High-Performance Germanium Nanowire-Based Lithium-Ion Battery Anodes Extending over 1000 Cycles Through in Situ Formation of a Continuous Porous Network

Kennedy, Tadhg; Mullane, Emma; Geaney, Hugh; Osiak, Michal; O’Dwyer, Colm; Ryan, Kevin M.

doi:10.1021/nl403979s

Cited by 331 publications

(366 citation statements)

References 43 publications

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“…[42] In the interim, the same phenomenon has been reported for Sb, Si, and Ge anodes. [35,43,44] This occurrence was also noted by Li et al, where a large amount of fusion between Si NWs was observed at both fully lithiated and delithiated states. [43] The mechanism of fusion is electrochemically initiated during charging as Li atoms can simultaneously bond at the point of contact between two adjacent NWs creating an M-Li-M bridge (Figure 3b).…”

Section: Lithium-assisted Weldingsupporting

confidence: 60%

“…In a recent study by our group on Ge NW anodes, it was shown that the addition of as little as 3 wt% VC to a 1 M LiPF 6 ethylene carbonate/dimethyl carbonate electrolyte can significantly improve the performance, with the electrode retaining 80% of its initial capacity after 200 cycles, compared to only 58% when using an additive-free electrolyte. [35] Similar improvements in the performance of Si NW electrodes through the use of electrolyte additives have also been reported. [36] The majority of these studies have focused on using additives that have previously shown promise in improving the performance of graphitic-based electrodes.…”

Section: Research Newssupporting

confidence: 59%

Section: Pore Formationmentioning

confidence: 99%

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Advances in the Application of Silicon and Germanium Nanowires for High‐Performance Lithium‐Ion Batteries

2016

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Li-alloying materials such as Si and Ge nanowires have emerged as the forerunners to replace the current, relatively low-capacity carbonaceous based Li-ion anodes. Since the initial report of binder-free nanowire electrodes, a vast body of research has been carried out in which the performance and cycle life has significantly progressed. The study of such electrodes has provided invaluable insights into the cycling behavior of Si and Ge, as the effects of repeated lithiation/delithiation on the material can be observed without interference from conductive additives or binders. Here, some of the key developments in this area are looked at, focusing on the problems encountered by Li-alloying electrodes in general (e.g., pulverization, loss of contact with current collector etc.) and how the study of nanowire electrodes has overcome these issues. Some key nanowire studies that have elucidated the consequences of the alloying/dealloying process on the morphology of Si and Ge are also considered, in particular looking at the impact that effects such as pore formation and lithium-assisted welding have on performance. Finally, the challenges for the practical implementation of nanowire anodes within the context of the current understanding of such systems are discussed.

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Section: Lithium-assisted Weldingsupporting

confidence: 60%

Section: Research Newssupporting

confidence: 59%

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Advances in the Application of Silicon and Germanium Nanowires for High‐Performance Lithium‐Ion Batteries

2016

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“…37 The capacities values obtained over 15 cycles were greater than previously reported values for Au-seeded Ge nanowires 36,42 and comparable to values reported for Ge nanowires catalyszd with Sn , and like In, it also reversibly alloys with Li. 6 Previous reports indicate that Au does not reversibly alloy with lithium causing Au-seeded Ge nanowires to suffer from significant capacity fading issues. 17 In has previously been shown to …”

Section: Electrochemical Experiments Of Ge Nanowires Synthesised Withmentioning

confidence: 99%

Rapid, Low-Temperature Synthesis of Germanium Nanowires from Oligosilylgermane Precursors

et al. 2017

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Type of publicationArticle (peer-reviewed) Link to publisher's versionhttp://dx.doi.org/10.1021/acs.chemmater.7b00714Access to the full text of the published version may require a subscription. 1032112; E-mail: christoph.marschner@tugraz.at; j.holmes@ucc.ie Rights AbstractNew oligosilylgermane compounds with weak Ge-H bonds have been used as precursors for the rapid synthesis of germanium (Ge) nanowires in high yields (>80 %), via a solution-liquid-solid (SLS) mechanism, using indium (In) nanoparticles as a seeding agent over a temperature range between 180 to 380 °C. Even at low growth temperatures, milligram quantities of Ge nanowires could be synthesized over a reaction period of between 5 to 10 minutes. The speed of release of Ge(0) into the reaction environment can be tuned by altering the precursor type, synthesis temperature and the presence or lack of an oxidizing agent, such as tri-n-octylphosphine oxide (TOPO). Energy dispersive X-ray analysis showed that silicon 2 atoms from the precursors were not incorporated into the structure of the Ge nanowires. As both In and Ge facilitate reversible alloying with Li, Li-ion battery anodes fabricated with these nanowires cycled efficiently with specific capacities, i.e. >1000 mAh g -1

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“…Electrochemical reactions were previously demonstrated effectively in fabricating meso-and nanoporous structures with well-controlled pore structure and chemical compositions, greatly improving the performance of electrode materials 25 . Different mechanisms were proposed for the formation of porous structures, for example, by galvanic replacement reactions 26 due to different reduction potentials or through a nanoscale Kirkendall effect due to different diffusion rates of migrating species [27][28][29] .…”

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High-rate lithiation-induced reactivation of mesoporous hollow spheres for long-lived lithium-ion batteries

et al. 2014

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Mechanical and chemical degradations of high-capacity anodes, resulting from lithiationinduced stress accumulation, volume expansion and pulverization, and unstable solidelectrolyte interface formation, represent major mechanisms of capacity fading, limiting the lifetime of electrodes for lithium-ion batteries. Here we report that the mechanical degradation on cycling can be deliberately controlled to finely tune mesoporous structure of the metal oxide sphere and optimize stable solid-electrolyte interface by high-rate lithiationinduced reactivation. The reactivated Co 3 O 4 hollow sphere exhibits a reversible capacity above its theoretical value (924 mAh g À 1 at 1.12 C), enhanced rate performance and a cycling stability without capacity fading after 7,000 cycles at a high rate of 5.62 C. In contrast to the conventional approach of mitigating mechanical degradation and capacity fading of anodes using nanostructured materials, high-rate lithiation-induced reactivation offers a new perspective in designing high-performance electrodes for long-lived lithium-ion batteries.

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High-Performance Germanium Nanowire-Based Lithium-Ion Battery Anodes Extending over 1000 Cycles Through in Situ Formation of a Continuous Porous Network

Abstract: Type of publicationArticle ( Access to the full text of the published version may require a subscription. Rights

Cited by 331 publications

References 43 publications

Advances in the Application of Silicon and Germanium Nanowires for High‐Performance Lithium‐Ion Batteries

Advances in the Application of Silicon and Germanium Nanowires for High‐Performance Lithium‐Ion Batteries

Rapid, Low-Temperature Synthesis of Germanium Nanowires from Oligosilylgermane Precursors

High-rate lithiation-induced reactivation of mesoporous hollow spheres for long-lived lithium-ion batteries

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