 3 O 4 by coating it with hybrid layer lithium titanate and carbon.

Language: Английский

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