Quasi-Steady-State Polarization Reveals the Interplay of Capacitive and Faradaic Processes in Capacitive Deionization
Abstract
Abstract We employ slow cyclic voltammetry to study the quasi‐steady‐state capacitive deionization (CDI) of aerated 10 mM NaCl from V cell =−0.2 to 2 V. The method allows for the deconvolution of capacitive and faradaic processes, which are significant even at low voltage, in conjunction with pH, conductivity, dissolved oxygen (DO), and electrode potential measurements. The pH at three locations and effluent DO data identify asymmetric electrosorption in the cell configured with pristine activated carbon electrodes, where charge is irreversibly consumed to produce H + /OH − instead of reversibly adsorbing Cl − /Na + . Implementing a reference electrode resolves ion adsorption as a function of the individual potential at each electrode. Near‐electrode pH probes reveal pH environments that diverge by up to 8 units during cell polarization and allow more accurate calculation of faradaic redox potentials in a flow‐by CDI cell. In the aerated NaCl solution that will be relevant to industrial‐scale water treatment, we find that DO reduction occurs to a greater degree than Na + adsorption at the cathode until DO removal becomes mass transfer limited at <−0.2 V vs. SHE. Two cell architectures – flow‐by and flow‐through – corroborate our findings. Finally, we reconcile all measurements to generatemore »
- Authors:
-
- Univ. of Kentucky, Lexington, KY (United States)
- Publication Date:
- Research Org.:
- West Virginia Univ., Morgantown, WV (United States)
- Sponsoring Org.:
- USDOE Office of Policy and International Affairs (PO); USDOE
- OSTI Identifier:
- 1533132
- Alternate Identifier(s):
- OSTI ID: 1389886
- Grant/Contract Number:
- PI0000017
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemElectroChem
- Additional Journal Information:
- Journal Volume: 4; Journal Issue: 9; Journal ID: ISSN 2196-0216
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electrochemistry; oxygen reduction; capacitors; electrodes; capacitive deionization; electrochemical water treatment
Citation Formats
Holubowitch, Nicolas, Omosebi, Ayokunle, Gao, Xin, Landon, James, and Liu, Kunlei. Quasi-Steady-State Polarization Reveals the Interplay of Capacitive and Faradaic Processes in Capacitive Deionization. United States: N. p., 2017.
Web. doi:10.1002/celc.201700082.
Holubowitch, Nicolas, Omosebi, Ayokunle, Gao, Xin, Landon, James, & Liu, Kunlei. Quasi-Steady-State Polarization Reveals the Interplay of Capacitive and Faradaic Processes in Capacitive Deionization. United States. https://doi.org/10.1002/celc.201700082
Holubowitch, Nicolas, Omosebi, Ayokunle, Gao, Xin, Landon, James, and Liu, Kunlei. Thu .
"Quasi-Steady-State Polarization Reveals the Interplay of Capacitive and Faradaic Processes in Capacitive Deionization". United States. https://doi.org/10.1002/celc.201700082. https://www.osti.gov/servlets/purl/1533132.
@article{osti_1533132,
title = {Quasi-Steady-State Polarization Reveals the Interplay of Capacitive and Faradaic Processes in Capacitive Deionization},
author = {Holubowitch, Nicolas and Omosebi, Ayokunle and Gao, Xin and Landon, James and Liu, Kunlei},
abstractNote = {Abstract We employ slow cyclic voltammetry to study the quasi‐steady‐state capacitive deionization (CDI) of aerated 10 mM NaCl from V cell =−0.2 to 2 V. The method allows for the deconvolution of capacitive and faradaic processes, which are significant even at low voltage, in conjunction with pH, conductivity, dissolved oxygen (DO), and electrode potential measurements. The pH at three locations and effluent DO data identify asymmetric electrosorption in the cell configured with pristine activated carbon electrodes, where charge is irreversibly consumed to produce H + /OH − instead of reversibly adsorbing Cl − /Na + . Implementing a reference electrode resolves ion adsorption as a function of the individual potential at each electrode. Near‐electrode pH probes reveal pH environments that diverge by up to 8 units during cell polarization and allow more accurate calculation of faradaic redox potentials in a flow‐by CDI cell. In the aerated NaCl solution that will be relevant to industrial‐scale water treatment, we find that DO reduction occurs to a greater degree than Na + adsorption at the cathode until DO removal becomes mass transfer limited at <−0.2 V vs. SHE. Two cell architectures – flow‐by and flow‐through – corroborate our findings. Finally, we reconcile all measurements to generate a map displaying how the potential is partitioned amongst the capacitive and faradaic processes occurring during CDI operation over a 2.2 V window.},
doi = {10.1002/celc.201700082},
journal = {ChemElectroChem},
number = 9,
volume = 4,
place = {United States},
year = {Thu May 11 00:00:00 EDT 2017},
month = {Thu May 11 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Examination of Water Electrolysis and Oxygen Reduction As Self-Discharge Mechanisms for Carbon-Based, Aqueous Electrolyte Electrochemical Capacitors
journal, February 2011
- Oickle, Alicia M.; Andreas, Heather A.
- The Journal of Physical Chemistry C, Vol. 115, Issue 10
Pathways to low-cost electrochemical energy storage: a comparison of aqueous and nonaqueous flow batteries
journal, January 2014
- Darling, Robert M.; Gallagher, Kevin G.; Kowalski, Jeffrey A.
- Energy & Environmental Science, Vol. 7, Issue 11, p. 3459-3477
Complementary surface charge for enhanced capacitive deionization
journal, April 2016
- Gao, X.; Porada, S.; Omosebi, A.
- Water Research, Vol. 92
Mechanistic insights into the use of oxide nanoparticles coated asymmetric electrodes for capacitive deionization
journal, February 2013
- Han, Linchen; Karthikeyan, K. G.; Anderson, M. A.
- Electrochimica Acta, Vol. 90
Investigation of oxygen reduction on activated carbon electrodes in alkaline solution
journal, May 2007
- Qu, Deyang
- Carbon, Vol. 45, Issue 6
Design of graphene-coated hollow mesoporous carbon spheres as high performance electrodes for capacitive deionization
journal, January 2014
- Wang, Hui; Shi, Liyi; Yan, Tingting
- J. Mater. Chem. A, Vol. 2, Issue 13
Limitation of Charge Efficiency in Capacitive Deionization
journal, January 2009
- Avraham, Eran; Bouhadana, Yaniv; Soffer, Abraham
- Journal of The Electrochemical Society, Vol. 156, Issue 6
Using capacitive deionisation for inland brackish groundwater desalination in a remote location
journal, January 2013
- Mossad, Mohamed; Zhang, Wei; Zou, Linda
- Desalination, Vol. 308
Novel Graphene-Like Electrodes for Capacitive Deionization
journal, November 2010
- Li, Haibo; Zou, Linda; Pan, Likun
- Environmental Science & Technology, Vol. 44, Issue 22
Requirements for performance characterization of C double-layer supercapacitors: Applications to a high specific-area C-cloth material
journal, June 2006
- Niu, Jianjun; Pell, Wendy G.; Conway, Brian E.
- Journal of Power Sources, Vol. 156, Issue 2
The feasibility of boron removal from water by capacitive deionization
journal, July 2011
- Avraham, Eran; Noked, Malachi; Soffer, Abraham
- Electrochimica Acta, Vol. 56, Issue 18
Thermodynamic cycle analysis for capacitive deionization
journal, April 2009
- Biesheuvel, P. M.
- Journal of Colloid and Interface Science, Vol. 332, Issue 1
Capacitive Deionization of NaCl Solutions at Non-Steady-State Conditions: Inversion Functionality of the Carbon Electrodes
journal, August 2011
- Bouhadana, Yaniv; Avraham, Eran; Noked, Malachi
- The Journal of Physical Chemistry C, Vol. 115, Issue 33
Dependence of the Capacitive Deionization Performance on Potential of Zero Charge Shifting of Carbon Xerogel Electrodes during Long-Term Operation
journal, January 2014
- Gao, Xin; Omosebi, Ayokunle; Landon, James
- Journal of The Electrochemical Society, Vol. 161, Issue 12
Tracking the structural arrangement of ions in carbon supercapacitor nanopores using in situ small-angle X-ray scattering
journal, January 2015
- Prehal, C.; Weingarth, D.; Perre, E.
- Energy & Environmental Science, Vol. 8, Issue 6
Graphene-containing flowable electrodes for capacitive energy storage
journal, October 2015
- Boota, M.; Hatzell, K. B.; Alhabeb, M.
- Carbon, Vol. 92, p. 142-149
Cell voltage versus electrode potential range in aqueous supercapacitors
journal, April 2015
- Dai, Zengxin; Peng, Chuang; Chae, Jung Hoon
- Scientific Reports, Vol. 5, Issue 1
A control system for operating and investigating reactors: The demonstration of parasitic reactions in the water desalination by capacitive de-ionization
journal, March 2011
- Bouhadana, Yaniv; Ben-Tzion, Moshe; Soffer, Abraham
- Desalination, Vol. 268, Issue 1-3
Surface-treated carbon electrodes with modified potential of zero charge for capacitive deionization
journal, April 2016
- Wu, Tingting; Wang, Gang; Zhan, Fei
- Water Research, Vol. 93
Capacitive deionization (CDI) for desalination and water treatment — past, present and future (a review)
journal, August 2008
- Oren, Yoram
- Desalination, Vol. 228, Issue 1-3
Electrochemistry and capacitive charging of porous electrodes in asymmetric multicomponent electrolytes
journal, June 2012
- Biesheuvel, P. M.; Fu, Y.; Bazant, M. Z.
- Russian Journal of Electrochemistry, Vol. 48, Issue 6
Water desalination via capacitive deionization: what is it and what can we expect from it?
journal, January 2015
- Suss, M. E.; Porada, S.; Sun, X.
- Energy & Environmental Science, Vol. 8, Issue 8
Side Reactions in Capacitive Deionization (CDI) Processes: The Role of Oxygen Reduction
journal, December 2016
- Shapira, Barak; Avraham, Eran; Aurbach, Doron
- Electrochimica Acta, Vol. 220
The Origins of Low Efficiency in Electrochemical De-Ionization Systems
journal, January 2016
- Shanbhag, S.; Whitacre, J. F.; Mauter, M. S.
- Journal of The Electrochemical Society, Vol. 163, Issue 14
Continuous operation of membrane capacitive deionization cells assembled with dissimilar potential of zero charge electrode pairs
journal, May 2015
- Omosebi, Ayokunle; Gao, Xin; Rentschler, Jeffery
- Journal of Colloid and Interface Science, Vol. 446
A systematic study on the changes in properties of an activated carbon cloth upon polarization
journal, February 2011
- Bayram, Edip; Ayranci, Erol
- Electrochimica Acta, Vol. 56, Issue 5
Proton-selective electrode for pH sensing
journal, December 2016
- Shapira, Barak; Avraham, Eran; Aurbach, Doron
- Electrochemistry Communications, Vol. 73
Three-Dimensional Graphene/Metal Oxide Nanoparticle Hybrids for High-Performance Capacitive Deionization of Saline Water
journal, August 2013
- Yin, Huajie; Zhao, Shenlong; Wan, Jiawei
- Advanced Materials, Vol. 25, Issue 43
Around the thermodynamic limitations of supercapacitors operating in aqueous electrolytes
journal, July 2016
- Fic, Krzysztof; Meller, Mikolaj; Menzel, Jakub
- Electrochimica Acta, Vol. 206
Capacitive Deionization using Biomass-based Microporous Salt-Templated Heteroatom-Doped Carbons
journal, May 2015
- Porada, Slawomir; Schipper, Florian; Aslan, Mesut
- ChemSusChem, Vol. 8, Issue 11
Comparison of salt adsorption capacity and energy consumption between constant current and constant voltage operation in capacitive deionization
journal, November 2014
- Kang, Junil; Kim, Taeyoung; Jo, Kyusik
- Desalination, Vol. 352
Several basic and practical aspects related to electrochemical deionization of water
journal, January 2009
- Bouhadana, Yaniv; Avraham, Eran; Soffer, Abraham
- AIChE Journal
Electrode reactions and adsorption/desorption performance related to the applied potential in a capacitive deionization process
journal, August 2010
- Lee, Jae-Hun; Bae, Wi-Sup; Choi, Jae-Hwan
- Desalination, Vol. 258, Issue 1-3
Desalination stability of capacitive deionization using ordered mesoporous carbon: Effect of oxygen-containing surface groups and pore properties
journal, November 2015
- Duan, Feng; Du, Xuan; Li, Yuping
- Desalination, Vol. 376
Asymmetric capacitive deionization utilizing nitric acid treated activated carbon fiber as the cathode
journal, September 2015
- Wu, Tingting; Wang, Gang; Dong, Qiang
- Electrochimica Acta, Vol. 176
Two-Dimensional Porous Electrode Model for Capacitive Deionization
journal, October 2015
- Hemmatifar, Ali; Stadermann, Michael; Santiago, Juan G.
- The Journal of Physical Chemistry C, Vol. 119, Issue 44
Electro-removal of arsenic(III) and arsenic(V) from aqueous solutions by capacitive deionization
journal, July 2016
- Fan, Chen-Shiuan; Tseng, Ssu-Chia; Li, Kung-Cheh
- Journal of Hazardous Materials, Vol. 312
Desalting by Means of Porous Carbon Electrodes
journal, January 1971
- Johnson, A. M.; Newman, John
- Journal of The Electrochemical Society, Vol. 118, Issue 3
Capacitive deionization as an electrochemical means of saving energy and delivering clean water. Comparison to present desalination practices: Will it compete?
journal, April 2010
- Anderson, Marc A.; Cudero, Ana L.; Palma, Jesus
- Electrochimica Acta, Vol. 55, Issue 12
Direct prediction of the desalination performance of porous carbon electrodes for capacitive deionization
journal, January 2013
- Porada, S.; Borchardt, L.; Oschatz, M.
- Energy & Environmental Science, Vol. 6, Issue 12
Determination of the electrode potential causing Faradaic reactions in membrane capacitive deionization
journal, August 2014
- Choi, Jae-Hwan
- Desalination, Vol. 347
On porous electrodes in electrolyte solutions
journal, October 1963
- de Levie, R.
- Electrochimica Acta, Vol. 8, Issue 10
The effect of the flow-regime, reversal of polarization, and oxygen on the long term stability in capacitive de-ionization processes
journal, January 2015
- Cohen, Izaak; Avraham, Eran; Bouhadana, Yaniv
- Electrochimica Acta, Vol. 153
Electrochemical Characterization of Activated Carbon-Fiber Cloth Polarizable Electrodes for Electric Double-Layer Capacitors
journal, January 1990
- Tanahashi, Ichiro
- Journal of The Electrochemical Society, Vol. 137, Issue 10
Surface charge enhanced carbon electrodes for stable and efficient capacitive deionization using inverted adsorption–desorption behavior
journal, January 2015
- Gao, Xin; Omosebi, Ayokunle; Landon, James
- Energy & Environmental Science, Vol. 8, Issue 3
Capacitive deionization with Ca-alginate coated-carbon electrode for hardness control
journal, August 2016
- Yoon, Hongsik; Lee, Jiho; Kim, Sang-Ryoung
- Desalination, Vol. 392
Review on the science and technology of water desalination by capacitive deionization
journal, October 2013
- Porada, S.; Zhao, R.; van der Wal, A.
- Progress in Materials Science, Vol. 58, Issue 8
Works referencing / citing this record:
Capacitive deionization using symmetric carbon electrode pairs
journal, January 2019
- Gao, X.; Omosebi, A.; Ma, Z.
- Environmental Science: Water Research & Technology, Vol. 5, Issue 4
Interconnected metal oxide CNT fibre hybrid networks for current collector-free asymmetric capacitive deionization
journal, January 2018
- Santos, Cleis; Lado, Julio J.; García-Quismondo, Enrique
- Journal of Materials Chemistry A, Vol. 6, Issue 23
Ti-based electrode materials for electrochemical sodium ion storage and removal
journal, January 2019
- Zhai, Haifa; Xia, Bao Yu; Park, Ho Seok
- Journal of Materials Chemistry A, Vol. 7, Issue 39
Maximizing Volumetric Removal Capacity in Capacitive Deionization by Adjusting Electrode Thickness and Charging Mode
journal, January 2018
- Santos, Cleis; Lado, Julio J.; García-Quismondo, Enrique
- Journal of The Electrochemical Society, Vol. 165, Issue 7