Suppressing the shuttle effect of bromine is essential for achieving high-energy-density long-cycle brominated sodium-ion batteries. Here, we propose a synergistic constraint strategy that combines physical confinement and chemical adsorption and design a NaBr@carbonized ZIF-8 cathode architecture via a simple NaBr dissolution-adsorption-recrystallization process. The obtained structure features abundant NaBr nano-crystallines uniformly embedded within carbonized ZIF-8 frameworks, forming a multi-core encapsulated composite. Systematic studies disclose synergistic physical and chemical interactions between NaBr and carbonized ZIF-8. Compact physical confinement alleviates volume change and electrolyte erosion, and robust chemical adsorption facilitates fast electron and ion transport and also stabilizes bromine active species. Owing to the improvement in the electrical, chemical, and volumetric properties, the composite design enables promising electrochemical performance, including a high reversible capacity of 254 mAh g-1 at 1 C, an excellent rate capability of 148 mAh g-1 at 10 C, and an outstanding capacity retention of 86% after 1000 cycles at 10 C. A synergistic physicochemical constraint strategy offers a promising pathway toward durable, high-performance Na–Br batteries, underscoring their potential for large-scale energy storage applications.
| [1] |
L. Wang, “A Brief Analysis of the Development and Trend of Lithium Ion Battery's Anode Materials,” [in Chinese], Journal of Changji University 04 (2020): 118–122.
|
| [2] |
Y. L. Wang, X. Wang, L. Y. Tian, Y. Y. Sun, and S. Ye, “Fixing of Highly Soluble Br2/Br-in Porous Carbon as a Cathode Material for Rechargeable Lithium Ion Batteries,” Journal of Materials Chemistry A 3 (2015): 1879–1883.
|
| [3] |
H. Yang, Y. Qiao, Z. Chang, H. Deng, P. He, and H. Zhou, “A Metal-Organic Framework as a Multifunctional Ionic Sieve Membrane for Long-Life Aqueous Zinc-Iodide Batteries,” Advanced Materials 32 (2020): 2004240.
|
| [4] |
F. Xiong, Q. An, L. Xia, et al., “Revealing the Atomistic Origin of the Disorder-Enhanced Na-Storage Performance in NaFePO4 Battery Cathode,” Nano Energy 57 (2019): 608–615.
|
| [5] |
J. Jiang, Y. Li, J. Liu, X. Huang, C. Yuan, and X. W. Lou, “Recent Advances in Metal Oxide-Based Electrode Architecture Design for Electrochemical Energy Storage,” Advanced Materials 24 (2012): 5166–5180.
|
| [6] |
B.-B. Peterson, E.-M. Andrews, F. Hung, and J.-C. Flake, “Carbonized Metal- Organic Framework Cathodes for Secondary Lithium-Bromine Batteries,” Journal of Power Sources 492 (2021): 229658.
|
| [7] |
L. Li, R. Li, S. Zhou, et al., “Core-Shell Ni/NiO Heterostructures as Catalytic Cathodes Enabling High-Performance Zinc Bromine Flow Batteries,” Carbon Neutralization 3 (2024): 222–232.
|
| [8] |
S. Cai, Q. Wang, N. Zhang, et al., “Recent Progress in Halogen-Doped Single-Atom Catalysts for Electrochemical Reactions,” Carbon Neutralization 4 (2025): e193.
|
| [9] |
Y. Jiang, P. Huang, M. Tong, et al., “Interpenetrating Network-Reinforced Gel Polymer Electrolyte for Ultra-Stable Lithium-Iodine Batteries,” Carbon Energy 6 (2024): e478.
|
| [10] |
R. Zhang, Z. Xu, Z. Hao, Z. Meng, X. Hao, and H. Tian, “Research Advances of Metal Fluoride for Energy Conversion and Storage,” Carbon Energy 7 (2025): e630.
|
| [11] |
J.-L. Weininger and F.-W. Secor, “Nonaqueous Lithium-Bromine Secondary Galvanic Cell,” Journal of the Electrochemical Society 121 (1974): 315.
|
| [12] |
M. Ding, R. Shi, J. Qu, and M. Tong, “Construction of Highly Stable LiI/LiBr-Based Nanocomposite Cathode via Triple Confinement Mechanisms for Lithium-Halogen Batteries,” Chinese Chemical Letters 34 (2023): 108248.
|
| [13] |
Z. Xu, K. Song, X. Chang, et al., “Layered Oxide Cathodes: A Comprehensive Review of Characteristics, Research, and Development in Lithium and Sodium Ion Batteries,” Carbon Neutralization 3 (2024): 832–856.
|
| [14] |
C. Avci, I. Imaz, A. Carné-Sánchez, et al., “Self-Assembly of Polyhedral Metal-Organic Framework Particles Into Three-Dimensional Ordered Superstructures,” Nature Chemistry 10 (2018): 78–84.
|
| [15] |
J. Zhang, C. Sun, S. Qu, et al., “Paradigm Metallothermic-Sulfidation-Carbonization Constructing ZIFs-Derived TMSs@Graphene/CNx Heterostructures for High-Capacity and Long-Life Energy Storage,” Nano Energy 111 (2023): 108401.
|
| [16] |
C. Liu, B. Wu, T. Liu, et al., “Metal-Organic Frameworks and Their Composites for Advanced Lithium-Ion Batteries: Synthesis, Progress and Prospects,” Journal of Energy Chemistry 89 (2024): 449–470.
|
| [17] |
X. Hao, J. Zhang, J. Wang, et al., “Metallothermic-Synchronous Construction of Compact Dual-Two-Dimensional MoS2-Graphene Composites for High-Capacity Lithium Storage,” Nano Energy 103 (2020): 107850.
|
| [18] |
D. Lv, L. Yang, R. Song, et al., “A Hierarchical Porous Hard Carbon@Si@Soft Carbon Material for Advanced Lithium-Ion Batteries,” Journal of Colloid and Interface Science 678 (2025): 336–342.
|
| [19] |
M. Xia, Y. Feng, J. Wei, A.-M. Rao, J. Zhou, and B. Lu, “A Rechargeable K/Br Battery,” Advanced Functional Materials 32 (2022): 2205879.
|
| [20] |
R.-D. Seals, R. Alexander, L.-T. Taylor, and J.-G. Dillard, “Core Electron Binding-Energy Study of Group IIb-VIIa Compounds,” Inorganic Chemistry 12 (1973): 2485–2487.
|
| [21] |
G. Deroubaix and P. Marcus, “X-Ray Photoelectron Spectroscopy Analysis of Copper and Zinc Oxides and Sulphides,” Surface and Interface Analysis 18 (1992): 39–46.
|
| [22] |
Y. Zhang, C. Wei, M. X. Wu, et al., “A High-Performance COF-Based Aqueous Zinc-Bromine Battery,” Chemical Engineering Journal 451 (2023): 138915.
|
| [23] |
F. Wang, H. Yang, J. Zhang, et al., “A Dual-Stimuli-Responsive Sodium-Bromine Battery With Ultrahigh Energy Density,” Advanced Materials 30 (2018): 1800028.
|
| [24] |
W. Feng, J. Yang, X. Wei, et al., “Boosting Ultra-Wide Temperature Sodium-Bromine Batteries via Chlorine-Bromine Activation,” Angewandte Chemie International Edition 64 (2025): e202503752.
|
| [25] |
H. Nie, X. Pan, J. Shang, et al., Spatial-Chemical Synergistic Confinement of Polybromides in Ion-Coordinated Hydrogel Polymer Electrolytes for High-Rate, Long-Life, and Wide-Temperature Na-Br2 Dual-Ion Batteries (2025). Available at SSRN: https://ssrn.com/abstract=5701927 or http://dx.doi.org/10.2139/ssrn.5701927.
|
| [26] |
G. Bauer, J. Drobits, C. Fabjan, H. Mikosch, and P. Schuster, “Raman Spectroscopic Study of the Bromine Storing Complex Phase in a Zinc-Flow Battery,” Journal of Electroanalytical Chemistry 427 (1997): 123–128.
|
| [27] |
M. Li, X. Li, G. Qin, et al., “Halogenated Ti3C2 MXenes With Electrochemically Active Terminals for High-Performance Zinc Ion Batteries,” ACS Nano 15 (2021): 1077–1085.
|
| [28] |
M.-E. Easton, A.-J. Ward, T. Hudson, P. Turner, A.-F. Masters, and T. Maschmeyer, “The Formation of High-Order Polybromides in a Room-Temperature Ionic Liquid: From Monoanions ([Br5]- to [Br11]-) to the Isolation of [PC16H36]2[Br24] as Determined by Van der Waals Bonding Radii,” Chemistry – A European Journal 21 (2015): 2961–2965.
|
RIGHTS & PERMISSIONS
2026 The Author(s). Carbon Neutralization published by Wenzhou University and John Wiley & Sons Australia, Ltd.