Front. Chem. Frontiers in Chemistry Front. Chem. 2296-2646 Frontiers Media S.A. 870564 10.3389/fchem.2022.870564 Chemistry Mini Review Recent Advances in Antimony Sulfide-Based Nanomaterials for High-Performance Sodium-Ion Batteries: A Mini Review Wang et al. Sb2S3-Based Nanomaterials for SIBs Wang Guangxin 1 † Guo Mingyi 1 * † Zhao Yunchao 1 2 Zhao Yibo 1 Tang Kun 1 Chen Zhijun 3 Stock Heinz-Rolf 1 Liu Yong 1 2 * 1 Research Center for High Purity Materials, Henan University of Science and Technology, Luoyang, China 2 Provincial and Ministerial Co-Construction of Collaborative Innovation Center for Non-Ferrous Metal New Materials and Advanced Processing Technology, Henan Key Laboratory of Non-Ferrous Materials Science and Processing Technology, School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang, China 3 Luoyang Bearing Research Institute Co., Ltd, Luoyang, China

Edited by: Jinlin Lu, Guangzhou Maritime College, China

Reviewed by: Zhenyu Xing, South China Normal University, China

Hongshuai Hou, Central South University, China

 *Correspondence: Mingyi Guo, gmy19910513@163.com; Yong Liu, liuyong209@haust.edu.cn

These authors have contributed equally to this work

This article was submitted to Nanoscience, a section of the journal Frontiers in Chemistry

 07 04 2022 2022 10 870564 07 02 2022 24 02 2022 Copyright © 2022 Wang, Guo, Zhao, Zhao, Tang, Chen, Stock and Liu. 2022 Wang, Guo, Zhao, Zhao, Tang, Chen, Stock and Liu

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Recently, sodium-ion batteries (SIBs) have attracted extensive attention as potential alternatives to lithium-ion batteries (LIBs) due to the abundance, even distribution, low cost, and environmentally friendly nature of sodium. However, sodium ions are larger than lithium ions so that the anode materials of LIBs are not suitable for SIBs. Therefore, many negative electrode materials have been investigated. Among them, Sb2S3-based nanomaterials have gradually become a research focus due to their high theoretical specific capacity, good thermal stability, simple preparation, and low price. In this review, the research progress of Sb2S3-based nanomaterials in the SIB field in recent years is summarized, including Sb2S3, Sb2S3/carbon composites, Sb2S3/graphene composites, and Sb2S3/MxSy composites. Furthermore, the challenges and prospects for the development of Sb2S3-based nanomaterials are also put forward. We hope this review will contribute to the design and manufacture of high-performance SIBs and promote its practical application.

 sodium-ion batteries electrochemical performance Sb2S3-based nanomaterials anode materials composites Introduction

Recently, lithium-ion batteries (LIBs) have developed rapidly and are extensively used in electronic devices such as notebook computers, electric vehicles, and mobile phones (Qin et al., 2017; Chong et al., 2018; Schmuch et al., 2018; Pang et al., 2019; Yuan et al., 2019; Wang et al., 2020; Tao et al., 2022). Nevertheless, the distribution of lithium on earth is uneven, and its reserves are limited. In addition, there are still some problems that need to be solved for LIBs, such as poor low-temperature performance, safety problems, and high cost (Liu G. et al., 2018; Xing et al., 2020; Sui D. et al., 2021; Wang et al., 2021c; Shi et al., 2021). As a potential substitute for LIBs in energy storage devices, SIBs have attracted extensive attention because sodium is much cheaper than lithium, environmentally friendly, and SIBs show the same energy storage mechanism as LIBs (Wang et al., 2018; Cao et al., 2020; Sui et al., 2020). However, the ionic radius of sodium ion (Na+: 102 p.m.) is larger than that of lithium ion (Li+: 76 p.m.), which will lead to difficulties in the sodiation/desodiation process combined with a greater volume change. Consequently, electrode materials matched with LIBs are not suitable for SIBs (Zhao and Arumugam, 2015; Wang et al., 2017; Liu Q. et al., 2019; Liu Y. et al., 2019; Hao et al., 2019; Sui et al., 2020). Therefore, it is critical to investigate SIB electrode materials with high reversible capacity and excellent cycle stability.

As an important type of electrode material for SIBs, anode materials have been widely studied (Tao et al., 2021). Until now, considerable achievements have been made in the research of SIB anode materials, such as layered transition metal oxides (Xiong et al., 2011; Ma et al., 2020; Li Y. et al., 2020), polyanionic compounds (Li et al., 2015; Yu et al., 2018; Guo et al., 2020; Sui Y. et al., 2021), metal sulfide composites (Cui et al., 2018; Zhao et al., 2020), or alloy composites (Liu et al., 2016; Tao et al., 2021). Metal sulfide anodes have a higher sodium storage capacity, and generally have lower redox potential, better electrochemical reversibility, and longer cycle life than metal oxides in charge/discharge reaction (Xie et al., 2018; Liu G. et al., 2019; Xu et al., 2019; Yao et al., 2019; Shan et al., 2020). Among them, Sb2S3 has a high theoretical capacity of 946 mA h g−1, and it is cheap and harmless to the environment (Zhu et al., 2015; Xie F. et al., 2019). Moreover, by combining the conversion reaction (Eq. 1) and alloying reaction (Eq. 2) between Na and S, Sb2S3 can produce a high-capacity anode and effectively play the role of S–Na and Sb–Na nanocomposites in SIBs (Yu et al., 2013; Liu et al., 2017). The following is the generally proposed electrochemical reaction mechanism between Sb 2 S 3 and Na + (Liu et al., 2017; Xie F. et al., 2019): Conversion reaction: Sb 2 S 3   +   6 Na +   +   6 e -   → 2 Sb  +   3 Na 2 S . Alloying reaction:  2 Sb  +   6 Na +   +   6 e -   → 2 Na 3 S .

Sb2S3-based anode materials, such as multi-shell hollow Sb2S3 (Xie F. et al., 2019), Sb2S3/graphene composites (Li C.-Y. et al., 2017; Zhao et al., 2021), Sb2S3@FeS2/N-graphene (SFS/C) (Cao et al., 2020), and L-Sb2S3/Ti3C2 composites (He et al., 2021), have been reported in the application field of SIBs. For instance, Xiong et al. reported about Sb2S3 with nanostructure on S-doped graphene sheets for high-performance anode materials of SIBs (Xiong et al., 2016). Based on the interaction of heterogeneous interfaces between different components of metal sulfide, Cao et al. reported Sb2S3@FeS2 with heteroatom-doped graphene as a superior SIB anode material (Cao et al., 2020). Xu et al. (2019) reviewed updated research on multiple phase transformation mechanisms and strategies to improve the performance of Sb- and Bi-based chalcogenides for SIBs. Liu et al. reviewed recent studies on Sb-based electrode materials for applications, storage mechanisms, and synthesis strategies in SIBs, LIBs, and LMBs (liquid metal batteries) (Liu Z. et al., 2018). However, so far as we know, critical reviews that focus on Sb2S3-based electrode nanomaterials specifically for SIBs have rarely been reported.

Herein, the research achievements and progresses of Sb2S3-based nanomaterials for SIBs in recent years are summarized (see Figure 1). In addition, some rational suggestions on the research and design of Sb2S3-based nanomaterials for SIBs in the future are also presented. Finally, we hope that this review can attract more attention and promote the practical applications of Sb2S3-based nanomaterials in the SIB field.

Bar chart of Sb2S3-based nanomaterials as anodes for SIBs in recent years.

 Research Progress of Sb<sub>2</sub>S<sub>3</sub>-Based Nanomaterials in High-Performance SIBs

Sb2S3 has advantages of low price, simple preparation, and good thermal stability (Xie F. et al., 2019; Cao et al., 2020). It is promising to be used as anode materials for high-capacity SIBs. A variety of Sb2S3-based anode materials have been reported. These are listed in Table 1.

Electrochemical performances of Sb2S3-based nanomaterials as anodes for SIBs.

Materials Initial Capacity [mAh g−1/Cycles] Rate capability [mAh g−1] Ref
Coulomb
Efficiency [%]
Sb2S3
 Sb2S3 72.4 195 (200) at 0.1 A g−1 − Fu et al. (2019)
 Amorphous Sb2S3 65 512 (100) at 0.05 A g−1 534 at 3 A g−1 Hwang et al. (2016)
 Sb2S3 micro tubes 37.1 201 (20) at 0.1 A g−1 286 at 0.2 A g−1 Jin Pan et al. (2017)
 Colloidal Sb2S3 − 580 (100) at 0.3 A g−1 620 at 1.2 A g−1 Kravchyk et al. (2020)
 Single crystal Sb2S3 50 579 (50) at 0.1 A g−1 358 at 1 A g−1 Pan et al. (2018a)
 Sb2S3 hollow microspheres 62 384 (50) at 0.2 A g−1 386 at 2 A g−1, 314 at 3 A g−1 Xie et al. (2018)
 Multi-shell Sb2S3 55 909 (50) at 0.1 A g−1 725 at 1 A g−1,604 at 2 A g−1 Xie et al. (2019a)
 2D-Sb2S3 - 500 (100) at 0.2 A g−1 300 at 2 A g−1 Yao et al. (2019)
 Sb2S3 77.6 38.6 (200) at 0.1 A g−1 109.5 at 1 A g−1, 95.1 at 2 A g−1 Zhao et al. (2020)
 Flower-like Sb2S3 72.9 641.7 (100) at 0.2 A g−1 597.9 at 1A g−1, 554.6 at 2 A g−1 Zhu et al. (2015)
Sb2S3/carbon composites
 Sb2S3@YP-43% 42.6 736.2 (100) at 0.23 A g−1 476.5 (1,000) at 1.2 A g−1 Chang et al. (2020b)
 Sb2S3/P/C 79 611 (100) at 0.05 A g−1 390 at 2 A g−1 Choi et al. (2016)
 Sb2S3/C 78 538 (100) at 0.2 A g−1 579 at 0.5A g−1, 557 at 1 A g−1 Choi et al. (2017)
 Sb2S3@C 38.2 267 (100) at 0.1 A g−1 283 at 1 A g−1 Dashairya et al. (2021)
 Sb2S3/SCS 68.8 455.8 (100) at 0.1 A g−1 392 (15) at 0.5 A g−1, 263 (20) at 1 A g−1 Deng et al. (2019)
 Sb2S3@N-C 80 765 (10) at 0.1 A g−1 625 (1,000) at 1 A g−1 Dong et al. (2019)
 Sb2S3@C rods 68.5 699.1 (100) at 0.1 A g−1 578 at 1.5A g−1, 429 at 3.2 A g−1 Hongshuai Hou et al. (2015)
 Sb2S3/C − 545.6 (100) at 0.2 A g−1 550.8 (70) at 0.2 A g−1 Ge et al. (2018)
 M-Sb2S3@DC − 326 (100) at 0.5 A g−1 451 at 1 A g−1,366 at 3 A g−1 Ge et al. (2020)
 Sb2S3/CM 64.7 426 (150) at 0.1 A g−1 − Jaramillo-Quintero et al. (2021)
 Sb2S3/Sb-CM 67.1 608 (150) at 0.1 A g−1 − Jaramillo-Quintero et al. (2021)
 Sb2S3/S-CM 66.9 675 (150) at 0.1 A g−1 552 at 1 A g−1, 481 at 2 A g−1 Jaramillo-Quintero et al. (2021)
 Sb2S3@CNTs 66.4 732 (110) at 0.05 A g−1 668 at 1 A g−1, 584 at 2 A g−1 Jiang et al. (2021)
 Sb2S3@MWCNTs 79.2 412.3 (50) at 0.05 A g−1 368.8 at 0.5 A g−1, 339.1 at 1 A g−1 Li et al. (2017b)
 Amorphous Sb2S3/CNT 77.8 704 (50) at 0.1 A g−1 601 at 2 A g−1,474 at 3 A g−1 Li et al. (2019)
 Sb2S3/CFC 76 736 (650) at 0.5 A g−1 649 (400) at 2 A g−1, 585 (400) at 5 A g−1 Liu et al. (2017)
 CPC/Sb2S3 80 443 at 0.1 A g−1 220 (200) at 1 A g−1 Mullaivananathan and Kalaiselvi, (2019)
 Sb2S3/CS 60 321 (200) at 0.2 A g−1 221 at 5 A g−1 Xie et al. (2019b)
 Sb2S3@CNF 57.4 267.8 (100) at 0.1 A g−1 221 at 1 A g−1,178 at 5 A g−1 Zhai et al. (2020)
 Sb2S3@NCFs 56.5 412 (50) at 0.05 A g−1 291 at 1 A g−1, 244 at 2 A g−1 Zhang et al. (2021b)
 SS/Sb@C-1 70.9 171 (200) at 0.1 A g−1 253.2 at 1A g−1, 202.8 at 2 A g−1 Zhao et al. (2020)
 SS/Sb@C-2 66.4 474.6 (200) at 0.1 A g−1 367 (150) at 1 A g−1,311.1 (150) at 2 A g−1 Zhao et al. (2020)
 Sb2S3/graphite 84 733 at 0.1 A g−1 656 (100) at 1 A g−1, 495 (100) at 10 A g−1 Zhao. and Manthiram, (2015)
Sb2S3/graphene composites
 SN-RGO/Sb2S3 57 507 (150) at 0.1 A g−1 443.46 at 1 A g−1, 364.89 at 2 A g−1 Bag et al. (2019)
 Sb2S3/RGO 55.9 262 (100) at 0.1 A g−1 210 at 1 A g−1 Dashairya et al. (2021)
 Sb2S3/RGO 75.6 220 (50) at 0.05 A g−1 − Dashairya and Saha, (2020)
 Sn@Sb2S3-RGO 69.8 597.6 (60) at 0.2 A g−1 541 (70) at 0.5 A g−1 Deng et al. (2018)
 Sb2S3/RGO 66.4 555 (70) at 0.1 A g−1 − Fan and Xie, (2019)
 Sb2S3/graphene − 760 (100) at 0.05 A g−1 420 (100) at 1.5 A g−1 Li et al. (2017a)
 Sb2S3/RGO − 687.7 (80) at 0.05 A g−1 495.1 (80) at 0.2 A g−1,414.8 (100) at 0.5 A g−1 Pan et al. (2018b)
 Sb2S3/RGO 52.6 652 (60) at 0.1 A g−1 527 at 1 A g−1, 381 at 2 A g−1 Wen et al. (2019)
 Sb2S3/RGO 85.7 581.2 (50) at 0.05 A g−1 309.8 (10) at 2 A g−1 Wu et al. (2017)
 Sb2S3/SGS − 524.4 (900) at 2 A g−1 591.6 at 5 A g−1 Xiong et al. (2016)
 RGO/Sb2S3 69.2 670 (50) at 0.05 A g−1 611 (5) at 1.5 A g−1, 520 (5) at 3 A g−1 Yu et al. (2013)
 Sb2S3@N-C/RGO 57.6 368 (200) at 0.2 A g−1 338 at 1 A g−1, 253 at 5 A g−1 Zhan et al. (2021)
 Sb2S3–graphene 55.9 881.2 (50) at 0.1 A g−1 536.4 at 1 A g−1 Zhao et al. (2021)
 S-RGO/Sb2S3 63.9 509 (200) at 0.1 A g−1 239 (2000) at 5 A g−1 Zhou et al. (2020b)
Sb2S3/MxSy composites
 Sb2S3@FeS2/N-graphene (SFS/C) 82.4 725.4 at 0.1 A g−1 645.6 at 1A g−1, 564.3 at 5 A g−1 Cao et al. (2020)
 Sb2S3-SnS2 77.9 616 (50) at 0.5 A g−1 510 at 10 A g−1 Fang et al. (2019)
 In2S3-Sb2S3@MCNTs − 454 (40) at 0.2 A g−1 402 at 1.6 A g−1,355 at 3.2 A g−1 Huang et al. (2018)
 Sb2S3/MoS2 NWs 82.9 800 at 0.1 A g−1 570 at 3.2 A g−1 Li P. et al. (2020)
 Sb2S3-Bi2S3@C@RGO 68.1 600.7 (150) at 1 A g−1 514.5 at 5 A g−1, 485.8 at 8 A g−1 Li et al. (2021)
 Sb2S3@SnS@C 79 516 (100) at 0.1 A g−1 442 (200) at 1 A g−1, 200 (1,300) at 5 A g−1 Lin et al. (2021)
 ZnS-Sb2S3@C 61.4 630 (120) at 0.1 A g−1 390.6 at 0.8 A g−1 Dong et al. (2017)
 SnS2/Sb2S3@RGO 82.3 642 (100) at 0.2 A g−1 593 at 2 A g−1, 567 at 4 A g−1 Wang et al. (2018)
 Sb2S3/MoS2@C (SMS@C) 79.5 623.2 at 0.1 A g−1 465.6 (100) at 1 A g−1, 411.5 (650) at 5 A g−1 Wang et al. (2021a)
 Sb2S3/MoS2 75.9 568.4 at 0.1 A g−1 423.2 (100) at 1 A g−1 Wang et al. (2021a)
 Sb2S3/MoS2 48.5 561 (100) at 0.1 A g−1 628 at 1A g−1, 507 at 2 A g−1 Zhang et al. (2018)
 α-Sb2S3@CuSbS2 82.2 506.7 (50) at 0.05 A g−1 293 at 3 A g−1 Zhou et al. (2020a)
Other composites
 Sb2S3@SnO2 54.2 582.9 (100) at 0.05 A g−1 441.6 at 1A g−1, 237.1 at 5 A g−1 Chang et al. (2020a)
 L-Sb2S3/Ti3C2 65.7 445.5 (100) at 0.1 A g−1 339.5 at 2 A g−1 He et al. (2021)
 Sb2S3@Ti3C2Tx 329 (100) at 0.1 A g−1 118 (500) at 2 A g−1 Ren et al. (2021)
 Sb2S3@PPy 63.7 881 (50) at 0.1 A g−1 390 (400) at 2 A g−1 Shi et al. (2019)
 Sb2S3/MMCN@PPy − 446 (50) at 0.1 A g−1 269 (300) at 1 A g−1 Yin et al. (2019)
 Sb2S3@m-Ti3C2Tx 51 156 (100) at 0.1 A g−1 72 (1000) at 2 A g−1 Zhang et al. (2021a)
 Sb2S3/PPy 70 427 (50) at 0.1 A g−1 236 (50) at 0.5 A g−1 Zheng et al. (2018)

Notes: 2D-Sb2S3 = two-dimensional Sb2S3; Sb2S3@YP-43% = 43% contents Sb2S3 mixed with YP80F active carbon (YP); Sb2S3/SCS, stibnite/sulfur-doped carbon sheet; M-Sb2S3@DC, metal-sulfides with double carbon; CM, carbon matrix; CNTs, carbon nanotubes; MWCNTs, multiwalled carbon nanotubes; CFC, carbon fiber cloth; CPC, coir pith derived carbon; Sb2S3/CS, Sb2S3 embedded in carbon–silicon oxide nanofibers; CNF, multichannel N-doped carbon nanofiber; NCFs = N-doped 3D carbon nanofibers; RGO, reduced graphene oxide; Sb2S3/SGS, Sb2S3/sulfur-doped graphene sheets; SN-RGO/Sb2S3 = sulfur, nitrogen dual doped RGO/Sb2S3; Sb2S3@N-C/RGO, Sb2S3/nitrogen-doped carbon/RGO; S-RGO/Sb2S3 = sulfur-doped RGO/Sb2S3; MCNTs, multiwalled carbon nanotubes; Sb2S3/MoS2 NWs, Sb2S3/MoS2 core-shell nanowires; PPy, polypyrrole.

 Sb<sub>2</sub>S<sub>3</sub>

To obtain Sb2S3 anodes with high energy density and capacity in SIBs, researchers prepared Sb2S3 with different morphologies, such as amorphous Sb2S3 (Hwang et al., 2016), flower-like Sb2S3 (Zhu et al., 2015), multi-shell Sb2S3 (Xie F. et al., 2019), or Sb2S3 hollow microspheres (Xie et al., 2018).

For example, Hwang et al. (2016) synthesized aspherical, amorphous α-Sb2S3 via a facile polyol route at room temperature, which is different from the previous routes of forming crystalline Sb2S3 at high temperature (mainly, hydrothermal method) (Zhu et al., 2015). As shown in Supplementary Figure S1A, α-Sb2S3 nanoparticles were composed of spherical aggregates of sub-component nanoparticles with diameters of 150–300 nm. When investigated as SIB anodes, the α-Sb2S3 nanoparticle electrode displayed a charge capacity of 512 mA h g−1 after 100 cycles at a current density of 50 mA g−1, and showed a better cycle performance and excellent rate performance, in contrast with the commercial crystal Sb2S3 electrode (Supplementary Figure S1B).

Moreover, two-dimensional (2D) nanomaterials with large surface area and ultrafine thickness have attracted more and more attention. For instance, Yao et al. (2019) designed 2D-Sb2S3 nanosheets by using a facile and scalable Li intercalation assisted stripping method. The 2D-Sb2S3 nanosheets (2D-SS) showed a good layered structure with a mean thickness of 3.8 nm (Supplementary Figure S1C). The large pore volume and large surface area of 2D-SS nanosheets are beneficial to the electrolyte penetration and the volume change during cycles. Therefore, 2D-SS nanosheet anodes showed remarkable rate capability and stable cycle performance in both SIBs and LIBs. When used in SIBs (Supplementary Figure S1D), the 2D-SS anode displayed a superior capacity of ∼500 mA h g−1 after 100 cycles at 200 mA g−1 current rate.

Recently, Sb2S3 materials with three-dimensional (3D) hierarchical architecture were designed and synthesized to expand the contact surface area of the electrode and electrolyte and adapt it to volume expansion (Jin Pan et al., 2017; Xie et al., 2018; Xie F. et al., 2019). Xie et al. (2018) used SbCl3 and L-cysteine as raw materials and successfully synthesized Sb2S3 hollow microspheres by a hydrothermal method. The SEM image and cycling performance of Sb2S3 hollow microspheres are shown in Supplementary Figures S1E,F. However, large internal voids in hollow structures can greatly reduce bulk energy density. In order to obtain a high volumetric energy density and maintain a high gravimetric energy density, Xie F. et al. (2019) synthesized multi-shell hollow Sb2S3 structures using the metal-organic framework templates (MOFs) (Supplementary Figure S1G). Used as an anode in SIBs (Supplementary Figure S1H), the multi-shell Sb2S3 exhibited reversible capacities of 909, 806, 725, and 604 mA h g−1 at various currents of 100, 400, 1,000, and 2,000 mA g−1, respectively, higher than the single-shell Sb2S3 structure.

 Sb<sub>2</sub>S<sub>3</sub>/Carbon Composites

Carbon materials have received considerable attention because of their superior characteristics, such as large specific surface area, high conductivity, excellent flexibility, and chemical stability (Tao et al., 2021). During the use of SIBs, Sb2S3 will undergo transformation and alloying reaction, which results in excessive volume expansion/contraction of the material, and hinders the application of Sb2S3 energy storage effect. Therefore, Sb2S3 is usually combined with carbon materials to inhibit the volume change, such as Sb2S3/carbon-rods (Hongshuai Hou et al., 2015), Sb2S3/carbon-nanotubes (Li J. et al., 2017; Li et al., 2019), Sb2S3/carbon-nanofiber (Zhai et al., 2020; Zhang Q. et al., 2021), or Sb2S3/heteroatom-doped carbon (Dong et al., 2019; Jaramillo-Quintero et al., 2021).

For instance, Hongshuai Hou et al. (2015) designed one-dimensional (1D) Sb2S3@C rods as a distinctive anode material to improve the electrochemical performance of SIBs via a solvothermal method (Supplementary Figure S2A). The Sb2S3@C rod electrode could deliver 699.1 mA h g−1 at a current rate of 100 mA g−1 after 100 cycles (Supplementary Figure S2B). Liu et al. (2017) reported a hydrothermal method for preparing Sb2S3 micro-nanospheres loaded on carbon fiber cloth (CFC). The obtained composite materials were denoted as SS/CFC. The flexible carbon fiber cloth was completely covered by spherical Sb2S3 in Supplementary Figure S2C, which could greatly accommodate the volume change (Guo et al., 2019). When used as electrodes for SIBs (Supplementary Figure S2D), SS/CFC electrodes exhibited an excellent initial discharge capacity of 1,048 mA h g−1 at 0.5 A g−1, and displayed a reversible capacity of 736 mA h g−1 after 650 cycles in the voltage range of 0.01–2.00 V. After two initial cycles, the corresponding Coulombic efficiency of SS/CFC rapidly increased to ∼100%.

To boost the storage performance of SIBs, Sb2S3 can be combined with carbon doped with heteroatoms (e.g., N, S, P, and Sb), thus improving the conductivity, the storage regions, and the active sites (Choi et al., 2016; Dong et al., 2019; Zhai et al., 2020; Jaramillo-Quintero et al., 2021). For instance, Zhao et al. (2020) utilized the oxygen-function group of phenolic resin and constructed Sb2S3 with hierarchical interfaces (antimony and sulfur-doped carbon) (Supplementary Figure S2E). The final obtained composites were denoted as SS/Sb@C. When evaluated as electrode materials for SIBs (Supplementary Figure S2F), SS/Sb@C delivered a reversible capacity of 474.6 mA h g−1 and a capacity retention rate of 97.1% after 200 cycles at 0.1 A g−1, showing better cyclic stability and superior rate capability than those of the Sb2S3 anodes without heteroatoms (38.6 mA h g−1). This was due to the double control synergy of Sb-shell structure and S-doped carbon structure, which effectively expanded the polysulfide diffusion path, enhanced the reversibility of conversion reaction, and thus improved the Na-storage capacity of SIBs (Yu et al., 2020; Wang et al., 2021b). This kind of reasonable design was expected to bring bright prospects for the design of metal sulfides as advanced anodes of SIBs.

 Sb<sub>2</sub>S<sub>3</sub>/Graphene Composites

Graphene has high specific surface area, which is convenient for constructing interconnected pore structures to form conductive networks. In addition, it can also provide a platform for the growth of active materials (Lv et al., 2016; Sui et al., 2020; Wang X. et al., 2021; Liu et al., 2021). The combination of Sb2S3 with graphene can provide excellent Na+ energy storage properties. Therefore, many composites have been designed in recent years, such as Sb2S3/RGO (RGO = reduced graphene oxide) (Yu et al., 2013; Wen et al., 2019), Sn@Sb2S3-RGO (tin assisted Sb2S3 decorated on RGO) (Deng et al., 2018), S-RGO/Sb2S3 (sulfur-doped RGO-based composite with Sb2S3) (Zhou X. et al., 2020), and Sb2S3/N-C/RGO (Sb2S3@nitrogen-doped carbon decorated on RGO) (Zhan et al., 2021), to improve the storage properties of SIBs.

For example, Yu et al. (2013) received a uniform coating of Sb2S3 on RGO (RGO/Sb2S3) through a solution-based synthesis method and applied it as SIB anode materials. The RGO/Sb2S3 composite with a small particle size of 15–30 nm allows Na+ to move in and out of the particles rapidly during charge and discharge process. In addition, the 2D-layered structure of graphene and Sb2S3 can form oriented layered composites with excellent properties. Compared with traditional synthesis techniques, the ultrasound sonochemical method can create particular reaction conditions, and make it possible to prepare nanostructured materials with special properties by acoustic cavitation effects. Zhao et al. (2021) synthesized a special amorphous nanostructure composite material of Sb2S3/graphene by an ultrasound sonochemical synthesis technique (Figure 2A). As can be seen from Figure 2B, Sb2S3 nanoparticles were tightly covered on the graphene nanosheets and evenly distributed on both sides. The Sb2S3/graphene nanocomposites with amorphous structure had good tolerance and adaptability to drastic volume changes. Compared to the crystalline counterpart (Li C.-Y. et al., 2017), the amorphous Sb2S3/graphene nanocomposite displayed a superior electrochemical property with a higher reversible capacity of 881.2 mA h g−1 at 0.1 A g−1 after 50 cycles (Figure 2C).

(A) Schematic illustration of the preparation process of the amorphous and crystalline Sb2S3/graphene composites; (B) TEM image of the amorphous Sb2S3–graphene composites; (C) cycle performances of the pristine Sb2S3 and amorphous and crystalline Sb2S3–graphene electrodes (denoted as Sb2S3-G-A and Sb2S3-G-C); (D) formation process of the Sb2S3/S-doped graphene nanocomposite (Sb2S3/SGS); (E) SEM and TEM images of the Sb2S3/SGS nanocomposite; (F) rate performances of the Sb2S3/SGS electrode and Sb2S3–graphene electrode (Sb2S3/GS) under different current density; (G) cycle performances of three experimental electrodes at 2 A g−1. (A–C) Reproduced with permission from Zhao et al. (2021). Copyright 2020, Elsevier. (D–G) Reproduced with permission from Xiong et al. (2016), Copyright 2016, American Chemical Society.

Furthermore, doping heteroatoms (e.g., N, P, S, Sn) on graphene-based materials by surface chemical modification can effectively improve the properties of SIBs (Xiong et al., 2016; Deng et al., 2018; Zhou X. et al., 2020; Zhan et al., 2021). For example, Xiong et al. (2016) obtained a unique Sb2S3/S-doped graphene anode material (denoted as Sb2S3/SGS) via firm chemical binding of nano-Sb2S3 structure on S-doped graphene nanosheets (SGS). Schematic illustration of the preparation process of the Sb2S3/SGS composite is displayed in Figure 2D. As shown in Figure 2E, Sb2S3 nanoparticles are wrapped by flexible SGS and exhibit a size of 30–80 nm. When tested at 0.05 A g−1 current rate, the Sb2S3/SGS anode reaches a high specific capacity of 792.8 mA h g−1 after 90 cycles (see Figure 2F). After 900 cycles at a higher current rate of 2 A g−1 (in Figure 2G), the Sb2S3/SGS anode still has an excellent cycle life, and the capacity retention rate is ∼83%.

 Sb<sub>2</sub>S<sub>3</sub>/M<sub> <italic>x</italic> </sub>S<sub> <italic>y</italic> </sub> Composites

Most metal sulfides (M x S y ) have hierarchical structures, and Na+ can easily move in the interlayers of metal sulfides without damaging their hierarchical structures (Tao et al., 2021). Thus, the use of binary metal sulfides to construct heterostructures to reduce the huge internal stress of alloy-based anodes and maintain the integrity of nanostructures has attracted extensive attention (Wang et al., 2018; Lin et al., 2021; Wang et al., 2019a). In this context, common metal sulfides (M x S y ), including SnS2 (Wang et al., 2018), ZnS (Dong et al., 2017), FeS2 (Cao et al., 2020), In2S3 (Huang et al., 2018), and Bi2S3 (Li et al., 2021), have been combined with Sb2S3 as anode materials of SIBs.

For example, a composite of multiwalled carbon nanotubes (MCNTs) and In2S3-Sb2S3 particles (denoted as I-S@MCNTs) with a unique morphology of formicary microspheres was formed to solve the poor cycling stability and rate performance of SIBs (Huang et al., 2018). As shown in Supplementary Figure S3A, the hierarchical spheres are assembled by crumpled nanosheets (5–8 nm), which significantly shorten the diffusion path and accelerate the transport rate of Na+. Similarly, Wang D. et al. (2021) designed an armored hydrangea-like Sb2S3/MoS2 heterostructure composite (denoted as SMS@C) as a superior SIB anode material (Supplementary Figure S3B). After 650 cycles at a higher current density of 5 A g−1, the SMS@C anode exhibited an enhanced cycling performance of 411.5 mA h g−1 (Supplementary Figure S3E). Additionally, Dong et al. (2017) designed a polyhedron composite (∼1.5 μm) with a ZnS inner-core structure and Sb2S3/C double-shell structure (ZnS-Sb2S3@C), capitalizing on full advantages of the zeolitic imidazolate framework (ZIF-8). The structure of ZnS-Sb2S3@C core-double shell composites had enough space to greatly adapt to the volume expansion during the repeated insertion/extraction of Na+, and exhibited a superior reversible capacity of 630 mA h g−1 at a current density of 0.1 A g−1 after 120 cycles with a high Coulombic efficiency of ∼100% (Supplementary Figures S3C,F).

Recently, a breakthrough about Sb2S3@FeS2 hollow nanorods used as high-performance SIB electrode materials was reported. Cao et al. (2020) embedded Sb2S3@FeS2 hollow nanorods (SFS) into a nitrogen-doped graphene matrix, and synthesized Sb2S3@FeS2/N-doped graphene composite (denoted as SFS/C) via a simple two-step solvothermal synthesis technique (Supplementary Figures S3D,G). The clever design of the heterostructure extremely accelerated the Na+ transport, and greatly alleviated the volume expansion under long-period performance (1,000 cycles) (Wu et al., 2019a; Wu et al., 2019b; Liu et al., 2022). The SFS/C anode displayed a superior reversible capacity of 725.4 mA h g−1 after 90 cycles at 0.1 A g−1 (see Supplementary Figure S3H). When tested even at 5 A g−1, the SFS/C anode had an excellent cycle performance with a capacity retention of ∼85.7% after 1,000 cycles (Supplementary Figure S3I).

 Other Composites

In addition to the aforementioned Sb2S3-based nanomaterials, polypyrrole (PPy) (Wang et al., 2016; Zheng et al., 2018), MXene (Mn+1XnTx, where M is the early transition metal, X represents C/N, and Tx is the surface functional group (-O, -OH or -F), n = 0,1,2,3,4. e.g., Ti3C2Tx, Ti3C2) (Wang et al., 2019b; Zhang H. et al., 2021; He et al., 2021), and metal oxides (e.g., SnO2) (Chang et al., 2020a) can also be combined with Sb2S3 to fabricate better SIB anodes.

For instance, Shi et al. (Yin et al., 2019) prepared Sb2S3/meso@microporous carbon nanofibers@polypyrrole composites (denoted as Sb2S3/MMCN@PPy) though a novel multi-step method combining polymerization, sulfidation and solvothermal process (Supplementary Figure S4A). SEM image of Sb2S3/MMCN@PPy composites is shown in Supplementary Figure S4B. When investigated as SIB anode, Sb2S3/MMCN@PPy composite exhibited a discharge capacity of 535.3 mA h g−1 at a current density of 100 mA g−1, and the discharge specific capacity could recover to 446 mA h g−1 after 50 cycles when returned to 100 mA g−1 current rate (Supplementary Figure S4C). Shi et al. (2019) synthesized Sb2S3@PPy coaxial nanorods via a hydrothermal method. When tested at 100 mA g−1, it showed a superior reversible capacity as high as 881 mA h g−1 after 50 cycles, which was higher than those reported of MWNTs@Sb2S3@PPy composites (Wang et al., 2016), flower-like Sb2S3/PPy microspheres (Zheng et al., 2018), and Sb2S3/MMCN@PPy composites (Yin et al., 2019).

Furthermore, MXene is considered as an outstanding matrix because of the effective diffusion and mobility for Na+ and excellent electronic conductivity. Ti3C2Tx is one of the most studied MXene materials, and the theoretical capacity is 352 mA h g−1 when used as the anode of SIBs (Zhang H. et al., 2021; He et al., 2021; Ren et al., 2021). For instance, Zhang H. et al. (2021); Ren et al. (2021) prepared Sb2S3@Ti3C2Tx composite and Sb2S3@m-Ti3C2Tx composite by a wet chemical method, in which Sb2S3 nanoparticles were in situ nucleated and grown uniformly on the surface of Ti3C2Tx nanosheets. It was found that Ti3C2Tx, as a conductive skeleton, could effectively alleviate the volume expansion of Sb2S3 during charge/discharge progress. In 2021, inspired by the stomatal structure from natural leaves, He et al. (2021) successfully synthesized Sb2S3/nitrogen-doped Ti3C2 composites (denoted as L-Sb2S3/Ti3C2) via a solvothermal method (Supplementary Figure S4D). L-Sb2S3/Ti3C2 composite showed a unique elm leaf-like morphology in Supplementary Figure S4E, with a length of 60–80 nm and a width of 30–40 nm, respectively. When used as SIB anode, L-Sb2S3/Ti3C2 composite displayed a high capacity of 502.2 mA h g−1 at a current rate of 100 mA g−1 from 0.01 to 3 V (Supplementary Figure S4F).

 Conclusion and Outlook

In this review, we briefly summarize the applications of Sb2S3-based nanomaterials for high-performance SIBs, mainly including Sb2S3, Sb2S3/carbon composites, Sb2S3/graphene composites, Sb2S3/M x S y composites, and other related composites. Although many significant works have been made in SIBs, there are still some problems that need to be solved, and we propose some possible directions for the anode research of SIBs in the future:

1) During the charge/discharge cycles, Sb2S3 nanoparticles are easy to accumulate because of their high surface activity energy. This results in a significant volume change and capacity declining. Therefore, it is necessary to design and fabricate more reasonable nanostructures, such as hierarchical hollow nanotubes or hierarchical spheres (Xie F. et al., 2019), to fully buffer the strain of volume change and further improve the cycling performance. In addition, some soft materials could be added to improve the flexibility, so as to avoid the collapse of the anode due to the volume expansion.

2) Carbonaceous materials are often the main choice to combine with Sb2S3 to build dense conductive physical barriers. However, the content of Sb2S3 and the corresponding specific capacity of composite materials are reduced. Therefore, the carbon content should be optimized so that the Sb2S3-based materials achieve better electrochemical performance. In addition, Sb2S3/carbonaceous composites fabricated by traditional synthesis techniques suffer from the poor mechanical adhesion and high interface resistance between Sb2S3 and carbonaceous materials. It is highly desirable to optimize the preparation methods and explore more carbonaceous materials (e.g., biochar, amorphous carbon) to establish compact conductive physical barriers to further enhance the electrochemical performance of Sb2S3-based materials.

3) Until now, the cycle lives of many Sb2S3-based materials have been tested at room temperature. In order to satisfy the demands of different applications, it is very urgent to explore Sb2S3-based anode materials that can cycle under either higher temperature (up to 60 °C) or lower (−20°C).

4) The mechanism of Na+ storage in Sb2S3-based nanomaterials and the phase changes during repeated charging/discharging still need to be explored. Operating technologies, such as in situ X-ray technology, in situ scanning probe microscopy, technologies based on synchronized X-rays, as well as in situ electron microscopy, are very helpful in acquiring time-related information and studying the mechanism of Na+ storage of Sb2S3-based nanomaterials. Therefore, more research using operating technology is needed to deeply understand Sb2S3-based electrode nanomaterials used in SIBs.

 Author Contributions

YL and GW conceived the idea. MG and GW wrote the draft. All authors contributed to the writing, discussion, and revision of the final version of the article.

 Funding

This work was financially supported by the Chinese 02 Special Fund (Grant No.2017ZX02408003) and the Chinese 1000 Plan for High Level Foreign Experts (Grant No. WQ20154100278).

 Conflict of Interest

Author ZC was employed by the company Luoyang Bearing Research Institute Co., Ltd.

The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest

 Publisher’s Note

All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors, and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.

 Supplementary Material

The Supplementary Material for this article can be found online at: https://www.frontiersin.org/articles/10.3389/fchem.2022.870564/full#supplementary-material

(A) SEM image of α-Sb2S3 nanoparticles; (B) cycle performance of α-Sb2S3 at 0.05 A g−1; (C) SEM image of the few-layer 2D-Sb2S3 nanosheets; (D) cyclic capacity of 2D-SS measured at 0.2 A g−1; (E) SEM image of Sb2S3 hollow microspheres; (F) cycling performances of three experimental Sb2S3 electrodes at 1A g−1; (g) SEM and TEM images of multi-shell Sb2S3; (H) comparison of the rate performance of multi-shell Sb2S3, single-shell Sb2S3, and pristine Sb2S3. (A,B) Adapted with permission from Hwang et al. (2016). Copyright 2013, The Royal Society of Chemistry. (C,D) Adapted with permission from Yao et al. (2019). Copyright 2018, Elsevier. (E,F) Adapted with permission from Xie et al. (2018). Copyright 2018, Springer. (G,H) Adapted with permission from Xie et al. (2019a). Copyright 2019, Elsevier.

(A) SEM image of Sb2S3@C rods; (B) cycle performance of Sb2S3@C rods at 0.1 A g−1; (C) SEM image of SS/CFC; (D) cycle performances of SS/CFC and SS powder at 0.5 A g−1; (E) SEM image of SS/Sb@C nanocomposites; (F) cycling performances of SS/Sb@C and Sb2S3 nanocomposites at 0.1 A g−1. (A,B) Adapted with permission from Hongshuai Hou et al. (2015). Copyright 2015, American Chemical Society. (C,D) Adapted with permission from Liu et al. (2017). Copyright 2017, The Royal Society of Chemistry. (E,F) Adapted with permission from Zhao et al. (2020). Copyright 2020, The Royal Society of Chemistry.

SEM images: (A) In2S3-Sb2S3@MCNTs microsphere, (B) Sb2S3/MoS2@C composite (SMS@C), (C) ZnS-Sb2S3@C polyhedron, and (D) Sb2S3@FeS2/N-graphene composite (SFS/C); (E) sodium storage properties of the SMS@C and SMS heterostructure at 5 A g−1; (F) rate capability of ZnS-Sb2S3@C core-shell SIB anode; (G) schematic illustration of the fabrication process of the SFS/C composite; (h) charge capability of the SFS/C anode at various rates; (I) cycle performances of Sb2S3, SFS, and SFS/C composites at a high rate of 5 A g−1. (A) Adapted with permission from Huang et al. (2018). Copyright 2018, Wiley-VCH. (B, E) Adapted with permission from Wang et al. (2021a). Copyright 2021, Elsevier. (c,f) Adapted with permission from Dong et al. (2017). Copyright 2017, American Chemical Society. (D,G–I) Adapted with permission from Cao et al. (2020). Copyright 2020, American Chemical Society.

(A) Schematic diagram of the formation process of the Sb2S3/MMCN@PPy composite; (B) SEM image of Sb2S3/MMCN@PPy composite; (C) rate capability performances of pure Sb2S3 and Sb2S3/MMCN@PPy composite; (D) schematic illustration of the synthetic process of L-Sb2S3/Ti3C2 composite; (E) SEM image of L-Sb2S3/Ti3C2 composite; (F) Rate capability performances of Sb2S3, Sb2S3/Ti3C2, and L-Sb2S3/Ti3C2. (A–C) Adapted with permission from Yin et al. (2019). Copyright 2019, Elsevier. (D–F) Adapted with permission from He et al. (2021). Copyright 2021, Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature.

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