Reversible Flat to Rippling Phase Transition in Fe Containing Layered Battery Electrode Materials

被引：22

作者：

Chen, Xi ^{[1
]}

Hwang, Sooyeon ^{[2
]}

Chisnell, Robin ^{[3
]}

Wang, Yichao ^{[1
]}

Wu, Fan ^{[1
]}

Kim, Sooran ^{[1
]}

Lynn, Jeffrey W. ^{[3
]}

Su, Dong ^{[2
]}

Li, Xin ^{[1
]}

机构：

[1] Harvard Univ, John A Paulson Sch Engn & Appl Sci, Cambridge, MA 02138 USA

[2] Brookhaven Natl Lab, Ctr Funct Nanomat, Upton, NY 11973 USA

[3] NIST, NIST Ctr Neutron Res, Gaithersburg, MD 20899 USA

来源：

ADVANCED FUNCTIONAL MATERIALS | 2018年 / 28卷 / 39期

基金：

美国国家科学基金会;

关键词：

Na-ion batteries; novel high-voltage phases; reversible hysteresis evolution; rippling of layered structures; ELECTROCHEMICAL PROPERTIES; STRUCTURAL EVOLUTION; HIGH-ENERGY; ION; PERFORMANCE; INSERTION; CATHODES; NI; SUBSTITUTION; ALKALI;

D O I：

10.1002/adfm.201803896

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Layered sodium transition metal oxides of NaTMO2 (TM = 3d transition metal) show unique capability to mix different compositions of Fe to the TM layer, a phenomenon that does not exist in LiTMO2. Here, a novel spontaneous TM layer rippling in the sodium ion battery cathode materials is reported, revealed by in situ X-ray diffraction, Cs-corrected scanning transmission electron microscopy, and density functional theory simulation, where the softening and distortion of FeO6 octahedra collectively drives the flat TM planes into rippled ones with inhomogeneous interlayer distance at high voltage. In such a rippling phase, charge and discharge of Na ions take different evolution pathways, resulting in an unusual hysteresis voltage loop. Importantly, upon discharge beyond a certain Na composition, the rippling TM layer will go back to flat, giving the reversibility of such structural evolution in the following cycles.

引用

页数：11

共 49 条

[1] X-RAY-DIFFRACTION LINE BROADENING - MODELING AND APPLICATIONS TO HIGH-TC SUPERCONDUCTORS [J].

BALZAR, D .

JOURNAL OF RESEARCH OF THE NATIONAL INSTITUTE OF STANDARDS AND TECHNOLOGY, 1993, 98 (03) :321-353

[2]

Berthelot R, 2011, NAT MATER, V10, P74, DOI [10.1038/nmat2920, 10.1038/NMAT2920]

[3] Layered-to-Rock-Salt Transformation in Desodiated NaxCrO2 (x 0.4) [J].

Bo, Shou-Hang ;

Li, Xin ;

Toumar, Alexandra J. ;

Ceder, Gerbrand .

CHEMISTRY OF MATERIALS, 2016, 28 (05) :1419-1429

[4] Role of van der Waals Forces in Thermodynamics and Kinetics of Layered Transition Metal Oxide Electrodes: Alkali and Alkaline-Earth Ion Insertion into V2O5 [J].

Carrasco, Javier .

JOURNAL OF PHYSICAL CHEMISTRY C, 2014, 118 (34) :19599-19607

[5] Origin of Structural Degradation During Cycling and Low Thermal Stability of Ni-Rich Layered Transition Metal-Based Electrode Materials [J].

Dixit, Mudit ;

Markovsky, Boris ;

Schipper, Florian ;

Aurbach, Doron ;

Major, Dan T. .

JOURNAL OF PHYSICAL CHEMISTRY C, 2017, 121 (41) :22628-22636

[6] Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides [J].

Gent, William E. ;

Lim, Kipil ;

Liang, Yufeng ;

Li, Qinghao ;

Barnes, Taylor ;

Ahn, Sung-Jin ;

Stone, Kevin H. ;

McIntire, Mitchell ;

Hong, Jihyun ;

Song, Jay Hyok ;

Li, Yiyang ;

Mehta, Apurva ;

Ermon, Stefano ;

Tyliszczak, Tolek ;

Kilcoyne, David ;

Vine, David ;

Park, Jin-Hwan ;

Doo, Seok-Kwang ;

Toney, Michael F. ;

Yang, Wanli ;

Prendergast, David ;

Chueh, William C. .

NATURE COMMUNICATIONS, 2017, 8

[7] Semiempirical GGA-type density functional constructed with a long-range dispersion correction [J].

Grimme, Stefan .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 2006, 27 (15) :1787-1799

[8] Effect of the Damping Function in Dispersion Corrected Density Functional Theory [J].

Grimme, Stefan ;

Ehrlich, Stephan ;

Goerigk, Lars .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 2011, 32 (07) :1456-1465

[9] A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu [J].

Grimme, Stefan ;

Antony, Jens ;

Ehrlich, Stephan ;

Krieg, Helge .

JOURNAL OF CHEMICAL PHYSICS, 2010, 132 (15)

[10]

Guignard M, 2013, NAT MATER, V12, P74, DOI [10.1038/NMAT3478, 10.1038/nmat3478]

← 1 2 3 4 5 →