SCIENCE CHINA Materials, Volume 64 , Issue 12 : 2938-2948(2021) https://doi.org/10.1007/s40843-021-1689-4

In-situ electropolymerized bipolar organic cathode for stable and high-rate lithium-ion batteries

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  • ReceivedJan 21, 2021
  • AcceptedApr 21, 2021
  • PublishedJun 25, 2021



the National Natural Science Foundation of China(51672188,52073211)


This work was supported by the National Natural Science Foundation of China (51672188 and 52073211).

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

Wang W conceived the ideas and performed the experiments and characterizations. Zhao C, Xiong P and Su H provided support for experimental feasibility. Xu Y supervised the project. Wang W wrote the paper; Yang J and Xu Y revised the paper. All authors contributed to the interpretation of the results and approved the final manuscript.

Author information

Wei Wang received her BSc degree from the Northeastern University in 2018. She is now a postgraduate under the supervision of Prof. Yunhua Xu at the School of Materials Science and Engineering, Tianjin University. Her current research mainly focuses on the synthesis and characterization of organic cathode materials for electrochemical energy storage devices.

Yunhua Xu is a professor at the School of Materials Science and Engineering, Tianjin University. He received PhD degree in materials physics and chemistry from the South China University of Technology in 2008. Prior to joining Tianjin University, he worked as a visiting student and postdoc at the University of California, Santa Barbara, Iowa State University and the University of Maryland, College Park, from 2006 to 2015. His research interests focus on electrochemical storage materials and devices.

Supplementary data

Supplementary information

Supporting data are available in the online version of the paper.


[1] Lu Y, Chen J. Prospects of organic electrode materials for practical lithium batteries. Nat Rev Chem, 2020, 4127-142 CrossRef Google Scholar

[2] Lu Y, Zhang Q, Li L, et al. Design strategies toward enhancing the performance of organic electrode materials in metal-ion batteries. Chem, 2018, 42786-2813 CrossRef Google Scholar

[3] Fan X, Liu B, Liu J, et al. Battery technologies for grid-level large-scale electrical energy storage. Trans Tianjin Univ, 2020, 2692-103 CrossRef Google Scholar

[4] Muench S, Wild A, Friebe C, et al. Polymer-based organic batteries. Chem Rev, 2016, 1169438-9484 CrossRef PubMed Google Scholar

[5] Schon TB, McAllister BT, Li PF, et al. The rise of organic electrode materials for energy storage. Chem Soc Rev, 2016, 456345-6404 CrossRef PubMed Google Scholar

[6] Liang Y, Yao Y. Positioning organic electrode materials in the battery landscape. Joule, 2018, 21690-1706 CrossRef Google Scholar

[7] Wang M, Lu W, Zhang H, et al. Organic electrode materials for non-aqueous K-ion batteries. Trans Tianjin Univ, 2021, 271-23 CrossRef Google Scholar

[8] Zhang L, Liu Z, Cui G, et al. Biomass-derived materials for electrochemical energy storages. Prog Polym Sci, 2015, 43136-164 CrossRef Google Scholar

[9] Poizot P, Gaubicher J, Renault S, et al. Opportunities and challenges for organic electrodes in electrochemical energy storage. Chem Rev, 2020, 1206490-6557 CrossRef PubMed Google Scholar

[10] Poizot P, Dolhem F, Gaubicher J. Progress in all-organic rechargeable batteries using cationic and anionic configurations: Toward low-cost and greener storage solutions?. Curr Opin Electrochem, 2018, 970-80 CrossRef Google Scholar

[11] Lee S, Hong J, Kang K. Redox-active organic compounds for future sustainable energy storage system. Adv Energy Mater, 2020, 102001445 CrossRef Google Scholar

[12] Luo C, Ji X, Hou S, et al. Azo compounds derived from electrochemical reduction of nitro compounds for high performance Li-ion batteries. Adv Mater, 2018, 301706498 CrossRef PubMed Google Scholar

[13] Luo C, Xu GL, Ji X, et al. Reversible redox chemistry of azo compounds for sodium-ion batteries. Angew Chem Int Ed, 2018, 572879-2883 CrossRef PubMed Google Scholar

[14] Häupler B, Wild A, Schubert US. Carbonyls: Powerful organic materials for secondary batteries. Adv Energy Mater, 2015, 51402034 CrossRef Google Scholar

[15] Zhao Q, Zhu Z, Chen J. Molecular engineering with organic carbonyl electrode materials for advanced stationary and redox flow rechargeable batteries. Adv Mater, 2017, 291607007 CrossRef PubMed Google Scholar

[16] Yang J, Xiong P, Shi Y, et al. Rational molecular design of benzoquinone-derived cathode materials for high-performance lithium-ion batteries. Adv Funct Mater, 2020, 301909597 CrossRef Google Scholar

[17] Lu Y, Hou X, Miao L, et al. Cyclohexanehexone with ultrahigh capacity as cathode materials for lithium-ion batteries. Angew Chem Int Ed, 2019, 587020-7024 CrossRef PubMed Google Scholar

[18] Oyaizu K, Nishide H. Radical polymers for organic electronic devices: A radical departure from conjugated polymers?. Adv Mater, 2009, 212339-2344 CrossRef Google Scholar

[19] Janoschka T, Hager MD, Schubert US. Powering up the future: Radical polymers for battery applications. Adv Mater, 2012, 246397-6409 CrossRef PubMed Google Scholar

[20] Charlton GD, Barbon SM, Gilroy JB, et al. A bipolar verdazyl radical for a symmetric all-organic redox flow-type battery. J Energy Chem, 2019, 3452-56 CrossRef Google Scholar

[21] Dai G, He Y, Niu Z, et al. A dual-ion organic symmetric battery constructed from phenazine-based artificial bipolar molecules. Angew Chem Int Ed, 2019, 589902-9906 CrossRef PubMed Google Scholar

[22] Liu T, Kim KC, Lee B, et al. Enhanced lithium storage of an organic cathode via the bipolar mechanism. ACS Appl Energy Mater, 2020, 33728-3735 CrossRef Google Scholar

[23] Wang HG, Wang H, Si Z, et al. A bipolar and self-polymerized phthalocyanine complex for fast and tunable energy storage in dual-ion batteries. Angew Chem Int Ed, 2019, 5810204-10208 CrossRef PubMed Google Scholar

[24] Sui D, Xu L, Zhang H, et al. A 3D cross-linked graphene-based honeycomb carbon composite with excellent confinement effect of organic cathode material for lithium-ion batteries. Carbon, 2020, 157656-662 CrossRef Google Scholar

[25] Wu J, Rui X, Wang C, et al. Nanostructured conjugated ladder polymers for stable and fast lithium storage anodes with high-capacity. Adv Energy Mater, 2015, 51402189 CrossRef Google Scholar

[26] Xie J, Gu P, Zhang Q. Nanostructured conjugated polymers: Toward high-performance organic electrodes for rechargeable batteries. ACS Energy Lett, 2017, 21985-1996 CrossRef Google Scholar

[27] Yang J, Shi Y, Sun P, et al. Optimization of molecular structure and electrode architecture of anthraquinone-containing polymer cathode for high-performance lithium-ion batteries. ACS Appl Mater Interfaces, 2019, 1142305-42312 CrossRef PubMed Google Scholar

[28] Yang J, Shi Y, Li M, et al. Performance enhancement of polymer electrode materials for lithium-ion batteries: From a rigid homopolymer to soft copolymers. ACS Appl Mater Interfaces, 2020, 1232666-32672 CrossRef PubMed Google Scholar

[29] Geng K, He T, Liu R, et al. Covalent organic frameworks: Design, synthesis, and functions. Chem Rev, 2020, 1208814-8933 CrossRef PubMed Google Scholar

[30] Zhao C, Chen Z, Wang W, et al. In situ electropolymerization enables ultrafast long cycle life and high-voltage organic cathodes for lithium batteries. Angew Chem Int Ed, 2020, 5911992-11998 CrossRef PubMed Google Scholar

[31] Zeng C, Wang B, Zhang H, et al. Electrochemical synthesis, deposition, and doping of polycyclic aromatic hydrocarbon films. J Am Chem Soc, 2021, 1432682-2687 CrossRef PubMed Google Scholar

[32] Zhang Q, Dong H, Hu W. Electrochemical polymerization for two-dimensional conjugated polymers. J Mater Chem C, 2018, 610672-10686 CrossRef Google Scholar

[33] Gu C, Huang N, Chen Y, et al. π-Conjugated microporous polymer films: Designed synthesis, conducting properties, and photoenergy conversions. Angew Chem Int Ed, 2015, 5413594-13598 CrossRef PubMed Google Scholar

[34] Gu C, Fei T, Lv Y, et al. Color-stable white electroluminescence based on a cross-linked network film prepared by electrochemical copolymerization. Adv Mater, 2010, 222702-2705 CrossRef PubMed Google Scholar

[35] Chen Q, Luo M, Hammershøj P, et al. Microporous polycarbazole with high specific surface area for gas storage and separation. J Am Chem Soc, 2012, 1346084-6087 CrossRef PubMed Google Scholar

[36] Friebe C, Hager MD, Winter A, et al. Metal-containing polymers via electropolymerization. Adv Mater, 2012, 24332-345 CrossRef PubMed Google Scholar

[37] Zhu Y, Zhang J, Chen Z, et al. Synthesis of nitrocarbazole compounds and their electrocatalytic oxidation of alcohol. Chin J Catal, 2016, 37533-538 CrossRef Google Scholar

[38] Kortekaas L, Lancia F, Steen JD, et al. Reversible charge trapping in bis-carbazole-diimide redox polymers with complete luminescence quenching enabling nondestructive read-out by resonance Raman spectroscopy. J Phys Chem C, 2017, 12114688-14702 CrossRef PubMed Google Scholar

[39] Qin L, Ma W, Hanif M, et al. Donor-node-acceptor polymer with excellent n-doped state for high-performance ambipolar flexible supercapacitors. Macromolecules, 2017, 503565-3572 CrossRef ADS Google Scholar

[40] Song Z, Zhan H, Zhou Y. Polyimides: Promising energy-storage materials. Angew Chem Int Ed, 2010, 498444-8448 CrossRef PubMed Google Scholar

[41] Li C, Xue J, Huang A, et al. Poly(N-vinylcarbazole) as an advanced organic cathode for potassium-ion-based dual-ion battery. Electrochim Acta, 2019, 297850-855 CrossRef Google Scholar

[42] Zhu L, Ding G, Xie L, et al. Conjugated carbonyl compounds as high-performance cathode materials for rechargeable batteries. Chem Mater, 2019, 318582-8612 CrossRef Google Scholar

[43] Jiang Q, Xiong P, Liu J, et al. A redox-active 2D metal-organic framework for efficient lithium storage with extraordinary high capacity. Angew Chem Int Ed, 2020, 595273-5277 CrossRef PubMed Google Scholar

[44] Xiong P, Yin H, Chen Z, et al. Thiourea-based polyimide/RGO composite cathode: A comprehensive study of storage mechanism with alkali metal ions. Sci China Mater, 2020, 631929-1938 CrossRef Google Scholar

  • Figure 1

    (a) Molecular structure, (b) HOMO and LUMO energy levels, and (c) n-type and p-type reactions of APCNDI.

  • Figure 2

    (a, c) Galvanostatic charge/discharge profiles of APCNDI cathode under different potential ranges at 1 A g−1, and (b, d) cycling performance of APCNDI cathode under different potential ranges of (a, b) 1.5–3.0 V and (c, d) 3.0–4.4 V at 1 A g−1. Schematic illustrations of the APCNDI cathode cycling in (e) 1.5–3.0 V, (f) 3.0–4.4 V, and (g) electrochemical polymerization reaction.

  • Figure 3

    (a) Digital images of PP separators and (b) electrolytes soaked with APCNDI electrodes after 500 cycles at 1 A g−1 under different voltage windows. (c) UV-vis spectra, (d) FTIR spectra, and (e) SEM images of pristine and cycled APCNDI cathodes in different voltage ranges of 1.5–3.0 and 1.5–4.4 V. (f) Reaction of in-situ electropolymerization.

  • Figure 4

    Electrochemical performance of APCNDI cathodes: (a) CV curves at 0.05 mV s−1, (b) selected charge/discharge profiles, (c) cycling performance in the voltage range from 1.5–4.4 V at 0.1 A  g−1, (d) rate performance, and (e) long-term cycling performance at 5 A g−1.

  • Figure 5

    (a) Galvanostatic charge/discharge profiles with marked points for FTIR and XPS tests. (b) FTIR spectra and (c) high-resolution N 1s and O 1s spectra of APCNDI cathode at different charge/discharge states marked in (a). (d) Mechanism illustration of the n- and p-type reactions of APCNDI.


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