Electrochemical characteristics of phosphorus doped silicon and graphite composite for the anode materials of lithium secondary batteries

Kong, Myung Ho; Noh, Jae Hyun; Byun, Dong Jin; Lee, Joong Kee

doi:10.1007/s10832-008-9471-9

Cited by 30 publications

(22 citation statements)

References 13 publications

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“…There have been a large number of ongoing studies of the Si anode materials in different forms, such as single crystals,46 polycrystalline thin films,27 amorphous films,47, 48 nanoparticles,49 nanowires,7, 50, 51 nanotubes,52 composites with conductive materials (carbon,31, 49, 53–58 nickel,7, 16 etc.) and doped Si 23, 31, 59, 60…”

Section: Si Versus Gementioning

confidence: 99%

In Situ TEM Experiments of Electrochemical Lithiation and Delithiation of Individual Nanostructures

Liu¹,

Liu²,

Kushima³

et al. 2012

Advanced Energy Materials

351

352

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Understanding the microscopic mechanisms of electrochemical reaction and material degradation is crucial for the rational design of high-performance lithium ion batteries (LIBs). A novel nanobattery assembly and testing platform inside a transmission electron microscope (TEM) has been designed, which allows a direct study of the structural evolution of individual nanowire or nanoparticle electrodes with near-atomic resolution in real time. In this review, recent progresses in the study of several important anode materials are summarized. The consistency between in situ and ex situ results is shown, thereby validating the new in situ testing paradigm. Comparisons between a variety of nanostructures lead to the conclusion that electrochemical reaction and mechanical degradation are material specifi c, size dependent, and geometrically and compositionally sensitive. For example, a highly anisotropic lithiation in Si is observed, in contrast to the nearly isotropic response in Ge. The Ge nanowires can develop a spongy network, a unique mechanism for mitigating the large volume changes during cycling. The Si nanoparticles show a critical size of ∼ 150 nm below which fracture is averted during lithiation, and above which surface cracking, rather than central cracking, is observed. In carbonaceous nanomaterials, the lithiated multi-walled carbon nanotubes (MWCNTs) are drastically embrittled, while few-layer graphene nanoribbons remain mechanically robust after lithiation. This distinct contrast manifests a strong 'geometrical embrittlement' effect as compared to a relatively weak 'chemical embrittlement' effect. In oxide nanowires, discrete cracks in ZnO nanowires are generated near the lithiation reaction front, leading to leapfrog cracking, while a mobile dislocation cloud at the reaction front is observed in SnO 2 nanowires. This contrast is corroborated by ab initio calculations that indicate a strong chemical embrittlement of ZnO, but not of SnO 2 , after a small amount of lithium insertion. In metallic nanowires such as Al, delithiation causes pulverization, and the product nanoparticles are held in place by the surface Li-Al-O glass tube, suggesting possible strategies for improving electrode cyclability by coatings. In addition, a new in situ chemical lithiation method is introduced for fast screening of battery materials by conventional TEM. Evidently, in situ nanobattery experiments inside TEM are a powerful approach for advancing the fundamental understanding of electrochemical reactions and materials degradation and therefore pave the way toward rational design of high-performance LIBs.

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Section: Si Versus Gementioning

confidence: 99%

In Situ TEM Experiments of Electrochemical Lithiation and Delithiation of Individual Nanostructures

Liu¹,

Liu²,

Kushima³

et al. 2012

Advanced Energy Materials

351

352

View full text Add to dashboard Cite

show abstract

“…The few studies that do exist on the lithiation of doped Si in nanostructured form are on dispersed powder mixtures, often involving amorphous Si [186] or polycrystalline nanoscale Si-graphite mixtures [187] and related nanoscale Si analogues. The doping contribution to conductivity and Li uptake (the reduction of Li upon insertion at the cost of an electron) is difficult to separate from the enhanced electrical conductivity of the entire material matrix, which becomes continually hole-doped while changing its structure, composition, and electrical nature.…”

Section: The Influence Of Doping and Conductivity On The Performance mentioning

confidence: 99%

Metal-assisted chemical etching of silicon and the behavior of nanoscale silicon materials as Li-ion battery anodes

2015

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This review outlines the developments and recent progress in metal-assisted chemical etching of silicon, summarizing a variety of fundamental and innovative processes and etching methods that form a wide range of nanoscale silicon structures. The use of silicon as an anode for Li-ion batteries is also reviewed, where factors such as film thickness, doping, alloying, and their response to reversible lithiation processes are summarized and discussed with respect to battery cell performance. Recent advances in improving the performance of silicon-based anodes in Li-ion batteries are also discussed. The use of a variety of nanostructured silicon structures formed by many different methods as Li-ion battery anodes is outlined, focusing in particular on the influence of mass loading, core-shell structure, conductive additives, and other parameters. The influence of porosity, dopant type, and doping level on the electrochemical response and cell performance of the silicon anodes are detailed based on recent findings. Perspectives on the future of silicon and related materials, and their compositional and structural modifications for energy storage via several electrochemical mechanisms, are also provided.

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“…Si-graphite mixtures [59,60] and related nanoscale Si analogues. The doping contribution to conductivity and Li uptake (reduction of Li upon insertion at the cost of an electron) is difficult to separate from enhanced electrical conductivity of the entire material matrix, which becomes continually hole-doped while changing its structure, composition and electrical nature.…”

Section: Introductionmentioning

confidence: 99%

The influence of carrier density and doping type on lithium insertion and extraction processes at silicon surfaces

McSweeney

Lotty

Glynn

et al. 2014

Electrochimica Acta

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Electrochemical characteristics of phosphorus doped silicon and graphite composite for the anode materials of lithium secondary batteries

Cited by 30 publications

References 13 publications

In Situ TEM Experiments of Electrochemical Lithiation and Delithiation of Individual Nanostructures

In Situ TEM Experiments of Electrochemical Lithiation and Delithiation of Individual Nanostructures

Metal-assisted chemical etching of silicon and the behavior of nanoscale silicon materials as Li-ion battery anodes

The influence of carrier density and doping type on lithium insertion and extraction processes at silicon surfaces

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