废旧电池再资源化制备高性能中熵合金催化剂及其性能研究

doi:10.11949/0438-1157.20240629

摘要/Abstract

摘要：

以从废旧三元锂离子电池中回收的镍钴锰（NCM）有价金属与钯（Pd）盐为原料，采用快速高温轰击方法制备含氮碳基体负载钯镍钴锰中熵合金纳米颗粒（Pd MEA@N-C）作为锂氧电池双功能催化剂，以实现废弃三元锂离子电池的循环使用，优化在氧还原/析出过程（ORR/OER）中放电产物过氧化锂（Li₂O₂）的可逆生成与分解。XRD、TEM表明Pd MEA成功制备，XPS表明Pd的引入有利于实现合金颗粒中电子排布的精准调控。以Pd MEA@N-C为正极材料组装锂氧电池测试性能，结果显示，在限制1000 mAh·g^-1的容量，200 mA·g^-1的电流密度条件下，过电位低至0.49 V；200 mA·g^-1的电流密度条件下进行深度充放电测试，充放电容量高达15491 mAh·g^-1；在循环82圈之后仍保持稳定状态。

关键词: 催化剂, NCM回收, Pd中熵合金, 电化学, ORR/OER, 反应动力学

Abstract:

Car electrification is a green and healthy way of contemporary travel, reducing exhaust emissions while avoiding excessive consumption of fossil fuels, but the generated waste power batteries will also pose a great threat to society. Nickels, cobalt, manganese (NCM) were recovered from waste ternary lithium-ion batteries and then were alloyed with palladium. The nitrogen carbon matrix supported palladium-nickel-cobalt-manganese medium-entropy alloy nanoparticles (Pd MEA@N-C) were prepared by rapid high-temperature bombardment as double-function catalysts for lithium-oxygen batteries, so as to realize the recycling of waste ternary lithium-ion batteries. The reversible formation and decomposition of lithium peroxide (Li₂O₂) as a discharge product in the oxygen reduction/precipitation process (ORR/OER) was optimized. XRD and TEM showed that the Pd MEA was formed successfully, and XPS showed that the introduction of Pd was conducive to the accurate regulation of electron configuration in alloy particles. The performance of lithium-oxygen batteries assembled with Pd MEA@N-C as the positive electrode material is tested. The results show that under the conditions of limiting the capacity to 1000 mAh·g^-1and the current density to 200 mA·g^-1, the overpotential was as low as 0.49 V. The deep charge and discharge test was carried out at the current density of 200 mA·g^-1, and the charge and discharge capacity was 15491 mAh·g^-1, which remained stable after 82 cycles.

Key words: catalyst, NCM recovery, Pd medium-entropy alloy, electrochemistry, ORR/OER, reaction kinetics

中图分类号:

TQ 152

郭珊, 田雨, 徐永滨, 王朋, 刘治明. 废旧电池再资源化制备高性能中熵合金催化剂及其性能研究[J]. 化工学报, 2025, 76(1): 231-240.

Shan GUO, Yu TIAN, Yongbin XU, Peng WANG, Zhiming LIU. Synthesis of a high-efficacy medium-entropy alloy catalyst via the recycling of spent batteries and its subsequent performance evaluation[J]. CIESC Journal, 2025, 76(1): 231-240.

图/表 12

图1 (a) Pd MEA@N-C的SEM图像；(b) Pd MEA@N-C的HAADF-STEM图像和粒径分布

Fig.1 (a) SEM image of Pd MEA@N-C; (b) TEM image (inset shows particle size distribution).of Pd MEA@N-C

图2 (a) Pd MEA@N-C纳米结构的HR-TEM图像；(b) Pd MEA@N-C(200)、(111)晶面的晶面间距；(c) Pd MEA@N-C纳米结构的FFT图像

Fig.2 (a) HR-TEM image of Pd MEA@N-C nanoparticle; (b) IFFT image of (200), (111) plane of Pd MEA nanoparticle; (c) FFT image of Pd MEA@N-C nanoparticle

图3 (a) Pd MEA@N-C纳米颗粒上的Ni、Co、Mn和Pd的线扫描信号；(b) Pd MEA@N-C的元素映射图

Fig.3 (a) The line scan signals of Ni, Co, Mn, and Pd across the Pd MEA@N-C nanoparticle; (b) Elemental mapping images of Pd MEA@N-C

图4 Pd MEA@N-C、NCM@N-C和N-C的XRD谱图

Fig.4 XRD patterns of Pd MEA@N-C, NCM@N-C and N-C

图5 Pd MEA@N-C、NCM@N-C和N-C Pd 3d、Ni 2p、Co 2p、Mn 2p、C 1s和N 1s的XPS光谱

Fig.5 High-resolution XPS spectra of Pd 3d, Ni 2p, Co 2p, Mn 2p, C 1s, and N 1s of Pd MEA@N-C, NCM@N-C and N-C

图6 Pd MEA@N-C和NCM@N-C的拉曼光谱

Fig.6 Raman spectrum of Pd MEA@N-C and NCM@N-C

图7 Pd MEA@N-C的孔径分布(a)和氮气吸脱附等温线(b)

Fig.7 Pore size distributions (a) and nitrogen adsorption-desorption isotherms (b) of Pd MEA@N-C

图8 电化学性能：(a) 0.1mV·s-1下Pd MEA@N-C、NCM@N-C和N-C电极的CV曲线；(b)三个电极在限制1000 mAh·g-1容量下200 mA·g-1电流密度的充放电曲线；(c)三个电极在200 mA·g-1下的初始深度放电-充电曲线；(d) Pd MEA@N-C电极在200 mA·g-1电流密度限制容量为500 mAh·g-1时的循环稳定性；(e) Pd MEA@N-C、NCM@N-C和N-C原始样品的EIS

Fig.8 Electrochemical performance: (a) CV curves of Pd MEA@N-C, NCM@N-C and N-C electrodes at 0.1 mV·s-1; (b) Discharge-charge curves of the three electrodes at a curtailed capacity of 1000 mAh·g-1 at 200 mA·g-1; (c) The initial deep discharge-charge curves of the three electrodes at 200 mA·g-1; (d) Cycling stability of Pd MEA@N-C electrode at 200 mA·g-1 with a limited capacity of 500 mAh·g-1; (e) EIS spectra of Pd MEA@N-C, NCM@N-C and N-C electrodes in the pristine

图9 (a) Pd MEA@N-C、NCM@N-C和N-C电极首圈充放电完成后的非原位XRD谱图；(b) Pd MEA@N-C、(c) NCM@N-C和(d) N-C电极放电1000 mAh·g-1的SEM图像

Fig.9 (a) Ex-situ XRD patterns of discharged and charged Pd MEA@N-C, NCM@N-C and N-C electrodes during the 1st cycle; SEM images after discharged to 1000 mAh·g-1 for (b) Pd MEA@N-C, (c) NCM@N-C and (d) N-C cathode

图10 (a) Pd MEA@N-C、(b) NCM@N-C和(c) N-C电极充电1000 mAh·g-1的SEM图像

Fig.10 SEM images after recharged to 1000 mAh·g-1 for (a) Pd MEA@N-C, (b) NCM@N-C and (c) N-C cathode

图11 (a) Pd MEA@N-C、NCM@N-C和N-C电极深度充放电完成后的非原位XRD谱图；(b) Pd MEA@N-C、(c) NCM@N-C和(d)N-C电极深度放电的SEM图像

Fig.11 (a) Ex-situ XRD patterns of the initial deep discharge-charge curves Pd MEA@N-C, NCM@N-C and N-C electrodes; SEM images after deep discharged for (b) Pd MEA@N-C, (c) NCM@N-C and (d) N-C cathode

图12 (a) Pd MEA@N-C、(b) NCM@N-C和(c) N-C电极深度充电的SEM图像

Fig.12 SEM images after deep charged for (a) Pd MEA@N-C, (b) NCM@N-C and (c) N-C cathode

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