Unraveling the role of Ti in the stability of positive layered oxide electrodes for rechargeable Na-ion batteries

Zarrabeitia, Maider; Gonzalo, Elena; Pasqualini, Marta; Ciambezi, M.; Lakuntza, Oier; Nobili, Francesco; Trapananti, A.; Cicco, Andrea Di; Aquilanti, Giuliana; Katcho, Nebil A.; Amo, Juan Miguel López del; Carrasco, Javier; Muñoz‐Márquez, Miguel Ángel; Rojo, Teófilo

doi:10.1039/c9ta02710f

Cited by 62 publications

(27 citation statements)

References 66 publications

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“…To compete with NVPF, it is important to design sodium layered oxides, which can reversibly release and uptake Na + ions via the least number of phase transitions so as to ensure long cycle life while being able to utilize their total capacity in Na‐ion full cells. Ti 4+ substitution for Fe or Mn in both P2 and O3 structures has been found beneficial by various studies in terms of rate capabilities and cycling stability . Among these findings, recent studies have shown that increasing the ionicity of the crystal lattice with Ti 4+ substitution, apart from increasing the redox potential, also helps in reducing number of phase transitions, hence enabling a better cyclability over a larger voltage window .…”

Section: Introductionsupporting

confidence: 71%

“…[12,[16][17][18][19][20][21][22][23] Among these findings, recent studies have shown that increasing the ionicity of the crystal lattice with Ti 4+ substitution, apart from increasing the redox potential, also helps in reducing number of phase transitions, hence enabling a better cyclability over a larger voltage window. They show greater rate capabilities than Li-ion via the least number of phase transitions so as to ensure long cycle life while being able to utilize their total capacity in Na-ion full cells.…”

Section: Introductionmentioning

confidence: 99%

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Reaching the Energy Density Limit of Layered O3‐NaNi_0.5Mn_0.5O₂ Electrodes via Dual Cu and Ti Substitution

Wang

Mariyappan

Vergnet

et al. 2019

Advanced Energy Materials

159

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counterparts, hence offering practical interest for grid applications where capabilities for smoothening fluctuations and low cost are the overriding factors. [1][2][3][4][5][6][7] Most of the Na-ion systems demonstrated till now use hard carbon (HC) as common negative electrode and either sodium layered oxides (Na x TMO 2 , 0 < x ≤ 1, TM = transition metals) or polyanionic compounds (Na 3 V 2 (PO 4 ) 2 F 3 ) as positive electrodes. [8][9][10][11] We have recently benchmarked such Na-ion full cells having sodium layered oxide electrodes with either O3 or P2 structures and TM/TM′ of different nature against Na 3 V 2 (PO 4 ) 2 F 3 /HC cells. [12] Whatever the figures of merit we have checked, such as specific energy, cyclability as well as rate capability, the 3D Na 3 V 2 (PO 4 ) 2 F 3 (NVPF) phase outperforms the layered phases, irrespective of its high molecular weight and modest capacity (128 mAh g −1 , equivalent to 2 Na + exchange). [13] Moreover, sodium based layered oxides reported so far, whatever O or P-type structures, suffer from low redox potential, limited reversible capacity versus carbon in Na-ion full cells (hardly 50% of their theoretical capacity), Na-driven structural instability and moisture sensitivity. [14,15] So how long will this supremacy of NVPF last?To compete with NVPF, it is important to design sodium layered oxides, which can reversibly release and uptake Na + ions Although being less competitive energy density-wise, Na-ion batteries are serious alternatives to Li-ion ones for applications where cost and sustainability dominate. O3-type sodium layered oxides could partially overcome the energy limitation, but their practical use is plagued by a reaction process that enlists numerous phase changes and volume variations while additionally being moisture sensitive. Here, it is shown that the double substitution of Ti for Mn and Cu for Ni in O3-NaNi 0.5 − y Cu y Mn 0.5 − z Ti z O 2 can alleviate most of these issues. Among this series, electrodes with specific compositions are identified that can reversibly release and uptake ≈0.9 sodium per formula unit via a smooth voltage-composition profile enlisting minor lattice volume changes upon cycling as opposed to ΔV/V≈23% in the parent NaNi 0.5 Mn 0.5 O 2 while showing a greater resistance against moisture. The positive attributes of substitution are rationalized by structure considerations supported by density functional theory (DFT) calculations. Electrodes with sustained capacities of ≈180 mAh g −1 are successfully implemented into 18 650 Na-ion cells having greater performances, energy density-wise (≈250 Wh L −1 ), than today's Na 3 V 2 (PO 4 ) 2 F 3 /HC Na-ion technology which excels in rate capabilities. These results constitute a step forward in increasing the practicality of Na-ion technology with additional opportunities for applications in which energy density prevails over rate capability.

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Section: Introductionsupporting

confidence: 71%

Section: Introductionmentioning

confidence: 99%

Reaching the Energy Density Limit of Layered O3‐NaNi_0.5Mn_0.5O₂ Electrodes via Dual Cu and Ti Substitution

Wang

Mariyappan

Vergnet

et al. 2019

Advanced Energy Materials

159

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“…Doping this phase with Ti (P2‐Na 2/3 Mn 0.8 Fe 0.1 Ti 0.1 O 2 ), it is possible to obtain a Co and Ni free cathode that exhibits an extraordinary capacity retention (>95% after 50 cycles) and reaches reversible capacities of more than 130 and 80 mAh g −1 for C/10 and 1C, respectively. [ 47,48 ] Recently, the addition of sacrificial salts in the P2 phases (e.g., NaN 3 , Na 3 P or Na 2 C 4 O 4 ) as additional sources of sodium has been explored, decreasing the irreversible capacity of the first cycle and increasing significantly the capacity and the capacity retention. [ 49–52 ] The O3‐type phases, due to the higher sodium content, provide higher capacities, such as the O3‐NaNi 0.5 Mn 0.5 O 2 phase that can deliver ≈105 and 125 mAh g −1 at rates of 24 and 4.8 mA g −1 , respectively, in the voltage range of 2.2–3.8 V. [ 53 ] The presence of other co‐dopant elements in the appropriate amounts such as Fe, Co, or Ti can improve long‐term cycling ability in addition to excellent specific energy density.…”

Section: Sodium Ion Batteries: Retrospective and Advancesmentioning

confidence: 99%

Na‐Ion Batteries—Approaching Old and New Challenges

Goikolea

Palomares

Wang

et al. 2020

Advanced Energy Materials

Self Cite

351

190

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are proving to be an emergent technology with potentially very attractive properties. They are potentially low cost and environmentally friendly with reduced supply risk. However, the development of NIBs faces various challenges such as low gravimetric and volumetric energy densities and difficulty in achieving broader voltage windows. Although early studies in NIBs date back to the 1970s, just like Li-ion battery (LIB) research, the commercialization of the former systems in 1991 by the team formed by Sony and Asahi Kasei marked a milestone not only in the field of energy storage technology but also in the evolution of the modern society. This technological breakthrough had been possible thanks to several preceding contributions, particularly the works by M. S Whittingham, [1] J. Goodenough, [2,3] and A. Yoshino [4] on the discovery of Li-ion intercalation materials (Nobel Laureates in Chemistry 2019). This important historical event polarized material science research toward Li-ion technology and slowed down considerably the advances in the field of sodium. However, at the end of the 2000s, mainly driven by the concerns about future lithium supply and the uneven worldwide distribution of its reserves and resources, the research on Na-ion reemerged and so did the number of articles published (Figure 1). The intercalation chemistry of both metal ions is very alike, and thus, the materials tested for NIBs could be similar to those used in Li-ion systems. Both systems share the same working principle, and therefore, in terms of manufacturing, the industry producing LIBs can be easily tuned towards NIB fabrication, which is an important asset to invest in and support this technology. NIBs started to reach the market in the early 2010s, about two decades after their Li counterparts. Nevertheless, the progress has been relatively fast due to the straightforward LIB equipment and facility transfer just mentioned. In the search of high performance, low cost, abundance, low environmental impact, long-term cyclability and safety, layered metal oxides, polyanionic compounds and Prussian blue analogues (PBAs) are among the most studied families of Na-ion cathode materials. On the anode side, metallic sodium exhibits the same operation and safety problems as lithium, and therefore, it cannot be considered an option in conventional NIBs. Thus, in this scenario, most of the research has been dominated by the use of disordered carbons, mainly hard carbons (HCs). Other prospective anodes

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“…added Fe and Ni into Na 0.67 MnO 2 and calcinated at 1200 °C to get the P′2‐type Na 0.67 [Ni 0.1 Fe 0.1 Mn 0.8 ]O 2 . As shown in Figure 6c, the O−Ni−O−Mn−O−Fe−O bond in the octahedra of TM layers can suppress the elongation of the Mn−O during the process of discharge, thus it can suppress the Jahn–Teller effect, [41] and other inactive metals (such as Mg, Ti, et al [42] …”

Section: Structural Evolutionmentioning

confidence: 99%

Structural Evolution in P2‐type Layered Oxide Cathode Materials for Sodium‐Ion Batteries

Liu

2021

ChemNanoMat

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Sodium‐ion batteries (SIBs) have attracted much attention due to their abundance, easy accessibility, and low cost. P2‐type layered oxide materials, as one of the most potential cathode candidates for SIBs, have been widely studied. However, various kinds of structural evolution during cycling are harmful to the stability. In the present Minireview, the phase transitions occurring in the process of charge/discharge are summarized, and the mechanism of structural rearrangement and phase transition are introduced. This Minireview is aimed at helping researchers understand the detailed structural evolution, and propose strategies of designing the P2‐type layered oxide cathodes with low strain.

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Unraveling the role of Ti in the stability of positive layered oxide electrodes for rechargeable Na-ion batteries

Abstract: The cycling stability explained through the Ti doping role on the Jahn Teller distortion.

Cited by 62 publications

References 66 publications

Reaching the Energy Density Limit of Layered O3‐NaNi_0.5Mn_0.5O₂ Electrodes via Dual Cu and Ti Substitution

Reaching the Energy Density Limit of Layered O3‐NaNi_0.5Mn_0.5O₂ Electrodes via Dual Cu and Ti Substitution

Na‐Ion Batteries—Approaching Old and New Challenges

Structural Evolution in P2‐type Layered Oxide Cathode Materials for Sodium‐Ion Batteries

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Unraveling the role of Ti in the stability of positive layered oxide electrodes for rechargeable Na-ion batteries

Abstract: The cycling stability explained through the Ti doping role on the Jahn Teller distortion.

Cited by 62 publications

References 66 publications

Reaching the Energy Density Limit of Layered O3‐NaNi0.5Mn0.5O2 Electrodes via Dual Cu and Ti Substitution

Reaching the Energy Density Limit of Layered O3‐NaNi0.5Mn0.5O2 Electrodes via Dual Cu and Ti Substitution

Na‐Ion Batteries—Approaching Old and New Challenges

Structural Evolution in P2‐type Layered Oxide Cathode Materials for Sodium‐Ion Batteries

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Reaching the Energy Density Limit of Layered O3‐NaNi_0.5Mn_0.5O₂ Electrodes via Dual Cu and Ti Substitution

Reaching the Energy Density Limit of Layered O3‐NaNi_0.5Mn_0.5O₂ Electrodes via Dual Cu and Ti Substitution