Bond Structure Engineering Induced the Mn Redox Stabilization Toward High‐Energy Mn‐Based Phosphate Cathode

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Май 9, 2024

Abstract Manganese (Mn) ‐based phosphate is poised for commercial applications driven by its cost‐effectiveness, robust NASICON framework, and multi‐dimensional Na + pathways. However, it encounters insufficient redox reactions rapid structural collapse with severe lattice distortion as the culprit. Herein, one meticulously engineered substitutional solid solution cathode (integrating 4 MnCr(PO ) 3 MnTi(PO , denoted NMCTP) proposed to regulate local crystal structure of Mn─O bond stabilize promote Mn reaction optimizing electrochemical performance. It uncovered that bulk framework stability constructed strongly symmetric lengths MnO 6 octahedrons strengthened covalency. In addition, sufficient utilization tightly correlated redistributed Na2 occupancy enhanced diffusion kinetics accelerated electron transportation. By virtue above merits, The NMCTP performs ultra‐high capacity (150.3 mAh g −1 at 0.1 C) appealing cycling (84.7% retention over 1000 cycles). Sodium storage mechanisms potential factors high potentials are unveiled in materials. This work sheds light on fire‐new strengthening view high‐performance Mn‐based cathodes.

Язык: Английский

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Ultralong Lifespan Zero‐Cobalt/Nickel Prussian Blue Analogs Cathode Realized by Solid Solution Reaction Sodium Storage Mechanism

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Июль 2, 2024

Abstract Despite their low cost and high specific capacity, the practical use of monoclinic Mn‐based Prussian blue analogs (Mn‐PBAs) is limited by poor cycling stability, primarily due to structural degradation caused multiple phase transitions Jahn–Teller effect associated with Mn 3+ ions throughout entire cycle. Herein, synergistic incorporation low‐cost Cu Fe into manganese sites Mn‐PBAs, ternary PBAs (T‐PBAs) achieve solid solution reaction Na + extraction insertion, successfully eliminating inherent multi‐phase transition from sodium storage mechanism T‐PBAs. Ex situ analysis density functional theory calculations are employed confirm that T‐PBAs consistently maintain a cubic smaller lattice distortion rather than occur in conventional three‐phase during charging discharging processes, forcefully inhibiting Therefore, showcase unprecedented stability at both room temperature (10 000 cycles 1 A g −1 ) −20 °C (over 3000 h, 4200 0.2 without distinct capacity degradation), More importantly, when paired commercial hard carbon, based sodium‐ion batteries exhibit excellent retention (2000 76.8%), showcasing immense potential applications.

Язык: Английский

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Unlocking highly reversible V5+/V4+ redox reaction and fast-stable Na storage in NASICON cathodes by electronic structure optimization and solid-solution behavior regulation

Nano Energy, Год журнала: 2024, Номер 128, С. 109842 - 109842

Опубликована: Июнь 5, 2024

Язык: Английский

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Promoting Layered Oxide Cathodes Based on Structural Reconstruction for Sodium‐Ion Batteries: Reversible Phase Transition, Stable Interface Regulation, and Multifunctional Intergrowth Structure

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Окт. 21, 2024

Abstract Layered transition‐metal oxides (Na x TMO 2 ) are one of the most promising cathode materials for sodium‐ion batteries due to their high theoretical specific capacities, good conductivity, and environmental friendliness. However, several key scientific issues Na still persist in practical applications: i) complex phase transitions during charge/discharge process owing slip layer; ii) tendency interface react with electrolyte, resulting structure degradation, iii) reactions between active H O as well CO on exposure air environment form alkaline substances surface. To understand electrochemical storage mechanisms solve these problems, modification strategies have been reported recently, including bulk doping, concentration gradient design, regulation, intergrowth construction. This review focuses reversible transitions, stable multifunctional material from inside outside. The future research directions also analyzed, providing guidance development commercial layered next‐generation energy systems.

Язык: Английский

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Electronic Confinement‐Restrained MnNa·${\mathrm{Mn}}_{{\mathrm{Na}}}^{\mathrm{\cdot}}$ Anti‐Site Defects in Sodium‐Rich Phosphates Toward Multi‐Electron Transfer and High Energy Efficiency

Advanced Materials, Год журнала: 2024, Номер 36(47)

Опубликована: Окт. 9, 2024

Abstract Sodium (Na) super‐ionic conductor structured Na 3 MnTi(PO 4 ) (NMTP) cathodes have garnered interest owing to their cost‐effectiveness and high operating voltages. However, the voltage hysteresis phenomenon triggered by anti‐site defects (‐ASD), namely, occupation of Mn 2+ in Na2 vacancies NMTP, leads sluggish diffusion kinetics low energy efficiency. This study employs an innovative electronic confinement‐restrained strategy achieve regulation ‐ASD. Partial replacement titanium (Ti) with electron‐rich vanadium (V) favors strong interactions , restraining migration. The results suggest that this can significantly increase vacancy formation migration barrier manganese (Mn), thus inhibiting ‐ASD formation. As proof concept, Na‐rich 3.5 MnTi 0.5 V (PO (NMTVP) material is designed, wherein interaction enhanced redox activity achieved more + storage under high‐voltage. NMTVP cathode delivered a reversible specific capacity up 182.7 mAh g −1 output excellent 513.8 Wh kg corresponding ≈3.2 electron transfer processes, efficiency increased 35.5% at 30 C. Through confinement effect interactions, provides novel perspectives for exploitation breakthrough high‐energy‐density materials Na‐ion batteries.

Язык: Английский

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K₂[(VOHPO₄)₂(C₂O₄)]·2H₂O as a high‐potential cathode material for potassium‐ion batteries

Battery energy, Год журнала: 2024, Номер 3(4)

Опубликована: Апрель 21, 2024

Abstract Potassium‐ion batteries (KIBs) represent a promising energy storage solution owing to the abundance of potassium resources. The efficacy KIBs relies significantly on electrochemical attributes both their electrode materials and electrolytes. In current investigation, we synthesized layered compound K 2 [(VOHPO 4 ) (C O )]·2H via heterogeneous nucleation approach assessed its viability as cathode material for KIBs. When integrated with salt‐concentrated electrolyte oxidation stability over 6 V, compounds exhibit high discharge potential 4.1 V (vs. + /K) alongside reversible capacity 106.2 mAh g −1 . Furthermore, there is no decay after 500 cycles at 100 mA This study shows promise metal organic frameworks high‐potential

Язык: Английский

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Win–win strategy: zinc-ion anchoring crosslinked hydrogels and regulating electronic structure to achieve V³⁺/V⁴⁺/V⁵⁺ redox reaction of Na₃V₂(PO₄)₃ with high thermal stability and zero strain characteristics

Journal of Materials Chemistry A, Год журнала: 2024, Номер 12(30), С. 19422 - 19439

Опубликована: Янв. 1, 2024

Zinc-ion anchoring crosslinked hydrogels and regulating electronic structure to achieve high performance of Na 3 V 2 (PO 4 ) .

Язык: Английский

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Toward High Performance of Na₄Fe₃(PO₄)₂P₂O₇ Cathode via Constructing a Porous Structure for Sodium-Ion Batteries

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 12(30), С. 11361 - 11368

Опубликована: Июль 13, 2024

Язык: 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, Год журнала: 2025, Номер unknown

Опубликована: Май 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.

Язык: Английский

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Regulating Bond Structure in Polyanion Cathode for Long-Cycle-Life Sodium-Ion Batteries

ACS Energy Letters, Год журнала: 2025, Номер unknown, С. 2778 - 2787

Опубликована: Май 15, 2025

Язык: Английский

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