Fabrication of helical SiO2@Fe–N doped C nanofibers and their applications as stable lithium ion battery anodes and superior oxygen reduction reaction catalysts
Introduction
Recently, mesoporous carbon nanomaterials have aroused great interest owning to their wide-ranging applications such as electrode materials[1], catalysts and supports [2], and adsorbent [3]. Generally, there are two methods to fabricate mesoporous carbon nanomaterials, the direct synthesis strategy is flexible in preparing mesoporous carbons from organic-organic self-assemblies [4]. The other is called nano-casting strategy, that is, hard templating method [5]. In 1999, Ryoo [6] and Hyeon [7] firstly prepared mesoporous carbons using a hard template of cubic mesoporous silica MCM-48. Thereafter, many other silicas such as SBA series[5], MSU-H [8] and HMS [9] were then utilized as the hard templates to construct mesoporous carbon materials. For example, Kim et al. [10] prepared mesoporous carbons with cubic structure using SBA-16 mesoporous silica template. Lee et al. [9] reported carbons with worm-hole framework meso-structures using hexagonal mesoporous silica template. Zhao et al. [11] have synthesized mesoporous carbon spheres with hierarchical foam-like structures using a dual templating method, spherical silica meso-cellular foams as the hard template and Pluronic F127 as the soft template. The obtained mesoporous carbon nanomaterials well replicated the morphology and meso-structure of the hard templates.
In recent years, considering the low intrinsic capacity (∼372 mA h g−1) of commercial graphitic anodes, mesoporous and nano carbons have been considered as substituted LIBs anode materials. In order to further improve their electrochemical performance, besides designing hierarchical nanostructures, two ways can be realized, one is doping, the other is encapsulating. Among various dopants like N, B, S and P [[12], [13], [14], [15], [16]], N-doped carbon nanomaterials have attracted enormous interest [17,18]. As reported, N-doped carbon materials can increase electric conductivity, the surface polarity, as well as electron-donor tendencies. Previously, we reported helical carbonaceous nanofibers containing 12.4 wt% N content, which achieved a reversible discharge capacity of 499 mA h g−1 after 100 cycles [19]. We also prepared carbonaceous nanorods with 7.87 wt% of N content and 551.3 m2 g−1of specific surface area. After 400 cycles, they gained a discharge capacity of 696.7 mA h g−1 [20].
Some materials which possess high theoretical specific capacity such as Si (∼4200 mA h g−1) and Fe3O4 (∼927 mA h g−1) were encapsulated in N-doped carbons to fabricate nanocomposites. Kim et al. [21] reported N-doped carbon nanotube encapsulated Si composite electrode materials, which exhibited a high capacity retention up to 79.4% after 200 cycles and rather good rate capability showing 914 mA h g−1 at a 10 C rate. Lee et al. [22] fabricated a N-doped carbon thin film encapsulated Fe3O4 composite, which showed a capacity of 850 mA h g−1 after 50 cycles and stable cycling performance. Moreover, via precise designing of nanostructures, SiO2 (∼1965 mA h g−1) materials can show good electrochemical performance in lithium storage despite of their sluggish Li+ diffusion properties and poor intrinsic electronic conductivity. For example, Jiao et al. [23] found that SiO2 spheres could achieve a specific capacity of 877 mA h g−1 after 500 cycles. Nakashima et al. [24] fabricated SiO2 hollow nanospheres with a uniform size of 30 nm, which gained a reversible capacity of 359 mA h g−1 at the 100th cycle. Chen’s research group constructed the hollow SiO2 nanocubes through a hard-templating method, and the hollow SiO2 nanocubes showed a stable discharge capacity (334 mA h g−1) after 500 cycles [25].
Furthermore, N-doped carbon nanocomposites can also act as attractive energy conversion catalysts, especially as the efficient electrocatalysts applied in oxygen reduction reactions (ORRs). Recently, N-doped carbon materials combined with metals (Pt, Fe and Pd) [[26], [27], [28]] or metal oxides (Fe3O4 and MnO2) [29,30] have aroused much attention. Ferrero et al. [31] prepared a highly efficient Fe/N doped hollow carbon ORR electrocatalyst via the nano-casting approach, which exhibited an outstanding (comparable to Pt/C) performance in acidic media and an excellent activity in basic media. They also showed that both N-sites and Fe–N coordination sites were involved in the catalytic reactions. A novel nonprecious metal catalyst composed of Fe3C nanoparticles entrapped in mesoporous Fe–N-doped carbon nanofibers was also reported [32]. They showed extraordinary ORR activity with −0.02 V of the onset potential and −0.140 V of the half-wave potential, which was comparable to the state-of-the-art Pt/C catalyst in alkaline and acidic medias. Liu et al. [33] fabricated Fe–N-doped porous carbon derived from petroleum asphalt by a templating method. Their remarkable ORR performance was attributed to the porous construction, high specific surface area, presence of pyridinic N, and the co-doping of Fe and N elements.
In this work, we prepared SiO2@Fe–N doped C nanofibers from SiO2 nanofibers encapsulated in Fe3+-doped m-phenylenediamine formaldehyde resin. The obtained SiO2@Fe–N doped C nanofibers were used as LIBs anode materials, moreover were investigated for electrocatalytic performance.
Section snippets
Chemicals
Ammonium hydroxide solution (25% in mass fraction) and tetraethyl orthosilicate (TEOS) were purchased from Chinasun Specialty Products Co., Ltd, Cetylpyridinium chloride (CPC) was delivered from TCI (Shanghai) Development Co., Ltd. Fmoc-Ala-OH was bought from GL Biochem (Shanghai). 1-Hexanol was supplied by Shanghai Macklin Biochemical Co., Ltd. Formaldehyde and ferric nitrate nonahydrate were bought from Sinopharm Group Co., Ltd., and m-phenylenediamine was supplied by Aladdin (Shanghai)
Results and discussion
The synthesis procedure of the SiO2@Fe–N–C nanofibers is illustrated in Scheme 1. Herein, helical mesoporous silica nanofibers were firstly prepared and then used as the hard template. After covering a layer of PF resin, the obtained SiO2@PF composite maintained the original helical fiber morphology (Fig. S1). The length and the diameter of SiO2@PF nanofibers are several microns and 150–200 nm, respectively. The thickness of the PF layer is 30–50 nm calculated from the TEM image. After
Conclusions
Helical SiO2@Fe–N doped C nanofibers were prepared by coating a layer of m-phenylenediamine formaldehyde resin on the surface of helical mesoporous silica nanofibers and ensuing carbonizing. When used as LIBs anode materials, the nanofibers exhibited excellent cycling performance, outstanding rating capability and low impedance. When applied as electrochemical catalysts, the ORR performance of SiO2@Fe–N doped C nanofibers is close to commercial 20% Pt/C. This work throws light on preparing
CRediT authorship contribution statement
Haoran Wang: Investigation, Writing - original draft. Wenjun Cai: Investigation, Formal analysis. Shun Wang: Formal analysis. Baozong Li: Writing - review & editing, Data curation. Yonggang Yang: Resources, Supervision. Yi Li: Resources, Supervision, Writing - review & editing. Qi-Hui Wu: Writing - review & editing.
Declaration of competing interests
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.
There is no any conflict of interest exiting in the submission of this manuscript, and the manuscript is approved by all authors for publication. All authors of this manuscript have directly participated in planning and analysis of this work. I would like to declare on behalf of my co-authors that the work described was
Acknowledgement
This work was supported by the National Natural Science Foundation of China (No. 51673141), the Project of Scientific and Technologic Infrastructure of Suzhou (SZS201905), and the Collaborative Innovation Center for New-type Urbanization and Social Governance of Jiangsu Province.
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