Rational design of Ti-based oxygen redox layered oxides for advanced sodium-ion batteries

Lee, Jaewoon; Koo, Sojung; Lee, Jun Young; Kim, Duho

doi:10.1039/d1ta00669j

Cited by 11 publications

(10 citation statements)

References 48 publications

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“…[3][4][5][6] Charge-compensation mechanisms via the generation of oxygen ions upon charging were first introduced with Li 2 MnO 3 as a representative Liexcess cathode for LIBs, which provided an intriguing possibility by enabling the exploitation of oxygen redox (OR) reactions for SIBs. [7][8][9] For a first application of an OR reaction in Na-based layered oxides, Li-excess O3-type Na[Li 1/3 Mn 2/3 ] O 2 with a Mn/Li ratio (R) of 2 was theoretically designed based on first-principles calculations, and then its desired structure and OR mechanism were also experimentally synthesized and identified. [10,11] The trigger for the OR reaction in Li 2 MnO 3 and Na[Li 1/3 Mn 2/3 ]O 2 originates from the fact that it is not straightforward to further oxidize Mn 4+ (3d-t 2g 3…”

Section: Doi: 101002/aenm202201319mentioning

confidence: 99%

Unified Picture of (Non)Hysteretic Oxygen Capacity in O3‐Type Sodium 3d Layered Oxides

Lee

Park

Choi

et al. 2022

Advanced Energy Materials

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A unified picture of the generalized mechanism that elucidates the (non)hysteretic oxygen capacities of O3‐type Na1−x[Li2/6Mn3/6M1/6]O2 (M = Mn4+, Ni4+, and Ti4+) layered oxides is suggested to provide a critical factor in inducing ideal reversibility for an oxygen redox (OR) reaction using the new concept, the “potential‐pillar” effect. Considering that there is no formation of interlayer oxygen–oxygen (OO) dimers at x = 1.0 in Na1−x[Li2/6Mn3/6Ti1/6]O2, the phase stabilities reveal that the biphasic reaction occurs in Na1−x[Li2/6Mn3/6Ni1/6]O2 (0.5 ≤ x ≤ 1.0), and the monophasic reaction takes place in Na1−x[Li2/6Mn3/6Ti1/6]O2 during desodiation. The electronic structures of cations and anions unambiguously show OR reactions over the full vacancy range, and the oxygen ions comprising TiO6 are relatively deactivated compared with those of NiO6 upon electrochemical OR reaction. This is deemed as an intriguing “potential‐pillar” effect, in which the chemically stiff Ti4+(3d)O(2p) bond locally retains a strong electrostatic repulsion between the mixed layers. This unified concept based on an in‐depth understanding of the three cathode models not only accounts for the origin of the (non)hysteretic oxygen capacities, but also provides an exciting local structure viewpoint for harnessing the full potential of OR reactions for high energy‐density sodium‐ion batteries.

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Section: Doi: 101002/aenm202201319mentioning

confidence: 99%

Unified Picture of (Non)Hysteretic Oxygen Capacity in O3‐Type Sodium 3d Layered Oxides

Lee

Park

Choi

et al. 2022

Advanced Energy Materials

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“…The electrode material of the insertion/extraction reaction type is still the researcher's favorite. As a classic candidate for insertion, titanium‐based anode materials have attracted great attention from the scientific community 16–18 …”

Section: Introductionmentioning

confidence: 99%

“…As a classic candidate for insertion, titanium-based anode materials have attracted great attention from the scientific community. [16][17][18] For titanium dioxide (TiO 2 ), it is one of the most potential SIB candidate materials due to its rich content, nonpolluting nature, stability, and safety. 19 Thanks to its own pseudo-capacitance behavior, TiO 2 has nice sodium storage performance.…”

Section: Introductionmentioning

confidence: 99%

TiO₂ bunchy hierarchical structure with effective enhancement in sodium storage behaviors

et al. 2022

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Bronze phase TiO2 [TiO2(B)] has great research potential for sodium storage since it has a higher theoretical capacity and ion mobility compared with other phases of TiO2. In this case, preparing porous TiO2(B) nanosheets, which can provide abundant sodium insertion channels, is the most effective way to improve transport kinetics. Here, we use the strong one‐dimensional TiO2 nanowires as the matrix for stringing these nanosheets together through a simple solvothermal method to build a bunchy hierarchical structure [TiO2(B)‐BH], which has fast pseudocapacitance behavior, high structural stability, and effective ion/electron transport. With the superiorities of this structure design, TiO2(B)‐BH has a higher capacity (131 vs. 70 mAh g−1 [TiO2‐NWs] at 0.5 C). And it is worth mentioning that the reversible capacity of up to 500 cycles can still be maintained at 85 mAh g−1 at a high rate of 10 C. Meanwhile, we also further analyzed the sodium storage mechanism through the ex‐situ X‐ray powder diffraction test, which proved the high structural stability of TiO2(B)‐BH in the process of sodiumization/de‐sodiumization. This strategy of uniformly integrating nanosheets into a matrix can also be extended to preparing electrode material structures of other energy devices.

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“…Anionic redox using oxygen ions is a new redox paradigm to obtain high-energy-density oxide cathodes for lithium- and sodium-ion batteries (LIBs and SIBs), surpassing conventional cationic redox reactions based on transition metals (TMs). − The intriguing oxygen redox (OR) at ∼4.5 V vs. Li + /Li was first introduced with a representative Li-excess layered oxide, Li 2 MnO 3 , also denoted as Li[Li 1/3 Mn 2/3 ]O 2 . It was found to deliver an extraordinary charge capacity. , Its fundamental redox mechanism originates from a redox-inactive Mn 4+ ion at an octahedral site coordinated with six oxygen ions in Li-excess Mn oxide. − Not only utilizing the Mn 4+ ion for OR but also several other strategies, such as increasing TM–O bond covalency, substituting TM for 3 d 0 or alkali metals, introducing TM vacancies in the TM layer, and using cation disordered structures, have been proposed. − However, the promising oxygen capacity of Li[Li 1/3 Mn 2/3 ]O 2 is not preserved in subsequent discharge processes, in addition to an unwanted voltage drop and capacity decrease.…”

Section: Introductionmentioning

confidence: 99%

Physicochemical Screen Effect of Li Ions in Oxygen Redox Cathodes for Advanced Sodium-Ion Batteries

et al. 2022

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Unlike in lithium-ion batteries (LIBs), in sodiumion batteries (SIBs), nonhysteretic oxygen redox (OR) reactions are observed in Li-excess Na-layered oxides. This necessitates an understanding of the reaction mechanism of an O3-type Li-excess Mn oxide, Na[Li 1/3 Mn 2/3 ]O 2 , a novel OR material designed for advanced SIBs. It could establish the role of Li in triggering nonhysteretic oxygen capacities during (de)sodiation. Three biphasic mechanisms were compared using first-principles calculations under the desodiation modes: (i) Na/vacancy ordering, (ii) Li migration in the NaO 2 layer, and (iii) in-plane Mn migration. The migrated Li ions generated a "physicochemical screen" effect upon electrochemical OR reactions in the oxide cathode. Thermodynamic formation energies showed different biphasic pathways upon charging in Na 1−x [Li 2/6 Mn 4/6 ]O 2 (NLMO) under the three modes. O−O bond population indicated that biphasic-reaction paths -i and -iii were derived from generating inter/ intralayer O−O dimers, and path-iii was triggered by the formation of a Mn−O 2 −Mn moiety. However, Li migration exhibited an ideal OR process (O 2− /O n− ) without forming anionic dimers. The electronic structures of Mn(3d) and O(2p) revealed that Li migration pushed lattice-based O(2p)-hole states to a high energy level, resulting in the chemical suppression of O 2 molecule formation. Selectively decoupled oxygen ordering indicated that the oxygen species coordinated with two Mn (O Mn2 ) derived from Li migration played an important role in nonhysteretic oxygen capacities during cycling. From these findings, we propose the "physicochemical screen" concept that physically suppresses interlayer O−O dimers and chemically hinders discretized O(2p)− O(2p) states formed by molecular O 2 . This could significantly impact the role of Li ions in Li-excess OR-layered oxides for SIBs.

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Rational design of Ti-based oxygen redox layered oxides for advanced sodium-ion batteries

Abstract: Considering Mn4+ (3d3)-based cations, various layered oxides (A[AyM1-y]O2, where A and M refer to alkali metals and transition metals, respectively) exhibiting oxygen-redox reactions have been investigated extensively to achieve high...

Cited by 11 publications

References 48 publications

Unified Picture of (Non)Hysteretic Oxygen Capacity in O3‐Type Sodium 3d Layered Oxides

Unified Picture of (Non)Hysteretic Oxygen Capacity in O3‐Type Sodium 3d Layered Oxides

TiO₂ bunchy hierarchical structure with effective enhancement in sodium storage behaviors

Physicochemical Screen Effect of Li Ions in Oxygen Redox Cathodes for Advanced Sodium-Ion Batteries

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Rational design of Ti-based oxygen redox layered oxides for advanced sodium-ion batteries

Abstract: Considering Mn4+ (3d3)-based cations, various layered oxides (A[AyM1-y]O2, where A and M refer to alkali metals and transition metals, respectively) exhibiting oxygen-redox reactions have been investigated extensively to achieve high...

Cited by 11 publications

References 48 publications

Unified Picture of (Non)Hysteretic Oxygen Capacity in O3‐Type Sodium 3d Layered Oxides

Unified Picture of (Non)Hysteretic Oxygen Capacity in O3‐Type Sodium 3d Layered Oxides

TiO2 bunchy hierarchical structure with effective enhancement in sodium storage behaviors

Physicochemical Screen Effect of Li Ions in Oxygen Redox Cathodes for Advanced Sodium-Ion Batteries

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TiO₂ bunchy hierarchical structure with effective enhancement in sodium storage behaviors