Na+ Migration Mediated Phase Transitions Induced by Electric Field in the Framework Structured Tungsten Bronze.

Framework structured tungsten bronzes serve as promising candidates for electrode materials in sodium-ion batteries (SIBs). However, the tungsten bronze framework structure changes drastically as mediated by the sodium ion concentration at high temperatures. While the three-dimensional ion channels facilitate fast ion storage and transport capabilities, the structural instability induced by Na+ migration is a big concern regarding the battery performance and safety, which unfortunately remains elusive. Here, we show the real-time experimental evidence of the phase transitions in framework structured Na0.36WO3.14 (triclinic phase) by applying different external voltages. The Na+-rich (Na0.48WO3, tetragonal phase) or -deficient (NaxWO3, x < 0.36, hexagonal phase) phase nucleates under the positive or negative bias, respectively. Combined with the theoretical calculations, the atomistic phase transition mechanisms associated with the Na+ migration are directly uncovered. Our work sheds light on the phase instability in sodium tungsten bronzes and paves the way for designing advanced SIBs with high-stability.

[1]  F. Krumeich.  The Complex Crystal Chemistry of Niobium Tungsten Oxides , 2022, Chemistry of Materials.

[2]  He Zheng,et al.  Cation Defect Mediated Phase Transition in Potassium Tungsten Bronze. , 2021, Inorganic chemistry.

[3]  He Zheng,et al.  Room-temperature oxygen vacancy migration induced reversible phase transformation during the anelastic deformation in CuO , 2021, Nature Communications.

[4]  M. Engelhard,et al.  Advanced low-flammable electrolytes for stable operation of high-voltage lithium-ion batteries. , 2021, Angewandte Chemie.

[5]  S. Meng,et al.  Atomistic Observation of Desodiation-Induced Phase Transition in Sodium Tungsten Bronze. , 2021, Journal of Physical Chemistry Letters.

[6]  Yanfeng Gao,et al.  Electronic properties, optical properties and diffusion behavior of WO3 with H+, Li+ and Na+ intercalated ions: A first-principles study , 2021 .

[7]  S. Meng,et al.  Irradiation and Size Effects on Redox Reaction Mechanisms in Iron Oxides , 2021 .

[8]  A. Lewandowski,et al.  Flammability parameters of lithium-ion battery electrolytes , 2020 .

[9]  Renhui Jiang,et al.  Coating‐Mediated Nanomechanical Behaviors of CuO Electrodes in Li‐ and Na‐Ion Batteries , 2020, Advanced Materials Interfaces.

[10]  S. Meng,et al.  Atomistic and dynamic structural characterizations in low-dimensional materials: recent applications of in situ transmission electron microscopy. , 2019, Microscopy.

[11]  Ya‐Xia Yin,et al.  A Stable Layered Oxide Cathode Material for High‐Performance Sodium‐Ion Battery , 2019, Advanced Energy Materials.

[12]  Lauren E. Marbella,et al.  Niobium tungsten oxides for high-rate lithium-ion energy storage , 2018, Nature.

[13]  G. Mulder,et al.  Sodium‐Ion Battery Materials and Electrochemical Properties Reviewed , 2018 .

[14]  Sen Xin,et al.  Stabilizing a High-Energy-Density Rechargeable Sodium Battery with a Solid Electrolyte , 2018 .

[15]  Zhenguo Yao,et al.  H-Nb2O5 wired by tetragonal tungsten bronze related domains as high-rate anode for Li-ion batteries , 2018 .

[16]  Yinghao Lv,et al.  Surface‐Coating‐Mediated Electrochemical Performance in CuO Nanowires during the Sodiation–Desodiation Cycling , 2018 .

[17]  B. P. Jelle,et al.  Electrochromism of Hexagonal Sodium Tungsten Bronze Nanorods , 2017 .

[18]  Yong‐Sheng Hu,et al.  Atomic‐Scale Monitoring of Electrode Materials in Lithium‐Ion Batteries using In Situ Transmission Electron Microscopy , 2017 .

[19]  Jun Lu,et al.  Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy , 2017, Nature Communications.

[20]  Shaofei Wang,et al.  Y-Doped NASICON-type LiZr2(PO4)3 Solid Electrolytes for Lithium-Metal Batteries , 2017 .

[21]  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.

[22]  Jianbo Wang,et al.  Atomic‐Scale Study of Cation Ordering in Potassium Tungsten Bronze Nanosheets , 2017, Advanced science.

[23]  John B Goodenough,et al.  An Aqueous Symmetric Sodium-Ion Battery with NASICON-Structured Na3 MnTi(PO4 )3. , 2016, Angewandte Chemie.

[24]  A. Soon,et al.  Unraveling the Intercalation Chemistry of Hexagonal Tungsten Bronze and Its Optical Responses , 2016 .

[25]  Yuyan Shao,et al.  Atomistic Conversion Reaction Mechanism of WO3 in Secondary Ion Batteries of Li, Na, and Ca. , 2016, Angewandte Chemie.

[26]  Minghui Yang,et al.  Tetragonal Tungsten Bronze Framework as Potential Anode for Na-Ion Batteries , 2016 .

[27]  Peter Lamp,et al.  Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction. , 2015, Chemical reviews.

[28]  N. Sharma,et al.  Sodium Distribution and Reaction Mechanisms of a Na3V2O2(PO4)2F Electrode during Use in a Sodium-Ion Battery , 2014 .

[29]  Jianbo Wang,et al.  Self-assembly of KxWO3 nanowires into nanosheets by an oriented attachment mechanism. , 2013, ACS applied materials & interfaces.

[30]  L. Gu,et al.  An FeF(3)·0.5H2O polytype: a microporous framework compound with intersecting tunnels for Li and Na batteries. , 2013, Journal of the American Chemical Society.

[31]  B. P. Jelle,et al.  Visible-Light-Driven Photochromism of Hexagonal Sodium Tungsten Bronze Nanorods , 2013 .

[32]  X. Mu,et al.  Top-Down Synthesis of Open Framework Fluoride for Lithium and Sodium Batteries , 2013 .

[33]  Ting Zhu,et al.  In Situ TEM Experiments of Electrochemical Lithiation and Delithiation of Individual Nanostructures , 2012 .

[34]  B. Tang,et al.  Microcrystalline sodium tungsten bronze nanowire bundles as efficient visible light-responsive photocatalysts. , 2010, Chemical communications.

[35]  Y. Chiang.  Building a Better Battery , 2010, Science.

[36]  P. Taberna,et al.  Monolithic Carbide-Derived Carbon Films for Micro-Supercapacitors , 2010, Science.

[37]  Chang Liu,et al.  Advanced Materials for Energy Storage , 2010, Advanced materials.

[38]  M. Armand,et al.  Building better batteries , 2008, Nature.

[39]  G. Henkelman,et al.  A climbing image nudged elastic band method for finding saddle points and minimum energy paths , 2000 .

[40]  Yan Yu,et al.  Progress of enhancing the safety of lithium ion battery from the electrolyte aspect , 2019, Nano Energy.

[41]  P. Balaya,et al.  NaVPO4F with high cycling stability as a promising cathode for sodium-ion battery , 2018 .