Diffusion Mechanism of Lithium Ion through Basal Plane of Layered Graphene

Yao, Fei; Güneş, Fethullah; Ta, Huy Q.; Lee, Seung Mi; Chae, Seung Jin; Sheem, Kyeu Yoon; Cojocaru, Costel Sorin; Xie, Si Shen; Lee, Young Hee

doi:10.1021/ja301586m

Cited by 369 publications

(290 citation statements)

References 49 publications

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“…Thus, the resulting sample shows a higher reversible capacity as an anode material for LIBs than normal N-doped graphene. The divacancy and Stone-Wales defects inevitably exist in the resulting N-doped graphene analogous particles 57,58 and would be beneficial for the adsorption of Li atoms according to previous reports 59,60 . However, graphene (approximately 568 mA h g À 1 ) (ref.…”

Section: Characterizationmentioning

confidence: 76%

High lithium anodic performance of highly nitrogen-doped porous carbon prepared from a metal-organic framework

2014

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Theoretical and experimental results have revealed that the lithium-ion storage capacity for nitrogen-doped graphene largely depends on the nitrogen-doping level. However, most nitrogen-doped carbon materials used for lithium-ion batteries are reported to have a nitrogen content of approximately 10 wt% because a higher number of nitrogen atoms in the two-dimensional honeycomb lattice can result in structural instability. Here we report nitrogen-doped graphene particle analogues with a nitrogen content of up to 17.72 wt% that are prepared by the pyrolysis of a nitrogen-containing zeolitic imidazolate framework at 800°C under a nitrogen atmosphere. As an anode material for lithium-ion batteries, these particles retain a capacity of 2,132 mA h g À 1 after 50 cycles at a current density of 100 mA g À 1 , and 785 mAh g À 1 after 1,000 cycles at 5 A g À 1 . The remarkable performance results from the graphene analogous particles doped with nitrogen within the hexagonal lattice and edges.

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Section: Characterizationmentioning

confidence: 76%

High lithium anodic performance of highly nitrogen-doped porous carbon prepared from a metal-organic framework

2014

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“…The special feature of nanocarbon anode materials is that they exhibit al arger voltage hysteresis between the chargea nd discharge processes than graphite, which resembles hard carbon materials. [14,86,87] Ta ble 1s ummarizes the anode performance with respect to the highlighted electrode materials published in the literature.…”

Section: Nanocarbons As Anodes In Libsmentioning

confidence: 99%

“…Therefore, lithium-ion diffusion through the basal plane cannot exclusively be observed. [73][74][75][76][77] To obtain ac omprehensive pictureo ft he mechanism of lithium diffusion in LIBs, our group fabricated highquality single-layer graphene with aw ell-definedb asal plane (Figure 10 a) and few-layer graphene with an enriched edge plane (Figure10b)t hrough CVD, as indicated in Figure 10 c. [87] We found that Li-ion diffusion perpendicular to the basal plane of graphene is facilitated by defects, whereas diffusion parallel to the plane is limited by steric hindrance originating from aggregated Li ions adsorbed on the abundant defect sites (Figure 10 d). Furthermore,w en oticed that the capacity of the graphene layers decreases continuously as the number of graphene layers increases (Figure 10 d).T his indicates corrosion of the metal current collector and the protective nature of graphene.Wepredicted that the critical layerthickness (l c )tosufficiently prohibit reactiono ft he substrate by using CVD-grown graphene layers is approximately six layers, independent of the defect population on the graphene layers (Figure 10 d).…”

Section: Graphene As An Anode Materialsmentioning

confidence: 99%

Carbon‐Based Materials for Lithium‐Ion Batteries, Electrochemical Capacitors, and Their Hybrid Devices

2015

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A rapidly developing market for portable electronic devices and hybrid electrical vehicles requires an urgent supply of mature energy-storage systems. As a result, lithium-ion batteries and electrochemical capacitors have lately attracted broad attention. Nevertheless, it is well known that both devices have their own drawbacks. With the fast development of nanoscience and nanotechnology, various structures and materials have been proposed to overcome the deficiencies of both devices to improve their electrochemical performance further. In this Review, electrochemical storage mechanisms based on carbon materials for both lithium-ion batteries and electrochemical capacitors are introduced. Non-faradic processes (electric double-layer capacitance) and faradic reactions (pseudocapacitance and intercalation) are generally explained. Electrochemical performance based on different types of electrolytes is briefly reviewed. Furthermore, impedance behavior based on Nyquist plots is discussed. We demonstrate the influence of cell conductivity, electrode/electrolyte interface, and ion diffusion on impedance performance. We illustrate that relaxation time, which is closely related to ion diffusion, can be extracted from Nyquist plots and compared between lithium-ion batteries and electrochemical capacitors. Finally, recent progress in the design of anodes for lithium-ion batteries, electrochemical capacitors, and their hybrid devices based on carbonaceous materials are reviewed. Challenges and future perspectives are further discussed.

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“…Particularly, the Li + diffusion mechanism was deeply investigated. [ 75 ] It was demonstrated that Li + diffusion perpendicular to the basal plane of graphene (obtained by CVD) is facilitated by defects, whereas diffusion parallel to the plane is limited by the steric hindrance that originates from aggregated Li ions adsorbed on the abundant defect sites which, also, lead to the previously described drawbacks (i.e., irreversible capacity and voltage hysteresis). Furthermore, the effects on the Li-ion storage properties of different sonication times (for liquidphase-exfoliated graphene), [ 76 ] methods of reduction for graphene oxide [77][78][79][80][81] and electrode preparations [ 82 ] were intensely studied, thus demonstrating again how the processing of this class of materials can strongly infl uence the electrochemical properties of graphene.…”

Section: Continuedmentioning

confidence: 99%

Critical Insight into the Relentless Progression Toward Graphene and Graphene‐Containing Materials for Lithium‐Ion Battery Anodes

et al. 2016

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that its extraordinary properties would enable revolutionary new technologies, which gave birth to the "graphene era". [ 3,4 ] Relying on this scenario, in 2013, the European Union launched the ¤1 billion "Graphene Flagship" project aimed to investigate the properties of this new form of carbon for various applications (e.g., electronics, sensors and energy storage devices), with the ambitious goal of guiding graphene from laboratories to commercial applications within a decade. [ 5,6 ] In the same period, the Chinese Government set up a similar investment to mass-produce graphene as thin fi lms (e.g., for touchscreen electrodes) and platelets (e.g., for use in batteries). [ 6 ] In the following years, hundreds of patents, mainly focused on manufacturing and application in energy storage, were fi led and the worldwide production of graphene and graphene-containing materials rapidly increased. Although a few Chinese industries claimed to already use graphene-containing materials for smartphone production, no revolutionary practical application relying on graphene has been yet developed. [ 6 ] Specifi cally with respect to the battery fi eld, a close analysis of the scientifi c literature reveals a struggle to meet the ambitious initial targets. A potential loss of focus from the fi nal application caused by hype and ease of publication on such a novel matter, together with the delivery of very misleading information [ 7,8 ] and erroneous statements [ 7 ] concerning the use of graphene in batteries are emerging as possible reasons of the ineffective graphene-era outburst. In this progress report, we do not focus on production and classifi cation of graphene and graphene-containing materials, which were already well reported in the past years. [ 3,[9][10][11] In contrast, due to the lack of an exhaustive analysis of the progression of the use of such materials in lithium-ion battery (LIB) anodes, we report here a critical evaluation of the most prominent research papers published from 2008 until the end of 2015. As shown in Figure 1 , three different stages of the graphene research in LIB anodes can be distinguished: a fi rst stationary phase between 2008 and 2010 where the lithium-ion storage properties of different graphene and graphene-containing materials were preliminarily explored, a second exponential stage, spanning from 2010 to 2014, where graphene and graphene-containing anode materials were broadly developed and investigated, and fi nally, a third phase, (i.e., starting from 2015), where the research seems to have approached a plateau. After Used as a bare active material or component in hybrids, graphene has been the subject of numerous studies in recent years. Indeed, from the fi rst report that appeared in late July 2008, almost 1600 papers were published as of the end 2015 that investigated the properties of graphene as an anode material for lithium-ion batteries. Although an impressive amount of data has been collected, a real advance in the fi eld still seems to be missing. In this framework, atten...

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Diffusion Mechanism of Lithium Ion through Basal Plane of Layered Graphene

Cited by 369 publications

References 49 publications

High lithium anodic performance of highly nitrogen-doped porous carbon prepared from a metal-organic framework

High lithium anodic performance of highly nitrogen-doped porous carbon prepared from a metal-organic framework

Carbon‐Based Materials for Lithium‐Ion Batteries, Electrochemical Capacitors, and Their Hybrid Devices

Critical Insight into the Relentless Progression Toward Graphene and Graphene‐Containing Materials for Lithium‐Ion Battery Anodes

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