Solvated Intercalation Compounds of Layered Chalcogenide and Oxide Bronzes

Schöllhorn, R.

doi:10.1016/b978-0-12-747380-2.50015-8

Cited by 37 publications

(9 citation statements)

References 96 publications

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“…The UV-Vis absorption spectrum (Fig. 3) is characterised by three bands, a pair at 15 470 and 16 600 cm 21 and one at 19 700 cm 21 which are respectively assigned to the 4 A 2 A 4 T 1 (P) of the tetrahedral cobalt and to 4 T 1g (F)A 4 A 2g (P) and 4 T 1g (F)A 4 T 1g (P) of the octahedral cobalt. 28 It appears that the colour in this family of compounds, ranging from green to blue, is due to the relative intensity of the two low energy bands and their energies rather than a difference in structure.…”

Section: Resultsmentioning

confidence: 99%

Ferrimagnetism in dicarboxylate‐bridged cobalt hydroxide layers

Kurmoo¹

1999

J. Mater. Chem.

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Section: Resultsmentioning

confidence: 99%

Ferrimagnetism in dicarboxylate‐bridged cobalt hydroxide layers

Kurmoo¹

1999

J. Mater. Chem.

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“…Given the reversible intercalation of H + ions into a NiOOH cathode and the pioneering work on Li intercalation into layered transition-metal sulfides by Robert Schöllhorn in Germany and Jean Rouxel in France, intercalation of Li into layered TiS 2 was suggested as a viable cathode for a rechargeable Li-ion battery. The layered TiS 2 has van der Waals bonding, rather than hydrogen bonding between the TiS 2 layers; see Figure .…”

Section: Organic Liquid-carbonate Electrolytesmentioning

confidence: 99%

“…A nonaqueous liquid electrolyte with a larger LUMOÀHOMO energy gap would enable design of a room-temperature cell with a higher voltage, but the only known liquid in which H þ ions are mobile is water. However, Li salts dissociate in 11 in Germany and Jean Rouxel 12 in France, intercalation of Li into layered TiS 2 was suggested as a viable cathode for a rechargeable Li-ion battery. The layered TiS 2 has van der Waals bonding, rather than hydrogen bonding between the TiS 2 layers; see Figure 4.…”

Section: Aqueous Electrolytesmentioning

confidence: 99%

Evolution of Strategies for Modern Rechargeable Batteries

2012

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This Account provides perspective on the evolution of the rechargeable battery and summarizes innovations in the development of these devices. Initially, I describe the components of a conventional rechargeable battery along with the engineering parameters that define the figures of merit for a single cell. In 1967, researchers discovered fast Na(+) conduction at 300 K in Na β,β''-alumina. Since then battery technology has evolved from a strongly acidic or alkaline aqueous electrolyte with protons as the working ion to an organic liquid-carbonate electrolyte with Li(+) as the working ion in a Li-ion battery. The invention of the sodium-sulfur and Zebra batteries stimulated consideration of framework structures as crystalline hosts for mobile guest alkali ions, and the jump in oil prices in the early 1970s prompted researchers to consider alternative room-temperature batteries with aprotic liquid electrolytes. With the existence of Li primary cells and ongoing research on the chemistry of reversible Li intercalation into layered chalcogenides, industry invested in the production of a Li/TiS2 rechargeable cell. However, on repeated recharge, dendrites grew across the electrolyte from the anode to the cathode, leading to dangerous short-circuits in the cell in the presence of the flammable organic liquid electrolyte. Because lowering the voltage of the anode would prevent cells with layered-chalcogenide cathodes from competing with cells that had an aqueous electrolyte, researchers quickly abandoned this effort. However, once it was realized that an oxide cathode could offer a larger voltage versus lithium, researchers considered the extraction of Li from the layered LiMO2 oxides with M = Co or Ni. These oxide cathodes were fabricated in a discharged state, and battery manufacturers could not conceive of assembling a cell with a discharged cathode. Meanwhile, exploration of Li intercalation into graphite showed that reversible Li insertion into carbon occurred without dendrite formation. The SONY corporation used the LiCoO2/carbon battery to power their initial cellular telephone and launched the wireless revolution. As researchers developed 3D transition-metal hosts, manufacturers introduced spinel and olivine hosts in the Lix[Mn2]O4 and LiFe(PO4) cathodes. However, current Li-ion batteries fall short of the desired specifications for electric-powered automobiles and the storage of electrical energy generated by wind and solar power. These demands are stimulating new strategies for electrochemical cells that can safely and affordably meet those challenges.

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“…In the early 1970s, Schöllhorn [8] in Germany and Rouxel [9] in France were exploring the chemistry of reversible Li intercalation into the Van der Waals gap of layered transition metal sulfides (Fig. 5).…”

Section: Layered Sulfide Cathodesmentioning

confidence: 99%

Rechargeable batteries: challenges old and new

Goodenough

2012

J Solid State Electrochem

355

231

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The challenges for rechargeable batteries are cost, safety, energy, density, life, and rate. Traditional rechargeable batteries based on aqueous electrolytes have good rate capabilities but limited energy density because the voltage for a long shelf-life is restricted to 1.5 V. The discovery of fast Na ion conductivity in β-alumina in 1967 introduced the novel concept of a solid oxide electrolyte and molten electrodes: the sodium-sulfur battery operates at 350°C. Interest in rechargeable batteries with aprotic electrolytes was further stimulated by the first energy crisis in the early 1970s. Since protons are not mobile in aprotic electrolytes, the Li + ion was the logical choice for the working ion, and on-going work on reversible Li intercalation into layered sulfides suggested the TiS 2 //Li cell, which was shown in 1976 to have a voltage of V≃2.2 V and good rate capability. However, the organic liquid carbonates used as electrolytes are flammable, and dendrites growing across the electrolyte from the lithium anode on repeated charge/discharge cycles short-circuited the cells with disastrous consequences. Safety concerns caused this effort to be dropped. However, substitution of the layered oxides LiMO 2 for the layered sulfides MS 2 and reversible intercalation of Li into graphitic carbon without dendrite formation at slow charging rates gave a safe rechargeable lithium ion battery (LIB) of large-enough energy density to enable the wireless revolution. Although carbon-buffered alloys now provide anodes that allow a fast charge and have a higher capacity, nevertheless a passivation layer permeable to Li + forms on the anode surface, and the Li + in the passivation layer is taken irreversibly from the cathode on the initial charge. Since the specific capacity of a cell with an insertion-compound cathode is limited by the latter, strategies to increase the specific capacity for a LIB powering an electric vehicle or storing electricity from wind or solar farms include a return to consideration of a solid electrolyte.

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Solvated Intercalation Compounds of Layered Chalcogenide and Oxide Bronzes

Cited by 37 publications

References 96 publications

Ferrimagnetism in dicarboxylate‐bridged cobalt hydroxide layers

Ferrimagnetism in dicarboxylate‐bridged cobalt hydroxide layers

Evolution of Strategies for Modern Rechargeable Batteries

Rechargeable batteries: challenges old and new

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