Electrochemical ESR and Voltammetric Studies of Lithium Ion Pairing with Electrogenerated 9,10-Anthraquinone Radical Anions Either Free in Acetonitrile Solution or Covalently Bound to Multiwalled Carbon Nanotubes

Wain, Andrew J.; Wildgoose, Gregory G.; Heald, C.; Jiang, Li; Jones, Timothy G. J.; Compton, Richard G.

doi:10.1021/jp040552u

Cited by 77 publications

(55 citation statements)

References 41 publications

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“…As shown in Scheme 1, we propose chemical interactions (1) between the cationic thienyl group of PEDOT and anionic semi-quinone group of PBDM, and (2) the neutral quinone group of PDBM and the neutral thiophene group of PEDOT, at present. Indeed mixing PDBM with PEDOT as suspension state in organic solvent gave some new IR peaks, one of which is an intense, sharp band at 1550 cm −1 in the near-IR for a semiquinone anion radical [19,20], although not described at the present paper.…”

Section: (A)mentioning

confidence: 59%

“…Following immersion into the PDBM solution, the absorption peak at 591 nm decreased in intensity, concomitantly there was an increase in absorption over the range from 714 to 1100 nm. Thus, it is obvious that the electron exchange reaction occurs in one direction between the neutral (oxidized) quinone and the neutral (reduced) thiophene [19,20]. Since the changing speed of the absorption peak at 591 nm was fast, it means that the electron exchange reaction was fast.…”

Section: (A)mentioning

confidence: 99%

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Significant effects of poly(3,4-ethylenedioxythiophene) additive on redox responses of poly(2,5-dihydroxy-1,4-benzoquinone-3,6-methylene) cathode for rechargeable Li batteries

Oyama

Sarukawa

Mochizuki

et al. 2009

Journal of Power Sources

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Section: (A)mentioning

confidence: 59%

Section: (A)mentioning

confidence: 99%

Significant effects of poly(3,4-ethylenedioxythiophene) additive on redox responses of poly(2,5-dihydroxy-1,4-benzoquinone-3,6-methylene) cathode for rechargeable Li batteries

Oyama

Sarukawa

Mochizuki

et al. 2009

Journal of Power Sources

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“…An 11 μm diameter carbon disk microelectrode working electrode purchased from BASi and a Pt mesh counter electrode were used. A Ag/AgNO 3 reference electrode was prepared as reported by Wain et al 19 using silver wire (99%) purchased from Alfa Aesar. All the potentials in this paper are reported with respect to the Li/Li + scale obtained using a conversion factor determined by measuring the potential of Ag/Ag + reference electrode versus a Li foil reference electrode in each electrolyte.…”

Section: Methodsmentioning

confidence: 99%

A Study of the Influence of Lithium Salt Anions on Oxygen Reduction Reactions in Li-Air Batteries

Gunasekara

Mukerjee

Plichta

et al. 2015

J. Electrochem. Soc.

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The influence of lithium salts on O 2 reduction reactions (ORR) in 1, 2-dimethoxyethane (DME) and tetraethylene glycol dimethyl ether (TEGDME) has been investigated. Microelectrode studies in a series of tetrabutylammonium salt (TBA salt)/DME-based electrolytes showed that O 2 solubility and diffusion coefficient are not significantly affected by the electrolyte anion. The ORR voltammograms on microelectrodes in these electrolytes exhibited steady-state limiting current behavior. In contrast, peak-shaped voltammograms were observed in Li + -conducting electrolytes suggesting a reduction of the effective electrode area by passivating ORR products as well as migration-diffusion control of the reactants at the microelectrode. FT-IR spectra have revealed that Li + ions are solvated to form solvent separated ion pairs of the type Li + (DME) n PF 6 − and Li + (TEGDME)PF 6 − in LiPF 6 -based electrolytes. On the other hand, the contact ion pairs (DME) m Li + (CF 3 SO 3 − ) and(TEGDME)Li + (CF 3 SO 3 − ) appear to form in LiSO 3 CF 3 -containing electrolytes. In the LiSO 3 CF 3 -based electrolytes the initial ORR product, superoxide (O 2 − ), is stabilized in solution by forming [(DME) m-1 (O 2 − )]Li + (CF 3 SO 3 − ) and [(TEGDME)(O 2 − )]Li + (CF 3 SO 3 − ) complexes. These soluble superoxide complexes are able to diffuse away from the electrode surface reaction sites to the bulk electrolyte in the electrode pores where they decompose to form Li 2 O 2 . This explains the higher capacity obtained in Li/O 2 cells utilizing LiCF 3 SO 3 /TEGDME electrolytes.The Li-air battery with a theoretical energy density many times higher than that of Li-ion batteries, 1 has gained world-wide attention as a potential energy source for the development of long range electrical vehicles as well as many other energy hungry applications in the defense and civilian sectors. The promise of the high theoretical energy density has not yet been translated into practical devices due to the shortcomings of the electrode and electrolyte materials used in the battery as well as an incomplete understanding of the chemical and electrochemical processes involved in its operation. In our previous publications we have shown the strong effect of nonaqueous solvents on the oxygen reduction reaction (ORR) electrochemistry in Li + -containing electrolytes. [2][3][4][5][6][7] We have also successfully employed a carbon microelectrode to quantify oxygen transport parameters and elucidate the influence of the Li salt on the reversibility of the ORR in tetrabutylammonium and lithium salt-containing electrolytes in dimethyl sulfoxide (DMSO). 8,9 It has become increasingly clear that the ORR in the non-aqueous Li-air battery is highly solvent controlled 10 with a secondary role of the Li salt through the solvates formed between the solvent and the salt. 11

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“…Compton et al studied the effect of lithium cation on the electrochemical behavior of anthraquinone adsorbed onto MWNTs. 104 Zhuang et al immobilized tetra-phenylporphyrin (TTP) onto SWNTs and studied the interaction between hemoglobin (Hb) and the TTP/SWNT film electrochemically. 105 Dong et al prepared a novel nanohybrid by attaching Pt nanoparticles and tetrakis(Nmethylpyridyl)porphyrin cobalt onto the CNTs.…”

Section: ·2 Functionalization With Organic Compoundsmentioning

confidence: 99%

Electrochemistry and Electroanalytical Applications of Carbon Nanotubes: A Review

et al. 2005

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Carbon nanotubes (CNTs) have been proved to be a novel type of nanostructure with unique structural, electronic and mechanical properties and have drawn extensive attention since their discovery. [1][2][3] Research over the past decade has revealed that the CNTs constitute a new form of carbon materials that are finding striking applications in many fields, such as energy conversion and storage, 4,5 electromechanical actuators, 6,7 chemical sensing 8 and so forth. Generally, the nanotubes can be divided into two categories: single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs). The former can be regarded as a graphene cylinder formed by rolling seamlessly a single graphene sheet along an (m,n) lattice vector in the sheet. The (m,n) indices is a central parameter governing the metallicity and chirality of the tubes. The latter is composed of coaxial multilayer graphene tubes with interlayer space of 0.34 nm. The diameter varies from 0.4 nm to 3 nm for the SWNTs and from 1.4 nm to 100 nm for the MWNTs (typical transmission electron microscopic images of the CNTs are shown in Fig. 1).Due to the unique physical and chemical properties and thus the striking applications in various research and industrial fields, the CNTs have drawn extensive interest over the past decade. To date, we have witnessed great successes in the synthesis of the CNTs and in understanding of their chemical and physical properties. Several excellent reviews concerning these issues have appeared in the literature. 9,10 Currently, increasing interests are being focused on the construction of the CNT-based functional nanodevices with novel properties for practical applications.On the other hand, the CNTs represent a new kind of carbonbased materials and are superior to other kinds of carbon materials commonly used in electrochemistry, such as glassy carbon (GC), graphite and diamond, mainly in the special structural features and unique electronic properties. As a result, besides their striking applications in other fields, study of the CNT electrochemistry thus far has revealed that these unique properties of the CNTs substantially make them useful for electrochemical investigations, e.g., electrocatalysis, direct electrochemistry of proteins and electroanalytical applications such as electrochemical sensors and biosensors. 11,12 The electroanalytical applications of the CNTs for construction of This review addresses recent developments in electrochemistry and electroanalytical chemistry of carbon nanotubes (CNTs). CNTs have been proved to possess unique electronic, chemical and structural features that make them very attractive for electrochemical studies and electrochemical applications. For example, the structural and electronic properties of the CNTs endow them with distinct electrocatalytic activities and capabilities for facilitating direct electrochemistry of proteins and enzymes from other kinds of carbon materials. These striking electrochemical properties of the CNTs pave the way to CNT-based bioelectrochemist...

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Electrochemical ESR and Voltammetric Studies of Lithium Ion Pairing with Electrogenerated 9,10-Anthraquinone Radical Anions Either Free in Acetonitrile Solution or Covalently Bound to Multiwalled Carbon Nanotubes

Cited by 77 publications

References 41 publications

Significant effects of poly(3,4-ethylenedioxythiophene) additive on redox responses of poly(2,5-dihydroxy-1,4-benzoquinone-3,6-methylene) cathode for rechargeable Li batteries

Significant effects of poly(3,4-ethylenedioxythiophene) additive on redox responses of poly(2,5-dihydroxy-1,4-benzoquinone-3,6-methylene) cathode for rechargeable Li batteries

A Study of the Influence of Lithium Salt Anions on Oxygen Reduction Reactions in Li-Air Batteries

Electrochemistry and Electroanalytical Applications of Carbon Nanotubes: A Review

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