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Title: Confined Interlayer Water Promotes Structural Stability for High-Rate Electrochemical Proton Intercalation in Tungsten Oxide Hydrates

Abstract

There is widespread interest in determining the structural features of redox-active electrochemical energy storage materials that enable simultaneous high power and high energy density. Here, we present the discovery that confined interlayer water in crystalline tungsten oxide hydrates, WO3·nH2O, enables highly reversible proton intercalation at subsecond time scales. By comparing the structural transformation kinetics and confined water dynamics of the hydrates with anhydrous WO3, we determine that the rapid electrochemical proton intercalation is due to the ability of the confined water layers to isolate structural transformations to two dimensions while stabilizing the structure along the third dimension. As a result, these water layers provide both structural flexibility and stability to accommodate intercalation-driven bonding changes. Furthermore, this provides an alternative explanation for the fast energy storage kinetics of materials that incorporate structural water and provides a new strategy for enabling high power and high energy density with redox-active layered materials containing confined fluids.

Authors:
 [1];  [2];  [1]; ORCiD logo [3];  [4];  [1];  [5]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [1]
  1. North Carolina State Univ., Raleigh, NC (United States)
  2. Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Univ. of California, Riverside, CA (United States)
  5. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST); SLAC National Accelerator Lab., Menlo Park, CA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1595247
Alternate Identifier(s):
OSTI ID: 1649453
Grant/Contract Number:  
AC02-76SF00515; 1810194; 653827; AC05-00OR22725; ECCS-1542015
Resource Type:
Accepted Manuscript
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 4; Journal Issue: 12; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Mitchell, James B., Geise, Natalie R., Paterson, Alisa R., Osti, Naresh C., Sun, Yangyunli, Fleischmann, Simon, Zhang, Rui, Madsen, Louis A., Toney, Michael F., Jiang, De-en, Kolesnikov, Alexander I., Mamontov, Eugene, and Augustyn, Veronica. Confined Interlayer Water Promotes Structural Stability for High-Rate Electrochemical Proton Intercalation in Tungsten Oxide Hydrates. United States: N. p., 2019. Web. doi:10.1021/acsenergylett.9b02040.
Mitchell, James B., Geise, Natalie R., Paterson, Alisa R., Osti, Naresh C., Sun, Yangyunli, Fleischmann, Simon, Zhang, Rui, Madsen, Louis A., Toney, Michael F., Jiang, De-en, Kolesnikov, Alexander I., Mamontov, Eugene, & Augustyn, Veronica. Confined Interlayer Water Promotes Structural Stability for High-Rate Electrochemical Proton Intercalation in Tungsten Oxide Hydrates. United States. doi:https://doi.org/10.1021/acsenergylett.9b02040
Mitchell, James B., Geise, Natalie R., Paterson, Alisa R., Osti, Naresh C., Sun, Yangyunli, Fleischmann, Simon, Zhang, Rui, Madsen, Louis A., Toney, Michael F., Jiang, De-en, Kolesnikov, Alexander I., Mamontov, Eugene, and Augustyn, Veronica. Tue . "Confined Interlayer Water Promotes Structural Stability for High-Rate Electrochemical Proton Intercalation in Tungsten Oxide Hydrates". United States. doi:https://doi.org/10.1021/acsenergylett.9b02040. https://www.osti.gov/servlets/purl/1595247.
@article{osti_1595247,
title = {Confined Interlayer Water Promotes Structural Stability for High-Rate Electrochemical Proton Intercalation in Tungsten Oxide Hydrates},
author = {Mitchell, James B. and Geise, Natalie R. and Paterson, Alisa R. and Osti, Naresh C. and Sun, Yangyunli and Fleischmann, Simon and Zhang, Rui and Madsen, Louis A. and Toney, Michael F. and Jiang, De-en and Kolesnikov, Alexander I. and Mamontov, Eugene and Augustyn, Veronica},
abstractNote = {There is widespread interest in determining the structural features of redox-active electrochemical energy storage materials that enable simultaneous high power and high energy density. Here, we present the discovery that confined interlayer water in crystalline tungsten oxide hydrates, WO3·nH2O, enables highly reversible proton intercalation at subsecond time scales. By comparing the structural transformation kinetics and confined water dynamics of the hydrates with anhydrous WO3, we determine that the rapid electrochemical proton intercalation is due to the ability of the confined water layers to isolate structural transformations to two dimensions while stabilizing the structure along the third dimension. As a result, these water layers provide both structural flexibility and stability to accommodate intercalation-driven bonding changes. Furthermore, this provides an alternative explanation for the fast energy storage kinetics of materials that incorporate structural water and provides a new strategy for enabling high power and high energy density with redox-active layered materials containing confined fluids.},
doi = {10.1021/acsenergylett.9b02040},
journal = {ACS Energy Letters},
number = 12,
volume = 4,
place = {United States},
year = {2019},
month = {10}
}

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