title: Origin and hysteresis of lithium compositional spatiodynamics within battery primary particles.
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.
authors: 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.
authors: Jongwoo
authors: J
authors: Lim
authors: Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305, USA.
authors: Yiyang
authors: Y
authors: Li
authors: Hummingbird Scientific, Lacey, WA 98516, USA.
authors: Daan Hein
authors: DH
authors: Alsem
authors: Department of Aeronautics and Astronautics, Stanford University, Stanford, CA 94305, USA.
authors: Hongyun
authors: H
authors: So
authors: Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305, USA.
authors: Sang Chul
authors: SC
authors: Lee
authors: Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
authors: Peng
authors: P
authors: Bai
authors: Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
authors: Daniel A
authors: DA
authors: Cogswell
authors: Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305, USA.
authors: Xuzhao
authors: X
authors: Liu
authors: Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305, USA.
authors: Norman
authors: N
authors: Jin
authors: Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
authors: Young-sang
authors: YS
authors: Yu
authors: Hummingbird Scientific, Lacey, WA 98516, USA.
authors: Norman J
authors: NJ
authors: Salmon
authors: Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
authors: David A
authors: DA
authors: Shapiro
authors: 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.
authors: Martin Z
authors: MZ
authors: Bazant
authors: Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
authors: Tolek
authors: T
authors: Tyliszczak
authors: 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.
authors: William C
authors: WC
authors: Chueh