Ion-Catalyzed Synthesis of Microporous Hard Carbon Embedded with Expanded Nanographite for Enhanced Lithium/Sodium Storage

Yu, Zhi‐Long; Xin, Sen; You, Ya; Yu, Le; Lin, Yue; Xu, Dong; Qiao, Chan; Huang, Zhihong; Yang, Ning; Yu, Shu‐Hong; Goodenough, John B

doi:10.1021/jacs.6b06673

Cited by 383 publications

(221 citation statements)

References 60 publications

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“…Thus, the N‐6/N‐Q ratio is an intrinsic parameter that reflects the relationships between the N configurations, carbon textures, and cyclic stabilities and is independent of the annealing temperature and time in the preparation of the N‐doped carbons. A larger graphene size will benefit the stability of the N configurations; the N configurations in a smaller graphene are less stable and will rapidly collapse during the sodiation/desodiation process and therefore show poor cycling stability . However, a larger graphene size implies a lower N/C ratio, which will lead to a lower reversible capacity according to Figure b.…”

Section: Resultsmentioning

confidence: 99%

Tailoring Highly N‐Doped Carbon Materials from Hexamine‐Based MOFs: Superior Performance and New Insight into the Roles of N Configurations in Na‐Ion Storage

Liu

Zhou

Song

2018

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106

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To prepare highly N-doped carbon materials (HNCs) as well as to determine the influence of N dopants on Na-ion storage performance, hexamine-based metal-organic frameworks are employed as new and efficient precursors in the preparation of HNCs. The HNCs possess reversible capacities as high as 160 and 142 mA h g at 2 A g (≈8 C) and 5 A g (≈20 C), respectively, and maintain values of 145 and 123 mA h g after 500 cycles, thus exhibiting excellent rate and long-term cyclic performance. Based on systematic analysis, a new insight into the roles of the different N configurations in Na-ion storage is proposed. The adsorption of Na ions on pyridinic-N (N-6) and pyrrolic-N (N-5) is fully irreversible, whereas the adsorption on graphitic-N (N-Q) is partially reversible and the adsorption on N-oxide (N-O) is fully reversible. More importantly, the N-6/N-Q ratio is an intrinsic parameter that reflects the relationship between the N configurations and carbon textures for N-doped carbons prepared from in situ pyrolysis of organic precursors. The cyclic stability and rate-performance improve with decreasing N-6/N-Q ratio. Therefore, this work is of great significance for the design of N-doped carbon electrodes with high performance for sodium ion batteries.

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Section: Resultsmentioning

confidence: 99%

Tailoring Highly N‐Doped Carbon Materials from Hexamine‐Based MOFs: Superior Performance and New Insight into the Roles of N Configurations in Na‐Ion Storage

Liu

Zhou

Song

2018

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106

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“…This suggests that the carbon components in these samples are highly graphitic. [12] Furthermore,t he existence of CÀNb onds also confirms that Na toms have been doped into the graphitic domains.I ti sw ell-known that N-doped carbon materials often exhibit impressive properties,s uch as good electrical conductivity. [13] To find out the forms of the existing Nspecies, we also analyzed the N1s spectra of the 3D carbon networks (Figure 3d).…”

mentioning

confidence: 85%

Spontaneous Weaving of Graphitic Carbon Networks Synthesized by Pyrolysis of ZIF‐67 Crystals

et al. 2017

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Three-dimensional (3D) networks of graphitic carbon are promising materials for energy storage and conversion devices because of their high electrical conductivity, which is promoted by the good interconnection between the carbon particles.H owever,i ti ss till difficult to directly synthesize such carbon networks.H erein, we report the novel synthesis of 3D graphitic carbon networks through the pyrolysis of nanosized ZIF-67 crystals.I nterestingly,t he unusual effect of downsizing the ZIF-67 crystals and the incorporation of catalytic Co nanoparticles was the spontaneous formation of graphitic networks.The obtained graphitic carbon networks showe xcellent electrochemical performance for the insertion and extraction of potassium ions.Several members of the carbon family,s uch as diamond, fullerene,g raphite,c arbon nanotubes,a nd graphene,h ave been well-studied and prepared by many different approaches.[1] Nanoporous carbons have attracted great interest in many research fields.T he high specific surface area and porosity of nanoporous carbons make them promising candidates for electrochemical energy storage (EES) and conversion devices.[2] Fors uch applications,n anoporous carbons with highly graphitic walls and good electrical conductivity are highly desirable. [3] In general, nanoporous carbons with highly graphitic structures are prepared by thermal pyrolysis of organic precursors at high temperatures (! 800 8 8C).[4] However,such thermal treatment is unfavorable for the large-scale preparation of nanoporous carbons because of the high energy consumption and complicated procedures.I nr ecent years,t he pyrolysis of metal-organic frameworks (MOFs;o rp orous coordination polymers (PCPs)) has been recognized as an effective approach to synthesize nanoporous carbons.[5] MOFs are porous crystalline materials formed by coordinative bonding between metal ions or clusters and organic linkers.[6] Theb reakable coordination bonds,a nd carbon-rich organic component make MOFs appropriate precursors for the preparation of nanoporous carbons.T he metal contents (e.g.C o) of MOFs have been shown to promote the formation of highly graphitic frameworks even at low temperatures. [7] Although the individual particles are highly graphitized, each particle is isolated from each other (i.e.t he particles are not interconnected to ah igh degree).[8] Thus,t he spaces between these particles seriously hinder the transportation of electrons,thus decreasing the electrical conductivity.Therefore,the development of 3D porous carbon networks with excellent connectivity between the carbon particles is highly important for achieving the optimized utilization of MOF-derived carbon materials in EES applications.Herein, we have carefully investigated the size-dependent pyrolysis of aC o-containing zeolitic imidazolate framework (ZIF-67). It is found that areduction in the size of the ZIF-67 particles can lead to as pontaneous welding of the resulting carbon particles,t hereby giving rise to the formation of 3D porous carbon network...

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“…[4,5] Thus, most research has turned to nongraphitic carbons including nanocarbons and hard carbons, [6][7][8][9][10] whose capacities are significantly higher than graphite. [4,5] Thus, most research has turned to nongraphitic carbons including nanocarbons and hard carbons, [6][7][8][9][10] whose capacities are significantly higher than graphite.…”

mentioning

confidence: 99%

Deactivating Defects in Graphenes with Al₂O₃ Nanoclusters to Produce Long‐Life and High‐Rate Sodium‐Ion Batteries

Lin

Zhang

Kong

et al. 2018

Advanced Energy Materials

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LIBs), delivers very limited reversible capacity in SIBs due to its inability to form stable low-stage graphite intercalation compounds (GICs). [4,5] Thus, most research has turned to nongraphitic carbons including nanocarbons and hard carbons, [6][7][8][9][10] whose capacities are significantly higher than graphite. It has been found that the structure could be well controlled to realize the high efficiency and reversibility. Our group has reported that the commercial carbon molecular sieves with abundant ultrasmall (0.3-0.5 nm) pores can achieve high efficiency and reversible capacity. [11] Intensive researches have also revealed that the nongraphitic carbons with low specific surface areas (SSA) exhibit a high electrochemical stability. [12][13][14][15][16] However, these carbons show limited rate capability and relatively low capacity. Thus, it is desired to improve the SSA to enhance the rate performance and capacity. Unfortunately, nongraphitic carbons with large SSA and a large number of defects typically exhibit an extremely low initial Coulombic efficiency (ICE) and unsatisfactory cyclic stability because of uncontrollable electrolyte decomposition and ineffective formation of a solid electrolyte interphase (SEI). In a previous report, we used reduced graphene oxide (rGO) as a model anode and found that an ether-based electrolyte can greatly suppress the Carbon materials are the most promising anodes for sodium-ion batteries (SIBs), but low initial Coulombic efficiency (ICE) and poor cyclic stability hinder their practical use. It is shown herein, that an effective but simple remedy for these problems can be achieved by deactivating defects in the carbon with Al 2 O 3 nanocluster coverage. A 3D porous graphene monolith (PGM) is used as the model material and Al 2 O 3 nanoclusters around 1 nm are grown on the defects of graphene. It is shown that these Al 2 O 3 nanoclusters suppress the decomposition of conductive sodium salt in the electrolyte, resulting in the formation of a thin and homogenous solid electrolyte interphase (SEI). In addition, Al 2 O 3 nanoclusters appear to reduce the detrimental etching of the SEI by hydrogen fluoride (HF) and improve its stability. Therefore, after the introduction of Al 2 O 3 nanoclusters, the ICE, cyclic stability, and rate capability of the PGM are greatly improved. A higher ICE (70.2%) and capacity retention (82.9% after 500 cycles at 0.5 A g −1 ) than those of normally reported for large surface area carbons are achieved. This work indicates a new way to deactivate defects and modify the SEI of carbon materials, and hopefully accelerate the commercialization of carbon materials as anode materials for SIBs.

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Ion-Catalyzed Synthesis of Microporous Hard Carbon Embedded with Expanded Nanographite for Enhanced Lithium/Sodium Storage

Cited by 383 publications

References 60 publications

Tailoring Highly N‐Doped Carbon Materials from Hexamine‐Based MOFs: Superior Performance and New Insight into the Roles of N Configurations in Na‐Ion Storage

Tailoring Highly N‐Doped Carbon Materials from Hexamine‐Based MOFs: Superior Performance and New Insight into the Roles of N Configurations in Na‐Ion Storage

Spontaneous Weaving of Graphitic Carbon Networks Synthesized by Pyrolysis of ZIF‐67 Crystals

Deactivating Defects in Graphenes with Al₂O₃ Nanoclusters to Produce Long‐Life and High‐Rate Sodium‐Ion Batteries

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Ion-Catalyzed Synthesis of Microporous Hard Carbon Embedded with Expanded Nanographite for Enhanced Lithium/Sodium Storage

Cited by 383 publications

References 60 publications

Tailoring Highly N‐Doped Carbon Materials from Hexamine‐Based MOFs: Superior Performance and New Insight into the Roles of N Configurations in Na‐Ion Storage

Tailoring Highly N‐Doped Carbon Materials from Hexamine‐Based MOFs: Superior Performance and New Insight into the Roles of N Configurations in Na‐Ion Storage

Spontaneous Weaving of Graphitic Carbon Networks Synthesized by Pyrolysis of ZIF‐67 Crystals

Deactivating Defects in Graphenes with Al2O3 Nanoclusters to Produce Long‐Life and High‐Rate Sodium‐Ion Batteries

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Deactivating Defects in Graphenes with Al₂O₃ Nanoclusters to Produce Long‐Life and High‐Rate Sodium‐Ion Batteries