Powerful oxidizing agents for the oxidative deintercalation of lithium from transition-metal oxides

Wizansky, Abigail R.; Rauch, P.; DiSalvo, Francis J.

doi:10.1016/0022-4596(89)90007-8

Cited by 112 publications

(75 citation statements)

References 9 publications

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“…This is quite consistent with observations of deintercalation products of many layered compounds 5 , 6 .…”

Section: Resultssupporting

confidence: 93%

“…For example, many of the transition metal dichalcogenides are easily intercalated by alkali metals, subsequently these compounds are then easily deintercalated with simple oxidizing agents, such as iodine 4 , 5 . We have shown that more powerful oxidizing agents, such as NO 2 PF 6 and MoF 6 can be used to deintercalate LiCoO 2 . Not only does intercalation/deintercalation give rise to new compounds not easily prepared by other methods, but the physical properties of these new compounds are usually distinct from the parent compounds 6 .…”

Section: Introductionmentioning

confidence: 99%

“…We have shown that more powerful oxidizing agents, such as NO 2 PF 6 and MoF 6 can be used to deintercalate LiCoO 2 . Not only does intercalation/deintercalation give rise to new compounds not easily prepared by other methods, but the physical properties of these new compounds are usually distinct from the parent compounds 6 .…”

Section: Introductionmentioning

confidence: 99%

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Ambient pressure synthesis of ternary group(V) nitrides

Rauch

DiSalvo

1992

Journal of Solid State Chemistry

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“…This is quite consistent with observations of deintercalation products of many layered compounds 5 , 6 .…”

Section: Resultssupporting

confidence: 93%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Ambient pressure synthesis of ternary group(V) nitrides

Rauch

DiSalvo

1992

Journal of Solid State Chemistry

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“…16 The redox potential of NO 2 ϩ /NO 2 is ca. To ensure a complete reaction, the amount of NO 2 BF 4 added was double the amount estimated from Reaction 1.…”

Section: Methodsmentioning

confidence: 99%

Phase Diagram of Li[sub x](Mn[sub y]Fe[sub 1−y])PO[sub 4] (0≤x, y≤1)

Yamada

Kudo²,

Liu³

2001

J. Electrochem. Soc.

337

381

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The room temperature ͑x, y͒ two-dimensional phase diagram of the olivine-type solid-solution, Li x (Mn y Fe 1Ϫy )PO 4 (0 р x, y р 1, orthorhombic, D 2h 16 : Pmnb), is determined. The x-dependent changes in the unit cell dimensions at various fixed Mn contents y are analyzed in detail. The manganese substitution for iron in the octahedral 4c sites induces 1, the two-phase Mn . The conversion, 2, is complete at around y ϭ 0.6. The phase instability, 3, makes the Mn-rich phase (y Ͼ 0.8) unsuitable for battery applications. The local lattice deformation around Mn 3ϩ is severe enough to induce significant selective damping in the extended X-ray absorption fine structure for Mn The oxidation ͑charge͒ of LiM 2ϩ PO 4 to M 3ϩ PO 4 induces a reduction in the unit cell volume. This shrinkage compensates for the volume expansion of the carbon anodes in the charge process and contributes to efficient use of volume in a practical lithium-ion cell. The opposite movement of lithium ions and electrons occurs during the discharge process, while the transition metal M is reduced from trivalent to divalent.The LiMPO 4 crystal has an orthorhombic unit cell (D 2h 16 , space group Pmnb,) which accommodates four units of LiMPO 4 .11 As a typical example, LiFePO 4 has unit-cell dimensions of a ϭ 6.008(1) Å, b ϭ 10.324(2) Å, and c ϭ 4.694(1) Å. Graphic representations of the crystal structure have been given in many references. 1,3,4,11 Both the Li and M atoms are in octahedral sites with Li located in the 4a and M in the 4c positions. The oxygen atoms are nearly hexagonal closed-packed and the M atoms occupy zigzag chains of corner-shared octahedra running parallel to the c axis in alternate a-c planes. These chains are bridged by corner-and edge-sharing (PO 4 ͒ 3Ϫ polyanions to form a host structure with strong three-dimensional bonding. The Li ϩ ions in 4a sites form continuous linear chains of edge-shared octahedra running parallel to the c axis in the other a-c planes, which makes two-dimensional motion possible.The charge-discharge reaction of the presently used materials, such as the layered rock salt systems, LiCoO 2 , LiNiO 2 ͑space group, R3 m), and a spinel framework system Li 0.5 MnO 2 ͑space groups: Fd3m) are all based on the M 4ϩ /M 3ϩ couple in edge-shared MO 6 octahedra in the closed-packed oxygen array which generates ca. 4 V '' 1,6 The stable nature of the olivine-type structure having a (PO 4 ͒ 3Ϫ polyanion with a strong P-O covalent bond provides not only excellent cycle-life but also a safe system. When the battery is fully charged, the reactivity to the combustion reaction with the organic electrolyte is low.6 Safety issues are of paramount importance in the design of consumer batteries, and this makes olivinetype materials particularly attractive as cathodes for lithium-ion battery systems.The energy density of olivine-type LiMPO 4 is equal to that of presently used materials, based on the theoretical charge-discharge capacity of ca. 170 mAh/g obtained from the M 3ϩ /M 2ϩ one-electron redox reaction of Li x MPO ...

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“…These include: (1) chemical oxidation of LiFePO 4 to heterosite FePO 4 by using NO 2 BF 4 in acetonitrile [54] or bromine dissolved in water [55] and (2) electrochemical Na insertion by using FePO 4 as the positive electrode and metallic Na foil as anode. The as-prepared NaFePO 4 demonstrated reversible insertion and extraction of Na ions into/from heterosite FePO 4 at 2.8 V. A discontinuity in the potential-composition curve has been detected in the vicinity of Na 0.65 FePO 4 , both on discharge and on charge, which corresponds to an electrochemical biphasic process involving a Na 0.7 FePO 4 phase in equilibrium with FePO 4 , as confirmed by ex situ X-ray diffraction measurement (Fig.…”

Section: Olivine Nafepomentioning

confidence: 99%

Electrode Materials for Sodium-Ion Batteries: Considerations on Crystal Structures and Sodium Storage Mechanisms

Wang

Shanmukaraj

et al. 2018

Electrochem. Energ. Rev.

247

122

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Sodium-ion batteries have been emerging as attractive technologies for large-scale electrical energy storage and conversion, owing to the natural abundance and low cost of sodium resources. However, the development of sodium-ion batteries faces tremendous challenges, which is mainly due to the difficulty to identify appropriate cathode materials and anode materials. In this review, the research progresses on cathode and anode materials for sodium-ion batteries are comprehensively reviewed. We focus on the structural considerations for cathode materials and sodium storage mechanisms for anode materials. With the worldwide effort, high-performance sodium-ion batteries will be fully developed for practical applications.

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Powerful oxidizing agents for the oxidative deintercalation of lithium from transition-metal oxides

Cited by 112 publications

References 9 publications

Ambient pressure synthesis of ternary group(V) nitrides

Ambient pressure synthesis of ternary group(V) nitrides

Phase Diagram of Li[sub x](Mn[sub y]Fe[sub 1−y])PO[sub 4] (0≤x, y≤1)

Electrode Materials for Sodium-Ion Batteries: Considerations on Crystal Structures and Sodium Storage Mechanisms

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