低合金化<strong>Mg-Ag</strong>镁空气电池阳极材料的电化学行为和放电性能

doi:10.11900/0412.1961.2023.00332

金属学报

2025, Vol. 61

Issue (6): 837-847 DOI: 10.11900/0412.1961.2023.00332

研究论文

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低合金化Mg-Ag镁空气电池阳极材料的电化学行为和放电性能

郝旭邦¹, 程伟丽¹^,²(

), 李戬², 王利飞¹, 崔泽琴¹, 闫国庆³, 翟凯³, 余晖⁴

1 太原理工大学材料科学与工程学院太原 030024
2 青海大学盐湖化工大型系列研究设施西宁 810016
3 山西瑞格金属新材料有限公司运城 043800
4 河北工业大学材料科学与工程学院天津 300132

Electrochemical Behavior and Discharge Performance of a Low-Alloyed Mg-Ag Alloy as Anode for Mg-Air Battery

HAO Xubang¹, CHENG Weili¹^,²(

), LI Jian², WANG Lifei¹, CUI Zeqin¹, YAN Guoqing³, ZHAI Kai³, YU Hui⁴

1 School of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China
2 Salt Lake Chemical Engineering Research Complex, Qinghai University, Xining 810016, China
3 Shanxi Regal Advanced Material Co. Ltd., Yuncheng 043800, China
4 School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300132, China

引用本文:

郝旭邦, 程伟丽, 李戬, 王利飞, 崔泽琴, 闫国庆, 翟凯, 余晖. 低合金化Mg-Ag镁空气电池阳极材料的电化学行为和放电性能[J]. 金属学报, 2025, 61(6): 837-847.
Xubang HAO, Weili CHENG, Jian LI, Lifei WANG, Zeqin CUI, Guoqing YAN, Kai ZHAI, Hui YU. Electrochemical Behavior and Discharge Performance of a Low-Alloyed Mg-Ag Alloy as Anode for Mg-Air Battery[J]. Acta Metall Sin, 2025, 61(6): 837-847.

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摘要:

镁空气电池具有高的理论放电电压(3.1 V)和比能量密度(6.8 kWh/kg)，且结构简单、成本低廉、安全性高，是理想的储能设备。然而，目前镁空气电池能够实现的放电电压和能量密度远低于理论值。为了协同提升镁空气电池的放电电压和比能量密度，本工作开发了低合金化Mg-1Ag (质量分数，%)阳极材料并研究了其微观组织、电化学行为和放电性能。结果表明，挤压态合金主要由均匀的等轴晶组成，平均晶粒尺寸为(14.19 ± 2.27) μm，展现出基极垂直于横向的织构，织构强度为11.05，Ag元素存在局部偏聚。以Mg-1Ag阳极组装的镁空气电池，在10 mA/cm²的电流密度下放电过程平稳，电池电压和比能量密度分别为1.344 V和1374.34 mWh/g。镁空气电池优异的放电性能主要与金属Ag在电极表面的再沉积、多裂纹的放电产物膜和较高体积分数的非基面取向晶粒有关。

关键词 ：镁空气电池, Mg-Ag合金, 微观组织, 放电性能, 电化学行为

Abstract：

Primary Mg-air batteries have attracted considerable attention in the field of standby emergency energy storage in the wilderness because of their high theoretical voltage (3.1 V) and appreciable specific energy (6.8 kWh/kg). However, because of the severe self-corrosion and sluggish anodic kinetics of Mg anodes, the actual performance of Mg-air batteries is far from the theoretical limits. To synergistically enhance the discharge voltage and specific energy of Mg-air batteries, a low-alloyed Mg-1Ag (mass fraction, %) anode was developed, and its microstructure, electrochemical behavior, and discharge properties were evaluated. The results showed that the extruded alloy mainly consisted of equiaxed grains with an average grain size of (14.19 ± 2.27) μm. The anode studied exhibited a typical extrusion texture with a basal pole perpendicular to the transverse direction, and the texture intensity was 11.05. Additionally, the extruded alloy was shown to exhibit localized segregation of Ag. The Mg-air battery based on the Mg-1Ag alloy as the anode exhibited a stable discharge process. In addition, the cell voltage and specific energy reached 1.344 V and 1374.34 mWh/g at 10 mA/cm², respectively. The acceptable discharge performance of the anode was mainly due to the redeposition of metal Ag on the electrode surface, the multi-cracked discharge product film, and the non-basal-oriented grains with a high-volume fraction.

Key words： Mg-air battery Mg-Ag alloy microstructure discharge performance electrochemical behavior

收稿日期: 2023-08-10

ZTFLH:

TG146.2

基金资助:国家自然科学基金项目(52375370);山西省自然科学基金项目(202103021224049);山西浙大新材料与化工研究院技术开发项目(2022SX-TD025);青海大学盐湖化工大型系列研究设施开放研究项目(2023-DXSSKF-Z02)

通讯作者: 程伟丽，chengweili7@126.com，主要从事先进镁基体材料开发及性能调控的研究

Corresponding author: CHENG Weili, professor, Tel: (0351)6010021, E-mail: chengweili7@126.com

作者简介: 郝旭邦，男，2000年生，硕士生

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链接本文:

https://www.ams.org.cn/CN/10.11900/0412.1961.2023.00332 或 https://www.ams.org.cn/CN/Y2025/V61/I6/837

图1 挤压态Mg-1Ag合金(Q1合金)的晶粒取向图、晶粒类型图和(0001)极图

图2 Q1合金的晶粒尺寸分布图

图3 Q1合金的SEM像及EDS元素分布图

图4 Q1合金的XRD谱

表1 Q1合金的EDS结果 (atomic fraction / %)

图5 Q1合金和HP Mg的开路电位、极化曲线阳极分支和阴极分支极化曲线及Nyquist图

表2 Q1合金和HP Mg的电化学参数

图6 合金的等效电路图

表3 根据电化学阻抗谱(EIS)数据拟合得出的电化学参数

图7 不同电流密度下Q1合金和HP Mg的放电曲线

图8 Q1合金和HP Mg的阳极效率和电池电压，比容量和比能量，以及近年镁空气电池阳极材料在10 mA/cm2下的放电性能统计[1~3,5~8,11,20~26]

图9 Q1合金在不同电流密度下放电10 h的表面和截面形貌SEM像

图10 Q1合金不同电流密度下放电产物的XPS

图11 Q1合金在不同电流密度和不同放电时间去产物表面形貌下的SEM像和放电10 h后去产物3D形貌

图12 Q1合金中基面取向和非基面取向晶粒的晶粒取向图，晶粒尺寸范围在0~14.19 μm内和大于14.19 μm晶粒取向图，基面取向晶粒且尺寸范围在0~14.19 μm内和大于14.19 μm晶粒取向图，及非基面取向晶粒且尺寸范围在0~14.19 μm内和大于14.19 μm晶粒取向图

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