Silicon Nanotube Battery Anodes

Park, Mi-Hee; Kim, Min; Joo, Jaebum; Kim, Kitae; Kim, Je Young; Ahn, S. T.; Cui, Yi; Cho, Jaephil

doi:10.1021/nl902058c

Cited by 1,418 publications

(1,035 citation statements)

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“…Pioneering works have found some success in addressing material instability through the nanostructural design of electrode architectures capable of reducing expansion and its consequences 15,[19][20][21][22][23][24][25][26] . The ultimate goal of such research is to incorporate a Si-based negative electrode into a lithium-ion full-cell, requiring the Si electrode to maintain a half-cell coulombic efficiency (CE) of 499.994% for 5,000 cycles 15 .…”

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confidence: 99%

“…These values, although somewhat unrealistic for current application needs, truly emphasize the importance of half-cell CEs to achieve a long-lasting LIB. Unfortunately, the electrode architectures presented in previous works 15,[19][20][21][22][23][24][25][26] , despite providing significant improvements to Si electrode performance, lack the needed CEs largely because the volume change during Si alloying and de-alloying renders the SEI at the Si-electrolyte interface mechanically unstable.…”

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Stable silicon-ionic liquid interface for next-generation lithium-ion batteries

et al. 2015

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We are currently in the midst of a race to discover and develop new battery materials capable of providing high energy-density at low cost. By combining a high-performance Si electrode architecture with a room temperature ionic liquid electrolyte, here we demonstrate a highly energy-dense lithium-ion cell with an impressively long cycling life, maintaining over 75% capacity after 500 cycles. Such high performance is enabled by a stable half-cell coulombic efficiency of 99.97%, averaged over the first 200 cycles. Equally as significant, our detailed characterization elucidates the previously convoluted mechanisms of the solid-electrolyte interphase on Si electrodes. We provide a theoretical simulation to model the interface and microstructural-compositional analyses that confirm our theoretical predictions and allow us to visualize the precise location and constitution of various interfacial components. This work provides new science related to the interfacial stability of Si-based materials while granting positive exposure to ionic liquid electrochemistry.

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Stable silicon-ionic liquid interface for next-generation lithium-ion batteries

et al. 2015

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“…Si is also one of the most important materials for thermoelectrics, where both nanosize and heavy doping are necessary to effectively scatter phonons and tune the electronic properties, respectively (13)(14)(15)(16). With rapid development in the past decade, Si has become one of the most promising candidates for lithium ion battery anode (17)(18)(19)(20)(21)(22)(23)(24)(25)(26), where Si nanoparticles with purity above 99% (wt %) and sizes below 150 nm have shown very high capacity without mechanical fracture during electrochemical cycling (27)(28)(29).…”

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Nanopurification of silicon from 84% to 99.999% purity with a simple and scalable process

Zong

Zhu

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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Silicon, with its great abundance and mature infrastructure, is a foundational material for a range of applications, such as electronics, sensors, solar cells, batteries, and thermoelectrics. These applications rely on the purification of Si to different levels. Recently, it has been shown that nanosized silicon can offer additional advantages, such as enhanced mechanical properties, significant absorption enhancement, and reduced thermal conductivity. However, current processes to produce and purify Si are complex, expensive, and energy-intensive. Here, we show a nanopurification process, which involves only simple and scalable ball milling and acid etching, to increase Si purity drastically [up to 99.999% (wt %)] directly from low-grade and low-cost ferrosilicon [84% (wt %) Si; ∼$1/kg]. It is found that the impurity-rich regions are mechanically weak as breaking points during ball milling and thus, exposed on the surface, and they can be conveniently and effectively removed by chemical etching. We discovered that the purity goes up with the size of Si particles going down, resulting in high purity at the sub-100-nm scale. The produced Si nanoparticles with high purity and small size exhibit high performance as Li ion battery anodes, with high reversible capacity (1,755 mAh g −1 ) and long cycle life (73% capacity retention over 500 cycles). This nanopurification process provides a complimentary route to produce Si, with finely controlled size and purity, in a diverse set of applications.Si | purification | nanoparticles | low grade | Li ion battery E lemental Si has a large impact on the development of modern society, with different purities and sizes widely used for different applications (1-6). Achieving precise purity control is a crucial step in the development of semiconductor devices, because impurities alter the basic properties (mechanical, optical, electrical, and thermal) of semiconductors substantially. For example, it is well-known that silicon wafers need to be refined to a purity of 99.9999999% (wt %) (nine nines) for integrated circuits. In the case of photovoltaics, it is regarded that the purity of Si needs to be above 99.9999% (wt %) (six nines) to enable long carrier diffusion length (2, 7). Also, it has also been shown that Si nanowires and nanoparticles can provide several advantages, such as absorption enhancement, efficient carrier extraction, and reduced requirements for material quality (8-12). Si is also one of the most important materials for thermoelectrics, where both nanosize and heavy doping are necessary to effectively scatter phonons and tune the electronic properties, respectively (13-16). With rapid development in the past decade, Si has become one of the most promising candidates for lithium ion battery anode (17-26), where Si nanoparticles with purity above 99% (wt %) and sizes below 150 nm have shown very high capacity without mechanical fracture during electrochemical cycling (27)(28)(29).Although Si, widely distributed in dusts, sands, and planets as various forms of sil...

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“…Проте, як показали подальші дослідження, у процесі електрохімічного впровадження / екстракції йонів літію в електродний матеріал на основі кремнію, останній зазнає значних об'ємних змін ( об'єм комірки в перерахунку на один атом кремнію для сполуки Li 4,4 Si більш, ніж у 4 рази перевищує об'єм комірки вихідного матеріалу, тобто спостерігається 400 % об'ємне розширення ґратки кремнію), що приводить до розтріскування та руйнування елект-роду [5,6]. Для подолання вказаної проблеми зменшували розміри частинок кремнію [7], покращу-вали електричний контакт між частинками кремнію за рахунок введення струмопровідних добавок (графіту і / або нанорозмірної вуглецевої сажі) в мікро-Si аноди [8], використовували кремнієві нано-трубки [9,10], нанодротини [11,12], 3D-пористі частинки кремнію [13,14]. Інший підхід передбачав застосування композиційних електродних матеріалів, сформованих з неактивної чи активної матриці-"господаря", в якій дисперговані частинки кремнію.…”

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The Current Formation Processes in Lithium Power Sources with SiO2 – C Composite Cathode

Myronyuk

Sachko

Mandzyuk

2015

PCSS

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Струмоутворюючі процеси в літієвих джерелах струму з композиційним катодом SiO 2 -C ДВНЗ "Прикарпатський національний університет імені Василя Стефаника", вул. Шевченка, 57, Івано-Франківськ, 76018, Україна, mandzyuk_vova@ukr.net У роботі, використовуючи методи гальваностатичного циклювання, циклічної вольтамперометрії та імпедансної спектроскопії, досліджений процес струмоутворення в літієвому джерелі струму (ЛДС) з композиційним катодом SiO 2 -22% C. Встановлено, що при розрядженні джерела в режимі С/20 його питома ємність становить 1757 мА•год/г. У циклах розрядження/зарядження ЛДС відбувається різкий спад питомої ємності (необоротна ємність після першого циклу перевищує 95 %) внаслідок утворення поверхневого твердотільного шару складу (ПТШ) складу LiF та сполуки Li х SiO 2 , в якій літій при зарядженні джерела не окислюється до йонного стану. З'ясовано, що впровадження в катодний матеріал йонів літію до значення х = 1,8 зумовлює зменшення їх коефіцієнта дифузії на 4 порядки (D Li = 2,2•10 -14 ÷ 2,1•10 -18 см 2 /с).Ключові слова: композит SiO 2 -C, літієве джерело струму, питома ємність, коефіцієнт дифузії.Стаття поступила до редакції 08.03.2015; прийнята до друку 15.06.2015.

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Silicon Nanotube Battery Anodes

Cited by 1,418 publications

References 31 publications

Stable silicon-ionic liquid interface for next-generation lithium-ion batteries

Stable silicon-ionic liquid interface for next-generation lithium-ion batteries

Nanopurification of silicon from 84% to 99.999% purity with a simple and scalable process

The Current Formation Processes in Lithium Power Sources with SiO2 – C Composite Cathode

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