New Investigations on the Surface Reactivity of Layered Lithium Oxides

被引：28

作者：

Andreu, Nathalie ^{[1
]}

Baraille, Isabelle ^{[1
]}

Martinez, Herve ^{[1
]}

Dedryvere, Remi ^{[1
]}

Loudet, Michel ^{[1
]}

Gonbeau, Danielle ^{[1
]}

机构：

[1] Univ Pau, UMR5254, IPREM ECP, F-64053 Pau 9, France

来源：

JOURNAL OF PHYSICAL CHEMISTRY C | 2012年 / 116卷 / 38期

关键词：

LINI1-YCOYO2; SOLID-SOLUTION; CO2; ADSORPTION; METAL-OXIDES; LI-7; NMR; LICOO2; ENERGY; XPS; MICROSTRUCTURE; TRANSITION; STABILITY;

D O I：

10.1021/jp304293u

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Density Functional Theory is applied to understand the large difference in surface reactivity of LiCoO2 due to Al/Co substitution which is experimentally observed. In this way, we explore the SO2 and CO2 adsorption modes on the (110) surface of LiCoO2 and alpha-LiAlO2. For SO2 adsorption, chemisorption produces sulfite species (for LiCoO2 and alpha-LiAlO2) and sulfate species (in the case of LiCoO2). We demonstrate that the modification of the surface reactivity when Co3+. ions are substituted by Al3+ ions is due to a change from an adsorption mode controlled by redox properties for LiCoO2 to a less energetically favorable adsorption mode controlled by acid base properties for alpha-LiAlO2. For CO2 adsorption, the formation of carbonate species is observed for both compounds, illustrating the fundamental difference in the factors controlling SO2 adsorption compared to CO2 adsorption.

引用

页码：20332 / 20341

页数：10

共 37 条

[1] Cobalt dissolution in LiCoO2-based non-aqueous rechargeable batteries [J].

Amatucci, GG ;

Tarascon, JM ;

Klein, LC .

SOLID STATE IONICS, 1996, 83 (1-2) :167-173

[2] Microstructure of LiCoO2 with and without "AIPO4" nanoparticle coating:: Combined STEM and XPS studies [J].

Appapillai, Anjuli T. ;

Mansour, Azzam N. ;

Cho, Jaephil ;

Shao-Horn, Yang .

CHEMISTRY OF MATERIALS, 2007, 19 (23) :5748-5757

[3] Adsorption of 3d Transition Elements on a TiO2(110) Surface [J].

Asaduzzaman, Abu Md. ;

Krueger, Peter .

JOURNAL OF PHYSICAL CHEMISTRY C, 2008, 112 (49) :19616-19619

[4]

Bader R. F. W., 1994, ATOMS MOL QUANTUM TH

[5] Electron-count control on adsorption upon reducible and irreducible clean metal-oxide surfaces [J].

Calatayud, M ;

Markovits, A ;

Minot, C .

CATALYSIS TODAY, 2004, 89 (03) :269-278

[6] Adsorption on perfect and reduced surfaces of metal oxides [J].

Calatayud, M ;

Markovits, A ;

Menetrey, M ;

Mguig, B ;

Minot, C .

CATALYSIS TODAY, 2003, 85 (2-4) :125-143

[7]

Czyzyk R., 1992, PHYS REV B, V46, P3729

[8] Possible Explanation for the Efficiency of Al-Based Coatings on LiCoO2: Surface Properties of LiCo1-xAlxO2 Solid Solution [J].

Daheron, L. ;

Dedryvere, R. ;

Martinez, H. ;

Flahaut, D. ;

Menetrier, M. ;

Delmas, C. ;

Gonbeau, D. .

CHEMISTRY OF MATERIALS, 2009, 21 (23) :5607-5616

[9] Surface Properties of LiCoO2 Investigated by XPS Analyses and Theoretical Calculations [J].

Daheron, L. ;

Martinez, H. ;

Dedryvere, R. ;

Baraille, I. ;

Menetrier, M. ;

Denage, C. ;

Delmas, C. ;

Gonbeau, D. .

JOURNAL OF PHYSICAL CHEMISTRY C, 2009, 113 (14) :5843-5852

[10] Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study [J].

Dudarev, SL ;

Botton, GA ;

Savrasov, SY ;

Humphreys, CJ ;

Sutton, AP .

PHYSICAL REVIEW B, 1998, 57 (03) :1505-1509

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