Electrochemical Properties of Al-Ga-In-Sn-Si Alloy Anodes and Seawater Dissolved Oxygen Batteries

doi:10.19894/j.issn.1000-0518.230332

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (5): 703-711.DOI: 10.19894/j.issn.1000-0518.230332

• Full Papers • Previous Articles Next Articles

Electrochemical Properties of Al-Ga-In-Sn-Si Alloy Anodes and Seawater Dissolved Oxygen Batteries

Hou-Ran WU¹^,², Chun-Ming HOU³, Ti-Gang DUAN²(), Li MA², Hai-Bing ZHANG², Jin-Tao WANG²

^1.State Key Laboratory of Advanced Technology for Materials Synthesis and Processing，Wuhan University of Technology，Wuhan 430070，China
^2.National Key Laboratory of Marine Corrosion and Protection，Luoyang Ship Material Research Institute，Qingdao 266237，China
^3.China Ship Scientific Research Center，Wuxi 214082，China

Received:2023-10-25 Accepted:2024-03-16 Published:2024-05-01 Online:2024-06-03
Contact: Ti-Gang DUAN
About author:duantigang@sunrui.net
Supported by:
the National Key R&D Progam of China(2022YFB3808800)

Abstract

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

CLC Number:

O646.6

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.

Figures/Tables 12

Fig.1 Structure design of seawater dissolved oxygen battery

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

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

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

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

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

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

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

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

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

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

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

References 35

1	TZENG Y C， CHEN R Y. The effect of the Zn content on the electrochemical performance of Al-Zn-Sn-Ga alloys［J］. Mater Chem Phys， 2023， 299： 127510.
2	ZHAO Q， ZHENG J X， DENG Y， et al. Regulating the growth of aluminum electrodeposits： towards anode-free Al batteries［J］. J Mater Chem A， 2020， 8（44）： 23231-23238.
3	冯壮壮，梅迪，朱世杰，等. 一次镁空气电池阳极材料研究进展［J］. 材料开发与应用， 2022， 37（6）： 12-21.
	FENG Z Z， MEI D， ZHU S J， et al. Research progress of anode materials for primary magnesium-air batteries［J］. Dev Appl Mater， 2022， 37（6）： 12-21.
4	ZHANG Z K， WANG Y B， WEI X F， et al. High energy efficiency and high discharge voltage of 2N-purity Al-based anodes for Al-air battery by simultaneous addition of Mn， Zn and Ga［J］. J Power Sources， 2023， 563： 232845.
5	WANG Y Y， LIU H L， JIA Z M， et al. The electrochemical performance of Al-Mg-Ga-Sn-xBi alloy used as the anodic material for Al-air battery in KOH electrolytes［J］. Crystals， 2022， 12（12）： 1785.
6	ABBAS M， SADAWY M， HOSNY A. Microstructure and electrochemical properties of Al-5Zn-0.2Sn-0.2Bi-xSb as a novel electrode for batteries applications［J］. J Alloys Compd， 2022， 923： 166303.
7	LIANG R， SU Y， SUI X L， et al. Effect of Mg content on discharge behavior of Al-0.05Ga-0.05Sn-0.05Pb-xMg alloy anode for aluminum-air battery［J］. J Solid State Electrochem， 2019， 23： 53-62.
8	ZHOU S G， TIAN C， ALZOABI S， et al. Performance of an Al-0.08Sn-0.08Ga-xMg alloy as an anode for Al-air batteries in alkaline electrolytes［J］. J Mater Sci， 2020， 55： 11477-11488.
9	WU Z B， ZHANG H T， GUO C， et al. Effects of indium， gallium， or bismuth additions on the discharge behavior of Al-Mg-Sn-based alloy for Al-air battery anodes in NaOH electrolytes［J］. J Solid State Electrochem， 2019， 23（8）： 2483-2491.
10	SUN Z G， LU H M. Performance of Al-0.5In as anode for Al-air battery in inhibited alkaline solutions［J］. J Electrochem Soc， 2015， 162（8）： A1617.
11	ZHANG H T， ZHENG Y Q， YIN G， et al. The influence of Ga， Sn， or Bi addition on the electrochemical behavior and discharge performance of Al-Zn-In anodes for Al-air batteries［J］. J Mater Sci， 2021， 56（18）： 11011-11026.
12	ZHUANG Z H， FENG Y， PENG C Q， et al. Effect of Ga on microstructure and electrochemical performance of Al-0.4Mg-0.05Sn-0.03Hg alloy as anode for Al-air batteries［J］. Trans Nonferrous Met Soc China， 2021， 31（9）： 2558-2569.
13	PARK I J， CHOI S R， KIM J G. Aluminum anode for aluminum-air battery-part Ⅱ： influence of In addition on the electrochemical characteristics of Al-Zn alloy in alkaline solution［J］. J Power Sources， 2017， 357： 47-55.
14	ZHANG C， WANG R C， FENG Y， et al. Effects of alloying elements on electrochemical performance of aluminum anodes［J］. J Cent South Univ Technol （Nat Sci）， 2012， 43（1）： 81-86.
15	HE J G， WEN J B， LI X D， et al. Influence of Ga and Bi on electrochemical performance of Al-Zn-Sn sacrificial anodes［J］. Trans Nonferrous Met Soc China， 2011， 21（7）： 1580-1586.
16	WANG Q， MIAO H， XUE Y J， et al. Performances of an Al-0.15Bi-0.15Pb-0.035Ga alloy as an anode for Al-air batteries in neutral and alkaline electrolytes［J］. RSC Adv， 2017， 7（42）： 25838-25847.
17	HERRAIZ-CARDONA I， ORTEGA E， PÉREZ-HERRANZ V. Impedance study of hydrogen evolution on Ni/Zn and Ni-Co/Zn stainless steel based electrodeposits［J］. Electrochim Acta， 2011， 56（3）： 1308-1315.
18	WU Z， ZHANG H， NAGAUMI H， et al. Effect of microstructure evolution on the discharge characteristics of Al-Mg-Sn-based anodes for Al-air batteries［J］. J Power Sources， 2022， 521： 230928.
19	WU Z B， ZHANG H T， ZOU J， et al. Effect of microstructure on discharge performance of Al-0.8Sn-0.05Ga-0.9Mg-1.0Zn （wt.%） alloy as anode for seawater-activated battery［J］. Mater Corros， 2020， 71（10）： 1680-1690.
20	ZHANG C， CAI Z Y， WANG R C， et al. Enhancing the electrochemical performance of Al-Mg-Sn-Ga alloy anode for Al-air battery by solution treatment［J］. J Electrochem Soc， 2021， 168（3）： 030519.
21	AN Q， HU H Y， LI N， et al. Strategies for improving flow rate control of hydrogen generated by Al-rich alloys for on-board applications［J］. Int J Hydrogen Energy， 2019， 44（51）： 27695-27703.
22	AN Q， GAO Q， WANG H C， et al. Insight into the indium-related morphology transformation and application for hydrogen production of Al-rich alloys［J］. J Alloys Compd， 2020， 842： 155864.
23	EVANS D S， PRINCE A. Thermal analysis of Ga-In-Sn system［J］. Met Sci， 1978， 12（9）： 411-414.
24	DAENEKE T， KHOSHMANESH K， MAHMOOD N， et al. Liquid metals： fundamentals and applications in chemistry［J］. Chem Soc Rev， 2018， 47（11）： 4073-4111.
25	XU S， ZHAO X， LIU J. Liquid metal activated aluminum-water reaction for direct hydrogen generation at room temperature［J］. Renewable Sustainable Energy Rev， 2018， 92： 17-37.
26	PANIAGUA ROJAS J， GONZáLEZ-HERNáNDEZ J E， CUBERO-SESIN J M， et al. Benchmarking of aluminum alloys processed by high-pressure torsion： Al-3%Mg alloy for high-energy density Al-air batteries［J］. Energy Fuels， 2023， 37（6）： 4632-4640.
27	SPERANDIO G F， SANTOS C M L， GALDINO A. Influence of silicon on the corrosion behavior of Al-Zn-In sacrificial anode［J］. J Mater Res Technol， 2021， 15： 614-622.
28	MA J J， WEN J B， REN F Z， et al. Electrochemical performance of Al-Mg-Sn based alloys as anode for Al-air battery［J］. J Electrochem Soc， 2016， 163（8）： A1759-A1764.
29	王金涛，段体岗，郭建章，等. 三维碳纤维基复合材料及其在海水溶解氧电池应用性能研究［J］. 材料导报， 2024， 38（4）： 218-223.
	WANG J T， DUAN T G， GUO J Z， et al. Three-dimensional carbon fiber matrix composites and application performance in seawater dissolved oxygen batteries［J］. Mater Rep， 2024， 38（4）： 218-223.
30	KAEWMANEEKUL T， LOTHONGKUM G. Effect of aluminium on the passivation of zinc-aluminium alloys in artificial seawater at 80 ℃［J］. Corros Sci， 2013， 66： 67-77.
31	ZHU C， YANG H X， WU A Q， et al. Modified alkaline electrolyte with 8-hydroxyquinoline and ZnO complex additives to improve Al-air battery［J］. J Power Sources， 2019， 432： 55-64.
32	WU Z B， ZHANG H T， ZOU J， et al. Enhancement of the discharge performance of Al-0.5Mg-0.1Sn-0.05Ga （wt.%） anode for Al-air battery by directional solidification technique and subsequent rolling process［J］. J Alloys Compd， 2020， 827： 154272.
33	WANG Q， MIAO H， XUE Y J， et al. Performances of an Al-0.15 Bi-0.15 Pb-0.035 Ga alloy as an anode for Al-air batteries in neutral and alkaline electrolytes［J］. RSC Adv， 2017， 7（42）： 25838-25847.
34	张一晗，张海兵，辛永磊，等. Al-Zn-In-Mg-Ti-Ga-Mn牺牲阳极在极地低温环境中的电化学性能［J］. 中国有色金属学报， 2023， 33（4）： 1209-1219.
	ZHANG Y H， ZHANG H B， XIN Y L， et al. Electrochemical performance of Al-Zn-ln-Mg-Ti-Ga-Mn sacrificial anode in polar low temperature environment［J］. Chin J Nonferrous Met， 2023， 33（4）： 1209-1219.
35	LI L， LIU H， YAN Y， et al. Effects of alloying elements on the electrochemical behaviors of Al-Mg-Ga-In based anode alloys［J］. Int J Hydrogen Energy， 2019， 44（23）： 12073-12084.

[1]	Dong-Yu ZHANG, Chun-Li WANG, Yong CHENG, Li-Min WANG. Research Progress of Antimony⁃Based Anode for Sodium/Potassium Ion Batteries： Failure Analysis and Solutions [J]. Chinese Journal of Applied Chemistry, 2024, 41(5): 616-636.
[2]	Rui-Yao WU, Dan-Dan OUYANG, Li-Li AI, An-Jie LIU, Hui ZHU, Xiao-Xin GAO, Jiao YIN. Research Progress of Biomass-Based Hard Carbon Anodes for Sodium-Ion Storage [J]. Chinese Journal of Applied Chemistry, 2024, 41(4): 496-511.
[3]	Sheng CHEN, Zu-Fei HU, Hong-Mei CAO, Zhen-Hua ZHAO, Yu-Dong ZHANG. Synthesis and Properties of Mg‑Doped Ni‑Rich Ternary Cathode Material LiNi_0.90Co_0.05Mn_0.05O₂ [J]. Chinese Journal of Applied Chemistry, 2024, 41(4): 568-576.
[4]	Ting-Ting GU, Ke ZHANG, Xin-Zhou ZHANG, Yang LIU, Wei-Cai SUN, Ai-Dong TAN, Jian-Guo LIU. Research Progress on Anodic Titanium‑Based Gas Diffusion Layer in Proton Exchange Membrane Electrolysis Cell [J]. Chinese Journal of Applied Chemistry, 2024, 41(3): 365-376.
[5]	Bing-Shuai CHEN, Hai-Tao ZHUO, Shu HUANG, Shao-Jun CHEN. Advances of High-Performance Polymer Binders for Silicon-Based Anodes [J]. Chinese Journal of Applied Chemistry, 2023, 40(5): 625-639.
[6]	Fang-Zheng HU, Xing GAO, Lei LIU, Tian-Heng YUAN, Ning CAO, Kai LI, Ya-Tao WANG, Jian-Hua LI, Hui-Qin LIAN, Xiao-Dong WANG, Xiu-Guo CUI. Advances in Black Phosphorus Anode Advantages and Optimization in Li-ion Battery Anodes [J]. Chinese Journal of Applied Chemistry, 2023, 40(4): 571-582.
[7]	Xue-Jian SHI, Wan-Qiang LIU, Chun-Li WANG, Yong CHENG, Li-Min WANG. Research Progress of Sb-based Anode Materials for Potassium Ion Batteries [J]. Chinese Journal of Applied Chemistry, 2023, 40(2): 210-228.
[8]	Jun-Ling MENG, Chuan TIAN, Na XU, Li-Na ZHAO, Hai-Xia ZHONG, Zhan-Lin XU. Research Progress of in Situ Exsolution of Electrode Surface of Solid Oxide Fuel Cells [J]. Chinese Journal of Applied Chemistry, 2023, 40(10): 1335-1346.
[9]	Fu-Yang WANG, Wei-Ming SONG, Li SUN, Jian FENG, Jun YE, Zhi-Qi YANG. Controllable Construction of Porous Nanocube FeSe₂/Graphene Composite for Efficient Na⁃Ion Storage [J]. Chinese Journal of Applied Chemistry, 2022, 39(5): 779-786.
[10]	Yu MENG, Qing ZHANG, Wen-Hao PENG, Xiao-Fei ZHU, De-Feng ZHOU. Preparation and Electrochemical Performance of Pr_0.8Sr_0.2Fe_0.7Ni_0.3O_3-_δ ⁃Pr_1.2Sr_0.8Ni_0.6Fe_0.4O₄₊_δ Composite Cathode [J]. Chinese Journal of Applied Chemistry, 2022, 39(5): 797-808.
[11]	Xiao-Feng WU, De-Shun CHEN, Wei MA, Ke-Ke HUANG. WO₃/Fe₂TiO₅ Composite Photoanode Deposited via Electrospray for Enhanced Photoelectrochemical Water Splitting [J]. Chinese Journal of Applied Chemistry, 2022, 39(4): 694-696.
[12]	Ya-Wei TANG, Lan-Lan XU, Xiao-Juan LIU. Effectively Improving the Electrocatalytic Activity of PrBaMn₂O₅₊_δ Anode by Doping Co， Ni and Fe [J]. Chinese Journal of Applied Chemistry, 2022, 39(10): 1543-1553.
[13]	CHENG Guang-Zeng, LIU Shuai, WANG Huan-Lei. Potential High-Performance Anode Material for Potassium Ion Batteries:Antimony [J]. Chinese Journal of Applied Chemistry, 2021, 38(2): 170-180.
[14]	WANG Jinying, QU Jiangying, LI Jielan, TANG Zhanlei, ZANG Yunhao, WANG Tao, GU Jianfeng, ZHOU Gang, GAO Feng. Two-Step Coating Synthesis of Silicon/Carbon Composite Based on Coal Tar Pitch and Its Lithium Battery Performance [J]. Chinese Journal of Applied Chemistry, 2020, 37(5): 562-569.
[15]	WANG Chunli,SUN Lianshan,ZHONG Ming,WANG Limin,CHENG Yong. Research Progress of Transition Metal and Compounds for Lithium-Sulfur Batteries [J]. Chinese Journal of Applied Chemistry, 2020, 37(4): 387-404.

Electrochemical Properties of Al-Ga-In-Sn-Si Alloy Anodes and Seawater Dissolved Oxygen Batteries

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 12

References 35

Related Articles 15

Recommended Articles

Metrics

Comments