Electron delocalization in cyanide-bridged coordination polymer electrodes for Li-ion batteries studied by soft x-ray absorption spectroscopy

Abstract

The electronic structure change during the reversible Li-ion storage reaction in a bimetallic MnFe-Prussian blue analogue (Li(x)K(0.14)Mn(1.43)[Fe(CN)(6)] center dot 6H(2)O) was investigated by soft x-ray absorption spectroscopy. The Mn L(2,3)-edgespectra revealed the unchanged Mn(2+) high-spin state regardless of Li-ion concentration (x). On the other hand, the Fe L(2,3)-edge spectra clearly revealed a reversible redox behavior as Fe(3+) Fe(2+) states with Li-ion insertion/extraction. Experimental findings suggested strong metal-to-ligand charge transfer in conjunction with the ligand-to-metal one. The resulting charge delocalization between the Fe and CN is considered to contribute to the high reversibility of the Li-ion storage process.