Application Of Lithium-sulfur Batteries Research Articles

A bifunctional thiobenzamide additive for improvement of cathode kinetics and anode stability in lithium-sulfur batteries

Lithium-sulfur batteries (LSBs) are considered as the key candidates for the next generation of energy storage devices. However, the practical applications of LSBs are hindered by the slow conversion of sulfur species and the inhomogeneous Li+ precipitation /stripping of lithium anode. Here, we report a bifunctional thiobenzamide electrolyte additive, 4-(trifluoromethyl) thiobenzamide (TFBCA), which synergistically improves cathode redox kinetics and anode stability. Polysulfides (LiPSn) are in-situ transferred to more reactive polysulfide intermediates (T-Sn-T), which significantly improve the liquid–solid reduction process by promoting the deposition dimension of Li2S. A LiF/Li3N-rich solid electrolyte interphase is formed with TFBCA, the uniform lithium deposition is achieved and the growth of lithium dendrites is suppressed. Correspondingly, LSBs with TFBCA show a high capacity (888 mAh·g−1 at 5C) and cycling stability (0.055 % per cycle after 600 cycles at 2C). Even under high sulfur loading (7.1 mg·cm−2) and low E/S ratio of 7, the LSBs also exhibit an areal capacity of 7 mAh·cm−2 after 50 cycles, and an energy density of 314 Wh·kg−1 is achieved for the pouch cell. This work demonstrates an efficient additive strategy through molecular structure design to construct high-performance LSBs.

Entrapment and Reactivation of Polysulfides in Conductive Amphiphilic Covalent Organic Frameworks Enabling Superior Capacity and Stability of Lithium-Sulfur Batteries.

Inhibiting the shuttle of polysulfides is of great significance for promoting the practical application of lithium-sulfur batteries (LSBs). Here, an imine-linked covalent organic framework@carbon nanotube (COF@CNT) interlayer composed of triazine and boroxine rings is constructed between the sulfur cathode and the separator for polysulfides reception and reutilization. The introduction of CNT imparts the conductor characteristic to the interlayer attributed to electron tunneling in thin COF shell, and creates a hierarchical porous architecture for accommodating polysulfides. The uniform distribution of amphiphilic adsorption sites in COF microporous structure not only enables efficient entrapment of polysulfides while allowing the penetration of Li+ ions, but also provides a stable electrocatalytic channel for bidirectional conversion of active sulfur to achieve the substantially improved capacity and stability. The interlayer-incorporated LSBs deliver an ultrahigh capacity of 1446mAg-1 at 0.1C and an ultralow capacity decay rate of 0.019% at 1C over 1500 cycles. Even at an electrolyte/sulfur ratio of 6µLmg-1, an outstanding capacity of 995mAhg-1 and capacity retention of 74.1% over 200 cycles at 0.2C are obtained. This work offers a compelling polysulfides entrapment and reactivation strategy for stimulating the study on ultra-stable LSBs.

Polymorph interface strategy presents avenues for kinetics-enhanced and dendrite-free lithium sulfur batteries

Shuttle effect and slow kinetic property are the challenges for the practical application of lithium-sulfur (Li-S) batteries. As an effective strategy, the polymorph effect is applied to rationally design multifunctional catalysts. Herein, the unique polymorph interface was constructed by different CoSe2 crystalline phases, and the systematic investigation on the sulfur cathodes and lithium anode is reported. Carbon nanofiber (CNF) derived from bacterial cellulose (BC) is used as a scaffold for disperse CoSe2 catalysts to construct electrically conductive highways. According to the experimental and calculation results, orthorhombic CoSe2 exhibits superior adsorption capacity and catalytic activity towards LiPSs, while cubic CoSe2 shows better electronic conductivity. Mixed phase CoSe2 not only balances the advantages of both, but also showcases impressive performance due to its unique polymorph interface structure. Besides, uniform lithium deposition can be also achieved. Consequently, the modified separators endow Li-S batteries with a high reversible discharge capacity (700 cycles at 1 C with only 0.063 % capacity decay per cycle) and excellent rate performance (702 mAh g−1 is maintained at 5 C). The pouch cell with separator modifications on both sides was assembled and exhibits a high discharge capacity. This work provides a polymorph interface strategy for the rational design of catalysts.

Ultrathin 2D-2D MXene-LDH Interlayer with High Polysulfide Adsorption Ability for Advanced Li-S Batteries.

Lithium-sulfur (Li-S) batteries are considered as promising energy storage systems due to the high energy density of 2600 W h kg-1. However, the practical application of Li-S batteries is hindered by the inadequate conductivity of sulfur and Li2S, as well as the shuttle effect caused by polysulfides during the charge-discharge process. Introducing a conductive interlayer between the cathode and the separator to physically resist polysulfides represents an effective and straightforward approach to mitigate the shuttle effect in Li-S batteries. In this paper, an ultrathin (<1 μm) 2D-2D MXene-LDH interlayer with high polysulfide adsorption ability was introduced to Li-S batteries. The synergistic effect between MXene and layered double hydroxide greatly improved the adsorption effect of the interlayers: the conductive Ti3C2Tx MXene chemically adsorbs polysulfides and promotes their fast transfer, and the NiCo-LDH alleviates the restack of MXene and facilitates Li+ diffusion. After inserting the MXene-LDH interlayer, the Li-S batteries exhibit an enhanced specific capacity of 1137.6 mA h g-1 at 0.1 C and retain 622.6 mA h g-1 after 100 cycles. The ultrathin 2D-2D interlayer offers a feasible way for the development of highly efficient and lightweight interlayers in Li-S batteries.

A Review of Electrospun Carbon-based Nanofibers Materials Used in Lithium-Sulfur Batteries.

Commercial lithium-ion batteries are gradually approaching their theoretical values (200-250 Wh kg-1), which cannot meet the fast-growing energy storage demands. Lithium-sulfur (Li-S) batteries are anticipated to supersede lithium-ion batteries as the next-generation energy storage system owing to their high theoretical specific capacity (1675 mAh g-1) and energy density (2600 Wh kg-1). Nonetheless, Li-S batteries encounter several challenges, including the inadequate conductivity of sulfur and lithium sulfide, sulfur's volume expansion, and the shuttle effect of lithium polysulfides, all of which significantly impact the practical utilization of Li-S batteries. Electrospun carbon-based nanofibers can simultaneously resolve these issues with their economical preparation, distinctive nanostructure, and exceptional flexibility. This review presents the most recent research findings on electrospun carbon-based nanofibers materials serving as sulfur hosts and interlayer components in Li-S batteries. We analyzed the impact of the material's structural design on the performance of Li-S batteries and the relative underlying mechanism. Finally, the current challenges and issues faced by carbon-based nanofibers composites in the application of Li-S batteries are summarized, and the future development trajectory are outlined.

N-Vacancy Enriched Porous BN Fibers for Enhanced Polysulfides Adsorption and Conversion in High-Performance Lithium-Sulfur Batteries.

Severe shuttle effect of soluble polysulfides and sluggish redox kinetics have been thought of as the critical issues hindering the extensive applications of lithium-sulfur batteries (LSBs). Herein, one-dimensional boron nitride (1D BN) fibers with abundant pores and sufficient N-vacancy defects were synthesized using a thermal crystallization following a pre-condensation step. The 1D structure of BN facilitates unblocked ions diffusion pathways during charge/discharge cycles. The embedded pores within the polar BN strengthen the immobilization of polysulfides via both physical confinement and chemical interaction. Moreover, the highly exposed active surface area and intentionally created N-vacancy sites substantially promote reaction kinetics by lowering the energy barriers of the rate-limiting steps. After incorporating with conductive carbon networks and elemental S, the as-prepared S/Nv-BN@CBC cathode of LSBs deliver an initial discharge capacity of up to 1347 mAh g-1 at 200 mA g-1, while maintaining a low decay rate of 0.03% per cycle over 1000 cycles at 1600 mA g-1. This work offers an effective strategy to mitigate the shuttle effect and highlights the significant potential of defect-engineered BN in accelerating the reaction kinetics of LSBs.

Universal design of three-dimensional porous graphene-iron based promotors for kinetically rationalized lithium-sulfur chemistry

Lithium-sulfur (Li-S) batteries are widely deemed to be one of the most potential candidates for future secondary batteries because of their remarkable energy density. Nevertheless, notorious polysulfide shuttling and retarded sulfur reaction kinetics pose significant obstacles to the further application of Li-S batteries. While rationally designed highly active electrocatalysts can facilitate polysulfide conversion, the universal and scalable synthesis strategies need to be developed. Herein, a universal synthetic strategy to construct a series of three-dimensional (3D) porous graphene-iron (3DGr-Fe) based electrocatalysts involving 3DGr-FeP, 3DGr-Fe3C, and 3DGr-Fe3Se4 is exploited for manipulating the Li-S redox reactions. It has been observed that the implementation of a 3D porous Gr architecture leads to the well-designed conductive networks, while the uniformly dispersed iron nanoparticles introduce an abundance of active sites, fostering the lithium polysulfide conversion, thereby bolstering the overall electrochemical performance. The Li-S battery with the 3DGr-Fe based electrocatalyst exhibits remarkable capacity retention of 94.8% upon 100 times at 0.2 C. Moreover, the soft-packaged Li-S pouch cell based on such a 3DGr-Fe electrocatalyst delivers superior capacity of 1060.71 mA h g−1 and guarantees for the continuous 30 min work of fan toy. This investigation gives comprehensive insights into the design, synthesis, and mechanism of 3DGr-Fe based electrocatalysts with high activity toward efficient and durable Li-S batteries.

Nitrogen-Doped Carbon and Metal-Nitrogen-Carbon Materials as Cathode Hosts for Li-S Batteries: Experimental Study and Mechanism Analysis.

Both nitrogen-doped carbon (NC) and metal-nitrogen-carbon (MNC) materials have been extensively investigated in lithium-sulfur batteries to alleviate the "shuttle effect". MNC are generally synthesized using NC as the parent material, wherein nitrogen atoms in NC serve as the "bridge" to coordinate with metal atoms. So far, an important scientific issue has not been settled: does the introduction of metal sites into NC certainly enhance the Li-S battery performance? In this work, NC and MNC materials derived from the same precursor, a nitrogen-rich porous polymer, are systematically compared as cathode hosts for Li-S battery through theoretical calculations and experimental investigation. Li-S cell with NC as the cathode sulfur host exhibits better cycle performance at low current densities (0.1 and 0.2C), whereas MNC materials predominate at higher current densities (such as 1C and 2C). Based on theoretical calculation and experimental results, it is concluded that the introduction of metal sites into NC through nitrogen bonding promoted the catalytic capability for faster sulfur redox reaction kinetics, whereas the adsorption energy toward polysulfides decreased. This work provides important guidance for more targeted design of advanced materials for lithium-sulfur battery application in the future.

Ultrathin Titanium Carbide-modified Separator for High-performance Lithium-Sulfur Batteries

Despite a high theoretical capacity, the practical application of lithium-sulfur batteries has been primarily limited by the migration of long-chained polysulfide species during the charge/ discharge processes. One effective approach to address the issues is design a funtional separator or interlayer. Here, we prepared a modified separator with an ultrathin layer of titanium carbide (TiC) using radio-frequency sputtering on a commercial Celgard polypropylene membrane. The 240-nm TiC coating layer can enhance the interfacial properties of Celgard separators in porosity, wettability, roughness, etc. Hence, via experimental and theoretical investigation, we discovered that TiC can efficiently adsorb polysulfides and boost charge transfer via strong covalent C–S bonds. Using a TiC-modified separator can impede the shuttle effect and improve the kinetics of sulfur conversion reactions. Thus, the Li-S batteries with TiC separator deliver excellent electrochemical performances with a good rate capability (717 mAh g−1 at 7.0 C) and an ultra-low decay rate of 0.058% per cycle over 800 cycles at a C-rate of 2.0 C. Furthermore, a high areal capacity of 4.3 mAh cm−2 was achieved with a high mass-loading of sulfur cathode up to 7.0 mg cm−2.

Amorphous bimetallic-organic framework enable accelerated redox kinetics and polysulfide trapping for lithium-sulfur batteries

Severe polysulfide dissolution and shuttling during charging and discharging are the main challenges hindering the practical application of lithium-sulfur (Li-S) batteries. Constructing functional separators is considered as an economical and convenient way to suppress the shuttle effect and improve the kinetics of Li-S chemistry. In this work, partially ligand-deficient amorphous bimetallic MOF material (aFeNi-MOF) is designed via a ligand competition strategy and employed as a separator modifier. The aFeNi-MOF not only promotes the rapid transportation of ions, but also enhances the chemisorption and catalytic capability on sulfur species, enabling accelerated redox kinetics and polysulfide trapping in Li-S batteries. Consequently, the assembled coin cell using aFeNi-MOF-modified separator delivered a high reversible capacity of 931.1 mAh/g at 1C, a long cycle life of more than 500 cycles and a low capacity decay of 0.084 % per cycle. Meanwhile, the areal capacity of 3.70 mAh cm−2 can be achieved under a high sulfur loading of 4.5 mg cm−2 and low electrolyte usage, meeting the requirement of areal capacity for commercial applications of Li-S batteries.

Mo2C-Co heterostructure with carbon nanosheets decorated carbon microtubules: Different means for high-performance lithium-sulfur batteries

The practical applications of lithium sulfur batteries (LSBs) are hindered by notorious shuttle effect and sluggish conversion kinetics of intermediate polysulfides. Herein, Mo2C-Co heterogeneous particles decorated two-dimensional (2D) carbon nanosheets grown on hollow carbon microtubes (CCC@MCC) are synthesized. Three-dimensional (3D) carbon framework with Mo2C-Co heterogeneous particles combines the conductivity, adsorption and catalysis, effectively trapping and accelerating the conversion of polysulfides. As evidenced experimentally, the hetero-structured Mo2C-Co with high Li+ diffusion coefficient enables uniform precipitation and complete oxidation of Li2S. Meanwhile, CCC@MCC is found to have multiple application possibilities for lithium-sulfur batteries. As an interlayer, the cells deliver an excellent capacity of 881.1 mAh/g at 2C and still retain 438.2 mAh/g after 500 cycles under the low temperature of 0 ℃. As a sulfur carrier, the cell with a sulfur loading of 7.0 mg cm−2 exhibits a high area capacity of 5.3 mAh cm−2. This work provides an effective strategy to prepare heterostructured material and imaginatively exploit the application potential of it.

Design of Coatings for Sulfur-Based Cathode Materials in Lithium-Sulfur Batteries: A review.

Lithium-sulfur batteries (LSBs) are considered next-generation energy storage and conversion solutions owing to their high theoretical specific capacity and the high abundance/low-cost of sulfur-based cathode materials. However, LSBs still encounter significant challenges, including the low conductivities of sulfur-based materials, severe volumetric expansion of sulfur during the discharge process, and the persistent "shuttle effect" of polysulfides. In recent years, a tremendous amount of research has been conducted to address the above challenges by developing coating and compositing materials and corresponding fabrication strategies for sulfur-based cathode materials. In this study, the surface coating, compositing materials, and fabrication methodologies of LSB cathodes are comprehensively reviewed in terms of advanced materials, structure/component characterization, functional mechanisms, and performance validation. Some technical challenges are analyzed in detail, and possible future research directions are proposed to overcome the challenges toward practical applications of lithium-sulfur batteries.

Multifunctional TiN-MXene-Co@CNTs Networks as Sulfur/Lithium Host for High-Areal-Capacity Lithium-Sulfur Batteries.

The inevitable shuttling and slow redox kinetics of lithium polysulfides (LiPSs) as well as the uncontrolled growth of Li dendrites have strongly limited the practical applications of lithium-sulfur batteries (LSBs). To address these issues, we have innovatively constructed the carbon nanotubes (CNTs) encapsulated Co nanoparticles in situ grown on TiN-MXene nanosheets, denoted as TiN-MXene-Co@CNTs, which could serve simultaneously as both sulfur/Li host to kill "three birds with one stone" to (1) efficiently capture soluble LiPSs and expedite their redox conversion, (2) accelerate nucleation/decomposition of solid Li2S, and (3) induce homogeneous Li deposition. Benefiting from the synergistic effects, the TiN-MXene-Co@CNTs/S cathode with a sulfur loading of 2.5 mg cm-2 could show a high reversible specific capacity of 1129.1 mAh g-1 after 100 cycles at 0.1 C, and ultralong cycle life over 1000 cycles at 1.0 C. More importantly, it even achieves a high areal capacity of 6.3 mAh cm-2 after 50 cycles under a sulfur loading as high as 8.9 mg cm-2 and a low E/S ratio of 5.0 μL mg-1. Besides, TiN-MXene-Co@CNTs as Li host could deliver a stable Li plating/striping behavior over 1000 h.

Nitrogen-Doped TiO2- x(B)/MXene Heterostructures for Expediting Sulfur Redox Kinetics and Suppressing Lithium Dendrites.

Practical application of lithium-sulfur (Li-S) batteries is severely impeded by the random shuttling of soluble lithium polysulfides (LiPSs), sluggish sulfur redox kinetics, and uncontrollable growth of lithium dendrites, particularly under high sulfur loading and lean electrolyte conditions. Here, nitrogen-doped bronze-phase TiO2(B) nanosheets with oxygen vacancies (OVs) grown in situ on MXenes layers (N-TiO2- x(B)-MXenes) as multifunctional interlayers are designed. The N-TiO2- x(B)-MXenes show reduced bandgap of 1.10eV and high LiPSs adsorption-conversion-nucleation-decomposition efficiency, leading to remarkably enhanced sulfur redox kinetics. Moreover, they also have lithiophilic nature that can effectively suppress dendrites growth. The cell based on the N-TiO2- x(B)-MXenes interlayer under sulfur loading of 2.5mg cm-2 delivers superior cycling performance with a high specific capacity of 690.7 mAh g-1 over 600 cycles at 1.0 C. It still has a notable areal capacity of 6.15 mAh cm-2 after 50 cycles even under a high sulfur loading of 7.2mg cm-2 and a low electrolyte-to-sulfur (E/S) ratio of 6.4 µL mg-1. The Li-symmetrical battery with the N-TiO2- x(B)-MXenes interlayer showcases a low over-potential fluctuation with 21.0mV throughout continuous lithium plating/stripping for 1000h. This work offers valuable insights into the manipulation of defects and heterostructures to achieve high-energy Li-S batteries.

Multifunctional Lithium Phytate/Carbon Nanotube Double-Layer-Modified Separators for High-Performance Lithium-Sulfur Batteries.

Li dendrite and the shuttle effect are the two primary hindrances to the commercial application of lithium-sulfur batteries (LSBs). Here, a multifunctional separator has been fabricated via successively coating carbon nanotubes (CNTs) and lithium phytate (LP) onto a commercial polypropylene (PP) separator to improve the performance of LSBs. The LP coating layer with abundant electronegative phosphate group as permselective ion sieve not only reduces the polysulfide shuttle but also facilitates uniform Li+ flux through the PP separator. And the highly conductive CNTs on the second layer act as a second collector to accelerate the reversible conversion of sulfide species. The synergistic effect of LP and CNTs further increases the electrolyte wettability and reaction kinetics of cells with a modified separator and suppresses the shuttle effect and growth of Li dendrite. Consequently, the LSBs present much enhanced rate performance and cyclic performance. It is expected that this study may generate an executable tactic for interface engineering of separator to accelerate the industrial application process of LSBs.

Flash Joule Heating: A Promising Method for Preparing Heterostructure Catalysts to Inhibit Polysulfide Shuttling in Li-S Batteries.

The "shuttle effect" issue severely hinders the practical application of lithium-sulfur (Li-S) batteries, which is primarily caused by the significant accumulation of lithium polysulfides in the electrolyte. Designing effective catalysts is highly desired for enhancing polysulfide conversion to address the above issue. Here, the one-step flash-Joule-heating route is employed to synthesize a W-W2C heterostructure on the graphene substrate (W-W2C/G) as a catalytic interlayer for this purpose. Theoretical calculations reveal that the work function difference between W (5.08eV) and W2C (6.31eV) induces an internal electric field at the heterostructure interface, accelerating the movement of electrons and ions, thus promoting the sulfur reduction reaction (SRR) process. The high catalytic activity is also confirmed by the reduced activation energy and suppressed polysulfide shuttling by in situ Raman analyses. With the W-W2C/G interlayer, the Li-S batteries exhibit an outstanding rate performance (665 mAh g-1 at 5.0 C) and cycle steadily with a low decay rate of 0.06% over 1000 cycles at a high rate of 3.0 C. Moreover, a high areal capacity of 10.9 mAh cm-2 (1381.4 mAh g-1) is obtained with a high area sulfur loading of 7.9mg cm-2 but a low electrolyte/sulfur ratio of 9.0 µL mg-1.

The important role of diatomite on multifunctional modified separator of Li-S battery

The commercial applications of lithium-sulfur (Li-S) batteries are limited by decreased cycling performance caused by the shuttle effect of polysulfides, slower kinetic reaction rates, and lithium anode dendrites. This study demonstrates the important role of diatomite (DT) in regulating cycle performance of modified separator for Li-S batteries. A multifunctional separator (Co/NC/DT) with DT as a carrier assembled high loading cobalt nanocluster is prepared. The N-doped carbon is immobilized via Si-N bond between DT and N-doped carbon. The depth profiles of XPS indicate that the ratio of pyrrolic N to pyridinic N of Co/NC/DT reaches 5.31 at the etching of 100 nm versus 0.83 for Co/NC at surface, which suggesting that mainly N species is pyrrolic N after the addition of DT. Theoretical calculations confirm that cobalt nanoclusters grown on pyrrolic N-doped carbon have a lower adsorption energy for active materials compared to that on pyridinic N-doped carbon and can reduce the energy barrier, especially only 0.09 eV for reduction from Li2S6 to Li2S4. In-situ X-ray diffraction analysis confirms Co/NC/DT can effectively promote formation of Li2S. Lithium anode in-situ optical microscopy observation shows the modified separator could reduce lithium dendrites effectively. Li-S battery assembled with the modified separator can reach an initial capacity of 1331.3 mAh g−1 at 0.2 C and cycle 1500 cycles at 1.0 C with a decay of only 0.039% per cycle. Through regulation of DT, Co/NC/DT accelerates the conversion from long-chain sulfur to short-chain sulfur and Li+ transfer rate, resulting in improving cycling performance.

Coupling bimetallic selenides with homogeneous mediators synergistically accelerating overall sulfur redox kinetics for high-performances lithium–sulfur batteries

The practical applications of lithium-sulfur batteries (LSBs) are hampered by poor electrical conductivity, severe shuttling of intermediate lithium polysulfides (LiPSs) and sluggish redox kinetics. Herein, we introduce a multifunctional catalytic system by integrating bimetallic ZnSe-CoSe2 with CoCp2 mediators, aimed at serving as redox kinetic accelerators in LSBs. In this design, the ZnSe-CoSe2 heterostructure with hierarchical pores and large surface area, is capable of immobilizing both soluble LiPSs and CoCp2 mediators, but also provides abundant active sites for catalyzing LiPSs conversions. Concurrently, the soluble CoCp2 mediators contribute to promoting the high-dimensional growth of Li2S and reducing the interface polarization. Electrochemical experiments and theoretical analyses reveal that the ZnSe-CoSe2/CoCp2 system synergistically accelerates overall sulfur redox kinetics. Consequently, the cell with the ZnSe-CoSe2/CoCp2 system under a sulfur loading of 2.3 mg cm−2 exhibits superior long-term cycling stability at 1.0C. Additionally, it achieves a remarkable areal capacity of 6.5 mAh cm−2 under a high sulfur loading of 8.0 mg cm−2 and a low electrolyte-to-sulfur ratio of 5.0 µL mg−1.

A First-Principles Study on the Anchoring Properties of Defective Single-Walled Carbon Nanotubes for Lithium-Sulfur Batteries

The application of lithium-sulfur (Li–S) batteries is impeded by the significant polysulfide shuttling phenomenon. Developing suitable anchoring material is an effective way to restrain this behavior. In this work, the anchoring performance of lithium polysulfide (LiPSs) on defective single-wall carbon nanotubes (DSWNT) is investigated by density functional theory. The results demonstrate that the DSWNT with three carbon vacancies (DSWNT-3) has the highest forming capacity and the strongest adsorption capacity, indicating it has the best anchoring effect of LiPSs. As the anchoring material of the cathode, DSWNT-3 has greater energy than solvent molecules to inhibit the dissolution of long-chain polysulfides. In general, DSWNT-3 demonstrates notable efficacy as an anchoring material for Li–S batteries, which establishes a theoretical foundation for exploring the anchoring characteristics of defects and their application in the cathode of Li–S batteries.

Template Evolution Induced Relay Self-Assembly for Mesoporous Carbonaceous Materials via Hydrothermal Carbonization.

Constructing carbonaceous materials with versatile surface structures still remains a great challenge due to limited self-assembly methods, especially at high temperatures. This study presents an innovative template evolution induced relay self-assembly (TEIRSA) for the fabrication of large polyoxometalate (POM)-mixed carbonaceous nanosheets featuring surface mesoporous structures through hydrothermal carbonization (HTC). The method employs POM and acetone as additives, cleverly modulating the Ostwald ripening-like process of P123-based micelles, effectively addressing the instability challenges inherent in traditional soft-template methods, especially within the demanding carbohydrate HTC process. Additionally, this method allows for the independent regulation of surface architectures through the selection of organic additives. The resulting nanosheets exhibit diverse surface morphologies, including surface spherical mesopores, 1D open channels, and smooth surfaces. Their unexpectedly versatile properties have swiftly garnered recognition, showing potential in the application of lithium-sulfur batteries.