It is highly desirable for the promising sodium storage possessing high rate and long stable capability,which are mainly hindered by the unstable yet conventional solvent-derived organic-rich solid electrolyte interph...It is highly desirable for the promising sodium storage possessing high rate and long stable capability,which are mainly hindered by the unstable yet conventional solvent-derived organic-rich solid electrolyte interphases.Herein,an electrolyte solvation chemistry is elaborately manipulated to produce an enhanced anion-derived and inorganic components-dominated solid electrolyte interphases by introducing a low permittivity(4.33)bis(2,2,2-trifluoroethyl)ether diluent into the sodium bis(trifluoromethylsulfonyl)imidedimethoxyethane-based high concentration electrolyte to obtain a localized high concentration electrolyte.The bis(2,2,2-trifluoroethyl)ether breaks the balance of original cation solvation structure and tends to interact with Na^(+)-coordinated dimethoxyethane solvent rather than Na^(+)in high concentration electrolyte,leaving an enhanced Coulombic interaction between Na^(+)and(FSO_(2))_(2)N^(-),and more(FSO_(2))_(2)N^(-)can enter the Na^(+)solvation shell,forming a further increased number of Na^(+)-(FSO_(2))_(2)N^(-)-dimethoxyethane clusters(from 82.0%for high concentration electrolyte to 94.3%for localized high concentration electrolyte)at a low salt dosage.The preferential reduction of this(FSO_(2))_(2)N^(-)-enriched clusters rather than the dimethoxyethane-dominated Na^(+)solvation structure produces an enhanced anion-derived and inorganic components-dominated solid electrolyte interphases.The reversible charge storage process of Na is decoupled by operando Raman along with a shift of D and G peaks.Benefiting from the enhanced anion-derived electrode-electrolyte interface,the commercial hard carbon anode in localized high concentration electrolyte shows a well rate capability(5 A g^(−1),70 mAh g^(−1)),cycle performance and stability(85%of initial capacity after 700 cycles)in comparison to that of high concentration electrolyte(68%)and low concentration electrolyte(only 5%after 400 cycles),indicative of uniqueness and superiorities towards stable Na storage.展开更多
Constructing anion-derived solid electrolyte interphase(SEI)by recruiting anions into the solvation sheath of Li+is extremely conducive to restrain the dendrite growth of Li metal anode.However,the presence of anions ...Constructing anion-derived solid electrolyte interphase(SEI)by recruiting anions into the solvation sheath of Li+is extremely conducive to restrain the dendrite growth of Li metal anode.However,the presence of anions in the solvation sheath of Li+is severely hindered by the solvents with strong coordinating ability in conventional electrolyte.Herein,we boost the content of anions in the primary solvation sheath of Li+by employing a solvent with low donor number,2-methyltetrahydrofuran,inducing an anion-derived SEI.As a result,the Li||Cu cells show a high average Coulombic efficiency(>99%)over 500 cycles and the Li||LiFePO4 cells under a low negative/positive capacity ratio of 2:1 exhibit an impressive capacity retention of 90%after 100 cycles.This work provides insights on constructing stable anion-derived SEI and offers guidance in designing electrolytes for stable Li metal batteries.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
基金partly supported by the Innovation Program of Dalian City of Liaoning Province(no.2019RJ03)National Natural Science Foundation of China(NSFC,no.51872035,22078052)
文摘It is highly desirable for the promising sodium storage possessing high rate and long stable capability,which are mainly hindered by the unstable yet conventional solvent-derived organic-rich solid electrolyte interphases.Herein,an electrolyte solvation chemistry is elaborately manipulated to produce an enhanced anion-derived and inorganic components-dominated solid electrolyte interphases by introducing a low permittivity(4.33)bis(2,2,2-trifluoroethyl)ether diluent into the sodium bis(trifluoromethylsulfonyl)imidedimethoxyethane-based high concentration electrolyte to obtain a localized high concentration electrolyte.The bis(2,2,2-trifluoroethyl)ether breaks the balance of original cation solvation structure and tends to interact with Na^(+)-coordinated dimethoxyethane solvent rather than Na^(+)in high concentration electrolyte,leaving an enhanced Coulombic interaction between Na^(+)and(FSO_(2))_(2)N^(-),and more(FSO_(2))_(2)N^(-)can enter the Na^(+)solvation shell,forming a further increased number of Na^(+)-(FSO_(2))_(2)N^(-)-dimethoxyethane clusters(from 82.0%for high concentration electrolyte to 94.3%for localized high concentration electrolyte)at a low salt dosage.The preferential reduction of this(FSO_(2))_(2)N^(-)-enriched clusters rather than the dimethoxyethane-dominated Na^(+)solvation structure produces an enhanced anion-derived and inorganic components-dominated solid electrolyte interphases.The reversible charge storage process of Na is decoupled by operando Raman along with a shift of D and G peaks.Benefiting from the enhanced anion-derived electrode-electrolyte interface,the commercial hard carbon anode in localized high concentration electrolyte shows a well rate capability(5 A g^(−1),70 mAh g^(−1)),cycle performance and stability(85%of initial capacity after 700 cycles)in comparison to that of high concentration electrolyte(68%)and low concentration electrolyte(only 5%after 400 cycles),indicative of uniqueness and superiorities towards stable Na storage.
基金supported by the National Key R&D Program of China(No.2022YFB2402200)the National Natural Science Foundation of China(Nos.22121005,22020102002,and 21835004)+1 种基金the Frontiers Science Center for New Organic Matter of Nankai University(No.63181206)the Haihe Laboratory of Sustainable Chemical Transformations.
文摘Constructing anion-derived solid electrolyte interphase(SEI)by recruiting anions into the solvation sheath of Li+is extremely conducive to restrain the dendrite growth of Li metal anode.However,the presence of anions in the solvation sheath of Li+is severely hindered by the solvents with strong coordinating ability in conventional electrolyte.Herein,we boost the content of anions in the primary solvation sheath of Li+by employing a solvent with low donor number,2-methyltetrahydrofuran,inducing an anion-derived SEI.As a result,the Li||Cu cells show a high average Coulombic efficiency(>99%)over 500 cycles and the Li||LiFePO4 cells under a low negative/positive capacity ratio of 2:1 exhibit an impressive capacity retention of 90%after 100 cycles.This work provides insights on constructing stable anion-derived SEI and offers guidance in designing electrolytes for stable Li metal batteries.
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.