In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still face...In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still faced with defects such as low intrinsic ionic conductivity,a narrow electrochemical window,and poor thermal stability.A crosslinking and fluorination molecular design strategy toward PDOL is proposed to tackle the issues above.The amorphous crosslinked structure effectively improves ionic conductivity by inhibiting long-chain crystallization.Especially,the antioxidant–CF_(3)groups,stable crosslinked structure,and reduced terminal hydroxyl groups significantly enhance the electrochemical oxidation stability with a superb high-voltage window of 4.7 V.In addition,the designed electrolyte also exhibits obviously improved thermal stability with no deformation at 120°C for 5 min.Furthermore,the semi-solid NCM811||Li batteries exhibit a favourable capacity retention of 88.8%after 150 cycles at 0.5 C.Even assembled with NCM622 cathode working at 4.5 V,the semi-solid batteries can still show a satisfactory capacity retention of 85.3%after 100 cycles at 0.5 C.Also,a 0.1 Ah NCM811||Li pouch cell with active materials loading of 9 mg/cm2 demonstrates satisfactory cycling stability and working ability,which shows promising practical application prospects.展开更多
The polymer-ceramic composite electrolyte is considered as one of promising electrolytes for solid-state battery.However,in previous research,ceramic particles are usually dispersed in polymer matrix and could not for...The polymer-ceramic composite electrolyte is considered as one of promising electrolytes for solid-state battery.However,in previous research,ceramic particles are usually dispersed in polymer matrix and could not form continuous Li+conductive channels.The agglomeration of ceramic particles could also lead to low ionic conductivity and poor interfacial electrode/electrolyte contact.In this paper,self-supported porous Li_(6.4)La_(3) Zr_(1.4)Ta_(0.6)O_(12)(LLZTO) electrolyte is synthesized by gelcasting process,which possesses three-dimensional(3D) interconnected pore channels and relatively high strength.The 1,3-dioxolane(DOL) could penetrate into the porous LLZTO framework for its excellent fluidity.The subsequent in situ polymerization process by thermal treatment could completely fill the internal pores and improve the interfacial contact with electrode.The resulting 3D composite electrolyte with dual continuous Li+transport channels in ceramic and polymer components exhibits high ionic conductivity of 2.8 × 10^(-4) S·cm^(-1) at room temperature and low Li/electrolyte interfacial resistance of 94 Ω·cm^(2) at 40 ℃.The corresponding Li/Li symmetric cell delivers stable voltage profiles for over 600 h under 0.1 and 0.2 mA·cm^(-2).The solid-state Li/LiFePO_(4) battery shows superior rate and cycling performance under 0.1 C and 0.2 C.This work guides the preparation of composite electrolyte with dual continuous Li+conductive paths as well as high ceramic ratio and interface modification strategy for solid-state Li metal battery.展开更多
1,3-dioxolane （DOL） was originally used to pretreat a lithium metal electrode to improve its interfacial characteristics. Electrochemical impedance spectra （EIS） meastLrements revealed that, after the DOL pretreat...1,3-dioxolane （DOL） was originally used to pretreat a lithium metal electrode to improve its interfacial characteristics. Electrochemical impedance spectra （EIS） meastLrements revealed that, after the DOL pretreatment, the lithium electrode had better interfacial stability during immersion in electrolyte and as repeated charge/discharge cycles. It was proved by SEaM that the pretreated one has smoother morphology and less dendrite after repeated charge/discharge cycles. Consequentially, benefiting from the better interface characteristics of the lithium electrode, the rechargeable lithium cell with a DOL-pretreated lithium anode had the obviously enhanced discharging performance and better cyclability.展开更多
Nine title compounds were synthesized. Their strucures were identified by means of IR, EA, 1H NMR and MS. The results from the primary biological test show that all the compounds have some activitiies of fungicide and...Nine title compounds were synthesized. Their strucures were identified by means of IR, EA, 1H NMR and MS. The results from the primary biological test show that all the compounds have some activitiies of fungicide and plant growth regulator. When R group is 2,4 Cl 2C 6H 3, compound 2 or compound 4 shows better biological activities.展开更多
1,3-dioxolane (DOL) is originally used to pretreat the lithium metal electrode in order to passivate lithium metal and improve its interface stability. Through electrochemical impedance spectra (EIS) and cathodic pola...1,3-dioxolane (DOL) is originally used to pretreat the lithium metal electrode in order to passivate lithium metal and improve its interface stability. Through electrochemical impedance spectra (EIS) and cathodic polarization measurements of pretreated and untreated electrodes, it was found that 1,3-dioxolane could form a stable passivating film on the surface of lithium electrode. And such film could enhance effectively the interfacial stability of lithium electrode, without depressing its kinetics characteristic. Consequentially, further tests of the cell-performance during repeated charge/discharge cycles showed that the cell with DOL pretreated anode had better discharging performance and longer cycle life because of the passivating and protective effects of 1,3-dioxolane pretreatment on lithium electrode.展开更多
1,3-dioxolane (DOL) was originally used to pretreat a lithium metal electrode to improve its interfacial characteristics. Electrochemical impedance spectra (EIS) measurements revealed that,after the DOL pretreatment,t...1,3-dioxolane (DOL) was originally used to pretreat a lithium metal electrode to improve its interfacial characteristics. Electrochemical impedance spectra (EIS) measurements revealed that,after the DOL pretreatment,the lithium electrode had better interfacial stability during immersion in electrolyte and as repeated charge/discharge cycles. It was proved by SEM that the pretreated one has smoother morphology and less dendrite after repeated charge/discharge cycles. Consequentially,benefiting from the better interface characteristics of the lithium electrode,the rechargeable lithium cell with a DOL-pretreated lithium anode had the obviously enhanced discharging performance and better cyclability.展开更多
Garnet-type ceramic Li-La_(3)Zr_(2)O_(12)(LLZO)stands out as a potential solid-state electrolyte,offering a promising alternative to conventional flammable liquid electrolytes.However,its large interfacial resistance ...Garnet-type ceramic Li-La_(3)Zr_(2)O_(12)(LLZO)stands out as a potential solid-state electrolyte,offering a promising alternative to conventional flammable liquid electrolytes.However,its large interfacial resistance with electrodes remains a significant challenge.In this research,we have successfully in-situ fabricated polymeric interface layers on both cathode and anode sides with LLZO.By tuning the gel-polymer interphase via fluoroethylene carbonate(FEC),known as FGPE,we have established a rapid Li^(+) transport channel by enhancing the solid-solid interfacial contact.This FGPE layer exhibits exceptional ionic conductivity of 1.38 mS/cm and a high Li-ion transference number of 0.64.Furthermore,FGPE effectively mitigates concentration polarization under high currents,thereby enabling a higher capacity output.In comparison to gel-polymer interphases with dimethyl carbonate(DMC)as the solvent(referred to as GPE),the Li|FGPE|Li symmetrical cell has demonstrated superior stability in plating/strapping performance over800h at a current density of 0.1 mA/cm^(2).Moreover,the Li|FGPE|LLZO|FGPE|LiFePO_(4) cell has exhibited commendable rate capability and has maintained a high capacity retention of 98.94%at 0.5 C after 200cycles.This study underscores an innovative approach in advancing in field of solid-state batteries,anticipated to be broadly applicable to other solid-state batteries by facilitating an abundance of robust solid-solid interfacial contacts.展开更多
基金the financial support from the National Natural Science Foundation of China (No. 52072390)the National High-Level Talents Special Support Program (Leading Talent of Technological Innovation)+2 种基金the China Postdoctoral Science Foundation (No. 2023M743648)the Young Scientists Fund of the National Natural Science Foundation of China (No. 52302330)the support from the Shanghai Emperor of Cleaning Hi-Tech Co.,LTD
文摘In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still faced with defects such as low intrinsic ionic conductivity,a narrow electrochemical window,and poor thermal stability.A crosslinking and fluorination molecular design strategy toward PDOL is proposed to tackle the issues above.The amorphous crosslinked structure effectively improves ionic conductivity by inhibiting long-chain crystallization.Especially,the antioxidant–CF_(3)groups,stable crosslinked structure,and reduced terminal hydroxyl groups significantly enhance the electrochemical oxidation stability with a superb high-voltage window of 4.7 V.In addition,the designed electrolyte also exhibits obviously improved thermal stability with no deformation at 120°C for 5 min.Furthermore,the semi-solid NCM811||Li batteries exhibit a favourable capacity retention of 88.8%after 150 cycles at 0.5 C.Even assembled with NCM622 cathode working at 4.5 V,the semi-solid batteries can still show a satisfactory capacity retention of 85.3%after 100 cycles at 0.5 C.Also,a 0.1 Ah NCM811||Li pouch cell with active materials loading of 9 mg/cm2 demonstrates satisfactory cycling stability and working ability,which shows promising practical application prospects.
基金financially supported by the National Natural Science Foundation of China (Nos.52173257 and 51872159)。
文摘The polymer-ceramic composite electrolyte is considered as one of promising electrolytes for solid-state battery.However,in previous research,ceramic particles are usually dispersed in polymer matrix and could not form continuous Li+conductive channels.The agglomeration of ceramic particles could also lead to low ionic conductivity and poor interfacial electrode/electrolyte contact.In this paper,self-supported porous Li_(6.4)La_(3) Zr_(1.4)Ta_(0.6)O_(12)(LLZTO) electrolyte is synthesized by gelcasting process,which possesses three-dimensional(3D) interconnected pore channels and relatively high strength.The 1,3-dioxolane(DOL) could penetrate into the porous LLZTO framework for its excellent fluidity.The subsequent in situ polymerization process by thermal treatment could completely fill the internal pores and improve the interfacial contact with electrode.The resulting 3D composite electrolyte with dual continuous Li+transport channels in ceramic and polymer components exhibits high ionic conductivity of 2.8 × 10^(-4) S·cm^(-1) at room temperature and low Li/electrolyte interfacial resistance of 94 Ω·cm^(2) at 40 ℃.The corresponding Li/Li symmetric cell delivers stable voltage profiles for over 600 h under 0.1 and 0.2 mA·cm^(-2).The solid-state Li/LiFePO_(4) battery shows superior rate and cycling performance under 0.1 C and 0.2 C.This work guides the preparation of composite electrolyte with dual continuous Li+conductive paths as well as high ceramic ratio and interface modification strategy for solid-state Li metal battery.
基金This project was financially supported by the Foundation of Science-Technology Research Program of Guangdong Prov-ince, China (No. 2003C105006).
文摘1,3-dioxolane （DOL） was originally used to pretreat a lithium metal electrode to improve its interfacial characteristics. Electrochemical impedance spectra （EIS） meastLrements revealed that, after the DOL pretreatment, the lithium electrode had better interfacial stability during immersion in electrolyte and as repeated charge/discharge cycles. It was proved by SEaM that the pretreated one has smoother morphology and less dendrite after repeated charge/discharge cycles. Consequentially, benefiting from the better interface characteristics of the lithium electrode, the rechargeable lithium cell with a DOL-pretreated lithium anode had the obviously enhanced discharging performance and better cyclability.
基金Supported by the Natural Science Foudation of Shandong Province(No.Q 99B16 ) and the National Natural ScienceFoundation of China(No.2 0 0 75 0 13)
文摘Nine title compounds were synthesized. Their strucures were identified by means of IR, EA, 1H NMR and MS. The results from the primary biological test show that all the compounds have some activitiies of fungicide and plant growth regulator. When R group is 2,4 Cl 2C 6H 3, compound 2 or compound 4 shows better biological activities.
文摘1,3-dioxolane (DOL) is originally used to pretreat the lithium metal electrode in order to passivate lithium metal and improve its interface stability. Through electrochemical impedance spectra (EIS) and cathodic polarization measurements of pretreated and untreated electrodes, it was found that 1,3-dioxolane could form a stable passivating film on the surface of lithium electrode. And such film could enhance effectively the interfacial stability of lithium electrode, without depressing its kinetics characteristic. Consequentially, further tests of the cell-performance during repeated charge/discharge cycles showed that the cell with DOL pretreated anode had better discharging performance and longer cycle life because of the passivating and protective effects of 1,3-dioxolane pretreatment on lithium electrode.
文摘1,3-dioxolane (DOL) was originally used to pretreat a lithium metal electrode to improve its interfacial characteristics. Electrochemical impedance spectra (EIS) measurements revealed that,after the DOL pretreatment,the lithium electrode had better interfacial stability during immersion in electrolyte and as repeated charge/discharge cycles. It was proved by SEM that the pretreated one has smoother morphology and less dendrite after repeated charge/discharge cycles. Consequentially,benefiting from the better interface characteristics of the lithium electrode,the rechargeable lithium cell with a DOL-pretreated lithium anode had the obviously enhanced discharging performance and better cyclability.
基金the National Natural Science Foundation of China(No.22105079)Natural Science Foundation of Guangdong Province(No.2023B1515130004)+1 种基金Guangdong Basic and Applied Basic Research Natural Science Funding(Nos.2023A1515010849 and 2024A1515012328)Key-Area Research and Development Program of Guangdong Province(No.2024B1111080003)。
文摘Garnet-type ceramic Li-La_(3)Zr_(2)O_(12)(LLZO)stands out as a potential solid-state electrolyte,offering a promising alternative to conventional flammable liquid electrolytes.However,its large interfacial resistance with electrodes remains a significant challenge.In this research,we have successfully in-situ fabricated polymeric interface layers on both cathode and anode sides with LLZO.By tuning the gel-polymer interphase via fluoroethylene carbonate(FEC),known as FGPE,we have established a rapid Li^(+) transport channel by enhancing the solid-solid interfacial contact.This FGPE layer exhibits exceptional ionic conductivity of 1.38 mS/cm and a high Li-ion transference number of 0.64.Furthermore,FGPE effectively mitigates concentration polarization under high currents,thereby enabling a higher capacity output.In comparison to gel-polymer interphases with dimethyl carbonate(DMC)as the solvent(referred to as GPE),the Li|FGPE|Li symmetrical cell has demonstrated superior stability in plating/strapping performance over800h at a current density of 0.1 mA/cm^(2).Moreover,the Li|FGPE|LLZO|FGPE|LiFePO_(4) cell has exhibited commendable rate capability and has maintained a high capacity retention of 98.94%at 0.5 C after 200cycles.This study underscores an innovative approach in advancing in field of solid-state batteries,anticipated to be broadly applicable to other solid-state batteries by facilitating an abundance of robust solid-solid interfacial contacts.
