With the increasing demand for high energy density energy storage device,Li metal has received intensive attention for its ultrahigh capacity and the lowest redox potential.LiNO_(3)is widely used as electrolyte additi...With the increasing demand for high energy density energy storage device,Li metal has received intensive attention for its ultrahigh capacity and the lowest redox potential.LiNO_(3)is widely used as electrolyte additive for ether electrolyte,which can improve the cycle performance of Li metal anode.Compared to ethers,carbonates are more suitable for Li metal batteries with high voltage cathode because they have a wider electrochemical window.However,LiNO_(3)performs poor solubility in carbonate electrolyte,restricting its application in high voltage Li battery.Herein,we presented a facile method to introduce abundant LiNO_(3)additive to carbonate electrolyte system by introducing LiNO_(3)-PAN es as the interlayer of the cell.LiNO_(3)-PAN es is in sufficient contact with the electrolyte so that it can continuously releases LiNO_(3)to assist the formation of Li_(2)N_(2)O_(2)-rich single nitrogenous component SEI layer on Li surface.With the help of LiNO_(3)-PAN es,Li metal anode shows excellent cycle stability even at a high current density of 4mA/cm^(2),so that the cycle performance of the full cells was significantly improved,whether in the anode-free Cu||LFP cell or the Li||NCM622 cell.展开更多
Although hybrid metal ion capacitors(MICs) are highly desired to achieve both high power density of supercapacitors and high energy density of rechargeable batteries, the mismatch problem of electrochemical kinetics o...Although hybrid metal ion capacitors(MICs) are highly desired to achieve both high power density of supercapacitors and high energy density of rechargeable batteries, the mismatch problem of electrochemical kinetics of negative and positive electrodes in MICs hampers the realization of this goal. Here, a new hybrid capacitor concept-potassium metal capacitor(PMC) is proposed for the first time, where potassium metal and commercial activated carbon(AC) without any modification are applied as negative and positive electrodes, respectively, and the electrolyte is the same as that of non-aqueous potassium ion batteries. The simplest PMC prototype exhibits a good combination of high energy density(184.9 Wh kg^(-1)) and power density(12.4 kW kg^(-1)), which benefits from the synergistic effect of potassium metal and AC electrode. The former experiences fast potassium plating/striping during charging and discharging, and the later possesses complex multiple charge behaviors driven by low potential of potassium metal. Specifically, below open-circuit voltage, transportation of solvated cations in AC pores plays an important role;beyond this voltage, synergy actions of cations and anions, including adsorption/desorption of solvated cations and anions, and ions exchange between them, dominate the capacitance contribution. This work enriches the types of MICs, and deepens the understanding of the energy storage mechanism of non-aqueous hybrid metal capacitors.展开更多
Although lithium metal has become a promising anode material for high-energy batteries owing to its high specific capacity and the lowest reduction potential,the continuous side reactions with electrolyte as well as t...Although lithium metal has become a promising anode material for high-energy batteries owing to its high specific capacity and the lowest reduction potential,the continuous side reactions with electrolyte as well as the safety problem caused by Li dendrite growth restrict Li anode’s practical application.Herein,we demonstrate that N-fluoropyridinium(ArF^(+))bis(trifluoromethane)sulfonimide(TFSI-)as an electrolyte additive can protect the lithium metal by both solid electrolyte interphase(SEI)protection and electrostatic repulsion mechanisms.The ArF+cations not only participate in forming F,Ncontaining SEI protective layer on Li surface,but also act as a cationic repellent during Li deposition to inhibit Li dendrite growth.As a result,the cycle performance of Li symmetric cells and Li||LiFePO_(4)full cells were significantly improved by using ArFTFSIadded electrolyte.This study provides an electrolyte additive strategy for Li anode realizing SEI protection and electrostatic repulsion simultaneously.展开更多
基金supported by the National Key R&D Program of China(No.2022YFB2402600)National Natural Science Foundation of China(No.22279166)+1 种基金Basic and Applied Basic Research Foundation of Guangdong Province-Regional joint fund project(No.2022B1515120019)the Fundamental Research Funds for the Central Universities,Sun Yat-Sen University(Nos.22qntd0101 and 22dfx01).
文摘With the increasing demand for high energy density energy storage device,Li metal has received intensive attention for its ultrahigh capacity and the lowest redox potential.LiNO_(3)is widely used as electrolyte additive for ether electrolyte,which can improve the cycle performance of Li metal anode.Compared to ethers,carbonates are more suitable for Li metal batteries with high voltage cathode because they have a wider electrochemical window.However,LiNO_(3)performs poor solubility in carbonate electrolyte,restricting its application in high voltage Li battery.Herein,we presented a facile method to introduce abundant LiNO_(3)additive to carbonate electrolyte system by introducing LiNO_(3)-PAN es as the interlayer of the cell.LiNO_(3)-PAN es is in sufficient contact with the electrolyte so that it can continuously releases LiNO_(3)to assist the formation of Li_(2)N_(2)O_(2)-rich single nitrogenous component SEI layer on Li surface.With the help of LiNO_(3)-PAN es,Li metal anode shows excellent cycle stability even at a high current density of 4mA/cm^(2),so that the cycle performance of the full cells was significantly improved,whether in the anode-free Cu||LFP cell or the Li||NCM622 cell.
基金supported by the National Key R&D Program of China (2022YFB2402600)the National Natural Science Foundation of China (22279166, 52203346)+1 种基金Guangdong Basic and Applied Basic Research Foundation (2022B1515120019)the Fundamental Research Funds for the Central Universities,Sun Yat-sen University(22qntd0101)。
文摘Although hybrid metal ion capacitors(MICs) are highly desired to achieve both high power density of supercapacitors and high energy density of rechargeable batteries, the mismatch problem of electrochemical kinetics of negative and positive electrodes in MICs hampers the realization of this goal. Here, a new hybrid capacitor concept-potassium metal capacitor(PMC) is proposed for the first time, where potassium metal and commercial activated carbon(AC) without any modification are applied as negative and positive electrodes, respectively, and the electrolyte is the same as that of non-aqueous potassium ion batteries. The simplest PMC prototype exhibits a good combination of high energy density(184.9 Wh kg^(-1)) and power density(12.4 kW kg^(-1)), which benefits from the synergistic effect of potassium metal and AC electrode. The former experiences fast potassium plating/striping during charging and discharging, and the later possesses complex multiple charge behaviors driven by low potential of potassium metal. Specifically, below open-circuit voltage, transportation of solvated cations in AC pores plays an important role;beyond this voltage, synergy actions of cations and anions, including adsorption/desorption of solvated cations and anions, and ions exchange between them, dominate the capacitance contribution. This work enriches the types of MICs, and deepens the understanding of the energy storage mechanism of non-aqueous hybrid metal capacitors.
基金This work was financially supported by the National Key R&D Program of China(No.2022YFB2402600)National Natural Science Foundation of China(No.22279166)+1 种基金Basic and Applied Basic Research Foundation of Guangdong Province-Regional joint fund project(No.2022B1515120019)the Fundamental Research Funds for the Central Universities,Sun Yat-Sen University(Nos.22qntd0101 and 22dfx01).
文摘Although lithium metal has become a promising anode material for high-energy batteries owing to its high specific capacity and the lowest reduction potential,the continuous side reactions with electrolyte as well as the safety problem caused by Li dendrite growth restrict Li anode’s practical application.Herein,we demonstrate that N-fluoropyridinium(ArF^(+))bis(trifluoromethane)sulfonimide(TFSI-)as an electrolyte additive can protect the lithium metal by both solid electrolyte interphase(SEI)protection and electrostatic repulsion mechanisms.The ArF+cations not only participate in forming F,Ncontaining SEI protective layer on Li surface,but also act as a cationic repellent during Li deposition to inhibit Li dendrite growth.As a result,the cycle performance of Li symmetric cells and Li||LiFePO_(4)full cells were significantly improved by using ArFTFSIadded electrolyte.This study provides an electrolyte additive strategy for Li anode realizing SEI protection and electrostatic repulsion simultaneously.