Arginine modification of hybrid cobalt/nitrogen Ti3C2Tx MXene and its application as a sulfur host for lithium-sulfur batteries
Abstract
The shuttling effect of lithium polysulfides (LiPSs) is one of the challenges facing the commercialization, which leads to a significant capacity degradation. This paper proposes a novel method to promote polysulfide transformation by employing arginine to regulate the layer spacing of cobalt-nitrogen doped
Keywords
INTRODUCTION
Lightweight and long service rechargeable batteries have been developed to satisfy the increasing demands of industrial needs, military progress and portable life[1-3]. Furthermore, the development of advanced electrochemical energy conversion and storage systems with a high energy density has been gaining significant attention[4-7]. Despite the various advantages of existing lithium-ion batteries, their low energy density based on the intercalation mechanism has severely hindered the scale-up fabrication of miniature batteries[5]. Lithium-sulfur (Li-S) batteries with high theoretical specific capacity (1,675 mAh g-1) and energy density (2,567 Wh kg-1) have attracted considerable attention as the next-generation batteries[8-11]. However, their low sulfur utilization, sluggish redox reaction kinetics, fast capacity fading, and low coulombic efficiency (CE) have hindered their commercialization[12,13].
To address these issues, several studies have reported the development of advanced sulfur host materials for the Li-S cathodes[14,15]. For example, carbon materials and conducting material with large specific surface area have been used to inhibit the shuttle effect of polysulfide. In particular, two-dimensional conductive carbon materials have been employed owing to their adjustable morphology and high electrical conductivity[16-18]. Nevertheless, the interactions are weak between polar lithium polysulfides (LiPSs) and the nonpolar hydrophobic carbon framework play a very limited role in slowing down the shuttle effect or preventing interfacial charge transfer, thus leading to sluggish reaction kinetics[17,19,20].
The application of
Several strategies have focused on increasing the layer spacing and modifying the
This paper reports the fabrication of amino acid-regulated Co, N-doped
MATERIALS AND METHODS
Materials
400 mesh powder of Ti3AlC2 was from XF Nano Technology Co., Ltd. (Nanjing, China), while serine, lysine, arginine, LiF, 4-dimethylaminopyridine (DMAP) and 1-(3-(dimethylamino) propyl)-3-ethylcarbimide hydrochloride (EDC), cobalt chloride hexahydrate were purchased from Titan Scientific Co., Ltd. (General-Reagent brand). Concentrated HCl (36.5%) was obtained from Sinopharm Chemical Reagent Co., Ltd.
Preparation of the Ti3C2Tx-Arg, Ti3C2Tx-Ser, Ti3C2Tx-Lys composites
The
Preparation of the Co-N@Ti3C2Tx-Arg @S cathode
Each of the Ti3C2TX-Arg, Ti3C2TX-Ser, and Ti3C2TX-Lys film was immersed in a CoCl2 solution (0.1 mol·L-1) for 2 h. After drying, each film was then annealed at 600 °C under an Ar atmosphere for 4 h (temperature rise of
The S composite cathode was prepared as follows
The
Characterization
The morphologies were imaged by a scanning electron microscope (SEM, ZEISS Sigma 300) at an increased voltage of 3 kV equipped with an energy-dispersive spectrometer (EDS, Oxford Xplore50, pure gold target with an accelerated voltage of 0.02 to 30 kV). The X-ray diffraction (XRD) patterns were recorded on a Rigaku Smart Lab (Japan) equipped with a CuKα light source (λ = 0.15406 nm). Samples were scanned in the diffraction angle (2θ) range of 5° to 60° at a scanning rate of 2°/min. The X-ray photoelectron spectroscopy (XPS) spectra were recorded on a Thermo Scientific K-Alpha model spectrometer. The entire spectral scan was performed with a universal energy of 100 eV and a step size of 1 eV. The Thermo Fisher DXR 2xi model Raman imaging microscope with a spectral resolution of less than 1.5 cm-1 was used for the Raman spectroscopy analysis.
Electrochemical measurements
The mass of sulfur in the electrode was in the range of 1.0-1.5 mg. The discs were then tested with CR2032 coin-type cells using lithium metal as the anode, Celgard 2400 as the separator, and the electrolyte solution was composed of a LiTFSI (1 M) dissolved in a solution of 1,3-dioxolane (DOL) and dimethoxymethane (DME) (v:v = 1:1) solution containing LiNO3 (1 wt.%) as the additive. The Charge and discharge measurements were conducted in the potential range of 1.5-3.0 V (vs. Li/Li+) on a LAND testing system. electrolyte amount was 20 µL mg-1. The cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were conducted using DE7000 potentiostat/galvanostat in the frequency range of 10 kHz to 0.1 Hz.
RESULTS AND DISCUSSION
Figure 1 illustrates the procedure for the synthesis of the Co-N@Ti3C2Tx-Ser, Co-N@Ti3C2Tx-Lys, and
The SEM results of the Ti3AlC2 and etched multilayer
Figure 2. SEM images of the (A and B) multilayer Ti3C2TX, (C-E) Ti3C2TX-Ser, and Ti3C2TX-Lys, and Ti3C2Tx-Arg, composites; (F-J) SEM image and EDS spectrum mapping: C, Co, and N elemental distribution of the
The schematic representation of the amino-acid-modified
Figure 3. (A) Schematic illustration of the
The possibility to employ each of the obtained composites as an S cathode was then investigated [Figure 4]. Free-standing
Figure 4. (A) Schematic illustration of the fabrication of the Co-N@Ti3C2TX-Arg/S electrodes for Li-S batteries. (B) Rate performances of the Co-N@Ti3C2TX-Ser/S, Co-N@Ti3C2TX-Lys /S, and Co-N@Ti3C2TX-Arg/S electrodes. (C) Long-term cycling of the Co-N@Ti3C2TX-Ser/S, Co-N@Ti3C2TX-Lys/S, and Co-N@Ti3C2TX-Arg/S electrodes. (D) CEs of the Co-N@Ti3C2TX-Ser/S, Co-N@Ti3C2TX-Lys /S and
CONCLUSIONS
This study reported the synthesis of Co, N doped
DECLARATIONS
Authors’ contributions
Synthesis and testing of materials, data collection, original manuscript writing: Zhang M
Validation and original manuscript revision: Zhang K
Data analysis: Wei W
manuscript Revision: Yuan H
Reviewing and editing: Chang J
Revision: Hao Y
Availability of data and materials
According to reasonable requirements, all of the data examined in this research can be obtained from the correspondents.
Financial support and sponsorship
This work was financially supported by the National Key Research and Development Program of China (Grants 2021YFA0715600, 2021YFA0717700), National Natural Science Foundation of China (52192610, 62274127, 62374128), Youth Project of Natural Science Basic Research Program of Shaanxi Province (2021JQ-189), Fundamental Research Funds for the Central Universities, and Innovation Fund of Xidian University.
Conflicts of interest
All authors declared that there are no conflicts of interest.
Ethical approval and consent to participate
Not applicable.
Consent for publication
Not applicable.
Copyright
© The Author(s) 2024.
Supplementary Materials
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Zhang, M.; Zhang, K.; Wei, W.; Yuan, H.; Chang, J.; Hao, Y. Arginine modification of hybrid cobalt/nitrogen
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