Nitrogen-Rich Mesoporous Carbon as Anode Material for High

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Nitrogen-Rich Mesoporous Carbon as Anode Material for High-Performance Sodium-Ion Batteries Huan Liu, M Jia, Ning Sun, Bin Cao, Renjie Chen, Qizhen Zhu, Feng Wu, Ning Qiao, and Bin Xu ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.5b06898 • Publication Date (Web): 20 Nov 2015 Downloaded from http://pubs.acs.org on November 21, 2015

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ACS Applied Materials & Interfaces

Nitrogen-Rich Mesoporous Carbon as Anode Material for High-Performance Sodium-Ion Batteries Huan Liu,† Mengqiu Jia,† Ning Sun,† Bin Cao,† Renjie Chen,‡ Qizhen Zhu†, Feng Wu,‡ Ning Qiao† and Bin Xu*,† †

State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology for Materials, Beijing University of Chemical Technology, Beijing 100029, China. ‡

School of Materials Science & Engineering, Beijing Key Laboratory of

Environmental Science and Engineering, Beijing Institute of Technology, Beijing 100081, China *Corresponding author. E-mail: [email protected]; Tel/Fax: 86-10-64434907.

Abstract Nitrogen-rich carbon with interconnected mesoporous structure has been simply prepared by nano-CaCO3 template method using polyaniline as carbon and nitrogen precursors. The preparation process includes in situ polymerization of aniline in nano-CaCO3 aqueous solution, carbonization of the composites and removal of the template with diluted hydrochloric acid. Nitrogen sorption shows the carbon enrich mesopores with a specific surface area of 113 m2 g-1. The X-ray photoelectron spectroscopic (XPS) analysis indicate the carbon has a high nitrogen content of 7.78 at%, in the forms of pyridinic, pyrrolic as well as graphilitic nitrogen. The nitrogen-rich mesoporous carbon shows a high reversible capacity of 338 mAh g-1 at a current density of 30 mA g-1, and good rate performance as well as ultra-long cycling durability (110.7 mAh g-1 at the current density of 500 mA g-1 over 800 cycles). The excellent sodium storage performance of the nitrogen-rich mesoporous carbon is 1

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attributed to its disordered structure with large interlayer distance, interconnected porosity and the enriched nitrogen heteroatoms. Keywords: Sodium-ion battery, Mesoporous carbon, Nitrogen-rich, Capacity, Cycle performance

1 INTRODUCTION During the past several decades, lithium ion batteries (LIBs) have attracted considerable attention because of their high energy density and good cycle performance. However, the limited storage and high cost nature of lithium resources make LIBs difficult to satisfy the requirement of large-scale energy storage. Because of the natural abundance of sodium resources, with the similar chemical characteristics to lithium, sodium-ion batteries (SIBs) are being recognized as one of the most promising alternatives for LIBs.1-4 However, the exploration of suitable anode materials for SIBs is more difficult than for LIBs as the ionic radius of Na is larger than that of the Li.5 The interstitial space of graphite, the most commonly used anode materials for LIBs, is not large enough to accommodate sodium ions and to allow reversible and rapid sodium ion insertion/extraction. Disordered carbon with large interlayer distance are regarded as one of the most suitable anode materials for SIBs. Various carbon materials such as carbon black,6 carbon spheres,7,

8

carbon

fibers,9-11 hollow carbon nanowires12 and porous carbon13-16 have been used as anode materials for SIBs. Although much progress has been realized, the electrochemical performance of the disordered carbon materials is still a challenge so far, because their capacity or/and cycling life could not satisfy the SIBs application demand. Compared to bulk carbon materials, porous carbon materials can offer significant improvements on power and energy density, which are attracting increasing interests 2


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for energy storage/conversion devices. The developed pores of the porous carbon materials provide sufficient contact area at the electrode/electrolyte interface, continuous electron conduction pathways, and easy strain relaxation during charge-discharge process.17,

18

Furthermore, doping with heteroatoms, particularly

nitrogen atoms, is an effective way to enhance the electrochemical performance of carbon materials as anode for LIBs and NIBs.17, 19-21 Various nitrogen-rich precursors, such as melamine resin,22 polyacrylonitrile,23 polypyrrole,21,

24

polyaniline,25,

26

gelatin17 and nitrogen-containing organic salt27 have been used to prepare nitrogen-rich porous carbons. The application of the nitrogen-rich porous carbon have been widely investigated as electrode materials for supercapacitors and lithium-ion batteries, but only a few works have been reported for application in sodium-ion batteries so far. Nitrogen doped porous carbon fibers prepared from polypyrole nanofibers by KOH activation shows a capacity of 296 mAh g-1 at 50 mA g-1 with satisfactory rate performance.9 Wang et al prepared nitrogen-doped porous carbon nanosheets by KOH activation of polypyrole-functionalized graphene, which can deliver a reversible capacity of 349.7 mAh g-1 at 50 mA g-1 with good rate capability.28 Nitrogen-doped ordered mesoporous carbon was synthesized from sucrose by a template carbonization using SBA-15 as template and post treatment with urea as nitrogen precursor for SIBs.15 Our group have recently synthesized nitrogen-doped mesoporous carbons by the co-pyrolysis of gelatin and magnesium citrate,29 which show a high reversible capacity of 360 mAh g-1 at 50 mA g-1 and stable cycling performance. These studies illuminate that porous structure and nitrogen-doping of the carbons play important roles in facilitating the Na ion transport and storage in SIBs. However, the high surface areas make the initial Coulombic efficiency of the carbons is generally lower than 40%, and both chemical activation26, 3



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29

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and silica template methods30 are tedious and complex. Herein, we synthesized nitrogen-rich carbon with interconnected porous structure

by nano-CaCO3 template method using polyaniline as carbon and nitrogen precursor. The preparation procedure is very simple, involving in situ polymerization of aniline in nano-CaCO3 aqueous solution, carbonization of the composites and removal of the template with diluted hydrochloric acid. The as-prepared carbon possesses a specific surface area of 113 m2 g-1 with a nitrogen content of 7.78 at%. It exhibits a high reversible capacity up to 338 mAh g-1 at a current density of 30 mA g-1 with an initial Coulombic efficiency of 54.2%, and also presents good rate capability and ultra-long cycling durability.

2 EXPERIMENTAL SECTION Synthesis of nitrogen-rich mesoporous carbon (NMC). All chemicals were used of analytical grade without further purifying. Commercial hydrophilic nano-CaCO3 (ca. 40 nm) was obtained from Shanxi Xintai Nanomater, China. The nitrogen-rich porous carbon was prepared using polyaniline (PANI) as nitrogen and carbon precursor, and commercial hydrophilic CaCO3 nanoparticles as template. The synthesis process includes three steps, in situ polymerization of aniline in nano-CaCO3 aqueous solution, carbonization of the composite of PANI/CaCO3, and removal of the template with diluted hydrochloric acid. Typically, 3 g sodium lauryl sulphate (SLS) and 1 g nano-CaCO3 was dissolved in 50 ml water under stirring to form a transparent solution, followed by the addition of 7.33 g ammonium peroxydisulfate (APS). After 1 g aniline was direct added to the reactor, the other 7 g aniline was added drop by drop. This addition process was completed within 70 min and carried out in the ultrasonic bath at 20(±2) °C. The reaction was continued for a further period of 90 4


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min and the resulting dark green polymerized colloidal dispersion was obtained. After filtered and washed with deionized water and acetone, and dried at 80 °C under vacuum, the PANI/CaCO3 composites were obtained. The composites were put into a tubular furnace and heated at 700 °C for 2 h with a ramp rate of 10 °C min-1 in N2 atmosphere to accomplish carbonization. Finally, the pyrolyzed products were washed with 1 M HCl and deionized water to remove the template. After being dried at 120 °C under vacuum for 8 h, the NMC sample was obtained. For comparison, nitrogen-rich carbon (NC) was prepared with the similar procedure to NMC only without CaCO3 template. Characterization. The morphology of the samples was observed by scanning electron microscopy (SEM; JSM-6701F) and transmission electron microscopy (TEM; JEOL-2100). The composition and crystallitic structure of the samples were characterized by powder X-ray diffraction (XRD; Bruker D8 with Cu Kα radiation) and X-ray photoelectron spectroscopy (XPS; ESCALAB 250). The Raman spectrum was tested on Renishaw 1000 Raman spectrometer using a 50 mW He-Ne laser (514 nm) with a CCD detector. The porosity parameters of the carbons were analyzed by nitrogen (77K) adsorption/desorption (Micromeritics ASAP 2460). The specific surface

area

(SBET)

was

obtained

according

to

the

conventional

Brunauer-Emmett-Teller (BET) method. The total pore volume (Vt) was calculated by counting the amount of the adsorbed N2 at a relative pressure of 0.99. Besides, the adsorption branch of the isotherm was used to calculate the pore size distribution through the Barrett-Joyner-Halenda (BJH) method. Electrochemical measurements. A slurry of active materials (80 wt%), conductive agent (Super-p, 10 wt%) and binder (PVDF, 10 wt%) in the NMP solvent was coated onto Cu foil. After dried at 120 °C for 12 h under vacuum, the as-prepared electrode 5



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was cut into pellets in a size of Φ10 mm, in which the mass loading was about 0.8 mg cm-2. The obtained pellet was used as working electrode to assemble the coin cell (2025-type) in an argon-filled glove box (Mikrouna, H2O, O2

Nitrogen-Rich Mesoporous Carbon as Anode Material for High

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