Synthesis, Characterization, and Electrochemical Behavior of LiMnxFe(1−x)PO4 Composites Obtained from Phenylphosphonate-Based Organic-Inorganic Hybrids

The synthesis of organic-inorganic hybrid compounds based on phenylphosphonate and their use as precursors to form LiMnxFe(1−x)PO4 composites containing carbonaceous substances with sub-micrometric morphology are presented. The experimental procedure includes the preliminary synthesis of Fe2+ and/or Mn2+ phenylphosphonates with the general formula Fe(1−x)Mnx[(C6H5PO3)(H2O)] (with 0 < x < 1), which are then mixed at different molar ratios with lithium carbonate. In this way the carbon, obtained from in situ partial oxidation of the precursor organic part, coats the LiMnxFe(1−x)PO4 particles. After a structural and morphological characterization, the electrochemical behavior of lithium iron manganese phosphates has been compared to the one of pristine LiFePO4 and LiMnPO4, in order to evaluate the doping influence on the material.

[1]  E. Olivetti,et al.  Lithium-Ion Battery Supply Chain Considerations: Analysis of Potential Bottlenecks in Critical Metals , 2017 .

[2]  Gilbert Laporte,et al.  Battery degradation and behaviour for electric vehicles: Review and numerical analyses of several models , 2017 .

[3]  M. Mathew,et al.  Simulation of lithium ion battery replacement in a battery pack for application in electric vehicles , 2017 .

[4]  Luca Pasquali,et al.  Automotive application of lithium-ion batteries: Control of commercial batteries in laboratory tests , 2014, 2014 IEEE 23rd International Symposium on Industrial Electronics (ISIE).

[5]  Gianluca Fabbri,et al.  Automotive application of lithium-ion batteries: A new generation of electrode materials , 2013, 2013 IEEE International Symposium on Industrial Electronics.

[6]  Jianqiu Li,et al.  A review on the key issues for lithium-ion battery management in electric vehicles , 2013 .

[7]  D. V. Safronov,et al.  Lithium diffusion in materials based on LiFePO4 doped with cobalt and magnesium , 2012, Inorganic Materials.

[8]  Xuejie Huang,et al.  Electrochemical performances of LiFe1−xMnxPO4 with high Mn content , 2011 .

[9]  M. Sendova-Vassileva,et al.  Carbon-coated nano-sized LiFe1−xMnxPO4 solid solutions (0 ≤ x ≤ 1) obtained from phosphate–formate precursors , 2011, Journal of Materials Science.

[10]  W. Cho,et al.  Li Ion Diffusivity and Improved Electrochemical Performances of the Carbon Coated LiFePO4 , 2011 .

[11]  D. V. Safronov,et al.  Kinetics of lithium deintercalation from LiFePO4 , 2011 .

[12]  B. Scrosati,et al.  Lithium batteries: Status, prospects and future , 2010 .

[13]  B. Chowdari,et al.  Storage performance of LiFe1 − xMnxPO4 nanoplates (x = 0, 0.5, and 1) , 2010 .

[14]  Zongping Shao,et al.  Mechanoactivation-assisted synthesis and electrochemical characterization of manganese lightly doped LiFePO4 , 2010 .

[15]  Jeffrey W. Fergus,et al.  Recent developments in cathode materials for lithium ion batteries , 2010 .

[16]  Gang Chen,et al.  Direct-hydrothermal synthesis of LiFe1−xMnxPO4 cathode materials , 2009 .

[17]  P. Prosini,et al.  Fitting of the voltage–Li+ insertion curve of LiFePO4 , 2009 .

[18]  M. Pasquali,et al.  Comparison between different ways to determine diffusion coefficient and by solving Fick’s equation for spherical coordinates , 2009 .

[19]  K. Lee,et al.  Electrochemical properties of LiFe0.9Mn0.1PO4/Fe2P cathode material by mechanical alloying , 2009 .

[20]  Feng Yang,et al.  Developments of lithium-ion batteries and challenges of LiFePO4 as one promising cathode material , 2009, Journal of Materials Science.

[21]  S. Franger,et al.  Chemistry and electrochemistry of lithium iron phosphate , 2008 .

[22]  M. Roberts,et al.  High-throughput studies of Li1−xMgx/2FePO4 and LiFe1−yMgyPO4 and the effect of carbon coating , 2008 .

[23]  Yoshihiro Yamada,et al.  Electrochemical study on Mn2+-substitution in LiFePO4 olivine compound , 2007 .

[24]  Chunsheng Wang,et al.  Ionic/Electronic Conducting Characteristics of LiFePO4 Cathode Materials The Determining Factors for High Rate Performance , 2007 .

[25]  M. Tabuchi,et al.  Structural and Surface Modifications of LiFePO4 Olivine Particles and Their Electrochemical Properties , 2006 .

[26]  G. Righini,et al.  A versatile method of preparation of carbon-rich LiFePO4: A promising cathode material for Li-ion batteries , 2005 .

[27]  Siqi Shi,et al.  Improving the rate performance of LiFePO4 by Fe-site doping , 2005 .

[28]  S. Dou,et al.  Physical and electrochemical properties of doped lithium iron phosphate electrodes , 2004 .

[29]  G. Righini,et al.  Versatile Synthesis of Carbon-Rich LiFePO4 Enhancing Its Electrochemical Properties , 2004 .

[30]  J. Barker,et al.  Lithium Iron(II) Phospho-olivines Prepared by a Novel Carbothermal Reduction Method , 2003 .

[31]  C. Bellitto,et al.  X-ray Single-Crystal Structure and Magnetic Properties of Fe[CH3PO3)]·H2O: A Layered Weak Ferromagnet , 2002 .

[32]  K. S. Nanjundaswamy,et al.  Phospho‐olivines as Positive‐Electrode Materials for Rechargeable Lithium Batteries , 1997 .

[33]  D. Aurbach,et al.  The mechanism of lithium intercalation in graphite film electrodes in aprotic media. Part 2. Potentiostatic intermittent titration and in situ XRD studies of the solid-state ionic diffusion , 1997 .

[34]  Robert A. Huggins,et al.  Application of A-C Techniques to the Study of Lithium Diffusion in Tungsten Trioxide Thin Films , 1980 .

[35]  R. Huggins,et al.  Determination of the Kinetic Parameters of Mixed‐Conducting Electrodes and Application to the System Li3Sb , 1977 .

[36]  H. Rietveld.  A profile refinement method for nuclear and magnetic structures , 1969 .

[37]  Santiangeli Adriano,et al.  Experimental analysis of the auxiliaries consumption in the energy balance of a pre-series plug-in hybrid-electric vehicle , 2014 .

[38]  Fabio Orecchini,et al.  EVs and HEVs Using Lithium-Ion Batteries , 2014 .

[39]  C. Bellitto,et al.  Iron(II) phosphonates: a new series of molecule-based weak ferromagnets , 2000 .