Oxidative-Stability Enhancement and Charge Transport Mechanism in Glyme–Lithium Salt Equimolar Complexes

Yoshida, Kazuki; Nakamura, Megumi; Kazue, Yuichi; Tachikawa, Naoki; Tsuzuki, Seiji; Seki, Shiro; Dokko, Kaoru; Watanabe, Masayoshi

doi:10.1021/ja203983r

Cited by 722 publications

(859 citation statements)

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“…117,122 Consequently, solvate ILs are suitable for use as electrolytes in lithium ion batteries [111][112][113][114] and lithium-sulfur batteries. [115][116][117][118][119][120] The most striking and significant findings of our research on solvate ILs are the formation criteria of solvate ILs, 101 the enhanced oxidation stability of coordinating solvents, 95 the low coordinating properties of solvate cations and anions, and their electrode reactions with graphite. 121,122 Figure 8 shows how the anionic structures of lithium salts affect the formation of solvate ILs.…”

Section: © -Conducting Ils and Solvate Ilsmentioning

confidence: 79%

“…95 This increase in oxidative stability is caused by the donation of lone pairs of the ether oxygen atoms to the Li + cation, resulting in the lowering in energy of the highest occupied molecular orbital (HOMO) of the coordinating glyme molecule; this energy change has been confirmed by ab initio molecular orbital calculations (Fig. 9).…”

Section: © -Conducting Ils and Solvate Ilsmentioning

confidence: 81%

“…[89][90][91][92] We explored a variety of such combinations and found that, in certain combinations, these materials have similar properties to conventional aprotic ILs. [93][94][95][96][97][98][99][100][101][102][103][104][105][106][107][108][109] We conclude that these mixtures can be categorized as "solvate ILs," i.e., liquids consisting of a salt and a solvent that strongly coordinates with cations or anions to form stable solvate ions. 110 Detailed studies of the solvate IL on the transport properties, [93][94][95][96][97][98][99] spectroscopic, [99][100][101][102][103] crystallographic, [100][101][102][103] electrochemical, [94][95][96]104,105 quantum mechanical characterizations, [106][107][108]…”

Section: © -Conducting Ils and Solvate Ilsmentioning

confidence: 91%

“…9). 95 The mechanism of ion conduction mechanism in [Li(glyme) 1 ][TFSA] solutions has been explored by NMR and electrochemical methods, and the experimental results strongly suggest that Li + cation conduction in the equimolar complex occurs by migration of [Li(glyme) 1 ] + cations, whereas the ligand exchange mechanism also occurs when interfacial electrochemical reactions of [Li(glyme) 1 ] + cations occur (Fig. 9).…”

Section: © -Conducting Ils and Solvate Ilsmentioning

confidence: 99%

“…Due to the increase in the oxidative stability of the glymes and the presence of the ligandexchange conduction mode, the solvate ILs can be used as battery electrolytes and are compatible with 4 V-class cathodes such as LiCoO 2 in the cell voltage range of 3.0-4.2 V. This is true regardless of the use of ether-based electrolytes because the ligand exchange rate is much faster than the electrode reaction rate. 95 The discovery that oxidative stability is increased by the coordination of solvent molecules to Li + has inspired many researchers to use concentrated organic 123 and aqueous 124 electrolyte solutions to widen the potential windows and to apply these electrolytes in innovative batteries.…”

Section: © -Conducting Ils and Solvate Ilsmentioning

confidence: 99%

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Design and Materialization of Ionic Liquids Based on an Understanding of Their Fundamental Properties

Watanabe

2016

Electrochemistry

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Ionic liquids (ILs) are defined as salts that have melting points lower than 100°C. Most are organic salts, and these may be designed and tailored to have suitable properties. ILs are recognized as a third group of solvents (and electrolytes), after water and organic solvents. They are characterized by their unique properties such as nonvolatilities, high thermal stabilities, and high ionic conductivities. In this article, our work on the design and preparation of ILs is briefly reviewed. The concept of ionicity is proposed as a metric to characterize the basic nature (dissociativity) of ILs, which is affected by the Lewis acidity/basicity of cations/anions (i.e., coulombic interactions), the directionality of interactions between cations and anions, and van der Waals interactions between ions. The ionicity of ILs is dominated by a subtle balance between coulombic and van der Waals interactions, which clearly discriminates ILs from conventional high-temperature inorganic molten salts. Here, the design of protic ILs for fuel cell electrolytes, electron-transporting ILs for dye-sensitized solar cell electrolytes, and Li + -conducting solvate ILs for lithium battery electrolytes are discussed based on an understanding of the fundamental properties of ILs. Furthermore, the combination of ILs with polymers and colloidal particles affords intriguing quasi-solid materials (ion gels), and the ion transport in these gels is decoupled from the mechanical relaxation time of these materials, yielding new solid electrolytes. The possibility of temperature and photo-sensitive solubility dependence of polymers in ILs allows the creation of stimuli-responsive materials. Finally, protic ILs/protic salts are demonstrated to be good precursors for N-doped carbon materials.

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Section: © -Conducting Ils and Solvate Ilsmentioning

confidence: 79%

Section: © -Conducting Ils and Solvate Ilsmentioning

confidence: 81%

Section: © -Conducting Ils and Solvate Ilsmentioning

confidence: 91%

Section: © -Conducting Ils and Solvate Ilsmentioning

confidence: 99%

Section: © -Conducting Ils and Solvate Ilsmentioning

confidence: 99%

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Design and Materialization of Ionic Liquids Based on an Understanding of Their Fundamental Properties

Watanabe

2016

Electrochemistry

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Ionic Liquids

Kar

Matuszek

MacFarlane

2019

Kirk-Othmer Encyclopedia of Chemical Technology

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An overview of the field of ionic liquids is presented, including the nomenclature and types of ionic liquids. Their synthesis and purification methods are described, along with typical characterisation procedures and general physico‐chemical properties. The various applications of ionic liquids are also summarised including in batteries, in green chemistry as low vapour pressure solvents, in medicinal chemistry and in protein stabilisation.

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Lithium Oxygen Battery

Byon

Thomas

Dokko

et al. 2019

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Amongst “beyond lithium‐ion battery (LIB)” candidates, lithium–oxygen (Li–O 2 ) (or lithium–air) batteries are highly appealing due to the high theoretical specific energy density of ∼3460 Wh kg −1 , which on a theoretical basis offers an improvement of up to six times that of LIBs. The aim of this article is to disseminate the current state‐of‐the‐art understanding of research‐level Li–O 2 batteries regarding the various chemical and electrochemical phenomena and elaborate upon the key strategies that improve battery performance. We first introduce the fundamentals of O 2 reduction/evolution electrochemistry in Li + containing nonaqueous media along with the nucleation and growth process of the solid lithium peroxide (Li 2 O 2 ) product occurring during discharge and its subsequent decomposition process during recharge. Owing to the insulating nature of Li 2 O 2 and high reactivity of reduced O 2 species including superoxide, peroxide, and singlet oxygen, significant scientific hurdles still need to be surmounted as highlighted by key challenges relating to the limitation in discharge capacity, high recharge overpotentials, poor cyclability, and the propensity of severe parasitic side reactions with the electrolyte solution and carbonaceous electrode. We elaborate upon these key challenges that are underpinning Li–O 2 batteries and the notable scientific, engineering, and materials science approaches taken to mitigate these challenges. Lastly, as research‐level cells typically operate with a pure O 2 source, we elaborate upon the additional complications and potential solutions associated with the inclusion of additional gases (N 2 , CO 2 , H 2 O, etc.) that would be present if the battery is operated in ambient air.

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Oxidative-Stability Enhancement and Charge Transport Mechanism in Glyme–Lithium Salt Equimolar Complexes

Cited by 722 publications

References 64 publications

Design and Materialization of Ionic Liquids Based on an Understanding of Their Fundamental Properties

Design and Materialization of Ionic Liquids Based on an Understanding of Their Fundamental Properties

Ionic Liquids

Lithium Oxygen Battery

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