Along with the keeping growing demand for high-energy-density energy storage system,high-voltage Li-metal batteries(LMBs)have attracted many attentions.In view of many defects of the commercial electrolytes,such as fl...Along with the keeping growing demand for high-energy-density energy storage system,high-voltage Li-metal batteries(LMBs)have attracted many attentions.In view of many defects of the commercial electrolytes,such as flammability,limited operation temperature range,and severe Li dendrite growth,non-flammable phosphate-based localized highly concentrated electrolytes(LHCE)have been explored as one of the safe electrolytes for LMBs.But until now there is rare report on wide-temperature range LMBs using phosphate-based electrolytes.Here,we prepare a wide-temperature LHCE,which is composed of lithium difluoro(oxalato)borate(LiDFOB),triethyl phosphate(TEP),and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(HFE),and explore the applicability in wide-temperature LMBs from−40 to 70℃.In the LHCE,both TEP and HFE are non-flammable,and Li^(+) is highly coordinated with TEP and DFOB^(−),which can effectively inhibit the TEP decomposition on anode,and facilitate the preferential reduction of DFOB^(−),thus obtain a robust solid electrolyte interphase(SEI)to suppress Li dendrite growth and side reactions.Therefore,this LHCE can not only endow Li/Cu and Li/Li cells with high Coulombic efficiency(CE)and long cycling lifespan,but also be applied to LiFePO_(4)(LFP)/Li and LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM523)/Li LMBs.Most importantly,the NCM523/Li LMBs with LHCE can deliver stable cycling performance at 4.5 V high-voltage and high-temperature(70℃),as well as excellent low-temperature capacity retention even though both charging and discharging process were carried out at−40℃.展开更多
Lithium metal batteries(LMBs)have attracted considerable interest for use in electric vehicles and as next-generation energy storage devices because of their high energy density.However,a significant practical drawbac...Lithium metal batteries(LMBs)have attracted considerable interest for use in electric vehicles and as next-generation energy storage devices because of their high energy density.However,a significant practical drawback with LMBs is the instability of the Li metal/electrolyte interface,with concurrent parasitic reactions and dendrite growth,that leads to low Coulombic efficiency and poor cycle life.Owing to the significant role of electrolytes in batteries,rationally designed electrolytes can improve the electrochemical performance of LMBs and possibly achieve fast charge and a wide range of working temperatures to meet various requirements of the market in the future.Although there are some review papers about electrolytes for LMBs,the focus has been on a single parameter or single performance separately and,therefore,not sufficient for the design of electrolytes for advanced LMBs for a wide range of working environments.This review presents a systematic summary of recent progress made in terms of electrolytes,covering the fundamental understanding of the mechanism,scientific challenges,and strategies to address drawbacks of electrolytes for high-performance LMBs.The advantages and disadvantages of various electrolyte strategies are also analyzed,yielding suggestions for optimum properties of electrolytes for advanced LMBs applications.Finally,the most promising research directions for electrolytes are discussed briefly.展开更多
Aqueous electrolytes are safe,economic,and environmentally friendly.However,they have a narrow potential window.On the other hand,organic electrolytes exhibit good thermodynamic stability but are inflammable and moist...Aqueous electrolytes are safe,economic,and environmentally friendly.However,they have a narrow potential window.On the other hand,organic electrolytes exhibit good thermodynamic stability but are inflammable and moisture sensitive.In this study,we prepared water-PEG-lipid ternary electrolytes(TEs).To combine the advantages of water,polyethylene glycol(PEG)and propylene carbonate(PC).The nonflammable mixed electrolytes exhibited a wide potential window of about 2.8 V due to the beneficial effects of PEG and PC.Using these TEs,a lithium manganate-active carbon ion capacitor could be operated at 2.4 V with an energy density of 32 Wh/kg,based on the total active electrode material(current density of 3.3 m A/cm^(2)).This value was significantly higher than that achieved using an aqueous electrolyte,thereby rationalizing the higher energy density.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22179142 and 22075314)The XPS characterization is supported by Nano-X(Vacuum Interconnected Nanotech Workstation,Chinese Academy of Sciences,Suzhou 215123,China).
文摘Along with the keeping growing demand for high-energy-density energy storage system,high-voltage Li-metal batteries(LMBs)have attracted many attentions.In view of many defects of the commercial electrolytes,such as flammability,limited operation temperature range,and severe Li dendrite growth,non-flammable phosphate-based localized highly concentrated electrolytes(LHCE)have been explored as one of the safe electrolytes for LMBs.But until now there is rare report on wide-temperature range LMBs using phosphate-based electrolytes.Here,we prepare a wide-temperature LHCE,which is composed of lithium difluoro(oxalato)borate(LiDFOB),triethyl phosphate(TEP),and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(HFE),and explore the applicability in wide-temperature LMBs from−40 to 70℃.In the LHCE,both TEP and HFE are non-flammable,and Li^(+) is highly coordinated with TEP and DFOB^(−),which can effectively inhibit the TEP decomposition on anode,and facilitate the preferential reduction of DFOB^(−),thus obtain a robust solid electrolyte interphase(SEI)to suppress Li dendrite growth and side reactions.Therefore,this LHCE can not only endow Li/Cu and Li/Li cells with high Coulombic efficiency(CE)and long cycling lifespan,but also be applied to LiFePO_(4)(LFP)/Li and LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM523)/Li LMBs.Most importantly,the NCM523/Li LMBs with LHCE can deliver stable cycling performance at 4.5 V high-voltage and high-temperature(70℃),as well as excellent low-temperature capacity retention even though both charging and discharging process were carried out at−40℃.
基金Financial support provided by the Australian Research Council(ARC)(Nos.FL210100050,LP160101629,and DP210101486)is gratefully acknowledgedMingnan Li acknowledges the Chinese Sponsorship Council for scholarship support(No.202106130006).
文摘Lithium metal batteries(LMBs)have attracted considerable interest for use in electric vehicles and as next-generation energy storage devices because of their high energy density.However,a significant practical drawback with LMBs is the instability of the Li metal/electrolyte interface,with concurrent parasitic reactions and dendrite growth,that leads to low Coulombic efficiency and poor cycle life.Owing to the significant role of electrolytes in batteries,rationally designed electrolytes can improve the electrochemical performance of LMBs and possibly achieve fast charge and a wide range of working temperatures to meet various requirements of the market in the future.Although there are some review papers about electrolytes for LMBs,the focus has been on a single parameter or single performance separately and,therefore,not sufficient for the design of electrolytes for advanced LMBs for a wide range of working environments.This review presents a systematic summary of recent progress made in terms of electrolytes,covering the fundamental understanding of the mechanism,scientific challenges,and strategies to address drawbacks of electrolytes for high-performance LMBs.The advantages and disadvantages of various electrolyte strategies are also analyzed,yielding suggestions for optimum properties of electrolytes for advanced LMBs applications.Finally,the most promising research directions for electrolytes are discussed briefly.
基金supported by the National Natural Science Foundation of China(No.11975043)the Natural Science Foundation of Shandong Province(No.ZR2017LEM011)。
文摘Aqueous electrolytes are safe,economic,and environmentally friendly.However,they have a narrow potential window.On the other hand,organic electrolytes exhibit good thermodynamic stability but are inflammable and moisture sensitive.In this study,we prepared water-PEG-lipid ternary electrolytes(TEs).To combine the advantages of water,polyethylene glycol(PEG)and propylene carbonate(PC).The nonflammable mixed electrolytes exhibited a wide potential window of about 2.8 V due to the beneficial effects of PEG and PC.Using these TEs,a lithium manganate-active carbon ion capacitor could be operated at 2.4 V with an energy density of 32 Wh/kg,based on the total active electrode material(current density of 3.3 m A/cm^(2)).This value was significantly higher than that achieved using an aqueous electrolyte,thereby rationalizing the higher energy density.