Laboratoire de Chimie de la Matière Condensée de Paris, CNRS UMR 7574, Chimie-ParisTech, UPMC Univ Paris 06, 11 rue P. et M. Curie, 75231 Paris Cedex 05, France.
Phys Chem Chem Phys. 2012 Jul 14;14(26):9500-10. doi: 10.1039/c2cp23501c. Epub 2012 May 31.
The broadband dielectric spectroscopy (BDS) technique (40 to 10(10) Hz) is used here to measure the electronic transport across all observed size scales of a Li(1.1)V(3)O(8)-polymer-gel composite material for lithium batteries. Different electrical relaxations are evidenced, resulting from the polarizations at the different scales of the architecture: (i) atomic lattice (small-polaron hopping), (ii) particles, (iii) clusters of particles, and finally (iv) sample-current collector interface. A very good agreement with dc-conductivity measurements on a single macro-crystal [M. Onoda and I. Amemiya, J. Phys.: Condens. Matter, 2003, 15, 3079.] shows that the BDS technique does allow probing the bulk (intrinsic) electrical properties of a material in the form of a network of particles separated by boundaries in a composite. Moreover, this study highlights a lowering of the surface electronic conductivity of Li(1.1)V(3)O(8) particles upon adsorption of polar ethylene carbonate (EC) and propylene carbonate (PC) that trap surface polarons. This result is meaningful as EC and PC are typical constituents of a liquid electrolyte of lithium batteries. It is thus suggested that interactions between active material particles and the liquid electrolyte play a role in the electronic transport within composite electrodes used in a lithium battery.
宽带介电谱(BDS)技术(40 至 10(10)Hz)用于测量用于锂电池的 Li(1.1)V(3)O(8)-聚合物凝胶复合材料在所有观察到的尺寸范围内的电子输运。结果表明,由于不同结构尺度上的极化作用,出现了不同的电弛豫:(i)原子晶格(小极化子跳跃),(ii)颗粒,(iii)颗粒簇,最后是(iv)样品-集流器界面。与单一大晶体上的直流导率测量非常吻合[M. Onoda 和 I. Amemiya,J. Phys.:Condens. Matter,2003,15,3079。]表明,BDS 技术确实允许以颗粒网络的形式探测复合材料中材料的体(本征)电性能,颗粒之间通过边界隔开。此外,这项研究强调了在吸附具有捕获表面极化子的极性碳酸亚乙酯(EC)和碳酸丙烯酯(PC)时,Li(1.1)V(3)O(8)颗粒的表面电子电导率降低。这一结果具有重要意义,因为 EC 和 PC 是锂电池液体电解质的典型成分。因此,建议活性材料颗粒与液体电解质之间的相互作用在锂电池用复合电极中的电子输运中起作用。