Study on structure and electrochemical properties of carbon-coated monoclinic Li3V2(PO4)3 using synchrotron based in situ X-ray diffraction and absorption

Monoclinic Li3V2(PO4)3, is a highly promising cathode material for lithium–ion rechargeable batteries. It has good ion mobility and high lithium capacity due to its ability to reversibly extract all three lithium ions. Here, we present, a systematic investigation of phase transitions and volume variations that occur during lithium extraction from the carbon-coated monoclinic phase of Li3V2(PO4)3 by synchrotron based in situ X-ray diffraction and X-ray absorption spectroscopy. This monoclinic Li3V2(PO4)3 illustrates complex behavior of four successive two-phase transitions upon extraction of all three lithium ions between 3.0 and 4.8 V vs. Li/Li+. Each XRD pattern of the intermediate compositions can be fully indexed in the monoclinic space group P21/n, with net volume reduction of 6.47%. In situ V K-edge XANES in combination with study of structural parameters is applied to find the vanadium valence state at plateau regions, which highlights the variations in electrochemical potential constraining to extraction of lithium ion from different crystal sites.

[1]  L. Nazar,et al.  Nanostructured Composites: A High Capacity, Fast Rate Li3V2(PO4)3/Carbon Cathode for Rechargeable Lithium Batteries , 2002 .

[2]  Feng Wu,et al.  Rate performance of Li3V2(PO4)3/C cathode material and its Li+ ion intercalation behavior , 2012 .

[3]  Yun‐Sung Lee,et al.  Synthesis and Electrochemical Properties of Nanocrystalline LiFePO 4 Obtained by Different Methods , 2011 .

[4]  M. Morcrette,et al.  A comparative structural and electrochemical study of monoclinic Li3Fe2(PO4)3 and Li3V2(PO4)3 , 2003 .

[5]  John B. Goodenough,et al.  Rechargeable batteries: challenges old and new , 2012, Journal of Solid State Electrochemistry.

[6]  Karim Zaghib,et al.  The phase transition behaviors of Li1−xMn0.5Fe0.5PO4 during lithium extraction studied by in situ X-ray absorption and diffraction techniques , 2009 .

[7]  Xiao‐Qing Yang,et al.  In Situ X-ray Absorption Spectroscopic Study on LiNi0.5Mn0.5O2 Cathode Material during Electrochemical Cycling , 2003 .

[8]  Yun-Sung Lee,et al.  LiMnPO4 - A next generation cathode material for lithium-ion batteries , 2013 .

[9]  Xianjun Zhu,et al.  Synthesis and performance of lithium vanadium phosphate as cathode materials for lithium ion batteries by a sol–gel method , 2008 .

[10]  Yunhui Huang,et al.  High-performance Li3V2(PO4)3/C cathode materials prepared via a sol–gel route with double carbon sources , 2012 .

[11]  K. Kang,et al.  Carbon supported, Al doped-Li3V2(PO4)3 as a high rate cathode material for lithium-ion batteries , 2012 .

[12]  L. Nazar,et al.  Electrochemical property: Structure relationships in monoclinic Li(3-y)V2(PO4)3. , 2003, Journal of the American Chemical Society.

[13]  I. Taniguchi,et al.  Synthesis of carbon-coated LiFePO4 nanoparticles with high rate performance in lithium secondary batteries , 2010 .

[14]  Yong Yang,et al.  Recent advances in the research of polyanion-type cathode materials for Li-ion batteries , 2011 .

[15]  J. Tu,et al.  Enhanced electrochemical performances of multi-walled carbon nanotubes modified Li3V2(PO4)3/C cathode material for lithium-ion batteries , 2011 .

[16]  S. Park,et al.  Atomistic Simulation Study of Monoclinic Li3V2(PO4)3 as a Cathode Material for Lithium Ion Battery: Structure, Defect Chemistry, Lithium Ion Transport Pathway, and Dynamics , 2012 .

[17]  Gang Chen,et al.  Preparation and electrochemical studies of Li3V2(PO4)3/Cu composite cathode material for lithium ion batteries , 2009 .

[18]  Yun‐Sung Lee,et al.  Crystal Structure Changes of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode Materials During the First Charge Investigated by in situ XRD , 2012 .

[19]  Jeremy Barker,et al.  The electrochemical insertion properties of sodium vanadium fluorophosphate, Na3V2(PO4)2F3 , 2006 .

[20]  Arumugam Manthiram,et al.  One-Pot Microwave-Hydrothermal Synthesis and Characterization of Carbon-Coated LiMPO4 (M = Mn , Fe, and Co) Cathodes , 2009 .

[21]  Yang-Kook Sun,et al.  Challenges facing lithium batteries and electrical double-layer capacitors. , 2012, Angewandte Chemie.

[22]  Yong Zhang,et al.  Effects of nickel-doped lithium vanadium phosphate on the performance of lithium-ion batteries , 2012 .

[23]  Haoshen Zhou,et al.  Enhancing the performances of Li-ion batteries by carbon-coating: present and future. , 2012, Chemical communications.

[24]  Bruno Scrosati,et al.  High‐Performance Carbon‐LiMnPO4 Nanocomposite Cathode for Lithium Batteries , 2010 .

[25]  Gerbrand Ceder,et al.  Experimental and Computational Study of the Structure and Electrochemical Properties of LixM2(PO4)3 Compounds with the Monoclinic and Rhombohedral Structure , 2002 .

[26]  K. Kang,et al.  Charge/Discharge Mechanism of Multicomponent Olivine Cathode for Lithium Rechargeable Batteries , 2011 .

[27]  James McBreen,et al.  In situ X-ray diffraction and X-ray absorption studies of high-rate lithium-ion batteries , 2001 .

[28]  G. Wen,et al.  Synthesis and electrochemical performance of Sn-doped Li3V2(PO4)3/C cathode material for lithium ion battery by microwave solid-state technique , 2012 .

[29]  M. Zhao,et al.  Effect of MgO nanolayer coated on Li3V2(PO4)3/C cathode material for lithium-ion battery , 2010 .

[30]  Matthieu Dubarry,et al.  Evaluation of commercial lithium-ion cells based on composite positive electrode for plug-in hybrid electric vehicle applications. Part I: Initial characterizations , 2011 .

[31]  M. Morcrette,et al.  In Situ X-Ray Diffraction during Lithium Extraction from Rhombohedral and Monoclinic Li3 V 2 ( PO 4 ) 3 , 2003 .

[32]  R. Dominko,et al.  A3V2(PO4)3 (A = Na or Li) probed by in situ X-ray absorption spectroscopy , 2012 .

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

[34]  Kondo‐François Aguey‐Zinsou,et al.  Synthesis and properties of Li3V2−xCex(PO4)3/C cathode materials for Li-ion batteries , 2012 .

[35]  Jung-Min Kim,et al.  The first cycle characteristics of Li[Ni1/3Co1/3Mn1/3]O2 charged up to 4.7 V , 2004 .

[36]  Jianwen Yang,et al.  Li3V2(PO4)3/C nanofibers composite as a high performance cathode material for lithium-ion battery , 2013 .

[37]  Shengkui Zhong,et al.  A novel method to synthesize LiVPO4F/C composite materials and its electrochemical Li-intercalation performances , 2009 .

[38]  J. Tu,et al.  Freeze-drying synthesis of Li3V2(PO4)3/C cathode material for lithium-ion batteries , 2012 .

[39]  J. Barker,et al.  Performance characteristics of lithium vanadium phosphate as a cathode material for lithium-ion batteries , 2003 .

[40]  Xiao‐Qing Yang,et al.  In situ X-ray absorption and diffraction studies of carbon coated LiFe1/4Mn1/4Co1/4Ni1/4PO4 cathode during first charge , 2009 .