title: Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes.
abstract: Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, USA.
authors.forename: Amit
authors.initials: A
authors.lastname: Kumar
authors.forename: Thomas M
authors.initials: TM
authors.lastname: Arruda
authors.forename: Alexander
authors.initials: A
authors.lastname: Tselev
authors.forename: Ilia N
authors.initials: IN
authors.lastname: Ivanov
authors.forename: Jamie S
authors.initials: JS
authors.lastname: Lawton
authors.forename: Thomas A
authors.initials: TA
authors.lastname: Zawodzinski
authors.forename: Oleg
authors.initials: O
authors.lastname: Butyaev
authors.forename: Sergey
authors.initials: S
authors.lastname: Zayats
authors.forename: Stephen
authors.initials: S
authors.lastname: Jesse
authors.forename: Sergei V
authors.initials: SV
authors.lastname: Kalinin
mesh_terms: D003460:Crystallization / Q000379:methods*; D004563:Electrochemistry / Q000379:methods; D004573:Electrolytes / Q000737:chemistry / Q000528:radiation effects; D004574:Electromagnetic Fields; D004595:Electroplating / Q000379:methods*; D007477:Ions / Q000737:chemistry / Q000528:radiation effects; D008094:Lithium / Q000737:chemistry* / Q000528:radiation effects*; D008422:Materials Testing; D053758:Nanoparticles / Q000737:chemistry*
chemical_list: D004573:Electrolytes; D007477:Ions; D008094:Lithium
references.citation: Nanotechnology. 2012 Aug 17;23(32):325402
references.pmid: 22825245
references.citation: Chem Soc Rev. 2006 Jan;35(1):29-38
references.pmid: 16365640
references.citation: Nat Nanotechnol. 2012 Feb 19;7(4):242-6
references.pmid: 22343383
references.citation: Nat Nanotechnol. 2010 Oct;5(10):749-54
references.pmid: 20802493
references.citation: Nat Chem. 2011 Aug 14;3(9):707-13
references.pmid: 21860460
references.citation: Nano Lett. 2011 Oct 12;11(10):4161-7
references.pmid: 21863801
references.citation: Science. 2005 Apr 1;308(5718):63-5
references.pmid: 15802593
references.citation: Nat Mater. 2012 Apr 29;11(6):530-5
references.pmid: 22543299
references.citation: Nat Mater. 2008 Apr;7(4):298-302
references.pmid: 18311143
references.citation: Nanotechnology. 2009 May 27;20(21):215201
references.pmid: 19423925