Al-Ga-In-Sn-Si合金阳极及海水溶解氧电池的电化学性能

doi:10.19894/j.issn.1000-0518.230332

摘要/Abstract

摘要：

通过Ga、In和Sn低熔点合金元素改性，成功制备了高负电位高活化Al-Ga-In-Sn-Si合金阳极，通过材料表征和电化学测试研究了Al-Ga-In-Sn-Si合金的腐蚀行为和电化学性能，并与碳纤维刷-石墨烯-铂（Pt-G@CFB）催化阴极搭建了海水溶解氧电池，考察了室内静态海水环境和实际海洋环境下电池不同恒电阻的长周期放电性能。结果表明，Al-Ga-In-Sn-Si合金的自腐蚀电位为-1.613 V（vs.Ag/AgCl），自腐蚀电流密度为1.431 mA/cm²。随着负载电阻的增加，电池电压上升，在室内静态和实海动态海水中2000 Ω的负载下海水溶解氧电池平均放电电压最高，分别为1.73和1.78 V，在1000 Ω的负载下平均能量密度最大，分别为549.85和653.44 Wh/kg。

关键词: Al-Ga-In-Sn-Si合金, 阳极, 海水溶解氧电池, 电化学性能, 放电行为

Abstract:

In this paper， a new type of Al-Ga-In-Sn-Si alloy anode with high negative potential and high activation was successfully prepared by modifying low melting point alloy elements such as Ga， In and Sn. The corrosion behavior and electrochemical performance of Al-Ga-In-Sn-Si alloy were studied through material characterization and electrochemical tests. A seawater dissolved oxygen battery was constructed with carbon fiber brush-graphene-platinum （Pt-G@CFB） catalytic cathode. The long period discharge performance of the battery under different constant resistance in indoor static and real dynamic seawater environment was investigated. The electrochemical test results of aluminum anode show that the self-corrosion potential of Al-Ga-In-Sn-Si alloy is -1.613 V（vs.Ag/AgCl）， and the self-corrosion current density is 1.431 mA/cm². The battery discharge test results show that the battery voltage rises with the increase of load resistance. The average discharge voltages of the dissolved oxygen battery in seawater are the highest， which are 1.73 and 1.78 V respectively， under the load of 2000 Ω in indoor static and real dynamic seawater， and the average energy densities are the highest under the load of 1000 Ω. They are 549.85 and 653.44 Wh/kg， respectively.

Key words: Al-Ga-In-Sn-Si alloy, Anode, Seawater dissolved oxygen battery, Electrochemical performance, Discharge behavior

中图分类号:

O646.6

吴厚燃, 侯春明, 段体岗, 马力, 张海兵, 王金涛. Al-Ga-In-Sn-Si合金阳极及海水溶解氧电池的电化学性能[J]. 应用化学, 2024, 41(5): 703-711.

Hou-Ran WU, Chun-Ming HOU, Ti-Gang DUAN, Li MA, Hai-Bing ZHANG, Jin-Tao WANG. Electrochemical Properties of Al-Ga-In-Sn-Si Alloy Anodes and Seawater Dissolved Oxygen Batteries[J]. Chinese Journal of Applied Chemistry, 2024, 41(5): 703-711.

图/表 12

图1 海水溶解氧电池结构设计图

Fig.1 Structure design of seawater dissolved oxygen battery

图2 Al-Ga-In-Sn-Si合金的XRD图谱

Fig.2 XRD pattern of Al-Ga-In-Sn-Si alloy

图3 Al-Ga-In-Sn-Si合金的EDS图像

Fig.3 EDS image of Al-Ga-In-Sn-Si alloy

图4 Al-Ga-In-Sn-Si合金的动电位极化曲线

Fig.4 Potentiodynamic polarization curve of Al-Ga-In-Sn-Si alloy

表1 Al-Ga-In-Sn-Si合金的腐蚀参数

Table 1 Corrosion parameters of Al-Ga-In-Sn-Si alloy in sea water

Samples	E_corr/V（vs.Ag/AgCl）	I_corr/（mA·cm^-2）	-β_c/（mV·dec^-１）	β_a/（mV·dec^-1）	R_p/（Ω·cm²）
Al-Ga-In-Sn-Si	-1.613	1.431	406.2	282.9	50.6

图5 Al-Ga-In-Sn-Si 合金的Nyquist图

Fig.5 Nyquist diagrams of Al-Ga-In-Sn-Si alloys

表2 拟合的EIS参数

Table 2 Fitted EIS parameters

Parameters	R_s/（Ω·cm²）	CPE₁/（F·cm^-2）	n₁	R_t/（Ω·cm²）	CPE₂/（F·cm^-2）	n₂	R₂/（Ω·cm²）	L₂/（H·cm²）	R_l/（Ω·cm²）
	5.68	5.21×10^-7	0.79	506.7	2.54×10^-6	1	34.26	1.99×10^-4	5.49×10^-5

图6 Al-Ga-In-Sn-Si合金阳极的恒电流极化曲线

Fig.6 Constant current polarization curve of Al-Ga-In-Sn-Si alloy anode

图7 海水溶解氧电池在室内静态海水（A）和实际动态海水（B）中电池电压-时间关系图

Fig.7 Diagram of battery volt-time relationship of seawater dissolved oxygen battery in indoor static seawater （A） and real dynamic seawater （B）

表3 海水溶解氧电池在室内静态和实际动态海水中放电的电池参数

Table 3 Battery parameters for discharge of seawater batteries in indoor static and real dynamic seawater

Battery	In indoor static seawater			In real dynamic seawater
Battery	2000 Ω	1000 Ω	500 Ω	2000 Ω	1000 Ω	500 Ω
Average voltage/V	1.73	1.63	1.51	1.78	1.64	1.53
Energy density/（W·h·kg^-1）	384.51	549.85	481.4	515.21	653.44	431.33

图8 Al-Ga-In-Sn-Si合金阳极在实际动态海水中的腐蚀形貌

Fig.8 Corrosion morphology of Al-Ga-In-Sn-Si alloy anode in real dynamic seawater

图9 Al-Ga-In-Sn-Si合金阳极腐蚀产物及去除腐蚀产物形貌A. surface microstructure after removal of corrosion products； B. surface morphology of Al-Ga-In-Sn-Si alloy anode after corrosion； C. EDS spectrum of Al-Ga-In-Sn-Si alloy after corrosion

Fig.9 Morphology of anode corrosion products and removal corrosion products of Al-Ga-In-Sn-Si alloy

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