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Dimensionally Controlled Lithiation of Chromium Oxide

Journal Article · · Chemistry of Materials
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  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Univ. of Illinois at Urbana-Champaign, IL (United States)
+ Show Author Affiliations

Oxide conversion reactions are an alternative approach for high capacity lithium ion batteries but are known to suffer from structural irreversibility associated with the phase separation and reconstitution of reduced metal species and Li2O. In particular, the morphology of the reduced metal species is thought to play a critical role in the electrochemical properties of a conversion material. Here we use a model electrode with alternating layers of chromium and chromium oxide to better understand and control these phase changes in real-time and at molecular length scales. Despite lacking crystallinity at the atomic scale, this superstructure is observed (with X-ray reflectivity, XR) to lithiate and delithiate in a purely one-dimensional manner, preserving the layered structure. The XR data show that the metal layers act as nucleation sites for the reduction of chromium in the conversion reaction. Irreversibility during delithiation is due to the formation of a ternary phase, LiCrO2, which can be further delithiated at higher potentials. The results reveal that the combination of confining lithiation to nanoscale sheets of Li2O and the availability of reaction sites in the metal layers in the layered structure is a strategy for improving the reversibility and mass transport properties that can be used in a wide range of conversion materials.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1371083
Alternate ID(s):
OSTI ID: 1248950
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 1 Vol. 28; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (3)

Thin Film RuO 2 Lithiation: Fast Lithium-Ion Diffusion along the Interface journal November 2018
Cr2O3 nanoparticles: a fascinating electrode material combining both surface-controlled and diffusion-limited redox reactions for aqueous supercapacitors journal September 2018
Chain length variation to probe the mechanism of accelerator additives in copper electrodeposition journal January 2019

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Related Subjects

25 ENERGY STORAGE
charge transport
energy storage (including batteries and capacitors)
materials and chemistry by design
synthesis (novel materials)