Application Of Lithium-sulfur Batteries Research Articles

Boosting Cathode Activity and Anode Stability of Lithium-Sulfur Batteries with Vigorous Iodic Species Triggered by Nitrate.

Lithium-sulfur (Li-S) battery with a sulfurized polyacrylonitrile cathode is a promising alternative to Li-ion systems. However, the sluggish charge transfer of cathode and accumulation of inactive Li on anode remain persistent challenges. An advanced electrolyte additive with function towards both cathode and anode holds great promise to address these issues. Herein, we present a new strategy to boost sulfur activity and rejuvenate dead Li simultaneously. In the polar electrolyte containing I2-LiNO3 additives, I3 -/IO3 - are triggered significantly by the reaction between NO3 - and I- ions. The I3 -/IO3 - are reactive to insulated Li2S product of cathode and inactive Li on anode, thus accelerating the conversion reaction of sulfur and recovering Li sources back to battery cycling. The in situ/ex situ spectroscopic and morphologic monitoring reveal the crucial role of iodine in promoting Li2S dissociation and inhibiting dendritic Li growth. With the modified electrolyte, the symmetric Li||Li cells deliver a lifespan of 4000 h with an overpotential less than 12 mV at 0.5 mA cm-2. For Li-S cells, 100 % capacity retention up to thousands of cycles and enhanced rate capability are available. This work demonstrates a feasible strategy on electrolyte engineering for practical applications of Li-S batteries.

MXene-Bimetallic Hybrids via Mixed Molten Salts Etching for Kinetics-Enhanced and Dendrite-Free Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries with high theoretical energy density (2600Whkg-1) are considered to be one of the most promising secondary batteries. However, the practical application of Li-S batteries is limited by the polysulfides shuttling and unstable lithium metal anodes. Herein, an asymmetric separator (CACNM@PP), composed of Co-Ni/MXene (CNM) on the cathode and Cu-Ag/MXene (CAM) on the anode for high-performance Li-S batteries is reported. For the cathode, CNM provides a synergistic effect by integrating Co, Ni, and MXene, resulting in strong chemical interactions and fast conversion kinetics for polysulfides. For the anode, CAM with abundant lithiophilicity active sites can lower the nucleation barrier of Li. Moreover, LiCl/LiF layers are generated in situ as an ion conductor layer during charging and discharging, inducing a uniform deposition of Li. Therefore, the assembled cells with the CACNM@PP separators harvest excellent electrochemical performance. This work provides novel insights into the development of commercially available high-energy density Li-S batteries with asymmetric separators.

Achieving a smooth “adsorption-diffusion-conversion” of polysulfides enabled by MnO2-ZnS p-n heterojunction for Li-S battery

The commercial application of lithium-sulfur batteries is primarily impeded by the constant shuttling of soluble polysulfides and sluggish redox kinetics. Nowadays, the discovery of the heterojunction, which combines materials with diverse properties, offers a new perspective for overcoming these obstacles. Herein, a functional coating separator for the lithium-sulfur battery is designed using a MnO2-ZnS p-n heterojunction with a spontaneous built-in electric field (BIEF). The MnO2 nanowire provides suitable adsorption capacity for polysulfides, while the abundant reactive sites brought by ZnS ensure efficient conversion. Moreover, the BIEF significantly facilitates the migration of electrons and polysulfides at the MnO2-ZnS interface, enabling a smooth “adsorption-diffusion-conversion” reaction mechanism. By serving as both the adsorption module and catalytic sites, this BIEF allows batteries utilizing separators modified with MnO2-ZnS heterojunction to achieve an impressive initial capacity of 1511.1 mAh g−1 at 0.1C and maintain a capacity decay rate of merely 0.048% per cycle at 2.0C after 1000 cycles. Even when increasing sulfur loading to 9.4 mg cm−2 in lean electrolyte (5.4 μL mg−1), the battery still exhibits an ultrahigh areal capacity of 6.0 mAh cm−2 after 100 cycles.

Constructing honeycomb-structured LaCoO3 as an efficient polysulfide converter on the separator to achieve practical lithium-sulfur batteries

Owing to its remarkable energy density and specific capacity, lithium-sulfur (Li-S) battery has emerged as one of the most promising energy storage devices. Nevertheless, the shuttle effect and the sluggish conversion of polysulfides significantly impede the practical application of Li-S batteries. Hence, a LaCoO3 functional material with a unique honeycomb structure was designed as an efficient polysulfide converter. The honeycomb-structured LaCoO3 not only exhibits strong bonding energy towards polysulfides but also possesses abundant adsorption sites on its surface. The LaCoO3 material also shows excellent catalytic properties to quickly convert the adsorbed and aggregated polysulfides, effectively suppressing the shuttle effect. Moreover, the honeycomb structure of LaCoO3 can facilitate the rapid wetting and infiltration of the electrolyte. Consequently, the Li-S cell with LaCoO3 functionalized separator provides an areal specific capacity of 3.10 mAh cm−2 after 150 cycles under high sulfur loading of 6.52 mg cm−2. Moreover, under practical conditions where the electrolyte content is as low as 7 μL mg−1 and the sulfur loading is 7.96 mg cm−2, the Li-S battery equipped with LaCoO3-separator can still provide an areal specific capacity of 5.93 mAh cm−2 after 50 cycles.

Mxene quantum dots decorated reduced graphene oxide networks as multifunctional electrocatalyst for advanced lithium–sulfur batteries

Lithium sulfur (Li-S) battery has shown great potential as an attractive rechargeable energy storage devices, but the shuttle behavior and slow conversion kinetics of the intermediate lithium polysulfides (LiPSs) are the main obstacles to the practical application of Li-S battery. Herein, a simple and scalable spray drying strategy was used to construct conductive polar Ti3C2 MXene quantum dots (QDs)-decorated reduced graphene oxide (rGO) microsphere (rGO@Ti3C2 QDs) as efficient electrocatalyst and absorbent for Li-S battery. Firstly, the DFT results show that Ti3C2 QDs can effectively adsorb and catalyze LiPSs conversion. This ability can be attributed to the Ti3C2 QDs can provide a large number of LiPSs catalytic active sites. In addition, the rGO provides physical LiPSs constraint and a flexible substrate to prevent QDs from aggregating. Moreover, both parts are conductive, effectively improving the electron/charge transfer. Therefore, this unique structure and composition show high LiPSs adsorption and catalysis, while allowing rapid Li+/electron transfer. As a result, the S/rGO@Ti3C2 QDs electrode provides high initial capacity (1185 mAh/g at 0.2C), good rate capability (758 mAh/g at 3C), and excellent long-term cyclability (500 cycles at 1C with low attenuation of 0.07% per cycle), as well as an excellent electrochemical performance even at high sulfur loading. Meanwhile, the Li-S pouch cell based on S/rGO@Ti3C2 QDs also achieved a high initial energy density of 230.9 Wh kg−1. This work may provide a promising strategy to obtain better electrochemical performance by introducing quantum dots into Li-S cathodes.

A highly efficient absorptive and catalytic self-supporting Fe2O3/CC host for high performance Li-S batteries

The lithium-sulfur (Li-S) battery is a promising energy storage system because of its high energy density and low cost. However, the shuttling of lithium polysulfides (LiPSs) and low conductivity of the S cathode are barriers to its practical application. Fe2O3 nanorods were grown on a carbon cloth (Fe2O3/CC) by a solvothermal reaction and calcination to obtain a cathode for the battery. The mesoporous structure of the Fe2O3 and the CC conducting network facilitates lithium-ion and electron transport. Meanwhile, the nanorod arrangement results in the exposure of more Fe2O3 active sites, which improves the adsorption and rapid conversion of LiPSs. As a result, a Li–S cell using a Fe2O3/CC cathode has a high capacity of 1 250 mAh g−1 at 0.1 C with an excellent life of over 100 cycles with a capacity retention of 67%. It also has a 70% capacity retention after 1 000 cycles at 0.2 C. The excellent electrochemical performance of the Fe2O3/CC cathode indicates its potential applications in Li-S batteries.

Boron doped MXenes as redox catalyst for highly efficient and reversible polysulfide conversion

Due to the accumulation of soluble polysulfides during the process reaction process, the shuttle effect emerges and significantly impacts the electrochemical performance. The development of novel efficient catalysts and adsorbents is a very popular way to fabricate the sulfur host materials. MXene as one of the most novel and popular materials have been wildly used in electrochemical energy storage. While the limited catalytic activity and adsorption capacity hindering its application in lithium sulfur batteries. Here, we introduced boron atoms as dopants in a creative modification of MXene (B-MXene). The introduced B atoms can effectively mitigate the “shuttle effect” through chemical adsorption, owing to their electron-deficient nature. Furthermore, the introduction of boron atoms and vacancy can modify the electronic structure, enhancing the catalytic activity of MXene by providing empty perpendicular-orientation orbitals. As a result, B-MXene exhibited excellent electrochemical performance, maintaining at 943 mA h g−1 at a current density of 1.0C, after 500cycles, with a corresponding decay rate as low as 0.046 %. This work proposes an efficient strategy to fabricate highly efficient electrocatalysts for advanced lithium-sulfur batteries (Li-S batteries).

Engineering Spin State in Spinel Co3O4 nanosheets by V‐Doping for Bidirectional Catalysis of Polysulfides in Lithium–Sulfur Batteries

AbstractThe slow bidirectional conversion and fast shuttling of lithium polysulfides (LiPSs) remain the main obstacles that inhibit the practical application of lithium sulfur batteries (LSBs). Here, by engineering the in‐spin state of spinel oxides, V doping‐induced hexagonal nanosheets (V‐Co3O4 NS) with intermediate spin state (IS, t2g5 eg1) can form stable bond order toward LiS* based on the ligand field theory and molecular orbital theory, thus effectively accelerating the sulfur conversion kinetics. Owing to these merits, the V‐Co3O4 NS modified separator base battery achieves a high areal capacity of 15.37 mAh cm−2 with sulfur loading of 15.4 mg cm−2, and it displays a low‐capacity attenuation of 0.015% each cycle at 3.0 C for 1900 cycles.

Efficient Host Materials for Lithium-Sulfur Batteries: Ultrafine CoP Nanoparticles in Black Phosphorus-Carbon Composite.

The pursuit of efficient host materials to address the sluggish redox kinetics of sulfur species has been a longstanding challenge in advancing the practical application of lithium-sulfur batteries. In this study, amorphous carbon layer loaded with ultrafine CoP nanoparticles prepared by a one-step in situ carbonization/phosphating method to enhance the inhibition of 2D black phosphorus (BP) on LiPSs shuttle. The carbon coating layer facilitates accelerated electron/ion transport, enabling the active involvement of BP in the conversion of soluble lithium polysulfides (LiPSs). Concurrently, the ultra-fine CoP nanoparticles enhance the chemical anchoring ability and introduce additional catalytic sites. As a result, S@BP@C-CoP electrodes demonstrate exemplary cycling stability (with a minimal capacity decay of 0.054 % over 500 cycles at 1 C) and superior rate performance (607.1 mAh g-1 at 5 C). Moreover, at a sulfur loading of 5.5 mg cm-2, the electrode maintains an impressive reversible areal capacity of 5.45 mAh cm-2 after 50 cycles at 0.1 C. This research establishes a promising approach, leveraging black phosphorus-based materials, for developing high-efficiency Li-S batteries.

Active sites-rich zeolitic imidazolate framework/MXene heterostructure modified separator with improved Li+ transport for high-performance Li-S batteries

The inevitable shuttling of lithium polysulfides (LiPSs) and poor redox kinetics restrict real-world applications of lithium-sulfur (Li-S) batteries, although they have been paid plentiful attention. Herein, a thin and multifunctional heterostructure (ZIF-L/MXene), consisting of leaf-like zeolitic imidazolate framework sheets (ZIF-L) and two-dimensional layered Ti3C2Tx MXene nanosheets, is developed for modification of polyolefin-based separators. A good combination of the merits of the ZIF-L and MXene can hinder the restacking of MXene nanosheets and achieve a large specific surface area, thus exposing plentiful active sites for adsorption and catalytic reaction of LiPSs. Taking these obviously synergistic effects, the ZIF-L/MXene heterostructure modified separators not only alleviate the shuttling of LiPSs but also promote their kinetics conversion. Furthermore, with an improved electrolyte affinity, the ZIF-L/MXene modified separators can accelerate the transport of Li+. Thus, the modified separator endows a Li-S cell with an admirable discharge capacity of 1371.7 mAh g-1 at 0.2 C and favorable cycling stability, with a slow capacity decay ratio of 0.075% per cycle during 500 cycles. Even under a sulfur loading of ~ 4.1 mg cm-2, the Li-S battery can achieve an excellent capacity of 990.6 mAh g-1 at 0.1 C and maintain an excellent cycling performance. The novel ZIF-L/MXene heterostructure modified separator in this work can provide an alternative strategy for designing thin and light separators for high-performance Li-S batteries, via the enhancement of redox kinetics and reduction of shuttling of the LiPSs.

Metal-Coordinated Covalent Organic Frameworks as Advanced Bifunctional Hosts for Both Sulfur Cathodes and Lithium Anodes in Lithium-Sulfur Batteries.

The shuttling of polysulfides on the cathode and the uncontrollable growth of lithium dendrites on the anode have restricted the practical application of lithium-sulfur (Li-S) batteries. In this study, a metal-coordinated 3D covalent organic framework (COF) with a homogeneous distribution of nickel-bis(dithiolene) and N-rich triazine centers (namely, NiS4-TAPT) was designed and synthesized, which can serve as bifunctional hosts for both sulfur cathodes and lithium anodes in Li-S batteries. The abundant Ni centers and N-sites in NiS4-TAPT can greatly enhance the adsorption and conversion of the polysulfides. Meanwhile, the presence of Ni-bis(dithiolene) centers enables uniform Li nucleation at the Li anode, thereby suppressing the growth of Li dendrites. This work demonstrated the effectiveness of integrating catalytic and adsorption sites to optimize the chemical interactions between host materials and redox-active intermediates, potentially facilitating the rational design of metal-coordinated COF materials for high-performance secondary batteries.

Electrocatalytic Mechanism and Sabatier Principle in C2N-Supported Atomically Dispersed Catalysts for the Sulfur Reduction Reaction in Lithium-Sulfur Batteries.

The sluggish kinetics of the sulfur reduction reaction (SRR) impedes the practical application of lithium-sulfur batteries (LSBs). Electrocatalysts are necessary to expedite the conversion of polysulfides. Here, we systematically investigate the chemical mechanisms and size dependence of catalytic activities toward the SRR from Li2S4 to Li2S on single-, double-, and triple-atom catalysts supported on C2N (Mn@C2N, where M is a 3d transitional metal and n = 1-3) as model systems by using first-principles calculations and a comprehensive electrocatalytic model. Our results reveal that the adsorption strength of the LiS• intermediate is identified as an optimal descriptor for catalytic activity. M1@C2N exhibits superior stability and exceptional activity compared to those of the other two catalyst types. Cu1@C2N exhibits the lowest overpotential of 0.426 V. Li embedding or a prelithiation strategy verifies the therein Sabatier principle. This work emphasizes the precise control of the active site structure and microenvironment in catalytic SRR and offers guidance for the design of electrocatalysts for metal-sulfur batteries.

Interfacial synergy of nanoengineered PANI/MnO2 for strong anchoring and fast conversion of polysulfides in Li-S batteries

The shuttle of polysulfides and slow sulfur redox kinetics are the two main issues in the practical application of lithium sulfur (Li-S) batteries. The interface-induced electric fields produced in MnO2-based conductive composites are proposed to solve the above obstacles. Herein, a novel hybrid structure of birnessite-MnO2 nanosheets in situ formed inside polyaniline nanotubes (NSs-MnO2@PANI) is prepared and applied as a catalytic host in Li-S batteries. The DFT calculation combined with experiments reveal the interface-induced electric field with a direction pointing from PANI to birnessite-MnO2 is created, which would induce interface charge redistribution and result in electron-rich MnO2 region and electron-deficient PANI region, optimizing the strong anchoring of polysulfides and their fast catalytic conversions. Owing to the interfacial synergy, the NSs-MnO2@PANI/S cathode delivers higher capacity than PANI/S at rates from 0.1 C (1473.7 vs. 467.5 mAh g−1) to 5 C (513.2 vs. 38.1 mAh g−1), with a low decay rate of 0.054% during 500 cycles at 0.2 C. Further, at an extremely high sulfur loading of 15.9 mg cm−2, the areal capacity achieves a high level of 10.2 mAh cm−2 at 0.05 C, with stable cycling at 1 C. Our work provides new insights for attaining high-energy and stable Li-S batteries.

Mesoporous NiCo2S4@rGO nanocomposites as sulfur carriers for high performance lithium sulfur batteries

It is of unprecedented significance to surmount the daunting challenges of lithium-sulfur battery due to its low cost and exceptionally high energy density. Herein, the mesoporous NiCo2S4@rGO nanocomposites were fabricated solvothermally with mesoporous NiCo2S4 nanoparticles dispersed on rGO and investigated as highly-efficient carriers for sulfur cathode in lithium-sulfur battery. The as-obtained NiCo2S4@rGO nanocomposites are featured with abundant mesopore, good electronic and ionic conductivity, excellent catalytic effect on the redox of lithium polysulfides conversion and strong adsorption, thus observably accelerating the redox kinetics of lithium polysulfides and suppressing the shuttle effect. Therefore, the NiCo2S4@rGO@S electrode delivers a high reversible specific discharge density of 785 mAh g−1 at 0.1 C after 100 cycles and exhibits good rate capability and cycling stability, verifying its great promising for the commercial application of lithium-sulfur battery.

Improved performance of lithium–sulfur battery with a free-standing cobalt-doped vanadium nitride carbon nanofiber interlayer

Lithium–sulfur batteries (LSBs) are considered promising devices for next-generation secondary battery owing to their low cost and high energy density. However, the practical application of LSB is hindered by the sluggish redox kinetics of sulfur and the shuttling effect of polysulfide. To address the above problems, cobalt-doped vanadium nitride/three-dimensional carbon nanofiber (Co-VN/3DNC) composites were synthesized based on non-woven fabrics. The Co-VN/3DNC interlayer can serve as a physical barrier directly for the shuttle effect alleviating in LSBs. The introduction of the Co atom can enrich the d-electron number of VN, improving the catalysis of LSBs redox reaction. The growth of curved carbon nanotubes (CNTs) on the surface of the intermediate layer can expose active adsorption-catalytic sites, accelerating polysulfide redox kinetics for LSBs. The electrochemical performance of the LSB is greatly enhanced by the synergistic effect of Co, VN, and 3DNC. The LSB with Co-VN/3DNC interlayer demonstrate a capacity of 1207.7 mAh g−1 at a current density of 0.1C, and retain a specific capacity of 918.2 mAh g−1 even after 250 cycles. This work provides an effective strategy for the intermediate layers design to improve the electrochemical performance of LSBs.

Efficient Co0.85Se-CNT sulfur cathode derived from strong catalyst-support interactions: Contribution of adsorption-catalysis mechanism to the redox kinetics of polysulfides

The sluggish conversion chemistry and the notorious ‘shuttle effect’ of lithium polysulfides (LiPSs) are hindering the widespread application of lithium-sulfur batteries (LSBs). Herein, N-doped carbon nanotubes arrays anchored with highly dispersed Co0.85Se nanoparticles were in-situ grown on 3D carbon paper substrates (Co0.85Se-CNT@CP) to promote redox kinetic. The derived sulfur cathode (S/Co0.85Se-CNT@CP) exhibited a sufficient chemisorption ability to accelerate the conversion kinetics and showed considerable capability (1210 mAh/g at 0.2C) and impressive cyclic stability (516 mAh/g at 2.0C after 500cycles). Even at a high loading of 6.0 mg cm−2, the assembled batteries performed a high capacity of 500 mAh/g at 2.0C after 500cycles. The exceptional performance is attributed to the following reasons: On the one hand, the highly efficient conductive carbon nanotubes not only offer sufficient accommodation space for sulfur, but also provide physically confinement for polysulfides. On the other hand, the Co0.85Se nanoclusters drove the transformation of more elemental sulfur to Li2S2/Li2S. In addition, the S/Co0.85Se-CNT@CP did not require conventional binders, thus enhanced surface the reaction kinetic and electron transfer. The associated conversion mechanism was studied by ex-situ XPS, and an adsorption-catalytic model was established to elucidate the electrochemical mechanism. This study proposes a feasible strategy to solve the severe LiPSs shuttling and the sluggish conversion kinetics of LSBs.

Sulfur electrode tolerance and polysulfide conversion promoted by the supramolecular binder with rare-earth catalysis in lithium-sulfur batteries

The binder that maintains electrode integrity and provides electron/ion transport channels is insufficient for high-performance lithium-sulfur (Li-S) batteries. Multifunctional and environmentally friendly binders with minimal lithium polysulfides (LiPSs) escape and accelerated LiPSs conversion kinetics are critical for sustainable Li-S batteries. Herein, we proposed a new versatile supramolecular polymer binder synthesized by hydrogen bonding crosslinking between hydrolysable polymer matrix and yttrium-pyridine complex in aqueous solutions, denoted as GB-Y. This unique environmental-friendly binder based on supramolecular chemistry could (1) maintain the integrity of sulfur cathode through the mechanical toughness contributed by synergistic effect of hydrogen bonds and robust chemical bonds, (2) anchor LiPSs by lithiophilic effects, and (3) accelerate LiPSs conversion by electrocatalysis of rare-earth catalysis sites (Y3+) as Lewis acids. With above benefits of GB-Y binder, the Li-S batteries with GB-Y binder deliver a high discharge capacity of 1201.5 mAh g−1 and an excellent cyclability over 800 cycles. This binder exhibits a commercial potential in view of capacity release under high-sulfur loading of 6.56 mg cm−2 with lean electrolyte (electrolyte/sulfur (E/S) ratio of 10 μl mg−1). This study provides a concept of binders with three efficacies, i.e. adhesion, adsorption, and catalysis, and offers an innovative and environmentally friendly strategy for the construction of advanced binder with supramolecular chemistry manner to promote the practical application of Li-S batteries.

NiS2-MoS2@MXene heterostructures for enhancing polysulfide adsorption and conversion of Li[sbnd]S battery

Lithium‑sulfur (LiS) batteries attract great interests due to their low cost and high energy density. However, the slow electrochemical reaction and shuttle effect hinder the commercial applications of LiS batteries. Herein, NMM (NiS2-MoS2@MXene) heterostructures containing a large number of defects were successfully prepared to provide more active sites for polysulfide catalysis and adsorption. The resulted battery exhibited exceptional electrochemical performance with the use of 20 wt% (NMM-20) conductive agent MXene. The battery assembled with NMM-20 has an excellent reversible capacity of 767.3 mAh g−1 after 800 cycles at 0.5C and the NMM-20 also showed excellent rate performance. Importantly, a favorable areal capacity of 5 mAh cm−2 was obtained under a high sulfur load of 7 mg cm−2. This work extends the preparation of heterogeneous materials and provides insight into the optimal addition amounts of conductive agents in heterostructures.

Ni-Ce bimetal doping and phosphating modulated MOF with improved catalysis and adsorption for high-performance lithium-sulfur battery applications

Lithium-sulfur batteries (LSBs) have received widespread attentions because of high specific capacity and low cost. However, the low sulfur utilization and shuttle effect limited their wide application. In this paper, phosphating Ni-Ce bimetallic nanoparticles embedded in multifunctional freestanding porous carbon with improved catalytic activity and confinement were prepared from MOF materials. Compared with monoatomic catalysts or other homonuclear diatomic mixtures, the catalytic-adsorptive synergistic effect of Ni-Ce doping in NiCe@CPS can provide more active sites to catalyze the conversion of lithium polysulfides (LiPSs) to improve the reaction kinetics effectively, meanwhile, the phosphides Ni2P and CeP can physically and chemically adsorb the LiPSs to further inhibit the shuttle effect. Moreover, the porous carbon structure not only provides abundant channels for Li+ transport and electrolyte permeation but greatly facilitates sulfur storage and mitigates the volume expansion during the cycling process. The battery assembled with NiCe@CPS cathode delivered a discharge-specific capacity of 1013 mAh g−1 at 0.1 C, and maintained 768 mAh g−1 after 100 cycles with a Coulombic efficiency of 95 %.

Progresses and Prospects of Asymmetrically Coordinated Single Atom Catalysts for Lithium−Sulfur Batteries

Lithium–sulfur batteries (LSBs) are widely regarded as promising next‐generation batteries due to their high theoretical specific capacity and low material cost. However, the practical applications of LSBs are limited by the shuttle effect of lithium polysulfides (LiPSs), electronic insulation of charge and discharge products, and slow LiPSs conversion reaction kinetics. Accordingly, the introduction of catalysts into LSBs is one of the effective strategy to solve the issues of the sluggished LiPS conversion. Because of their nearly 100% atom utilization and high electrocatalytic activity, single‐atom catalysts (SACs) have been widely used as reaction mediators for LSBs' reactions. Excitingly, the SACs with asymmetric coordination structures have exhibited intriguing electronic structures and superior catalytic activities when compared to the traditional M–N4 active sites. In this review, we systematically describe the recent advancements in the installation of asymmetrically coordinated single‐atom structure as reactions catalysts in LSBs, including asymmetrically nitrogen coordinated SACs, heteroatom coordinated SACs, support effective asymmetrically coordinated SACs, and bimetallic coordinated SACs. Particularly noteworthy is the discussion of the catalytic conversion mechanism of LiPSs spanning asymmetrically coordinated SACs. Finally, a perspective on the future developments of asymmetrically coordinated SACs in LSB applications is provided.