Stability of Prismatic and Octahedral Coordination in Layered Oxides and Sulfides Intercalated with Alkali and Alkaline-Earth Metals

Radin, Maxwell D.; Ven, Anton Van der

doi:10.1021/acs.chemmater.6b03454

Cited by 86 publications

(111 citation statements)

References 61 publications

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“…relative positions of the TM d-and oxygen p-states). Additionally, PBE accurately predicts voltage trends, 47,[62][63][64][65] defect formation energies 66 and TM layer stacking sequences 67 of layered TM oxide materials. Adding a Hubbard correction parameter (i.e.…”

Section: Resultsmentioning

confidence: 84%

Unraveling the Effects of Al Doping on the Electrochemical Properties of LiNi_0.5Co_0.2Mn_0.3O₂Using First Principles

Dixit

Markovsky

Aurbach

et al. 2017

J. Electrochem. Soc.

125

108

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One of the prevailing approaches to tune properties of materials is lattice doping with metal cations. Aluminum is a common choice, and numerous studies have demonstrated the ability of Al 3+ doping to stabilize different positive electrode materials, such as Li [Ni-Co-Mn] In recent decades, rechargeable batteries have demonstrated tremendous promise as alternate energy storage devices. In particular, Li-ion batteries (LIB) have revolutionized electronic devices, ranging from portable electronics to electric vehicles (EVs), due to their excellent power and energy density.1 The bottleneck of LIB in terms of capacity and performance is often considered to be the nature of the positive electrodes (cathodes).1-6 Among the cathode materials for LIB, layered transition metal (TM) oxides (LiTMO 2, TM = Ni, Co, Mn) are very promising candidates, and in particular LiCoO 2 . However, in spite of the commercialization and wide use of LiCoO 2 in portable LIB, it suffers from several drawbacks. Key disadvantages include high cost and safety concerns associated with cobalt.2-6 Other limitations of LiCoO 2 include low practical capacity (140 mAhg −1 ) and oxygen loss on charge. 7-10 Consequently, in a quest to move beyond LiCoO 2 , a new class of mixed transition metal oxides were designed, wherein Ni and Mn were introduced into the material (i.e. Li[Ni x Co y Mn z ]O 2 or simply NCM).11,12 The Ni-rich variants of these materials have emerged as the most promising low-cost and high capacity alternatives to the already mature LiCoO 2 . 10,13,14,11 These Nirich materials show improved performance; however, the capacities and stabilities are still too low for practical commercialization for EVs. 12Key hurdles in the commercialization of these materials for EV applications are associated with oxygen release at high voltages and cation migration, which leads to structural transformations. 15,16 Recently, it has been demonstrated that oxygen loss and cation migration are concurrent events. 16,17 To address these challenges, lattice doping of cations 18 has been adopted to improve the performance of these materials, and various cations were explored.18-24 A particularly promising dopant for these materials is Al, although its effect is still not fully understood. Early theoretical studies proposed that Al substitution in LiCoO 2 25 and NCMs 26 could increase the intercalation potential, and these predictions were verified experimentally. 27 Various studies reported beneficial effects of Al doping on LiCoO 2 and LiNiO 2 and NCMs. ), and found that Al doping reduces the reversible capacity, but significantly improves the thermal stability of the electrode in the de-intercalated state.36 Al doping in Li-rich-Mn-rich NCMs has also improved the thermal stabilities of these materials. 37 In a detailed theoretical study, Dianat et al. studied the effect of Al doping on Li-Mn-Ni-O based cathode materials.38 They reported that Al doping stabilizes the partially intercalated states, but increases the Li-diffusion barriers. Park et al. studie...

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Section: Resultsmentioning

confidence: 84%

Unraveling the Effects of Al Doping on the Electrochemical Properties of LiNi_0.5Co_0.2Mn_0.3O₂Using First Principles

Dixit

Markovsky

Aurbach

et al. 2017

J. Electrochem. Soc.

125

108

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“…35 shows neither distinct biphasic processes nor the formation of new O3 phases. Such complex patterns at the end of charge are not unique and have been reported previously in O3-type layered compounds, such as Na x Mn 1/3 Fe 2/3 O 2 , Li x CoO 2 and Li x NiO 2 , [34][35][36][37] with "ABAB" stacking and is termed O1-type according to the Delmas notation for layered oxides [38] when approaching the full extraction of alkaline ions. Such a pattern cannot be indexed easily with any known structure, therefore likely arises from a compositional and/or structural defective compound.…”

Section: Resultsmentioning

confidence: 94%

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

152

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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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“…[75,76] Therefore, when ions are present between the metal oxide sheets, the O1 structure is destabilized. Section 2.1).…”

Section: Crystallographymentioning

confidence: 99%

“…[7,8,76,282] For example, O3 Na x CoO 2 undergoes a first-order transformation to P′3 when deintercalated beyond x ≈ 0.8, [57] as shown in Figure 24. In large part, this can be attributed to the fact that Na + ions, unlike Li + ions, are large enough to reside in prismatic coordination, making the P2 and P3 structures stable at intermediate compositions.…”

Section: Wwwadvancedsciencenewscommentioning

confidence: 99%

Narrowing the Gap between Theoretical and Practical Capacities in Li‐Ion Layered Oxide Cathode Materials

Radin

Sina

et al. 2017

Advanced Energy Materials

Self Cite

538

566

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Although layered lithium oxides have become the cathode of choice for state‐of‐the‐art Li‐ion batteries, substantial gaps remain between the practical and theoretical energy densities. With the aim of supporting efforts to close this gap, this work reviews the fundamental operating mechanisms and challenges of Li intercalation in layered oxides, contrasts how these challenges play out differently for different materials (with emphasis on Ni–Co–Al (NCA) and Ni–Mn–Co (NMC) alloys), and summarizes the extensive corpus of modifications and extensions to the layered lithium oxides. Particular emphasis is given to the fundamental mechanisms behind the operation and degradation of layered intercalation electrode materials as well as novel modifications and extensions, including Na‐ion and cation‐disordered materials.

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Stability of Prismatic and Octahedral Coordination in Layered Oxides and Sulfides Intercalated with Alkali and Alkaline-Earth Metals

Cited by 86 publications

References 61 publications

Unraveling the Effects of Al Doping on the Electrochemical Properties of LiNi_0.5Co_0.2Mn_0.3O₂Using First Principles

Unraveling the Effects of Al Doping on the Electrochemical Properties of LiNi_0.5Co_0.2Mn_0.3O₂Using First Principles

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

Narrowing the Gap between Theoretical and Practical Capacities in Li‐Ion Layered Oxide Cathode Materials

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Stability of Prismatic and Octahedral Coordination in Layered Oxides and Sulfides Intercalated with Alkali and Alkaline-Earth Metals

Cited by 86 publications

References 61 publications

Unraveling the Effects of Al Doping on the Electrochemical Properties of LiNi0.5Co0.2Mn0.3O2Using First Principles

Unraveling the Effects of Al Doping on the Electrochemical Properties of LiNi0.5Co0.2Mn0.3O2Using First Principles

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

Narrowing the Gap between Theoretical and Practical Capacities in Li‐Ion Layered Oxide Cathode Materials

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Product

Resources

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Unraveling the Effects of Al Doping on the Electrochemical Properties of LiNi_0.5Co_0.2Mn_0.3O₂Using First Principles

Unraveling the Effects of Al Doping on the Electrochemical Properties of LiNi_0.5Co_0.2Mn_0.3O₂Using First Principles

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