Formation and impact of nanoscopic oriented phase domains in electrochemical crystalline electrodes.

Autor: Chen W; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA.; Materials Research Laboratory, University of Illinois, Urbana, IL, USA., Zhan X; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA.; Materials Research Laboratory, University of Illinois, Urbana, IL, USA., Yuan R; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA., Pidaparthy S; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA., Yong AXB; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA.; Materials Research Laboratory, University of Illinois, Urbana, IL, USA., An H; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA.; Materials Research Laboratory, University of Illinois, Urbana, IL, USA., Tang Z; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA., Yin K; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA., Patra A; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA.; Materials Research Laboratory, University of Illinois, Urbana, IL, USA., Jeong H; Department of Mechanical Science and Engineering, University of Illinois, Urbana, IL, USA., Zhang C; Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana, IL, USA., Ta K; Department of Chemistry, University of Illinois, Urbana, IL, USA.; Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, IL, USA., Riedel ZW; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA.; Materials Research Laboratory, University of Illinois, Urbana, IL, USA., Stephens RM; Shell International Exploration and Production Inc., Houston, TX, USA., Shoemaker DP; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA.; Materials Research Laboratory, University of Illinois, Urbana, IL, USA., Yang H; Materials Research Laboratory, University of Illinois, Urbana, IL, USA.; Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana, IL, USA.; Department of Chemistry, University of Illinois, Urbana, IL, USA., Gewirth AA; Materials Research Laboratory, University of Illinois, Urbana, IL, USA.; Department of Chemistry, University of Illinois, Urbana, IL, USA.; Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, IL, USA., Braun PV; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA.; Materials Research Laboratory, University of Illinois, Urbana, IL, USA.; Department of Mechanical Science and Engineering, University of Illinois, Urbana, IL, USA.; Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana, IL, USA.; Department of Chemistry, University of Illinois, Urbana, IL, USA.; Beckman Institute for Advanced Science and Technology, University of Illinois, Urbana, IL, USA., Ertekin E; Materials Research Laboratory, University of Illinois, Urbana, IL, USA.; Department of Mechanical Science and Engineering, University of Illinois, Urbana, IL, USA., Zuo JM; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA. jianzuo@illinois.edu.; Materials Research Laboratory, University of Illinois, Urbana, IL, USA. jianzuo@illinois.edu., Chen Q; Department of Materials Science and Engineering, University of Illinois, Urbana, IL, USA. qchen20@illinois.edu.; Materials Research Laboratory, University of Illinois, Urbana, IL, USA. qchen20@illinois.edu.; Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana, IL, USA. qchen20@illinois.edu.; Department of Chemistry, University of Illinois, Urbana, IL, USA. qchen20@illinois.edu.; Beckman Institute for Advanced Science and Technology, University of Illinois, Urbana, IL, USA. qchen20@illinois.edu.
Jazyk: angličtina
Zdroj: Nature materials [Nat Mater] 2023 Jan; Vol. 22 (1), pp. 92-99. Date of Electronic Publication: 2022 Oct 24.
DOI: 10.1038/s41563-022-01381-4
Abstrakt: Electrochemical phase transformation in ion-insertion crystalline electrodes is accompanied by compositional and structural changes, including the microstructural development of oriented phase domains. Previous studies have identified prevailingly transformation heterogeneities associated with diffusion- or reaction-limited mechanisms. In comparison, transformation-induced domains and their microstructure resulting from the loss of symmetry elements remain unexplored, despite their general importance in alloys and ceramics. Here, we map the formation of oriented phase domains and the development of strain gradient quantitatively during the electrochemical ion-insertion process. A collocated four-dimensional scanning transmission electron microscopy and electron energy loss spectroscopy approach, coupled with data mining, enables the study. Results show that in our model system of cubic spinel MnO 2 nanoparticles their phase transformation upon Mg 2+ insertion leads to the formation of domains of similar chemical identity but different orientations at nanometre length scale, following the nucleation, growth and coalescence process. Electrolytes have a substantial impact on the transformation microstructure ('island' versus 'archipelago'). Further, large strain gradients build up from the development of phase domains across their boundaries with high impact on the chemical diffusion coefficient by a factor of ten or more. Our findings thus provide critical insights into the microstructure formation mechanism and its impact on the ion-insertion process, suggesting new rules of transformation structure control for energy storage materials.
(© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)
Databáze: MEDLINE
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