Carbon-halogen bond substitution enables high-utilization four-electron iodine redox in noncorrosive dilute electrolytes

Zhiheng Shi; Yongchao Tang; Yue Wei; Guigui Liu; Haolong Huang; Jintu Qi; Zhenfeng Feng; Minghui Ye; Yufei Zhang; Zhipeng Wen; Xiaoqing Liu; Qi Yang; Chunyi Zhi; Cheng Chao Li

doi:10.1038/s41467-026-69743-z

Carbon-halogen bond substitution enables high-utilization four-electron iodine redox in noncorrosive dilute electrolytes

Zhiheng Shi
, Yongchao Tang
, Yue Wei
, Guigui Liu
, Haolong Huang
, Jintu Qi
, Zhenfeng Feng
, Minghui Ye
, Yufei Zhang
, Zhipeng Wen
, Xiaoqing Liu
, Qi Yang
, Chunyi Zhi^*
, Cheng Chao Li^*

^*Corresponding author for this work

Department of Materials Science and Engineering

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

1 Citation (Scopus)

Abstract

Aqueous Zn | |I2 batteries, involving I^-/I⁰/I⁺ redox, are promising yet usually facing low I₂ utilization dominated by I⁰/I⁺ redox, especially under high loadings. Unlocking alternative pathway to I⁰/I⁺ redox, preferably in noncorrosive dilute electrolytes, is a crucial solution. Here, we report a pathway towards more thermodynamically favorable I⁰/I⁺ redox, via a unique carbon-halogen bond substitution. This pathway is realized with a low-concentrated (0.7 M), noncorrosive organohalide additive (2-bromoacetamide, BrAce), triggering a reversible Br-C···I⁽⁰⁾ and C-I⁽⁺⁾-Br bond substitution. Compared with conventional interhalogen bonding (I-Br) pathway, this pathway synchronously lowers the barrier for I⁰/I⁺ redox and strengthens the anti-hydrolysis of I⁺ species, by elaborately regulating axial δ hole activity of interhalogen bond (I^(δ+)-Br). Notably, this pathway enables sustainable operation of four-electron Zn | |I₂ batteries with high I₂ loading (8.6 ~ 24.0 mg cm^-2), featuring improved performances: (1) high I₂ utilizations (55% ~ 80%) at high rates (5.8 ~ 46.4 mA cm^-2), (2) long lifespan ( formula presented 400 cycles) with practical areal capacity ( ~ 3.85 mA h cm^-2) and 99.5% retention even at 47.5 mA cm^-2. This pathway opens an exciting research direction to unlock unusual halogen chemistry for scalable, high-energy, sustainable aqueous batteries. © The Author(s) 2026

Original language	English
Article number	3048
Journal	Nature Communications
Volume	17
Online published	21 Feb 2026
DOIs	https://doi.org/10.1038/s41467-026-69743-z
Publication status	Published - 2026

Funding

This research was funded by National Natural Science Foundation of China (52371216, 22305037, U24A20569, 52271204), Science and Technology Foundation of Shenzhen (JCYJ20190808153609561), Guangdong Basic and Applied Basic Research Foundation (2024A1515011920, 2023A1515030173, 2021A1515110952), Guangdong Provincial Key Laboratory of Plant Resources Biorefinery (2021B1212010011), Open Research Fund of Songshan Lake Materials Laboratory (2021SLABFN04), and Research Start-up Fund of GDUT (263113425). The authors also would like to thank the Analysis and Test Center of Guangdong University of Technology for the NMR and FTIR measurements.

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@article{b5e54227e65c4ada8d7427a1743e2dcb,

title = "Carbon-halogen bond substitution enables high-utilization four-electron iodine redox in noncorrosive dilute electrolytes",

abstract = "Aqueous Zn | |I2 batteries, involving I-/I0/I+ redox, are promising yet usually facing low I2 utilization dominated by I0/I+ redox, especially under high loadings. Unlocking alternative pathway to I0/I+ redox, preferably in noncorrosive dilute electrolytes, is a crucial solution. Here, we report a pathway towards more thermodynamically favorable I0/I+ redox, via a unique carbon-halogen bond substitution. This pathway is realized with a low-concentrated (0.7 M), noncorrosive organohalide additive (2-bromoacetamide, BrAce), triggering a reversible Br-C···I(0) and C-I(+)-Br bond substitution. Compared with conventional interhalogen bonding (I-Br) pathway, this pathway synchronously lowers the barrier for I⁰/I⁺ redox and strengthens the anti-hydrolysis of I+ species, by elaborately regulating axial δ hole activity of interhalogen bond (I(δ+)-Br). Notably, this pathway enables sustainable operation of four-electron Zn | |I2 batteries with high I2 loading (8.6 \textasciitilde{} 24.0 mg cm-2), featuring improved performances: (1) high I2 utilizations (55\% \textasciitilde{} 80\%) at high rates (5.8 \textasciitilde{} 46.4 mA cm-2), (2) long lifespan ( formula presented 400 cycles) with practical areal capacity ( \textasciitilde{} 3.85 mA h cm-2) and 99.5\% retention even at 47.5 mA cm-2. This pathway opens an exciting research direction to unlock unusual halogen chemistry for scalable, high-energy, sustainable aqueous batteries. {\textcopyright} The Author(s) 2026",

author = "Zhiheng Shi and Yongchao Tang and Yue Wei and Guigui Liu and Haolong Huang and Jintu Qi and Zhenfeng Feng and Minghui Ye and Yufei Zhang and Zhipeng Wen and Xiaoqing Liu and Qi Yang and Chunyi Zhi and Li, \{Cheng Chao\}",

year = "2026",

doi = "10.1038/s41467-026-69743-z",

language = "English",

volume = "17",

journal = "Nature Communications",

issn = "2041-1723",

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TY - JOUR

T1 - Carbon-halogen bond substitution enables high-utilization four-electron iodine redox in noncorrosive dilute electrolytes

AU - Shi, Zhiheng

AU - Tang, Yongchao

AU - Wei, Yue

AU - Liu, Guigui

AU - Huang, Haolong

AU - Qi, Jintu

AU - Feng, Zhenfeng

AU - Ye, Minghui

AU - Zhang, Yufei

AU - Wen, Zhipeng

AU - Liu, Xiaoqing

AU - Yang, Qi

AU - Zhi, Chunyi

AU - Li, Cheng Chao

PY - 2026

Y1 - 2026

N2 - Aqueous Zn | |I2 batteries, involving I-/I0/I+ redox, are promising yet usually facing low I2 utilization dominated by I0/I+ redox, especially under high loadings. Unlocking alternative pathway to I0/I+ redox, preferably in noncorrosive dilute electrolytes, is a crucial solution. Here, we report a pathway towards more thermodynamically favorable I0/I+ redox, via a unique carbon-halogen bond substitution. This pathway is realized with a low-concentrated (0.7 M), noncorrosive organohalide additive (2-bromoacetamide, BrAce), triggering a reversible Br-C···I(0) and C-I(+)-Br bond substitution. Compared with conventional interhalogen bonding (I-Br) pathway, this pathway synchronously lowers the barrier for I⁰/I⁺ redox and strengthens the anti-hydrolysis of I+ species, by elaborately regulating axial δ hole activity of interhalogen bond (I(δ+)-Br). Notably, this pathway enables sustainable operation of four-electron Zn | |I2 batteries with high I2 loading (8.6 ~ 24.0 mg cm-2), featuring improved performances: (1) high I2 utilizations (55% ~ 80%) at high rates (5.8 ~ 46.4 mA cm-2), (2) long lifespan ( formula presented 400 cycles) with practical areal capacity ( ~ 3.85 mA h cm-2) and 99.5% retention even at 47.5 mA cm-2. This pathway opens an exciting research direction to unlock unusual halogen chemistry for scalable, high-energy, sustainable aqueous batteries. © The Author(s) 2026

AB - Aqueous Zn | |I2 batteries, involving I-/I0/I+ redox, are promising yet usually facing low I2 utilization dominated by I0/I+ redox, especially under high loadings. Unlocking alternative pathway to I0/I+ redox, preferably in noncorrosive dilute electrolytes, is a crucial solution. Here, we report a pathway towards more thermodynamically favorable I0/I+ redox, via a unique carbon-halogen bond substitution. This pathway is realized with a low-concentrated (0.7 M), noncorrosive organohalide additive (2-bromoacetamide, BrAce), triggering a reversible Br-C···I(0) and C-I(+)-Br bond substitution. Compared with conventional interhalogen bonding (I-Br) pathway, this pathway synchronously lowers the barrier for I⁰/I⁺ redox and strengthens the anti-hydrolysis of I+ species, by elaborately regulating axial δ hole activity of interhalogen bond (I(δ+)-Br). Notably, this pathway enables sustainable operation of four-electron Zn | |I2 batteries with high I2 loading (8.6 ~ 24.0 mg cm-2), featuring improved performances: (1) high I2 utilizations (55% ~ 80%) at high rates (5.8 ~ 46.4 mA cm-2), (2) long lifespan ( formula presented 400 cycles) with practical areal capacity ( ~ 3.85 mA h cm-2) and 99.5% retention even at 47.5 mA cm-2. This pathway opens an exciting research direction to unlock unusual halogen chemistry for scalable, high-energy, sustainable aqueous batteries. © The Author(s) 2026

UR - https://www.scopus.com/pages/publications/105034926694

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-105034926694&origin=recordpage

U2 - 10.1038/s41467-026-69743-z

DO - 10.1038/s41467-026-69743-z

M3 - RGC 21 - Publication in refereed journal

C2 - 41723120

SN - 2041-1723

VL - 17

JO - Nature Communications

JF - Nature Communications

M1 - 3048

ER -

Carbon-halogen bond substitution enables high-utilization four-electron iodine redox in noncorrosive dilute electrolytes

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