Crystal structure stabilization, electrochemical properties, and morphology of P2-type Na0.67Mn0.625Fe0.25Ni0.125O2 for Na-ion battery cathodes

Garg, Uma; Rexhausen, William; Smith, Nathaniel; Harris, Jay E.; Qu, Deyang; Guptasarma, P.

doi:10.1016/j.jpowsour.2019.05.025

Cited by 6 publications

(4 citation statements)

References 28 publications

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“…Guptasarma et al reported that the P2-OP4 phase t r a n s i t i o n w a s c o m p l e t e l y s u p p r e s s e d i n Na 0.67 Mn 0.625 Fe 0. performance was improved. 28 Villevieille et al revealed that the maintenance of the P2 phase could improve the specific capacity of the cathode material. 29 Yang et al hindered the electrolyte decomposition and suppressed the P2-OP4 structure transition by Al 2 O 3 atomic layered deposition coating on the Na 0.67 Zn 0.1 Mn 0.9 O 2 electrode.…”

Section: Introductionmentioning

confidence: 99%

“…A lot of studies have been conducted to suppress the disadvantageous structural transition and enhance the cyclic stability of P2-phase Fe/Mn-based cathode materials. Guptasarma et al reported that the P2-OP4 phase transition was completely suppressed in Na 0.67 Mn 0.625 Fe 0.25 Ni 0.125 O 2 cathode materials and the cyclic performance was improved . Villevieille et al revealed that the maintenance of the P2 phase could improve the specific capacity of the cathode material .…”

Section: Introductionmentioning

confidence: 99%

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Simultaneously Enhancing Structural Stability and Cationic Redox in Na_0.67Mn_0.75Fe_0.25O₂ through a Synergy of Multisite Substitution

Kong

et al. 2021

J. Phys. Chem. C

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P2-type Na0.67Mn0.75Fe0.25O2 cathode materials with low cost and high specific capacity have aroused much interest for sodium-ion batteries. Nevertheless, the cyclic and structural stabilities need to be improved for practical application. Herein, we tune the activity and reversibility of the cationic redox and the structure stability in Na0.67Mn0.75Fe0.25O2 by doping Mg/Ca/F into multi-Na/TM/O sites, respectively. The capacity performance at a high rate and cyclic stability are significantly enhanced. The mechanism of the synergy has been revealed by means of an X-ray photoelectronic spectrometer, neutron powder diffraction, ex situ/in situ X-ray diffraction, and so on. The improvement of the rate performance is mostly due to the broadening of the interlayer spacing caused by the element doping and the decrease of the Na-ion diffusion barrier, which facilitates Na-ion diffusion. The reduced transitional metal (TM)–O bond length demonstrates that the bonding energy has been strengthened, which benefits the structural stability and the cycling stability. Moreover, the synergy of multisite substitution suppresses the P2-OP4 phase transition at a high voltage and further improves the cycle stability. The Mg doping also activates Mn3+/Mn4+ redox and increases the intensity of Mn3+/Mn4+ redox. The ratio of Mn3+/Mn4+ is reduced by Ca substitution. Therefore, the Jahn–Teller effect, which is harmful to the structural stability, is restrained. The insights into the synergy of multisite substitution proposed in this study may also be helpful in the design of other cathode materials.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Simultaneously Enhancing Structural Stability and Cationic Redox in Na_0.67Mn_0.75Fe_0.25O₂ through a Synergy of Multisite Substitution

Kong

et al. 2021

J. Phys. Chem. C

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“…The cracking makes more active material surfaces to be exposed to the electrolyte, resulting in formation of more CEI films. 45,46 Therefore, the Nb-doping can inhibit the continuous generation of CEI film by stabilizing the material structure.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…It is generally believed that the volume expansion/contraction of the cathode materials during the Na intercalation/extraction process causes cracking of the surface CEI film. The cracking makes more active material surfaces to be exposed to the electrolyte, resulting in formation of more CEI films. , Therefore, the Nb-doping can inhibit the continuous generation of CEI film by stabilizing the material structure.…”

Section: Resultsmentioning

confidence: 99%

Enhanced Ionic Transport and Structural Stability of Nb-Doped O3-NaFe_0.55Mn_0.45–xNb_xO₂ Cathode Material for Long-Lasting Sodium-Ion Batteries

Zhang

Yuan

Soule

et al. 2020

ACS Appl. Energy Mater.

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Sodium-ion batteries (SIBs) are promising candidates for inexpensive and sustainable energy storage devices for the widespread utilization of intermittent renewable energy because of the natural abundance of sodium raw materials. However, since the ionic radius of Na + is inherently larger than that of Li + , Na-based intercalation materials often suffer from poor stability and slow reaction kinetics. Regarding SIB cathodes, layered transition metals oxides (Na x TMO 2 ) show promising theoretical capacities but low stability. In this work, a series of O3-NaFe 0.55 Mn 0.45−x Nb x O 2 (x = 0, 0.01, 0.02, and 0.03) compounds are synthesized and show superior stability and rate-capability compared with the pure oxide. For instance, the best-performing sample, NaFe 0.55 Mn 0.44 Nb 0.01 O 2 , has a specific capacity of 127 mAh g −1 and 80% capacity retention over 100 cycles at 0.1 C. Ex situ X-ray diffraction (XRD) result shows that the Nb incorporation could suppress TMO 2 slip and reduce the energy barrier of the O3−P3 phases' transition. When coupled with a hard carbon (HC) anode in a full cell, the battery exhibits significant weight and volume energy and power densities. It is believed that Nb-doping enlarges lattice spacing of the oxide and partially reduces Mn 4+ to Mn 3+ , increasing the ionic conductivity of the cathodic materials.

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P2-type low-cost and moisture-stable cathode for sodium-ion batteries

Wang,

Sun,

Yuan

et al. 2024

Chinese Chemical Letters

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Crystal structure stabilization, electrochemical properties, and morphology of P2-type Na0.67Mn0.625Fe0.25Ni0.125O2 for Na-ion battery cathodes

Cited by 6 publications

References 28 publications

Simultaneously Enhancing Structural Stability and Cationic Redox in Na_0.67Mn_0.75Fe_0.25O₂ through a Synergy of Multisite Substitution

Simultaneously Enhancing Structural Stability and Cationic Redox in Na_0.67Mn_0.75Fe_0.25O₂ through a Synergy of Multisite Substitution

Enhanced Ionic Transport and Structural Stability of Nb-Doped O3-NaFe_0.55Mn_0.45–xNb_xO₂ Cathode Material for Long-Lasting Sodium-Ion Batteries

P2-type low-cost and moisture-stable cathode for sodium-ion batteries

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Crystal structure stabilization, electrochemical properties, and morphology of P2-type Na0.67Mn0.625Fe0.25Ni0.125O2 for Na-ion battery cathodes

Cited by 6 publications

References 28 publications

Simultaneously Enhancing Structural Stability and Cationic Redox in Na0.67Mn0.75Fe0.25O2 through a Synergy of Multisite Substitution

Simultaneously Enhancing Structural Stability and Cationic Redox in Na0.67Mn0.75Fe0.25O2 through a Synergy of Multisite Substitution

Enhanced Ionic Transport and Structural Stability of Nb-Doped O3-NaFe0.55Mn0.45–xNbxO2 Cathode Material for Long-Lasting Sodium-Ion Batteries

P2-type low-cost and moisture-stable cathode for sodium-ion batteries

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About

Simultaneously Enhancing Structural Stability and Cationic Redox in Na_0.67Mn_0.75Fe_0.25O₂ through a Synergy of Multisite Substitution

Simultaneously Enhancing Structural Stability and Cationic Redox in Na_0.67Mn_0.75Fe_0.25O₂ through a Synergy of Multisite Substitution

Enhanced Ionic Transport and Structural Stability of Nb-Doped O3-NaFe_0.55Mn_0.45–xNb_xO₂ Cathode Material for Long-Lasting Sodium-Ion Batteries