Durable Organic Anode Material With High Mass-Loading for Proton Batteries

Abstract

Organic materials are highly compelling candidates for next-generation electrodes. However, low mass-loading and poor cycle stability in aqueous electrolyte during repetitive charge-discharge process significantly undermine its practical deployment. Here, indanthrone (IDT), characterized with extended conjugated π-system and rigid planar structure, was developed as a high-performance proton-storage material. Electrochemical analyses and theoretical calculations identify two carbonyl (C=O) and two imine (C = N) groups as the active proton-hosting sites. Importantly, two additional carbonyls flanking the imines remain inactive owing to intramolecular hydrogen bonds, which enhance the chemical and electrochemical robustness of IDT and underpin extended cycling. As a result, a full MnO₂@GF//IDT cell delivers ultra-stable operation for over 20,000 cycles at a high mass loading of 8 mg cm^-2, demonstrating durable performance and practical relevance. These results establish a structure-function blueprint for organic proton batteries and highlight IDT as a promising, scalable proton-storage material.

Keywords

high mass loading / internal hydrogen bond / long-term durability / Mn-based cathode / proton battery

References

[1] Y. Liang and Y. Yao, “Designing Modern Aqueous Batteries,” Nature Reviews Materials 8, no. 2 (2022): 109–122.

[2] D. Chao, W. Zhou, F. Xie, et al., “Roadmap for Advanced Aqueous Batteries: From Design of Materials to Applications,” Science Advances 6, no. 21 (2020): eaba4098.

[3] P. P. Lopes and V. R. Stamenkovic, “Past, Present, and Future of Lead–Acid Batteries,” Science 369, no. 6506 (2020): 923–924.

[4] J. Huang, L. Yan, D. Bin, X. Dong, Y. Wang, and Y. Xia, “An Aqueous Manganese–Lead Battery for Large-Scale Energy Storage,” Journal of Materials Chemistry A 8, no. 12 (2020): 5959–5967.

[5] J. Liu, C. Xu, Z. Chen, S. Ni, and Z. X. Shen, “Progress in Aqueous Rechargeable Batteries,” Green Energy & Environment 3, no. 1 (2018): 20–41.

[6] Y. Liu, J. Yu, M. Jiang, et al., “A More Economical Choice for the Cathode Material of Ni-MH Batteries With High Electrochemical Performances: 3D Flower-like Ni–Fe LDHs,” International Journal of Hydrogen Energy 47, no. 97 (2022): 41087–41096.

[7] A. B. Béléké, E. Higuchi, H. Inoue, and M. Mizuhata, “Durability of Nickel–Metal Hydride (Ni–MH) Battery Cathode Using Nickel–Aluminum Layered Double Hydroxide/Carbon (Ni–Al LDH/C) Composite,” Journal of Power Sources 247 (2014): 572–578.

[8] Z. Zhao, X. Liu, M. Zhang, et al., “Development of Flow Battery Technologies Using the Principles of Sustainable Chemistry,” Chemical Society Reviews 52, no. 17 (2023): 6031–6074.

[9] B. Li and J. Liu, “Progress and Directions in Low-Cost Redox-Flow Batteries for Large-Scale Energy Storage,” National Science Review 4, no. 1 (2017): 91–105.

[10] X. Ye, X. Xiao, Z. Wu, Y. Zhan, X. Wu, and S. Liu, “Recent Advances in Rechargeable Aqueous Magnesium-Ion Batteries,” Journal of Materials Chemistry A 12, no. 35 (2024): 23337–23363.

[11] A. von Wald Cresce and K. Xu, “Aqueous Lithium-ion Batteries,” Carbon Energy 3, no. 5 (2021): 721–751.

[12] L. E. Blanc, D. Kundu, and L. F. Nazar, “Scientific Challenges for the Implementation of Zn-Ion Batteries,” Joule 4, no. 4 (2020): 771–799.

[13] X. Ma, Q. Wang, X. Zhang, et al., “Highly Reversible Zinc Anode Enabled by a Trace-Amount Additive With pH Buffering Capability,” Energy & Environmental Science 18, no. 2 (2025): 982–990.

[14] Y. Li, X. Ma, X. Zhang, et al., “High Zn(002)-Preferential Orientation Enabled by a Proton Additive for Dendrite-Free Zinc Anodes,” Energy & Environmental Science 17, no. 23 (2024): 9205–9214.

[15] J. Huang, Z. Guo, Y. Ma, D. Bin, Y. Wang, and Y. Xia, “Recent Progress of Rechargeable Batteries Using Mild Aqueous Electrolytes,” Small Methods 3, no. 1 (2019): 1800272.

[16] G. Li, L. Sun, S. Zhang, et al., “Developing Cathode Materials for Aqueous Zinc Ion Batteries: Challenges and Practical Prospects,” Advanced Functional Materials 34, no. 5 (2024): 2301291.

[17] Y. Liu, G. He, H. Jiang, I. P. Parkin, P. R. Shearing, and D. J. L. Brett, “Cathode Design for Aqueous Rechargeable Multivalent Ion Batteries: Challenges and Opportunities,” Advanced Functional Materials 31, no. 13 (2021): 2010445.

[18] W. Ling, H. Wang, Z. Chen, et al., “Intrinsic Structure Modification of Electrode Materials for Aqueous Metal-Ion and Metal-Air Batteries,” Advanced Functional Materials 31, no. 5 (2021): 2006855.

[19] M. Shi, P. Das, Z. S. Wu, T. Liu, and X. Zhang, “Aqueous Organic Batteries Using the Proton as a Charge Carrier,” Advanced Materials 35, no. 42 (2023): 2302199.

[20] Y. Xu, X. Wu, and X. Ji, “The Renaissance of Proton Batteries,” Small Structures 2, no. 5 (2021): 2000113.

[21] X. Wu, J. J. Hong, W. Shin, et al., “Diffusion-Free Grotthuss Topochemistry for High-Rate and Long-Life Proton Batteries,” Nature Energy 4, no. 2 (2019): 123–130.

[22] W. Chen, G. Li, A. Pei, et al., “A Manganese–Hydrogen Battery With Potential for Grid-Scale Energy Storage,” Nature Energy 3, no. 5 (2018): 428–435.

[23] Z. Zhu, W. Wang, Y. Yin, et al., “An Ultrafast and Ultra-Low-Temperature Hydrogen Gas–Proton Battery,” Journal of the American Chemical Society 143, no. 48 (2021): 20302–20308.

[24] H. Jiang, W. Shin, L. Ma, et al., “A High-Rate Aqueous Proton Battery Delivering Power Below -78°C via an Unfrozen Phosphoric Acid,” Advanced Energy Materials 10, no. 28 (2020): 2000968.

[25] L. Yan, J. Huang, Z. Guo, X. Dong, Z. Wang, and Y. Wang, “Solid-State Proton Battery Operated at Ultralow Temperature,” ACS Energy Letters 5, no. 2 (2020): 685–691.

[26] H. Guo and C. Zhao, “An Emerging Chemistry Revives Proton Batteries,” Small Methods 8, no. 6 (2024): 2300699.

[27] X. Wang, Y. Xie, K. Tang, C. Wang, and C. Yan, “Redox Chemistry of Molybdenum Trioxide for Ultrafast Hydrogen-Ion Storage,” Angewandte Chemie International Edition 57, no. 36 (2018): 11569–11573.

[28] H. Jiang, J. J. Hong, X. Wu, et al., “Insights on the Proton Insertion Mechanism in the Electrode of Hexagonal Tungsten Oxide Hydrate,” Journal of the American Chemical Society 140, no. 37 (2018): 11556–11559.

[29] W. Chen, Y. Jin, J. Zhao, N. Liu, and Y. Cui, “Nickel-Hydrogen Batteries for Large-Scale Energy Storage,” Proceedings of the National Academy of Sciences 115, no. 46 (2018): 11694–11699.

[30] S. Yuan, X. Huang, T. Kong, L. Yan, and Y. Wang, “Organic Electrode Materials for Energy Storage and Conversion: Mechanism, Characteristics, and Applications,” Accounts of Chemical Research 57, no. 10 (2024): 1550–1563.

[31] Q. Zhao, Y. Ni, Y. Lu, et al., “Dual Active Site Covalent Organic Framework Anode Enables Stable Aqueous Proton Batteries,” Angewandte Chemie International Edition 64, no. 14 (2025): e202424025.

[32] D. Shen, A. M. Rao, J. Zhou, and B. Lu, “High-Potential Cathodes With Nitrogen Active Centres for Quasi-Solid Proton-Ion Batteries,” Angewandte Chemie International Edition 61, no. 22 (2022): e202201972.

[33] L. Yan, Y. Qi, X. Dong, Y. Wang, and Y. Xia, “Ammonium-Ion Batteries With a Wide Operating Temperature Window From -40 to 80°C,” eScience 1, no. 2 (2021): 212–218.

[34] S. Wu, H. Guo, and C. Zhao, “Challenges and Opportunities for Proton Batteries: From Electrodes, Electrolytes to Full-Cell Applications,” Advanced Functional Materials 34, no. 40 (2024): 2405401.

[35] Y. Cui, J. Yang, H. Wang, et al., “Unleashing High-efficiency Proton Storage: Innovative Design of Ladder-type Organic Molecules,” Carbon Energy 7, no. 4 (2025): e680.

[36] X. Yang, Y. Ni, Y. Lu, et al., “Designing Quinone-Based Anodes With Rapid Kinetics for Rechargeable Proton Batteries,” Angewandte Chemie International Edition 61, no. 39 (2022): e202209642.

[37] F. Yue, Z. Tie, Y. Zhang, S. Bi, Y. Wang, and Z. Niu, “Proton Chemistry Induced Long-Cycle Air Self-Charging Aqueous Batteries,” Angewandte Chemie International Edition 61, no. 40 (2022): e202208513.

[38] Y. Yang, S. Wang, Y. Duan, et al., “Flux Synthesis of Robust Polyimide Covalent Organic Frameworks With High-Density Redox Sites for Efficient Proton Batteries,” Angewandte Chemie International Edition 64, no. 6 (2025): e202418394.

[39] H. Guo and C. Wang, “Practical Organic Batteries: Concepts to Realize High Mass Loading With High Performance,” Chemsuschem 17, no. 6 (2024): e202301586.

[40] X. Wang, J. Zhou, and W. Tang, “Poly(Dithieno[3,2-b:2′,3′-d]Pyrrole) Twisting Redox Pendants Enabling High Current Durability in All-Organic Proton Battery,” Energy Storage Materials 36 (2021): 1–9.

[41] F. Yue, Z. Tie, S. Deng, S. Wang, M. Yang, and Z. Niu, “An Ultralow Temperature Aqueous Battery With Proton Chemistry,” Angewandte Chemie International Edition 60, no. 25 (2021): 13882–13886.

[42] Y. Wang, C. Wang, W. Wang, et al., “Organic Hydronium-Ion Battery With Ultralong Life,” ACS Energy Letters 8, no. 3 (2023): 1390–1396.

[43] H. Zhang, R. Zhang, F. Ding, C. Shi, and N. Zhao, “Hydrogen Bonding Regulation Enables Indanthrone as a Stable and High-Rate Cathode for Lithium-Ion Batteries,” Energy Storage Materials 51 (2022): 172–180.

[44] J. Liu, K. Guo, W. Guo, J. Chang, Y. Li, and F. Bao, “Superconjugated Anthraquinone Carbonyl-Based Covalent Organic Framework as Anode Material for High-Performance Aqueous Ammonium-Ion Batteries,” Angewandte Chemie International Edition 64, no. 14 (2025): e202424494.

[45] C. Peng, F. Wang, Q. Chen, et al., “Proton-Coupled Chemistry Enabled p–n Conjugated Bipolar Organic Electrode for High-Performance Aqueous Symmetric Battery,” Advanced Functional Materials 21 (2024): 2401001.

[46] T. Shi, G. Li, Y. Han, et al., “Oxidized Indanthrone as a Cost-Effective and High-Performance Organic Cathode Material for Rechargeable Lithium Batteries,” Energy Storage Materials 50 (2022): 265–273.

[47] H. Qiu, M. Shi, P. Zhang, et al., “An Electron-Delocalized Sp² -N Hybridized Organic Electrode Enables Sustainable and High-Efficiency Electrochemical Ammonium Removal,” Chemical Science 16, no. 22 (2025): 9895–9904.

[48] T. Chen, H. Banda, L. Yang, et al., “High-Rate, High-Capacity Electrochemical Energy Storage in Hydrogen-Bonded Fused Aromatics,” Joule 7, no. 5 (2023): 986–1002.

[49] Z. Guo, J. Huang, X. Dong, et al., “An Organic/Inorganic Electrode-Based Hydronium-Ion Battery,” Nature Communications 11, no. 1 (2020): 959.

[50] W. Han, M. Li, Y. Ma, and J. Yang, “Dianhydride-Based Polyimide as Organic Electrode Materials for Aqueous Hydronium-Ion Battery,” Electrochimica Acta 403 (2022): 139550.

[51] K. C. S. Lakshmi, B. Vedhanarayanan, H. Y. Cheng, X. Ji, H. H. Shen, and T. W. Lin, “Molecularly Engineered Organic Copolymers as High Capacity Cathode Materials for Aqueous Proton Battery Operating at Sub-Zero Temperatures,” Journal of Colloid and Interface Science 619 (2022): 123–131.

[52] Y. Ma, Y. Wei, W. Han, et al., “Proton Intercalation/De-intercalation Chemistry in Phenazine-based Anode for Hydronium-ion Batteries,” Angewandte Chemie International Edition 62, no. 47 (2023): e202314259.

[53] T. Sun, H. Du, S. Zheng, J. Shi, and Z. Tao, “High Power and Energy Density Aqueous Proton Battery Operated at - 90 ° C,” Advanced Functional Materials 31, no. 16 (2021): 2010127.

[54] H. Wang, G. Liu, W. Zhou, Y. Wang, and X. Dong, “High-Potential and Stable Organic Cathode for Rechargeable Batteries With Fast-Charging and Wide-Temperature Adaptability,” Angewandte Chemie 19 (2024): e202416874.

[55] M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al. Gaussian 16 Rev. C.01, Wallingford, CT, 2016.

[56] A. D. McLean and G. S. Chandler, “Contracted Gaussian Basis Sets for Molecular Calculations. I. Second Row Atoms, Z =11–18,” The Journal of Chemical Physics 72, no. 10 (1980): 5639–5648.

[57] S. Grimme, J. Antony, S. Ehrlich, and H. Krieg, “A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu,” The Journal of Chemical Physics 132, no. 15 (2010): 154104.

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