Role of structural hydroxyl groups in enhancing performance of electrochemically-synthesized bilayer V2O5

doi:10.1016/j.nanoen.2018.09.005

Title: Role of structural hydroxyl groups in enhancing performance of electrochemically-synthesized bilayer V₂O₅

Abstract

Nanostructured electrode materials represent a promising path forward to dramatically improving the performance of both Li-ion and beyond Li-ion battery systems; however, difficulties in characterizing the structural and electrochemical changes that take place in nanoscale systems, which are often poorly crystalline or amorphous, make it difficult to develop design rules for synthesizing new materials with optimal performance. Bilayered vanadium oxide-based materials (BL-V₂O₅) are an ideal platform for understanding the underlying physicochemical properties that determine capacity in nanomaterials, with electrochemically-synthesized V₂O₅ (EC-V₂O₅) exhibiting particularly high capacities. In this work we provide evidence that the source of high practical capacity in EC-V₂O₅ is the presence of “structural hydroxyl groups” that are an intrinsic feature of the electrochemical synthesis method. Using both in situ and ex situ characterization methods, we demonstrate that structural OH species are highly stable and persist in the structure during reversible cycling. We hypothesize three important roles for structural OH groups: they maintain a sufficient interlayer spacing to allow the physical diffusion of cations over multiple cycles; they maintain a consistent solvating environment in the bilayer regardless of structural H₂O content; and they reduce the symmetry of vanadium polyhedra to favor electron transfer over pseudocapacitive adsorption, making it possiblemore »« less

Authors:

Tepavcevic, Sanja ^[1];

^[1]; Lopes, Pietro P. ^[1]; Bachhav, Mukesh ^[2]; Key, Baris ^[1]; Valero-Vidal, Carlos ^[3]; Crumlin, Ethan J. ^[3]; Stamenkovic, Vojislav R. ^[1]; Markovic, Nenad M. ^[1]

Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Michigan, Ann Arbor, MI (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: 2018-09-04

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

OSTI Identifier:: 1478486

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Nano Energy

Additional Journal Information:: Journal Volume: 53; Journal Issue: C; Journal ID: ISSN 2211-2855

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; bilayered V2O5; electrochemical synthesis; hydrated oxide; nanostructured electrode; structural OH; universal intercalation host

Citation Formats


                    Tepavcevic, Sanja, Connell, Justin G., Lopes, Pietro P., Bachhav, Mukesh, Key, Baris, Valero-Vidal, Carlos, Crumlin, Ethan J., Stamenkovic, Vojislav R., and Markovic, Nenad M. Role of structural hydroxyl groups in enhancing performance of electrochemically-synthesized bilayer V2O5.  United States: N. p., 2018. 
        Web.  doi:10.1016/j.nanoen.2018.09.005.

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                    Tepavcevic, Sanja, Connell, Justin G., Lopes, Pietro P., Bachhav, Mukesh, Key, Baris, Valero-Vidal, Carlos, Crumlin, Ethan J., Stamenkovic, Vojislav R., & Markovic, Nenad M. Role of structural hydroxyl groups in enhancing performance of electrochemically-synthesized bilayer V2O5.  United States.  doi:10.1016/j.nanoen.2018.09.005.

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                    Tepavcevic, Sanja, Connell, Justin G., Lopes, Pietro P., Bachhav, Mukesh, Key, Baris, Valero-Vidal, Carlos, Crumlin, Ethan J., Stamenkovic, Vojislav R., and Markovic, Nenad M. Tue .  
        "Role of structural hydroxyl groups in enhancing performance of electrochemically-synthesized bilayer V2O5".  United States.  doi:10.1016/j.nanoen.2018.09.005.  https://www.osti.gov/servlets/purl/1478486.

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@article{osti_1478486,

  title        = {Role of structural hydroxyl groups in enhancing performance of electrochemically-synthesized bilayer V2O5},

  author       = {Tepavcevic, Sanja and Connell, Justin G. and Lopes, Pietro P. and Bachhav, Mukesh and Key, Baris and Valero-Vidal, Carlos and Crumlin, Ethan J. and Stamenkovic, Vojislav R. and Markovic, Nenad M.},

  abstractNote = {Nanostructured electrode materials represent a promising path forward to dramatically improving the performance of both Li-ion and beyond Li-ion battery systems; however, difficulties in characterizing the structural and electrochemical changes that take place in nanoscale systems, which are often poorly crystalline or amorphous, make it difficult to develop design rules for synthesizing new materials with optimal performance. Bilayered vanadium oxide-based materials (BL-V2O5) are an ideal platform for understanding the underlying physicochemical properties that determine capacity in nanomaterials, with electrochemically-synthesized V2O5 (EC-V2O5) exhibiting particularly high capacities. In this work we provide evidence that the source of high practical capacity in EC-V2O5 is the presence of “structural hydroxyl groups” that are an intrinsic feature of the electrochemical synthesis method. Using both in situ and ex situ characterization methods, we demonstrate that structural OH species are highly stable and persist in the structure during reversible cycling. We hypothesize three important roles for structural OH groups: they maintain a sufficient interlayer spacing to allow the physical diffusion of cations over multiple cycles; they maintain a consistent solvating environment in the bilayer regardless of structural H2O content; and they reduce the symmetry of vanadium polyhedra to favor electron transfer over pseudocapacitive adsorption, making it possible to access close to theoretical capacity. Furthermore, these insights have broad implications for understanding the performance of a variety of hydrated oxide systems, and indicate that the formation of covalently-bound hydroxyoxide species can lead to further improvements in the performance of nanoscale materials.},

  doi          = {10.1016/j.nanoen.2018.09.005},

  journal      = {Nano Energy},

  number       = C,

  volume       = 53,

  place        = {United States},

  year         = {2018},

  month        = {9}

}

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DOI: 10.1016/j.nanoen.2018.09.005

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Works referencing / citing this record:

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Advanced Energy Materials, Vol. 10, Issue 4
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Similar Records

Title: Role of structural hydroxyl groups in enhancing performance of electrochemically-synthesized bilayer V2O5

Abstract

Citation Formats

Pseudo‐Zn–Air and Zn‐Ion Intercalation Dual Mechanisms to Realize High‐Areal Capacitance and Long‐Life Energy Storage in Aqueous Zn Battery journal, July 2019

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Title: Role of structural hydroxyl groups in enhancing performance of electrochemically-synthesized bilayer V₂O₅

Pseudo‐Zn–Air and Zn‐Ion Intercalation Dual Mechanisms to Realize High‐Areal Capacitance and Long‐Life Energy Storage in Aqueous Zn Battery
journal, July 2019

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journal, December 2019