Recent Advances in Transition Metal Dichalcogenide Cathode Materials for Aqueous Rechargeable Multivalent Metal-Ion Batteries

Abstract

The generation of renewable energy is a promising solution to counter the rapid increase in energy consumption. Nevertheless, the availability of renewable resources (e.g., wind, solar, and tidal) is non-continuous and temporary in nature, posing new demands for the production of next-generation large-scale energy storage devices. Because of their low cost, highly abundant raw materials, high safety, and environmental friendliness, aqueous rechargeable multivalent metal-ion batteries (AMMIBs) have recently garnered immense attention. However, several challenges hamper the development of AMMIBs, including their narrow electrochemical stability, poor ion diffusion kinetics, and electrode instability. Transition metal dichalcogenides (TMDs) have been extensively investigated for applications in energy storage devices because of their distinct chemical and physical properties. The wide interlayer distance of layered TMDs is an appealing property for ion diffusion and intercalation. This review focuses on the most recent advances in TMDs as cathode materials for aqueous rechargeable batteries based on multivalent charge carriers (Zn²⁺, Mg²⁺, and Al³⁺). Through this review, the key aspects of TMD materials for high-performance AMMIBs are highlighted. Furthermore, additional suggestions and strategies for the development of improved TMDs are discussed to inspire new research directions.

Keywords: aluminum-ion batteries; aqueous multivalent metal-ion batteries; magnesium-ion batteries; transition metal dichalcogenide; zinc-ion batteries.

Figure 7

(a) TEM image of VS₂ nanosheets, (b) cyclic performance of VS₂ nanosheets at 500 mA g⁻¹. Reprinted with permission from He et al. [81] Copyright 2017,WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim. (c) Rate capability of VS₄, (d) cyclic performance of VSe₂ nanosheets at 100 and 500 mA g⁻¹. Reprinted with permission from Wu et al. [83] Copyright 2020, Wiley-VCH GmbH.

Figure 8

(a) TEM image of G-MoS₂ nanosheet, (b) cyclic performance of G-MoS₂ and B-MoS₂ with Mg nanoparticle (N-Mg) and bulk Mg (B-Mg) anodes at 20 mA g⁻¹. Reprinted with permission from Liang et al. [88] Copyright 2011, WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim.(c) TEM image of WSe₂ nanosheets, (d) cyclic performance of WSe₂ nanosheets at 50 mA g⁻¹. Reprinted with permission from Xu et al. [93] Copyright 2020, Elsevier Inc.

Figure 1

(a) Brief summary of recent reviews on transition metal dichalcogenides (TMD) materials, (b) Year-wise publication plot for TMD materials including MoS₂, VS₂, WS₂, and TiS₂ in the period of 2010–2020. (searched by Google Scholar, 2 June 2021), (c) The applications of TMDs in the period of 2010–2020.

Figure 2

(a) TMDs with the MX₂ structure consisting of M from the 16 transition metals indicated by the red dotted box and X from the three halogen elements indicated by the green dotted box, (b) layered structure of MX₂.

Figure 3

(a) Polytype structure of TMDs (1T, 2H, and 3R). Reprinted with permission from Coogan et al. [61] Copyright 2021, Royal Society of Chemistry. (b) Polytype structure of MoS₂. Reprinted with permission from Song et al. [62] Copyright 2015, Royal Society of Chemistry.

Figure 4

Direct bandgap and interlayer distance of various types of TMD.

Figure 5

(a) Transmission electron microscopy (TEM) image of MoS₂ (left:MoS₂ with oxygen incorporation, right: bulk MoS₂). (b) cyclic voltammetry curves of MoS₂-O (pink) and bulk MoS₂ (light blue) at a scan rate of 0.1 mV s⁻¹. (c) Rate capability of MoS₂-O and bulk MoS₂ at various current densities. Reprinted with permission from Liang et al. [77] Copyright 2019, American Chemical Society. (d) Illustration for the preparation of E-MoS₂. (e) Rate capability of E-MoS₂ at various current densities. Reprinted with permission from Li et al. [78] Copyright 2018, Elsevier B.V.

Figure 6

(a) TEM image of defect-rich MoS₂ nanosheets, (b) cyclic performance of defect-rich MoS₂ nanosheets at 200 mA g⁻¹. Reprinted with permission from Xu et al. [79] Copyright 2018, Elsevier B.V. (c) TEM image of tubular MoS₂, (d) cyclic performance of tubular MoS₂ at 500 mA g⁻¹. Reprinted with permission from Yang et al. [80] Copyright 2020, ESG Publication.

Figure 9

(a) TEM image of freestanding MoS₂-graphene foam composite with glucose (E-MG), (b) cyclic performance of bulk-MoS₂, MoS₂-graphene foam without glucose (MG), and E-MG at 20 mA g⁻¹. Reprinted with permission from Fan et al. [104] Copyright 2017, WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim. (c) Schematic of the MoX₂ structure (X: S, Se) with M1 and M2 site, (d) coulombic efficiency of MoX₂ at 100 mA g⁻¹. Reprinted with permission from Divya et al. [106] Copyright 2020, WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim.

Figure 10

Cyclic performance of (a) TiS₂ and (b) Cu_0.31Ti₂S₄ at room temperature and 50 °C at 5 mA g⁻¹. Reprinted with permission from Geng et al. [108] Copyright 2017, American Chemical Society. (c) Schematic structure of Al insertion sites in Mo₆S₈, (d) cyclic performance of Mo₆S₈. Reprinted with permission from Geng et al. [109] Copyright 2015, American Chemical Society.

Figure 11

(a) Schematic showing the difficulty in the intercalation of Zn hydrates into bulk MoS₂ owing to the large energy barrier between the layers, (b) the expanded interlayer distance that supports the diffusion of Zn²⁺, (c) hydrophobicity control by the Zn–H₂O–O interaction, (d) theoretical energy barrier between MoS₂ and MoS₂–O depending on the hydration level of Zn²⁺. Reprinted with permission from Liang et al. [77] Copyright 2019, American Chemical Society.

Figure 12

(a) Schematic diagram of the supercritical fluid (SCF) procedure to synthesize TMDs. Reprinted with permission from Truong et al. [90] Copyright 2017, American Chemical Society.(b) Illustration of two Mg adsorption positions (H and T sites) on MoS₂ nanoribbon:. Reprinted with permission from Yang et al. [87] Copyright 2012, American Chemical Society.

Figure 13

(a) Schematic for the synthesis of E-MG. (b) Scanning electron microscopy (SEM) image of free-standing MoS₂/graphene foam. Reprinted with permission from Fan et al. [104] Copyright 2017, WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim. (c) The atomic structure with the expanded interlayer distance of MoS₂. Reprinted with permission from Li et al. [78] Copyright 2018, Elsevier B.V.

Figure 14

(a) Schematic of a rechargeable MoS₂ cathode with different phases (1T- and 2H-MoS₂). (b) The adsorption sites and diffusion pathway of Zn²⁺ (left:2H phase MoS₂and right: 1T phase MoS₂). (c) Calculation of Zn²⁺ diffusion energy barrier on the1T and 2H phases. Reprinted with permission from Liu et al. [75] Copyright 2020, Elsevier B.V.