First principles study of the crystal, electronic structure, and diffusion mechanism of polaron-Na vacancy of Na3MnPO4CO3for Na-ion battery applications

Debbichi, M.; Debbichi, Lamjed; Dinh, Van An; Lebègue, Sébastien

doi:10.1088/1361-6463/aa518d

Cited by 19 publications

(16 citation statements)

References 29 publications

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“…Na 3 MnPO 4 CO 3 showed two plateaus corresponding to the Mn 3+ /Mn 2+ and Mn 3+ /Mn 4+ redox couples with an average voltage of 3.7 V, which is in agreement with the theoretical value . Ex situ XAFS implied that both of Mn 3+ /Mn 2+ and Mn 3+ /Mn 4+ redox couples can be activated during cycling (Figure b).…”

Section: Manganese‐based Polyanionic Compoundssupporting

confidence: 86%

“…Moreover, in situ XRD revealed that Na + (de)insertion from Na 3 MnPO 4 CO 3 follows a reversible solid solution type mechanism (Figure c) . However, Na 3 MnPO 4 CO 3 showed inferior rate capabilities, although it has 3D diffusion pathways with low activation barriers . This is due to the low electronic conductivity, which can be improved by introducing carbon .…”

Section: Manganese‐based Polyanionic Compoundsmentioning

confidence: 99%

“…However, Na 3 MnPO 4 CO 3 showed inferior rate capabilities, although it has 3D diffusion pathways with low activation barriers . This is due to the low electronic conductivity, which can be improved by introducing carbon . For instance, the composite of reduced graphene oxide (rGO) and nanosized Na 3 MnPO 4 CO 3 obtained via a hydrothermal method shows a reversible capacity of 181 mAh g −1 , corresponding to 1.9‐e Mn 2+ /Mn 3+ /Mn 4+ reactions (Figure d) .…”

Section: Manganese‐based Polyanionic Compoundsmentioning

confidence: 99%

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Research Progress in Multielectron Reactions in Polyanionic Materials for Sodium‐Ion Batteries

Liang

Gong

et al. 2018

Small Methods

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www.advancedsciencenews.com www.small-methods.com and Co). The opportunities and critical issues in this interesting field have also been proposed and discussed for further investigations. Vanadium-Based Polyanionic CompoundsThe versatile coordinations and oxidation states of V ions enable V-containing polyanionic compositions extreme structural diversity. [22] In addition, multiple oxidation states of V (+2 -+5) in these structures might be accessed in a common voltage range (0-4.5 V). [23] These make V-based polyanionic compounds highly suitable for the realization of multielectron reactions. NASICON-Na 3 V 2 (PO 4 ) 3Na 3 V 2 (PO 4 ) 3 adopts a well-known NASICON structure that has rhombohedral phase with high-temperature R-3c symmetry and monoclinic phase with low-temperature C2/c symmetry resulting from Na-vacancy order/disorder. [24,25] Typically, the NASICON framework is built from V 2 (PO 4 ) 3 "lantern units" constructed by corner-sharing VO 6 octahedra and PO 4 tetrahedra. There are two Na sites: 6b Na(1) sites that locate between two adjacent V 2 (PO 4 ) 3 lantern units and 18e Na(2) sites that situate between two PO 4 tetrahedra, allowing multiple Na extraction and insertion and a 3D Na diffusion channel (Figure 2d). [25,26] NASICON-type materials show extremely versatile compounds like so on. Chen et al. and Jian et al. have published excellent reviews on NASICON-structured materials for energy storage. [34,35] Here, we mainly focus on the multielectron reactions of these materials. Na 3 V 2 (PO 4 ) 3 shows promising electrochemical performances: moderate voltage (3.4 V), decent capacity (117 mAh g −1 ), ultralong cycling life, and excellent rate performance due to robust structure and fast Na + ion transport in NASICON framework. [34] This compound attracts extensive attentions as one of the most promising cathode materials for SIBs. [24,26,30,31,[36][37][38][39][40][41][42][43][44][45][46][47][48] Accessibility of the Third NaThe electrochemical extraction of Na + would result in NaV 2 (PO 4 ) 3 via a two-phase reaction, which is a 1-e reaction per V ion. [38] X-ray absorption near edge structure (XANES) further proved that the valence of vanadium ion is +4 after charging to 4.0 V. [36] However, the third Na + ion in Na 3 V 2 (PO 4 ) 3 is inaccessible even charging the electrode up to 4.6 V (Figure 1a). [48] Recently, Jian et al. have determined that all Na + ions at Na(2) sites can be extracted while those at Na(1) maintain in their positions during chemical oxidation using the NO 2 BF 4 as the oxidant. [37] The seemingly impossible extraction of Na + toward V 2 (PO 4 ) 3 recalls a result reported nearly 30 years ago. [49] All the Na + ions have been chemically extracted from Na 3 V 2 (PO 4 ) 3 using Cl 2 as the oxidant to yield a V 2 (PO 4 ) 3 . It is surprising that NO 2 BF 4 cannot oxidize Na 3 V 2 (PO 4 ) 3 to V 2 (PO 4 ) 3 , since the redox potential of the NO 2 + /NO 2 redox (4.8 V) is much higher than that of the Cl 2 /Cl − redox (4.1 V) although the later one is estimated in the aqueous s...

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Section: Manganese‐based Polyanionic Compoundssupporting

confidence: 86%

Section: Manganese‐based Polyanionic Compoundsmentioning

confidence: 99%

Section: Manganese‐based Polyanionic Compoundsmentioning

confidence: 99%

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Research Progress in Multielectron Reactions in Polyanionic Materials for Sodium‐Ion Batteries

Liang

Gong

et al. 2018

Small Methods

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“…DFT calculations with the +U correction were employed to study the structure, electronic structure, intercalation voltages, and Na diffusion mechanism in NMPC. [219] The authors demonstrated that NMCP possesses three preferred diffusion pathways, including one interblock pathway with activation energy (E a ) of 0.85 eV and two interblock diffusion pathways with E a values of 0.56 and 0.64 eV (Figure 19c). The NMCP shows a low diffusion barrier for ion transportation, which is needed to achieve a fast charging rate (Figure 19d).…”

Section: Other Mixed Iron/manganese Multivalent Anion Materialsmentioning

confidence: 99%

“…Reproduced with permission. [219] Copyright 2016, IOP Publishing. e) Schematic illustration of the extraction sequence of Na ions from Na(2) and Na(1) sites and corresponding oxidation states of Mn in the first cation coordination shell surrounding the Na ions.…”

Section: Wwwadvancedsciencenewscommentioning

confidence: 99%

High‐Abundance and Low‐Cost Metal‐Based Cathode Materials for Sodium‐Ion Batteries: Problems, Progress, and Key Technologies

Chen

Liu

Wang

et al. 2019

Advanced Energy Materials

224

149

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Recently, room-temperature stationary sodium-ion batteries (SIBs) have received extensive investigations for large-scale energy storage systems (EESs) and smart grids due to the huge natural abundance and low cost of sodium. The SIBs share a similar "rocking-chair" sodium storage mechanism with lithium-ion batteries; thus, selecting appropriate electrodes with a low cost, satisfactory electrochemical performance, and high reliability is the key point for the development for SIBs. On the other hand, the carefully chosen elements in the electrodes also largely determine the cost of SIBs. Therefore, earth-abundantmetal-based compounds are ideal candidates for reducing the cost of electrodes. Among all the high-abundance and low-cost metal elements, cathodes containing iron and/or manganese are the most representative ones that have attracted numerous studies up till now. Herein, recent advances on both ironand manganese-based cathodes of various types, such as polyanionic, layered oxide, MXene, and spinel, are highlighted. The structure-function property for the iron-and manganese-based compounds is summarized and analyzed in detail. With the participation of iron and manganese in sodium-based cathode materials, real applications of room-temperature SIBs in large-scale EESs will be greatly promoted and accelerated in the near future.

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Engineering of Polyanion Type Cathode Materials for Sodium‐Ion Batteries: Toward Higher Energy/Power Density

Zhang

et al. 2020

Adv Funct Materials

156

115

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The development of high energy/power density sodium-ion batteries (SIBs) is still challenged by the high redox potential of Na/Na + and large radius of Na + ions, thus requiring extensive further improvement to, in particular, enhance the capacity and voltage of cathode materials. Among the various types of cathodes, the polyanion cathodes have emerged as the most pragmatic option due to their outstanding thermostability, unique inductive effect, and flexible structures. In this Review, a critical overview of the design principles and engineering strategies of polyanion cathodes that could have a pivotal role in developing high energy/power density SIBs are presented. Specifically, the engineering of polyanion cathode materials for higher voltage and specific capacity to increase energy density is discussed. The way in which morphology control, architectural design, and electrode processing have been developed to increase power density for SIBs is also analyzed. Finally, the remaining challenges and the future research direction of this field are presented.

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First principles study of the crystal, electronic structure, and diffusion mechanism of polaron-Na vacancy of Na₃MnPO₄CO₃for Na-ion battery applications

Cited by 19 publications

References 29 publications

Research Progress in Multielectron Reactions in Polyanionic Materials for Sodium‐Ion Batteries

Research Progress in Multielectron Reactions in Polyanionic Materials for Sodium‐Ion Batteries

High‐Abundance and Low‐Cost Metal‐Based Cathode Materials for Sodium‐Ion Batteries: Problems, Progress, and Key Technologies

Engineering of Polyanion Type Cathode Materials for Sodium‐Ion Batteries: Toward Higher Energy/Power Density

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