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2024 Volume 43 Issue 7
2024, 43(7): 100276
doi: 10.1016/j.cjsc.2024.100276
Abstract:
Moreover, the work also inspires and provides ideas for the application of silicon in the liquid electrolyte battery (LEB) system. It is well known that as a typical alloying type anode, silicon has long been recognized as one of the most promising anode materials for lithium-ion batteries to replace graphite due to its extremely high specific capacity. However, owing to the huge volume expansion of Si during Li alloying and dealloying; the Si anode always experiences inevitable pulverization, making it very difficult to achieve rapid and stable cycling in current LEB. Therefore, it is highly expected that a function coating later with the similar concept of constriction-susceptible, could be applied in the LEB system to improve its performance.
Moreover, the work also inspires and provides ideas for the application of silicon in the liquid electrolyte battery (LEB) system. It is well known that as a typical alloying type anode, silicon has long been recognized as one of the most promising anode materials for lithium-ion batteries to replace graphite due to its extremely high specific capacity. However, owing to the huge volume expansion of Si during Li alloying and dealloying; the Si anode always experiences inevitable pulverization, making it very difficult to achieve rapid and stable cycling in current LEB. Therefore, it is highly expected that a function coating later with the similar concept of constriction-susceptible, could be applied in the LEB system to improve its performance.
2024, 43(7): 100290
doi: 10.1016/j.cjsc.2024.100290
Abstract:
Developing efficient bifunctional catalysts for urea oxidation reaction (UOR)/hydrogen evolution reaction (HER) is important for energy-saving hydrogen production. Herein, a catalyst with crystalline-amorphous heterostructure supported by NiCo alloy on nickel foam (NiCoO-MoOx/NC) is reported for the first time. Through simple molybdenum salt etching, 2D NiCo alloy nanosheets are transformed into a unique 3D cycad-leaf-like structure with a super-hydrophilic surface. Simultaneously, the synergistic effect between crystalline NiCoO and amorphous MoOx improves the UOR and HER activity, merely requiring 1.28 V and ‒45 mV potentials to reach ±10 mA cm−2, respectively. Particularly, the UOR kinetics of NiCoO-MoOx/NC is enhanced significantly than that of NiCoO/NC. The electronic structure of NiCoO is modified by MoOx, enabling the rapid generation of NiOOH and CoOOH active species, which would accelerate the synergistic electrocatalytic oxidation of urea molecules. This work inspires the designing of highly active and -stable bifunctional catalysts for urea assisted H2 production.
Developing efficient bifunctional catalysts for urea oxidation reaction (UOR)/hydrogen evolution reaction (HER) is important for energy-saving hydrogen production. Herein, a catalyst with crystalline-amorphous heterostructure supported by NiCo alloy on nickel foam (NiCoO-MoOx/NC) is reported for the first time. Through simple molybdenum salt etching, 2D NiCo alloy nanosheets are transformed into a unique 3D cycad-leaf-like structure with a super-hydrophilic surface. Simultaneously, the synergistic effect between crystalline NiCoO and amorphous MoOx improves the UOR and HER activity, merely requiring 1.28 V and ‒45 mV potentials to reach ±10 mA cm−2, respectively. Particularly, the UOR kinetics of NiCoO-MoOx/NC is enhanced significantly than that of NiCoO/NC. The electronic structure of NiCoO is modified by MoOx, enabling the rapid generation of NiOOH and CoOOH active species, which would accelerate the synergistic electrocatalytic oxidation of urea molecules. This work inspires the designing of highly active and -stable bifunctional catalysts for urea assisted H2 production.
2024, 43(7): 100299
doi: 10.1016/j.cjsc.2024.100299
Abstract:
The sp2 carbon-conjugated covalent organic frameworks (COFs) with fully π-conjugated lattice and high chemical stability are promising but challenging to achieve heterogeneous photocatalysts. Herein, we report the design and synthesis of a novel palladium porphyrin-based sp2 carbon-conjugated COF (PdPor-sp2c-COF) with an eclipsed AA stacking 2D structure. Interestingly, PdPor-sp2c-COF showed high crystallinity, good chemical stability, and a broad absorption of visible light. Moreover, compared to our previously reported metal-free Por-sp2c-COF, PdPor-sp2c-COF displayed an improved photocatalytic performance in the selective aerobic oxidation of sulfides under green light irradiation. The systematic mechanism studies testified that the enhanced photocatalytic performance can be ascribed to the promoted energy transfer pathway by PdPor-sp2c-COF during photocatalytic process. Our study clearly demonstrated that it is favorable to promote the energy transfer pathway in sp2 carbon-conjugated COFs to enhance the photocatalytic property by using metalloporphyrin-based molecular building blocks, which will inspire us to design and synthesize novel photocatalyst based on COFs for the selective aerobic oxidation.
The sp2 carbon-conjugated covalent organic frameworks (COFs) with fully π-conjugated lattice and high chemical stability are promising but challenging to achieve heterogeneous photocatalysts. Herein, we report the design and synthesis of a novel palladium porphyrin-based sp2 carbon-conjugated COF (PdPor-sp2c-COF) with an eclipsed AA stacking 2D structure. Interestingly, PdPor-sp2c-COF showed high crystallinity, good chemical stability, and a broad absorption of visible light. Moreover, compared to our previously reported metal-free Por-sp2c-COF, PdPor-sp2c-COF displayed an improved photocatalytic performance in the selective aerobic oxidation of sulfides under green light irradiation. The systematic mechanism studies testified that the enhanced photocatalytic performance can be ascribed to the promoted energy transfer pathway by PdPor-sp2c-COF during photocatalytic process. Our study clearly demonstrated that it is favorable to promote the energy transfer pathway in sp2 carbon-conjugated COFs to enhance the photocatalytic property by using metalloporphyrin-based molecular building blocks, which will inspire us to design and synthesize novel photocatalyst based on COFs for the selective aerobic oxidation.
2024, 43(7): 100300
doi: 10.1016/j.cjsc.2024.100300
Abstract:
In summary, these molecular knots with dynamic structures can be prepared by simply self-assembly procedure and their remarkable structures can be well determined by X-ray crystallography. These dynamic behaviors of molecular knots can be monitored by experimental technologies and theoretical simulations, which is relevant for biological systems as proteins often form dynamic chiral knots in ways that we cannot grasp well. In all, the advancements in these tight molecular knots will help us to figure out the behaviors of proteins in biological systems.
In summary, these molecular knots with dynamic structures can be prepared by simply self-assembly procedure and their remarkable structures can be well determined by X-ray crystallography. These dynamic behaviors of molecular knots can be monitored by experimental technologies and theoretical simulations, which is relevant for biological systems as proteins often form dynamic chiral knots in ways that we cannot grasp well. In all, the advancements in these tight molecular knots will help us to figure out the behaviors of proteins in biological systems.
2024, 43(7): 100301
doi: 10.1016/j.cjsc.2024.100301
Abstract:
Electrocatalytic carbon dioxide reduction reaction (eCO2RR) represents one of the most promising technologies for sustainable conversion of CO2 to value-added products. Although metal-organic frameworks (MOFs) can be vastly functionalized to create active sites for CO2RR, low intrinsic electrical conductivity always make MOFs unfavorable candidates for eCO2RR. Besides, studies on how to regulate eCO2RR activity of MOFs from linkers’ functionalities viewpoint lag far behind when compared with assembly of multinuclear metal-centered clusters. In this work, non-toxic bismuth(III) oxide (Bi2O3) was incorporated into a series of 2D MOFs (ZrLX) established from Zr-oxo clusters and triazine-centered 3-c linkers with different functionalities (LX = 1∼5) to give composites ZrLX/Bi2O3. To investigate how functionalities on linkers distantly tune the eCO2RR performance of MOFs, electron-donating/withdrawing groups were installed at triazine core or benzoate terminals. It was found that ZrL2/Bi2O3 (‒F functionalized on triazine core) exhibits the best eCO2RR performance with highest Faradaic efficiency of 96.73% at ‒1.07 V vs. RHE, largest electroactive surface (Cdl = 4.23 mF cm−2) and highest electrical conductivity (5.54 × 10−7 S cm−1), highlighting tuning linker functionalities and hence electronic structure as an alternative way to regulate eCO2RR.
Electrocatalytic carbon dioxide reduction reaction (eCO2RR) represents one of the most promising technologies for sustainable conversion of CO2 to value-added products. Although metal-organic frameworks (MOFs) can be vastly functionalized to create active sites for CO2RR, low intrinsic electrical conductivity always make MOFs unfavorable candidates for eCO2RR. Besides, studies on how to regulate eCO2RR activity of MOFs from linkers’ functionalities viewpoint lag far behind when compared with assembly of multinuclear metal-centered clusters. In this work, non-toxic bismuth(III) oxide (Bi2O3) was incorporated into a series of 2D MOFs (ZrLX) established from Zr-oxo clusters and triazine-centered 3-c linkers with different functionalities (LX = 1∼5) to give composites ZrLX/Bi2O3. To investigate how functionalities on linkers distantly tune the eCO2RR performance of MOFs, electron-donating/withdrawing groups were installed at triazine core or benzoate terminals. It was found that ZrL2/Bi2O3 (‒F functionalized on triazine core) exhibits the best eCO2RR performance with highest Faradaic efficiency of 96.73% at ‒1.07 V vs. RHE, largest electroactive surface (Cdl = 4.23 mF cm−2) and highest electrical conductivity (5.54 × 10−7 S cm−1), highlighting tuning linker functionalities and hence electronic structure as an alternative way to regulate eCO2RR.
Mn-modulated Co–N–C oxygen electrocatalysts for robust and temperature-adaptative zinc-air batteries
2024, 43(7): 100302
doi: 10.1016/j.cjsc.2024.100302
Abstract:
Flexible zinc-air batteries (FZABs) are featured with safety and high theoretical capacity and become one of the ideal energy supply devices for flexible electronics. However, the lack of cost-effective electrocatalysts remains a major obstacle to their commercialization. Herein, we synthesized a porous dodecahedral nitrogen-doped carbon material with Co and Mn bimetallic co-embedding (CoxMn1−x@NC) as a highly efficient oxygen reduction reaction (ORR) catalyst for ZABs. The incorporation of Mn effectively modulates the electronic structure of Co sites, which may lead to optimized energetics with oxygen-containing intermediates thereby significantly enhancing catalytic performance. Notably, the optimized Co4Mn1@NC catalyst exhibits superior E1/2 (0.86 V) and jL (5.96 mA cm−2) compared to Pt/C and other recent reports. Moreover, aqueous ZAB using the Co4Mn1@NC as a cathodic catalyst demonstrates a high peak power density of 163.9 mW cm−2 and maintains stable charging and discharging for over 650 h. Furthermore, FZAB based on the Co4Mn1@NC can steadily operate within the temperature range of -10 °C to 40 °C, demonstrating the potential for practical applications in complex climatic conditions.
Flexible zinc-air batteries (FZABs) are featured with safety and high theoretical capacity and become one of the ideal energy supply devices for flexible electronics. However, the lack of cost-effective electrocatalysts remains a major obstacle to their commercialization. Herein, we synthesized a porous dodecahedral nitrogen-doped carbon material with Co and Mn bimetallic co-embedding (CoxMn1−x@NC) as a highly efficient oxygen reduction reaction (ORR) catalyst for ZABs. The incorporation of Mn effectively modulates the electronic structure of Co sites, which may lead to optimized energetics with oxygen-containing intermediates thereby significantly enhancing catalytic performance. Notably, the optimized Co4Mn1@NC catalyst exhibits superior E1/2 (0.86 V) and jL (5.96 mA cm−2) compared to Pt/C and other recent reports. Moreover, aqueous ZAB using the Co4Mn1@NC as a cathodic catalyst demonstrates a high peak power density of 163.9 mW cm−2 and maintains stable charging and discharging for over 650 h. Furthermore, FZAB based on the Co4Mn1@NC can steadily operate within the temperature range of -10 °C to 40 °C, demonstrating the potential for practical applications in complex climatic conditions.
2024, 43(7): 100305
doi: 10.1016/j.cjsc.2024.100305
Abstract:
In summary, we have successfully synthesized Pd-TiO2 (PT) catalysts using evaporation induced self-assembly method. The PT catalyst features a high specific surface area and abundant Pd sites, enabling Ullmann cross-coupling reactions at reduced reaction temperatures. Additionally, due to the anchoring of Pd sites within the mesoporous TiO2 framework, PT maintains high stability and catalytic activity even after 8 catalytic cycles, presenting promising prospects for applications in photocatalytic Ullmann coupling and other C-X bond activation reactions.
In summary, we have successfully synthesized Pd-TiO2 (PT) catalysts using evaporation induced self-assembly method. The PT catalyst features a high specific surface area and abundant Pd sites, enabling Ullmann cross-coupling reactions at reduced reaction temperatures. Additionally, due to the anchoring of Pd sites within the mesoporous TiO2 framework, PT maintains high stability and catalytic activity even after 8 catalytic cycles, presenting promising prospects for applications in photocatalytic Ullmann coupling and other C-X bond activation reactions.
2024, 43(7): 100307
doi: 10.1016/j.cjsc.2024.100307
Abstract:
This work demonstrates that the introduction of ionic liquids into COF system can markedly improve the artificial photosynthesis diluted CO2 reduction activity. Furthermore, it provides a novel and promising strategy towards the practical application of solar photocatalysis for directly enriching and converting diluted CO2 to fuels with industrial exhaust gas.
This work demonstrates that the introduction of ionic liquids into COF system can markedly improve the artificial photosynthesis diluted CO2 reduction activity. Furthermore, it provides a novel and promising strategy towards the practical application of solar photocatalysis for directly enriching and converting diluted CO2 to fuels with industrial exhaust gas.
2024, 43(7): 100309
doi: 10.1016/j.cjsc.2023.100309
Abstract:
In summary, we synthesized Co2VO4/Ni and Co2VO4/C with heterogeneous structures and evaluated their performance as anode materials for lithium-ion batteries. Using first-principles DFT calculations, we examined the impact of metallic nickel and non-metallic carbon on the crystal structure, migration barrier, adsorption energy, and electronic properties of Co2VO4/X (X = Ni, C). Our results indicated that Co2VO4/Ni exhibited higher active electron density, leading to enhanced lithium-ion diffusion and superior rate performance. Conversely, Co2VO4/C demonstrated superior adsorption performance and greater stability for lithium ions, resulting in enhanced cycling performance. However, the limited capacity of carbon materials restricted the overall capacity of Co2VO4/C. Therefore, the metal heterostructure exhibited a higher reversible capacity. This study provides fundamental insights into the influence of these heterostructures on the lithium-ion intercalation mechanism, contributing to the design and development of improved anode materials for lithium-ion batteries.
In summary, we synthesized Co2VO4/Ni and Co2VO4/C with heterogeneous structures and evaluated their performance as anode materials for lithium-ion batteries. Using first-principles DFT calculations, we examined the impact of metallic nickel and non-metallic carbon on the crystal structure, migration barrier, adsorption energy, and electronic properties of Co2VO4/X (X = Ni, C). Our results indicated that Co2VO4/Ni exhibited higher active electron density, leading to enhanced lithium-ion diffusion and superior rate performance. Conversely, Co2VO4/C demonstrated superior adsorption performance and greater stability for lithium ions, resulting in enhanced cycling performance. However, the limited capacity of carbon materials restricted the overall capacity of Co2VO4/C. Therefore, the metal heterostructure exhibited a higher reversible capacity. This study provides fundamental insights into the influence of these heterostructures on the lithium-ion intercalation mechanism, contributing to the design and development of improved anode materials for lithium-ion batteries.
2024, 43(7): 100312
doi: 10.1016/j.cjsc.2024.100312
Abstract:
Recently, we introduced a sharp oil/water-free interface to suppress the intrinsic van der Waals packing and direct the 2D self-assembly of POCs. The pre-organized cage layers were then in-situ crosslinked into continuous ultrathin cage nanofilms less than 8 nm in thickness. These networked cage nanofilms exhibit outstanding intrinsic water permeability at the 10−5 cm2 s−1 scale, which is 1–2 orders of magnitude higher than that of traditional polymeric membranes, and comparable to that of other nanofluidic membranes such as MOFs, COFs, and GO membranes. Molecular dynamics simulations revealed 1D water chains within the networked cage, mirroring features found in biological water channels. Moreover, the channel microenvironments, including hydrophilicity and steric hindrance, can be manipulated by a simple anion exchange strategy. The resulting “smart” membrane can even perform graded molecular sieving by ionically associating light-responsive anions to cage windows. As a proof-of-concept, continuous separation of three organic dyes in a single-stage, single-membrane process was exemplified. This achievement holds great promise for advancing the development of bio-inspired ultrathin nanofilms, particularly in the realms of smart separation technologies and nanofluidic devices.
Recently, we introduced a sharp oil/water-free interface to suppress the intrinsic van der Waals packing and direct the 2D self-assembly of POCs. The pre-organized cage layers were then in-situ crosslinked into continuous ultrathin cage nanofilms less than 8 nm in thickness. These networked cage nanofilms exhibit outstanding intrinsic water permeability at the 10−5 cm2 s−1 scale, which is 1–2 orders of magnitude higher than that of traditional polymeric membranes, and comparable to that of other nanofluidic membranes such as MOFs, COFs, and GO membranes. Molecular dynamics simulations revealed 1D water chains within the networked cage, mirroring features found in biological water channels. Moreover, the channel microenvironments, including hydrophilicity and steric hindrance, can be manipulated by a simple anion exchange strategy. The resulting “smart” membrane can even perform graded molecular sieving by ionically associating light-responsive anions to cage windows. As a proof-of-concept, continuous separation of three organic dyes in a single-stage, single-membrane process was exemplified. This achievement holds great promise for advancing the development of bio-inspired ultrathin nanofilms, particularly in the realms of smart separation technologies and nanofluidic devices.
2024, 43(7): 100313
doi: 10.1016/j.cjsc.2024.100313
Abstract:
In summary, several effective strategies have recently been proposed to mitigate the Li/SSE interfacial issue and extend the lifespan of solid-state lithium metal batteries (SSLMBs). These approaches encompass Li or anode scaffolds, Li/SSE interlayers, and SSE design, addressing the fundamental limitation of SSLMBs from various perspectives. The design principles, which involve multiple disciplines and interdisciplinary collaboration, cover aspects ranging from Li-metal nucleation and growth to interfacial contact stability. The success achieved thus far underscores the importance of interface engineering in solid-state systems and the efficacy of synergistic strategies. Future research should focus on SSLMBs capable of operating within a wide temperature range, especially below 0 °C, and at low stacking pressures, to expedite the commercialization of SSLMBs.
In summary, several effective strategies have recently been proposed to mitigate the Li/SSE interfacial issue and extend the lifespan of solid-state lithium metal batteries (SSLMBs). These approaches encompass Li or anode scaffolds, Li/SSE interlayers, and SSE design, addressing the fundamental limitation of SSLMBs from various perspectives. The design principles, which involve multiple disciplines and interdisciplinary collaboration, cover aspects ranging from Li-metal nucleation and growth to interfacial contact stability. The success achieved thus far underscores the importance of interface engineering in solid-state systems and the efficacy of synergistic strategies. Future research should focus on SSLMBs capable of operating within a wide temperature range, especially below 0 °C, and at low stacking pressures, to expedite the commercialization of SSLMBs.
2024, 43(7): 100320
doi: 10.1016/j.cjsc.2024.100320
Abstract:
In summary, the ultrathin multimetallic phosphochalcogenides photocatalysts exhibit excellent photocatalytic activity. Among them, the ultrathin structure can provide more active sites, which is conducive to CO2 adsorption and activation, while the Cu–In dual sites act as tandem catalytic sites to accelerate C=O bond activation and C–C bond coupling. Despite this research has significant scientific value and theoretical significance for achieving carbon emission reduction and resource utilization of CO2 as well as guiding the design and preparation of highly efficient multimetallic 2D layered catalysts, the bottlenecks of large-scale preparation and the considerations on cost, stability and longevity of these 2D catalysts for industrial applications still remain a significant challenge. Furthermore, improving product selectivity and integrating such catalytic processes into existing industrial systems will contribute significantly to sustainable industrialization.
In summary, the ultrathin multimetallic phosphochalcogenides photocatalysts exhibit excellent photocatalytic activity. Among them, the ultrathin structure can provide more active sites, which is conducive to CO2 adsorption and activation, while the Cu–In dual sites act as tandem catalytic sites to accelerate C=O bond activation and C–C bond coupling. Despite this research has significant scientific value and theoretical significance for achieving carbon emission reduction and resource utilization of CO2 as well as guiding the design and preparation of highly efficient multimetallic 2D layered catalysts, the bottlenecks of large-scale preparation and the considerations on cost, stability and longevity of these 2D catalysts for industrial applications still remain a significant challenge. Furthermore, improving product selectivity and integrating such catalytic processes into existing industrial systems will contribute significantly to sustainable industrialization.
2024, 43(7): 100333
doi: 10.1016/j.cjsc.2024.100333
Abstract:
Zero-dimensional (0D) hybrid metal halides are considered as promising light-emitting materials due to their unique broadband emission from self-trapped excitons (STEs). Despite substantial progress in the development of these materials, the photoluminescence quantum yields (PLQY) of hybrid Sb-Br analogs have not fully realized the capabilities of these materials, necessitating a better fundamental understanding of the structure–property relationship. Here, we have achieved a pressure-induced emission in 0D (EATMP)SbBr5 (EATMP = (2-aminoethyl)trimethylphosphanium) and the underlying mechanisms are investigated using in situ experimental characterization and first-principles calculations. The pressure-induced reduction in the overlap between STE states and the ground state results in the suppression of phonon-assisted non-radiative decay. The PL evolution is systematically demonstrated to be controlled by the pressure-regulated exciton–phonon coupling, which can be quantified using Huang–Rhys factor S. Through detailed studies of the S-PLQY relation in a series of 0D hybrid antimony halides, we establish a quantitative structure–property relationship that regulating S value toward 21 leads to the optimized emission. This work not only sheds light on pressure-induced emission in 0D hybrid metal halides but also provides valuable insights into the design principles for enhancing the PLQY in this class of materials.
Zero-dimensional (0D) hybrid metal halides are considered as promising light-emitting materials due to their unique broadband emission from self-trapped excitons (STEs). Despite substantial progress in the development of these materials, the photoluminescence quantum yields (PLQY) of hybrid Sb-Br analogs have not fully realized the capabilities of these materials, necessitating a better fundamental understanding of the structure–property relationship. Here, we have achieved a pressure-induced emission in 0D (EATMP)SbBr5 (EATMP = (2-aminoethyl)trimethylphosphanium) and the underlying mechanisms are investigated using in situ experimental characterization and first-principles calculations. The pressure-induced reduction in the overlap between STE states and the ground state results in the suppression of phonon-assisted non-radiative decay. The PL evolution is systematically demonstrated to be controlled by the pressure-regulated exciton–phonon coupling, which can be quantified using Huang–Rhys factor S. Through detailed studies of the S-PLQY relation in a series of 0D hybrid antimony halides, we establish a quantitative structure–property relationship that regulating S value toward 21 leads to the optimized emission. This work not only sheds light on pressure-induced emission in 0D hybrid metal halides but also provides valuable insights into the design principles for enhancing the PLQY in this class of materials.
2024, 43(7): 100337
doi: 10.1016/j.cjsc.2024.100337
Abstract:
Lithium-sulfur (Li-S) batteries are one of promising energy storage systems. However, rapid capacity attenuation caused by shuttle effect of soluble polysulfides is one of major challenges in practical application. The separator modification is one complementary countermeasure besides the construction of sulfur host materials in the cathode. MXene is one type of outstanding candidates for promoting redox kinetics of sulfur species. Herein, recent advances of MXene-based materials as separator modifiers are summarized. The importance of high conductivity and catalytic effects in promoting catalytic conversion of polysulfides and suppressing shuttle effect of polysulfides has been highlighted. The superiority of MXene for improving reversible capacity and cycling stability has been demonstrated. New strategies for the design of MXene-based separator modifiers are proposed to improve energy density and lifetime. The review provides new perspectives for future development of high-performance Li-S batteries.
Lithium-sulfur (Li-S) batteries are one of promising energy storage systems. However, rapid capacity attenuation caused by shuttle effect of soluble polysulfides is one of major challenges in practical application. The separator modification is one complementary countermeasure besides the construction of sulfur host materials in the cathode. MXene is one type of outstanding candidates for promoting redox kinetics of sulfur species. Herein, recent advances of MXene-based materials as separator modifiers are summarized. The importance of high conductivity and catalytic effects in promoting catalytic conversion of polysulfides and suppressing shuttle effect of polysulfides has been highlighted. The superiority of MXene for improving reversible capacity and cycling stability has been demonstrated. New strategies for the design of MXene-based separator modifiers are proposed to improve energy density and lifetime. The review provides new perspectives for future development of high-performance Li-S batteries.
