Critical roles of molybdate anions in enhancing capacitive and oxygen evolution behaviors of LDH@PANI nanohybrids

doi:10.1016/S1872-2067(20)63724-X

Abstract

Abstract:

Low-overpotential layered hydroxides (LDHs) with high theoretical capacity are promising electrodes for supercapaterry and oxygen evolution reaction; however, the low electronic conductivity and insufficient active sites of bulk LDHs increase the internal resistance and reduce the capacity and oxygen-production efficiency of electrodes. Herein, we prepared a polyaniline-coated NiCo-layered double hydroxide intercalated with MoO₄^2- (M-LDH@PANI) composite electrode using a two-step method. As the amount of MoO₄^2- in the LDH increases, acicular microspheres steadily evolve into flaky microspheres with a high surface area, providing more active electrochemical sites. Moreover, the amorphous PANI coating of M-LDH boosts the electronic conductivity of the composite electrode. Accordingly, the M-LDH@PANI at an appropriate level of MoO₄^2- exhibits significantly enhanced energy storage and catalytic performance. Experimental analyses and theoretical calculations reveal that a small amount of MoO₄^2- is conducive to the expansion of LDH interlayer spacing, while an excessive amount of MoO₄^2- combines with the H atoms of LDH, thus competing with OH^-, resulting in reduced electrochemical performance. Moreover, M-LDH flaky microspheres can efficiently modulate deprotonation energy, greatly accelerating surface redox reactions. This study provides an explanation for an unconventional mechanism, and a method for the modification of LDH-based materials for anion intercalation.

Key words: Layered hydroxide LDH, PANI, MoO₄^2-, Intercalated hierarchical structures, Supercapaterry, Electrocatalyst

Qiang Hu, Hua Wang, Feifei Xiang, Qiaoji Zheng, Xinguo Ma, Yu Huo, Fengyu Xie, Chenggang Xu, Dunmin Lin, Jisong Hu. Critical roles of molybdate anions in enhancing capacitive and oxygen evolution behaviors of LDH@PANI nanohybrids[J]. Chinese Journal of Catalysis, 2021, 42(6): 980-993.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63724-X

https://www.cjcatal.com/EN/Y2021/V42/I6/980

Figures/Tables 7

Fig. 1. Schematic representations of the two-step fabrication route for LDH, M-LDH and M-LDH@PANI architecture grown on NF.

Fig. 2. (a-c) SEM images of LDH, M-LDH-0.5 and M-LDH@PANI-0.5; (d,e) TEM and HRTEM images of LDH; (f,g) TEM and HRTEM images of M-LDH-0.5; (h-j) TEM and HRTEM images of M-LDH@PANI-0.5; (k) The corresponding element mappings images of M-LDH@PANI-0.5.

Fig. 3. (a) Schematic crystal structure of M-LDH; (b,c) XRD patterns of LDH, M-LDH-x and M-LDH@PANI-0.5; (d) FTIR spectra of LDH, M-LDH-0.5 and M-LDH@PANI-0.5; (e-i) High-resolution XPS spectra of Ni 2p, Co 2p, Mo 3d, O1s and N1s in LDH and M-LDH@PANI-0.5.

Fig. 4. (a) Comparative CV curves of LDH, M-LDH-x and M-LDH@PANI-0.5 electrodes at scan rate of 5 mV s-1; (b) CV curves of M-LDH@PANI-0.5 electrode at different scan rates; (c) Power law dependence of redox peak current on scan rate for LDH, M-LDH-x and M-LDH@PANI-0.5 electrodes; (d) GCD curves of M-LDH@PANI-0.5 electrode at different current densities; (e) Comparative GCD curves of LDH, M-LDH-x and M-LDH@PANI-0.5 electrodes at a current density of 1 A g-1; (f) Specific capacities of LDH, M-LDH-x and M-LDH@PANI-0.5 electrodes as function of current density; (g) Nyquist plots of LDH, M-LDH-0.5 and M-LDH@PANI-0.5 electrodes; (h) Cycling stability of M-LDH@PANI-0.5 electrode at a current density of 5 A g-1; (i) A comparison of improvement ability of our strategy with the values of previously reported similar electrodes.

Fig. 5. (a) Side views of pristine double-layer Co0.5Ni0.5-LDH; MoO42- (b) inside and (c) outside interface of Co0.5Ni0.5-LDH; (d) Stacked MoO42- inside interface of Co0.5Ni0.5-LDH; (e) MoO42- inside and outside interface of Co0.5Ni0.5-LDH; (f) The calculated deprotonation energy of pristine, one-layer MoO42- inside, one-layer MoO42- outside, MoO42- inside and outside the interface and two-layer MoO42- inside the interface of Co0.5Ni0.5-LDH, respectively; (g) Charge density difference isosurfaces for the deprotonation process on two-layer MoO42- inside the interface of Co0.5Ni0.5-LDH; yellow and blue areas indicate charge depletion and charge accumulation zones, respectively (isosurface value is 0.01 eV/?3).

Fig. 6. (a) Schematic of device fabrication; (b) Cyclic voltammetry curves of HSC at various voltage windows at 10 mV s-1; (c) GCD curves of HSC at various voltage windows at 1 A g-1; (d) CV curves of HSC at different scan rates; (e) GCD curves of HSC device at different current densities; (f) Specific capacity of HSC device at different current densities; (g) Comparison of the Ragone plots of the present and reported devices; and (h) cycling stability at a current density of 3 A g-1.

Fig. 7. (a) Polarization curves of LDH, M-LDH-x and M-LDH@PANI-0.5, respectively; (b) Tafel plots of LDH, M-LDH-x and M-LDH@PANI-0.5, respectively; (c) Free energy profiles for the OER over 2L MoO42- inside LDH at zero potential (U = 0), equilibrium potential for oxygen evolution (U = 1.23 V), and minimum potential (U = 1.61 V) where all steps run downhill; (d) Stability test of M-LDH@PANI-0.5 for 34 h in 1.0 M KOH.

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