Origin and hysteresis of lithium compositional spatiodynamics within battery primary particles

Jongwoo Lim; Yiyang Li; Daan Hein Alsem; Hongyun So; Sang Chul Lee; Peng Bai; Daniel A Cogswell; Xuzhao Liu; Norman Jin; Young-sang Yu; Norman J Salmon; David A Shapiro; Martin Z Bazant; Tolek Tyliszczak; William C Chueh

doi:10.1126/science.aaf4914

Origin and hysteresis of lithium compositional spatiodynamics within battery primary particles

Science. 2016 Aug 5;353(6299):566-71. doi: 10.1126/science.aaf4914.

Authors

Affiliations

¹ Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305, USA. Stanford Institute for Materials & Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA.
² Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305, USA.
³ Hummingbird Scientific, Lacey, WA 98516, USA.
⁴ Department of Aeronautics and Astronautics, Stanford University, Stanford, CA 94305, USA.
⁵ Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
⁶ Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
⁷ Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305, USA. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA. Department of Mathematics, Massachusetts Institute of Technology, Cambridge, MA 02139, USA. SUNCAT Interfacial Science and Catalysis, Stanford University, Stanford, CA 94305, USA.
⁸ Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305, USA. Stanford Institute for Materials & Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA. wchueh@stanford.edu.

PMID: 27493180
DOI: 10.1126/science.aaf4914

Abstract

The kinetics and uniformity of ion insertion reactions at the solid-liquid interface govern the rate capability and lifetime, respectively, of electrochemical devices such as Li-ion batteries. Using an operando x-ray microscopy platform that maps the dynamics of the Li composition and insertion rate in Li(x)FePO4, we found that nanoscale spatial variations in rate and in composition control the lithiation pathway at the subparticle length scale. Specifically, spatial variations in the insertion rate constant lead to the formation of nonuniform domains, and the composition dependence of the rate constant amplifies nonuniformities during delithiation but suppresses them during lithiation, and moreover stabilizes the solid solution during lithiation. This coupling of lithium composition and surface reaction rates controls the kinetics and uniformity during electrochemical ion insertion.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.