A High Capacity Li-Ion Cathode: The Fe(III/VI) Super-Iron Cathode

Licht, Stuart

doi:10.3390/en3050960

Cited by 28 publications

(17 citation statements)

References 42 publications

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“…Salts of higher oxidation states of iron ranging from þ4 to þ8 have also been synthesized in laboratory (Atanasov, 1999;Bielski, 1990;Bielski and Thomas, 1987;Dedushenko et al, 2008;Hoppe and Mader, 1990;Jeannot et al, 2002;Kokarovtseva et al, 1972;Kopelev et al, 1990Kopelev et al, , 1992Kopelev, 1997;Perfiliev and Sharma, 2008;Perfiliev et al, 2006;Perfliev, 2002). Ferrate(VI) Fe VI O 2À 4 has been of great interest because of its role as an oxidant and hydroxylating agent in industrial and water treatment processes, such as the development of a "super iron" battery, green chemistry synthesis, and non-chlorine oxidation for pollutant remediation (Bartzatt and Carr, 1986;Carr et al, 1985;Johnson et al, 2008;Hornstein, 1994, 1996;Licht et al, 1999;Licht and Yu, 2008;Sharma, 2002a;Sharma et al, 2005a,b) Ferrate(VI) provides an environmentally benign high energy density cathode for batteries (Licht et al, 2009(Licht et al, , 1999Licht, 2010;Licht and TelVered, 2004). Selective oxidations by ferrate(VI) can be utilized in synthesizing organic compounds without producing toxic by-products (Southwell, 2003).…”

Section: Introductionmentioning

confidence: 98%

Oxidation of inorganic contaminants by ferrates (VI, V, and IV)–kinetics and mechanisms: A review

Sharma

2011

Journal of Environmental Management

253

143

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Section: Introductionmentioning

confidence: 98%

Oxidation of inorganic contaminants by ferrates (VI, V, and IV)–kinetics and mechanisms: A review

Sharma

2011

Journal of Environmental Management

253

143

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“…Ferrates are soluble in water and have a broad portfolio of applications in energy materials, green organic synthesis, and treating merging contaminants and toxins in water. [15][16][17][18][19] Fe(VI) can perform multimodal actions in water treatment which include oxidation, disinfection, and coagulation. The benign nature of ferrates has advantages over other conventional disinfectants (e.g.…”

Section: Introductionmentioning

confidence: 99%

Ferryl and Ferrate Species: Mössbauer Spectroscopy Investigation

Sharma¹,

Zbořil²

2015

Croat. Chem. Acta

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High-valent iron species of oxidation states +4, +5, and +6, have been involved as intermediates in enzymatic reactions, in green organic synthesis, and in purification and disinfection of water. Many of these species have been synthesized to understand their role in different systems, which include ferryl complexes (oxoiron(IV) (Fe IV =O), oxoiron(V) (Fe V =O)), iron(IV / V / VI)-nitride complexes, and ferrates ((Fe VI O4 2-, Fe(VI), Fe V O4 3-, Fe(V), and Fe IV O4 4-, Fe(IV)). Ferryl and iron-nitride complexes have organic ligands surrounded at the iron center and are soluble in non-aqueous solvent. Comparatively, ferrate species are tetraoxyanions and are soluble in water. This paper presents Mössbauer spectroscopy as a tool to distinguish different oxidation states of iron and to gain information on the geometry and structure of high-valent iron complexes. Examples are given to demonstrate the application of Mössbauer spectroscopy in learning mechanisms of thermal decomposition of ferrates, encapsulation of heavy metals by ferrates, and oxidation of thiols by ferrates.

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“…Hence, we have studied, or introduced, a range of multiple electron per molecule redox materials for charge storage. These range from the two electron redox chemistry of solid sulfur, 1 to the three electron redox chemistry of hexavalent super irons 2,3 or aluminium, 4 as well as multiple electron per molecule transfer in peroxides, 5 polyiodides, 6 permanganates, 7 metal chalcogenides, 8 iodates, 9 and stannates; 10 selective examples are cited in the references.…”

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confidence: 99%

Nanoparticle Facilitated Charge Transfer and Voltage of a High Capacity VB₂ Anode

Licht

Ghosh

Wang

et al. 2011

Electrochem. Solid-State Lett.

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The storage of multiple electrons per molecule provides opportunities to greatly enhance electrochemical energy capacity. VB 2 releases, via electrochemical oxidation, 11 electrons per molecule at a favorable, electrochemical potential. Coupled with an air cathode, this 4060 mAh=g intrinsic capacity anode, has energy capacity greater than that of gasoline. Nanochemical improvements of VB 2 are probed to facilitate charge transfer and discharge voltage. Nanoparticle formation is accomplished with a planetary ball mill media (tungsten carbide) with hardness comparable to that of VB 2 (8-9 Mohs 2 ). Mechanochemical synthesized, VB 2 nanorods, exhibit higher voltage, sustain higher rate, and depth of discharge than macroscopic VB 2 .Transformative advances are needed to increase the battery energy density for devices ranging from hearing aids to electric cars. The storage of multiple electrons per molecular site provides opportunities to greatly enhance electrochemical energy capacity. Hence, we have studied, or introduced, a range of multiple electron per molecule redox materials for charge storage. These range from the two electron redox chemistry of solid sulfur, 1 to the three electron redox chemistry of hexavalent super irons 2,3 or aluminium, 4 as well as multiple electron per molecule transfer in peroxides, 5 polyiodides, 6 permanganates, 7 metal chalcogenides, 8 iodates, 9 and stannates; 10 selective examples are cited in the references.The most compelling case to date for high energy density multielectron charge storage is the multiple electron oxidation of a vanadium boride anode 11,12 which when coupled with air as a cathode (as used in Zn-Air batteries), delivers greater energy storage capacity than gasoline. 13 VB 2 undergoes an extraordinary 11 electron per molecule oxidation, and provides an intrinsic 11 faraday, per 72.6 g mol À1 molecular weight, which is an anode capacity of 4060 mAh=g. With a density, d ¼ 5.10 kg=l, it has a capacity 20,700 Ah=l. This is respectively 10-fold or 3.5-fold higher than the volumetric capacity of lithium or zinc. Discharge of all 11 electrons per molecule occurs at a singular, favorable anodic potential, which includes oxidation of the tetravalent transition metal ion, V(þ4 þ5), and each of the two boron's 2xB(À2 þ3). 12,13 Borides are prone to decomposition in the alkaline media which passivates anodic discharge. 14 This is overcome with a zirconia coating, which sustains effective alkaline discharge and stabilizes the borides in contact with the alkaline electrolyte. 11,13,15 Recently, a series of VB x (x ¼ 0.25, 0.5 and 1) were prepared by a mechanochemical synthesis and observed to deliver an anodic capacity twice higher than the theoretical capacity of Zn. 16 Based on experimental discharge, we had previously estimated that the discharge potential of the high capacity VB 2 =air battery was 1.3 V. An improved estimate of the potential for the VB 2 =air discharge is attained here from available enthalpy and entropy of the reaction components. 17,18 These allow us to ...

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A High Capacity Li-Ion Cathode: The Fe(III/VI) Super-Iron Cathode

Cited by 28 publications

References 42 publications

Oxidation of inorganic contaminants by ferrates (VI, V, and IV)–kinetics and mechanisms: A review

Oxidation of inorganic contaminants by ferrates (VI, V, and IV)–kinetics and mechanisms: A review

Ferryl and Ferrate Species: Mössbauer Spectroscopy Investigation

Nanoparticle Facilitated Charge Transfer and Voltage of a High Capacity VB₂ Anode

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A High Capacity Li-Ion Cathode: The Fe(III/VI) Super-Iron Cathode

Cited by 28 publications

References 42 publications

Oxidation of inorganic contaminants by ferrates (VI, V, and IV)–kinetics and mechanisms: A review

Oxidation of inorganic contaminants by ferrates (VI, V, and IV)–kinetics and mechanisms: A review

Ferryl and Ferrate Species: Mössbauer Spectroscopy Investigation

Nanoparticle Facilitated Charge Transfer and Voltage of a High Capacity VB2 Anode

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Nanoparticle Facilitated Charge Transfer and Voltage of a High Capacity VB₂ Anode