Quantum Spin Exchange Interactions to Accelerate the Redox Kinetics in Li-S Batteries

doi:10.1007/s40820-023-01319-8

Abstract

Abstract:

Spin-engineering with electrocatalysts have been exploited to suppress the “shuttle effect” in Li-S batteries. Spin selection, spin-dependent electron mobility and spin potentials in activation barriers can be optimized as quantum spin exchange interactions leading to a significant reduction of the electronic repulsions in the orbitals of catalysts. Herein, we anchor the MgPc molecules on fluorinated carbon nanotubes (MgPc@FCNT), which exhibits the single active Mg sites with axial displacement. According to the density functional theory calculations, the electronic spin polarization in MgPc@FCNT not only increases the adsorption energy toward LiPSs intermediates but also facilitates the tunneling process of electron in Li-S batteries. As a result, the MgPc@FCNT provides an initial capacity of 6.1 mAh cm⁻² even when the high sulfur loading is 4.5 mg cm⁻², and still maintains 5.1 mAh cm⁻² after 100 cycles. This work provides a new perspective to extend the main group single-atom catalysts enabling high-performance Li-S batteries.

Key words: Metal phthalocyanines, Spin polarization, Electrocatalysis, Li-S batteries

Yu Du, Weijie Chen, Yu Wang, Yue Yu, Kai Guo, Gan Qu, Jianan Zhang. Quantum Spin Exchange Interactions to Accelerate the Redox Kinetics in Li-S Batteries[J]. Nano-Micro Letters, 2024, 16(1): 100-.

Yu Du, Weijie Chen, Yu Wang, Yue Yu, Kai Guo, Gan Qu, Jianan Zhang. [J]. Nano-Micro Letters, 2024, 16(1): 100-.

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URL: https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-023-01319-8

https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/100

Figures/Tables 5

Fig. 1 a Schematic illustration of the fabricated single-metal active sites. b HAADF-STEM image of MgPc@FCNT. c EELS spectrum of Mg L-edge. d FT-IR spectra e Raman spectra and f XRD patterns of MgPc@FCNT, MgPc@CNT, FCNT and MgPc

Fig. 2 a XPS spectra of Mg 1s for MgPc@FCNT, MgPc@CNT and MgPc. b Magnetization curves (M-H) of MgPc@FCNT and MgPc@CNT. The inset shows hysteresis loop with enlarged x-axis. c EPR spectra of MgPc@FCNT, MgPc@CNT. The inset shows the spin numbers. d Mg K-edge XANES of MgPc@FCNT and MgPc. FT-EXAFS spectra and fitting curves of e MgPc@FCNT and f MgPc. g UPS spectra h Tauc plots and i HOMO/LUMO level alignment obtained through experiments

Fig. 3 a CV curves. b Li ion diffusion coefficient derived from CV profiles. c Tafel slope of peak 3. d Potentiostatic discharge profiles at 2.05 V. e CV curves of symmetric cells. f Galvanostatic charge curves and g LSV curves. h EIS plots of MgPc@FCNT, MgPc@CNT, FCNT and CNT. i Activation energy barriers at a given discharge voltage for MgPc@FCNT, MgPc@CNT, FCNT and CNT

Fig. 4 a Rate performance for MgPc@FCNT, MgPc@CNT, FCNT and CNT. b GCD profiles at 0.2 C. c Q2/Q1 at different rates. d 2D pseudo-color in-situ XRD patterns of MgPc@FCNT during the GCD processes. Cycling performance e at 0.5 C and f at 2 C. g Cycling performance with high sulfur loading at 0.1 C

Fig. 5 The calculated DOS for MgPc@FCNT and MgPc@CNT a before and c after the adsorption of Li₂S₄. The PDOS of 3s/2p orbitals of Mg b before and d after the adsorption of Li₂S₄. Charge distribution diagrams of e MgPc@FCNT and f MgPc@CNT. g Binding energies between MgPc@FCNT, MgPc@CNT, FCNT, CNT and Li₂S_n (n = 1, 2, 4, 6, 8)/S₈

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