Polymer solid electrolytes(SPEs)based on the[solvate-Li+]complex structure have promising prospects in lithium metal batteries(LMBs)due to their unique ion transport mechanism.However,the solvation structure may compr...Polymer solid electrolytes(SPEs)based on the[solvate-Li+]complex structure have promising prospects in lithium metal batteries(LMBs)due to their unique ion transport mechanism.However,the solvation structure may compromise the mechanical performance and safety,hindering practical application of SPEs.In this work,a composite solid electrolyte(CSE)is designed through the organic-inorganic syner-gistic interaction among N,N-dimethylformamide(DMF),polycarbonate(PC),and Mg_(2)B_(2)O_(5) in poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP).Flame-retardant Mg_(2)B_(2)O_(5) nanowires provide non-flammability to the prepared CSEs,and the addition of PC improves the dispersion of Mg_(2)B_(2)O_(5) nanowires.Simultaneously,the organic-inorganic synergistic action of PC plasticizer and Mg_(2)B_(2)O_(5) nanowires pro-motes the dissociation degree of LiTFSI and reduces the crystallinity of PVDF-HFP,enabling rapid Li ion transport.Additionally,Raman spectroscopy and DFT calculations confirm the coordination between Mg atoms in Mg_(2)B_(2)O_(5) and N atoms in DMF,which exhibits Lewis base-like behavior attacking adjacent C-F and C-H bonds in PVDF-HFP while inducing dehydrofluorination of PVDF-HFP.Based on the syner-gistic coupling of Mg_(2)B_(2)O_(5),PC,and DMF in the PVDF-HFP matrix,the prepared CSE exhibits superior ion conductivity(9.78×10^(-4) s cm^(-1)).The assembled Li symmetric cells cycle stably for 3900 h at a current density of 0.1 mA cm^(-2) without short circuit.The LFP||Li cells assembled with PDL-Mg_(2)B_(2)O_(5)/PC CSEs show excellent rate capability and cycling performance,with a capacity retention of 83.3%after 1000 cycles at 0.5 C.This work provides a novel approach for the practical application of organic-inorganic Synergistic CSEs in LMBs.展开更多
The key challenges in aqueous zinc-manganese dioxide batteries(MnO_(2)//Zn)are their poor electrochemical kinetics and stability,which are mainly due to low conductivity and the inevitable dissolution of MnO_(2).A syn...The key challenges in aqueous zinc-manganese dioxide batteries(MnO_(2)//Zn)are their poor electrochemical kinetics and stability,which are mainly due to low conductivity and the inevitable dissolution of MnO_(2).A syn-ergistic combination of a Co-doped𝜎σ-MnO_(2)electrode(Co-MnO_(2))and a Co(CH_(3)COO)_(2)•4H_(2)O(CoAc)electrolyte additive is here developed to design a high-performance aqueous MnO_(2)//Zn battery(denoted as a Co-MnO_(2)//Zn battery with CoAc).The introduction of Co ions(Co^(3+)/Co^(2+))into the𝜎σ-MnO_(2)electrode is achieved via a facile one-step electrodeposition method.Benefitting from the synergistic coupling effect of the Co-MnO_(2)electrode and the CoAc electrolyte additive,the fabricated Co-MnO_(2)//Zn battery with CoAc shows a commendable dis-charge capacity of 313.8 mAh g^(−1)at 0.5 A g^(−1),excellent rate performance,excellent durability over 1000 cycles(∼92%capacity retention at 1.0 A g^(−1))and admirable energy density(439.3 Wh kg^(−1)),which is a significant improvement compared with an un-doped𝜎σ-MnO_(2)//Zn battery.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.51604089,51874110,22173066,and 21903058)Natural Science Foundation of Heilongjiang Province(Grant No.YQ2021B004).
文摘Polymer solid electrolytes(SPEs)based on the[solvate-Li+]complex structure have promising prospects in lithium metal batteries(LMBs)due to their unique ion transport mechanism.However,the solvation structure may compromise the mechanical performance and safety,hindering practical application of SPEs.In this work,a composite solid electrolyte(CSE)is designed through the organic-inorganic syner-gistic interaction among N,N-dimethylformamide(DMF),polycarbonate(PC),and Mg_(2)B_(2)O_(5) in poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP).Flame-retardant Mg_(2)B_(2)O_(5) nanowires provide non-flammability to the prepared CSEs,and the addition of PC improves the dispersion of Mg_(2)B_(2)O_(5) nanowires.Simultaneously,the organic-inorganic synergistic action of PC plasticizer and Mg_(2)B_(2)O_(5) nanowires pro-motes the dissociation degree of LiTFSI and reduces the crystallinity of PVDF-HFP,enabling rapid Li ion transport.Additionally,Raman spectroscopy and DFT calculations confirm the coordination between Mg atoms in Mg_(2)B_(2)O_(5) and N atoms in DMF,which exhibits Lewis base-like behavior attacking adjacent C-F and C-H bonds in PVDF-HFP while inducing dehydrofluorination of PVDF-HFP.Based on the syner-gistic coupling of Mg_(2)B_(2)O_(5),PC,and DMF in the PVDF-HFP matrix,the prepared CSE exhibits superior ion conductivity(9.78×10^(-4) s cm^(-1)).The assembled Li symmetric cells cycle stably for 3900 h at a current density of 0.1 mA cm^(-2) without short circuit.The LFP||Li cells assembled with PDL-Mg_(2)B_(2)O_(5)/PC CSEs show excellent rate capability and cycling performance,with a capacity retention of 83.3%after 1000 cycles at 0.5 C.This work provides a novel approach for the practical application of organic-inorganic Synergistic CSEs in LMBs.
基金the NSFC(51702123)Shandong Province Higher Educational Youths Innovation Science and Technol-ogy Program(2019KJA018)+1 种基金the University of Jinan Science and Technology Planning Project(XKY2034)S.H.Yang thanks the start-up research funding from the University of Jinan.
文摘The key challenges in aqueous zinc-manganese dioxide batteries(MnO_(2)//Zn)are their poor electrochemical kinetics and stability,which are mainly due to low conductivity and the inevitable dissolution of MnO_(2).A syn-ergistic combination of a Co-doped𝜎σ-MnO_(2)electrode(Co-MnO_(2))and a Co(CH_(3)COO)_(2)•4H_(2)O(CoAc)electrolyte additive is here developed to design a high-performance aqueous MnO_(2)//Zn battery(denoted as a Co-MnO_(2)//Zn battery with CoAc).The introduction of Co ions(Co^(3+)/Co^(2+))into the𝜎σ-MnO_(2)electrode is achieved via a facile one-step electrodeposition method.Benefitting from the synergistic coupling effect of the Co-MnO_(2)electrode and the CoAc electrolyte additive,the fabricated Co-MnO_(2)//Zn battery with CoAc shows a commendable dis-charge capacity of 313.8 mAh g^(−1)at 0.5 A g^(−1),excellent rate performance,excellent durability over 1000 cycles(∼92%capacity retention at 1.0 A g^(−1))and admirable energy density(439.3 Wh kg^(−1)),which is a significant improvement compared with an un-doped𝜎σ-MnO_(2)//Zn battery.