Elsevier

Nano Energy

Volume 90, Part B, December 2021, 106602
Nano Energy

Intimately-coordinated carbon nitride-metal sulfide with high π-d conjugation for efficient battery performance

https://doi.org/10.1016/j.nanoen.2021.106602Get rights and content

Highlights

  • Hybrid of metal sulfide and carbon nitride with high π-d conjugation is prepared.

  • The optimized material shows 2031 mA h g−1 at 1 A g−1 with inverse capacity growth.

  • Significant enhancement in electrochemical dynamics is observed during cycling.

  • With cycling, particle size become confined into 1–3 nm with uniform distribution.

  • Carbon nitride acts as efficient matrix based on strong π-d hybridization.

Abstract

In this investigation, a hybrid of metal sulfide and carbon nitride (CN) is synthesized by in-situ chemical conversion between metallic species and a single precursor of carbon, nitrogen and sulfur elements through a strong π-d conjugation approach. It is observed that the local chemical alteration in the vicinity of N atom in the CN template triggers the formation of a highly π-conjugated CN system and efficient π-d hybridization at heterointerface. This is accelerated by partial substitution of the Fe atom for Mn ions in the MnS phase which significantly enhances the battery performance, delivering 2031 mA h g−1 after 500 cycles with inverse capacity growth. Via systematic in-depth characterizations, it is found that the gradual increase of Li-ion diffusion coefficients and charge transfer kinetics for repeated cycling is ascribed to the highly dispersed and uniform particles that are confined within the CN template through a strong π-d hybridization.

Introduction

Carbon nitride (CN) has been receiving significant attention as a 2D π-conjugated framework which can accommodate intriguing electron-transfer-related functionalities in the fields of energy storage and conversion [1]. Based on a π-extended polymeric structure and diverse redox moieties, chemically-modified CN has been utilized as an anode electrode in lithium ion battery (LIB) systems [2], [3], [4], [5]. However, the relatively low performance of CN for Li+ ion storage is a persistent issue which hinders the commercialization process. The N-rich chemical environment of CN also degrades electrical conductivity which affects battery performance [6], [7]. In order to catch up on rapid progress in the field of secondary batteries [8], [9], one approach to mitigate the issue could be to establish the highly efficient π-d conjugation system based on a CN framework which enables multielectron-transfer energy storage with high electrochemical kinetic. This can be realized through intimately-coupled hybridization with metallic species which gives rise to facile hybridization of π orbitals of CN framework and d orbitals of transition metals [10], [11], [12], [13], [14], [15].

In-situ chemical conversion of a single molecular precursor containing C, N and S with metallic species is a perfect methodology for deriving an efficient π-d conjugation system based on strong covalent bonding character in the heterointerface of a CN-based system. In addition, the low thermodynamic stability of sulfur would be significantly stabilized via covalent bonding with a transition metal ion, resulting in the full utilization of sulfur contents from a precursor [6], [16], [17], [18]. Furthermore, a particular metal compound grown in-situ as a result of the covalent bonding with metal species can substantially contribute towards large specific capacity with its own storage mechanism. However, to the best of our knowledge, there has been no reports on the direct synthesis of transition bimetallic sulfide hybridized CN nanostructures and their application in Li-ion batteries.

In this study, we report for the first time on the highly π-d conjugated hybrid structure of CN and iron substituted manganese sulfide (FMC) with intimate coupling through in-situ chemical transition (Fig. 1A). The Fe-MnO2 nanosheets (NSs) are selected as the source for making the corresponding sulfides owing to their high surface reactivity resulting from their 2D configuration and well-defined crystal structure [19], [20]. The addition of Fe cation is highly beneficial in amplifying π-d conjugation and electrochemical performance with a specific capacity of 2031 mA h g−1 after 500 cycles. A series of systematic electrochemical/microscopic measurements with structural calculations toward Li+ ion binding are conducted to investigate the role of CN species and the concomitant π-d hybridization effect on electrochemical properties affecting the LIB system.

Section snippets

Results and discussion

Details of the experimental procedure for the synthesis of Fe-MnS/CN hybrids and their characterizations are described in Supporting Information (SI). All the FMC exhibit α-MnS phase with Fm-3m space group (JCPDS 88-2223) and show an increase in crystallite size from FMC1 to FMC5 based on the Scherrer equation (Fig. S1 and Table S1). It should be noted that the calcination temperature of 700 °C is optimal to form a single α-MnS phase without affecting the purity of manganese oxide (Fig. S2).

Conclusions

In this investigation, we synthesized a hybrid structure composed of CN and Fe-substituted α-MnS on the basis of efficient π-d hybridization via in-situ chemical transition. By regulating the amount of precursors, facile tuning in polymerization degree in the vicinity of N atom in CN could be achieved, effectively leading to a highly π-conjugated system of CN and π-d hybridization, which was accelerated by Fe substitution in the Mn site of the MnS phase. The novel chemical structure

CRediT authorship contribution statement

Jang Mee Lee: Conceptualization, Methodology, Investigation, Writing – original draft. Premkumar Selvarajan: Software, Validation. Sungho Kim: Methodology, Formal analysis. Gurwinder Singh: Formal analysis. Stalin Joseph: Formal analysis. Jae-Hun Yang: Formal analysis. Jiabao Yi: Validation, Writing – review & editing. Ajayan Vinu: Conceptualization, Supervision, Writing – review & editing.

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.

Acknowledgements

One of the authors A. Vinu acknowledges the University of Newcastle for the start-up grant for establishing the Global Innovative Center for Advanced Nanomaterials. NEXAFS experiments were financially supported by The Australian Synchrotron.

Dr. Jang Mee Lee received her Ph.D degree (2018) in inorganic chemistry from Ewha Womans University (Korea). Her research focuses on the synthesis and characterization of 2-dimensional inorganic nanosheet-based nanohybrids for diverse applications such as photocatalysis, Li/Na/K-ion battery, supercapacitor and electrocatalysis. For a mechanism understanding, she is also working on the in-depth characterizations of high-performing nanomaterials, such as in-situ x-ray absorption spectroscopy

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  • Cited by (0)

    Dr. Jang Mee Lee received her Ph.D degree (2018) in inorganic chemistry from Ewha Womans University (Korea). Her research focuses on the synthesis and characterization of 2-dimensional inorganic nanosheet-based nanohybrids for diverse applications such as photocatalysis, Li/Na/K-ion battery, supercapacitor and electrocatalysis. For a mechanism understanding, she is also working on the in-depth characterizations of high-performing nanomaterials, such as in-situ x-ray absorption spectroscopy (XAS) and the FEFF fitting to gain the crystallographic information. Currently, she is working as Research Associate in Global Innovative Centre for Advanced Nanomaterials (GICAN) at The University of Newcastle.

    Dr. Selvarajan Premkumar has awarded Ph.D., in Physics from Madurai Kamaraj University, India, in the field of materials characterization and density functional theory. He pursued his postdoctoral research in Indian Institute of Science, India under the supervision of Prof, Umapathy. He joined Prof. Ajayan Vinu’s research group as a visiting research associate. His field of research interest is developing novel materials for energy storage and conversion applications and predict the mechanisms by computational chemistry. He has adequate knowledge in synthesis of nanoporous activated carbon for CO2 adsorption, energy storage and energy conversion.

    Dr. Sungho Kim received a Ph.D. degree in materials science & engineering at The University of Newcastle, Australia in 2021. He is currently working as researcher in GCRF at GIST. His research interests focus on the highly ordered mesoporous N-rich carbon nitrides and their hybrid materials for applications in electrochemical energy storage and conversion such as secondary batteries and electrocatalysis.

    Dr. Gurwinder Singh is currently working as Research Fellow in Global Innovative Centre for Advanced Nanomaterials at the University of Newcastle, Australia. He received his Ph.D. degree in materials sciences from the University of South Australia and his research primarily focuses on carbon capture using nanoporous materials. He has published 39 articles including review and research articles in high-quality materials science-based journals including Chemical Society Reviews and Advanced Materials. His contribution to the research has been acknowledged in the form of 1580 google scholar citations with an h-index of 18.

    Dr. Stalin Joseph is a Research Associate at the Global Innovative Center for Advanced nanomaterials (GICAN), University of Newcastle. He received his Ph.D. degree (2018) from the department of environmental engineering at University of South Australia. He completed his post-graduation from Vels University, Chennai. During his masters’ he was awarded the UQ summer internship program award in 2012 and successfully completed the project on “synthesis of novel nanoporous carbon nitride using MOF as template”. His research interests focus on conversion of industrial wastes into nanoporous carbon based materials for supercapacitors, batteries, energy storage devices and CO2 capture and conversion.

    Dr. Jae-Hun Yang has been working as a Lecturer in the Global Innovative Center for Advanced Nanomaterials, University of Newcastle, Australia since 2017. He received his Ph.D. degree in chemistry at Seoul National University in 2005. His research areas are the 2D inorganic-inorganic, inorganic/organic nanohybrids and porous materials for the photocatalysis, energy conversion and bio-medical applications. Recently his research is focused on the photocatalytic water-splitting for the hydrogen production and the photocatalytic carbon dioxide conversion to the usable chemicals such as CO, methanol, methane, etc.

    Dr. Jiabao Yi is an Associate professor in the Global Innovative Center for Advanced Nanomaterials, University of Newcastle, Australia. His research areas include diluted magnetic semiconductors, soft/hard magnetic materials and their applications in data storage, bioapplications and environment applications as well as advanced electronic materials for energy storage and conversion. He has been awarded several prestigious fellowships, such as Lee Kuan Yew postdoctoral fellowship, Queen Elizabeth II fellow and Future Fellowship.

    Prof. Ajayan Vinu is a Professor and the Direct of GICAN at UON. He was working as a full professor and ARC Future Fellow at the University of South Australia and the University of Queensland. Prior coming to Australia, he had been working as a research group leader at the National Institute for Materials Science, Japan. His research is mainly focused on developing new approaches to create nanoporosity in nitrides, carbon, conducting polymers, metal nitrides, metallosilicates, graphenes, silicas, sulfides, fullerenes, and biomolecules with tunable structures and pore diameters and their potential applications in energy, environmental, biomedical and catalysis technology.

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