New Insights into Anionic Redox in P2-Type Oxide Cathodes for Sodium-Ion Batteries

Nano Letters, Год журнала: 2024, Номер 24(43), С. 13615 - 13623

Опубликована: Окт. 17, 2024

Manganese/nickel-based layered transition metal oxides have caught the attention of studies as promising cathodes for sodium-ion batteries (SIBs). It is reported that utilizing both cationic and anionic redox reactions a method higher energy density cathodes. However, reaction comes at expense irreversible oxygen release. Hence, Li-Mg cosubstituted P2-Na

Язык: Английский

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Optimization Strategies of Na3V2(PO4)3 Cathode Materials for Sodium-Ion Batteries

Nano-Micro Letters, Год журнала: 2024, Номер 17(1)

Опубликована: Окт. 4, 2024

Abstract Na 3 V 2 (PO 4 ) (NVP) has garnered great attentions as a prospective cathode material for sodium-ion batteries (SIBs) by virtue of its decent theoretical capacity, superior ion conductivity and high structural stability. However, the inherently poor electronic sluggish diffusion kinetics NVP give rise to inferior rate performance unsatisfactory energy density, which strictly confine further application in SIBs. Thus, it is significance boost sodium storage material. Up now, many methods have been developed optimize electrochemical In this review, latest advances optimization strategies improving are well summarized discussed, including carbon coating or modification, foreign-ion doping substitution nanostructure morphology design. The highlighted, involving Na, V, PO 3− sites, include single-site doping, multiple-site single-ion multiple-ion so on. Furthermore, challenges prospects high-performance also put forward. It believed that review can provide useful reference designing developing toward large-scale

Язык: 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, Год журнала: 2025, Номер unknown

Опубликована: Март 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.

Язык: Английский

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A Phase‐Transition–Free Sodium Vanadium Phosphate Cathode via Medium‐Entropy Engineering for Superior Sodium Ion Batteries

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 15, 2025

Abstract Na 3 V 2 (PO 4 ) , based on multi‐electron reactions between 3+ /V 4+ 5+ is a promising cathode material for SIBs. However, its practical application hampered by the inferior conductivity, large barrier of and stepwise phase transition. Herein, these issues are addressed constructing medium‐entropy (Na 3.2 1.1 Ti 0.2 Al Cr Mn Ni 0.1 ME‐NVP) with strong ME─O bond highly occupied Na2 sites. Benefiting from effect, ME‐NVP manifests phase‐transition–free reaction mechanism, two reversible plateaus at 3.4 (V 4.0 ), small volume change (2%) during + insertion/extraction processes, as confirmed comprehensive in/ex situ characterizations. Moreover, kinetics analysis illuminates superior diffusion ability ME‐NVP. Thus, realizes remarkable rate capability 67 mA h g −1 50C long‐term lifespan over 10 000 cycles (capacity retention 81.3%). Theoretical calculations further illustrate that weak binding ion in channel responsible rapid diffusion, accounting kinetics. rigid MEO 6 octahedral feasible rearrangement ions can suppress transition, thus endowing an ultrastable cathode. This work highlights significant role engineering advancing output voltage, cycling stability, polyanionic cathodes.

Язык: Английский

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P2-Na0.67Mn0.7Ni0.2Co0.1O2 stabilized by optimal active facets for sodium-ion batteries

Journal of Colloid and Interface Science, Год журнала: 2025, Номер 684, С. 523 - 530

Опубликована: Янв. 7, 2025

Язык: Английский

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Ultrafast Preparation of High‐Entropy NASICON Cathode Enables Stabilized Multielectron Redox and Wide‐Temperature (−50–60 °C) Workability in Sodium‐Ion Batteries

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 22, 2025

Abstract Avoiding severe structural distortion, irreversible phase transition, and realizing the stabilized multielectron redox are vital for promoting development of high‐performance NASICON‐type cathode materials sodium‐ion batteries (SIBs). Herein, a high‐entropy Na 3.45 V 0.4 Fe Ti Mn 0.45 Cr 0.35 (PO 4 ) 3 (HE‐Na TMP) material is prepared by ultrafast high‐temperature shock, which inhibits possibility separation achieves reversible stable transfer 2.4/2.8 e − at voltage range 2.0–4.45/1.5–4.45 versus + /Na (the capacity 137.2/162.0 mAh g −1 ). The galvanostatic charge/discharge in‐situ X‐ray diffraction tests indicate sequential reactions approximate solid solution transition behavior HE‐Na TMP. Density functional theory calculations analyze migration pathways energy barriers, further confirming superior reaction kinetics Accordingly, TMP exhibits outstanding wide temperature applicability can operate stably in −50–60 °C, accompanied retention 92.8% after 400 cycles −40 °C 73.7 even −50 °C. assembled hard carbon//HE‐Na full‐cell offers an density ≈301 Wh kg based on total anode active mass, verifying application feasibility This work provides innovative pathway to rationally fabricate cathodes SIBs.

Язык: 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, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: 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, Год журнала: 2025, Номер unknown, С. 104166 - 104166

Опубликована: Март 1, 2025

Язык: Английский

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Achieving Fast Ion/Electron Transportation and Smooth Phase Transition in Polyanion Cathode by the High Entropy Strategy

Advanced Energy Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 20, 2025

Abstract Polyanion compounds arouse significant interest as cathode materials for sodium‐ion batteries due to their large 3D lattice structures and stable frameworks. Nonetheless, it remains a great challenge polyanion cathodes achieve both considerable rate capability long‐term cycling lifespan. Herein, high entropy NASICON‐type cathode, Na 3.6 VMn 0.4 Fe Ti 0.1 Zr (PO 4 ) 3 (HE‐NVMFTZP), is successfully synthesized the first time exhibits superior sodium storage performance. Specifically, delivers reversible capacity of 110 mAh g −1 , remarkable (78.5 even at 20 C), an ultralong lifespan (80.6% after 10 000 cycles which outperforms all reported metal‐substituted NASICON electrodes. Moreover, in expanded voltage window 1.5–4.3 V, HE‐NVMFTZP electrode impressive 177.4 (≈494 Wh kg ). Comprehensive experimental characterizations first‐principles calculations reveal that effect facilitates ion/electron transportation alleviates volume expansion phase transition during charge/discharge process. This work provides facile strategy on local structural engineering effectively boost performance can shed light design high‐capacity materials.

Язык: Английский

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Enhancing Kinetics in Sodium Super Ion Conductor Na₃MnTi(PO₄)₃ through Microbe-Assisted and Structural Optimization

ACS Applied Materials & Interfaces, Год журнала: 2024, Номер 16(17), С. 22035 - 22047

Опубликована: Апрель 19, 2024

Sodium (Na) super ion conductor (NASICON) structure Na3MnTi(PO4)3 (NMTP) is considered a promising cathode for sodium-ion batteries due to its reversible three-electron reaction. However, the inferior electronic conductivity and sluggish reaction kinetics limit practical applications. Herein, we successfully constructed three-dimensional cross-linked porous architecture NMTP material (AsN@NMTP/C) by natural microbe of Aspergillus niger (AsN), different cathodes was optimized adjusting transition metal Mn/Ti ratios. Both approaches effectively altered structure, not only improving controlling Na+ diffusion pathways but also enhancing electrochemical material. The resultant AsN@NMTP/C-650, sintered at 650 °C, exhibits better performance with higher reactions corresponding voltage platforms Ti4+/3+, Mn3+/2+, Mn4+/3+ around 2.1, 3.6, 4.1 V (vs Na+/Na), respectively. capacity retention rate up 89.3% after 1000 cycles 2C rate. Moreover, series results confirms that Na3.4Mn1.2Ti0.8(PO4)3 has most excellent when ratio 1.2/0.8, high 96.59 mAh g–1 97.1% 500 cycles.

Язык: Английский

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