Exploring the Charge Compensation Mechanism of P2-Type Na0.6Mg0.3Mn0.7O2 Cathode Materials for Advanced Sodium-Ion Batteries

Cheng, Chen; Ding, Manling; Yan, Tianran; Dai, Kun; Mao, Jing; Zhang, Nian; Zhang, Liang; Guo, Jinghua

doi:10.3390/en13215729

Cited by 17 publications

(15 citation statements)

References 46 publications

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“…[ 49 ] The pre‐edge features are further split into t 2g (529.7 eV) and e g (531.8 eV) states because of the synergistic effect of the octahedral crystal field and exchange energy. [ 49,50 ] Because the pre‐edge feature is dominated by the TM 3d state hybridized with the O 2p state, the integrated pre‐edge intensity provides information about the hybridization strength between TM and O. [ 44,49 ] For NAM01, the evolution of the integrated pre‐edge intensity agrees well with that of the Ni oxidation state, further identifying the participation of reversible oxygen redox at high voltage according to RCM.…”

Section: Resultsmentioning

confidence: 94%

Anionic Redox Activities Boosted by Aluminum Doping in Layered Sodium‐Ion Battery Electrode

et al. 2022

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Prussian blue compounds, [4] have been extensively explored. Among these candidates, P2-type layered transition metal (TM) oxides (Na x TMO 2 , 0.5 ≤ x ≤ 0.8) have attracted much attention because of their relatively high theoretical capacities and low costs. [5] Nevertheless, Na x TMO 2 materials usually undergo an undesired P2-O2 phase transition in high-voltage regions, leading to a large volume change, rapid capacity decay, and poor lifetime. [5b,6] Recently, this issue has been largely mitigated by doping inactive material elements (such as Li, [7] Mg, [6] Ti, [8] Al, [9] and Zn [10] ) in TM layers, but at the expense of specific capacity.Apart from the cationic redox, the utilization of anionic redox activities provides a new avenue for attaining high-capacity electrode materials. Nevertheless, the nature of the oxygen redox chemistry is still under active debate, and the representative hypotheses mainly include the following: i) Tarascon et al. visualized the formation of (OO) n− peroxo-like dimers with shortened OO distances in Li-rich layered electrode materials; [11] ii) Bruce et al. proposed that the localized electron holes on O atoms, rather than true O 2 2− peroxide, could be generated upon Li + removal; [12] while iii) Ceder et al. suggested that the nonbonding oxygen states from LiOLi structural configurations in alkalirich and disordered systems are responsible for the oxygen redox reaction. [13] More recently, the formation of molecular O 2 trapped Sodium-ion batteries (SIBs) have attracted widespread attention for large-scale energy storage, but one major drawback, i.e., the limited capacity of cathode materials, impedes their practical applications. Oxygen redox reactions in layered oxide cathodes are proven to contribute additionally high specific capacity, while such cathodes often suffer from irreversible structural transitions, causing serious capacity fading and voltage decay upon cycling, and the formation process of the oxidized oxygen species remains elusive. Herein, a series of Al-doped P2-type Na 0.6 Ni 0.3 Mn 0.7 O 2 cathode materials for SIBs are reported and the corresponding charge compensation mechanisms are investigated qualitatively and quantitatively. The combined analyses reveal that Al doping boosts the reversible oxygen redox reactions through the reductive coupling reactions between orphaned O 2p states in NaOAl local configurations and Ni 4+ ions, as directly evidenced by X-ray absorption fine structure results. Additionally, Al doping also induces an increased interlayer spacing and inhibits the unfavorable P2 to O2 phase transition upon desodiation/sodiation, which is common in P2-type Mn-based cathode materials, leading to the great improvement in capacity retention and rate capability. This work provides deeper insights into the development of structurally stable and high-capacity layered cathode materials for SIBs with anion-cation synergetic contributions.

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Section: Resultsmentioning

confidence: 94%

Anionic Redox Activities Boosted by Aluminum Doping in Layered Sodium‐Ion Battery Electrode

et al. 2022

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“…for which a third of the TM layers can be filled by mono-or divalent elements such as Li [17][18][19][20][21][22][23][24][25][26][27][28][29], Mg [46][47][48][49][50][51][52][53][54][55][56], and Zn [57][58][59] to induce an average oxidation state of Mn of 4+. Hence, the extraction of sodium ions in the structure is not theoretically possible because of the difficulty of the oxidation of Mn 4+ to higher valence states in an octahedral environment, in which the electrolyte does not decompose.…”

Section: Sodium-deficient Layered Structuresmentioning

confidence: 99%

“…Sodium-deficient layered compounds, Na x [A y TM 1-y ]O 2 (A: Li [17][18][19][20][21][22][23][24][25][26][27][28][29], Mg [46][47][48][49][50][51][52][53][54][55][56], Zn [57][58][59][60], Ni [61][62][63][64][65][66], or Cu The prismatic environment for sodium ions enables maintenance of the large interlayer distances during de/sodiation, which is beneficial for facile diffusion of sodium ions and smooth phase transitions. However, in addition to the aforementioned merits, the sodium deficiency in the compounds results in small charge capacities (80-150 mAh g −1 ), thereby resulting in an abnormal CE in the first cycle that should be circumvented for their adoption in practical applications.…”

Section: Sodium-deficient Layered Structuresmentioning

confidence: 99%

Section: Sodium-deficient Layered Structuresmentioning

confidence: 99%

“…The selection of elements in transition metal layers is of great importance in improving the reversibility and controlling the operation voltage of the anionic redox reaction, namely, Na x [A y TM 1-y ]O 2 (A: Li [17][18][19][20][21][22][23][24][25][26][27][28][29], Na [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45], Mg [46][47][48][49][50][51][52][53][54][55][56], Zn [57][58][59][60], Ni [61][62][63][64][65][66]…”

Section: Introductionmentioning

confidence: 99%

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Recent Advances in Electrode Materials with Anion Redox Chemistry for Sodium-Ion Batteries

Voronina

Myung

2021

Energy Mater Adv

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The development of sodium-ion batteries (SIBs), which are promising alternatives to lithium-ion batteries (LIBs), offers new opportunities to address the depletion of Li and Co resources; however, their implementation is hindered by their relatively low capacities and moderate operation voltages and resulting low energy densities. To overcome these limitations, considerable attention has been focused on anionic redox reactions, which proceed at high voltages with extra capacity. This manuscript covers the origin and recent development of anionic redox electrode materials for SIBs, including state-of-the-art P2- and O3-type layered oxides. We sequentially analyze the anion activity–structure–performance relationship in electrode materials. Finally, we discuss remaining challenges and suggest new strategies for future research in anion-redox cathode materials for SIBs.

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Unleashing the Potential of Sodium‐Ion Batteries: Current State and Future Directions for Sustainable Energy Storage

Singh

Islam

Meena

et al. 2023

Adv Funct Materials

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Rechargeable sodium‐ion batteries (SIBs) are emerging as a viable alternative to lithium‐ion battery (LIB) technology, as their raw materials are economical, geographically abundant (unlike lithium), and less toxic. The matured LIB technology contributes significantly to digital civilization, from mobile electronic devices to zero electric‐vehicle emissions. However, with the increasing reliance on renewable energy sources and the anticipated integration of high‐energy‐density batteries into the grid, concerns have arisen regarding the sustainability of lithium due to its limited availability and consequent price escalations. In this context, SIBs have gained attention as a potential energy storage alternative, benefiting from the abundance of sodium and sharing electrochemical characteristics similar to LIBs. Furthermore, high‐entropy chemistry has emerged as a new paradigm, promising to enhance energy density and accelerate advancements in battery technology to meet the growing energy demands. This review uncovers the fundamentals, current progress, and the views on the future of SIB technologies, with a discussion focused on the design of novel materials. The crucial factors, such as morphology, crystal defects, and doping, that can tune electrochemistry, which should inspire young researchers in battery technology to identify and work on challenging research problems, are also reviewed.

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Exploring the Charge Compensation Mechanism of P2-Type Na0.6Mg0.3Mn0.7O2 Cathode Materials for Advanced Sodium-Ion Batteries

Cited by 17 publications

References 46 publications

Anionic Redox Activities Boosted by Aluminum Doping in Layered Sodium‐Ion Battery Electrode

Anionic Redox Activities Boosted by Aluminum Doping in Layered Sodium‐Ion Battery Electrode

Recent Advances in Electrode Materials with Anion Redox Chemistry for Sodium-Ion Batteries

Unleashing the Potential of Sodium‐Ion Batteries: Current State and Future Directions for Sustainable Energy Storage

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