Elsevier

Journal of Power Sources

Volume 408, 31 December 2018, Pages 111-119
Journal of Power Sources

Selenium-infiltrated mesoporous carbon composite cathode for a high-capacity lithium-chalcogen battery: Effects of carbon structure and dopant on the rate-capability and cyclic stability

https://doi.org/10.1016/j.jpowsour.2018.09.095Get rights and content

Highlights

  • Three-types of selenium/carbon (Se/C) cathodes for Lisingle bondSe battery are prepared.

  • They have three carbon frameworks with different structure and dopant.

  • The ordered mesoporous carbon (OMC) improves rate-capability of Se/C cathode.

  • The Se/C cathode with N-doped OMC delivers the excellent cyclic stability.

  • The lithiated Si/Gr– Se/NOMC full-cell demonstrates promising cyclic stability.

Abstract

A selenium/carbon (Se/C) composite has been suggested as an excellent substitute cathode material due to its high theoretical volumetric capacity. However, it exhibits severe capacity decay, which is caused by the dissolution of active materials as well as shuttle effect. One effective strategy to alleviate this dissolution is to confine the Se within porous carbon frameworks. Here, we report the effects of carbon structure and dopant on the electrochemical performances of Se infiltrated carbon composites with three types carbons; (i) nitrogen-doped ordered mesoporous carbon (NOMC), (ii) sulfur-doped ordered mesoporous carbon (SOMC), and (iii) macroporous spherical carbon, which have different porosities and dopants. The Se/C cathodes are prepared by meting selenium-sulfur compound and then evaporating sulfur from the compound, providing nanoscale space for efficient electrolyte access to the reaction site. Among the three composite cathodes, the Se/NOMC exhibits the highest rate-capability and cyclic stability due to an abundance of cylindrical mesopores (4–5 nm pore diameter) that can provide enough electrolyte diffusion path and effectively impede the dissolution of selenium. As a result, the Se/NOMC has a high volumetric capacity of 1605 mAh cm−3 and excellent capacity retention of 100% during 500 cycles at 0.648 A h cm−3 (C-rate of C/2.5).

Introduction

The lithium-sulfur (Lisingle bondS) battery continues to pose substantial difficulty in practical utilization due to the severe initial capacity decay caused by the dissolution of polysulfides and shuttle effect, despite its large volumetric capacity (3296 mAh cm−3) [[1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12], [13], [14]]. Proposed solutions such as coating sulfur/carbon (S/C) composites and/or modifying the electrolyte to decrease the dissolution of high-order lithium-polysuflides (Li2Sx, 4 ≤ x ≤ 8) are not satisfactory because their methods do not solve the ultimate problem of the low electrical conductivity of S (∼insulator) [[15], [16], [17], [18]]. The Se which has much higher electrical conductivity (10−3 S cm−1) than S (5 × 10−28 S cm−1) has been considered as a new cathode material in place of S [6,8,9,[19], [20], [21], [22]]. Se composites also provides outstanding volumetric capacity (3239 mAh cm−3) and gravimetric capacity (678 mAh g−1) [6,8,9,[19], [20], [21], [22]]. K. Eom et al. reported that Se not only improves the electrical conductivity of Sesingle bondS/C cathode materials but also forms a more stable solid electrolyte interphase (SEI) on the anode because Se can be preferentially dissolved and diffused to the anode [6]. Despite these advantages, severe capacity decay caused by shuttle effect in the Se/C and S/C composites continues to occur, when the active materials is not confined effectively into the carbon framework during cycling [6,8,9,[19], [20], [21], [22]]. To trap the Se, Liu et al. introduced selenium/metal-organic frameworks derived porous carbon microcubes (Se/CMCs) for cathode materials, which showed approximately 42.3% of capacity retention after 500 cycles at 0.2 C rate [11]. Meanwhile, Lv et al. studied selenium/nitrogen-doped carbon scaffolds (Se/NCSs) and the effect of dopant on the electrochemical performance. From the unique architecture of NCSs, the Se/NCSs showed 65.9% of capacity retention after 500 cycles at 1C rate, indicating there was still weak interaction between Se and carbon host materials [14]. Given the low cyclic stability for Se/C cathodes, technical advance has been needed to suppress the dissolution of lithium-polyselenides. Among the various factors related to the dissolution, carbon plays crucial roles in Se/C cathodes, since the carbon can physically and/or chemically trap Se and its soluble intermediates and complement the low electrical conductivity of chalcogens [7,8,[10], [11], [12], [13], [14]].

In this study, we aim to demonstrate the effects of the carbon framework in a Se/C cathode on electrochemical performances such as rate-capability and cyclic stability. For the systematic investigation, three different types of carbon with various structure and dopants as host materials for Se/C cathodes are prepared; (i) nitrogen-doped ordered mesoporous carbon (NOMC), (ii) sulfur-doped ordered mesoporous carbon (SOMC) and (iii) macroporous carbon (Ketjen black).

Section snippets

Synthesis of nitrogen-doped ordered mesoporous carbon (NOMC) and sulfur-doped ordered mesoporous carbon (SOMC)

Nitrogen-doped ordered mesoporous carbon (NOMC), and sulfur-doped ordered mesoporous carbon were synthesized using an ordered mesoporous silica (OMS) template, which is a well-known method described in the literature [23,24]. First, 1,10- phenanthroline and a p-toluene sulfonic acid catalyst for NOMC and p-toluenesulfonic for SOMC were sonicated in 6 g acetone acid, respectively. Then, the solution was poured into 3 g of OMS for the incipient wetness impregnation process. After the impregnation

Materials characterizations

Fig. 1 shows simplified scheme for the fabrication of Se/C composites, where the Se is uniformly distributed throughout the pores of the carbon for an effective electrochemical reaction. The Se/C composites are prepared via a melt-diffusion and evaporation method employing three types of carbons with different structures and dopants: (i) nitrogen-doped ordered mesoporous carbon (NOMC), (ii) sulfur-doped ordered mesoporous carbon (SOMC), and (iii) Ketjen black 600JD (KB600). During

Conclusions

In this work, we have studied the effects of carbon structure and dopant on the electrochemical performances of Se infiltrated carbon composites with three types of carbons such as NOMC, SOMC, and KB600. Among the three types of Se/C cathodes, the Se/NOMC exhibits the highest rate-capability having the capacity decrement of 28% when increasing the C-rate from C/5 to 4C, and the highest capacity retention of 100%, with an average volumetric capacity of 1605 mAh cm−3 at 0.648 A cm−3 (C-rate of

Acknowledgments

This research was supported by the National Research Foundation of Korea Basic Science Research Program (NRF-2017R1C1B2010814) and Radiation Technology R&D program (NRF-2017M2A2A6A02070819)) funded by the Ministry of Science and ICT, KOREA HYDRO & NUCLEAR POWER CO., LTD, and the GIST Research Institute (GRI) grant funded by the GIST, Korea.

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