Ion- and Electron-Transport Properties of a Single Particle of Disordered Carbon during the Lithium Insertion Reaction

Nishizawa, Masatoyo; Koshika, Hiromichi; Hashitani, Ryuichi; Itoh, Takashi; Abe, Takayuki; Uchida, Isamu

doi:10.1021/jp990604t

Cited by 30 publications

(15 citation statements)

References 23 publications

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“…Amorphous carbon is known to be composed of small carbon sheets [209], and is of interest due to a much higher capacity than graphitized carbon. Li-ion diffusivity in amorphous carbon has been calculated to be 5.40 × 10 −6 cm 2 s −1 at 300 K; Li-ion diffusivities in graphite and modified graphite materials are summarized in Tables 17 and 18 [206][207][208][210][211][212][213][214][215][216][217][218][219]. Note that Li-ion diffusivity in amorphous carbon is generally much greater than that in graphitized carbon.…”

Section: Ionic Conduction In Anode Materialsmentioning

confidence: 99%

A review of conduction phenomena in Li-ion batteries

Park

Zhang

Chung

et al. 2010

Journal of Power Sources

1,478

1,059

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Section: Ionic Conduction In Anode Materialsmentioning

confidence: 99%

A review of conduction phenomena in Li-ion batteries

Park

Zhang

Chung

et al. 2010

Journal of Power Sources

1,478

1,059

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“…Moreover, these materials are usually evaluated in the form of composite porous films consisting of powder active materials, conductive agents, and organic polymer binders. In order to overcome these complexities, we have recently developed a microelectrode-based system for investigating single particles of battery active materials, [4][5][6][7][8][9][10][11] in which a filament microelectrode is attached to the particle and serves as a current collector. Because the measured current is in the nanoampere range, the internal resistance (iR) potential drop is negligibly small.…”

mentioning

confidence: 99%

In Situ Observation of LiNiO[sub 2] Single-Particle Fracture during Li-Ion Extraction and Insertion

Dokko

Nishizawa

Horikoshi

et al. 1999

Electrochem. Solid-State Lett.

108

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Electrochemical lithium-ion extraction/insertion properties of Li 1-x NiO 2 single particles were investigated by attaching a filament microelectrode to the particle in 1 mol/dm 3 LiClO 4 /ethylene carbonate + propylene carbonate electrolyte. High-resolution cyclic voltammograms and galvanostatic chronopotentiograms were recorded. In addition, we observed in situ particle fracture during charge-discharge using an optical microscope equipped with a charge-coupled device camera. We found that the particle fractures when it is polarized above 4.2 V vs. Li/Li + . This phenomenon was explained by the change in crystal parameters expected to occur for x > 0.75 in Li 1-x NiO 2 .Lithium insertion materials have been widely investigated as electrodes for lithium-ion batteries. 1-3 The electrochemical behavior of insertion materials is extremely complicated because it involves mass transport within the solid, solid-state redox reactions and changes in crystal structure. Moreover, these materials are usually evaluated in the form of composite porous films consisting of powder active materials, conductive agents, and organic polymer binders. In order to overcome these complexities, we have recently developed a microelectrode-based system for investigating single particles of battery active materials, 4-11 in which a filament microelectrode is attached to the particle and serves as a current collector. Because the measured current is in the nanoampere range, the internal resistance (iR) potential drop is negligibly small. Thus far, we have reported on the electrochemical performances of single particles of oxide cathodes (positive electrodes) such as LiCoO 2 , 5,6 LiNiO 2 , 6 LiMn 2 O 4 , 5,7 and carbonaceous anode mesocarbon microbeads 8-11 of lithium-ion batteries from both kinetic and thermodynamic points of view. By using this technique, it is possible to obtain high-resolution electrochemical data because of the absence of interference by additives such as organic binders and conductive materials.In this work, we report the in situ observation of morphology changes of LiNiO 2 particles and thereby demonstrate a useful feature of our microelectrode-based technique. LiNiO 2 is a promising cathode material exhibiting a reversible rechargeable capacity greater than 150 mAh/g, 12-14 however it exhibits structural instability. 13 This instability has been explained by crystallographic stress induced by charge/discharge which may damage the crystal structure. 13 Investigation of changes in particle morphology is a key issue, because fracture of the particle may disconnect the electrical network within the composite electrode, thereby reducing battery cycle life. 11 We present here the successful observation of particle fracture using a microelectrode-based system coupled with a charge coupled device (CCD) camera-equipped microscope. 6 Experimental The LiNiO 2 used in this work was prepared via the citrate process, 5-7,15 which is based on the thermal decomposition of citrate precursors with good homogeneity. A stoichiometric mi...

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“…Mesocarbon microbeads have been used in similar applications and measurements were performed on a single mesocarbon microbead injected with lithium ions [96]. A novel form of hollow CS fabricated from nanographene has been used as an anode material in lithium ion cells and has shown an even greater reversible capacity of 600 mAhg −1 [97].…”

Section: Electrical Transport In Carbon Microspheresmentioning

confidence: 99%

The electrical transport properties of nitrogen doped carbon microspheres

Wright

Marsicano

Keartland

et al. 2014

Materials Chemistry and Physics

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A suite of four samples of nitrogen doped carbon microspheres, each with a different level of nitrogen dopant, was synthesised in a horizontal chemical vapour deposition reaction. The samples were characterized using scanning electron microscopy, Raman spectroscopy and electron paramagnetic resonance spectroscopy. Scanning electron microscopy showed that microspheres were produced by the reaction. Raman spectroscopy confirmed the graphitic nature of the samples. Electron paramagnetic resonance spectroscopy determined that nitrogen was present in the graphitic lattice and was used as a non-destructive technique to measure the amount of substitutional nitrogen present in the samples. In order to perform electrical transport measurements an automated magneto-transport measurement station was developed in the laboratory. This transport station was computer controlled and contained all of the necessary hardware and software required to perform magneto-electrical transport measurements. Variable temperature electrical transport measurements were performed on all samples to determine their conductive properties. Resistance measurements showed that two of the samples were semiconductors while the other two samples displayed a transition to metallic behaviour at higher temperatures. This transition can be ascribed to the thermal desorption of nitrogen dopant. Models were fitted to the data and the semiconducting behaviour is best explained by a model of fluctuation induced tunnelling while the metallic behaviour is best explained by a quasi-1 dimensional metallic term based on electron-phonon interactions. The IV characteristics of two of the samples display increasing non-linearity of the current's voltage dependence with decreasing temperature. The other two samples exhibit this behaviour at lower temperatures while higher temperature IV data displays a current saturation with increasing voltage. The same models used to explain the resistance measurements can be used to explain the IV characteristics data extremely well. The magnetoresistance data taken with the direction of current flow orientated both parallel and perpendicular to the field, show a transition from negative to positive magnetoresistance with decreasing temperature. The results of these experiments are inconclusive, as a theoretical model of magnetoresistance in systems that conduct via fluctuation induced tunnelling is not well defined. A comparison between the resistance measurements of all four samples was made to determine the effect of nitrogen doping on the samples' ii Abstract electronic transport properties. The result of this comparison was indeterminate. This was due to samples with identical nitrogen dopant levels displaying vastly different conductive properties and indicates that very strict synthesis conditions need to be adhered to in order to ensure sample quality. Resistance measurements were rerun on the two samples that displayed purely semiconducting behaviour to investigate the possibility of atmospheric doping. It was foun...

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Ion- and Electron-Transport Properties of a Single Particle of Disordered Carbon during the Lithium Insertion Reaction

Cited by 30 publications

References 23 publications

A review of conduction phenomena in Li-ion batteries

A review of conduction phenomena in Li-ion batteries

In Situ Observation of LiNiO[sub 2] Single-Particle Fracture during Li-Ion Extraction and Insertion

The electrical transport properties of nitrogen doped carbon microspheres

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