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Title: Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry

Authors:
;  [1];  [1]; ;
  1. Energy Sciences Directorate, Brookhaven National Laboratory, Upton, New York 11973, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388016
DOE Contract Number:
SC0012673
Resource Type:
Journal Article
Resource Relation:
Journal Name: Accounts of Chemical Research; Journal Volume: 49; Journal Issue: 9; Related Information: m2M partners with Stony Brook University (lead); Brookhaven National Laboratory; Columbia University; Georgia Institute of Technology; Oak Ridge National Laboratory; Rensselaer Polytechnic Institute; University of California, Berkeley; University of North Carolina at Chapel Hill
Country of Publication:
United States
Language:
English
Subject:
energy storage (including batteries and capacitors), charge transport, mesostructured materials

Citation Formats

Durham, Jessica L., Poyraz, Altug S., Takeuchi, Esther S., Marschilok, Amy C., and Takeuchi, Kenneth J.. Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry. United States: N. p., 2016. Web. doi:10.1021/acs.accounts.6b00318.
Durham, Jessica L., Poyraz, Altug S., Takeuchi, Esther S., Marschilok, Amy C., & Takeuchi, Kenneth J.. Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry. United States. doi:10.1021/acs.accounts.6b00318.
Durham, Jessica L., Poyraz, Altug S., Takeuchi, Esther S., Marschilok, Amy C., and Takeuchi, Kenneth J.. 2016. "Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry". United States. doi:10.1021/acs.accounts.6b00318.
@article{osti_1388016,
title = {Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry},
author = {Durham, Jessica L. and Poyraz, Altug S. and Takeuchi, Esther S. and Marschilok, Amy C. and Takeuchi, Kenneth J.},
abstractNote = {},
doi = {10.1021/acs.accounts.6b00318},
journal = {Accounts of Chemical Research},
number = 9,
volume = 49,
place = {United States},
year = 2016,
month = 8
}
  • Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and massmore » of the final system. Material multi-functionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cation can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multi-mechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM’O) or phosphorous oxides (MM’PO) where M = Ag and M’ = V or Fe. One discharge process can be described as reduction-displacement where Ag + is reduced to Ag 0 and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in-situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional capacity, determining the kinetically and thermodynamically preferred reduction processes at various states of discharge is critical to elucidating the mechanism. Specific advanced in-situ and ex-situ characterization techniques are conducive to gaining insight regarding the electrochemical behavior of these multifunctional materials over multiple length scales. At the material level, optical microscopy, scanning electron microscopy, and local conductivity measurement via a nanoprobe can track the discharge mechanism of an isolated single particle. At the mesoscale electrode level, in-situ data from synchrotron based energy dispersive X-ray diffraction (EDXRD) within fully intact steel batteries can be used to spatially map the distribution of silver metal generated through reduction displacement as a function of discharge depth and discharge rate. As illustrated here, appropriate design of materials with multiple electrochemically active metal centers and properties tuned through strategically conceptualized materials synthesis may provide a path toward the next generation of high energy content electroactive materials and systems. In conclusion, full understanding of the multiple electrochemical mechanisms can be achieved only by utilizing advanced characterization tools over multiple length scales.« less
  • The wholeversusthe sum of its parts; contributions of nanoscale iron-containing materials to the bulk electrochemistry of composite electrodes.
  • The wholeversusthe sum of its parts; contributions of nanoscale iron-containing materials to the bulk electrochemistry of composite electrodes.
  • Lithium chlorate, LiClO/sub 3/, has reported melting points of 127.6/sup 0/ and 129/sup 0/C. The specific conductance of molten lithium chlorate at 130/sup 0/C is relatively high compared to common aqueous electrolytic solutions at room temperature. Therefore, lithium chlorate offers the chance to operate a new lithium battery system at a temperature betwee 130/sup 0/ and 150/sup 0/C. It was found experimentally that lithium chlorate is stable in the potential range between 3.2 and 4.6V relative to an Li reference electrode. An Li-Cl/sub 2/ secondary battery system was observed to have an open-circuit potential of 3.97V, making an Li-Cl/sub 2/more » secondary battery in molten lithium chlorate possible, in principle. A lithium-lithium chlorate primary battery system is also possible. Lithium negative electrode performance was found to be hindered by corrosion and possible runaway reactions with LiClO/sub 3/. Dendrite formation on charging was observed. The solubility of Li/sub 2/O and LiCl in LiClO/sub 3/ at 145/sup 0/C is 7.5 X 10/sup -5/ and 1.78 X 10/sup -3/ mol/cm/sup 3/, respectively. The diffusion coefficients are 1.5 X 10/sup -7/ for Li/sub 2/O and 3.4 X 10/sup -7/ cm/sup 2//sec for LiCl. Platinum appeared to be an inert positive electrode for chlorate, chlorine, or oxygen reactions fo runs on the order of several hours. Nickel shows an active-passive behavior which is complex. Nickel appears suitable for use in a primary cell for the cathodic discharge of LiClO/sub 3/, but it does not appear suitable for a Cl/sub 2/ or O/sub 2/ electrode.« less
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