Atomic Structure and Kinetics of NASICON NaxV2(PO4)3 Cathode for Sodium‐Ion Batteries

Na3V2(PO4)(3) is one of the most important cathode materials for sodiumion batteries, delivering about two Na extraction/insertion from/into the unit structure. To understand the mechanism of sodium storage, a detailed structure of rhombohedral Na3V2(PO4)(3) and its sodium extracted phase of NaV2(PO4)(3) are investigated at the atomic scale using a variety of advanced techniques. It is found that two different Na sites (6b, M1 and 18e, M2) with different coordination environments co-exist in Na3V2(PO4)(3), whereas only one Na site (6b, M1) exists in NaV2(PO4)(3). When Na is extracted from Na3V2(PO4)(3) to form NaV2(PO4)(3), Na+ occupying the M2 site (CN = 8) is extracted and the rest of the Na remains at M1 site (CN = 6). In addition, the Na atoms are not randomly distributed, possibly with an ordered arrangement in M2 sites locally for Na3V2(PO4)(3). Na+ ions at the M1 sites in Na3V2(PO4)(3) tend to remain immobilized, suggesting a direct M2- to -M2 conduction pathway. Only Na occupying the M2 sites can be extracted, suggesting about two Na atoms able to be extracted from the Na3V2(PO4)(3) structure.

[1]  Lin Gu,et al.  Rutile-TiO2 nanocoating for a high-rate Li4Ti5O12 anode of a lithium-ion battery. , 2012, Journal of the American Chemical Society.

[2]  F. Lange,et al.  7Li and 6Li Solid-State NMR Studies of Structure and Dynamics in LiNbO3−WO3 Solid Solutions , 1997 .

[3]  L. Nazar,et al.  Charge ordering in lithium vanadium phosphates: electrode materials for lithium-ion batteries. , 2003, Journal of the American Chemical Society.

[4]  Liquan Chen,et al.  Room-temperature stationary sodium-ion batteries for large-scale electric energy storage , 2013 .

[5]  J. Gopalakrishnan,et al.  Vanadium phosphate (V2(PO4)3): a novel NASICO N-type vanadium phosphate synthesized by oxidative deintercalation of sodium from sodium vanadium phosphate (Na3V2(PO4)3) , 1992 .

[6]  Yue Wu,et al.  NMR study of liquid to solid transition in a glass forming metallic system. , 2008, The Journal of chemical physics.

[7]  C. Grey,et al.  Linking local environments and hyperfine shifts: a combined experimental and theoretical (31)P and (7)Li solid-state NMR study of paramagnetic Fe(III) phosphates. , 2010, Journal of the American Chemical Society.

[8]  Y. Ishii,et al.  Enhanced sensitivity and resolution in (1)H solid-state NMR spectroscopy of paramagnetic complexes under very fast magic angle spinning. , 2005, Journal of the American Chemical Society.

[9]  A. Panich,et al.  Influence of molecular motions on NQR echoes , 2004 .

[10]  K. Nassau,et al.  Lithium ion conduction in rapidly quenched Li2O‐Al2O3, Li2O‐Ga2O3, and Li2O‐Bi2O3 glasses , 1980 .

[11]  W. W. Warren.  Nuclear quadrupolar relaxation in monatomic liquids , 1974 .

[12]  C. Dobson,et al.  Paramagnetic shift probes in high-resolution solid-state NMR , 1987, Nature.

[13]  A. D. Bain,et al.  Studies of lithium ion dynamics in paramagnetic cathode materials using (6)Li 1D selective inversion methods. , 2012, Solid state nuclear magnetic resonance.

[14]  C. Slichter.  Principles of magnetic resonance , 1963 .

[15]  Yong‐Sheng Hu,et al.  New insight into the atomic structure of electrochemically delithiated O3-Li(₁-x)CoO₂ (0 ≤ x ≤ 0.5) nanoparticles. , 2012, Nano letters.

[16]  Shinichi Komaba,et al.  P2-type Na(x)[Fe(1/2)Mn(1/2)]O2 made from earth-abundant elements for rechargeable Na batteries. , 2012, Nature materials.

[17]  D. Amm,et al.  Hydroxide-ion dynamics in cesium hydroxide: a deuteron nuclear magnetic resonance study , 1986 .

[18]  Igor V. Zatovsky,et al.  NASICON-type Na3V2(PO4)3 , 2010, Acta crystallographica. Section E, Structure reports online.

[19]  Seong‐Hyeon Hong,et al.  Spark plasma sintering of Al substituted LiHf2(PO4)3 solid electrolytes , 2005 .

[20]  M. Whittingham,et al.  What can we learn about battery materials from their magnetic properties , 2011 .

[21]  C. Delmas,et al.  Analysis of the 7Li NMR signals in the Monoclinic Li3Fe2(PO4)3 and Li3V2(PO4)3 Phases , 2010 .

[22]  Montse Casas-Cabanas,et al.  Room-temperature single-phase Li insertion/extraction in nanoscale Li(x)FePO4. , 2008, Nature materials.

[23]  J. P. Boilot,et al.  Relation Structure-Fast Ion Conduction in the NASICON Solid Solution , 1988 .

[24]  Paolo Ballirano,et al.  Rietveld refinements on laboratory energy dispersive X-ray diffraction (EDXD) data , 2001 .

[25]  C. Dobson,et al.  Paramagnetic ions as structural probes in solid-state NMR: Distance measurements in crystalline lanthanide acetates , 1993 .

[26]  Gerbrand Ceder,et al.  Electrode Materials for Rechargeable Sodium‐Ion Batteries: Potential Alternatives to Current Lithium‐Ion Batteries , 2012 .

[27]  N. Sergeev,et al.  NMR investigation of natrolite structure , 2001 .

[28]  Lin Gu,et al.  Direct atomic-scale confirmation of three-phase storage mechanism in Li4Ti5O12 anodes for room-temperature sodium-ion batteries , 2013, Nature Communications.

[29]  J. W. Akitt.  Multinuclear studies of aluminium compounds , 1989 .

[30]  Yuesheng Wang,et al.  A zero-strain layered metal oxide as the negative electrode for long-life sodium-ion batteries , 2013, Nature Communications.

[31]  Huilin Pan,et al.  Carbon coated Na3V2(PO4)3 as novel electrode material for sodium ion batteries , 2012 .

[32]  Lin Gu,et al.  Lithium Storage in Li4Ti5O12 Spinel: The Full Static Picture from Electron Microscopy , 2012, Advanced materials.

[33]  C. Masquelier,et al.  α-Na3M2(PO4)3 (M = Ti, Fe): absolute cationic ordering in NASICON-type phases. , 2011, Journal of the American Chemical Society.

[34]  B. C. Gerstein,et al.  Oxidation states of vanadium in V-P-O oxidation catalysts31P NMR by spin-echo mapping , 1991 .

[35]  H. Lukefahr,et al.  NMR and studies of non-Fermi-liquid behaviour in disordered heavy-fermion systems , 1996 .

[36]  E. Prince,et al.  Fast ion transport in the NASICON analog Na3Sc2(PO4)3: Structure and conductivity☆ , 1983 .

[37]  R. M. Cotts,et al.  PROTON MOTION, KNIGHT SHIFTS, AND QUADRUPOLAR EFFECTS IN THE LANTHANUM- HYDROGEN SYSTEM , 1963 .

[38]  Jing Zhou,et al.  Superior Electrochemical Performance and Storage Mechanism of Na3V2(PO4)3 Cathode for Room‐Temperature Sodium‐Ion Batteries , 2013 .

[39]  Masayoshi Ishida,et al.  Novel titanium-based O3-type NaTi(0.5)Ni(0.5)O2 as a cathode material for sodium ion batteries. , 2014, Chemical communications.

[40]  Zhenguo Yang,et al.  Reversible Sodium Ion Insertion in Single Crystalline Manganese Oxide Nanowires with Long Cycle Life , 2011, Advanced materials.

[41]  K. Kang,et al.  A new high-energy cathode for a Na-ion battery with ultrahigh stability. , 2013, Journal of the American Chemical Society.

[42]  P. D. Ellis,et al.  Aluminum-27 NMR spectroscopy of iron-bearing montmorillonite clays , 1990 .

[43]  Xia Lu,et al.  Sodium Storage and Transport Properties in Layered Na2Ti3O7 for Room‐Temperature Sodium‐Ion Batteries , 2013 .

[44]  Xiqian Yu,et al.  A size-dependent sodium storage mechanism in Li4Ti5O12 investigated by a novel characterization technique combining in situ X-ray diffraction and chemical sodiation. , 2013, Nano letters.

[45]  Donghan Kim,et al.  Sodium‐Ion Batteries , 2013 .

[46]  Teófilo Rojo,et al.  Na-ion batteries, recent advances and present challenges to become low cost energy storage systems , 2012 .

[47]  Lin Gu,et al.  Direct observation of lithium staging in partially delithiated LiFePO4 at atomic resolution. , 2011, Journal of the American Chemical Society.

[48]  John B. Goodenough,et al.  Li2NaV2(PO4)3: A 3.7 V Lithium-Insertion Cathode with the Rhombohedral NASICON Structure , 2001 .

[49]  J. Colin,et al.  Na2[(VO)2(HPO4)2C2O4].2H2O: crystal structure determination from combined powder diffraction and solid-state NMR. , 2006, Inorganic chemistry.

[50]  D Carlier,et al.  Electrochemical investigation of the P2–NaxCoO2 phase diagram. , 2011, Nature materials.

[51]  Junmei Zhao,et al.  Monodisperse iron phosphate nanospheres: preparation and application in energy storage. , 2012, ChemSusChem.

[52]  Lin Gu,et al.  Highly ordered staging structural interface between LiFePO4 and FePO4. , 2012, Physical chemistry chemical physics : PCCP.

[53]  Kazuma Gotoh,et al.  Electrochemical Na Insertion and Solid Electrolyte Interphase for Hard‐Carbon Electrodes and Application to Na‐Ion Batteries , 2011 .

[54]  J. Rodríguez-Carvajal,et al.  Magnetic structural studies of the two polymorphs of Li3Fe2(PO4)3: Analysis of the magnetic ground state from super-super exchange interactions , 2001 .

[55]  G. Goward,et al.  The Challenge of Paramagnetism in Two-Dimensional 6,7Li Exchange NMR , 2007 .

[56]  Junmei Zhao,et al.  Disodium Terephthalate (Na2C8H4O4) as High Performance Anode Material for Low‐Cost Room‐Temperature Sodium‐Ion Battery , 2012 .

[57]  Carlos Pecharromán,et al.  Relationship between Activation Energy and Bottleneck Size for Li+ Ion Conduction in NASICON Materials of Composition LiMM‘(PO4)3; M, M‘ = Ge, Ti, Sn, Hf , 1998 .

[58]  Kathryn E. Toghill,et al.  A multifunctional 3.5 V iron-based phosphate cathode for rechargeable batteries. , 2007, Nature materials.