A pseudocapacitive molecule-induced strategy to construct flexible high-performance asymmetric supercapacitors

Abstract

The combination of high-voltage windows and bending stability remains a challenge for supercapacitors. Here, we present an “advantage-complementary strategy” using sodium lignosulfonate as a pseudocapacitive molecule to regulate the spatial stacking pattern of graphene oxide and the interfacial architectures of graphene oxide and polyaniline. Flexible and sustainable sodium lignosulfonate-based electrodes are successfully developed, showing perfect bending stability and high electronic conductivity and specific capacitance (521 F·g⁻¹ at 0.5 A·g^–1). Due to the resulting rational interfacial structure and stable ion-electron transport, the asymmetric supercapacitors provide a wide voltage window reaching 1.7 V, outstanding bending stability and high energy-power density of 83.87 Wh·kg^–1 at 3.4 kW·kg^–1. These properties are superior to other reported cases of asymmetric energy enrichment. The synergistic strategy of sodium lignosulfonate on graphene oxide and polyaniline is undoubtedly beneficial to advance the process for the construction of green flexible supercapacitors with remarkably wide voltage windows and excellent bending stability.

Graphical abstract

Keywords

molecular synergy / pseudocapacitive lignosulfonate / flexible electronic devices / asymmetric supercapacitor / wide voltage windows

References

[1] Li B, Yu M, Li Z, Yu C, Wang H, Li Q. Constructing flexible all-solid-state supercapacitors from 3D nanosheets active bricks via 3D manufacturing technology: a perspective review. Advanced Functional Materials, 2022, 32(29): 202201166

[2] Zhao D, Zhu Y, Cheng W, Chen W, Wu Y, Yu H. Cellulose: cellulose-based flexible functional materials for emerging intelligent electronics. Advanced Materials, 2021, 33(28): 2000619

[3] Lv T, Liu M, Zhu D, Gan L, Chen T. Nanocarbon-based materials for flexible all-solid-state supercapacitors. Advanced Materials, 2018, 30(17): e1705489

[4] Du P, Liu H C, Yi C, Wang K, Gong X. Polyaniline-modified oriented graphene hydrogel film as the free-standing electrode for flexible solid-state supercapacitors. ACS Applied Materials & Interfaces, 2015, 7(43): 23932–23940

[5] Yang C, Zhang L, Hu N, Yang Z, Wei H, Zhang Y. Reduced graphene oxide/polypyrrole nanotube papers for flexible all-solid-state supercapacitors with excellent rate capability and high energy density. Journal of Power Sources, 2016, 302: 39–45

[6] Heng Y, Teng G, Chi Y, Hu D. Construction of biomass-derived hybrid organogel electrodes with a cross-linking conductive network for high-performance all-solid-state supercapacitors. Biomacromolecules, 2022, 23(3): 913–925

[7] Zhao D, Chen C, Zhang Q, Chen W, Liu S, Wang Q, Liu Y, Li J, Yu H. High performance, flexible, solid-state supercapacitors based on a renewable and biodegradable mesoporous cellulose membrane. Advanced Energy Materials, 2017, 7(18): 1700739

[8] Liu L, Yu X, Zhang W, Lv Q, Hou L, Fautrelle Y, Ren Z, Cao G, Lu X, Li X. Strong magnetic-field-engineered porous template for fabricating hierarchical porous Ni-Co-Zn-P nanoplate arrays as battery-type electrodes of advanced all-solid-state supercapacitors. ACS Applied Materials & Interfaces, 2022, 14(2): 2782–2793

[9] Zhou L, Cao H, Zhu S, Hou L, Yuan C. Hierarchical micro-/mesoporous N- and O-enriched carbon derived from disposable cashmere: a competitive cost-effective material for high-performance electrochemical capacitors. Green Chemistry, 2015, 17(4): 2373–2382

[10] Zhao D, Pang B, Zhu Y, Cheng W, Cao K, Ye D, Si C, Xu G, Chen C, Yu H. A stiffness-switchable, biomimetic smart material enabled by supramolecular reconfiguration. Advanced Materials, 2022, 34(10): 2107857

[11] Jiang G, Wang G, Zhu Y, Cheng W, Xu G, Zhao D, Yu H. A scalable bacterial cellulose ionogel for multisensory electronic skin. Research, 2022, 2022: 9814767

[12] Zhang Q, Chen C, Chen W, Pastel G, Guo X, Liu S, Wang Q, Liu Y, Li J, Yu H, Hu L. Nanocellulose-enabled, all-nanofiber, high-performance supercapacitor. ACS Applied Materials & Interfaces, 2019, 11(6): 5919–5927

[13] Chen C, Zhang Y, Li Y, Dai J, Song J, Yao Y, Gong Y, Kierzewski I, Xie J, Hu L. All-wood, low tortuosity, aqueous, biodegradable supercapacitors with ultra-high capacitance. Energy & Environmental Science, 2017, 10(2): 538–545

[14] Bora A, Mohan K, Doley S, Dolui S K. Flexible asymmetric supercapacitor based on functionalized reduced graphene oxide aerogels with wide working potential window. ACS Applied Materials & Interfaces, 2018, 10(9): 7996–8009

[15] Sahoo R, Pham D T, Lee T H, Luu T H T, Seok J, Lee Y H. Redox-driven route for widening voltage window in asymmetric supercapacitor. ACS Nano, 2018, 12(8): 8494–8505

[16] Asl M S, Hadi R, Salehghadimi L, Tabrizi A G, Farhoudian S, Babapoor A, Pahlevani M. Flexible all-solid-state supercapacitors with high capacitance, long cycle life, and wide operational potential window: recent progress and future perspectives. Journal of Energy Storage, 2022, 50: 104223

[17] MalekALuXShearingP RBrettD J LHeG. Strategic comparison of membrane-assisted and membrane-less water electrolyzers and their potential application in direct seawater splitting (DSS). Green Energy & Environment, 2022, 2468–0257

[18] Liu Z, Zhao Z, Xu A, Li W, Qin Y. Facile preparation of graphene/polyaniline composite hydrogel film by electrodeposition for binder-free all-solid-state supercapacitor. Journal of Alloys and Compounds, 2021, 875: 159931

[19] Wang H, Yan T, Liu P, Chen G, Shi L, Zhang J, Zhong Q, Zhang D. In situ creating interconnected pores across 3D graphene architectures and their application as high performance electrodes for flow-through deionization capacitors. Journal of Materials Chemistry A, 2014, 2: 4739–4750

[20] Wang F, Dong X, Wang K, Duan W, Gao M, Zhai Z, Zhu C, Wang W. Laser-induced nitrogen-doped hierarchically porous graphene for advanced electrochemical energy storage. Carbon, 2019, 150: 396–407

[21] Dang H X, Barz D P J. Graphene electrode functionalization for high performance hybrid energy storage with vanadyl sulfate redox electrolytes. Journal of Power Sources, 2022, 517: 230712

[22] Lei H, Tu J, Li S, Huang Z, Luo Y, Yu Z, Jiao S. Graphene-encapsulated selenium@polyaniline nanowires with three-dimensional hierarchical architecture for high-capacity aluminum-selenium batteries. Journal of Materials Chemistry A, 2022, 10(28): 15146–15154

[23] Lin D, Li Y. Recent advances of aqueous rechargeable zinc-iodine batteries: challenges, solutions, and prospects. Advanced Materials, 2022, 34(23): 2108856

[24] Wang Y, Liu H, Ji X, Wang Q, Tian Z, Liu S. Recent advances in lignosulfonate filled hydrogel for flexible wearable electronics: a mini review. International Journal of Biological Macromolecules, 2022, 212: 393–401

[25] Kai D, Tan M J, Chee P L, Chua Y K, Yap Y L, Loh X J. Towards lignin-based functional materials in a sustainable world. Green Chemistry, 2016, 18(5): 1175–1200

[26] Ajjan F N, Casado N, Rębiś T, Elfwing A, Solin N, Mecerreyes D, Inganäs O. Inganäs. High performance PEDOT/lignin biopolymer composites for electrochemical supercapacitors. Journal of Materials Chemistry A, 2016, 4(5): 1838–1847

[27] Peng Z, Zou Y, Xu S, Zhong W, Yang W. High-performance biomass-based flexible solid-state supercapacitor constructed of pressure-sensitive lignin-based and cellulose hydrogels. ACS Applied Materials & Interfaces, 2018, 10(26): 22190–22200

[28] Mondal S, Rana U, Malik S. Reduced graphene oxide/Fe₃O₄/polyaniline nanostructures as electrode materials for an all-solid-state hybrid supercapacitor. Journal of Physical Chemistry C, 2017, 121(14): 7573–7583

[29] Joshi R, Adhikari A, Dey A, Lahiri I. Green reduction of graphene oxide as a substitute of acidic reducing agents for supercapacitor applications. Materials Science and Engineering B, 2023, 287: 116128

[30] Liu R, Ding T, Deng P, Yan X, Xiong F, Chen J, Wu Z. Preparation of LCST regulable DES-lignin-g-PNVCL thermo-responsive polymer by ARGET-ATRP. International Journal of Biological Macromolecules, 2022, 194: 358–365

[31] Li Z, Shi Q, Ma X, Li Y, Wen K, Qin L, Chen H, Huang W, Zhang F, Lin Y, Marks T J, Huang H. Efficient room temperature catalytic synthesis of alternating conjugated copolymers via C–S bond activation. Nature Communications, 2022, 13(1): 144

[32] Li W, Lu H, Zhang N, Ma M. Enhancing the properties of conductive polymer hydrogels by freeze-thaw cycles for high-performance flexible supercapacitors. ACS Applied Materials & Interfaces, 2017, 9(23): 20142–20149

[33] Li R, Lu Z, Cai Y, Jiang F, Tang C, Chen Z, Zheng J, Pi J, Zhang R, Liu J, Chen Z B, Yang Y, Shi J, Hong W, Xia H. Switching of charge transport pathways via delocalization changes in single-molecule metallacycles junctions. Journal of the American Chemical Society, 2017, 139(41): 14344–14347

[34] Zou Y, Zhang Z, Zhong W, Yang W. Hydrothermal direct synthesis of polyaniline, graphene/polyaniline and N-doped graphene/polyaniline hydrogels for high performance flexible supercapacitors. Journal of Materials Chemistry A, 2018, 6(19): 9245–9256

[35] Kotal M, Kim H, Roy S, Oh I K. Sulfur and nitrogen co-doped holey graphene aerogel for structurally resilient solid-state supercapacitors under high compressions. Journal of Materials Chemistry A, 2017, 5(33): 17253–17266

[36] Shi J L, Du W C, Yin Y X, Guo Y G, Wan L J. Hydrothermal reduction of three-dimensional graphene oxide for binder-free flexible supercapacitors. Journal of Materials Chemistry A, 2014, 2(28): 10830–10834

[37] Chang L, Peng Z, Zhang T, Yu C, Zhong W. Nacre-inspired composite films with high mechanical strength constructed from MXenes and wood-inspired hydrothermal cellulose-based nanofibers for high performance flexible supercapacitors. Nanoscale, 2021, 13(5): 3079–3091

[38] Yang Y, Zhu T, Shen L, Liu Y, Zhang D, Zheng B, Gong K, Zheng J, Gong X. Recent progress in the all-solid-state flexible supercapacitors. SmartMat, 2022, 3(3): 1103

[39] Xu C, Jiang W Y, Guo L, Shen M, Li B, Wang J Q. High supercapacitance performance of nitrogen-doped Ti₃C₂T_x prepared by molten salt thermal treatment. Electrochimica Acta, 2022, 403: 139528

[40] Augustyn V, Come J, Lowe M A, Kim J W, Taberna P L, Tolbert S H, Abruña H D, Simon P, Dunn B. High-rate electrochemical energy storage through Li⁺ intercalation pseudocapacitance. Nature Materials, 2013, 12(6): 518–522

[41] Kim S K, Kim Y K, Lee H, Lee S B, Park H S. Superior pseudocapacitive behavior of confined lignin nanocrystals for renewable energy-storage materials. ChemSusChem, 2014, 7(4): 1196–1196

[42] Dai L, Ma M, Xu J, Si C, Wang X, Liu Z, Ni Y. All-lignin-based hydrogel with fast pH-stimuli responsiveness for mechanical switching and actuation. Chemistry of Materials, 2020, 32(10): 4324–4330

[43] Jin K, Zhang W, Wang Y, Guo X, Chen Z, Li L, Zhang Y, Wang Z, Chen J, Sun L, Zhang T. In-situ hybridization of polyaniline nanofibers on functionalized reduced graphene oxide films for high-performance supercapacitor. Electrochimica Acta, 2018, 285: 221–229

[44] Zhu L, Hao C, Wang X, Guo Y. Fluffy Cotton-Like GO/Zn–Co–Ni Layered Double Hydroxides Form from a Sacrificed Template GO/ZIF-8 for High Performance Asymmetric Supercapacitors. ACS Sustainable Chemistry & Engineering, 2020, 8(31): 11618–11629

[45] Jha S, Mehta S, Chen Y, Ma L, Renner P, Parkinson D Y, Liang H. Correction to “design and synthesis of lignin-based flexible supercapacitors”. ACS Sustainable Chemistry & Engineering, 2020, 8(25): 9597–9598

[46] Choi B G, Yang M, Hong W H, Choi J W, Huh Y S. 3D macroporous graphene frameworks for supercapacitors with high energy and power densities. ACS Nano, 2012, 6(5): 4020–4028

[47] Liu N, Su Y, Wang Z, Wang Z, Xia J, Chen Y, Zhao Z, Li Q, Geng F. Electrostatic-interaction-assisted construction of 3D networks of manganese dioxide nanosheets for flexible high-performance solid-state asymmetric supercapacitors. ACS Nano, 2017, 11(8): 7879–7888

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