Enhanced interfacial lithium storage in nanocomposites of transition metals with LiF and Li2O:: Comparison of DFT calculations and experimental studies

被引：82

作者：

Zhukovskii, Yu. F. ^{[1
,2
]}

Kotomin, E. A. ^{[2
]}

Balaya, P. ^{[2
,3
,4
]}

Maier, J. ^{[2
]}

机构：

[1] Latvian State Univ, Inst Solid State Phys, Theoret Lab Nonlinear Proc, LV-1063 Riga, Latvia

[2] Max Planck Inst Solid State Res, Stuttgart, Germany

[3] Natl Univ Singapore, Engn Sci Programme, Singapore 117548, Singapore

[4] Natl Univ Singapore, Dept Mech Engn, Singapore 117548, Singapore

来源：

SOLID STATE SCIENCES | 2008年 / 10卷 / 04期

关键词：

Me/LiX nanocomposites; interfacial Li storage; ab initio calculations;

D O I：

10.1016/j.solidstatesciences.2007.12.030

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Me/LiX nanocomposites (Me - transition metal and X = F or O) exhibit extra lithium storage, with pseudo-capacitive behavior and high-rate performance. While LiX surface layers or the interfacial core serves as hosts for extra Li, atoms of contacting transition metal serve as electron sinks, depending on Me electronegativity. To verify the mechanism, we have performed comparative DFT-LCAO calculations on the polar Ti vertical bar Li vertical bar Li2O(1 1 1) and non-polar Cu vertical bar Li vertical bar LiF(001) interfaces with extra Li atoms inserted inside both 2D interfaces, gradually changing their concentration. Theoretical calculations confirm validity of this interfacial model for explanation of the extra storage capacity at low potentials. The diffusion barrier for extra Li atom along the Me/LiX interface is markedly smaller than the Li penetration barrier into the bulk. (C) 2007 Elsevier Masson SAS. All rights reserved.

引用

页码：491 / 495

页数：5

共 16 条

[1] Nano-ionics in the context of lithium batteries [J].

Balaya, P. ;

Bhattacharyya, A. J. ;

Jamnik, J. ;

Zhukovskii, Yu. F. ;

Kotomin, E. A. ;

Maier, J. .

JOURNAL OF POWER SOURCES, 2006, 159 (01) :171-178

[2] Fully reversible homogeneous and heterogeneous Li storage in RuO2 with high capacity [J].

Balaya, P ;

Li, H ;

Kienle, L ;

Maier, J .

ADVANCED FUNCTIONAL MATERIALS, 2003, 13 (08) :621-625

[3] ON THE ELASTIC PROPERTIES OF LITHIUM, SODIUM AND POTASSIUM OXIDE - AN ABINITIO STUDY [J].

DOVESI, R ;

ROETTI, C ;

FREYRIAFAVA, C ;

PRENCIPE, M ;

SAUNDERS, VR .

CHEMICAL PHYSICS, 1991, 156 (01) :11-19

[4]

HAY PJ, 1985, J CHEM PHYS, V82, P299, DOI [10.1063/1.448975, 10.1063/1.448799, 10.1063/1.448800]

[5] Nanocrystallinity effects in lithium battery materials - Aspects of nano-ionics. Part IV [J].

Jamnik, J ;

Maier, J .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2003, 5 (23) :5215-5220

[6] On the origin of the extra electrochemical capacity displayed by MO/Li cells at low potential [J].

Laruelle, S ;

Grugeon, S ;

Poizot, P ;

Dollé, M ;

Dupont, L ;

Tarascon, JM .

JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2002, 149 (05) :A627-A634

[7] Li-storage via heterogeneous reaction in selected binary metal fluorides and oxides [J].

Li, H ;

Balaya, P ;

Maier, J .

JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2004, 151 (11) :A1878-A1885

[8] Reversible formation and decomposition of LiF clusters using transition metal fluorides as precursors and their application in rechargeable Li batteries [J].

Li, H ;

Richter, G ;

Maier, J .

ADVANCED MATERIALS, 2003, 15 (09) :736-739

[9] Nanoionics: ion transport and electrochemical storage in confined systems [J].

Maier, J .

NATURE MATERIALS, 2005, 4 (11) :805-815

[10] Nano-sized transition-metaloxides as negative-electrode materials for lithium-ion batteries [J].

Poizot, P ;

Laruelle, S ;

Grugeon, S ;

Dupont, L ;

Tarascon, JM .

NATURE, 2000, 407 (6803) :496-499

← 1 2 →