Over-limiting Current and Control of Dendritic Growth by Surface Conduction in Nanopores
Understanding over-limiting current (faster than diffusion) is a long-standing challenge in electrochemistry with applications in desalination and energy storage. Known mechanisms involve either chemical or hydrodynamic instabilities in unconfined electrolytes. Here, it is shown that over-limiting c...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | en_US |
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Nature Publishing Group
2014
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| Online Access: | http://hdl.handle.net/1721.1/92552 https://orcid.org/0000-0002-3171-7982 |
| _version_ | 1811077576691548160 |
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| author | Han, Ji-Hyung Bai, Peng Bazant, Martin Z. Khoo, Edwin Sze Lun |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Han, Ji-Hyung Bai, Peng Bazant, Martin Z. Khoo, Edwin Sze Lun |
| author_sort | Han, Ji-Hyung |
| collection | MIT |
| description | Understanding over-limiting current (faster than diffusion) is a long-standing challenge in electrochemistry with applications in desalination and energy storage. Known mechanisms involve either chemical or hydrodynamic instabilities in unconfined electrolytes. Here, it is shown that over-limiting current can be sustained by surface conduction in nanopores, without any such instabilities, and used to control dendritic growth during electrodeposition. Copper electrodeposits are grown in anodized aluminum oxide membranes with polyelectrolyte coatings to modify the surface charge. At low currents, uniform electroplating occurs, unaffected by surface modification due to thin electric double layers, but the morphology changes dramatically above the limiting current. With negative surface charge, growth is enhanced along the nanopore surfaces, forming surface dendrites and nanotubes behind a deionization shock. With positive surface charge, dendrites avoid the surfaces and are either guided along the nanopore centers or blocked from penetrating the membrane. |
| first_indexed | 2024-09-23T10:45:13Z |
| format | Article |
| id | mit-1721.1/92552 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T10:45:13Z |
| publishDate | 2014 |
| publisher | Nature Publishing Group |
| record_format | dspace |
| spelling | mit-1721.1/925522022-09-27T14:42:42Z Over-limiting Current and Control of Dendritic Growth by Surface Conduction in Nanopores Han, Ji-Hyung Bai, Peng Bazant, Martin Z. Khoo, Edwin Sze Lun Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department of Mathematics Khoo, Edwin Sze Lun Han, Ji-Hyung Bai, Peng Bazant, Martin Z. Understanding over-limiting current (faster than diffusion) is a long-standing challenge in electrochemistry with applications in desalination and energy storage. Known mechanisms involve either chemical or hydrodynamic instabilities in unconfined electrolytes. Here, it is shown that over-limiting current can be sustained by surface conduction in nanopores, without any such instabilities, and used to control dendritic growth during electrodeposition. Copper electrodeposits are grown in anodized aluminum oxide membranes with polyelectrolyte coatings to modify the surface charge. At low currents, uniform electroplating occurs, unaffected by surface modification due to thin electric double layers, but the morphology changes dramatically above the limiting current. With negative surface charge, growth is enhanced along the nanopore surfaces, forming surface dendrites and nanotubes behind a deionization shock. With positive surface charge, dendrites avoid the surfaces and are either guided along the nanopore centers or blocked from penetrating the membrane. Korea (South). Ministry of Education, Science and Technology (MEST) (National Research Foundation of Korea. Basic Science Research Program. 2012R1A6A3A03039224) Singapore. Agency for Science, Technology and Research (National Science Scholarship) International Business Machines Corporation (Faculty Award) Saint-Gobain Corporation. Northboro R&D Center 2014-12-30T17:52:05Z 2014-12-30T17:52:05Z 2014-11 2014-08 Article http://purl.org/eprint/type/JournalArticle 2045-2322 http://hdl.handle.net/1721.1/92552 Han, Ji-Hyung, Edwin Khoo, Peng Bai, and Martin Z. Bazant. “Over-Limiting Current and Control of Dendritic Growth by Surface Conduction in Nanopores.” Sci. Rep. 4 (November 14, 2014): 7056. https://orcid.org/0000-0002-3171-7982 en_US http://dx.doi.org/10.1038/srep07056 Scientific Reports Creative Commons Attribution http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf Nature Publishing Group Nature Publishing Group |
| spellingShingle | Han, Ji-Hyung Bai, Peng Bazant, Martin Z. Khoo, Edwin Sze Lun Over-limiting Current and Control of Dendritic Growth by Surface Conduction in Nanopores |
| title | Over-limiting Current and Control of Dendritic Growth by Surface Conduction in Nanopores |
| title_full | Over-limiting Current and Control of Dendritic Growth by Surface Conduction in Nanopores |
| title_fullStr | Over-limiting Current and Control of Dendritic Growth by Surface Conduction in Nanopores |
| title_full_unstemmed | Over-limiting Current and Control of Dendritic Growth by Surface Conduction in Nanopores |
| title_short | Over-limiting Current and Control of Dendritic Growth by Surface Conduction in Nanopores |
| title_sort | over limiting current and control of dendritic growth by surface conduction in nanopores |
| url | http://hdl.handle.net/1721.1/92552 https://orcid.org/0000-0002-3171-7982 |
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