Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and...Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and lithium metal consumption caused by polysulfide corrosion.Herein we design a dualfunction PMMA/PPC/LiNO3composite as an artificial solid electrolyte interphase(PMCN-SEI)to protect Li metal anode.This SEI offers multiple sites of C=O for polysulfide anchoring to constrain corrosion of Li metal anode.The lithiated polymer group and Li3N in PMCN-SEI can homogenize lithium-ion deposition behavior to achieve a dendrite-free anode.As a result,the PMCN-SEI protected Li metal anode enables the Li||Li symmetric batteries to maintain over 300 cycles(1300 h)at a capacity of 5 m Ah cm^(-2),corresponding to a cumulative capacity of 3.25 Ah cm^(-2).Moreover,Li-S batteries assembled with 20μm of Li metal anode(N/P=1.67)still deliver an initial capacity of 1166 m A h g-1at 0.5C.Hence,introducing polycarbonate polymer/inorganic composite SEI on Li provides a new solution for achieving the high energy density of Li-S batteries.展开更多
Lithium-ion battery has greatly changed our lifestyle and the solid electrolyte interphase(SEI)covered on the graphite anode determines the service life of a battery.The formation method and the formation temperature ...Lithium-ion battery has greatly changed our lifestyle and the solid electrolyte interphase(SEI)covered on the graphite anode determines the service life of a battery.The formation method and the formation temperature at initial cycle of a battery determine the feature of the SEI.Herein,we investigate the gap of formation behavior in both a half cell(graphite matches with lithium anode)and a full cell(graphite matches with NCM,short for LiNixCoyMn1-x-yO2)at different temperatures.We conclude that high temperature causes severe side reactions and low temperature will result in low ionic conductive SEI layer,the interface formed at room temperature owns the best ionic conductivity and stability.展开更多
Lithium-metal batteries with high energy/power densities have significant applications in electronics,electric vehicles,and stationary power plants.However,the unstable lithium-metal-anode/electrolyte interface has in...Lithium-metal batteries with high energy/power densities have significant applications in electronics,electric vehicles,and stationary power plants.However,the unstable lithium-metal-anode/electrolyte interface has induced insufficient cycle life and safety issues.To improve the cycle life and safety,understanding the formation of the solid electrolyte interphase(SEI)and growth of lithium dendrites near the anode/electrolyte interface,regulating the electrodeposition/electrostripping processes of Li^(+),and developing multiple approaches for protecting the lithium-metal surface and SEI layer are crucial and necessary.This paper comprehensively reviews the research progress in SEI and lithium dendrite growth in terms of their classical electrochemical lithium plating/stripping processes,interface interaction/nucleation processes,anode geometric evolution,fundamental electrolyte reduction mechanisms,and effects on battery performance.Some important aspects,such as charge transfer,the local current distribution,solvation,desolvation,ion diffusion through the interface,inhibition of dendrites by the SEI,additives,models for dendrite formation,heterogeneous nucleation,asymmetric processes during stripping/plating,the host matrix,and in situ nucleation characterization,are also analyzed based on experimental observations and theoretical calculations.Several technical challenges in improving SEI properties and reducing lithium dendrite growth are analyzed.Furthermore,possible future research directions for overcoming the challenges are also proposed to facilitate further research and development toward practical applications.展开更多
Highly safe and efficient rechargeable lithium batteries have become an indispensable component of the intelligent society powering smart electronics and electric vehicles.This review summarizes the formation principl...Highly safe and efficient rechargeable lithium batteries have become an indispensable component of the intelligent society powering smart electronics and electric vehicles.This review summarizes the formation principle,chemical compositions,and theoretical models of the solid electrolyte interphase(SEI)on the anode in the lithium battery,involving the functions and influences of the electroactive materials.The discrepancies of the SEI on different kinds of anode materials,as well as the choice and design of the electrolytes are detailedly clarified.Furthermore,the design strategies to obtain a stable and efficient SEI are outlined and discussed.Last but not least,the challenges and perspectives of artificial SEI technology are briefly proposed for the development of high-efficiency batteries in practice.展开更多
Lithium(Li)metal is regarded as the best anode material for lithium metal batteries(LMBs)due to its high theoretical specific capacity and low redox potential.However,the notorious dendrites growth and extreme instabi...Lithium(Li)metal is regarded as the best anode material for lithium metal batteries(LMBs)due to its high theoretical specific capacity and low redox potential.However,the notorious dendrites growth and extreme instability of the solid electrolyte interphase(SEI)layers have severely retarded the commercialization process of LMBs.Herein,a double-layered polymer/alloy composite artificial SEI composed of a robust poly(1,3-dioxolane)(PDOL)protective layer,Sn and LiCl nanoparticles,denoted as PDOL@Sn-LiCl,is fabricated by the combination of in-situ substitution and polymerization processes on the surface of Li metal anode.The lithiophilic Sn-LiCl multiphase can supply plenty of Li-ion transport channels,contributing to the homogeneous nucleation and dense accumulation of Li metal.The mechanically tough PDOL layer can maintain the stability and compact structure of the inorganic layer in the long-term cycling,and suppress the volume fluctuation and dendrites formation of the Li metal anode.As a result,the symmetrical cell under the double-layered artificial SEI protection shows excellent cycling stability of 300 h at 5.0 mA·cm^(−2)for 1 mAh·cm^(−2).Notably,the Li||LiFePO_(4)full cell also exhibits enhanced capacity retention of 150.1 mAh·g^(−1)after 600 cycles at 1.0 C.Additionally,the protected Li foil can effectively resist the air and water corrosion,signifying the safe operation of Li metal in practical applications.This present finding proposed a different tactic to achieve safe and dendrite-free Li metal anodes with excellent cycling stability.展开更多
Ionic liquids have been paid much attention and are considered to replace the conventional organic electrolyte and solve the safety issues by virtue of nonvolatility,non-flammability,high ionic conductivity and extend...Ionic liquids have been paid much attention and are considered to replace the conventional organic electrolyte and solve the safety issues by virtue of nonvolatility,non-flammability,high ionic conductivity and extended electrochemical steady window.The paper introduces ionic liquids electrolyte on basis of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI),which shows a wide electrochemical window (0.5-4.5 V vs.Li+/Li),and is theoretically feasible as an electrolyte for Li/LiFePO4batteries to improve the safety.Linear sweep voltammetry (LSV) was performed to investigate the electrochemical stability window of the polymer electrolyte.Interfacial resistance for Li/electrolyte/Li symmetric cells and Li/electrolyte/LiFePO4 cells were studied by electrochemical impedance spectroscopy (EIS).The results showed that additive vinylene carbonate (VC) enhances the formation of solid electrolyte interphase film to protect lithium anodes from corrosion and improves the compatibility of ionic liquid electrolyte towards lithium anodes.Accordingly,Li/LiFePO4cells delivers the initial discharge capacity of 124 mAh g-1 at a current rate of 0.1C in the ionic liquid electrolyte (EMITFSI+0.8 mol L-1LiTFSI+5 wt%VC),and shows better cyclability than in the ionic liquid electrolyte without VC.展开更多
The development of sodium-ion full cells is seriously suppressed by the incompatibility between electrodes and electrolytes. Most representatively, high-voltage ester-based electrolytes required by the cathodes presen...The development of sodium-ion full cells is seriously suppressed by the incompatibility between electrodes and electrolytes. Most representatively, high-voltage ester-based electrolytes required by the cathodes present poor interfacial compatibility with the anodes due to unstable solid electrode interphase(SEI). Herein, Fe S@N,S-C(spindle-like Fe S nanoparticles individually encapsulated in N,S-doped carbon) with excellent structural stability is synthesized as a potential sodium anode material. It exhibits exceptional interfacial stability in ester-based electrolyte(1 M NaClO_(4) in ethylene carbonate/propylene carbonate with 5% fluoroethylene carbonate) with long-cycling lifespan(294 days) in Na|Fe S@N,S-C coin cell and remarkable cyclability in pouch cell(capacity retention of 82.2% after 170 cycles at 0.2 A g^(-1)).DFT calculation reveals that N,S-doping on electrode surface could drive strong repulsion to solvated Na_(2) and preferential adsorption to ClO_(4)^(-) anion, guiding the anion-rich inner Helmholtz plane.Consequently, a robust SEI with rich inorganic species(NaCl and Na_(2)O) through the whole depth stabilizes the electrode–electrolyte interface and protects its integrity. This work brings new insight into the role of electrode’s surface properties in interfacial compatibility that can guide the design of more versatile electrodes for advanced rechargeable metal-ion batteries.展开更多
Electrolytes additives are ubiquitous and indispensable in all electrochemical devices. In this sense, the principle and the classification of film-forming additives for lithium ion secondary batteries are described. ...Electrolytes additives are ubiquitous and indispensable in all electrochemical devices. In this sense, the principle and the classification of film-forming additives for lithium ion secondary batteries are described. The film formation mechanism and research progress of the pyrazole derivatives, organic halogenide, esters and derivatives, boron compounds and inorganic compounds are introduced. Emphasis is focused on the principles and film-forming mechanisms of each additive. The development of film-forming additives is forecasted and prospected.展开更多
基金supported by the Jilin Province Science and Technology Department Program(YDZJ202201ZYTS304)the Science and Technology Project of Jilin Provincial Education Department(JJKH20220428KJ)+3 种基金the Jilin Province Science and Technology Department Program(YDZJ202101ZYTS047)the National Natural Science Foundation of China(21905110,21905041,22279045,22102020)the Special foundation of Jilin Province Industrial Technology Research and Development(2019C042)the Fundamental Research Funds for the Central Universities(2412020FZ008)。
文摘Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and lithium metal consumption caused by polysulfide corrosion.Herein we design a dualfunction PMMA/PPC/LiNO3composite as an artificial solid electrolyte interphase(PMCN-SEI)to protect Li metal anode.This SEI offers multiple sites of C=O for polysulfide anchoring to constrain corrosion of Li metal anode.The lithiated polymer group and Li3N in PMCN-SEI can homogenize lithium-ion deposition behavior to achieve a dendrite-free anode.As a result,the PMCN-SEI protected Li metal anode enables the Li||Li symmetric batteries to maintain over 300 cycles(1300 h)at a capacity of 5 m Ah cm^(-2),corresponding to a cumulative capacity of 3.25 Ah cm^(-2).Moreover,Li-S batteries assembled with 20μm of Li metal anode(N/P=1.67)still deliver an initial capacity of 1166 m A h g-1at 0.5C.Hence,introducing polycarbonate polymer/inorganic composite SEI on Li provides a new solution for achieving the high energy density of Li-S batteries.
基金supported by National Key Research and Development Program(2016YFA0202500)the National Natural Science Foundation of China(21776019)Beijing Natural Science Foundation(L182021)。
文摘Lithium-ion battery has greatly changed our lifestyle and the solid electrolyte interphase(SEI)covered on the graphite anode determines the service life of a battery.The formation method and the formation temperature at initial cycle of a battery determine the feature of the SEI.Herein,we investigate the gap of formation behavior in both a half cell(graphite matches with lithium anode)and a full cell(graphite matches with NCM,short for LiNixCoyMn1-x-yO2)at different temperatures.We conclude that high temperature causes severe side reactions and low temperature will result in low ionic conductive SEI layer,the interface formed at room temperature owns the best ionic conductivity and stability.
基金supported primarily by the National Key Research and Development Program of China(2020YFA0710303)National Natural Science Foundation of China(No.22109025)Natural Science Foundation of Fujian Province,China(2021J05121).
文摘Lithium-metal batteries with high energy/power densities have significant applications in electronics,electric vehicles,and stationary power plants.However,the unstable lithium-metal-anode/electrolyte interface has induced insufficient cycle life and safety issues.To improve the cycle life and safety,understanding the formation of the solid electrolyte interphase(SEI)and growth of lithium dendrites near the anode/electrolyte interface,regulating the electrodeposition/electrostripping processes of Li^(+),and developing multiple approaches for protecting the lithium-metal surface and SEI layer are crucial and necessary.This paper comprehensively reviews the research progress in SEI and lithium dendrite growth in terms of their classical electrochemical lithium plating/stripping processes,interface interaction/nucleation processes,anode geometric evolution,fundamental electrolyte reduction mechanisms,and effects on battery performance.Some important aspects,such as charge transfer,the local current distribution,solvation,desolvation,ion diffusion through the interface,inhibition of dendrites by the SEI,additives,models for dendrite formation,heterogeneous nucleation,asymmetric processes during stripping/plating,the host matrix,and in situ nucleation characterization,are also analyzed based on experimental observations and theoretical calculations.Several technical challenges in improving SEI properties and reducing lithium dendrite growth are analyzed.Furthermore,possible future research directions for overcoming the challenges are also proposed to facilitate further research and development toward practical applications.
基金supported partially by the project of the State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources(Nos.LAPS21004 and LAPS202114)National Natural Science Foundation of China(Nos.52272200,51972110,52102245,and 52072121)+6 种基金Beijing Science and Technology Project(No.Z211100004621010)Beijing Natural Science Foundation(Nos.2222076 and 2222077)Hebei Natural Science Foundation(No.E2022502022)Huaneng Group Headquarters Science and Technology Project((No.HNKJ20-H88)2022 Strategic Research Key Project of Science and Technology Commission of the Ministry of Education,China Postdoctoral Science Foundation(No.2022M721129)the Fundamental Research Funds for the Central Universities(Nos.2022MS030,2021MS028,2020MS023,and 2020MS028)the NCEPU“Double First-Class”Program.
文摘Highly safe and efficient rechargeable lithium batteries have become an indispensable component of the intelligent society powering smart electronics and electric vehicles.This review summarizes the formation principle,chemical compositions,and theoretical models of the solid electrolyte interphase(SEI)on the anode in the lithium battery,involving the functions and influences of the electroactive materials.The discrepancies of the SEI on different kinds of anode materials,as well as the choice and design of the electrolytes are detailedly clarified.Furthermore,the design strategies to obtain a stable and efficient SEI are outlined and discussed.Last but not least,the challenges and perspectives of artificial SEI technology are briefly proposed for the development of high-efficiency batteries in practice.
基金support from the National Natural Science Foundation of China(Nos.22075042 and 52102310)Shanghai Rising-Star Program(No.22QA1400300)+2 种基金the Natural Science Foundation of Shanghai(No.20ZR1401400)the Shanghai Scientific and Technological Innovation Project(No.22520710100)the Fundamental Research Funds for the Central Universities,and the Donghua University(DHU)Distinguished Young Professor Program(No.LZB2021002).
文摘Lithium(Li)metal is regarded as the best anode material for lithium metal batteries(LMBs)due to its high theoretical specific capacity and low redox potential.However,the notorious dendrites growth and extreme instability of the solid electrolyte interphase(SEI)layers have severely retarded the commercialization process of LMBs.Herein,a double-layered polymer/alloy composite artificial SEI composed of a robust poly(1,3-dioxolane)(PDOL)protective layer,Sn and LiCl nanoparticles,denoted as PDOL@Sn-LiCl,is fabricated by the combination of in-situ substitution and polymerization processes on the surface of Li metal anode.The lithiophilic Sn-LiCl multiphase can supply plenty of Li-ion transport channels,contributing to the homogeneous nucleation and dense accumulation of Li metal.The mechanically tough PDOL layer can maintain the stability and compact structure of the inorganic layer in the long-term cycling,and suppress the volume fluctuation and dendrites formation of the Li metal anode.As a result,the symmetrical cell under the double-layered artificial SEI protection shows excellent cycling stability of 300 h at 5.0 mA·cm^(−2)for 1 mAh·cm^(−2).Notably,the Li||LiFePO_(4)full cell also exhibits enhanced capacity retention of 150.1 mAh·g^(−1)after 600 cycles at 1.0 C.Additionally,the protected Li foil can effectively resist the air and water corrosion,signifying the safe operation of Li metal in practical applications.This present finding proposed a different tactic to achieve safe and dendrite-free Li metal anodes with excellent cycling stability.
基金Sponsored by the Natural Science Foundation of Heilongjiang Province of China (Grant No.B2007-05)the Natural Scientific Research Innovation Foundation in Harbin Institute of Technology (Grant No.HIT.NSRIF.2009121)
文摘Ionic liquids have been paid much attention and are considered to replace the conventional organic electrolyte and solve the safety issues by virtue of nonvolatility,non-flammability,high ionic conductivity and extended electrochemical steady window.The paper introduces ionic liquids electrolyte on basis of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI),which shows a wide electrochemical window (0.5-4.5 V vs.Li+/Li),and is theoretically feasible as an electrolyte for Li/LiFePO4batteries to improve the safety.Linear sweep voltammetry (LSV) was performed to investigate the electrochemical stability window of the polymer electrolyte.Interfacial resistance for Li/electrolyte/Li symmetric cells and Li/electrolyte/LiFePO4 cells were studied by electrochemical impedance spectroscopy (EIS).The results showed that additive vinylene carbonate (VC) enhances the formation of solid electrolyte interphase film to protect lithium anodes from corrosion and improves the compatibility of ionic liquid electrolyte towards lithium anodes.Accordingly,Li/LiFePO4cells delivers the initial discharge capacity of 124 mAh g-1 at a current rate of 0.1C in the ionic liquid electrolyte (EMITFSI+0.8 mol L-1LiTFSI+5 wt%VC),and shows better cyclability than in the ionic liquid electrolyte without VC.
基金supported by the National Natural Science Foundation of China (U1804129, 21771164)the Program for Young Scholar of Changjiang Scholars+1 种基金Zhongyuan Youth Talent Support Program of Henan ProvinceZhengzhou University Youth Innovation Program。
文摘The development of sodium-ion full cells is seriously suppressed by the incompatibility between electrodes and electrolytes. Most representatively, high-voltage ester-based electrolytes required by the cathodes present poor interfacial compatibility with the anodes due to unstable solid electrode interphase(SEI). Herein, Fe S@N,S-C(spindle-like Fe S nanoparticles individually encapsulated in N,S-doped carbon) with excellent structural stability is synthesized as a potential sodium anode material. It exhibits exceptional interfacial stability in ester-based electrolyte(1 M NaClO_(4) in ethylene carbonate/propylene carbonate with 5% fluoroethylene carbonate) with long-cycling lifespan(294 days) in Na|Fe S@N,S-C coin cell and remarkable cyclability in pouch cell(capacity retention of 82.2% after 170 cycles at 0.2 A g^(-1)).DFT calculation reveals that N,S-doping on electrode surface could drive strong repulsion to solvated Na_(2) and preferential adsorption to ClO_(4)^(-) anion, guiding the anion-rich inner Helmholtz plane.Consequently, a robust SEI with rich inorganic species(NaCl and Na_(2)O) through the whole depth stabilizes the electrode–electrolyte interface and protects its integrity. This work brings new insight into the role of electrode’s surface properties in interfacial compatibility that can guide the design of more versatile electrodes for advanced rechargeable metal-ion batteries.
文摘Electrolytes additives are ubiquitous and indispensable in all electrochemical devices. In this sense, the principle and the classification of film-forming additives for lithium ion secondary batteries are described. The film formation mechanism and research progress of the pyrazole derivatives, organic halogenide, esters and derivatives, boron compounds and inorganic compounds are introduced. Emphasis is focused on the principles and film-forming mechanisms of each additive. The development of film-forming additives is forecasted and prospected.
