Mechanism of Na+ Insertion in Alkali Vanadates and Its Influence on Battery Performance
Sodium-ion batteries may become an alternative to the widespread lithium-ion technology due to cost and kinetic advantages provided that cyclability is improved. For this purpose, the interplay between electrochemical and structural processes is key and is demonstrated in this work for Na2.46V6O16 (...
| Main Authors: | , , , , , , , , , |
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| Format: | Journal Article |
| Language: | English |
| Published: |
2017
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| Online Access: | https://hdl.handle.net/10356/84094 http://hdl.handle.net/10220/42954 |
| _version_ | 1826114719121932288 |
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| author | Hartung, Steffen Bucher, Nicolas Franklin, Joseph B. Wise, Anna M. Lim, Linda Y. Chen, Han-Yi Weker, Johanna Nelson Michel-Beyerle, Maria-Elisabeth Toney, Michael F. Srinivasan, Madhavi |
| author2 | School of Materials Science & Engineering |
| author_facet | School of Materials Science & Engineering Hartung, Steffen Bucher, Nicolas Franklin, Joseph B. Wise, Anna M. Lim, Linda Y. Chen, Han-Yi Weker, Johanna Nelson Michel-Beyerle, Maria-Elisabeth Toney, Michael F. Srinivasan, Madhavi |
| author_sort | Hartung, Steffen |
| collection | NTU |
| description | Sodium-ion batteries may become an alternative to the widespread lithium-ion technology due to cost and kinetic advantages provided that cyclability is improved. For this purpose, the interplay between electrochemical and structural processes is key and is demonstrated in this work for Na2.46V6O16 (NVO) and Li2.55V6O16 employing operando synchrotron X-ray diffraction. When NVO is cycled between 4.0 and 1.6 V, Na-ions reversibly occupy two crystallographic sites, which results in remarkable cyclability. Upon discharge to 1.0 V, however, Na-ions occupy also interstitial sites, inducing irreversible structural change with some loss of crystallinity concomitant with a decrease in capacity. Capacity fading increases with the ionic radius of the alkali ions (K+ > Na+ > Li+), suggesting that smaller ions stabilize the structure. This correlation of structural variation and electrochemical performance suggests a route toward improving cycling stability of a sodium-ion battery. Its essence is a minor Li+-retention in the A2+xV6O16 structure. Even though the majority of Li-ions are replaced by the abundant Na+, the residual Li-ions (≈10%) are sufficient to stabilize the layered structure, diminishing the irreversible structural damage. These results pave the way for further exploitation of the role of small ions in lattice stabilization that increases cycling performance. |
| first_indexed | 2024-10-01T03:43:43Z |
| format | Journal Article |
| id | ntu-10356/84094 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T03:43:43Z |
| publishDate | 2017 |
| record_format | dspace |
| spelling | ntu-10356/840942021-01-10T11:07:06Z Mechanism of Na+ Insertion in Alkali Vanadates and Its Influence on Battery Performance Hartung, Steffen Bucher, Nicolas Franklin, Joseph B. Wise, Anna M. Lim, Linda Y. Chen, Han-Yi Weker, Johanna Nelson Michel-Beyerle, Maria-Elisabeth Toney, Michael F. Srinivasan, Madhavi School of Materials Science & Engineering School of Physical and Mathematical Sciences Energy Research Institute @ NTU (ERI@N) In operando Irreversible Na+-insertion Sodium-ion batteries may become an alternative to the widespread lithium-ion technology due to cost and kinetic advantages provided that cyclability is improved. For this purpose, the interplay between electrochemical and structural processes is key and is demonstrated in this work for Na2.46V6O16 (NVO) and Li2.55V6O16 employing operando synchrotron X-ray diffraction. When NVO is cycled between 4.0 and 1.6 V, Na-ions reversibly occupy two crystallographic sites, which results in remarkable cyclability. Upon discharge to 1.0 V, however, Na-ions occupy also interstitial sites, inducing irreversible structural change with some loss of crystallinity concomitant with a decrease in capacity. Capacity fading increases with the ionic radius of the alkali ions (K+ > Na+ > Li+), suggesting that smaller ions stabilize the structure. This correlation of structural variation and electrochemical performance suggests a route toward improving cycling stability of a sodium-ion battery. Its essence is a minor Li+-retention in the A2+xV6O16 structure. Even though the majority of Li-ions are replaced by the abundant Na+, the residual Li-ions (≈10%) are sufficient to stabilize the layered structure, diminishing the irreversible structural damage. These results pave the way for further exploitation of the role of small ions in lattice stabilization that increases cycling performance. NRF (Natl Research Foundation, S’pore) Accepted version 2017-07-20T03:40:29Z 2019-12-06T15:38:13Z 2017-07-20T03:40:29Z 2019-12-06T15:38:13Z 2016 Journal Article Hartung, S., Bucher, N., Franklin, J. B., Wise, A. M., Lim, L. Y., Chen, H.-Y., et al. (2016). Mechanism of Na+ Insertion in Alkali Vanadates and Its Influence on Battery Performance. Advanced Energy Materials, 6(9), 1502336-. 1614-6832 https://hdl.handle.net/10356/84094 http://hdl.handle.net/10220/42954 10.1002/aenm.201502336 en Advanced Energy Materials © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the author created version of a work that has been peer reviewed and accepted for publication by Advanced Energy Materials, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [http://dx.doi.org/10.1002/aenm.201502336]. 44 p. application/pdf |
| spellingShingle | In operando Irreversible Na+-insertion Hartung, Steffen Bucher, Nicolas Franklin, Joseph B. Wise, Anna M. Lim, Linda Y. Chen, Han-Yi Weker, Johanna Nelson Michel-Beyerle, Maria-Elisabeth Toney, Michael F. Srinivasan, Madhavi Mechanism of Na+ Insertion in Alkali Vanadates and Its Influence on Battery Performance |
| title | Mechanism of Na+ Insertion in Alkali Vanadates and Its Influence on Battery Performance |
| title_full | Mechanism of Na+ Insertion in Alkali Vanadates and Its Influence on Battery Performance |
| title_fullStr | Mechanism of Na+ Insertion in Alkali Vanadates and Its Influence on Battery Performance |
| title_full_unstemmed | Mechanism of Na+ Insertion in Alkali Vanadates and Its Influence on Battery Performance |
| title_short | Mechanism of Na+ Insertion in Alkali Vanadates and Its Influence on Battery Performance |
| title_sort | mechanism of na insertion in alkali vanadates and its influence on battery performance |
| topic | In operando Irreversible Na+-insertion |
| url | https://hdl.handle.net/10356/84094 http://hdl.handle.net/10220/42954 |
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