Investigation of graphitic carbon foams/LiNiPO4 composites

The characterization of composites consisting of graphitic carbon foams coated with a structured lithium nickel phosphate is reported. The LiNiPO4 as cathode material for lithium-ion batteries is prepared by a Pechini-assisted sol-gel process. The coating is performed by soaking the graphitic carbon foams in aqueous solutions containing lithium, nickel salts, and phosphates at 70 °C for 2–4 h and then by treating in flowing air and nitrogen. The formation of the olivine-like structured LiNiPO4 is confirmed by X-ray diffraction analysis performed on powders prepared under very similar conditions. However, crystalline reflections attributed to Li4P2O7 and to Ni3P as secondary phases have been observed. The morphological investigation revealed the presence of a layer on the graphitic foams that consists of interconnected blend of grains with different size. The voltammetric curves show values of the mean peak maxima in the anodic region between 5.1–5.3 V and in the cathodic region at ~4.9 V. The electrochemical measurements deliver a discharge specific capacity of 86 mAhg−1 (at discharge rate of C/10 and RT). The electrochemical impedance spectroscopy data confirm an increase of the electrical resistance after cycling and the decrease of the ionic contribution which indicate the formation/growth of phases behaving like resistors.

[1]  J. Yamaki,et al.  Cathode properties of phospho-olivine LiMPO4 for lithium secondary batteries , 2001 .

[2]  M. Whittingham,et al.  Some transition metal (oxy)phosphates and vanadium oxides for lithium batteries , 2005 .

[3]  D. Aurbach,et al.  A comparison among LiPF6, LiPF3(CF2CF3)3 (LiFAP), and LiN(SO2CF2CF3)2 (LiBETI) solutions: electrochemical and thermal studies , 2003 .

[4]  D. Kovacheva,et al.  Vibrational spectra of R(PO3)3 metaphosphates (R = Ga, In, Y, Sm, Gd, Dy) , 2001 .

[5]  A. Yamada,et al.  Olivine-type cathodes: Achievements and problems , 2003 .

[6]  Jan L Allen,et al.  LiNiPO4-LiCoPO4 solid solutions as cathodes , 2004 .

[7]  Yong‐Mook Kang,et al.  Effects of Fe doping on the electrochemical performance of LiCoPO4/C composites for high power-density cathode materials , 2009 .

[8]  W. Jaegermann,et al.  Developments in nanostructured LiMPO4 (M = Fe, Co, Ni, Mn) composites based on three dimensional carbon architecture. , 2012, Chemical Society reviews.

[9]  Craig A. J. Fisher,et al.  Lithium Battery Materials LiMPO4 (M = Mn, Fe, Co, and Ni): Insights into Defect Association, Transport Mechanisms, and Doping Behavior , 2008 .

[10]  Bruce Dunn,et al.  Three-dimensional battery architectures. , 2004, Chemical reviews.

[11]  W. Jaegermann,et al.  Investigation on LiCoPO4 powders as cathode materials annealed under different atmospheres , 2012, Journal of Solid State Electrochemistry.

[12]  W. Jaegermann,et al.  Preparation and characterization of carbon foams–LiCoPO4 composites , 2012 .

[13]  M. Whittingham,et al.  Lithium batteries and cathode materials. , 2004, Chemical reviews.

[14]  W. Jaegermann,et al.  Synthesis and characterization of three-dimensional carbon foams–LiFePO4 composites , 2011 .

[15]  Anubhav Jain,et al.  Phosphates as Lithium-Ion Battery Cathodes: An Evaluation Based on High-Throughput ab Initio Calculations , 2011 .

[16]  M. Minakshi,et al.  Synthesis and characterization of olivine LiNiPO4 for aqueous rechargeable battery , 2011 .

[17]  Michael Schmidt,et al.  Lithium fluoroalkylphosphates: a new class of conducting salts for electrolytes for high energy lithium-ion batteries , 2001 .

[18]  Robert Spotnitz,et al.  Theoretical evaluation of high-energy lithium metal phosphate cathode materials in Li-ion batteries , 2007 .

[19]  A. Mauger,et al.  Structural characteristics of lithium nickel phosphate studied using analytical electron microscopy and raman spectroscopy , 2006 .

[20]  Doron Aurbach,et al.  The study of capacity fading processes of Li-ion batteries: major factors that play a role , 2003 .

[21]  L. Nazar,et al.  Nanostructured materials for lithium-ion batteries: surface conductivity vs. bulk ion/electron transport. , 2007, Faraday discussions.

[22]  B. N. Popov,et al.  Studies on Capacity Fade of Lithium-Ion Batteries , 2000 .

[23]  K. Nikolowski,et al.  Phase Transitions Occurring upon Lithium Insertion−Extraction of LiCoPO4 , 2007 .

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

[25]  T. Olczak,et al.  Electrochemical characterization of a lithiated mixed nickel-cobalt oxide (LiNi0.5Co0.5O2) prepared by sol-gel process , 1997 .

[26]  Jan L. Allen,et al.  Ni3+/Ni2+ redox potential in LiNiPO4 , 2005 .

[27]  Sai-Cheong Chung,et al.  Crystal Chemistry of the Olivine-Type Li ( Mn y Fe1 − y ) PO 4 and ( Mn y Fe1 − y ) PO 4 as Possible 4 V Cathode Materials for Lithium Batteries , 2001 .

[28]  H. Ehrenberg,et al.  Electrochemical and structural study of LiCoPO4-based electrodes , 2004 .

[29]  W. Jaegermann,et al.  Investigation on 3-dimensional carbon foams/LiFePO4 composites as function of the annealing time under inert atmosphere , 2011 .

[30]  John B. Goodenough,et al.  Effect of Structure on the Fe3 + / Fe2 + Redox Couple in Iron Phosphates , 1997 .

[31]  Nathalie Ravet,et al.  Electroactivity of natural and synthetic triphylite , 2001 .

[32]  Jaephil Cho,et al.  Who will drive electric vehicles, olivine or spinel? , 2011 .

[33]  K. Amine,et al.  OLIVINE LICOPO4 AS 4.8 V ELECTRODE MATERIAL FOR LITHIUM BATTERIES , 1999 .

[34]  L. Nazar,et al.  Nano-network electronic conduction in iron and nickel olivine phosphates , 2004, Nature materials.

[35]  F. García-Alvarado,et al.  Influence of the structure on the electrochemical performance of lithium transition metal phosphates as cathodic materials in rechargeable lithium batteries : A new high-pressure form of LiMPO4 (M = Fe and Ni) , 2001 .

[36]  Z. Bakenov,et al.  Physical and electrochemical properties of LiMnPO4/C composite cathode prepared with different conductive carbons , 2010 .

[37]  B. Scrosati,et al.  Characterization of phospho-olivines as materials for Li-ion cell cathodes , 2002 .

[38]  Tadeusz Bak,et al.  Modification in the electronic structure of cobalt bronze LixCoO2 and the resulting electrochemical properties , 1989 .