Elsevier

Energy Storage Materials

Volume 50, September 2022, Pages 696-717
Energy Storage Materials

Two-dimensional host materials for lithium-sulfur batteries: A review and perspective

https://doi.org/10.1016/j.ensm.2022.06.009Get rights and content

Abstract

Rechargeable lithium-sulfur (Li–S) batteries are considered as promising candidates for next-generation energy storage devices due to their high capacity and high energy density. However, their large-scale practical applications suffer from a series of challenges, such as the insulating nature of sulfur, the shuttle effect of soluble lithium polysulfides (LiPSs), and the volume expansion upon lithiation. Numerous research work proved that modification of the cathodes with host materials is efficient for alleviating these issues. Two-dimensional (2D) materials have recently emerged as a candidate of choice for the sulfur host materials. Herein, a comprehensive review of the recent advances in 2D sulfur host materials is presented, including the mechanism of Li–S batteries and the basic requirement for hosts. Furthermore, different types of 2D hosts are summarized and discussed in detail. Finally, an outlook of possible research directions, challenges, and perspectives are presented. This review paves the way for the rational design of 2D host materials for Li-S battery applications.

Introduction

Energy storage has become an important issue with global concern because of the growing energy demand and the limited resource of fossil fuels [1], [2], [3]. Among all the energy storage technologies, lithium-sulfur (Li–S) batteries have received a great deal of attention since they were first proposed in the early 1960s [4], [5]. Except for the natural abundance and low cost of sulfur, the high theoretical specific capacity (1675 mAh g−1) and high theoretical specific energy (2500 Wh kg−1) are also appealing features to provide Li–S batteries with a practical energy density of 400–600 Wh kg−1, which is around twice that of LIBs [6], [7], [8], [9]. Despite these promising features, the practical large-scale applications of Li-S cells are still limited by the low sulfur utilization and poor long-term cycling, which are mainly resulted from three factors: (1) the poor conductivity of sulfur and its discharge products Li2S2 and Li2S; (2) a severe volumetric expansion upon cycling; and (3) the dissolution of lithium polysulfide (LiPS) intermediates in liquid electrolytes, triggering a shuttle process [10], [11], [12], [13]. Among those problems, the dissolution of LiPSs into the electrolyte is the most notorious and intractable issue. To solve this harmful shuttle problem, considerable efforts have been made, which include cathode functionalization, separator modification, and electrolyte customization [14], [15], [16], [17], [18]. A large number of research work prove that the design and engineering of sulfur host materials capable of confining active sulfur intermediates or accelerating the conversion of polysulfides can be effective ways to improve the capacity and cycle stability of sulfur cathodes [19], [20], [21], [22] (Fig. 1).

The successful exfoliation of graphite into single atomic layers of graphene in 2004 opened a new realm of two-dimensional (2D) materials research [23], [24]. Compared with other nanomaterials, such as nanoparticles or nanowires, 2D materials not only have adjustable and uniformly exposed lattice planes, large specific surface area, and excellent mechanical properties, but also possess electronic properties that change significantly with thickness [25], [26]. Because of these merits, 2D materials have already played important roles in nearly every component of Li-S batteries, such as active materials, hosts, protective layers, conductive additives, and reaction promoters [27], [28], [29]. For example, Chen's group designed a selective functionalized boron nitride nanosheets/graphene film as an interlayer for Li-S batteries [30]. The interlayer not only decreases the charge transfer resistance but also mitigates the shuttling problem, leading to significantly improved capacity with an initial specific capacity of 1100 mAh g−1 at 3C. Huang et al. synthesized an ultrathin graphene oxide (GO) as a separator with high mechanical strength for Li-S batteries [31]. Shao and coworkers summarized the recent applications of 2D materials for the key components (such as sulfur cathodes, separators/interlayers, and anodes) of Li-S batteries [28]. Nevertheless, a comprehensive review of the anchoring mechanism or catalytic effects of 2D nanomaterials as sulfur hosts in Li–S batteries has not yet been published. Herein, we give a thorough review on the design and preparation of 2D host materials for sulfur cathode in Li–S batteries. First, we briefly introduce the fundamental electrochemistry and challenges of Li-S batteries. Then, we discuss the specific types of 2D host materials, such as carbon materials, metal compounds, metal-organic frameworks (MOFs), and so on. Finally, we summarize the whole review by giving a conclusion and outlook.

Section snippets

Mechanism of Li–S batteries

In 1962, Herbert and Ulam first introduced elemental sulfur as the cathode and proposed the electrochemical reaction 2Li + S ↔ Li2S [32]. In 1979, Rauh et al. demonstrated that Li metal is quite stable to very concentrated solutions of Li2Sn (n=1,2,4,6 and 8) in Tetrahydrofuran (THF) and other aprotic organic solvents [33], [34]. Since then, numerous investigations have been conducted to investigate the high-performance Li-S batteries for almost 40 years.

The mechanism of the charging and

2D carbon-based materials

Carbon materials such as graphene and carbon nanosheets have been investigated as 2D host materials due to their large specific area, good electronic conductivity, and mechanical stabilities [64], [65], [66], [67], [68]. Many efforts have been devoted to developing 2D carbon-based materials as sulfur hosts in recent years.

Conclusion and outlook

Li–S batteries have fulfilled a breakthrough over the last few years. Researchers found that the degree of polysulfide dissolution in electrolyte is closely related to the performance of Li-S batteries. Thus, understanding the mechanism of the anchoring effect and catalytic effects is very important for designing and modifying high-performance 2D electrode materials. In this review, recent advances in various 2D sulfur host materials have been comprehensively discussed. Based on the characters

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 Research Grants Council of the Hong Kong Special Administrative Region, China (Project No. PolyU152178/20E), the Hong Kong Polytechnic University (SAC1), and Science and Technology Program of Guangdong Province of China (Project No. 2020A0505090001).

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