As an essential part of the performance improvement of lithium metal batteries,the acquisition of dense(LiF-rich solid electrolyte interphase(SEI))has always been an urgent problem to be solved.Herein,we synthesized Z...As an essential part of the performance improvement of lithium metal batteries,the acquisition of dense(LiF-rich solid electrolyte interphase(SEI))has always been an urgent problem to be solved.Herein,we synthesized Zeolitic Imidazolate Frameworks(ZIFs)modified by two different functional groups(-NH_(2),-CH_(3))and used them as the fillers of polyethylene oxide(PEO)composite solid electrolytes to explore the catalytic effect of groups on LiF generation at the Li/electrolytes interface.In a LiFePO 4||SPE||Li cell test,the PEO-ZIF-NH_(2)with LiF-rich SEI exhibits enhanced cycling performance,which was 3.8 times longer than that of PEO-ZIF-CH_(3).The formation mechanism of LiF-rich SEI was investigated using first-principles calculation,revealing that ZIFs-NH_(2)makes the C-F bond in TFSI-longer compared with ZIFs-CH_(3),which leads to easier breakage of the C-F bond and promoted the formation of LiF.The simple design idea of using organic catalysis to generate more stable SEI provides a new aspect for preparing high-performance lithium metal batteries.展开更多
The B3LYP/6-31G^＊ level of theory was used to optimize trans-[Pt（NH3）（Am）G-L], where Am = quinoline or thiazole and L is chosen as the model for functional groups of peptide side chains, and for adenine and guani...The B3LYP/6-31G^＊ level of theory was used to optimize trans-[Pt（NH3）（Am）G-L], where Am = quinoline or thiazole and L is chosen as the model for functional groups of peptide side chains, and for adenine and guanine sites of DNA as the ultimate target of platinum anticancer drugs. Bond dissociating energy and stability energy of complexes are chosen to study detailedly thermodynamic character of possible difunctional adducts model. In order to investigate the influence of a polarizable environment on the energy of the Pt-L bond formation, we adopt a new bonding energy formula brought forward by Lippard and his coworkers： △H（Sol） = △H（SCF） ＋ △G（Solv）, which is quite appropriate to compare with what is found in experimental studies. Our calculated results demonstrate that N-containing ligands are more favored in view of thermodynamics both in gas phrase and in solution. However, it is worthly to be noted that addition of solvation free energies result in moderate correction of bonding energy in relative ordering, and the largest ones both present in imidazole ligand, not in guanine ligand. Finally, the nature of bond is analyzed in terms of partial charges distribution based on NBO population.展开更多
基金This work was financially supported by the National Natural Science Foundation of China(No.11872054)the Natural Science Foundation of Hunan Province(Nos.2020JJ5530,2020JJ2026,and 2021JJ30643)the Science and Technology Innovation Project of Hunan Province(No.2018RS3091).
文摘As an essential part of the performance improvement of lithium metal batteries,the acquisition of dense(LiF-rich solid electrolyte interphase(SEI))has always been an urgent problem to be solved.Herein,we synthesized Zeolitic Imidazolate Frameworks(ZIFs)modified by two different functional groups(-NH_(2),-CH_(3))and used them as the fillers of polyethylene oxide(PEO)composite solid electrolytes to explore the catalytic effect of groups on LiF generation at the Li/electrolytes interface.In a LiFePO 4||SPE||Li cell test,the PEO-ZIF-NH_(2)with LiF-rich SEI exhibits enhanced cycling performance,which was 3.8 times longer than that of PEO-ZIF-CH_(3).The formation mechanism of LiF-rich SEI was investigated using first-principles calculation,revealing that ZIFs-NH_(2)makes the C-F bond in TFSI-longer compared with ZIFs-CH_(3),which leads to easier breakage of the C-F bond and promoted the formation of LiF.The simple design idea of using organic catalysis to generate more stable SEI provides a new aspect for preparing high-performance lithium metal batteries.
基金This work was supported by the Science Foundation of Jinan University (639)
文摘The B3LYP/6-31G^＊ level of theory was used to optimize trans-[Pt（NH3）（Am）G-L], where Am = quinoline or thiazole and L is chosen as the model for functional groups of peptide side chains, and for adenine and guanine sites of DNA as the ultimate target of platinum anticancer drugs. Bond dissociating energy and stability energy of complexes are chosen to study detailedly thermodynamic character of possible difunctional adducts model. In order to investigate the influence of a polarizable environment on the energy of the Pt-L bond formation, we adopt a new bonding energy formula brought forward by Lippard and his coworkers： △H（Sol） = △H（SCF） ＋ △G（Solv）, which is quite appropriate to compare with what is found in experimental studies. Our calculated results demonstrate that N-containing ligands are more favored in view of thermodynamics both in gas phrase and in solution. However, it is worthly to be noted that addition of solvation free energies result in moderate correction of bonding energy in relative ordering, and the largest ones both present in imidazole ligand, not in guanine ligand. Finally, the nature of bond is analyzed in terms of partial charges distribution based on NBO population.
