多功能磷化铁碳布(FeP/CC)中间层高效催化多硫化物实现锂硫电池的高容量与高稳定性

doi:10.6023/A23010010

摘要/Abstract

锂硫电池高的比能量密度(2600 Wh•kg⁻¹), 使其成为一种很有前景的储能系统. 然而, 在氧化还原反应中, 中间产物多硫化物(LiPSs)的穿梭效应, 以及缓慢的电化学反应动力学导致阴极和阳极的严重降解, 使容量迅速衰减. 在此, 制备了一种多功能磷化铁碳布(FeP/CC)中间层, 为锂硫电池提供了更多的活性位点, 不仅可以物理捕获多硫化物(LiPSs)以抑制穿梭效应, 确保稳定的循环, 而且对LiPSs具有催化能力, 有助于提高电化学反应动力学. 带有FeP/CC中间层的锂硫电池可实现1329 mAh•g⁻¹的首圈放电容量, 在100圈循环后, 仍然能保持在1100 mAh•g⁻¹的可逆容量, 并且FeP/CC表现出优异的对LiPS吸附与催化转化能力. 这种多功能FeP/CC中间层为高稳定性以及高容量的锂硫电池提供了一种可行的思路.

关键词: 锂硫电池, 磷化铁, 催化转化, 中间层

With the progress of science and the development of human society, traditional energy is increasingly exhausted, and low energy density lithium ion battery is not enough to support the demand for energy, so the development of high capacity of clean energy system is imminent. Unlike Li-ion batteries, Li-sulfur batteries have a high specific energy density (2600 Wh•kg⁻¹), making them a promising energy storage system. However, in oxidation-reduction reaction, the shuttle effect of intermediate polysulfides (LiPSs) and slow electrochemical reaction kinetics lead to severe degradation of the cathode and anode, resulting in rapid capacity decay. In this paper, a multifunctional FeP/carbon cloth (FeP/CC) interlayer was prepared by hydrothermal synthesis. The FeP grows evenly in a “needle” shape on a smooth carbon cloth. This structure provides more active sites for Li-S batteries and greatly improves the electrochemical reaction kinetics by utilizing the catalytic ability of phosphate to Li-S batteries. In addition, carbon cloth (CC), as the matrix, can also play the role of “physical domain limiting”, thereby physically trapping LiPSs, inhibiting the shuttle effect and ensuring the cycle stability. In subsequent electrochemical tests, the FeP/CC interlayer lithium-sulfur battery had a first cycle discharge capacity of 1329 mAh•g⁻¹ and a reversible capacity of 1100 mAh•g⁻¹ after 100 cycles. When the sulfur load reaches 3.4 mg•cm⁻² and the current density is 1 C, the cyclic capacity is stable at 495 mAh•g⁻¹. In addition, FeP/CC showed excellent adsorption and catalytic conversion ability for LiPSs in visual adsorption experiments and ultraviolet spectrum tests. This multifunctional FeP/CC interlayer provides a feasible idea for the development of high stability and high capacity lithium-sulfur batteries.

Key words: lithium-sulfur battery, iron phosphide, catalytic conversion, interlayer

引用此文

周俊粮, 赵振新, 武庭毅, 王晓敏. 多功能磷化铁碳布(FeP/CC)中间层高效催化多硫化物实现锂硫电池的高容量与高稳定性[J]. 化学学报, 2023, 81(4): 351-358.

Junliang Zhou, Zhenxin Zhao, Tingyi Wu, Xiaomin Wang. Efficient Catalytic Conversion of Polysulfides in Multifunctional FeP/Carbon Cloth Interlayer for High Capacity and Stability of Lithium-sulfur Batteries[J]. Acta Chimica Sinica, 2023, 81(4): 351-358.

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图/表 8

图1. FeP/CC制备流程图以及锂硫电池组装工作原理图

Figure 1. Flow chart of FeP/CC preparation and working principle of lithium-sulfur battery assembly

图2. (a, b) FeOOH/CC中间层的SEM图; (c, d) FeP/CC中间层的SEM图; (e, f) P和Fe的EDS能谱图; (g, h) FeP/CC与FeOOH/CC的光学图片

Figure 2. (a, b) The SEM image of FeOOH/CC interlayer; (c, d) the SEM image of FeP/CC interlayer; (e, f) the EDS spectra of P and Fe, respectively; (g, h) the optical pictures of FeP/CC and FeOOH/CC, respectively

图3. (a) FeOOH和(b) FeP的XRD图谱

Figure 3. XRD patterns of (a) FeOOH and (b) FeP

图4. (a) 电极材料对多硫化物的光学吸附实验以及紫外光谱分析图谱; (c) Li2S6吸附后FeP/CC复合材料的高分辨率S 2p; (b) P 2p和(d) FeP/CC复合材料吸附Li2S6前后的Fe 2p峰

Figure 4. (a) Optical adsorption experiment and ultraviolet spectrum analysis of polysulfides on electrode materials; (c) high-resolution S 2p of FeP/CC composites after Li2S6 adsorption; (b) P 2p and (d) Fe 2p peaks of FeP/CC composites before and after Li2S6 adsorption

图5. (a) 首圈充放电曲线; (b) 倍率测试曲线; (c) 0.1 C小电流长循环; (d) 0.1 mV?s?1下不同锂硫电池的CV曲线; (e) 反应前的阻抗; (f) 循环100圈之后的阻抗

Figure 5. (a) The charge/discharge curves for the first cycle; (b) the magnification test curves; (c) the long cycle at 0.1 C low current; (d) the CV curves of different lithium-sulfur batteries at 0.1 mV?s?1; (e) the impedance before reaction; (f) the impedance after 100 cycles

图6. (a) KB//S热重曲线; (b) 不同电池的高负载实验; (c) 循环100圈之后的锂片形貌图

Figure 6. (a) KB//S thermogravimetric curve; (b) high load experiments of different batteries; (c) the morphology of lithium sheet after 100 cycles

图7. 不同扫速(0.1~0.5 mV?s?1)的CV曲线图以及对应的离子扩散速率曲线

Figure 7. The CV curves for different sweep rates (0.1~0.5 mV?s?1) and the corresponding ion diffusion rate curves

图8. (a, b) 对称电池的CV以及阻抗图; (c, d) 对照组与实验组沉积曲线

Figure 8. (a, b) The CV and impedance plots of the symmetric cell; (c, d) the deposition curves of the control and experimental groups

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