Elsevier

Composites Communications

Volume 22, December 2020, 100447
Composites Communications

Lignin-derived nitrogen-doped porous ultrathin layered carbon as a high-rate anode material for sodium-ion batteries

https://doi.org/10.1016/j.coco.2020.100447Get rights and content

Highlights

  • Nitrogen-doped porous ultrathin layered carbon (LC) was prepared via annealing alkaline lignin with melamine and urea.

  • High specific capacity and good cycling stability are obtained for LC.

  • It was proved that LC’s special porous ultrathin structure can greatly enhance its electrochemical performance.

Abstract

Nitrogen-doped porous ultrathin layered carbon (LC) was prepared via annealing alkaline lignin with melamine and urea. As the anode material of sodium-ion batteries, the as-prepared LC shows high reversible capacity, outstanding rate performance and excellent cycling performance. In particular, the ultrathin graphitic carbon with large surface area and pore volume provide abundant sodium storage active sites, delivering a higher initial capacity of 320.5 mAh g−1 in the voltage range of 0.01–3 V at a current density of 0.1 C (1C = 30 mA g−1). Besides, the structure defects resulted from the doping of N also benefits to its high capacity. Capacitive and diffusion contribution calculation and EIS analysis proved the improved the Na+-ion storage kinetics due to LC's unique porous ultrathin structure, resulting in outstanding rate performance. LC delivers a high capacity of 138.7 mAh g−1 at 5 C. Besides, LC's porous ultrathin structure also guarantees its stable cycling performance. Even at a high current density of 5 C, there's no obvious capacity decay after 4000 cycles. This work presents an alternative approach for the synthesis of high-rate carbonaceous anode materials for sodium-ion batteries from low cost and sustainable feedstock.

Introduction

Recently, sodium-ion batteries (SIBs) have attracted more and more attention due to its environment friendly, low cost, the wide distribution of resources and similar working principles with lithium-ion batteries (LIBs) [[1], [2], [3], [4], [5], [6], [7]]. With regard to the anode materials for SIBs, the previous research mainly focused on non-carbon-based materials (such as alloys, metal oxides, and phosphorus) and carbonaceous materials [4,8]. Non-carbon-based materials delivered high capacity, but their poor cycling performance, low rate capability, large volume expansion and high cost greatly limit their practical use in SIBs [5]. In contrast, carbonaceous materials occupy the advantages of high abundance, excellent cycling performance and low charge-discharge plateau, allowing them to be promising candidates of anode materials for SIBs [9].

Hard carbon, one of the most used carbonaceous materials for SIBs, has been investigated thoroughly owing to its high specific capacity and facile synthesis [[10], [11], [12], [13], [14]]. However, hard carbon still faces the severe capacity decay during long-term cycling, and usually suffers from a inferior rate performance. Designing new nanostructures and doping heteroatoms are the major strategies to improve their electrochemical performances, especially for their cycling performance and rate performance [13,15]. Li et al. [13] prepared hard carbon microspheres (HCMs) from a single source of sodium lignin sulfonate. Due to the enlarged interlayer spacing, the existence of few defects and low specific surface area, the prepared HCMs, exhibits a high reversible capacity of 339 mAh g−1, a high ICE, and stable cycling performance. High nitrogen content hard carbon spheres with improved graphitization and ingenious mesoporous structure was synthesized via a hydrothermal and carbonization processes [16]. The obtained hard carbon spheres deliver a high sodium storage capacity of 334.7 mAh g−1, and a high rate capability of 93.9 mAh g−1 at a current density of 5 A g−1. More importantly, the sodium-ion storage mechanism was investigated by in-situ Raman tests. It is revealed that the discharge plots could be separated into two parts: the adsorption part of Na+(the slop region above 0.3 V) and adsorption-intercalation part of Na+ (the slop region below 0.3 V). Besides, nitrogen and atomic Ni co-doped carbon material [17], microporous sulfur-doped carbon microtubes [18] and phosphorus-doped hard carbon nanofibers [19] were also prepared and delivered excellent sodium storage capability.

The source of the present prepared hard carbon electrode materials are mainly costly carbonaceous precursors, such as sugar, polymers and/or organics, which raise the cost concerns of SIBs [[20], [21], [22]]. Lignin is the second most abundant renewable biomass on Earth [23,24], which was an ideal resource to produce carbon.

Herein, nitrogen-doped porous ultrathin layered carbon (LC) was obtained via annealing alkaline lignin with the assistance of melamine and urea. The obtained LC exhibits high reversible capacity, outstanding rate performance and excellent cycling performance. In particular, the ultrathin carbon with large surface area, high pore volume and high nitrogen content provide abundant sodium storage active sites, delivering a higher initial capacity of 320.5 mAh g−1. Capacitive and diffusion contribution calculation and EIS analysis proved that the LC's unique porous ultrathin structure significantly improves the Na+ storage kinetics. LC delivers a high capacity of 138.7 mAh g−1 even at 5 C. Besides, LC's porous ultrathin structure also guarantees stable cycling performance. Even at 5 C, there's no obvious capacity decay at after 4000 cycles for LC electrode. This work presents a cheap alternative route for the synthesis of high-rate carbonaceous anode materials for sodium-ion batteries.

Section snippets

Materials

Alkaline lignin purchased from Geyi Energy (Anhui province, PR China) was used as raw material for the porous carbon. Analytical reagent urea and melamine were purchased from Aladdin Industrial Inc., China. Ultra-pure water was used for all experiments.

Preparation of LC

LC was prepared as following: Firstly, 2 g melamine, 10 g urea and 2 g alkaline lignin were mixed with water as solvent to form a lignin/melamine/urea solution for 1 hours at room temperature; Subsequently, the solution was heated and stirred to

Result and discussion

The preparation procedures of the porous nitrogen-doped ultrathin layered carbon (LC)are illustrated in Scheme 1. Alkali lignin, urea and melamine was firstly dissolved into and mixed into a homogeneous liquid phase. After that, lignin/urea/melamine solution was transformed into lignin/urea/melamine composite by evaporating water. During the evaporation process, urea and melamine crystallize and distribute into lignin uniformly. Then the composite was annealed with the protection of N2. During

Conclusion

Porous nitrogen-doped ultrathin layered carbon (LC) was prepared via a simple method with lignin, urea and melamine as the sources. In this process, the participation of urea and melamine not only enhance the N content of LC, but also plays a vital role in the formation of the porous ultrathin layer morphology. The as-prepared LC exhibits high sodium ion storage capacity, outstanding rate performance and excellent cycling performance. By analysis, the excellent electrochemical performance of LC

CRediT authorship contribution statement

Suli Chen: Conceptualization, Methodology, Data curation, Writing - original draft. Fan Feng: Investigation. Zi-Feng Ma: Writing - review & editing, Supervision, Funding acquisition, Project administration.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This work was supported by the Natural Science Foundation of China (21938005, 21676165), the Science & Technology Commission of Shanghai Municipality (19DZ1205500), the National Key Research and Development Program (2016YFB0901505).

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