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

被引：39

作者：

Asakura, Daisuke ^{[1
]}

Okubo, Masashi ^{[1
]}

Mizuno, Yoshifumi ^{[1
]}

Kudo, Tetsuichi ^{[1
]}

Zhou, Haoshen ^{[1
]}

Amemiya, Kenta ^{[2
]}

de Groot, Frank M. F. ^{[3
]}

Chen, Jeng-Lung ^{[4
,5
]}

Wang, Wei-Cheng ^{[4
,5
]}

Glans, Per-Anders ^{[4
]}

Chang, Chinglin ^{[5
]}

Guo, Jinghua ^{[4
]}

Honma, Itaru ^{[6
]}

机构：

[1] Natl Inst Adv Ind Sci & Technol, Energy Technol Res Inst, Tsukuba, Ibaraki 3058568, Japan

[2] High Energy Accelerator Res Org, IMSS, Photon Factory, Tsukuba, Ibaraki 3050801, Japan

[3] Univ Utrecht, Dept Inorgan Chem & Catalysis, NL-3584 Utrecht, Netherlands

[4] Univ Calif Berkeley, Lawrence Berkeley Lab, Adv Light Source, Berkeley, CA 94720 USA

[5] Tamkang Univ, Dept Phys, Tamsui 250, Taiwan

[6] Tohoku Univ, Inst Multidisciplinary Res Adv Mat, Sendai, Miyagi 9808577, Japan

来源：

PHYSICAL REVIEW B | 2011年 / 84卷 / 04期

关键词：

PRUSSIAN BLUE ANALOGS; LITHIUM INTERCALATION BEHAVIOR; TRANSITION-METAL COMPOUNDS; ORGANIC FRAMEWORKS; EDGE; DICHROISM; LICOO2; REDOX;

D O I：

10.1103/PhysRevB.84.045117

中图分类号：

T [工业技术];

学科分类号：

08 ;

摘要：

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.

引用

页数：6

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