Interfacial lithium-ion transfer at the LiMn2O4 thin film electrode/aqueous solution interface

Nakayama, Noriaki; Nozawa, Takeshi; Iriyama, Yasutoshi; Abe, Takeshi; Ogumi, Zempachi; Kikuchi, Kenji

doi:10.1016/j.jpowsour.2007.06.113

Cited by 81 publications

(48 citation statements)

References 19 publications

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“…It means that not the simple desolvation process of cations but the complicated charge transfer kinetics dominates the rate-limiting factor in the PC-based electrolytes, which suffers from the considerably slow cation transfer reaction at the electrode/electrolyte interface in organic electrolytes compared to aqueous electrolytes. 49 Given the fact that the smaller activation energy for Na + transfer between solid and electrolyte interface than that for Li + , 50 we deduce that the It is also worth mentioning that the capacitance in LiBF 4 /PC is lower than that in LiClO 4 /PC, even when the conductivities of the two electrolytes are similar as shown in Table III. Since hydrofluoric acid (HF) is generated in fluorine-containing electrolytes, such as LiBF 4 and LiPF 6 , the surface of the TiN electrode might be corroded by HF.…”

Section: Resultsmentioning

confidence: 74%

Impact of Electrolyte on Pseudocapacitance and Stability of Porous Titanium Nitride (TiN) Monolithic Electrode

Hasegawa

Kitada

Kawasaki

et al. 2014

J. Electrochem. Soc.

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We report the fabrication of porous titanium nitride (TiN) monoliths through the ammonolysis of porous TiO 2 monoliths prepared via the sol-gel process accompanied by phase separation. The obtained TiN monoliths possess good mechanical strength as well as excellent electric conductivity with a superconducting transition at T c ∼5.0 K. We have investigated the electrochemical properties of the porous TiN monoliths as an electrode using various electrolytes. The results reveal that the pseudocapacitance of TiN increases in the order of K + < Na + < Li + contrary to the case of EDL capacitance in neutral aqueous electrolytes. It is also found that acidic and strongly basic electrolytes are not suitable due to high corrosivity, while there is no significant deterioration when neutral aqueous electrolytes and organic electrolytes are used.Titanium nitride (TiN) exhibits significant potential in various electrochemical applications 1-8 owing to the unique intrinsic features such as excellent electric conductivity, high mechanical strength, and good chemical and thermal stabilities. One of the promising electrode applications of TiN electrodes is pseudocapacitors. 3-5 Meanwhile, the previous efforts devoted to the study on TiN materials disclose that the slightly oxidized layer is formed on TiN surface, 9-11 which indicates the oxidized surface significantly contributes to the interfacial reaction between electrolyte and electrode involving surface corrosion by polarization. Hence, fundamental understandings of the electrochemistry and stability of TiN surface are indispensable for the practical use of TiN pseudocapacitors. Nevertheless, there are only a few studies reported on the electrochemistry of TiN associated with surface corrosion chemistry. 9,12-14 The research from a longitudinal perspective, which is of importance from an application perspective, is especially limited to the investigation in KOH aqueous solution. 3,13 The recent upsurge of interest in TiN electrodes therefore desires comprehensive studies on the electrochemistry of TiN in a variety of electrolytes.In most cases, composite electrodes prepared from slurry composed of active materials, binders and conductive additives (generally carbon) are employed. However, the composite electrodes are not suitable for the fundamental studies, because the additives and the mixing process to prepare the slurry may change various properties, such as morphology and surface chemistry, of the electrode materials, which makes it difficult to obtain intrinsic information on the active material itself. On the other hand, porous monolithic electrodes [15][16][17][18] can overcome these issues, as they consist of a single piece of bulk electrode without any binders. In order to fabricate the monolithic electrodes, the control of pore properties is crucial, because porous structures are indispensable to allow the electrolyte to penetrate inside of the monolithic electrodes. 19 To date, we have developed the phase-separation method, a sol-gel process accompanied by spinod...

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Section: Resultsmentioning

confidence: 74%

Impact of Electrolyte on Pseudocapacitance and Stability of Porous Titanium Nitride (TiN) Monolithic Electrode

Hasegawa

Kitada

Kawasaki

et al. 2014

J. Electrochem. Soc.

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“…100 Another major specificity of LiABs relates to the ion transport as well as Li þ insertion kinetics associated with the electrolyte. Similarly, Nakayame et al 102 measured for a LiMn 2 O 4 thin film electrode a Li transfer resistance of 4 kU and estimated an activation energy for Li þ transfer of nearly 50 kJ/mol at room temperature in an organic electrolyte whereas these values reduce to 20 U and 24 kJ/mol, respectively in a water electrolyte. Similarly, Nakayame et al 102 measured for a LiMn 2 O 4 thin film electrode a Li transfer resistance of 4 kU and estimated an activation energy for Li þ transfer of nearly 50 kJ/mol at room temperature in an organic electrolyte whereas these values reduce to 20 U and 24 kJ/mol, respectively in a water electrolyte.…”

Section: Specificities Of Li-aqueous Batteriesmentioning

confidence: 85%

Perspectives in Lithium Batteries

Poizot

Dolhem

Gaubicher

et al. 2015

Lithium Process Chemistry

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“…[1][2][3][4] It was also shown that intercalation of solvated cations is kinetically more facile as compared to the reaction of ions without the solvation shell. 5,6 These findings imply that the contribution of ion desolvation to the reaction activation barrier could be dominant.…”

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confidence: 99%

Transport and Kinetic Aspects of Alkali Metal Ions Intercalation into AVPO₄F Framework

Nikitina

Fedotov

Vassiliev

et al. 2017

J. Electrochem. Soc.

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The effect of the cation nature is explored for the reaction of alkali metal ions intercalation into the AVPO 4 F material. Application of electrochemical methods allowed determining the key diffusional and kinetic parameters for Li + , Na + and K + intercalation reactions. The obtained formal redox potential values, apparent diffusion coefficients and charge transfer resistance values are contrasted, providing the possibility to assess the variation in the reaction energetics for metal ion insertion/extraction. The observed differences in reaction rates are rationalized in terms of different contributions of ion desolvation and transition through adsorbate layer/electrode interface for various ions. The mechanism of ion intercalation reactions is still poorly understood in spite of the obvious importance of intercalating systems in metal-ion batteries development for applications in energy conversion and storage. The research in the field of establishing ion intercalation kinetic patterns is mainly focused on evaluating charge transfer resistance parameters and diffusion coefficients for materials with presumably higher energy density and rate capability, while the fundamental aspects of the reaction mechanisms are typically overlooked. However, the research aimed at finding the limiting step of intercalation reaction might provide additional non-empirical approaches to control the rate of the intercalation reaction. In this regard, fundamental studies exploring the effects of solvent and cation nature on the overall reaction rate are of primary importance.In a series of recent publications, the intercalation reaction rate was shown to be highly dependent on the solvent nature, providing an implication to consider ion transfer rather than electron transfer or ion insertion into the host matrix step to be rate limiting. [1][2][3][4] It was also shown that intercalation of solvated cations is kinetically more facile as compared to the reaction of ions without the solvation shell. 5,6 These findings imply that the contribution of ion desolvation to the reaction activation barrier could be dominant. On the other hand, the reaction rate was shown to be dependent on the structure of electrode/electrolyte interface (EEI) especially in cases when adsorbate layers are formed at high potentials at the electrode surface (solid electrolyte interface, SEI, on anode, or cathode/electrolyte interface, CEI).2 All these results point to the complex interplay between the energetics of ion desolvation and the transition of the ion through the EEI. Variation of the solvent nature cannot be applied to distinguish between these two contributions, as changing the solvent results in simultaneous changes in the EEI structure, desolvation energy and the preexponential factor, which is determined by the solvent effective frequency. Variation of the intercalating ion provides another possibility to assess the mechanism of the intercalation reaction. The desolvation energy contributions should be very different for ions of different charge...

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Interfacial lithium-ion transfer at the LiMn2O4 thin film electrode/aqueous solution interface

Cited by 81 publications

References 19 publications

Impact of Electrolyte on Pseudocapacitance and Stability of Porous Titanium Nitride (TiN) Monolithic Electrode

Impact of Electrolyte on Pseudocapacitance and Stability of Porous Titanium Nitride (TiN) Monolithic Electrode

Perspectives in Lithium Batteries

Transport and Kinetic Aspects of Alkali Metal Ions Intercalation into AVPO₄F Framework

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Interfacial lithium-ion transfer at the LiMn2O4 thin film electrode/aqueous solution interface

Cited by 81 publications

References 19 publications

Impact of Electrolyte on Pseudocapacitance and Stability of Porous Titanium Nitride (TiN) Monolithic Electrode

Impact of Electrolyte on Pseudocapacitance and Stability of Porous Titanium Nitride (TiN) Monolithic Electrode

Perspectives in Lithium Batteries

Transport and Kinetic Aspects of Alkali Metal Ions Intercalation into AVPO4F Framework

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Transport and Kinetic Aspects of Alkali Metal Ions Intercalation into AVPO₄F Framework