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Title: Rational design of efficient electrode–electrolyte interfaces for solid-state energy storage using ion soft landing

Abstract

Here, the rational design of improved electrode-electrolyte interfaces (EEI) for energy storage is critically dependent on a molecular-level understanding of ionic interactions and nanoscale phenomena. The presence of non-redox active species at EEI has been shown to strongly influence Faradaic efficiency and long-term operational stability during energy storage processes. Herein, we achieve substantially higher performance and long-term stability of EEI prepared with highly-dispersed discrete redox-active cluster anions (50 ng of pure ~0.7 nm size molybdenum polyoxometalate anions (POM) anions on 25 mg (≈ 0.2 wt%) carbon nanotube (CNT) electrodes) by complete elimination of strongly coordinating non-redox species through ion soft-landing (SL). For the first time, electron microscopy provides atomically-resolved images of individual POM species directly on complex technologically relevant CNT electrodes. In this context, SL is established as a versatile approach for the controlled design of novel surfaces for both fundamental and applied research in energy storage.

Authors:
 [1];  [1];  [2];  [1];  [1];  [1];  [2];  [1];  [1];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Univ. of Oregon, Eugene, OR (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1253857
Report Number(s):
PNNL-SA-113159
Journal ID: ISSN 2041-1723; ncomms11399
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Prabhakaran, Venkateshkumar, Mehdi, B. Layla, Ditto, Jeffrey J., Engelhard, Mark H., Wang, Bingbing, Gunaratne, K. Don D., Johnson, David C., Browning, Nigel D., Johnson, Grant E., and Laskin, Julia. Rational design of efficient electrode–electrolyte interfaces for solid-state energy storage using ion soft landing. United States: N. p., 2016. Web. doi:10.1038/ncomms11399.
Prabhakaran, Venkateshkumar, Mehdi, B. Layla, Ditto, Jeffrey J., Engelhard, Mark H., Wang, Bingbing, Gunaratne, K. Don D., Johnson, David C., Browning, Nigel D., Johnson, Grant E., & Laskin, Julia. Rational design of efficient electrode–electrolyte interfaces for solid-state energy storage using ion soft landing. United States. doi:10.1038/ncomms11399.
Prabhakaran, Venkateshkumar, Mehdi, B. Layla, Ditto, Jeffrey J., Engelhard, Mark H., Wang, Bingbing, Gunaratne, K. Don D., Johnson, David C., Browning, Nigel D., Johnson, Grant E., and Laskin, Julia. Thu . "Rational design of efficient electrode–electrolyte interfaces for solid-state energy storage using ion soft landing". United States. doi:10.1038/ncomms11399. https://www.osti.gov/servlets/purl/1253857.
@article{osti_1253857,
title = {Rational design of efficient electrode–electrolyte interfaces for solid-state energy storage using ion soft landing},
author = {Prabhakaran, Venkateshkumar and Mehdi, B. Layla and Ditto, Jeffrey J. and Engelhard, Mark H. and Wang, Bingbing and Gunaratne, K. Don D. and Johnson, David C. and Browning, Nigel D. and Johnson, Grant E. and Laskin, Julia},
abstractNote = {Here, the rational design of improved electrode-electrolyte interfaces (EEI) for energy storage is critically dependent on a molecular-level understanding of ionic interactions and nanoscale phenomena. The presence of non-redox active species at EEI has been shown to strongly influence Faradaic efficiency and long-term operational stability during energy storage processes. Herein, we achieve substantially higher performance and long-term stability of EEI prepared with highly-dispersed discrete redox-active cluster anions (50 ng of pure ~0.7 nm size molybdenum polyoxometalate anions (POM) anions on 25 mg (≈ 0.2 wt%) carbon nanotube (CNT) electrodes) by complete elimination of strongly coordinating non-redox species through ion soft-landing (SL). For the first time, electron microscopy provides atomically-resolved images of individual POM species directly on complex technologically relevant CNT electrodes. In this context, SL is established as a versatile approach for the controlled design of novel surfaces for both fundamental and applied research in energy storage.},
doi = {10.1038/ncomms11399},
journal = {Nature Communications},
number = ,
volume = 7,
place = {United States},
year = {2016},
month = {4}
}

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Works referenced in this record:

Electrochemical energy storage in a sustainable modern society
journal, January 2014


Electricity Now and When
journal, November 2011


Hybrid energy storage: high voltage aqueous supercapacitors based on activated carbon–phosphotungstate hybrid materials
journal, January 2014

  • Suárez-Guevara, J.; Ruiz, V.; Gomez-Romero, P.
  • J. Mater. Chem. A, Vol. 2, Issue 4
  • DOI: 10.1039/C3TA14455K

Hybrid supercapacitor-battery materials for fast electrochemical charge storage
journal, March 2014

  • Vlad, A.; Singh, N.; Rolland, J.
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep04315

Challenges Facing Lithium Batteries and Electrical Double-Layer Capacitors
journal, September 2012

  • Choi, Nam-Soon; Chen, Zonghai; Freunberger, Stefan A.
  • Angewandte Chemie International Edition, Vol. 51, Issue 40
  • DOI: 10.1002/anie.201201429

Materials for electrochemical capacitors
journal, November 2008

  • Simon, Patrice; Gogotsi, Yury
  • Nature Materials, Vol. 7, Issue 11
  • DOI: 10.1038/nmat2297

Building better batteries
journal, February 2008

  • Armand, M.; Tarascon, J.-M.
  • Nature, Vol. 451, Issue 7179, p. 652-657
  • DOI: 10.1038/451652a

Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013

  • Goodenough, John B.; Park, Kyu-Sung
  • Journal of the American Chemical Society, Vol. 135, Issue 4
  • DOI: 10.1021/ja3091438

A review of electrode materials for electrochemical supercapacitors
journal, January 2012

  • Wang, Guoping; Zhang, Lei; Zhang, Jiujun
  • Chemical Society Reviews, Vol. 41, Issue 2, p. 797-828
  • DOI: 10.1039/C1CS15060J

Where Do Batteries End and Supercapacitors Begin?
journal, March 2014


V 2 O 5 -Anchored Carbon Nanotubes for Enhanced Electrochemical Energy Storage
journal, October 2011

  • Sathiya, M.; Prakash, A. S.; Ramesha, K.
  • Journal of the American Chemical Society, Vol. 133, Issue 40
  • DOI: 10.1021/ja207285b

Hybrid Organic-Inorganic Materials—In Search of Synergic Activity
journal, February 2001


Brushed-on flexible supercapacitor sheets using a nanocomposite of polyaniline and carbon nanotubes
journal, November 2010


One-step spray processing of high power all-solid-state supercapacitors
journal, August 2013

  • Huang, Chun; Grant, Patrick S.
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep02393

Chemical Vapor Deposition Growth of Crystalline Monolayer MoSe2
journal, April 2014

  • Wang, Xingli; Gong, Yongji; Shi, Gang
  • ACS Nano, Vol. 8, Issue 5, p. 5125-5131
  • DOI: 10.1021/nn501175k

Atomic layer deposition of vanadium oxide on carbon nanotubes for high-power supercapacitor electrodes
journal, January 2012

  • Boukhalfa, Sofiane; Evanoff, Kara; Yushin, Gleb
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee21110f

In Operando X-ray Absorption Fine Structure Studies of Polyoxometalate Molecular Cluster Batteries: Polyoxometalates as Electron Sponges
journal, March 2012

  • Wang, Heng; Hamanaka, Shun; Nishimoto, Yoshio
  • Journal of the American Chemical Society, Vol. 134, Issue 10
  • DOI: 10.1021/ja2117206

Fabrication of network films of conducting polymer-linked polyoxometallate-stabilized carbon nanostructures
journal, February 2006


Decoupled catalytic hydrogen evolution from a molecular metal oxide redox mediator in water splitting
journal, September 2014


Soft landing of ions as a means of surface modification
journal, January 1977

  • Franchetti, V.; Solka, B. H.; Baitinger, W. E.
  • International Journal of Mass Spectrometry and Ion Physics, Vol. 23, Issue 1
  • DOI: 10.1016/0020-7381(77)80004-1

Soft landing of mass-selected gold clusters: Influence of ion and ligand on charge retention and reactivity
journal, February 2015


Soft Landing of Complex Molecules on Surfaces
journal, July 2011


Soft- and reactive landing of ions onto surfaces: Concepts and applications: CONCEPTS AND APPLICATIONS
journal, April 2015

  • Johnson, Grant E.; Gunaratne, Don; Laskin, Julia
  • Mass Spectrometry Reviews, Vol. 35, Issue 3
  • DOI: 10.1002/mas.21451

Electrospray Ion Beam Deposition of Clusters and Biomolecules
journal, April 2006

  • Rauschenbach, Stephan; Stadler, Frank L.; Lunedei, Eugenio
  • Small, Vol. 2, Issue 4, p. 540-547
  • DOI: 10.1002/smll.200500479

Ambient Ion Soft Landing
journal, April 2011

  • Badu-Tawiah, Abraham K.; Wu, Chunping; Cooks, R. Graham
  • Analytical Chemistry, Vol. 83, Issue 7, p. 2648-2654
  • DOI: 10.1021/ac102940q

Soft-landing preparative mass spectrometry
journal, January 2012

  • Verbeck, Guido; Hoffmann, William; Walton, Barbara
  • The Analyst, Vol. 137, Issue 19
  • DOI: 10.1039/c2an35550g

Ion/surface reactions and ion soft-landing
journal, January 2005

  • Gologan, Bogdan; Green, Jason R.; Alvarez, Jormarie
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 7
  • DOI: 10.1039/b418056a

In-situ enrichment of phosphopeptides on MALDI plates modified by ambient ion landing : MALDI plates modification by ion landing
journal, September 2012

  • Krásný, Lukáš; Pompach, Petr; Strohalm, Martin
  • Journal of Mass Spectrometry, Vol. 47, Issue 10
  • DOI: 10.1002/jms.3081

Surface Modification and Patterning Using Low-Energy Ion Beams:  Si−O Bond Formation at the Vacuum/Adsorbate Interface
journal, January 2002

  • Evans, Chris; Wade, Nathan; Pepi, Federico
  • Analytical Chemistry, Vol. 74, Issue 2
  • DOI: 10.1021/ac010928p

Chemically Modified Multiwalled Carbon Nanotubes Electrodes with Ferrocene Derivatives through Reactive Landing
journal, February 2011

  • Pepi, Federico; Tata, Alessandra; Garzoli, Stefania
  • The Journal of Physical Chemistry C, Vol. 115, Issue 11
  • DOI: 10.1021/jp1100472

Electron-Transfer Kinetics of Microperoxidase-11 Covalently Immobilised onto the Surface of Multi-Walled Carbon Nanotubes by Reactive Landing of Mass-Selected Ions
journal, July 2009

  • Mazzei, Franco; Favero, Gabriele; Frasconi, Marco
  • Chemistry - A European Journal, Vol. 15, Issue 30
  • DOI: 10.1002/chem.200900887

Chemical Modification of Graphene via Hyperthermal Molecular Reaction
journal, September 2014

  • Dubey, Girjesh; Urcuyo, Roberto; Abb, Sabine
  • Journal of the American Chemical Society, Vol. 136, Issue 39
  • DOI: 10.1021/ja5046499

In Situ Bioconjugation and Ambient Surface Modification Using Reactive Charged Droplets
journal, February 2015

  • He, Qing; Badu-Tawiah, Abraham K.; Chen, Suming
  • Analytical Chemistry, Vol. 87, Issue 6
  • DOI: 10.1021/ac504111f

Design and performance of a high-flux electrospray ionization source for ion soft landing
journal, January 2015

  • Gunaratne, K. Don D.; Prabhakaran, Venkateshkumar; Ibrahim, Yehia M.
  • The Analyst, Vol. 140, Issue 9
  • DOI: 10.1039/C5AN00220F

Electrospray droplet sources for thin film deposition
journal, November 2006


Electrospraying route to nanotechnology: An overview
journal, March 2008


Electrospray Deposition as a Method To Fabricate Functionally Active Protein Films
journal, April 1999

  • Morozov, Victor N.; Morozova, Tamara Ya.
  • Analytical Chemistry, Vol. 71, Issue 7
  • DOI: 10.1021/ac9808775

Electrospray Deposition as a Method for Mass Fabrication of Mono- and Multicomponent Microarrays of Biological and Biologically Active Substances
journal, August 1999

  • Morozov, Victor N.; Morozova, Tamara Ya.
  • Analytical Chemistry, Vol. 71, Issue 15
  • DOI: 10.1021/ac981412h

Electrospray deposition of carbon nanotubes in vacuum
journal, January 2007


Electrospray Deposition of C 60 on a Hydrogen-Bonded Supramolecular Network
journal, April 2008

  • Saywell, Alex; Magnano, Graziano; Satterley, Christopher J.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 20
  • DOI: 10.1021/jp7119944

PEMFC electrode preparation by electrospray: Optimization of catalyst load and ionomer content
journal, May 2009


Capacitive energy storage in micro-scale devices: recent advances in design and fabrication of micro-supercapacitors
journal, January 2014

  • Beidaghi, Majid; Gogotsi, Yury
  • Energy & Environmental Science, Vol. 7, Issue 3
  • DOI: 10.1039/c3ee43526a

A comparison of single-wall carbon nanotube electrochemical capacitor electrode fabrication methods
journal, March 2012


Controlling the Charge State and Redox Properties of Supported Polyoxometalates via Soft Landing of Mass-Selected Ions
journal, October 2014

  • Gunaratne, K. Don D.; Johnson, Grant E.; Andersen, Amity
  • The Journal of Physical Chemistry C, Vol. 118, Issue 48
  • DOI: 10.1021/jp505050m

Transition from “Supercapacitor” to “Battery” Behavior in Electrochemical Energy Storage
journal, January 1991

  • Conway, B. E.
  • Journal of The Electrochemical Society, Vol. 138, Issue 6, p. 1539-1548
  • DOI: 10.1149/1.2085829

Ionic-liquid materials for the electrochemical challenges of the future
journal, July 2009

  • Armand, Michel; Endres, Frank; MacFarlane, Douglas R.
  • Nature Materials, Vol. 8, Issue 8, p. 621-629
  • DOI: 10.1038/nmat2448

A High-Performance Graphene Oxide-Doped Ion Gel as Gel Polymer Electrolyte for All-Solid-State Supercapacitor Applications
journal, February 2013

  • Yang, Xi; Zhang, Fan; Zhang, Long
  • Advanced Functional Materials, Vol. 23, Issue 26
  • DOI: 10.1002/adfm.201203556

Adsorption of ammonia on activated carbon from aqueous solutions
journal, July 2008

  • Long, Xiang‐Li; Cheng, Hua; Xin, Zhi‐Ling
  • Environmental Progress, Vol. 27, Issue 2
  • DOI: 10.1002/ep.10252

Adsorption of Ammonium Ion by Multi-walled Carbon Nanotube: Kinetics and Thermodynamic Studies
journal, January 2013


Electrochemical Stability of Ionic Liquids: General Influences and Degradation Mechanisms
journal, August 2014

  • De Vos, Nils; Maton, Cédric; Stevens, Christian V.
  • ChemElectroChem, Vol. 1, Issue 8
  • DOI: 10.1002/celc.201402086

Polyoxometalate-Based Molecular Materials
journal, February 1998

  • Coronado, Eugenio; Gómez-García, Carlos J.
  • Chemical Reviews, Vol. 98, Issue 1
  • DOI: 10.1021/cr970471c

Distribution of molybdenum oxidation states in reduced molybdenum/titania catalysts: correlation with benzene hydrogenation activity
journal, February 1990

  • Quincy, Roger B.; Houalla, Marwan.; Proctor, Andrew.
  • The Journal of Physical Chemistry, Vol. 94, Issue 4
  • DOI: 10.1021/j100367a058

Spectrosopic and paramagnetic properties of molybdenum oxyhydroxide films electrochemically formed from the Keggin-type (PMo 12 O 40 ) 3− complex
journal, October 2003

  • Nakayama, Masaharu; Ii, Takahiro; Ogura, Kotaro
  • Journal of Materials Research, Vol. 18, Issue 10
  • DOI: 10.1557/JMR.2003.0349

A Raman and XPS investigation of supported molybdenum oxide thin films. 2. Reactions with hydrogen sulfide
journal, October 1993

  • Spevack, Perry A.; McIntyre, N. S.
  • The Journal of Physical Chemistry, Vol. 97, Issue 42
  • DOI: 10.1021/j100144a021

Electrochromic molybdenum trioxide thin film preparation and characterization
journal, September 1990

  • Belanger, Daniel; Laperriere, Guylaine
  • Chemistry of Materials, Vol. 2, Issue 5
  • DOI: 10.1021/cm00011a004

X-ray photoelectron spectroscopic investigation of nanocrystalline calcium silicate hydrates synthesised by reactive milling
journal, June 2006


SEM, XPS, and FTIR studies of MoO3 dispersion on mesoporous silicate MCM-41 by calcination
journal, November 2003


Old Metal Oxide Clusters in New Applications: Spontaneous Reduction of Keggin and Dawson Polyoxometalate Layers by a Metallic Electrode for Improving Efficiency in Organic Optoelectronics
journal, May 2015

  • Vasilopoulou, Maria; Douvas, Antonios M.; Palilis, Leonidas C.
  • Journal of the American Chemical Society, Vol. 137, Issue 21
  • DOI: 10.1021/jacs.5b01889

A review of focused ion beam milling techniques for TEM specimen preparation
journal, June 1999


    Works referencing / citing this record:

    Formation Mechanism and Reversible Expansion and Shrinkage of Magnesium-Based Homochiral Metal-Organic Nanotubes
    journal, December 2016

    • Liu, Min; Feng, Jian-Shen; Bao, Song-Song
    • Chemistry - A European Journal, Vol. 23, Issue 5
    • DOI: 10.1002/chem.201603776

    Observing the colloidal stability of iron oxide nanoparticles in situ
    journal, January 2019

    • Hufschmid, Ryan; Teeman, Eric; Mehdi, B. Layla
    • Nanoscale, Vol. 11, Issue 27
    • DOI: 10.1039/c9nr03709h

    Formation Mechanism and Reversible Expansion and Shrinkage of Magnesium-Based Homochiral Metal-Organic Nanotubes
    journal, December 2016

    • Liu, Min; Feng, Jian-Shen; Bao, Song-Song
    • Chemistry - A European Journal, Vol. 23, Issue 5
    • DOI: 10.1002/chem.201603776

    Observing the colloidal stability of iron oxide nanoparticles in situ
    journal, January 2019

    • Hufschmid, Ryan; Teeman, Eric; Mehdi, B. Layla
    • Nanoscale, Vol. 11, Issue 27
    • DOI: 10.1039/c9nr03709h