Pair distribution function analysis and Mossbauer study of defects in microwave-hydrothermal LiFePO4

被引:29
作者
Bini, Marcella [1 ]
Ferrari, Stefania [1 ]
Capsoni, Doretta [1 ]
Mustarelli, Piercarlo [1 ]
Spina, Gabriele [2 ]
Del Giallo, Franco [3 ]
Lantieri, Marco [3 ]
Leonelli, Cristina [4 ]
Rizzuti, Antonino [5 ]
Massarotti, Vincenzo [1 ]
机构
[1] Univ Pavia, Dipartimento Chim, Sez Chim Fis, I-27100 Pavia, Italy
[2] Univ Florence, Dipartimento Fis & Astron, I-50019 Sesto Fiorentino, FI, Italy
[3] Ist Sistemi Complessi CNR, I-50019 Sesto Fiorentino, FI, Italy
[4] Univ Modena & Reggio Emilia, Dipartimento Ingn Mat & Ambiente, I-41125 Modena, Italy
[5] Politecn Bari, Dipartimento Ingn Acque & Chim, I-70125 Bari, Italy
关键词
LI-ION; X-RAY; ELECTROCHEMICAL-BEHAVIOR; ELECTRODE MATERIALS; LITHIUM BATTERIES; DIFFRACTION; STATE; FE; ORDER; NMR;
D O I
10.1039/c1ra00525a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Olivine-type LiFePO4 is nowadays one of the most important cathode materials of choice for high-energy lithium ion batteries. Its intrinsic defectivity, and chiefly the so-called lithium iron anti-site, is one of the most critical issues when envisaging electrochemical applications. This paper reports a combined diffractometric (Synchrotron Radiation XRD with Rietveld and PDF analyses) and spectroscopic (Mossbauer) approach able to give a thorough characterization of the material defectivity. Such analytical procedure has been applied to a sample prepared following an innovative microwave-assisted hydrothermal synthesis route that, in a few minutes, allowed us to obtain a well crystallized material. PDF analysis, which is applied for the first time to this type of battery material, reveals the presence of disorder possibly due to Li/Fe exchange or to a local symmetry lowering. A 5% amount of iron on the lithium site has been detected both by PDF as well as by Mossbauer spectroscopy, which revealed a small percentage of Fe3+ on the regular sites.
引用
收藏
页码:250 / 258
页数:9
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