Unveiling the pseudocapacitive charge storage mechanisms of nanostructured vanadium nitrides using in-situ analyses

Abdoulaye Djire; Priyanka Pande; Aniruddha Deb; Jason B. Siegel; Olabode T. Ajenifujah; Lilin He; Alice E. Sleightholme; Paul G. Rasmussen; Levi T. Thompson

doi:10.1016/j.nanoen.2019.03.003

Unveiling the pseudocapacitive charge storage mechanisms of nanostructured vanadium nitrides using in-situ analyses

Abdoulaye Djire, Priyanka Pande, Aniruddha Deb, Jason B. Siegel, Olabode T. Ajenifujah, Lilin He, Alice E. Sleightholme, Paul G. Rasmussen, Levi T. Thompson

SANS & Spin Echo

University of Michigan, Ann Arbor

Research output: Contribution to journal › Article › peer-review

61 Scopus citations

Abstract

The future of energy storage devices relies on energy storage systems with both high energy and power densities. Supercapacitors, a hybrid of capacitors and batteries, have the potential to deliver both high energy and power densities. Materials suitable for supercapacitors are those capable of storing charges via faradaic redox reactions or pseudocapacitive reactions in addition to electrostatic double-layer storage. High-surface-area early transition metal nitrides such as vanadium nitride (VN) have promising properties for use in energy storage devices, especially supercapacitors, due to their pseudocapacitive charge storage mechanisms. The nature of their pseudocapacitive function, however, remains poorly understood. Further development of these materials requires a detailed understanding of their pseudocapacitive charge storage mechanisms. This paper reports a detailed and comprehensive analysis of the pseudocapacitive charge-storage mechanisms of the VN material in aqueous alkaline electrolytes using in-situ small angle neutron scattering (SANS) and in-situ x-ray absorption spectroscopy (XAS) combined with physical and electrochemical characterization techniques. Contrary to conventional wisdom that large pores are more accessible to electrolyte ions and thus store more charge, our results showed that pseudocapacitive charge storage mechanism for VN in aqueous alkaline media is induced by the insertion/extraction of anions (i.e. OH ⁻ , OD ⁻ ) in and out of micropores. The anion insertion/extraction leads to the reduction/oxidation of the V metal, as the material was electrochemically charged and dis-charged within its operating potential window. These results suggest that high pseudocapacitances in excess of 1300 Fg ^-1 could be achieved by the VN material in 1.2 V aqueous alkaline electrolytes. This work undoubtedly provides a clear and generic conceptual and fundamental characterization approach for energy storage devices and related systems.

Original language	English
Pages (from-to)	72-81
Number of pages	10
Journal	Nano Energy
Volume	60
DOIs	https://doi.org/10.1016/j.nanoen.2019.03.003
State	Published - Jun 2019

Bibliographical note

Publisher Copyright:
© 2019

Funding

The authors acknowledge technical and financial support from the Automotive Research Center (ARC) in accordance with Cooperative Agreement W56HZV-14-2-0001, Army Tank Command and Army Research Office (grant number W911NF-11-1-0465), and Michigan Memorial Phoenix Project Seed grant. The XAS measurements were performed at the DND-CAT (5-BM-D) beam-line at APS, supported by the E.I. DuPont de Nemours and Co., the Dow Chemical Company, the National Science Foundation (grant DMR-9304725) and the State of Illinois. The SANS data were collected at ORNL's High Flux Isotope Reactor, sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy. The authors thank Dr. Jason Gaudet for his help with collecting the SANS data. The authors acknowledge technical and financial support from the Automotive Research Center (ARC) in accordance with Cooperative Agreement W56HZV-14-2-0001 , Army Tank Command and Army Research Office (grant number W911NF-11-1-0465 ), and Michigan Memorial Phoenix Project Seed grant. The XAS measurements were performed at the DND-CAT (5-BM-D) beam-line at APS , supported by the E.I. DuPont de Nemours and Co., the Dow Chemical Company, the National Science Foundation (grant DMR-9304725 ) and the State of Illinois. The SANS data were collected at ORNL's High Flux Isotope Reactor, sponsored by the Scientific User Facilities Division , Office of Basic Energy Sciences , US Department of Energy . The authors thank Dr. Jason Gaudet for his help with collecting the SANS data.

Funders	Funder number
Army Tank Command and Army Research Office
E.I. DuPont de Nemours and Co.
Michigan Memorial Phoenix
National Science Foundation	DMR-9304725
U.S. Department of Energy
Army Research Office	W911NF-11-1-0465
Dow Chemical Company
Automotive Research Center	W56HZV-14-2-0001
American Pediatric Society

Keywords

Micropores
Pseudocapacitance
Supercapacitors
Transition-metal vanadium nitrides

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10.1016/j.nanoen.2019.03.003

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title = "Unveiling the pseudocapacitive charge storage mechanisms of nanostructured vanadium nitrides using in-situ analyses",

abstract = " The future of energy storage devices relies on energy storage systems with both high energy and power densities. Supercapacitors, a hybrid of capacitors and batteries, have the potential to deliver both high energy and power densities. Materials suitable for supercapacitors are those capable of storing charges via faradaic redox reactions or pseudocapacitive reactions in addition to electrostatic double-layer storage. High-surface-area early transition metal nitrides such as vanadium nitride (VN) have promising properties for use in energy storage devices, especially supercapacitors, due to their pseudocapacitive charge storage mechanisms. The nature of their pseudocapacitive function, however, remains poorly understood. Further development of these materials requires a detailed understanding of their pseudocapacitive charge storage mechanisms. This paper reports a detailed and comprehensive analysis of the pseudocapacitive charge-storage mechanisms of the VN material in aqueous alkaline electrolytes using in-situ small angle neutron scattering (SANS) and in-situ x-ray absorption spectroscopy (XAS) combined with physical and electrochemical characterization techniques. Contrary to conventional wisdom that large pores are more accessible to electrolyte ions and thus store more charge, our results showed that pseudocapacitive charge storage mechanism for VN in aqueous alkaline media is induced by the insertion/extraction of anions (i.e. OH − , OD − ) in and out of micropores. The anion insertion/extraction leads to the reduction/oxidation of the V metal, as the material was electrochemically charged and dis-charged within its operating potential window. These results suggest that high pseudocapacitances in excess of 1300 Fg -1 could be achieved by the VN material in 1.2 V aqueous alkaline electrolytes. This work undoubtedly provides a clear and generic conceptual and fundamental characterization approach for energy storage devices and related systems.",

keywords = "Micropores, Pseudocapacitance, Supercapacitors, Transition-metal vanadium nitrides",

author = "Abdoulaye Djire and Priyanka Pande and Aniruddha Deb and Siegel, {Jason B.} and Ajenifujah, {Olabode T.} and Lilin He and Sleightholme, {Alice E.} and Rasmussen, {Paul G.} and Thompson, {Levi T.}",

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year = "2019",

month = jun,

doi = "10.1016/j.nanoen.2019.03.003",

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AU - Djire, Abdoulaye

AU - Pande, Priyanka

AU - Deb, Aniruddha

AU - Siegel, Jason B.

AU - Ajenifujah, Olabode T.

AU - He, Lilin

AU - Sleightholme, Alice E.

AU - Rasmussen, Paul G.

AU - Thompson, Levi T.

PY - 2019/6

Y1 - 2019/6

N2 - The future of energy storage devices relies on energy storage systems with both high energy and power densities. Supercapacitors, a hybrid of capacitors and batteries, have the potential to deliver both high energy and power densities. Materials suitable for supercapacitors are those capable of storing charges via faradaic redox reactions or pseudocapacitive reactions in addition to electrostatic double-layer storage. High-surface-area early transition metal nitrides such as vanadium nitride (VN) have promising properties for use in energy storage devices, especially supercapacitors, due to their pseudocapacitive charge storage mechanisms. The nature of their pseudocapacitive function, however, remains poorly understood. Further development of these materials requires a detailed understanding of their pseudocapacitive charge storage mechanisms. This paper reports a detailed and comprehensive analysis of the pseudocapacitive charge-storage mechanisms of the VN material in aqueous alkaline electrolytes using in-situ small angle neutron scattering (SANS) and in-situ x-ray absorption spectroscopy (XAS) combined with physical and electrochemical characterization techniques. Contrary to conventional wisdom that large pores are more accessible to electrolyte ions and thus store more charge, our results showed that pseudocapacitive charge storage mechanism for VN in aqueous alkaline media is induced by the insertion/extraction of anions (i.e. OH − , OD − ) in and out of micropores. The anion insertion/extraction leads to the reduction/oxidation of the V metal, as the material was electrochemically charged and dis-charged within its operating potential window. These results suggest that high pseudocapacitances in excess of 1300 Fg -1 could be achieved by the VN material in 1.2 V aqueous alkaline electrolytes. This work undoubtedly provides a clear and generic conceptual and fundamental characterization approach for energy storage devices and related systems.

AB - The future of energy storage devices relies on energy storage systems with both high energy and power densities. Supercapacitors, a hybrid of capacitors and batteries, have the potential to deliver both high energy and power densities. Materials suitable for supercapacitors are those capable of storing charges via faradaic redox reactions or pseudocapacitive reactions in addition to electrostatic double-layer storage. High-surface-area early transition metal nitrides such as vanadium nitride (VN) have promising properties for use in energy storage devices, especially supercapacitors, due to their pseudocapacitive charge storage mechanisms. The nature of their pseudocapacitive function, however, remains poorly understood. Further development of these materials requires a detailed understanding of their pseudocapacitive charge storage mechanisms. This paper reports a detailed and comprehensive analysis of the pseudocapacitive charge-storage mechanisms of the VN material in aqueous alkaline electrolytes using in-situ small angle neutron scattering (SANS) and in-situ x-ray absorption spectroscopy (XAS) combined with physical and electrochemical characterization techniques. Contrary to conventional wisdom that large pores are more accessible to electrolyte ions and thus store more charge, our results showed that pseudocapacitive charge storage mechanism for VN in aqueous alkaline media is induced by the insertion/extraction of anions (i.e. OH − , OD − ) in and out of micropores. The anion insertion/extraction leads to the reduction/oxidation of the V metal, as the material was electrochemically charged and dis-charged within its operating potential window. These results suggest that high pseudocapacitances in excess of 1300 Fg -1 could be achieved by the VN material in 1.2 V aqueous alkaline electrolytes. This work undoubtedly provides a clear and generic conceptual and fundamental characterization approach for energy storage devices and related systems.

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Unveiling the pseudocapacitive charge storage mechanisms of nanostructured vanadium nitrides using in-situ analyses

Abstract

Bibliographical note

Funding

Keywords

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