Li-I_(2) batteries have attracted much interest due to their high capacity,exceptional rate performance,and low cost.Even so,the problems of unstable Li anode/electrolyte interface and severe polyiodide shuttle in Li-...Li-I_(2) batteries have attracted much interest due to their high capacity,exceptional rate performance,and low cost.Even so,the problems of unstable Li anode/electrolyte interface and severe polyiodide shuttle in Li-I_(2) batteries need to be tackled.Herein,the interfacial reactions on the Li anode and I_(2) cathode have been effectively optimized by employing a well-designed gel polymer electrolyte strengthened by cross-linked Ti-O/Si-O(GPETS).The interpenetrating network-reinforced GPETS with high ionic conductivity(1.88×10^(-3)S cm^(-1)at 25℃)and high mechanical strength endows uniform Li deposition/stripping over 1800 h(at 1.0mA cm^(-2),with a plating capacity of 3.0mAh cm^(-2)).Moreover,the GPETS abundant in surface hydroxyls is capable of capturing soluble polyiodides at the interface and accelerating their conversion kinetics,thus synergistically mitigating the shuttle effect.Benefiting from these properties,the use of GPETS results in a high capacity of 207 mAh g^(-1)(1 C)and an ultra-low fading rate of 0.013%per cycle over 2000 cycles(5 C).The current study provides new insights into advanced electrolytes for Li-I_(2) batteries.展开更多
锌碘电池由于具有比容量高(211 mAh·g^(-1))、氧化还原电势理想(~0.54 V vs.H^(+)/H)、安全性高、锌和碘自然界储量丰富及价格低廉等特点而被广泛研究。然而,锌碘电池也存在一些缺陷,如碘及多碘离子导电性低、中间产物易溶于电解...锌碘电池由于具有比容量高(211 mAh·g^(-1))、氧化还原电势理想(~0.54 V vs.H^(+)/H)、安全性高、锌和碘自然界储量丰富及价格低廉等特点而被广泛研究。然而,锌碘电池也存在一些缺陷,如碘及多碘离子导电性低、中间产物易溶于电解液、多碘离子转化反应速率缓慢及易发生穿梭效应等。目前,构筑碘正极载体材料是解决上述问题的常用有效策略。本文从设计理念、构筑方法、工作原理、电化学性能等方面综述近年锌碘电池中碘正极载体材料的研究进展,探究载体材料的组成、结构及形貌与锌碘电池电化学性能间的内在构效关系,揭示载体材料的物理限域与化学吸附/催化对电化学性能的协同增效机制。最后,结合碘载体材料当前存在的问题指明其未来可能的发展方向,如探索反应机理、催化中间产物转化、组装测试软包电池等。展开更多
The arylthio-substituted tetrathiafuivalenes （Ar-S-TTFs） are electron donors having three reversible states, neutral, cation radical, and dica- tion. The charge-transfer （CT） between Ar-S-TTFs （TTF1--TTF3） and i...The arylthio-substituted tetrathiafuivalenes （Ar-S-TTFs） are electron donors having three reversible states, neutral, cation radical, and dica- tion. The charge-transfer （CT） between Ar-S-TTFs （TTF1--TTF3） and iodine （12） is reported herein. TTF1--TTF3 show the CT with 12 in the CH2C12 solution, but they are not completely converted into cation radical state. In CT complexes of TTF1--TTF3 with 12, the charged states of Ar-S-TTFs are distinct from those in solution. TTF1 is at cation radical state, and TTF2--TTF3 are oxidized to dication. The iodine components in complexes show various structures including 1-D chain of V-shaped （Is）-, and 2-D and 3-D iodine networks composed of 12 and （13）^- .展开更多
Aqueous zinc-iodine(Zn-I_(2))batteries are promising candidates for low-cost grid-scale energy storage systems.However,the long-term stability and energy density of the Zn-I_(2)batteries are largely hindered by the la...Aqueous zinc-iodine(Zn-I_(2))batteries are promising candidates for low-cost grid-scale energy storage systems.However,the long-term stability and energy density of the Zn-I_(2)batteries are largely hindered by the lack of feasible and scalable methods that coherently suppress polyiodide shuttling and Zn dendrites growth,especially at high current densities.Herein,a flexible,thin and lightweight poly(3,4-ethy lenedioxythiophene):polystyrene sulfonate(PEDOT:PSS)nanopaper is designed as an“anion-cation regulation”synergistic interlayer to tackle the above issues.The PEDOT:PSS interlayer exhibits a 3D nanofibrous network with uniformly distributed mesopores,abundant polar groups and intrinsic conductivity,which renders an even Zn^(2+)flux at Zn anode and facilitates homogeneous current distributions at I_(2)cathode.Meanwhile,such interlayer can act as physiochemical shield to enhance the utilization of I_(2)cathode via the coulombic repulsion and chemical adsorption effect against polyiodide shuttling.Thus,long-term dendrite-free Zn plating/stripping is achieved at simultaneous high current density and high areal capacity(550 h at 10 m A cm^(-2)/5 m Ah cm^(-2)).Zn-I_(2)batteries harvest a high capacity(230 m Ah g^(-1)at 0.1 A g^(-1))and an ultralong lifespan(>20000 cycles)even at 10 A g^(-1).This work demonstrates the potential use of the multifunctional interlayers for Zn-I_(2)battery configuration innovation by synergistic regulation of cations and anions at the electrodes/electrolyte interface.展开更多
Bottom-up construction of highly complex architecture from simple components remains one of the long-standing challenges in chemistry.Herein two supramolecular isomers based on large trigonal prismatic Pd_(3)L^(1)_(6)...Bottom-up construction of highly complex architecture from simple components remains one of the long-standing challenges in chemistry.Herein two supramolecular isomers based on large trigonal prismatic Pd_(3)L^(1)_(6)building block are reported.Significantly,they can be controllably obtained by adjusting the solute concentration during crystal growth.Specifically,the square shape crystals,α-[Pd_(3)L^(1)_(6)](PF_(6))_(12)in the cubic system with I143 m space group,can be isolated from a high-concentration solution of Pd_(3)L^(1)_(6).Interestingly,a mesoporous cage assembled from eight Pd_(3)L^(1)_(6)units with a diameter of 24Åis observed in the crystal structure.For the low-concentration solution of Pd_(3)L^(1)_(6),the rectangular shape crystalsβ-[Pd_(3)L^(1)_(6)](PF_(6))_(12)are obtained,which crystallize in the hexagonal system with P 63/m space group,and display two-dimension packing pattern and one-dimension mesoporous channels(diameter ca.22Å)along the c axis.Moreover,the two supramolecular isomers were used as nanoporous reactors to induce the specific formation of polyiodides with different compositions and shapes as evidenced from single crystal X-ray diffraction studies.These findings provide a reference in targeting functional crystalline mesoporous supramolecular materials from a single complex building unit.展开更多
The potential reactions between natural polysaccharides and iodine and their products have been explored for a long time. Due to the complex factors that can in？uence these reactions, a clear-cut mechanism ...The potential reactions between natural polysaccharides and iodine and their products have been explored for a long time. Due to the complex factors that can in？uence these reactions, a clear-cut mechanism has not yet been developed. Starch-iodine complexes, especially the amylose-iodine complex, are the most investigated of the polysaccharide-iodine reactions, and the study of this reaction can be used as a basis for the investigation of other polysaccharide-iodine reactions. In this paper, significant aspects of the reaction were introduced, including the influence of the polysaccharide structure on the properties of the resulting complexes, the relationship between the concentration of CaCl2 and formation of the final products, as well as the form of the polyiodides in these complexes. The interior structure and the surface morphology of the complexes were discussed, along with the progress in research related to this reaction.展开更多
The dielectric properties of tetramethylammonium monoiodide and pentaiodide were investigated in broad temperature range(-150℃till+50℃).It was demonstrated that the structural organization of the polyiodide chain co...The dielectric properties of tetramethylammonium monoiodide and pentaiodide were investigated in broad temperature range(-150℃till+50℃).It was demonstrated that the structural organization of the polyiodide chain containing I...I charge-assisted halogen bonds influenced the parameters and the mechanism of electric conductivity of considered compound.The impedance spectroscopic measurements revealed that the direct current electric conductivity of pentaiodide salt is around four orders of magnitude higher than that of corresponding monoiodide.Moreover,pentaiodide demonstrates the hopping mechanism of conductivity.展开更多
基金Natural Science Foundation of the Jiangsu Higher Education Institutions of China,Grant/Award Number:22KJB150004Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20200047+1 种基金National Natural Science Foundation of China,Grant/Award Numbers:22209062,22222902Youth Talent Promotion Project of Jiangsu Association for Science and Technology of China,Grant/Award Number:JSTJ-2022-023。
文摘Li-I_(2) batteries have attracted much interest due to their high capacity,exceptional rate performance,and low cost.Even so,the problems of unstable Li anode/electrolyte interface and severe polyiodide shuttle in Li-I_(2) batteries need to be tackled.Herein,the interfacial reactions on the Li anode and I_(2) cathode have been effectively optimized by employing a well-designed gel polymer electrolyte strengthened by cross-linked Ti-O/Si-O(GPETS).The interpenetrating network-reinforced GPETS with high ionic conductivity(1.88×10^(-3)S cm^(-1)at 25℃)and high mechanical strength endows uniform Li deposition/stripping over 1800 h(at 1.0mA cm^(-2),with a plating capacity of 3.0mAh cm^(-2)).Moreover,the GPETS abundant in surface hydroxyls is capable of capturing soluble polyiodides at the interface and accelerating their conversion kinetics,thus synergistically mitigating the shuttle effect.Benefiting from these properties,the use of GPETS results in a high capacity of 207 mAh g^(-1)(1 C)and an ultra-low fading rate of 0.013%per cycle over 2000 cycles(5 C).The current study provides new insights into advanced electrolytes for Li-I_(2) batteries.
文摘锌碘电池由于具有比容量高(211 mAh·g^(-1))、氧化还原电势理想(~0.54 V vs.H^(+)/H)、安全性高、锌和碘自然界储量丰富及价格低廉等特点而被广泛研究。然而,锌碘电池也存在一些缺陷,如碘及多碘离子导电性低、中间产物易溶于电解液、多碘离子转化反应速率缓慢及易发生穿梭效应等。目前,构筑碘正极载体材料是解决上述问题的常用有效策略。本文从设计理念、构筑方法、工作原理、电化学性能等方面综述近年锌碘电池中碘正极载体材料的研究进展,探究载体材料的组成、结构及形貌与锌碘电池电化学性能间的内在构效关系,揭示载体材料的物理限域与化学吸附/催化对电化学性能的协同增效机制。最后,结合碘载体材料当前存在的问题指明其未来可能的发展方向,如探索反应机理、催化中间产物转化、组装测试软包电池等。
文摘The arylthio-substituted tetrathiafuivalenes （Ar-S-TTFs） are electron donors having three reversible states, neutral, cation radical, and dica- tion. The charge-transfer （CT） between Ar-S-TTFs （TTF1--TTF3） and iodine （12） is reported herein. TTF1--TTF3 show the CT with 12 in the CH2C12 solution, but they are not completely converted into cation radical state. In CT complexes of TTF1--TTF3 with 12, the charged states of Ar-S-TTFs are distinct from those in solution. TTF1 is at cation radical state, and TTF2--TTF3 are oxidized to dication. The iodine components in complexes show various structures including 1-D chain of V-shaped （Is）-, and 2-D and 3-D iodine networks composed of 12 and （13）^- .
基金supported by the Outstanding Youth Scientist Foundation of Hunan Province(Grant No.2021JJ10017)the National Natural Science Foundation of China(Grant No.52173229)。
文摘Aqueous zinc-iodine(Zn-I_(2))batteries are promising candidates for low-cost grid-scale energy storage systems.However,the long-term stability and energy density of the Zn-I_(2)batteries are largely hindered by the lack of feasible and scalable methods that coherently suppress polyiodide shuttling and Zn dendrites growth,especially at high current densities.Herein,a flexible,thin and lightweight poly(3,4-ethy lenedioxythiophene):polystyrene sulfonate(PEDOT:PSS)nanopaper is designed as an“anion-cation regulation”synergistic interlayer to tackle the above issues.The PEDOT:PSS interlayer exhibits a 3D nanofibrous network with uniformly distributed mesopores,abundant polar groups and intrinsic conductivity,which renders an even Zn^(2+)flux at Zn anode and facilitates homogeneous current distributions at I_(2)cathode.Meanwhile,such interlayer can act as physiochemical shield to enhance the utilization of I_(2)cathode via the coulombic repulsion and chemical adsorption effect against polyiodide shuttling.Thus,long-term dendrite-free Zn plating/stripping is achieved at simultaneous high current density and high areal capacity(550 h at 10 m A cm^(-2)/5 m Ah cm^(-2)).Zn-I_(2)batteries harvest a high capacity(230 m Ah g^(-1)at 0.1 A g^(-1))and an ultralong lifespan(>20000 cycles)even at 10 A g^(-1).This work demonstrates the potential use of the multifunctional interlayers for Zn-I_(2)battery configuration innovation by synergistic regulation of cations and anions at the electrodes/electrolyte interface.
基金the National Natural Science Foundation for Distinguished Young Scholars of China(No.22025107)the National Youth Top-notch Talent Support Program of China,the Key Science and Technology Innovation Team of Shaanxi Province(Nos.2019TD-007 and 2019JLZ-02)the FM&EM International Joint Laboratory of Northwest University.
文摘Bottom-up construction of highly complex architecture from simple components remains one of the long-standing challenges in chemistry.Herein two supramolecular isomers based on large trigonal prismatic Pd_(3)L^(1)_(6)building block are reported.Significantly,they can be controllably obtained by adjusting the solute concentration during crystal growth.Specifically,the square shape crystals,α-[Pd_(3)L^(1)_(6)](PF_(6))_(12)in the cubic system with I143 m space group,can be isolated from a high-concentration solution of Pd_(3)L^(1)_(6).Interestingly,a mesoporous cage assembled from eight Pd_(3)L^(1)_(6)units with a diameter of 24Åis observed in the crystal structure.For the low-concentration solution of Pd_(3)L^(1)_(6),the rectangular shape crystalsβ-[Pd_(3)L^(1)_(6)](PF_(6))_(12)are obtained,which crystallize in the hexagonal system with P 63/m space group,and display two-dimension packing pattern and one-dimension mesoporous channels(diameter ca.22Å)along the c axis.Moreover,the two supramolecular isomers were used as nanoporous reactors to induce the specific formation of polyiodides with different compositions and shapes as evidenced from single crystal X-ray diffraction studies.These findings provide a reference in targeting functional crystalline mesoporous supramolecular materials from a single complex building unit.
基金supported by the Fundamental Research Funds for the Central Universities(JC2015-03)National Natural Science Foundation of China(31470417)+1 种基金Beijing Municipal Natural Science Foundation(6182031)Author of National Excellent Doctoral Dissertations of China(201458)
文摘The potential reactions between natural polysaccharides and iodine and their products have been explored for a long time. Due to the complex factors that can in？uence these reactions, a clear-cut mechanism has not yet been developed. Starch-iodine complexes, especially the amylose-iodine complex, are the most investigated of the polysaccharide-iodine reactions, and the study of this reaction can be used as a basis for the investigation of other polysaccharide-iodine reactions. In this paper, significant aspects of the reaction were introduced, including the influence of the polysaccharide structure on the properties of the resulting complexes, the relationship between the concentration of CaCl2 and formation of the final products, as well as the form of the polyiodides in these complexes. The interior structure and the surface morphology of the complexes were discussed, along with the progress in research related to this reaction.
基金The Government of Russian Federation decree No.211,agreement No.02.A03.21.0011the Ministry of Education and Science of the Russian Federation.4.1157.2017/4.6.
文摘The dielectric properties of tetramethylammonium monoiodide and pentaiodide were investigated in broad temperature range(-150℃till+50℃).It was demonstrated that the structural organization of the polyiodide chain containing I...I charge-assisted halogen bonds influenced the parameters and the mechanism of electric conductivity of considered compound.The impedance spectroscopic measurements revealed that the direct current electric conductivity of pentaiodide salt is around four orders of magnitude higher than that of corresponding monoiodide.Moreover,pentaiodide demonstrates the hopping mechanism of conductivity.
