Electrochemical storage mechanism of sodium in carbon materials: A study from soft carbon to hard carbon

Cheng, Dejian; Zhou, Xinlin; Hu, Huanying; Li, Zenghui; Chen, Jun; Miao, Lei; Ye, Xiaoji; Zhang, Haiyan

doi:10.1016/j.carbon.2021.06.066

Cited by 98 publications

(77 citation statements)

References 54 publications

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“…[5,6] Carbon materials are highly preferable in response to the exploration of PIB anode candidates because of their collective merits. [7][8][9] As for graphite, a commercial anode material for lithium-ion batteries, it suffers severe volume expansion upon repeated K + insertion/extraction. [10,11] Furthermore, the storage mechanism associated with ion intercalation via KC 8 only affords a mediocre theoretical specific capacity (279 mAh g −1 ).…”

Section: Introductionmentioning

confidence: 99%

Boosting K⁺ Capacitive Storage in Dual‐Doped Carbon Crumples with B–N Moiety via a General Protic‐Salt Synthetic Strategy

Lian

Zhou

You

et al. 2021

Adv Funct Materials

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The heteroatom co-doped carbonaceous anodes have readily attracted great attention in potassium-ion batteries (PIBs), owing to their augmented carbon interlayer distances and increased K + storage sites to induce enhanced capacity value. Nevertheless, the synergistic effect of dual-doped heteroatoms is still unclear and lacks systematic explorations. In addition, traditional synthetic routes are cumbersome with template removal step, which are normally deficient in product scalability. Herein, a generic protic-salt strategy is devised to realize sulfur-, phosphorus-or boron-nitrogen dual-doped carbon (SNC, PNC, or BNC) via varying the types of protic precursors (e.g., the acid). Throughout comprehensive instrumental probing and theoretical simulation, it is identified that the presence of B-N moiety can harvest high adsorption capability of K + and hence exhibit more obvious pseudocapacitance behavior than bare N-doped carbon counterpart. As a PIB anode, the BNC electrode displays an impressive reversible capacity (360.5 mAh g −1 at 0.1 A g −1 ) and cycle stability (125.4 mAh g −1 at 1 A g −1 after 3000 cycles). In situ/ex situ characterizations further reveal the origin of the excellent electrochemical properties of the BNC electrode. Such a tailorable protic-salt derived anode material offers new possibilities to advance PIB devices.

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Section: Introductionmentioning

confidence: 99%

Boosting K⁺ Capacitive Storage in Dual‐Doped Carbon Crumples with B–N Moiety via a General Protic‐Salt Synthetic Strategy

Lian

Zhou

You

et al. 2021

Adv Funct Materials

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“…The impact of the structural characteristics of the soft templated carbons on their electrochemical performance was evaluated in half‐cells using sodium metal as the counter electrode and 1 m NaPF 6 in ethylene carbonate and dimethyl carbonate (EC:DMC, 1:1 v/v) as the electrolyte, between 0.005 and 3 V. The galvanostatic discharge–charge profiles at 30 mA g −1 ( Figure a) show a common behavior: discharge curves (sodium insertion) display a sloping region above 0.1 V, predominantly associated with adsorption at edge or basal defects or insertion into enlarged interlayer spaces, and a flatter plateau region below 0.1 V, arising from Na storage within internal or “closed” pores (Figure 2d–f). [ 5,10,35–37 ] Overall, ST1500 presents the highest initial Coulombic efficiency (65%, Figure 2h) and first and second cycle capacities (523 and 354 mAh g −1 , respectively), predominantly plateau‐derived, consistent with having the highest internal pore volume and the lowest surface area and number of defects. In contrast, ST1000 shows a large and mostly sloped capacity in the first cycle, which decreases substantially in the second cycle.…”

Section: Resultsmentioning

confidence: 95%

Elucidation of the Solid Electrolyte Interphase Formation Mechanism in Micro‐Mesoporous Hard‐Carbon Anodes

Alptekin

Olsson

et al. 2021

Adv Materials Inter

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The microstructure of hard carbons can be designed to maximize their performance as anodes for sodium‐ion batteries. However, the nature of the electrolyte is also decisive in the capacity and long‐term stability. Here, hard carbons with a tailored bimodal pore network of internal micropores interconnected through mesopores are studied as sodium‐ion battery anodes. The evolution of their solid electrolyte interphase (SEI) is analyzed in three different electrolytes (NaPF6 in an ether‐based solvent, and NaPF6 or NaClO4 in a carbonate‐based system). Combining experiments with density functional theory calculations, it is proposed that formation of the SEI is mainly controlled by the decomposition of the salt anion. This process occurs through the intermediate functionalization of the carbon surface by the decomposed anion fragments. It is suggested that the innermost SEI sub‐layer governs the performance and long‐term stability of the anode. While the presence of a fluorine‐containing salt appears to have a determining role in the SEI stability, the electrochemical decomposition of carbonate‐based solvents is detrimental for the long‐term stability as the interfacial resistance increases. In contrast, the ether‐based system enables stable long‐term cycling as the interphase remains almost intact once the first fluorine‐rich SEI layer is formed.

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“…First, the initial three curves of the NSC-600 electrode at the scan rate of 0.2 mV s −1 from 0.005 to 3.0 V are depicted in Figure 3A. The irreversible cathodic peak at around 0.88 V presented in the first cathodic scan, which is disappeared in the subsequent scans, should be ascribed to the decomposition of electrolyte to passivate the surface as well as the generation of solid electrolyte interface (SEI) (Eshetu et al, 2019;Cheng et al, 2021;Fan et al, 2021). In addition, another broad cathodic peak in the low voltage from 0.71 V to 0.005 V should be ascribed to the intercalation of Na + into the carbonaceous skeleton (Kumar et al, 2016).…”

Section: Resultsmentioning

confidence: 99%

Improving the Sodium Storage Performance of Porous Carbon Derived From Covalent Organic Frameworks Through N, S Co-Doping

Zhang¹,

Zhang²,

Zhang³

et al. 2022

Front. Mater.

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Heteroatom doping, which has long been considered as one of the most efficient approaches to significantly enhance the sodium storage ability of carbonaceous anodes, has drawn increasing attention. Compared with single doping, dual doping can introduce more defects and accelerate ionic diffusion. In addition, the synergistic effect between the dual doped atoms can significantly improve the electrochemical performances. Besides, exploring novel precursors with excellent properties, which can induce porous structure and rapid pathways for electrons/ions in the resultant carbonaceous anode, is still full of challenges. Herein, nitrogen and sulfur–co-doped urchin-like porous carbon (NSC) was fabricated through a combined strategy including carbonization and subsequent sulfidation, using covalent organic frameworks (COFs) as precursors. Because of the dual doping–endowed rich defects, high electronic conductivity, and favorable capacitive behavior, the resultant NSC exhibited excellent sodium storage performances, delivering superior sodium storage capacity (483.5 mAh g−1 at 0.1 A g−1 after 100 cycles) and excellent cycling stability up to 1,000 cycles (231.6 mAh g−1 at 1.0 A g−1). Importantly, such remarkable electrochemical performances of the resultant carbonaceous anode may shed light on the efficient conversion of COFs to functional materials.

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Electrochemical storage mechanism of sodium in carbon materials: A study from soft carbon to hard carbon

Cited by 98 publications

References 54 publications

Boosting K⁺ Capacitive Storage in Dual‐Doped Carbon Crumples with B–N Moiety via a General Protic‐Salt Synthetic Strategy

Boosting K⁺ Capacitive Storage in Dual‐Doped Carbon Crumples with B–N Moiety via a General Protic‐Salt Synthetic Strategy

Elucidation of the Solid Electrolyte Interphase Formation Mechanism in Micro‐Mesoporous Hard‐Carbon Anodes

Improving the Sodium Storage Performance of Porous Carbon Derived From Covalent Organic Frameworks Through N, S Co-Doping

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Electrochemical storage mechanism of sodium in carbon materials: A study from soft carbon to hard carbon

Cited by 98 publications

References 54 publications

Boosting K+ Capacitive Storage in Dual‐Doped Carbon Crumples with B–N Moiety via a General Protic‐Salt Synthetic Strategy

Boosting K+ Capacitive Storage in Dual‐Doped Carbon Crumples with B–N Moiety via a General Protic‐Salt Synthetic Strategy

Elucidation of the Solid Electrolyte Interphase Formation Mechanism in Micro‐Mesoporous Hard‐Carbon Anodes

Improving the Sodium Storage Performance of Porous Carbon Derived From Covalent Organic Frameworks Through N, S Co-Doping

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Boosting K⁺ Capacitive Storage in Dual‐Doped Carbon Crumples with B–N Moiety via a General Protic‐Salt Synthetic Strategy

Boosting K⁺ Capacitive Storage in Dual‐Doped Carbon Crumples with B–N Moiety via a General Protic‐Salt Synthetic Strategy