Low-temperature heat capacities of the solid compound Zn（C4H7O5）2（s） were measured in a temperature range from 78 to 374 K, with an automated adiabatic calorimeter. A solid-to-solid phase transition occurred in th...Low-temperature heat capacities of the solid compound Zn（C4H7O5）2（s） were measured in a temperature range from 78 to 374 K, with an automated adiabatic calorimeter. A solid-to-solid phase transition occurred in the temperature range of 295？322 K. The peak temperature, the enthalpy, and entropy of the phase transition were determined to be （316.269±1.039） K, （11.194±0.335） kJ？mol-1, and （35.391±0.654） J？K-1？mol-1, respectively. The experimental values of the molar heat capacities in the temperature regions of 78？295 K and 322？374 K were fitted to two polynomial equations of heat capacities（Cp,m） with reduced temperatures（X） and [X = f（T）], with the help of the least squares method, respectively. The smoothed molar heat capacities and thermodynamic functions of the compound, relative to that of the standard reference temperature 293.15 K, were calculated on the basis of the fitted polynomials and tabulated with an interval of 5 K. In addition, the possible mechanism of thermal decomposition of the compound was inferred by the result of TG-DTG analysis.展开更多
Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinet...Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinetics of divalent charge Zn^(2+)in the cathode materials caused by the strong electrostatic interaction and their unsatisfactory cycle life hinder the development of ZIBs.Herein,organic cations and Zn^(2+)ions co-pre-inserted vanadium oxide([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O are reported as the cathode for ultra-stable aqueous ZIBs,in which the weaker electrostatic interactions between Zn^(2+)and organic ion-pinned vanadium oxide can induce the high reversibility of Zn^(2+)insertion and extraction,thereby improving the cycle life.It is demonstrated that([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O cathodes deliver a discharge capacity of 181 mA h g^(-1)at8 A g^(-1)and ultra-long life span(99.5%capacity retention after 2000 cycles).A reversible Zn^(2+)/H^(+)ions(de)intercalation storage process and pseudocapacitive charge storage are characterized.The weaker interactions between organic ion and Zn^(2+)open a novel avenue for the design of highly reversible cathode materials with long-term cycling stability.展开更多
Zn(CF_(3)SO_(3))_(2)as an electrolyte has been widely used to improve the electrochemical performance for ZIBs due to that the bulky CF_(3)SO_(3)-can reduce the solvation effect of Zn^(2+)and promote the ionic diffusi...Zn(CF_(3)SO_(3))_(2)as an electrolyte has been widely used to improve the electrochemical performance for ZIBs due to that the bulky CF_(3)SO_(3)-can reduce the solvation effect of Zn^(2+)and promote the ionic diffusion.Herein,we found that Zn(CF_(3)SO_(3))_(2)electrolyte can induce different electrochemical mechanisms from ZnSO_(4)electrolyte.Compared to the ZnSO^(4)electrolyte,the HNaV_(6)O_(16)·4H2_(O)electrode with Zn(CF_(3)SO_(3))_(2)electrolyte exhibits a high capacity of 444 mAh·g^(-1)at 500 mA·g^(-1)with a capacity retention of 92.3%after 80 cycles.Even,at a high rate of 5 Ag-1,the HNaV_(6)O_(16)·4H_(2)O electrode delivers an initial discharge capacity of 328 mAh·g^(-1)with a capacity retention of 93.7%after 1000 cycles.Differing from the mechanism with ZnSO4 electrolyte,the excellent cycle stability of HNaV_(6)O_(16)·4H_(2)Oelectrode can be attributed to the in-situ phase transformation to ZnxV_(2)O_(5)·nH_(2)O based on the co-intercalation of Zn^(2+)/H^(+).展开更多
基金National Natural Science Foundation of China(12175254,U1832119)National Key R&D Program of China(2021YFE0104800)+2 种基金International Partnership Program of Chinese Academy of Sciences(121631KYSB20200039)International Cooperation Project of Shanghai Science and Technology Commission(20520750200)National Centre for Research and Development(WPC2/1/SCAPOL/2021)。
基金the National Natural Science Foundation of China(No.20673050).
文摘Low-temperature heat capacities of the solid compound Zn（C4H7O5）2（s） were measured in a temperature range from 78 to 374 K, with an automated adiabatic calorimeter. A solid-to-solid phase transition occurred in the temperature range of 295？322 K. The peak temperature, the enthalpy, and entropy of the phase transition were determined to be （316.269±1.039） K, （11.194±0.335） kJ？mol-1, and （35.391±0.654） J？K-1？mol-1, respectively. The experimental values of the molar heat capacities in the temperature regions of 78？295 K and 322？374 K were fitted to two polynomial equations of heat capacities（Cp,m） with reduced temperatures（X） and [X = f（T）], with the help of the least squares method, respectively. The smoothed molar heat capacities and thermodynamic functions of the compound, relative to that of the standard reference temperature 293.15 K, were calculated on the basis of the fitted polynomials and tabulated with an interval of 5 K. In addition, the possible mechanism of thermal decomposition of the compound was inferred by the result of TG-DTG analysis.
基金supported by the funding from the National Natural Science Foundation of China(grant nos.51902187,52072224,and 51732007)the Natural Science Foundation of Shandong Province(ZR2018BEM010)+3 种基金the Science Fund for Distinguished Young Scholars of Shandong Province(ZR2019JQ16)the Fundamental Research Funds of Shandong UniversityYoung Elite Scientist Sponsorship Program by CAST(YESS)the support from Collaborative Innovation Center of Technology and Equipment for Biological Diagnosis and Therapy in Universities of Shandong
文摘Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinetics of divalent charge Zn^(2+)in the cathode materials caused by the strong electrostatic interaction and their unsatisfactory cycle life hinder the development of ZIBs.Herein,organic cations and Zn^(2+)ions co-pre-inserted vanadium oxide([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O are reported as the cathode for ultra-stable aqueous ZIBs,in which the weaker electrostatic interactions between Zn^(2+)and organic ion-pinned vanadium oxide can induce the high reversibility of Zn^(2+)insertion and extraction,thereby improving the cycle life.It is demonstrated that([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O cathodes deliver a discharge capacity of 181 mA h g^(-1)at8 A g^(-1)and ultra-long life span(99.5%capacity retention after 2000 cycles).A reversible Zn^(2+)/H^(+)ions(de)intercalation storage process and pseudocapacitive charge storage are characterized.The weaker interactions between organic ion and Zn^(2+)open a novel avenue for the design of highly reversible cathode materials with long-term cycling stability.
基金This study was financially supported by the National Natural Science Foundation of China(No.51772193)China Postdoctral Science Foundation(No.2019T250254).
文摘Zn(CF_(3)SO_(3))_(2)as an electrolyte has been widely used to improve the electrochemical performance for ZIBs due to that the bulky CF_(3)SO_(3)-can reduce the solvation effect of Zn^(2+)and promote the ionic diffusion.Herein,we found that Zn(CF_(3)SO_(3))_(2)electrolyte can induce different electrochemical mechanisms from ZnSO_(4)electrolyte.Compared to the ZnSO^(4)electrolyte,the HNaV_(6)O_(16)·4H2_(O)electrode with Zn(CF_(3)SO_(3))_(2)electrolyte exhibits a high capacity of 444 mAh·g^(-1)at 500 mA·g^(-1)with a capacity retention of 92.3%after 80 cycles.Even,at a high rate of 5 Ag-1,the HNaV_(6)O_(16)·4H_(2)O electrode delivers an initial discharge capacity of 328 mAh·g^(-1)with a capacity retention of 93.7%after 1000 cycles.Differing from the mechanism with ZnSO4 electrolyte,the excellent cycle stability of HNaV_(6)O_(16)·4H_(2)Oelectrode can be attributed to the in-situ phase transformation to ZnxV_(2)O_(5)·nH_(2)O based on the co-intercalation of Zn^(2+)/H^(+).
