Metal phosphosulfides(MPS_(x)),especially BiPS_(4),have emerged as promising anode candidates for sodiumion batteries,distinguished by distinctive multinary redox chemistry,open tunnel-type structure,and high theoreti...Metal phosphosulfides(MPS_(x)),especially BiPS_(4),have emerged as promising anode candidates for sodiumion batteries,distinguished by distinctive multinary redox chemistry,open tunnel-type structure,and high theoretical capacity(>1000 m Ah g^(-1)).However,their practical implementation is fundamentally limited by polysulfide dissolution/shuttling and structural instability during prolonged cycling.Herein,we develop a groundbreaking two-stage metal-organic framework(MOF)-engineered compositing strategy through which Bi-MOF-derived BiPS_(4)/C pillars are robustly armored with conductive Ni-HHTP(HHTP=2,3,6,7,10,11-hexahydroxytriphenylene)nanorods.Density functional theory calculations reveal that this design achieves dual functionality:increased carrier density for enhanced charge transport dynamics and effective polysulfide adsorption to inhibit dissolution.The fabricated BiPS_(4)/C@Ni-HHTP composite delivers remarkable electrochemical properties,including high initial charge/discharge specific capacities of 1063.6/1181.3 mAh g^(-1)at 0.1 A g^(-1)and outstanding long-term stability with 99.2% capacity retention after 2000 cycles at 2 A g^(-1).Such superb performance stems from the perfect synergy of the inherent high-capacity redox behavior of BiPS_(4),the buffering effect of MOF-derived carbon,and the conductivity,adsorption sites and mechanical resilience of Ni-HHTP.This work establishes a new design paradigm for MPS_(x)materials,demonstrating how to simultaneously overcome conductivity limitations and shuttle effects in conversion-type electrodes.展开更多
Metal phosphosulfides have been recognized as advanced anode materials for sodium/potassium ion batteries due to their high theoretical capacities and the incorporation of the advantage of metal sulfides and phosphate...Metal phosphosulfides have been recognized as advanced anode materials for sodium/potassium ion batteries due to their high theoretical capacities and the incorporation of the advantage of metal sulfides and phosphates. However, they also suffer from the shortcomings of frustrating cycling stability due to the large volume expansion and unsatisfactory electrical conductivity. Herein, hexapod cobalt phosphosulfide nanodots based nanorods encapsulating into N, P, and S hetero-atoms tri-doped carbon framework(Co P/CoS_(2) @NPSC) have been triumphantly designed and synthesized. The six nanorods constructed hexapod framework and multi-atom doped carbon matrix not only provides more active sites, but also contribute to maintain the structure integrity from avoiding the agglomeration of internal Co P and CoS_(2) nanodots. The synergistic effect between Co P and CoS_(2) components, as well as the Co P/CoS_(2) and the NPSC carbon framework can improve the electrochemical conductivity. Besides, the kinetics analysis demonstrated that N/P/S tri-doping could greatly increase the interlayer distance and introduce enough active sites, which effectively facilitate the transport, adsorption, insertion and diffusion of Na^(+)and K^(+).Co P/CoS_(2) @NPSC demonstrated excellent electrochemical properties and battery performances including excellent cycle stability with 404.63 m Ah/g at 5.0 A/g around 700 cycles for SIBs and 115.33 m Ah/g at5.0 A/g around 800 cycles for PIBs. This presented strategy establishes a novel and adaptable method for the integration of doped carbon with metal phosphosulfide and guides a new research approach and direction for secondary batteries electrode materials.展开更多
Herein,phosphorus-mediated sulfur nanoparticles encapsulated in reduced graphene oxide nanosheets(P-SrGO-T)were successfully synthesized as the cathode for sodium ion battery by a ball milling and the following therma...Herein,phosphorus-mediated sulfur nanoparticles encapsulated in reduced graphene oxide nanosheets(P-SrGO-T)were successfully synthesized as the cathode for sodium ion battery by a ball milling and the following thermal treatment.A series of covalent bonds,such as P–S,C–S–C,C–O–P and C–S–P,are formed in this process,which are in favor of fixing the sulfur and suppressing the parasitic shuttle effect of polysulfide.Benefiting from the graphene sheets and these covalent bonds,a high reversible capacity of 637.4 m Ah/g was achieved in P-SrGO-T after 100 cycles at the current density of 0.2 A/g.In addition,P-SrGO-T also delivers a high-rate capacity(330.7 m Ah/g at 5 A/g)attributing to low charge transfer resistance and faster ion diffusion kinetic.This work pushes the progress forward in developing phosphosulfide cathode for sodium ion batteries.展开更多
In this article,P-NiS_(2)/Ni_(x)P electrocatalysts were synthesized by dealloying the Ni-Al precursor followed by phosphosulfide treatment.We found that the hybrid structure of P-NiS_(2)/Ni_(x)P provides rich active s...In this article,P-NiS_(2)/Ni_(x)P electrocatalysts were synthesized by dealloying the Ni-Al precursor followed by phosphosulfide treatment.We found that the hybrid structure of P-NiS_(2)/Ni_(x)P provides rich active sites for the surface hydrogen evolution reaction (HER),and the doping of P enhances the electronic conductivity of electrodes.In particular,the obtained electrode shows a low overpotential of 196 mV at 10 mA cm^(-2)and a small Tafel slope of only 110 mV dec^(-1)in the HER.Meanwhile,longterm constant current electrolysis test experiments indicate that P-NiS_(2)/Ni_(x)P has good service stability.This research will help to open a new window on the design and fabrication of HER electrocatalysts.展开更多
Lithium-sulfur (Li-S) battery as one of the most attractive candidates for energy storage systems has attracted extensive interests.Herein,for the first time,hierarchical flower-like cobalt phosphosulfide architecture...Lithium-sulfur (Li-S) battery as one of the most attractive candidates for energy storage systems has attracted extensive interests.Herein,for the first time,hierarchical flower-like cobalt phosphosulfide architectures (defined as "CoSP") derived from Prussian blue analogue (PBA) was fabricated through the conversion of Co-based PBA in PxSy atmosphere.The as-prepared polar CoSP could effectively trap polysulfides through the formation of strong chemical bonds.In addition,after the combination of CoSP with high conductive rGO,the obtained CoSP/rGO as sulfur host material exhibits ultralow capacity decay rate of 0.046% per cycle over 900 cycles at a current density of 1 C.The excellent performance could be attributed to the shortened lithium diffusion pathways,fastened electron transport ability during polysulfide conversion,and increased much more anchor active sites to polysulfides,which is expected to be a promising material for Li-S batteries.It is believed that the as-prepared CoSP/rGO architectures will shed light on the development of novel promising materials for Li-S batteries with high cycle stability.展开更多
基金Financial supports from the National Natural Science Foundation of China(Grant Number:22265018)the Key Project of Natural Science Foundation of Jiangxi Province(Grant Number:20232ACB204010)+1 种基金the Graduate Innovative Special Fund Projects of Jiangxi Province(Grant Number:YC2024-B034)the Jiangxi Province Key Laboratory of Lithiumion Battery Materials and Application(Grant Number:2024SSY05202)are gratefully acknowledged。
文摘Metal phosphosulfides(MPS_(x)),especially BiPS_(4),have emerged as promising anode candidates for sodiumion batteries,distinguished by distinctive multinary redox chemistry,open tunnel-type structure,and high theoretical capacity(>1000 m Ah g^(-1)).However,their practical implementation is fundamentally limited by polysulfide dissolution/shuttling and structural instability during prolonged cycling.Herein,we develop a groundbreaking two-stage metal-organic framework(MOF)-engineered compositing strategy through which Bi-MOF-derived BiPS_(4)/C pillars are robustly armored with conductive Ni-HHTP(HHTP=2,3,6,7,10,11-hexahydroxytriphenylene)nanorods.Density functional theory calculations reveal that this design achieves dual functionality:increased carrier density for enhanced charge transport dynamics and effective polysulfide adsorption to inhibit dissolution.The fabricated BiPS_(4)/C@Ni-HHTP composite delivers remarkable electrochemical properties,including high initial charge/discharge specific capacities of 1063.6/1181.3 mAh g^(-1)at 0.1 A g^(-1)and outstanding long-term stability with 99.2% capacity retention after 2000 cycles at 2 A g^(-1).Such superb performance stems from the perfect synergy of the inherent high-capacity redox behavior of BiPS_(4),the buffering effect of MOF-derived carbon,and the conductivity,adsorption sites and mechanical resilience of Ni-HHTP.This work establishes a new design paradigm for MPS_(x)materials,demonstrating how to simultaneously overcome conductivity limitations and shuttle effects in conversion-type electrodes.
基金supported by the National Natural Science Foundation of China (Nos. 52472194, 52101243)Natural Science Foundation of Guangdong Province, China (No. 2023A1515012619)the Science and Technology Planning Project of Guangzhou (No. 202201010565)。
文摘Metal phosphosulfides have been recognized as advanced anode materials for sodium/potassium ion batteries due to their high theoretical capacities and the incorporation of the advantage of metal sulfides and phosphates. However, they also suffer from the shortcomings of frustrating cycling stability due to the large volume expansion and unsatisfactory electrical conductivity. Herein, hexapod cobalt phosphosulfide nanodots based nanorods encapsulating into N, P, and S hetero-atoms tri-doped carbon framework(Co P/CoS_(2) @NPSC) have been triumphantly designed and synthesized. The six nanorods constructed hexapod framework and multi-atom doped carbon matrix not only provides more active sites, but also contribute to maintain the structure integrity from avoiding the agglomeration of internal Co P and CoS_(2) nanodots. The synergistic effect between Co P and CoS_(2) components, as well as the Co P/CoS_(2) and the NPSC carbon framework can improve the electrochemical conductivity. Besides, the kinetics analysis demonstrated that N/P/S tri-doping could greatly increase the interlayer distance and introduce enough active sites, which effectively facilitate the transport, adsorption, insertion and diffusion of Na^(+)and K^(+).Co P/CoS_(2) @NPSC demonstrated excellent electrochemical properties and battery performances including excellent cycle stability with 404.63 m Ah/g at 5.0 A/g around 700 cycles for SIBs and 115.33 m Ah/g at5.0 A/g around 800 cycles for PIBs. This presented strategy establishes a novel and adaptable method for the integration of doped carbon with metal phosphosulfide and guides a new research approach and direction for secondary batteries electrode materials.
基金sponsored by National Natural Science Foundation of China(Nos.21701017,52002052)。
文摘Herein,phosphorus-mediated sulfur nanoparticles encapsulated in reduced graphene oxide nanosheets(P-SrGO-T)were successfully synthesized as the cathode for sodium ion battery by a ball milling and the following thermal treatment.A series of covalent bonds,such as P–S,C–S–C,C–O–P and C–S–P,are formed in this process,which are in favor of fixing the sulfur and suppressing the parasitic shuttle effect of polysulfide.Benefiting from the graphene sheets and these covalent bonds,a high reversible capacity of 637.4 m Ah/g was achieved in P-SrGO-T after 100 cycles at the current density of 0.2 A/g.In addition,P-SrGO-T also delivers a high-rate capacity(330.7 m Ah/g at 5 A/g)attributing to low charge transfer resistance and faster ion diffusion kinetic.This work pushes the progress forward in developing phosphosulfide cathode for sodium ion batteries.
基金supported by the National Natural Science Foundation of China (Grant No. 51661018)。
文摘In this article,P-NiS_(2)/Ni_(x)P electrocatalysts were synthesized by dealloying the Ni-Al precursor followed by phosphosulfide treatment.We found that the hybrid structure of P-NiS_(2)/Ni_(x)P provides rich active sites for the surface hydrogen evolution reaction (HER),and the doping of P enhances the electronic conductivity of electrodes.In particular,the obtained electrode shows a low overpotential of 196 mV at 10 mA cm^(-2)and a small Tafel slope of only 110 mV dec^(-1)in the HER.Meanwhile,longterm constant current electrolysis test experiments indicate that P-NiS_(2)/Ni_(x)P has good service stability.This research will help to open a new window on the design and fabrication of HER electrocatalysts.
基金the Academy of Sciences large apparatus United Fund of China (No.U182345)National Natural Science Foundation of China (No.21471091)+3 种基金Guangdong Province Science and Technology Plan Project for Public Welfare Fund and Ability Construction Project (No.2017A010104003)Shenzhen Science and Technology Research and Development Funds (No.JCYJ20170818104441521)the Fundamental Research Funds of Shandong University (No. 2018JC022)the Taishan Scholar Project of Shandong Province (No.ts201511004).
文摘Lithium-sulfur (Li-S) battery as one of the most attractive candidates for energy storage systems has attracted extensive interests.Herein,for the first time,hierarchical flower-like cobalt phosphosulfide architectures (defined as "CoSP") derived from Prussian blue analogue (PBA) was fabricated through the conversion of Co-based PBA in PxSy atmosphere.The as-prepared polar CoSP could effectively trap polysulfides through the formation of strong chemical bonds.In addition,after the combination of CoSP with high conductive rGO,the obtained CoSP/rGO as sulfur host material exhibits ultralow capacity decay rate of 0.046% per cycle over 900 cycles at a current density of 1 C.The excellent performance could be attributed to the shortened lithium diffusion pathways,fastened electron transport ability during polysulfide conversion,and increased much more anchor active sites to polysulfides,which is expected to be a promising material for Li-S batteries.It is believed that the as-prepared CoSP/rGO architectures will shed light on the development of novel promising materials for Li-S batteries with high cycle stability.
