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To obtain a high-performance extended gate field-effect transistor for pH detection, hafnium nitride (HfN) was first fabricated on an indium tin oxide on polyethylene terephthalate (ITO/PET) substrate using a high-power impulse magnetron sputter system (HiPIMS) in this study. It can be easily applied in biomedical diagnostic and environmental monitoring applications with the advantages of flexible, disposable, cost-effective, and reliable components. Various duty cycle conditions in HiPIMSs were designed to investigate the corresponding sensing performance and material properties including surface morphology and composition. As the duty cycle increased, the grain size of HfN increased. Additionally, X-ray photoelectron spectroscopy (XPS) analysis illustrated the presence of HfOxNy on the deposited HfN surface. Both behaviors could result in a better pH sensing performance based on the theory of the site-binding model. Subsequently, HfN with a 15% duty cycle exhibited excellent pH sensitivity and linearity, with values of 59.3 mV/pH and 99.8%, respectively; its hysteresis width and drift coefficient were -1 mV and 0.5 mV/h, respectively. Furthermore, this pH-sensing performance remained stable even after 2000 repeated bending cycles. These results indicate the potential and feasibility of this HiPIMS-deposited HfN for future wearable chemical applications.
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An in situ polymerization strategy is regarded as a promising approach to fabricate gel polymer electrolytes (GPEs) and improve interface contact between the electrolyte and electrodes, in which the initiator is initially dissolved in the precursor solution. Herein, aluminum trifluoromethanesulfonate (Al(OTf)3) is preloaded onto a separator sheet as the initiator to trigger the ring-opening reaction of 1,3-dioxolane (DOL). The polymer matrix near the separator has a higher crystallization degree than that far away from the separator. Fluoroethyl carbonate (FEC) is further introduced as a liquid plasticizer to produce an amorphous GPE for enhanced ionic conductivity and interfacial stability. As a result, the as-synthesized FEC based GPE exhibits a substantial ionic conductivity of 1.5 × 10-4 S cm-1 at room temperature, an expanded electrochemical window of 4.8 V, and a high Li+ transference number of 0.63. The symmetric Li|Li cell exhibits a stable lifespan for 650 h at 1 mA cm-2 and 1 mA h cm-2. Moreover, the LiFePO4 full cell exhibits stable cycling for 300 cycles at 1C with a capacity retention of 94.5%. This work provides a novel idea for the in situ synthesis of advanced GPEs toward practical application of solid-state lithium metal batteries.
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Lithium (Li) metal anode (LMA) is one of the most promising anodes for high energy density batteries. However, its practical application is impeded by notorious dendrite growth and huge volume expansion. Although the three-dimensional (3D) host can enhance the cycling stability of LMA, further improvements are still necessary to address the key factors limiting Li plating/stripping behavior. Herein, porous copper (Cu) foam (CF) is thermally infiltrated with molten Li-rich Li-zinc (Li-Zn) binary alloy (CFLZ) with variable Li/Zn atomic ratio. In this process, the LiZn intermetallic compound phase self-assembles into a network of mixed electron/ion conductors that are distributed within the metallic Li phase matrix and this network acts as a sublevel skeleton architecture in the pores of CF, providing a more efficient and structured framework for the material. The as-prepared CFLZ composite anodes are systematically investigated to emphasize the roles of the tunable lithiophilicity and hierarchical structure of the frameworks. Meanwhile, a thin layer of Cu-Zn alloy with strong lithiophilicity covers the CF scaffold itself. The CFLZ with high Zn content facilitates uniform Li nucleation and deposition, thereby effectively suppressing Li dendrite growth and volume fluctuation. Consequently, the hierarchical and lithiophilic framework shows low Li nucleation overpotential and highly stable Coulombic efficiency (CE) for 200 cycles in conventional carbonate based electrolyte. The full cell coupled with LiFePO4 (LFP) cathode demonstrates high cycle stability and rate performance. This work provides valuable insights into the design of advanced dendrite-free 3D LMA toward practical application.
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We report an electron-insulating layer of Li2O nanoparticles passivating a Li-rich Li-Cu-Zn ternary alloy as an advanced Li anode. The insulating layer ensures Li deposition below the top protective layer and inhibits side reactions effectively. Additionally, the ternary alloy framework offers superior lithiophilicity and robust mechanical stability. Galvanostatic measurements demonstrate a prolonged lifespan of symmetric cells for over 1200 h at 1 mA cm-2 and 1 mA h cm-2.
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Poly(lactic acid) (PLA) and Poly(butylene succinate) (PBS) were chosen as raw materials and melt blended by a twin screw extruder and pelletized; then, the pellets were extruded into filaments; after that, various PBS/PLA blending samples were prepared by Fused Deposition Molding (FDM) 3D printing technology using the filaments obtained and the effect of the dosage of PBS on technological properties of 3D-printed specimens was investigated. For comparison, the PLA specimen was also prepared by FDM printing. The tensile strength, tensile modulus, thermal stability, and hydrophilicity became poorer with increasing the dosage of PBS, while the flexural strength, flexural modulus, impact strength, and crystallinity increased first and then decreased. The blend containing 10% PBS (10% PBS/PLA) had the greatest flexural strength of 60.12 MPa, tensile modulus of 2360.04 MPa, impact strength of 89.39 kJ/m2, and crystallinity of 7.4%, which were increased by 54.65%, 61.04%, 14.78%, and 51.02% compared to those of printed PLA, respectively; this blend also absorbed the least water than any other specimen when immersed in water. Different from the transparent PLA filament, 10% PBS/PLA filament presented a milky white appearance. The printed 10% PBS/PLA specimen had a smooth surface, while the surface of the printed PLA was rough. All the results indicated that the printed 10% PBS/PLA specimen had good comprehensive properties, including improved mechanical properties, crystallization performance, and surface quality than PLA, as well as proper wettability and water absorption. The prominent conclusion achieved in this work was that 10% PBS/PLA should be an ideal candidate for biodegradable feedstock among all the PBS/PLA blends for FDM 3D printing.
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Wood flour-poly(butylene succinate)-poly(lactic acid) biocomposite samples were prepared by fused-deposition-molding 3D-printing technology, and modifications with glycerol and a silane coupling agent (KH550) were carried out. The samples were then hydrothermally aged. Modification with glycerol and KH550 enhanced the hydrophilicity of the samples and increased their tensile strength. Hydrothermal aging clearly whitened the surfaces of all the samples and made them more hydrophobic. Meanwhile, their tensile properties and thermal stability became poor; a higher hydrothermal aging temperature affected the mechanical properties more negatively. The modified samples turned out to be more resistant to the hydrothermal aging, and modification with KH550 could improve the anti-hydrothermal aging properties of the samples better than that with glycerol, where the tensile properties and the cross-sectional morphologies of the fractured specimens were concerned. Generally, the effects of hydrothermal aging temperature on the physico-mechanical properties of the printed specimens were greater than those by hydrothermal aging time.
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Developing improved anode materials is critical to the performance enhancement and the lifespan prolonging of sodium-ion batteries (SIBs). In this context, carbon-based nanostructures have emerged as a promising candidate. In this work, we have synthesized N, B, and P tri-doped carbon (NBPC) spheres using a one-step carbonization method. The as-prepared NBPC exhibits exceptional properties, including an expanded layer space, sufficient structural defects, and enhanced electrical conductivity. These characteristics synergistically contribute to the remarkable rate capability and ultra-long lifespan when NBPC is employed as an anode material for SIBs. The as-prepared NBPC demonstrates a reversible capacity of 290.6 mAh/g at 0.05 A/g, with a capacity retention of 98.4% after 800 cycles. Furthermore, NBPC exhibits an impressively ultra-long cycle life of 2400 cycles at 1.0 A/g with a reversible capacity of 140.2 mAh/g. First principle calculations confirm that the introduction of N, B, and P heteroatoms in carbon enhances the binding strength of sodium ions within NBPC. This work presents a novel approach for fabricating advanced anode materials, enabling the development of long-life SIBs for practical applications.
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Li-rich dual-phase Li-Cu alloy is a promising candidate toward practical application of Li metal anode due to its in situ formed unique three-dimensional (3D) skeleton of electrochemical inert LiCux solid-solution phase. Since a thin layer of metallic Li phase appears on the surface of as-prepared Li-Cu alloy, the LiCux framework cannot regulate Li deposition efficiently in the first Li plating process. Herein, a lithiophilic LiC6 headspace is capped on the upper surface of the Li-Cu alloy, which can not only offer free space to accommodate Li deposition and maintain dimensional stability of the anode, but also provide abundant lithiophilic sites and guide Li deposition effectively. This unique bilayer architecture is fabricated via a facile thermal infiltration method, where the Li-Cu alloy layer with an ultrathin thickness around 40 µm occupies the bottom of a carbon paper (CP) sheet, and the upper part of this 3D porous framework is reserved as the headspace for Li storage. Notably, the molten Li can quickly convert these carbon fibers of the CP into lithiophilic LiC6 fibers while the CP is touched with the liquid Li. The synergetic effect between the LiC6 fibers framework and LiCux nanowires scaffold can ensure a uniform local electric field and stable Li metal deposition during cycling. As a consequence, the CP capped ultrathin Li-Cu alloy anode demonstrates excellent cycling stability and rate capability.
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Lithium metal is deemed a promising anode material for the next-generation batteries with high specific energy. Unfortunately, the growth of Li dendrites and infinite volume change during cycling, caused by the "hostless" feature of metallic Li, have posed a great challenge to the commercialization of Li metal anode. The introduction of appropriate host materials for Li metal is highly desirable. In this work, a N, P dual-doped 3D carbon derived from low-cost quantitative filter paper (NPCQP) is designed and fabricated for direct using as a host for Li metal anode. The resulting NPCQP host achieves a high deposition/stripping Coulombic efficiency of above 97.5 % with a low nucleation overpotential. Moreover, the NPCQP@Li symmetric cells enable an excellent long-term cycling performance (1000 h) with an ultralow voltage hysteresis (12 mV) and stable interface behavior. When paired with the commercial LiFePO4 cathode, the full cell with NPCQP@Li anode displays impressive long-term cyclic stability and rate capability, outperforming the counter cell with bare Li anode. This contribution sheds light on the rational design of viable host for practical lithium metal anodes.
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Constructing an artificial solid electrolyte interphase (SEI) layer is an effective strategy for solving uncontrolled Li dendrite growth resulting from an unstable and heterogeneous Li/electrolyte interface. Herein, we develop a hybrid layer of a LiZn alloy and a polyethylene oxide (PEO) polymer to protect the Li metal anode for achieving a Li dendrite-free Li metal anode surface. The LiZn alloy is advantageous for fast Li+ transport, and is uniformly dispersed in the PEO matrix to regulate electronic and Li+ ion flux distributions homogeneously. Furthermore, the flexible PEO network can alleviate the volume change during cycling. The synergistic effect enables Li deposition underneath the hybrid film. Hence, the hybrid protection film results in significantly improved cycling stability with respect to the pristine Li metal anode. A symmetric Li/Li cell with a composite protective layer can be cycled for over 1000 h at a current density of 1 mA cm-2 with a fixed capacity of 1 mA h cm-2, and a full cell with a high areal capacity of the LiFePO4 (2.45 mA h cm-2) cathode exhibits an outstanding cycling performance.
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Epithelial malignant transformation and tumorous development were believed to be closely associated with the loss of its microenvironment integrity and homeostasis. The tumor-suppressive molecules Maspin and p53 were demonstrated to play a crucial role in body epithelial and immune homeostasis. Downregulation of Maspin and mutation of p53 were frequently associated with malignant transformation and poor prognosis in various human cancers. In this review, we focused on summarizing the progress of the molecular network of Maspin in studying epithelial tumorous development and its response to clinic treatment and try to clarify the underlying antitumor mechanism. Notably, Maspin expression was reported to be transcriptionally activated by p53, and the transcriptional activity of p53 was demonstrated to be enhanced by its acetylation through inhibition of HDAC1. As an endogenous inhibitor of HDAC1, Maspin possibly potentiates the transcriptional activity of p53 by acetylating the p53 protein. Hereby, it could form a "self-propelling" antitumor mechanism. Thus, we summarized that, upon stimulation of cellular stress and by integrating with p53, the aroused Maspin played the epigenetic surveillant role to prevent the epithelial digressional process and retune the epithelial homeostasis, which is involved in activating host immune surveillance, regulating the inflammatory factors, and fine-tuning its associated cell signaling pathways. Consequentially, in a normal physiological condition, activation of the above "self-propelling" antitumor mechanism of Maspin and p53 could reduce cellular stress (e.g., chronic infection/inflammation, oxidative stress, transformation) effectively and achieve cancer prevention. Meanwhile, designing a strategy of mimicking Maspin's epigenetic regulation activity with integrating p53 tumor-suppressive activity could enhance the chemotherapy efficacy theoretically in a pathological condition of cancer.
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The sluggish redox reaction kinetics for aprotic Li-O2 batteries (LOBs) caused by the insulating discharge product of Li2O2 could result in the poor round-trip efficiency, low rate capability, and cyclic stability. To address these challenges, we herein fabricated NiCo2S4 supported on reduced graphene oxide (NiCo2S4@rGO), the surface of which is further modified via a unique low-pressure capacitive-coupled nitrogen plasma (CCPN-NiCo2S4@rGO). The high ionization environment of the plasma could etch the surface of NiCo2S4@rGO, introducing effective nitrogen doping. The as-prepared CCPN-NiCo2S4@rGO has been employed as an efficient catalyst for advanced LOBs. The electrochemical analysis, combined with theoretical calculations, reveals that the N-doping can effectively improve the thermodynamics and kinetics for LiO2 adsorption, giving rise to a well-knit Li2O2 formation on CCPN-NiCo2S4@rGO. The LOBs based on the CCPN-NiCo2S4@rGO oxygen electrode deliver a low overpotential of 0.75 V, a high discharge capacity of 10,490 mA h g-1, and an improved cyclic stability (more than 110 cycles). This contribution may pave a promising avenue for facile surface engineering of the electrocatalyst in LOBs and other energy storage systems.
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Recent advances in wearable and implantable electronics have increased the demand for biocompatible integrated energy storage systems. Conducting polymers, such as polyaniline (PANi), have been suggested as promising electrode materials for flexible biocompatible energy storage systems, based on their intrinsic structural flexibility and potential polymer chain compatibility with biological interfaces. However, due to structural disorder triggering insufficient electronic conductivity and moderate electrochemical stability, PANi still cannot fully satisfy the requirements for flexible and biocompatible energy storage systems. Herein, we report a biocompatible physiological electrolyte activated flexible supercapacitor encompassing crystalline tetra-aniline (c-TANi) as the active electrode material, which significantly enhances the specific capacitance and electrochemical cycling stability with chloride electrochemical interactions. The crystallization of TANi endows it with sufficient electronic conductivity (8.37 S cm-1) and a unique Cl- dominated redox charge storage mechanism. Notably, a fully self-healable and biocompatible supercapacitor has been assembled by incorporating polyethylene glycol (PEG) with c-TANi as a self-healable electrode and a ferric-ion cross-linked sodium polyacrylate (Fe3+-PANa)/0.9 wt% NaCl as a gel electrolyte. The as-prepared device exhibits a remarkable capacitance retention even after multiple cut/healing cycles. With these attractive features, the c-TANi electrode presents a promising approach to meeting the power requirements for wearable or implantable electronics.
Assuntos
Compostos de Anilina , Cloretos , Capacitância Elétrica , Eletrodos , EletrólitosRESUMO
Lithium-oxygen batteries (LOBs) with ultrahigh theoretical energy density have emerged as one appealing candidate for next-generation energy storage devices. Unfortunately, some fundamental issues remain unsettled, involving large overpotential and inferior rate capability, mainly induced by the sluggish reaction kinetics and parasitic reactions at the cathode. Hence, the pursuit of suitable catalyst capable of efficiently catalyzing the oxygen redox reaction and eliminating the side-product generation, become urgent for the development of LOBs. Here, we report a universal synthesis approach to fabricate a suite of mildly oxidized MXenes (mo-Nb2CTx, mo-Ti3C2Tx, and mo-V2CTx) as cathode catalysts for LOBs. The readily prepared mo-MXenes possess expanded interlayer distance to accommodate massive Li2O2 formation, and in-situ-formed light metal oxide to enhance the electrocatalytic activity of MXenes. Taken together, the mo-V2CTx manages to deliver a high specific capacity of 22752 mAh g-1 at a current density of 100 mA g-1, and a long lifespan of 100 cycles at 500 mA g-1. More impressively, LOBs with mo-V2CTx can continuously operate for 90, 89, and 70 cycles, respectively, under a high current density of 1000, 2000, and 3000 mA g-1 with a cutoff capacity of 1000 mAh g-1. The theoretical calculations further reveal the underlying mechanism lies in the optimized surface, where the overpotentials for the formation/decomposition of Li2O2 are significantly reduced and the catalytic kinetics is accelerated. This contribution offers a feasible strategy to prepare MXenes as efficient and robust electrocatalyst toward advanced LOBs and other energy storage devices.
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Witnessing compositional evolution and identifying the catalytically active moiety of electrocatalysts is of paramount importance in Li-S chemistry. Nevertheless, this field remains elusive. We report the scalable salt-templated synthesis of Se-vacancy-incorporated MoSe2 architecture (SeVs-MoSe2 ) and reveal the phase evolution of the defective precatalyst in working Li-S batteries. The interaction between lithium polysulfides and SeVs-MoSe2 is probed to induce the transformation from SeVs-MoSe2 to MoSeS. Furthermore, operando Raman spectroscopy and exâ situ X-ray diffraction measurements in combination with theoretical simulations verify that the effectual MoSeS catalyst could help promote conversion of Li2 S2 to Li2 S, thereby boosting the capacity performance. The Li-S battery accordingly exhibits a satisfactory rate and cycling capability even with and elevated sulfur loading and lean electrolyte conditions (7.67â mg cm-2 ; 4.0â µL mg-1 S ). This work elucidates the design strategies and catalytic mechanisms of efficient electrocatalysts bearing defects.
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Lithium-sulfur (Li-S) batteries are promising candidates for next-generation energy storage, yet they are plagued by the notorious polysulfide shuttle effect and sluggish redox kinetics. While rationally designed redox mediators can facilitate polysulfide conversion, favorable bidirectional sulfur electrocatalysis remains a formidable challenge. Herein, selective dual-defect engineering (i.e., introducing both N-doping and Se-vacancies) of a common MoSe2 electrocatalyst is used to manipulate the bidirectional Li2 S redox. Systematic theoretical prediction and detailed electrokinetic analysis reveal the selective electrocatalytic effect of the two types of defects, thereby achieving a deeper mechanistic understanding of the bidirectional sulfur electrochemistry. The Li-S battery using this electrocatalyst exhibits excellent cyclability, with a low capacity decay rate of 0.04% per cycle over 1000 cycles at 2.0 C. More impressively, the potential for practical applications is highlighted by a high areal capacity (7.3 mAh cm-2 ) and the construction of a flexible pouch cell. Such selective electrocatalysis created by dual-defect engineering is an appealing approach toward working Li-S systems.
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Although lithium-sulfur (Li-S) batteries have long been touted as next-generation energy storage devices, the rampant dendrite growth at the anode side and sluggish redox kinetics at the cathode side drastically impede their practical application. Herein, a dual-functional fibrous skeleton implanted with single-atom Co-Nx dispersion is devised as an advanced modificator to realize concurrent regulation of both electrodes. The rational integration of single-atomic Co-Nx sites could convert the fibrous carbon skeleton from lithiophobic to lithiophilic, helping assuage the dendritic formation for the Li anode. Meanwhile, the favorable electrocatalytic activity from the Co-Nx species affording a lightweight feature effectively enables expedited bidirectional conversion kinetics of sulfur electrochemistry, thereby inhibiting the polysulfide shuttle. Moreover, the interconnected porous framework endows the entire skeleton with good mechanical robustness and fast electron/ion transportation. Benefiting from the synergistic effects between atomically dispersed Co-Nx sites and three-dimensional conductive networks, the integrated Li-S full batteries can achieve a reversible areal capacity (>7.0 mAh cm-2) at a sulfur loading of 6.9 mg cm-2. This work might be beneficial to the development of practically viable Li-S batteries harnessing single-atom mediators.
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MXenes are an emerging class of highly conductive two-dimensional (2D) materials with electrochemical storage features. Oriented macroscopic Ti3C2Tx fibers can be fabricated from a colloidal 2D nematic phase dispersion. The layered conductive Ti3C2Tx fibers are ideal candidates for constructing high-speed ionic transport channels to enhance the electrochemical capacitive charge storage performance. In this work, we assemble Ti3C2Tx fibers with a high degree of flake orientation by a wet spinning process with controlled spinning speeds and morphology of the spinneret. In addition to the effects of cross-linking of magnesium ions between Ti3C2Tx flakes, the electronic conductivity and mechanical strength of the as-prepared fibers have been improved to 7200 S cm-1 and 118 MPa, respectively. The oriented Ti3C2Tx fibers present a volumetric capacitive charge storage capability of up to 1360 F cm-3 even in a Mg-ion based neutral electrolyte, with contributions from both nanofluidic ion transport and Mg-ion intercalation pseudocapacitance. The oriented 2D Ti3C2Tx driven nanofluidic channels with great electronic conductivity and mechanical strength endows the MXene fibers with attributes for serving as conductive ionic cables and active materials for fiber-type capacitive electrochemical energy storage, biosensors, and potentially biocompatible fibrillar tissues.
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The construction of aqueous Zn-ion hybrid capacitors (ZICs) reconciling high energy/power density is practically meaningful yet remains a grand challenge. Herein, a high-capacitance and long-life ZIC is demonstrated by 3D printing of a Ti3C2 MXene cathode, affording optimized carrier transport, facile electrolyte penetration, and ample porosity. The 3D-printable additive-free MXene ink with desirable rheological property is derived by a fast gelation process employing a trace amount of divalent cations, which overcomes the tedious post-treatments required for additive removal. The thus-fabricated 3D-printed (3DP) MXene cathode results in a dual-ion storage mechanism to synergize pseudocapacitive behavior of H+ and electrical double-layer capacitive behavior of Zn2+, which is systematically probed by a wide suite of in situ/ex situ electroanalytic characterizations. The 3DP MXene cathode accordingly exhibits a favorable areal capacitance of 1006.4 mF cm-2 at 0.38 mA cm-2 and excellent rate capability (184.4 F g-1 at 10 A g-1), outperforming the state-of-the-art ZICs. More impressively, ZIC full cells comprising a 3DP MXene cathode and a 3DP Zn anode deliver a competitive energy/power density of 0.10 mWh cm-2/5.90 mW cm-2 as well as an ultralong lifespan (86.5% capacity retention over 6000 cycles at 10 mA cm-2).
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Li-S batteries (LSBs) have received extensive attention owing to their remarkable theoretical capacity (1672 mA h g-1) and high energy density (2600 W h kg-1), which are far beyond those of the state-of-the-art Li-ion batteries (LIBs). However, the retarded sulfur reaction kinetics and fatal shuttle effect have hindered the practical implementations of LSBs. In response, constructing electrocatalysts for Li-S systems has been considered an effective strategy to date. Particularly, size engineering-enabled electrocatalysts show high activity in the sulfur redox reaction, considerably contributing to the latest advances in Li-S system research. In this tutorial review, we provide a systematic summary of nano- to atomic-scale electrocatalysts employed in Li-S chemistry, aiming at figuring out the working mechanism of size engineering-enabled electrocatalysts in the sulfur redox reaction and guiding the rational construction of advanced LSBs toward practically viable applications.