Phase boundary propagation kinetics predominately limit the rate capability of NASICON-type Na3+xMnxV2-x(PO4)3 (0≤x≤1) materials

Anishchenko, Dmitrii V.; Zakharkin, Maxim V.; Nikitina, Victoria A.; Stevenson, Keith J.; Antipov, Evgeny V.

doi:10.1016/j.electacta.2020.136761

Cited by 31 publications

(30 citation statements)

References 49 publications

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“…Anishchenko et al studied the kinetics of Na + diffusion into Mn-swapped materials Na 3+ x V 2− x Mn x (PO 4 ) 3 ( x = 0, 0.1, 0.5, 1) by comparing the effect of Mn substitution and electrochemical outputs of the materials in a stable voltage window (2.5–3.8 V). 56 From CV comparisons, the authors witnessed that increases in the Mn content progressively widened the solid solution regions, i.e. , caused decreases in ionic diffusion coefficients (Fig.…”

Section: The Extent Of Mn2+ Swapping In Na3v2(po4)3 and Evolution Of New Nasicon Derivativesmentioning

confidence: 99%

The advent of manganese-substituted sodium vanadium phosphate-based cathodes for sodium-ion batteries and their current progress: a focused review

et al. 2022

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Section: The Extent Of Mn2+ Swapping In Na3v2(po4)3 and Evolution Of New Nasicon Derivativesmentioning

confidence: 99%

The advent of manganese-substituted sodium vanadium phosphate-based cathodes for sodium-ion batteries and their current progress: a focused review

et al. 2022

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“…Structural and capacity degradation upon high voltage cycling has also been observed in Mn-rich Na 3+y V 2−y Mn y (PO 4 ) 3 cathodes. [21,22] However, it is not yet clear what role concomitant local structural and electronic processes occurring at higher voltages play in the abovementioned issues. Specifically, the interplay between the removal of Na + ions from Na (1) and Na (2) sites and the oxidation of V 4+ to V 5+ as well as Mn 3+ to Mn 4+ and associated changes to (V/Mn)O 6 local environments makes it difficult to separate individual contributions to the observed electrode degradation phenomena.…”

Section: Introductionmentioning

confidence: 99%

“…In the present work, we have designed a series of Mg 2+ -substituted NASICON cathodes with compositions Na 3+y V 2−y Mg y (PO 4 ) 3 akin to previously studied Mn 2+ -substituted NVP compounds. [21,22] The electrochemical inactivity of Mg 2+ entails that V redox centers are solely responsible for Na + exchange in the Na 3+y V 2−y Mg y (PO 4 ) 3 cathodes, which enables us to follow structural and electrochemical (de)sodiation processes during charge-discharge more clearly than in the structurally and compositionally similar V 3+ -Mn 2+ system. Specifically, this study allows us to evaluate the impact of metal mixing on the V site on the Na (de)intercalation mechanism, on the electrochemical reversibility, and on Na + diffusion kinetics, without the complications of multimetal redox processes on chargedischarge.…”

Section: Introductionmentioning

confidence: 99%

Elucidating the Impact of Mg Substitution on the Properties of NASICON‐Na₃₊_yV₂₋_yMg_y(PO₄)₃ Cathodes

Ghosh

Barman

Gonzalez-Correa

et al. 2021

Adv Funct Materials

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Vanadium multi-redox based NASICON-Na z V 2-y M y (PO 4 ) 3 (3 ≤ z ≤ 4; M = Al 3+ , Cr 3+ and Mn 2+ ) cathodes are particularly attractive for Na-ion battery applications due to their high Na insertion voltage (>3.5 V vs. Na + /Na 0 ), reversible storage capacity (~150 mA h g -1 ) and rate performance. However, their practical application is hindered by rapid capacity fade due to bulk structural rearrangements at high potentials involving complex redox and local structural changes. To decouple these factors, we have studied a series of Mg 2+ substituted Na 3+y V 2y Mg y (PO 4 ) 3 (0 ≤ y ≤ 1) cathodes for which the only redox-active species is vanadium. Whilst X-ray diffraction (XRD) confirms the formation of solid solutions between the y = 0 and 1 end members, X-ray absorption spectroscopy and solid-state nuclear magnetic resonance reveal a complex evolution of the local structure upon progressive Mg 2+ substitution for V 3+ . Concurrently, the intercalation voltage rises from 3.35 to 3.45 V, due to increasingly more ionic V-O bonds, and the sodium (de)intercalation mechanism transitions from a two-phase for y ≤ 0.5 to a solid solution process for y ≥ 0.5, as confirmed by inoperando XRD, whilst Na-ion diffusion kinetics follow a non-linear trend across the compositional series.

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“…A broad range of transition metals have been incorporated into the NASICON-type NVP (see ref and references therein). Among them, the V for Mn substitution looks the most attractive as it allows activating the electrochemical extraction of more than two Na + cations and enhancing the capacity and energy density. , The obtained solid solutions demonstrate good durability and rate performance that renders them suitable for further practical applications. − Moreover, the presence of four Na cations in the substituted Na 4 MnV(PO 4 ) 3 opens up a theoretical possibility to reach an electrochemical capacity of up to 222 mA h/g.…”

Section: Introductionmentioning

confidence: 99%

Hydrothermal Microwave-Assisted Synthesis of Na_3+xV_2–yMn_y(PO₄)₂F₃ Solid Solutions as Potential Positive Electrodes for Na-Ion Batteries

Iarchuk

Sheptyakov

Abakumov

2021

ACS Appl. Energy Mater.

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Hydrothermal microwave-assisted synthesis of Mn-substituted Na 3+x V 2−y Mn y (PO 4 ) 2 F 3 positive electrode materials for Na-ion batteries resulted in phase-pure solid solutions with y ≤ 0.6. According to joint Rietveld refinement from the X-ray and neutron powder diffraction data, the solid solution adopts a highly disordered tetragonal I4/mmm structure [a = 6.4695(1) Å, c = 10.6402(3) Å for Na 3.6 V 1.4 Mn 0.6 (PO 4 ) 2 F 3 ]. Electron energy loss spectroscopy (EELS) revealed the Mn 2+ and V 3+ oxidation states, whereas the charge compensation for the heterovalent V 3+ → Mn 2+ substitution occurs by a corresponding increase in the Na content. Electrochemical tests on carbon-coated Na 3.6 V 1.4 Mn 0.6 (PO 4 ) 2 F 3 revealed the ability to reversibly (de)intercalate Na + in the potential range of 2.5−4.6 V versus Na/Na + with ∼108 mA h/g discharge capacity, ∼3.7% volume change, and >50% capacity retention at 10 C rate. Post-mortem EELS analysis revealed that the redox process up to 3.8 V is dominated by the Mn 2+ /Mn 3+ pair, whereas in the 3.8− 4.6 V region, the V 3+ /"V 4+ " pair is active where "V 4+ " is a result of disproportionation into V 3+ and V 5+ . A promising application of the Mn-doped materials as positive electrodes in sodium-ion batteries is demonstrated by a steady-functioning Na 3.6 V 1.4 Mn 0.6 (PO 4 ) 2 F 3 /hard carbon full cell with the specific energy of 312 Wh per kg of cathode.

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Phase boundary propagation kinetics predominately limit the rate capability of NASICON-type Na3+xMnxV2-x(PO4)3 (0≤x≤1) materials

Cited by 31 publications

References 49 publications

The advent of manganese-substituted sodium vanadium phosphate-based cathodes for sodium-ion batteries and their current progress: a focused review

The advent of manganese-substituted sodium vanadium phosphate-based cathodes for sodium-ion batteries and their current progress: a focused review

Elucidating the Impact of Mg Substitution on the Properties of NASICON‐Na₃₊_yV₂₋_yMg_y(PO₄)₃ Cathodes

Hydrothermal Microwave-Assisted Synthesis of Na_3+xV_2–yMn_y(PO₄)₂F₃ Solid Solutions as Potential Positive Electrodes for Na-Ion Batteries

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Phase boundary propagation kinetics predominately limit the rate capability of NASICON-type Na3+xMnxV2-x(PO4)3 (0≤x≤1) materials

Cited by 31 publications

References 49 publications

The advent of manganese-substituted sodium vanadium phosphate-based cathodes for sodium-ion batteries and their current progress: a focused review

The advent of manganese-substituted sodium vanadium phosphate-based cathodes for sodium-ion batteries and their current progress: a focused review

Elucidating the Impact of Mg Substitution on the Properties of NASICON‐Na3+yV2−yMgy(PO4)3 Cathodes

Hydrothermal Microwave-Assisted Synthesis of Na3+xV2–yMny(PO4)2F3 Solid Solutions as Potential Positive Electrodes for Na-Ion Batteries

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Elucidating the Impact of Mg Substitution on the Properties of NASICON‐Na₃₊_yV₂₋_yMg_y(PO₄)₃ Cathodes

Hydrothermal Microwave-Assisted Synthesis of Na_3+xV_2–yMn_y(PO₄)₂F₃ Solid Solutions as Potential Positive Electrodes for Na-Ion Batteries