Interface-Sensitive Charge Storage and Activation Behavior of Mn(1,3,5-Benzenetricarboxylic Acid (BTC))-Derived Mn<sub>3</sub>O<sub>4</sub>/Carbon Cathodes for Aqueous Zinc-Ion Batteries

In this study, we couple precise interface engineering via alternating current electrophoretic deposition (AC–EPD) with performance-enhancing structural transformation via annealing, enabling the development of high-performance, stable, and tunable Mn-based cathodes for aqueous zinc-ion batteries (Z...

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Main Authors: Jieun Lee, Byoungnam Park
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/12/2566
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author Jieun Lee
Byoungnam Park
author_facet Jieun Lee
Byoungnam Park
author_sort Jieun Lee
collection DOAJ
description In this study, we couple precise interface engineering via alternating current electrophoretic deposition (AC–EPD) with performance-enhancing structural transformation via annealing, enabling the development of high-performance, stable, and tunable Mn-based cathodes for aqueous zinc-ion batteries (ZIBs). Using AC–EPD to fabricate Mn(BTC) (BTC = 1,3,5-benzenetricarboxylic acid) cathodes followed by thermal annealing to synthesize MOF-derived Mn<sub>3</sub>O<sub>4</sub> offers a synergistic approach that addresses several key challenges in aqueous ZIB systems. The Mn<sub>3</sub>O<sub>4</sub> cathode prepared via AC–EPD from Mn(BTC) exhibited a remarkable specific capacity of up to 430 mAh/g at a current density of 200 mA/g. Interestingly, the capacity continued to increase progressively with cycling, suggesting dynamic structural or interfacial changes that improved Zn<sup>2+</sup> transport and utilization over time. Such capacity enhancement behavior during prolonged cycling at elevated rates has not been observed in previously reported Mn<sub>3</sub>O<sub>4</sub>-based ZIB systems. Kinetic analysis further revealed that the charge storage process is predominantly governed by diffusion-controlled mechanisms. This behavior can be attributed to the intrinsic characteristics of the Mn<sub>3</sub>O<sub>4</sub> phase formed from the MOF precursor, where the bulk redox reactions involving Zn<sup>2+</sup> insertion require ion migration into the electrode interior. Even though the electrode was processed as an ultrathin film with enhanced electrolyte contact, the charge storage remains limited by solid-state ion diffusion rather than fast surface-driven reactions, reinforcing the diffusion-dominant nature of the system.
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spelling doaj-art-ad17da32ce1c411981a9038353db62a62025-08-20T03:29:45ZengMDPI AGMolecules1420-30492025-06-013012256610.3390/molecules30122566Interface-Sensitive Charge Storage and Activation Behavior of Mn(1,3,5-Benzenetricarboxylic Acid (BTC))-Derived Mn<sub>3</sub>O<sub>4</sub>/Carbon Cathodes for Aqueous Zinc-Ion BatteriesJieun Lee0Byoungnam Park1Department of Materials Science and Engineering, Hongik University, 72-1, Sangsu-dong, Mapo-gu, Seoul 04066, Republic of KoreaDepartment of Materials Science and Engineering, Hongik University, 72-1, Sangsu-dong, Mapo-gu, Seoul 04066, Republic of KoreaIn this study, we couple precise interface engineering via alternating current electrophoretic deposition (AC–EPD) with performance-enhancing structural transformation via annealing, enabling the development of high-performance, stable, and tunable Mn-based cathodes for aqueous zinc-ion batteries (ZIBs). Using AC–EPD to fabricate Mn(BTC) (BTC = 1,3,5-benzenetricarboxylic acid) cathodes followed by thermal annealing to synthesize MOF-derived Mn<sub>3</sub>O<sub>4</sub> offers a synergistic approach that addresses several key challenges in aqueous ZIB systems. The Mn<sub>3</sub>O<sub>4</sub> cathode prepared via AC–EPD from Mn(BTC) exhibited a remarkable specific capacity of up to 430 mAh/g at a current density of 200 mA/g. Interestingly, the capacity continued to increase progressively with cycling, suggesting dynamic structural or interfacial changes that improved Zn<sup>2+</sup> transport and utilization over time. Such capacity enhancement behavior during prolonged cycling at elevated rates has not been observed in previously reported Mn<sub>3</sub>O<sub>4</sub>-based ZIB systems. Kinetic analysis further revealed that the charge storage process is predominantly governed by diffusion-controlled mechanisms. This behavior can be attributed to the intrinsic characteristics of the Mn<sub>3</sub>O<sub>4</sub> phase formed from the MOF precursor, where the bulk redox reactions involving Zn<sup>2+</sup> insertion require ion migration into the electrode interior. Even though the electrode was processed as an ultrathin film with enhanced electrolyte contact, the charge storage remains limited by solid-state ion diffusion rather than fast surface-driven reactions, reinforcing the diffusion-dominant nature of the system.https://www.mdpi.com/1420-3049/30/12/2566MOFZIBinterfaceAC-EPDcharge storage
spellingShingle Jieun Lee
Byoungnam Park
Interface-Sensitive Charge Storage and Activation Behavior of Mn(1,3,5-Benzenetricarboxylic Acid (BTC))-Derived Mn<sub>3</sub>O<sub>4</sub>/Carbon Cathodes for Aqueous Zinc-Ion Batteries
Molecules
MOF
ZIB
interface
AC-EPD
charge storage
title Interface-Sensitive Charge Storage and Activation Behavior of Mn(1,3,5-Benzenetricarboxylic Acid (BTC))-Derived Mn<sub>3</sub>O<sub>4</sub>/Carbon Cathodes for Aqueous Zinc-Ion Batteries
title_full Interface-Sensitive Charge Storage and Activation Behavior of Mn(1,3,5-Benzenetricarboxylic Acid (BTC))-Derived Mn<sub>3</sub>O<sub>4</sub>/Carbon Cathodes for Aqueous Zinc-Ion Batteries
title_fullStr Interface-Sensitive Charge Storage and Activation Behavior of Mn(1,3,5-Benzenetricarboxylic Acid (BTC))-Derived Mn<sub>3</sub>O<sub>4</sub>/Carbon Cathodes for Aqueous Zinc-Ion Batteries
title_full_unstemmed Interface-Sensitive Charge Storage and Activation Behavior of Mn(1,3,5-Benzenetricarboxylic Acid (BTC))-Derived Mn<sub>3</sub>O<sub>4</sub>/Carbon Cathodes for Aqueous Zinc-Ion Batteries
title_short Interface-Sensitive Charge Storage and Activation Behavior of Mn(1,3,5-Benzenetricarboxylic Acid (BTC))-Derived Mn<sub>3</sub>O<sub>4</sub>/Carbon Cathodes for Aqueous Zinc-Ion Batteries
title_sort interface sensitive charge storage and activation behavior of mn 1 3 5 benzenetricarboxylic acid btc derived mn sub 3 sub o sub 4 sub carbon cathodes for aqueous zinc ion batteries
topic MOF
ZIB
interface
AC-EPD
charge storage
url https://www.mdpi.com/1420-3049/30/12/2566
work_keys_str_mv AT jieunlee interfacesensitivechargestorageandactivationbehaviorofmn135benzenetricarboxylicacidbtcderivedmnsub3subosub4subcarboncathodesforaqueouszincionbatteries
AT byoungnampark interfacesensitivechargestorageandactivationbehaviorofmn135benzenetricarboxylicacidbtcderivedmnsub3subosub4subcarboncathodesforaqueouszincionbatteries