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Origin of capacitance decay for a flower-like δ-MnO2 aqueous supercapacitor electrode: The quantitative surface and electrochemical analysis
•Low cyclic stability of layered δ-MnO2 supercapacitor electrode was investigated.•Na+ ions intercalation on the electrode surface was observed via EDAX and XPS analysis.•Slow charge/discharge process leads to permanent intercalation of Na+ electrolytic ion.•Prolonged cyclic test shows Na+ ions repl...
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| Published in: | Journal of alloys and compounds 2022-02, Vol.892, p.162199, Article 162199 |
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| container_start_page | 162199 |
| container_title | Journal of alloys and compounds |
| container_volume | 892 |
| creator | Justin Raj, C. Manikandan, Ramu Sivakumar, Periyasamy Opar, David O. Dennyson Savariraj, A. Cho, Won-Je Jung, Hyun Kim, Byung Chul |
| description | •Low cyclic stability of layered δ-MnO2 supercapacitor electrode was investigated.•Na+ ions intercalation on the electrode surface was observed via EDAX and XPS analysis.•Slow charge/discharge process leads to permanent intercalation of Na+ electrolytic ion.•Prolonged cyclic test shows Na+ ions replaced some host K ions in layered δ-MnO2.
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Herein, we report the electrochemical energy storage performance of δ-MnO2 (K-birnessite MnO2) as supercapacitor electrode material in Na2SO4 aqueous electrolyte. The electrode exhibited considerable electrochemical performances due to the fast intercalation/deintercalation reactions of Na+ on the pseudocapacitive MnO2 surface. However, a long-term cyclic stability test of the electrode at a low specific current (1 A g−1) demonstrated a decline in its initial capacitance value to the tune of ~ 21%. To quantify the above discrepancy, the electrochemical intercalation of Na+ ions on the electrode surface was quantitatively studied employing electrochemical impedance spectroscopy, EDAX analysis and X-ray photoelectron spectroscopy. Further, the surface of the electrode was analyzed by performing complete charge and charge/discharge measurements at a low specific current of 0.1 A g−1. These results disclosed that, besides the surface intercalation/deintercalation reactions, some Na+ ions have permanently substituted into the bulk (layer) of δ-MnO2 by replacing the host K ions from the layered nanostructure. Thus, this finding suggests that Na+ ions replaced in the site of K in δ-MnO2 considerably affect the electrochemical properties of the supercapacitor electrode. |
| doi_str_mv | 10.1016/j.jallcom.2021.162199 |
| format | article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_journals_2620965507</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><els_id>S0925838821036094</els_id><sourcerecordid>2620965507</sourcerecordid><originalsourceid>FETCH-LOGICAL-c337t-2d2c3d40d61fe8ce5e898b26a84f3cad6939e5e1e9751946e52db478c6e021cf3</originalsourceid><addsrcrecordid>eNqFkM1OGzEUhS0EEiHlEZAssZ7UPzMemw1CEbSVqLKBtWXs68bTyTixZ6jyEH0bnoNnqlHCuitLV9858vkQuqJkQQkVX7tFZ_rexs2CEUYXVDCq1AmaUdnyqhZCnaIZUaypJJfyHF3k3BFCqOJ0hv6uUvgVBhw9tmZrbBjNYAE7sGaPfUzYYN_HP5CqPvwG_P5W_RxWDJvdBHHKOE9bSMdggaEHO6bo4AY_rQHvJjOMpXEMr1DQ5E2pNoP75OwaNsGavtxMv88hf0Fn3vQZLo_vHD0_3D8tv1ePq28_lnePleW8HSvmmOWuJk5QD9JCA1LJFyaMrD23xgnFVTlSUG1DVS2gYe6lbqUVUARZz-fo-tC7TbEsyaPu4pTKJ7JmghElmoa0hWoOlE0x5wReb1PYmLTXlOgP87rTR_P6w7w-mC-520MOyoTXAElnG6BodSGV3drF8J-Gf-pikpw</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2620965507</pqid></control><display><type>article</type><title>Origin of capacitance decay for a flower-like δ-MnO2 aqueous supercapacitor electrode: The quantitative surface and electrochemical analysis</title><source>ScienceDirect Journals</source><creator>Justin Raj, C. ; Manikandan, Ramu ; Sivakumar, Periyasamy ; Opar, David O. ; Dennyson Savariraj, A. ; Cho, Won-Je ; Jung, Hyun ; Kim, Byung Chul</creator><creatorcontrib>Justin Raj, C. ; Manikandan, Ramu ; Sivakumar, Periyasamy ; Opar, David O. ; Dennyson Savariraj, A. ; Cho, Won-Je ; Jung, Hyun ; Kim, Byung Chul</creatorcontrib><description>•Low cyclic stability of layered δ-MnO2 supercapacitor electrode was investigated.•Na+ ions intercalation on the electrode surface was observed via EDAX and XPS analysis.•Slow charge/discharge process leads to permanent intercalation of Na+ electrolytic ion.•Prolonged cyclic test shows Na+ ions replaced some host K ions in layered δ-MnO2.
[Display omitted]
Herein, we report the electrochemical energy storage performance of δ-MnO2 (K-birnessite MnO2) as supercapacitor electrode material in Na2SO4 aqueous electrolyte. The electrode exhibited considerable electrochemical performances due to the fast intercalation/deintercalation reactions of Na+ on the pseudocapacitive MnO2 surface. However, a long-term cyclic stability test of the electrode at a low specific current (1 A g−1) demonstrated a decline in its initial capacitance value to the tune of ~ 21%. To quantify the above discrepancy, the electrochemical intercalation of Na+ ions on the electrode surface was quantitatively studied employing electrochemical impedance spectroscopy, EDAX analysis and X-ray photoelectron spectroscopy. Further, the surface of the electrode was analyzed by performing complete charge and charge/discharge measurements at a low specific current of 0.1 A g−1. These results disclosed that, besides the surface intercalation/deintercalation reactions, some Na+ ions have permanently substituted into the bulk (layer) of δ-MnO2 by replacing the host K ions from the layered nanostructure. Thus, this finding suggests that Na+ ions replaced in the site of K in δ-MnO2 considerably affect the electrochemical properties of the supercapacitor electrode.</description><identifier>ISSN: 0925-8388</identifier><identifier>EISSN: 1873-4669</identifier><identifier>DOI: 10.1016/j.jallcom.2021.162199</identifier><language>eng</language><publisher>Lausanne: Elsevier B.V</publisher><subject>Aqueous electrolytes ; Capacitance ; Chemical reactions ; Electrochemical analysis ; Electrochemical impedance spectroscopy ; Electrode materials ; Electrodes ; Energy storage ; Impedance spectroscopy ; Intercalation ; Ion intercalation ; Layered nanostructure ; Manganese dioxide ; Manganese oxide ; Photoelectrons ; Spectrum analysis ; Stability tests ; Supercapacitor ; Supercapacitors ; Surface stability</subject><ispartof>Journal of alloys and compounds, 2022-02, Vol.892, p.162199, Article 162199</ispartof><rights>2021 Elsevier B.V.</rights><rights>Copyright Elsevier BV Feb 5, 2022</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c337t-2d2c3d40d61fe8ce5e898b26a84f3cad6939e5e1e9751946e52db478c6e021cf3</citedby><cites>FETCH-LOGICAL-c337t-2d2c3d40d61fe8ce5e898b26a84f3cad6939e5e1e9751946e52db478c6e021cf3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,786,790,27957,27958</link.rule.ids></links><search><creatorcontrib>Justin Raj, C.</creatorcontrib><creatorcontrib>Manikandan, Ramu</creatorcontrib><creatorcontrib>Sivakumar, Periyasamy</creatorcontrib><creatorcontrib>Opar, David O.</creatorcontrib><creatorcontrib>Dennyson Savariraj, A.</creatorcontrib><creatorcontrib>Cho, Won-Je</creatorcontrib><creatorcontrib>Jung, Hyun</creatorcontrib><creatorcontrib>Kim, Byung Chul</creatorcontrib><title>Origin of capacitance decay for a flower-like δ-MnO2 aqueous supercapacitor electrode: The quantitative surface and electrochemical analysis</title><title>Journal of alloys and compounds</title><description>•Low cyclic stability of layered δ-MnO2 supercapacitor electrode was investigated.•Na+ ions intercalation on the electrode surface was observed via EDAX and XPS analysis.•Slow charge/discharge process leads to permanent intercalation of Na+ electrolytic ion.•Prolonged cyclic test shows Na+ ions replaced some host K ions in layered δ-MnO2.
[Display omitted]
Herein, we report the electrochemical energy storage performance of δ-MnO2 (K-birnessite MnO2) as supercapacitor electrode material in Na2SO4 aqueous electrolyte. The electrode exhibited considerable electrochemical performances due to the fast intercalation/deintercalation reactions of Na+ on the pseudocapacitive MnO2 surface. However, a long-term cyclic stability test of the electrode at a low specific current (1 A g−1) demonstrated a decline in its initial capacitance value to the tune of ~ 21%. To quantify the above discrepancy, the electrochemical intercalation of Na+ ions on the electrode surface was quantitatively studied employing electrochemical impedance spectroscopy, EDAX analysis and X-ray photoelectron spectroscopy. Further, the surface of the electrode was analyzed by performing complete charge and charge/discharge measurements at a low specific current of 0.1 A g−1. These results disclosed that, besides the surface intercalation/deintercalation reactions, some Na+ ions have permanently substituted into the bulk (layer) of δ-MnO2 by replacing the host K ions from the layered nanostructure. Thus, this finding suggests that Na+ ions replaced in the site of K in δ-MnO2 considerably affect the electrochemical properties of the supercapacitor electrode.</description><subject>Aqueous electrolytes</subject><subject>Capacitance</subject><subject>Chemical reactions</subject><subject>Electrochemical analysis</subject><subject>Electrochemical impedance spectroscopy</subject><subject>Electrode materials</subject><subject>Electrodes</subject><subject>Energy storage</subject><subject>Impedance spectroscopy</subject><subject>Intercalation</subject><subject>Ion intercalation</subject><subject>Layered nanostructure</subject><subject>Manganese dioxide</subject><subject>Manganese oxide</subject><subject>Photoelectrons</subject><subject>Spectrum analysis</subject><subject>Stability tests</subject><subject>Supercapacitor</subject><subject>Supercapacitors</subject><subject>Surface stability</subject><issn>0925-8388</issn><issn>1873-4669</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNqFkM1OGzEUhS0EEiHlEZAssZ7UPzMemw1CEbSVqLKBtWXs68bTyTixZ6jyEH0bnoNnqlHCuitLV9858vkQuqJkQQkVX7tFZ_rexs2CEUYXVDCq1AmaUdnyqhZCnaIZUaypJJfyHF3k3BFCqOJ0hv6uUvgVBhw9tmZrbBjNYAE7sGaPfUzYYN_HP5CqPvwG_P5W_RxWDJvdBHHKOE9bSMdggaEHO6bo4AY_rQHvJjOMpXEMr1DQ5E2pNoP75OwaNsGavtxMv88hf0Fn3vQZLo_vHD0_3D8tv1ePq28_lnePleW8HSvmmOWuJk5QD9JCA1LJFyaMrD23xgnFVTlSUG1DVS2gYe6lbqUVUARZz-fo-tC7TbEsyaPu4pTKJ7JmghElmoa0hWoOlE0x5wReb1PYmLTXlOgP87rTR_P6w7w-mC-520MOyoTXAElnG6BodSGV3drF8J-Gf-pikpw</recordid><startdate>20220205</startdate><enddate>20220205</enddate><creator>Justin Raj, C.</creator><creator>Manikandan, Ramu</creator><creator>Sivakumar, Periyasamy</creator><creator>Opar, David O.</creator><creator>Dennyson Savariraj, A.</creator><creator>Cho, Won-Je</creator><creator>Jung, Hyun</creator><creator>Kim, Byung Chul</creator><general>Elsevier B.V</general><general>Elsevier BV</general><scope>AAYXX</scope><scope>CITATION</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>20220205</creationdate><title>Origin of capacitance decay for a flower-like δ-MnO2 aqueous supercapacitor electrode: The quantitative surface and electrochemical analysis</title><author>Justin Raj, C. ; Manikandan, Ramu ; Sivakumar, Periyasamy ; Opar, David O. ; Dennyson Savariraj, A. ; Cho, Won-Je ; Jung, Hyun ; Kim, Byung Chul</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c337t-2d2c3d40d61fe8ce5e898b26a84f3cad6939e5e1e9751946e52db478c6e021cf3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Aqueous electrolytes</topic><topic>Capacitance</topic><topic>Chemical reactions</topic><topic>Electrochemical analysis</topic><topic>Electrochemical impedance spectroscopy</topic><topic>Electrode materials</topic><topic>Electrodes</topic><topic>Energy storage</topic><topic>Impedance spectroscopy</topic><topic>Intercalation</topic><topic>Ion intercalation</topic><topic>Layered nanostructure</topic><topic>Manganese dioxide</topic><topic>Manganese oxide</topic><topic>Photoelectrons</topic><topic>Spectrum analysis</topic><topic>Stability tests</topic><topic>Supercapacitor</topic><topic>Supercapacitors</topic><topic>Surface stability</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Justin Raj, C.</creatorcontrib><creatorcontrib>Manikandan, Ramu</creatorcontrib><creatorcontrib>Sivakumar, Periyasamy</creatorcontrib><creatorcontrib>Opar, David O.</creatorcontrib><creatorcontrib>Dennyson Savariraj, A.</creatorcontrib><creatorcontrib>Cho, Won-Je</creatorcontrib><creatorcontrib>Jung, Hyun</creatorcontrib><creatorcontrib>Kim, Byung Chul</creatorcontrib><collection>CrossRef</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Journal of alloys and compounds</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Justin Raj, C.</au><au>Manikandan, Ramu</au><au>Sivakumar, Periyasamy</au><au>Opar, David O.</au><au>Dennyson Savariraj, A.</au><au>Cho, Won-Je</au><au>Jung, Hyun</au><au>Kim, Byung Chul</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Origin of capacitance decay for a flower-like δ-MnO2 aqueous supercapacitor electrode: The quantitative surface and electrochemical analysis</atitle><jtitle>Journal of alloys and compounds</jtitle><date>2022-02-05</date><risdate>2022</risdate><volume>892</volume><spage>162199</spage><pages>162199-</pages><artnum>162199</artnum><issn>0925-8388</issn><eissn>1873-4669</eissn><abstract>•Low cyclic stability of layered δ-MnO2 supercapacitor electrode was investigated.•Na+ ions intercalation on the electrode surface was observed via EDAX and XPS analysis.•Slow charge/discharge process leads to permanent intercalation of Na+ electrolytic ion.•Prolonged cyclic test shows Na+ ions replaced some host K ions in layered δ-MnO2.
[Display omitted]
Herein, we report the electrochemical energy storage performance of δ-MnO2 (K-birnessite MnO2) as supercapacitor electrode material in Na2SO4 aqueous electrolyte. The electrode exhibited considerable electrochemical performances due to the fast intercalation/deintercalation reactions of Na+ on the pseudocapacitive MnO2 surface. However, a long-term cyclic stability test of the electrode at a low specific current (1 A g−1) demonstrated a decline in its initial capacitance value to the tune of ~ 21%. To quantify the above discrepancy, the electrochemical intercalation of Na+ ions on the electrode surface was quantitatively studied employing electrochemical impedance spectroscopy, EDAX analysis and X-ray photoelectron spectroscopy. Further, the surface of the electrode was analyzed by performing complete charge and charge/discharge measurements at a low specific current of 0.1 A g−1. These results disclosed that, besides the surface intercalation/deintercalation reactions, some Na+ ions have permanently substituted into the bulk (layer) of δ-MnO2 by replacing the host K ions from the layered nanostructure. Thus, this finding suggests that Na+ ions replaced in the site of K in δ-MnO2 considerably affect the electrochemical properties of the supercapacitor electrode.</abstract><cop>Lausanne</cop><pub>Elsevier B.V</pub><doi>10.1016/j.jallcom.2021.162199</doi></addata></record> |
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| ispartof | Journal of alloys and compounds, 2022-02, Vol.892, p.162199, Article 162199 |
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| source | ScienceDirect Journals |
| subjects | Aqueous electrolytes Capacitance Chemical reactions Electrochemical analysis Electrochemical impedance spectroscopy Electrode materials Electrodes Energy storage Impedance spectroscopy Intercalation Ion intercalation Layered nanostructure Manganese dioxide Manganese oxide Photoelectrons Spectrum analysis Stability tests Supercapacitor Supercapacitors Surface stability |
| title | Origin of capacitance decay for a flower-like δ-MnO2 aqueous supercapacitor electrode: The quantitative surface and electrochemical analysis |
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