Porosity Development at Li-Rich Layered Cathodes in All-Solid-State Battery during In Situ Delithiation.

Structural evolutions are crucial for determining the performance of high-voltage lithium, manganese-rich layered cathodes. Moreover, interface between electrode and electrolyte plays a critical role in governing ionic transfer in all-solid-state batteries. Here, we unveil two different types of porous structure in Li1.2Ni0.2Mn0.6O2 cathode with LiPON solid-state electrolyte. Nanopores are found near the cathode/electrolyte interface at pristine state, where cation mixing, phase transformation, oxygen loss, and Mn reduction are also found. In situ Li+ extraction induces the evolution of nanovoids, initially formed near the interface then propagated into the bulk. Despite the development of nanovoids, layered structure is conserved, suggesting the nature of nanopores and nanovoids are different and their impact would be divergent. This work demonstrates the intrinsic interfacial layer, as well as the dynamic scenario of nanovoid formation inside high-capacity layered cathode, which helps to understand the performance fading in cathodes and offers insight into the all-solid-state battery design.

[1]  William E. Gent,et al.  Persistent and partially mobile oxygen vacancies in Li-rich layered oxides , 2021, Nature Energy.

[2]  Zachary D. Hood,et al.  Elucidating Interfacial Stability between Lithium Metal Anode and Li Phosphorus Oxynitride via In Situ Electron Microscopy. , 2020, Nano letters.

[3]  L. Gu,et al.  Direct observation of defect-aided structural evolution in Ni-rich layered cathode. , 2020, Angewandte Chemie.

[4]  K. Amine,et al.  Injection of oxygen vacancies in the bulk lattice of layered cathodes , 2019, Nature Nanotechnology.

[5]  Hong Li,et al.  Practical Evaluation of Li-Ion Batteries , 2019, Joule.

[6]  C. Wolverton,et al.  Dynamic imaging of crystalline defects in lithium-manganese oxide electrodes during electrochemical activation to high voltage , 2019, Nature Communications.

[7]  Y. Meng,et al.  Quantifying inactive lithium in lithium metal batteries , 2018, Nature.

[8]  Wu Xu,et al.  Direct Visualization of Li Dendrite Effect on LiCoO2 Cathode by In Situ TEM. , 2018, Small.

[9]  Zhenzhong Yang,et al.  Formation, Structural Variety, and Impact of Antiphase Boundaries on Li Diffusion in LiCoO2 Thin-Film Cathodes. , 2018, The journal of physical chemistry letters.

[10]  Y. Ukyo,et al.  Interfacial Atomic Structures of Single-Phase Li2MnO3 Thin Film with Superior Initial Charge-Discharge Behavior , 2018 .

[11]  Yong‐Sheng Hu,et al.  In Situ Atomic-Scale Observation of Electrochemical Delithiation Induced Structure Evolution of LiCoO2 Cathode in a Working All-Solid-State Battery. , 2017, Journal of the American Chemical Society.

[12]  Ji‐Guang Zhang,et al.  Li‐ and Mn‐Rich Cathode Materials: Challenges to Commercialization , 2017 .

[13]  Yi Cui,et al.  Reviving the lithium metal anode for high-energy batteries. , 2017, Nature nanotechnology.

[14]  Y. Meng,et al.  Understanding and Controlling Anionic Electrochemical Activity in High-Capacity Oxides for Next Generation Li-Ion Batteries , 2017 .

[15]  S. Passerini,et al.  Lithium‐ and Manganese‐Rich Oxide Cathode Materials for High‐Energy Lithium Ion Batteries , 2016 .

[16]  M. Bugnet,et al.  Spatially resolved surface valence gradient and structural transformation of lithium transition metal oxides in lithium-ion batteries. , 2016, Physical chemistry chemical physics : PCCP.

[17]  Y. Meng,et al.  Effects of cathode electrolyte interfacial (CEI) layer on long term cycling of all-solid-state thin-film batteries , 2016 .

[18]  Rahul Malik,et al.  The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. , 2016, Nature chemistry.

[19]  N. Dudney,et al.  In Situ STEM-EELS Observation of Nanoscale Interfacial Phenomena in All-Solid-State Batteries. , 2016, Nano letters.

[20]  Doron Aurbach,et al.  Promise and reality of post-lithium-ion batteries with high energy densities , 2016 .

[21]  Yizhou Zhu,et al.  First principles study on electrochemical and chemical stability of solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries , 2016 .

[22]  J. Tarascon,et al.  Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries , 2015, Science.

[23]  Karsten Reuter,et al.  Interfacial challenges in solid-state Li ion batteries. , 2015, The journal of physical chemistry letters.

[24]  Guoying Chen,et al.  Unravelling structural ambiguities in lithium- and manganese-rich transition metal oxides , 2015, Nature Communications.

[25]  Guoying Chen,et al.  Phosphorus Enrichment as a New Composition in the Solid Electrolyte Interphase of High-Voltage Cathodes and Its Effects on Battery Cycling , 2015 .

[26]  Jianming Zheng,et al.  Structural and Chemical Evolution of Li- and Mn-Rich Layered Cathode Material , 2015 .

[27]  Miaofang Chi,et al.  Solid Electrolyte: the Key for High‐Voltage Lithium Batteries , 2015 .

[28]  B. Polzin,et al.  Functioning Mechanism of AlF3 Coating on the Li- and Mn-Rich Cathode Materials , 2014 .

[29]  Kang Xu,et al.  Electrolytes and interphases in Li-ion batteries and beyond. , 2014, Chemical reviews.

[30]  H. Yamasaki,et al.  Dielectric Modification of 5V‐Class Cathodes for High‐Voltage All‐Solid‐State Lithium Batteries , 2014 .

[31]  Gerbrand Ceder,et al.  Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries , 2014, Science.

[32]  Ji‐Guang Zhang,et al.  Corrosion/fragmentation of layered composite cathode and related capacity/voltage fading during cycling process. , 2013, Nano letters.

[33]  K. Amine,et al.  Nanoscale Phase Separation, Cation Ordering, and Surface Chemistry in Pristine Li1.2Ni0.2Mn0.6O2 for Li-Ion Batteries , 2013 .

[34]  Debasish Mohanty,et al.  Investigating phase transformation in the Li1.2Co0.1Mn0.55Ni0.15O2 lithium-ion battery cathode during high-voltage hold (4.5 V) via magnetic, X-ray diffraction and electron microscopy studies , 2013 .

[35]  Lijun Wu,et al.  Combining In Situ Synchrotron X‐Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium‐Ion Batteries , 2013 .

[36]  J. Colin,et al.  Evolutions of Li1.2Mn0.61Ni0.18Mg0.01O2 during the Initial Charge/Discharge Cycle Studied by Advanced Electron Microscopy , 2012 .

[37]  Miaofang Chi,et al.  Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical study , 2011 .

[38]  D. Abraham,et al.  Structural study of Li2MnO3 by electron microscopy , 2009 .

[39]  Y. Meng,et al.  Cation Ordering in Layered O3 Li[NixLi1/3-2x/3Mn2/3-x/3]O2 (0 ≤ x ≤ 1/2) Compounds , 2005 .

[40]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.

[41]  G. Ceder,et al.  Identification of cathode materials for lithium batteries guided by first-principles calculations , 1998, Nature.

[42]  Gerbrand Ceder,et al.  Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides , 1997 .

[43]  G. Jellison,et al.  A Stable Thin‐Film Lithium Electrolyte: Lithium Phosphorus Oxynitride , 1997 .