Exceptionally highly stable cycling performance and facile oxygen-redox of manganese-based cathode materials for rechargeable sodium batteries

Konarov, Aishuak; Jo, Jae Hyeon; Choi, Ji Ung; Bakenov, Zhumabay; Yashiro, Hitoshi; Kim, Jongsoon; Myung, Seung Taek

doi:10.1016/j.nanoen.2019.02.042

Cited by 110 publications

(102 citation statements)

References 44 publications

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“…The cells retained 36%, 45%, 67%, and 87% of the initial capacity for 100 cycles for the x = 0.0, 0.05, 0.1, and 0.2 electrodes, respectively. [37] This is due to the additional charge transfer of high-valence transition metal clusters, which is consistent with the results of Maitra et al [30] The spectrum returned to its initial state when the electrode was discharged to 1.5 V, indicating the occurrence of a reversible oxygen-redox reaction. This indicates reversible sodium storage capability.…”

Section: Resultssupporting

confidence: 91%

Controlled Oxygen Redox for Excellent Power Capability in Layered Sodium‐Based Compounds

Kim

Konarov

et al. 2019

Advanced Energy Materials

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resources. [1][2][3][4][5] However, because of the slightly higher standard electrode potential of sodium (−2.7 V vs the standard hydrogen electrode (SHE)) than lithium (−3.02 V vs SHE), high-capacity electrode materials are needed for SIBs to compensate for their lower operation voltage and to achieve energy densities comparable to those of LIBs. It can be assumed that the cost of SIBs can be lowered relative to that of LIBs because of the cost-effectiveness of sodium resources. [6] These factors encourage us to explore potential highenergy-density cathode materials for SIBs.Among the various crystal structures of Na-containing compounds, layered structures have been intensively investigated because of their high capacity delivered under moderate operation conditions. The related layered structures are classified as O3, P2, P3, etc., according to the stacking sequence of the transition metals and alkali ions. [7][8][9] Layered sodium transition metal oxides of the form Na x MO 2 (M = Mn, Fe, Co, Ni, Cr, etc.) are stable in the P2 structure for Na contents (x) in the range of 0.3-0.7. This structure enables sodium ion diffusion between the two face-sharing trigonal prismatic sites such that P2-type layered materials generally exhibit higher discharge capacities than other layered materials. [10][11][12][13][14][15][16][17][18] Na 0.67 MnO 2 is one of the most common compounds among P2-type materials. [19][20][21][22][23] It delivers a high discharge capacity of over 175 mAh g −1 but exhibits severe capacity fade during cycling. One of the main reasons for this capacity fade is the structural disintegration caused by the Jahn-Teller effect of Mn 3+ ions in the MnO 6 octahedra, with elongation of the Mn 3+ -O distance along one direction. This Jahn-Teller effect can be mitigated by increasing the overall Mn oxidation state by substituting Mn with other elements, such as Ni, Co, Fe, Mg, and Al. [24][25][26][27][28][29] For example, improved cyclability was achieved in Mg-substituted Na 0.67 Mn 1−x Mg x O 2 (0.0 ≤ x ≤ 0.2) by suppressing the electrochemical activity of the Jahn-Teller Mn 3+ ions; however, this improvement was attained at the expense of the specific capacity. [26] Recently, Yabuuchi et al. [27] introduced a high-capacity P2-type Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 material that exhibited capacities of over 150 mAh g −1 on charge and 220 mAh g −1 on discharge by raising the upper voltage cut-off to 4.6 V. Note that the average oxidation state of Mn in the compound is ≈3.85+, meaning that it cannot exhibit such a high charge capacity. The A high-rate of oxygen redox assisted by cobalt in layered sodium-based compounds is achieved. The rationally designed Na 0.6 [Mg 0.2 Mn 0.6 Co 0.2 ]O 2 exhibits outstanding electrode performance, delivering a discharge capacity of 214 mAh g −1 (26 mA g −1 ) with capacity retention of 87% after 100 cycles. High rate performance is also achieved at 7C (1.82 A g −1 ) with a capacity of 107 mAh g −1 . Surprisingly, the Na 0.6 [Mg 0.2 Mn 0.6 Co 0.2 ]O 2 compound is able to deliver...

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Section: Resultssupporting

confidence: 91%

Controlled Oxygen Redox for Excellent Power Capability in Layered Sodium‐Based Compounds

Kim

Konarov

et al. 2019

Advanced Energy Materials

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“…During initial charging, the (002), (004), and (104) peaks, representative of the evolution of the c and a lattice parameters of the oxide, shifted to higher angle with rapid attenuation of intensity. [ 18 ] Meanwhile, it is worth mentioning that a new peak with a wide full width at half maximum (FWHM) appeared around 17°, which can be rationally attributed to the formation of the high‐voltage Z phase generally accompanying anionic redox reaction in Na‐deficient layered oxides at high voltages. [ 19 ] It is correlated with the d Q /d V observation of a plateau at around 3.6 V (Figure S5, Supporting Information), indicative of the phase transition from the original P2 to a Z phase.…”

Section: Figuresupporting

confidence: 56%

Stabilizing Reversible Oxygen Redox Chemistry in Layered Oxides for Sodium‐Ion Batteries

Cao

Qiao

et al. 2020

Advanced Energy Materials

108

123

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premise of guaranteeing electrochemical stability upon cycling. [2] Not rigidly limited to conventional redox reactions based on transition metal (TM) centers, redox activity centered at the oxide anions is emergently viewed as a promising strategy to effectively increase the energy density of SIBs. [3] When conventional cationic and novel anionic activities are triggered simultaneously, several cathodes delivering boosted capacities break the shackle of reversible TM redox couples. [4] As a representative example, Mn-based layered cathodes Na x [M y Mn 1−y ]O 2 (M = Li, Mg and Zn) deliver considerable capacity in the initial discharge process by employing the Mn-based and oxygen-related redox reactions simultaneously. [5] Based on the experience of Li-rich layered cathode materials, the utilization of these attractive anionic redox capacities would accompany harmful irreversible processes induced by excessive oxygen oxidation during charging process. [6] More importantly, irreversible lattice oxygen loss inevitably triggers deleterious migration of TM and structural distortion upon cycling, resulting in capacity decay, fading of the output potential and sluggish kinetics. [7] Therefore, the foremost challenge would focus on not only triggering unconventional anionic redox capacity but also stabilizing reversible these oxygen-related reactions. [5d,8] However, puzzled by foggy charge compensation mechanism between TM based and oxygenrelated redox processes, it is difficult to identify the reversible and irreversible anionic redox reactions. [9] Specifically, based on typically obtained "S-shape" discharge voltage profiles, no distinct boundary between TM and oxygen reduction reactions can be observed. [5b,10] More importantly, despite the existence of undesirable lattice oxygen loss during charging, high discharge capacities can still be obtained, which are actually caused by a reduction of TM couples beyond the pristine state. [9,11] In this case, comprehensive and in-depth characterizations including the valence change of TM and oxygen, O 2 evolution, surface/ bulk oxygen states, among others, are required to make a clear assignment of TM-based and oxygen-related redox capacity, which is essentially helpful for the development of anionic redox activity and inform subsequent materials selection. [3c,5a,12] Furthermore, in sodium-ion batteries, the trigger of anionic redox reactions is typically by the introduction of NaOM configuration, in which M is defined as the Li, Na, Mg and Zn within TM layer. [4c,5a,8,12c,13] Meanwhile, the Tarascon group has proved that lowering the energy of the transition metal d Triggering oxygen-related activity is demonstrated as a promising strategy to effectively boost energy density of layered cathodes for sodium-ion batteries. However, irreversible lattice oxygen loss will induce detrimental structure distortion, resulting in voltage decay and cycle degradation. Herein, a layered structure P2-type Na 0.66 Li 0.22 Ru 0.78 O 2 cathode is designed, delivering reversible ...

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“…However, the larger ionic radius and sluggish kinetics of Na raise difficulties for the construction of SIBs with high energy/power densities and long lifespan. Therefore, it is paramount to exploit advanced host materials with a large framework with abundant ion channels …”

Section: Introductionmentioning

confidence: 99%

High‐Performance Manganese Hexacyanoferrate with Cubic Structure as Superior Cathode Material for Sodium‐Ion Batteries

Tang

Feng

et al. 2020

Adv Funct Materials

171

161

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Sodium manganese hexacyanoferrate (NaxMnFe(CN)6) is one of the most promising cathode materials for sodium‐ion batteries (SIBs) due to the high voltage and low cost. However, its cycling performance is limited by the multiple phase transitions during Na+ insertion/extraction. In this work, a facile strategy is developed to synthesize cubic and monoclinic structured NaxMnFe(CN)6, and their structure evolutions are investigated through in situ X‐ray diffraction (XRD), ex situ Raman, and X‐ray photoelectron spectroscopy (XPS) characterizations. It is revealed that the monoclinic phase undergoes undesirable multiple two‐phase reactions (monoclinic ↔ cubic ↔ tetragonal) due to the large lattice distortions caused by the Jahn–Teller effects of Mn3+, resulting in poor cycling performances with 38% capacity retention. The cubic NaxMnFe(CN)6 with high structural symmetry maintains the structural stability during the repeated Na+ insertion/extraction process, demonstrating impressive electrochemical performances with specific capacity of ≈120 mAh g−1 at 3.5 V (vs Na/Na+), capacity retention of ≈70% over 500 cycles at 200 mA g−1. In addition, the TiO2//C‐MnHCF full battery is fabricated with an energy density of 111 Wh kg−1, suggesting the great potential of cubic NaxMnFe(CN)6 for practical energy storage applications.

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Exceptionally highly stable cycling performance and facile oxygen-redox of manganese-based cathode materials for rechargeable sodium batteries

Cited by 110 publications

References 44 publications

Controlled Oxygen Redox for Excellent Power Capability in Layered Sodium‐Based Compounds

Controlled Oxygen Redox for Excellent Power Capability in Layered Sodium‐Based Compounds

Stabilizing Reversible Oxygen Redox Chemistry in Layered Oxides for Sodium‐Ion Batteries

High‐Performance Manganese Hexacyanoferrate with Cubic Structure as Superior Cathode Material for Sodium‐Ion Batteries

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