Carbon Nanocages//Tungsten Trioxide Nanorods Supercapacitors with in situ Polymerized Gel Electrolytes

doi:10.6023/A21030087

Abstract

Asymmetric supercapacitors can effectively increase the energy density of supercapacitors, and the key is to develop high-performance electrode materials and electrolytes. Hierarchical carbon nanocages are promising electrode materials for supercapacitors because of the large specific surface area, coexisting micro-meso-macropore, good conductivity and high stability. By introducing pseudocapacitance and improving wettability via N&S dual-doping, the N&S dual-doped carbon nancages (NSCNC) exhibit a high specific capacity of 337 F?g^-1 at 1 A?g^-1 within the potential window of 0~1 V in 1 mol?L^-1 H₂SO₄solution. Hydrated tungsten trioxide (WO₃?0.6H₂O) nanorods can achieve the insertion/de-insertion of H⁺ via the redox reaction between W⁶⁺/W⁵⁺, and exhibit a high specific capacity of 454 F?g^-1 at 5 A?g^-1 within the potential window of –0.55~0.3 V. The solid-state asymmetric supercapacitor (SASC) with NSCNC and WO₃?0.6H₂O nanorods as positive and negative electrodes, and in situ polymerized gel electrolyte (IPGE/H₂SO₄) as solid electrolyte has the working voltage of 1.5 V. And the rate performance of the SASC is very close to that of the H-type device with 1 mol?L^-1 H₂SO₄ solution as electrolyte, much better than the counterpart with the traditional gel electrolyte of polyvinyl alcohol/sulfuric acid (PVA/H₂SO₄). The much improved SASC performance is attributed to the establishment of the effective charge transfer interface between the IPGE/H₂SO₄ and the electrode materials, which enhances the transfer of H⁺ ions and thereby much reduces theIR drop. The energy density of the SASC with IPGE/H₂SO₄ is 22.31 Wh?kg^-1 at 0.375 kW?kg^-1 (0.5 A?g^-1) and 8.55 Wh?kg^-1 at 7.5 kW?kg^-1 (10 A?g^-1), locating at the top-ranking of literatures. The SASC also exbibits excellent cycling stability, with the capacity retention of 95.2% after 4000 cycles at 5 A?g^-1. This study not only demonstrates the excellent energy storage performance of NSCNC//WO₃?0.6H₂O supercapacitors in acidic electrolytes, but also provides a new in-situ polymerized gel electrolyte for building high-performance SASCs.

Key words: supercapacitor, acidic electrolyte, in situ polymerized gel electrolyte, hierarchical carbon nanocage, hydrated tungsten trioxide nanorod

Cite this article

Runzhou Gao, Guochang Li, Yiqun Chen, Yu Zeng, Jie Zhao, Qiang Wu, Lijun Yang, Xizhang Wang, Zheng Hu. Carbon Nanocages//Tungsten Trioxide Nanorods Supercapacitors with in situ Polymerized Gel Electrolytes[J]. Acta Chimica Sinica, 2021, 79(6): 755-762.

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Fig. & Tab. 5

Figure 1. Morphology and structure characterizations of NSCNC and WO3?0.6H2O nanorods. (a) SEM and TEM images, (b) S2p and (c) N1s XPS spectra of NSCNC. (d) TEM image, (e) XRD pattern and (f) W4f XPS spectrum of WO3?0.6H2O nanorods.

Figure 2. Electrochemical performance of NSCNC. (a) CV curves. (b) GCD curves. (c) Relationship of capacitance vs. current density. (d) Capacitance retention and Coulombic efficiency during cycling test.

Figure 3. Electrochemical performance of WO3?0.6H2O nanorods. (a) CV curves. (b) GCD curves. (c) Relationship of capacitance vs. current density. (d) Capacitance retention and Coulombic efficiency during cycling test.

Figure 4. Formation of IPGE/H2SO4 and schematic diagrams of interfaces of gel electrolyte-electrode materials. (a) Photographs of the precursor solution and IPGE/H2SO4. (b) SEM image of IPGE/H2SO4-NSCNC electrode. (c) Schematic diagram of IPGE/H2SO4-electrode materials interface. (d) Schematic diagram of PVA/H2SO4-electrode materials interface

Figure 5. Electrochemical performance of three asymmetric supercapacitors. (a) Relationships of capacitance vs. current density. (b) IR drops at different current densities. (c) Ragone plots. (d) Cycling stabilities.

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