Title: Morphological Evolution of Multilayer Ni/NiO Thin Film Electrodes during Lithiation

Abstract

Oxide conversion reactions in lithium ion batteries are challenged by substantial irreversibility associated with significant volume change during the phase separation of an oxide into lithia and metal species (e.g., NiO + 2Li⁺ + 2e^– → Ni + Li₂O). In this work, we demonstrate that the confinement of nanometer-scale NiO layers within a Ni/NiO multilayer electrode can direct lithium transport and reactivity, leading to coherent expansion of the multilayer. The morphological changes accompanying lithiation were tracked in real-time by in-operando X-ray reflectivity (XRR) and ex-situ cross-sectional transmission electron microscopy on well-defined periodic Ni/NiO multilayers grown by pulsed-laser deposition. Comparison of pristine and lithiated structures reveals that the nm-thick nickel layers help initiate the conversion process at the interface and then provide an architecture that confines the lithiation to the individual oxide layers. XRR data reveal that the lithiation process starts at the top and progressed through the electrode stack, layer by layer resulting in a purely vertical expansion. Longer term cycling showed significant reversible capacity (~800 mA h g^–1 after ~100 cycles), which we attribute to a combination of the intrinsic bulk lithiation capacity of the NiO and additional interfacial lithiation capacity. These observations provide new insight into the rolemore » of metal/metal oxide interfaces in controlling lithium ion conversion reactions by defining the relationships between morphological changes and film architecture during reaction.« less

Authors:

Evmenenko, Guennadi ^[1]; Fister, Timothy T. ^[2]; Buchholz, D. Bruce ^[1]; Li, Qianqian ^[3]; Chen, Kan-Sheng ^[1]; Wu, Jinsong ^[4]; Dravid, Vinayak P. ^[1]; Hersam, Mark C. ^[5]; Fenter, Paul ^[2]; Bedzyk, Michael J. ^[1]

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+ Show Author Affiliations

1. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
2. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
3. Northwestern Univ., Evanston, IL (United States). Northwestern University Atomic and Nanoscale Characterization Experimental Center, EPIC
4. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering; Northwestern Univ., Evanston, IL (United States). Northwestern University Atomic and Nanoscale Characterization Experimental Center, EPIC
5. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering and Dept. of Chemistry

Publication Date:

Fri Jul 15 00:00:00 EDT 2016

Research Org.:

Energy Frontier Research Centers (EFRC) (United States). Center for Electrochemical Energy Science (CEES)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

OSTI Identifier:

1388324

Grant/Contract Number:  

AC02-06CH11357; DMR-1121262

Resource Type:

Accepted Manuscript

Journal Name:

ACS Applied Materials and Interfaces

Additional Journal Information:

Journal Volume: 8; Journal Issue: 31; Related Information: CEES partners with Argonne National Laboratory (lead); University of Illinois, Urbana-Champaign; Northwest University; Journal ID: ISSN 1944-8244

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; energy storage (including batteries and capacitors); charge transport; materials and chemistry by design; synthesis (novel materials); conversion reaction; lithium-ion battery; multilayer thin-film electrodes; nickel oxide