In situ quantification and visualization of lithium transport with neutrons.

A real-time quantification of Li transport using a nondestructive neutron method to measure the Li distribution upon charge and discharge in a Li-ion cell is reported. By using in situ neutron depth profiling (NDP), we probed the onset of lithiation in a high-capacity Sn anode and visualized the enrichment of Li atoms on the surface followed by their propagation into the bulk. The delithiation process shows the removal of Li near the surface, which leads to a decreased coulombic efficiency, likely because of trapped Li within the intermetallic material. The developed in situ NDP provides exceptional sensitivity in the temporal and spatial measurement of Li transport within the battery material. This diagnostic tool opens up possibilities to understand rates of Li transport and their distribution to guide materials development for efficient storage mechanisms. Our observations provide important mechanistic insights for the design of advanced battery materials.

[1]  J. Mondori,et al.  Mechanism leading to irreversible capacity loss in Li ion rechargeable batteries , 1995 .

[2]  Yoyo Hinuma,et al.  Lithium Diffusion in Graphitic Carbon , 2010, 1108.0576.

[3]  J. Besenhard,et al.  Kinetics of Li insertion into polycrystalline and nanocrystalline `SnSb' alloys investigated by transient and steady state techniques , 1999 .

[4]  S. Yanase,et al.  Observation of Lithium Isotope Effect Accompanying Electrochemical Insertion of Lithium into Tin , 2000 .

[5]  Yi Cui,et al.  Nanoporous silicon networks as anodes for lithium ion batteries. , 2013, Physical chemistry chemical physics : PCCP.

[6]  J. Dahn,et al.  Anomalous, high-voltage irreversible capacity in tin electrodes for lithium batteries , 2003 .

[7]  Patrick Willmann,et al.  A combined Mössbauer spectroscopy and x-ray diffraction operando study of Sn-based composite anode materials for Li-ion accumulators , 2012, Journal of Solid State Electrochemistry.

[8]  R. Huggins,et al.  Chemical diffusion in intermediate phases in the lithium-tin system , 1980 .

[9]  Martin Winter,et al.  Electrochemical lithiation of tin and tin-based intermetallics and composites , 1999 .

[10]  Guangyuan Zheng,et al.  Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries , 2013, Nature Communications.

[11]  G. Hwang,et al.  Surface effects on the structure and lithium behavior in lithiated silicon: A first principles study , 2013 .

[12]  Bruno Scrosati,et al.  Lithium Rocking Chair Batteries: An Old Concept? , 1992 .

[13]  Emanuel Peled,et al.  The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model , 1979 .

[14]  G. Henkelman,et al.  Lithium insertion in nanostructured TiO(2)(B) architectures. , 2013, Accounts of chemical research.

[15]  John B. Goodenough,et al.  Neutron Depth Profiling Applications to Lithium-Ion Cell Research , 2009 .

[16]  Young-Il Jang,et al.  Electrochemically-driven solid-state amorphization in lithium-silicon alloys and implications for lithium storage , 2003 .

[17]  N. Imanishi,et al.  Li-ion diffusion behavior in Sn, SnO and SnO2 thin films studied by galvanostatic intermittent titration technique , 2010 .

[18]  G. Pellissier,et al.  The Oxidation of Tin II . The Morphology and Mode of Growth of Oxide Films on Pure Tin , 1961 .

[19]  G. Pellissier,et al.  The Oxidation of Tin I . The Kinetics of Oxidation of Pure Tin and the Effects of Temperature and Oxygen Pressure , 1961 .

[20]  P. Notten,et al.  In Situ Neutron Depth Profiling: A Powerful Method to Probe Lithium Transport in Micro‐Batteries , 2011, Advanced materials.

[21]  Jae-Hun Kim,et al.  Li-alloy based anode materials for Li secondary batteries. , 2010, Chemical Society reviews.

[22]  W. Boggs.  The Oxidation of Tin III . The Mechanisms of Oxidation of Pure Tin and Their Dependence on Time and Oxygen Pressure , 1961 .

[23]  R. G. Downing,et al.  Neutron Depth Profiling: Overview and Description of NIST Facilities , 2018, Journal of research of the National Institute of Standards and Technology.

[24]  John P. Sullivan,et al.  In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode , 2010, Science.

[25]  C. C. Ahn,et al.  Nanocrystalline and Thin Film Germanium Electrodes with High Lithium Capacity and High Rate Capabilities , 2004 .

[26]  C. Grey,et al.  In situ solid-state NMR spectroscopy of electrochemical cells: batteries, supercapacitors, and fuel cells. , 2013, Accounts of chemical research.

[27]  P. K. Trojan,et al.  Engineering materials and their applications , 1975 .

[28]  Adam T. Timmons,et al.  In Situ AFM Measurements of the Expansion of Nanostructured Sn–Co–C Films Reacting with Lithium , 2009 .

[29]  Marco Stampanoni,et al.  Visualization and Quantification of Electrochemical and Mechanical Degradation in Li Ion Batteries , 2013, Science.