Microvoltammetric Studies on Single Particle Voltammetry of LiNiO&lt;sub&gt;2&lt;/sub&gt; and LiCoO&lt;sub&gt;2&lt;/sub&gt;. In situ Observation of Particle Splitting during Li-ion Extraction/Insertion

Waki, Shinichi; Dokko, Kaoru; Matsue, Tomokazu; Uchida, Isamu

doi:10.5796/kogyobutsurikagaku.65.954

Cited by 10 publications

(3 citation statements)

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“…28 Another study reported the deformation and fracturing of individual particles of LiCoO 2 and LiNiO 2 . 29 Here we report the electrochemistry, conductivity, and visual changes associated with the electrochemical reduction of small individual particles of Ag 2 VO 2 PO 4 . These small particles are aggregates of several crystallites, thus the function of grain boundaries within a particle were examined without complication of the variety of interactions occurring within a bulk electrode.…”

Section: Introductionmentioning

confidence: 96%

Electrochemical reduction of an Ag₂VO₂PO₄particle: dramatic increase of local electronic conductivity

Kirshenbaum

Bock

Brady

et al. 2015

Phys. Chem. Chem. Phys.

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Previously, we reported that electrodes containing silver vanadium phosphate (Ag2VO2PO4) powder exhibit a 15,000 fold increase in conductivity after discharge, concurrent with the formation of silver metal. In this study, in order to disentangle the complex nature of electrodes composed of electroactive powders, an electrochemical reduction of individual particles of Ag2VO2PO4 was conducted, to more directly probe the intrinsic materials properties of Ag2VO2PO4. Specifically, individual particle conductivity data from a nanoprobe system combined with SEM and optical imaging results revealed that the depth of discharge within an Ag2VO2PO4 particle is closely linked to the conductivity increase. Notably, the formation of silver metal may affect both inter- and intraparticle conductivity of the Ag2VO2PO4 material.

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Section: Introductionmentioning

confidence: 96%

Electrochemical reduction of an Ag₂VO₂PO₄particle: dramatic increase of local electronic conductivity

Kirshenbaum

Bock

Brady

et al. 2015

Phys. Chem. Chem. Phys.

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“…To date the majority of these single entity studies has focused on micron-sized particles for ion intercalation. [26][27][28][29][30][31] In this work, we explore immobilized single viologen RACs (~830 nm in diameter) with electrochemical interrogation using nanoelectrodes and the scanning electrochemical microscope (SECM, Scheme 1). [18,[32][33][34][35][36][37] Through SECM feedback imaging, single RACs were located to make contact for direct charge/discharge measurements.…”

Section: Introductionmentioning

confidence: 99%

Impact of Charge Transport Dynamics and Conditioning on Cycling Efficiency within Single Redox Active Colloids

et al. 2018

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Redox active colloids (RACs) are flowable suspensions for sizeexclusion redox flow batteries that exchange billions of electrons per particle. Single particle measurements via bulk electrolysis and voltammetry provided an accelerated platform for evaluating the role of state of charge and conditioning on RAC performance. We used scanning electrochemical microscopy to image, isolate, and interrogate RACs (830 nm diameter) with a 300 nm probe. Deep electrolysis of the particles evidenced capacity losses, but this conditioning simultaneously led to increased Coulombic efficiency. On the other hand, shallow cycling using voltammetry for over 150 cycles showed improved charge recovery and gradual changes in the particle's diffusional regimes. Raman spectroelectrochemistry on few RACs confirmed that degradation occurred upon deep cycling but that shallow cycling was not as detrimental, albeit with low capacity access. The methodologies presented herein provide a stepwise viewpoint of the progression of RAC function with cycling, linking bulk behavior with that of individual particles.[a] Z.

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“…In addition, we also studied the in situ conductance of a single MCMB particle as a reference for discussing the results of composite films. In order to achieve the electrochemical measurements focusing on a single particle, a metal filament was maneuvered to make electrical contact with the particle. , By piecing together the results obtained by using IDA electrodes and filament electrodes, we discuss the electrochemical behavior of the composite film and the effect of conductive additives.…”

Section: Introductionmentioning

confidence: 99%

Microelectrode Techniques for in Situ Measurements on Electrical Conductance of a Carbon Particle and Its Composite Film during Electrochemical Lithium Insertion/Extraction

1998

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Novel electrochemical techniques based on a filament-type and an array-type microelectrodes were developed to study in situ the conductance change of a carbon particle and its composite film during electrochemical lithium insertion/extraction reactions. Mesocarbon microbeads (MCMB, Osaka Gas Co.) heat treated at 1000 °C were investigated in an organic solution containing 1 M LiClO4 as the electrolyte. Measurements focusing on a single MCMB particle were achieved by attaching a molybdenum-filament microelectrode to the particle; they have shown that both the voltammogram and conductance profile of MCMB itself were stable in amplitudes and shapes for successive lithium insertion. Another kind of measurement using an array-type microelectrode was performed on a composite film consisting of MCMBs and poly(vinylidene fluoride), which is an actual form of MCMB in the use for lithium secondary batteries. The composite film was prepared on an interdigitated array of nickel microelectrodes to measure in situ its conductance change. It was found that the conductance of the composite film decreased rapidly, being accompanied by a decrease of redox capacity of the film. By considering the stable behavior of MCMB itself, we concluded that the electrical contact between MCMBs was broken due probably to the volume change of MCMB induced by the lithium insertion/extraction reactions. Addition of acetylene black to the composite greatly improved the interparticle connection. In addition to these practically important results, it is also suggested that there exist at least two different insertion sites within the MCMB. As demonstrated here, microelectrode-based techniques are unique and an effective approach to study battery active materials from both fundamental and practical standpoints.

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Microvoltammetric Studies on Single Particle Voltammetry of LiNiO<sub>2</sub> and LiCoO<sub>2</sub>. In situ Observation of Particle Splitting during Li-ion Extraction/Insertion

Cited by 10 publications

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Electrochemical reduction of an Ag₂VO₂PO₄particle: dramatic increase of local electronic conductivity

Electrochemical reduction of an Ag₂VO₂PO₄particle: dramatic increase of local electronic conductivity

Impact of Charge Transport Dynamics and Conditioning on Cycling Efficiency within Single Redox Active Colloids

Microelectrode Techniques for in Situ Measurements on Electrical Conductance of a Carbon Particle and Its Composite Film during Electrochemical Lithium Insertion/Extraction

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Microvoltammetric Studies on Single Particle Voltammetry of LiNiO<sub>2</sub> and LiCoO<sub>2</sub>. In situ Observation of Particle Splitting during Li-ion Extraction/Insertion

Cited by 10 publications

References 0 publications

Electrochemical reduction of an Ag2VO2PO4particle: dramatic increase of local electronic conductivity

Electrochemical reduction of an Ag2VO2PO4particle: dramatic increase of local electronic conductivity

Impact of Charge Transport Dynamics and Conditioning on Cycling Efficiency within Single Redox Active Colloids

Microelectrode Techniques for in Situ Measurements on Electrical Conductance of a Carbon Particle and Its Composite Film during Electrochemical Lithium Insertion/Extraction

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Product

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Electrochemical reduction of an Ag₂VO₂PO₄particle: dramatic increase of local electronic conductivity

Electrochemical reduction of an Ag₂VO₂PO₄particle: dramatic increase of local electronic conductivity