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Title: Anisotropic Mg Electrodeposition and Alloying with Ag-based Anodes from Non-Coordinating Mixed-Metal Borohydride Electrolytes for Mg Hybrid Batteries

Authors:
; ; ;
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1417084
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Electrochimica Acta
Additional Journal Information:
Journal Volume: 229; Journal Issue: C; Related Information: CHORUS Timestamp: 2018-01-16 11:25:42; Journal ID: ISSN 0013-4686
Publisher:
Elsevier
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Wetzel, David J., Malone, Marvin A., Gewirth, Andrew A., and Nuzzo, Ralph G. Anisotropic Mg Electrodeposition and Alloying with Ag-based Anodes from Non-Coordinating Mixed-Metal Borohydride Electrolytes for Mg Hybrid Batteries. United Kingdom: N. p., 2017. Web. doi:10.1016/j.electacta.2017.01.077.
Wetzel, David J., Malone, Marvin A., Gewirth, Andrew A., & Nuzzo, Ralph G. Anisotropic Mg Electrodeposition and Alloying with Ag-based Anodes from Non-Coordinating Mixed-Metal Borohydride Electrolytes for Mg Hybrid Batteries. United Kingdom. doi:10.1016/j.electacta.2017.01.077.
Wetzel, David J., Malone, Marvin A., Gewirth, Andrew A., and Nuzzo, Ralph G. Wed . "Anisotropic Mg Electrodeposition and Alloying with Ag-based Anodes from Non-Coordinating Mixed-Metal Borohydride Electrolytes for Mg Hybrid Batteries". United Kingdom. doi:10.1016/j.electacta.2017.01.077.
@article{osti_1417084,
title = {Anisotropic Mg Electrodeposition and Alloying with Ag-based Anodes from Non-Coordinating Mixed-Metal Borohydride Electrolytes for Mg Hybrid Batteries},
author = {Wetzel, David J. and Malone, Marvin A. and Gewirth, Andrew A. and Nuzzo, Ralph G.},
abstractNote = {},
doi = {10.1016/j.electacta.2017.01.077},
journal = {Electrochimica Acta},
number = C,
volume = 229,
place = {United Kingdom},
year = {Wed Mar 01 00:00:00 EST 2017},
month = {Wed Mar 01 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.electacta.2017.01.077

Citation Metrics:
Cited by: 2works
Citation information provided by
Web of Science

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  • Successful strategies for stabilizing electrodeposition of reactive metals, including lithium, sodium, and aluminum are a requirement for safe, high-energy electrochemical storage technologies that utilize these metals as anodes. Unstable deposition produces high-surface area dendritic structures at the anode/electrolyte interface, which causes premature cell failure by complex physical and chemical processes that have presented formidable barriers to progress. Here, it is reported that hybrid electrolytes created by infusing conventional liquid electrolytes into nanoporous membranes provide exceptional ability to stabilize Li. Electrochemical cells based on γ-Al2O3 ceramics with pore diameters below a cut-off value above 200 nm exhibit long-term stability even atmore » a current density of 3 mA cm-2. The effect is not limited to ceramics; similar large enhancements in stability are observed for polypropylene membranes with less monodisperse pores below 450 nm. These findings are critically assessed using theories for ion rectification and electrodeposition reactions in porous solids and show that the source of stable electrodeposition in nanoporous electrolytes is fundamental.« less
  • Cited by 12
  • Graphical abstract: The fitting results of R{sub sei} and R{sub ct} of three graphite/Li cells. Besides three graphite/Li cells show the similar R{sub sei}, the NG198/Li cell demonstrates a higher R{sub ct} value in all test temperatures. Especially, the R{sub ct} at 333 K is even up to 355.8 Ω cm{sup 2}. Obviously, the narrow distribution of edge plane for NG198 caused this result, and then greatly restricts its cell capacity. By contrast, CMB with bigger specific surface area and more Li{sup +} insertion points shows lower resistance at room temperature, which should help to improve its capacity. - Highlights:more » • SEI film is closely related to graphite structures and formation temperature. • The graphite with bigger surface area and more Li{sup +} insertion points behaves better. • The graphite with narrow edge plane is uncompetitive for ionic liquid electrolyte. - Abstract: The electrochemical behaviors of natural graphite (NG198), artificial graphite (AG360) and carbon microbeads (CMB) in an ionic liquid based electrolyte are investigated by cyclic voltammetry (CV). The surface and structure of three graphite materials are characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD) before and after cycling. It is found that solid electrolyte interface (SEI) is closely related to graphite structure. Benefiting from larger specific surface area and more dispersed Li{sup +} insertion points, CMB shows a better Li{sup +} insertion/de-insertion behavior than NG198 and AG360. Furthermore, electrochemical impedance spectra (EIS) prove that the SEI of different graphite electrodes has different intrinsic resistance and Li{sup +} penetrability. By comparison, CMB behaves better cell performances than AG360, while the narrow edge plane makes NG198 uncompetitive as a potential anode for the ionic liquids (ILs)-type Li-ion battery.« less
  • Graphical abstract: “Lithium aggregates” usually cause a significant decrease in Li{sup +} mobility and transfer efficiency. Therefore, as important as the problem of SEI, the content of lithium salt and the interaction between Li{sup +} and ILs’ anions should be taken into consideration in the optimization of ILs-based electrolytes for Li-ion batteries. - Highlights: • “Lithium aggregates” in piperidinium-based electrolytes are evidenced by IR and NMR. • High LiPF{sub 6} content could decrease Li{sup +} mobility due to “ionic aggregates”. • Lithium salt concentration is an important factor affecting graphite performances. - Abstract: The variations in LiPF{sub 6} concentration leadmore » to the very different electrochemical performances of carbon microbeads anodes in the piperidinium-based hybrid electrolytes. The “two peaks” behaviors of lithium plating observed in cyclic voltammetry tests, and some detailed changes in infrared spectra and nuclear magnetic resonance indicates that the formation of “ionic aggregates” related to lithium ions”. Therefore, the excessive lithium salts in the piperidinium-based hybrid electrolytes, usually cause a significant decrease in Li{sup +} mobility and transfer efficiency. The main behaviors are that, when LiPF{sub 6} concentrations increased from 0.2 to 1.2 mol kg{sup −1}, the apparent migration energies (E{sub a}) increase largely from 8.83 to 21.16 kJ mol{sup −1}, while the lithium transference numbers (t{sub Li{sup +}}) drop markedly from 0.538 to 0.292.« less