Rechargeable Li metal batteries using Li metal anodes have attracted worldwide interest because of their high energy density. The critical barriers limiting their commercial application include uncontrolled dendritic ...Rechargeable Li metal batteries using Li metal anodes have attracted worldwide interest because of their high energy density. The critical barriers limiting their commercial application include uncontrolled dendritic Li growth and the unstable Li-electrolyte interface. Considerable efforts have been directed towards solving these problems, e.g., modifying the electrolyte, creating artificial interfacial layers for the Li metal, and constructing three-dimensional structures for the Li metal. However, stabilizing the Li metal interface remains challenging because of the highly reactive nature of the Li metal. In this study, we utilize a Li-ion conducting hybrid film comprising a garnet-type ion conductor and a poly（ethylene oxide）-based polymer electrolyte as a protective layer to stabilize the Li-electrolyte interface and mitigate the growth of Li dendrites. The hybrid ion-conducting layer can block Li dendrites from proliferating and accommodate Li volume expansion because of its robust mechanical properties. Moreover, the ion-conducting layer allows Li deposition only underneath it, rather than on the surface, functioning as a permanent protective layer to ensure the stability of the Li metal over a long cycling life. The dendrite-inhibiting effect of the ion-conducting protective layer is visually evidenced by in situ microscopy using planar batteries. The protective Li metal anode exhibits excellent cycling stability and low voltage hysteresis （-15 mV at 0.2 mA-cm-2） for a cycle life as long as 1,000 h. It also shows a high Coulombic efficiency （-99.5%） in a full cell against a LiFePO4 cathode, exhibiting promise for application in Li metal batteries. Our results imply that the ion-conducting protective layer markedly improves the metal anode, yielding safe, long-life, and high-energy-density batteries.展开更多
All-solid-state Li metal batteries(ASSLBs)using inorganic solid electrolyte(SE)are considered promising alternatives to conventional Li-ion batteries,offering improved safety and boosted energy density.While significa...All-solid-state Li metal batteries(ASSLBs)using inorganic solid electrolyte(SE)are considered promising alternatives to conventional Li-ion batteries,offering improved safety and boosted energy density.While significant progress has been made on improving the ionic conductivity of SEs,the degradation and instability of Li metal/inorganic SE interfaces have become the critical challenges that limit the coulombic efficiency,power performance,and cycling stability of ASSLBs.Understanding the mechanisms of complex/dynamic interfacial phenomena is of great importance in addressing these issues.Herein,recent studies on identifying,understanding,and solving interfacial issues on anode side in ASSLBs are comprehensively reviewed.Typical issues at Li metal/SE interface include Li dendrite growth/propagation,SE cracking,physical contact loss,and electrochemical reactions,which lead to high interfacial resistance and cell failure.The causes of these issues relating to the chemical,physical,and mechanical properties of Li metal and SEs are systematically discussed.Furthermore,effective mitigating strategies are summarized and their effects on suppressing interfacial reactions,improving interfacial Li-ion transport,maintaining interfacial contact,and stabilizing Li plating/stripping are highlighted.The in-depth mechanistic understanding of interfacial issues and complete investigations on current solutions provide foundations and guidance for future research and development to realize practical application of high-performance ASSLB.展开更多
Rechargeable magnesium batteries(RMBs)have attracted tremendous attention in energy storage ap-plications in term of high abundance,high specific capacity and remarkable safety of metallic magne-sium(Mg)anode.However,...Rechargeable magnesium batteries(RMBs)have attracted tremendous attention in energy storage ap-plications in term of high abundance,high specific capacity and remarkable safety of metallic magne-sium(Mg)anode.However,a serious passivation of Mg anode in the conventional electrolytes leads to extremely poor plating/stripping performance,further hindering its applications.Herein,we propose a convenient method to construct an artificial interphase layer on Mg anode by substitution and alloy-ing reactions between SbCl_(3) and Mg.This Sb-based artificial interphase layer containing mainly MgCl_(2) and Mg_(3) Sb_(2) endows the significantly improved interfacial kinetics and electrochemical performance of Mg anode.The overpotential of Mg plating/stripping in conventional Mg(TFSI)2/DME electrolytes is vastly reduced from over 2 V to 0.25-0.3 V.Combining experiments and calculations,we demonstrate that un-der the uniform distribution of MgCl_(2) and Mg_(3) Sb_(2),an electric field with a favorable potential gradient is formed on the anode surface,which enables swift Mg^(2+)migration.Meanwhile,this layer can inhibit the decomposition of electrolytes to protect anode.This work provides an in-depth exploration of the artificial solid-electrolyte interface(SEI)construction,and a more achievable and safe path to realize the application of metallic Mg anode in RMBs.展开更多
文摘Rechargeable Li metal batteries using Li metal anodes have attracted worldwide interest because of their high energy density. The critical barriers limiting their commercial application include uncontrolled dendritic Li growth and the unstable Li-electrolyte interface. Considerable efforts have been directed towards solving these problems, e.g., modifying the electrolyte, creating artificial interfacial layers for the Li metal, and constructing three-dimensional structures for the Li metal. However, stabilizing the Li metal interface remains challenging because of the highly reactive nature of the Li metal. In this study, we utilize a Li-ion conducting hybrid film comprising a garnet-type ion conductor and a poly（ethylene oxide）-based polymer electrolyte as a protective layer to stabilize the Li-electrolyte interface and mitigate the growth of Li dendrites. The hybrid ion-conducting layer can block Li dendrites from proliferating and accommodate Li volume expansion because of its robust mechanical properties. Moreover, the ion-conducting layer allows Li deposition only underneath it, rather than on the surface, functioning as a permanent protective layer to ensure the stability of the Li metal over a long cycling life. The dendrite-inhibiting effect of the ion-conducting protective layer is visually evidenced by in situ microscopy using planar batteries. The protective Li metal anode exhibits excellent cycling stability and low voltage hysteresis （-15 mV at 0.2 mA-cm-2） for a cycle life as long as 1,000 h. It also shows a high Coulombic efficiency （-99.5%） in a full cell against a LiFePO4 cathode, exhibiting promise for application in Li metal batteries. Our results imply that the ion-conducting protective layer markedly improves the metal anode, yielding safe, long-life, and high-energy-density batteries.
基金supported by the Outstanding Youth Fund Project by the Department of Science and Technology of Jiangsu Province(Grant No.BK20220045)the Key R&D Project funded by the Department of Science and Technology of Jiangsu Province(Grant No.BE2020003)+6 种基金Key Program-Automobile Joint Fund of National Natural Science Foundation of China(Grant No.U1964205)General Program of National Natural Science Foundation of China(Grant No.51972334)General Program of National Natural Science Foundation of Beijing(Grant No.2202058)Cultivation project of leading innovative experts in Changzhou City(CQ20210003)National Overseas High-level Expert recruitment Program(Grant No.E1JF021E11)Talent Program of Chinese Academy of Sciences,“Scientist Studio Program Funding”from Yangtze River Delta Physics Research Center,and Tianmu Lake Institute of Advanced Energy Storage Technologies(Grant No.TIESSS0001)Science and Technology Research Institute of China Three Gorges Corporation(Grant No.202103402)
文摘All-solid-state Li metal batteries(ASSLBs)using inorganic solid electrolyte(SE)are considered promising alternatives to conventional Li-ion batteries,offering improved safety and boosted energy density.While significant progress has been made on improving the ionic conductivity of SEs,the degradation and instability of Li metal/inorganic SE interfaces have become the critical challenges that limit the coulombic efficiency,power performance,and cycling stability of ASSLBs.Understanding the mechanisms of complex/dynamic interfacial phenomena is of great importance in addressing these issues.Herein,recent studies on identifying,understanding,and solving interfacial issues on anode side in ASSLBs are comprehensively reviewed.Typical issues at Li metal/SE interface include Li dendrite growth/propagation,SE cracking,physical contact loss,and electrochemical reactions,which lead to high interfacial resistance and cell failure.The causes of these issues relating to the chemical,physical,and mechanical properties of Li metal and SEs are systematically discussed.Furthermore,effective mitigating strategies are summarized and their effects on suppressing interfacial reactions,improving interfacial Li-ion transport,maintaining interfacial contact,and stabilizing Li plating/stripping are highlighted.The in-depth mechanistic understanding of interfacial issues and complete investigations on current solutions provide foundations and guidance for future research and development to realize practical application of high-performance ASSLB.
基金financially supported by the Fundamental Re-search Funds for the Central Universities(No.2021CDJXDJH003)the Chongqing Technology Innovation and Application Devel-opment Project(No.CSTB2022TIAD-KPX0028).
文摘Rechargeable magnesium batteries(RMBs)have attracted tremendous attention in energy storage ap-plications in term of high abundance,high specific capacity and remarkable safety of metallic magne-sium(Mg)anode.However,a serious passivation of Mg anode in the conventional electrolytes leads to extremely poor plating/stripping performance,further hindering its applications.Herein,we propose a convenient method to construct an artificial interphase layer on Mg anode by substitution and alloy-ing reactions between SbCl_(3) and Mg.This Sb-based artificial interphase layer containing mainly MgCl_(2) and Mg_(3) Sb_(2) endows the significantly improved interfacial kinetics and electrochemical performance of Mg anode.The overpotential of Mg plating/stripping in conventional Mg(TFSI)2/DME electrolytes is vastly reduced from over 2 V to 0.25-0.3 V.Combining experiments and calculations,we demonstrate that un-der the uniform distribution of MgCl_(2) and Mg_(3) Sb_(2),an electric field with a favorable potential gradient is formed on the anode surface,which enables swift Mg^(2+)migration.Meanwhile,this layer can inhibit the decomposition of electrolytes to protect anode.This work provides an in-depth exploration of the artificial solid-electrolyte interface(SEI)construction,and a more achievable and safe path to realize the application of metallic Mg anode in RMBs.
