Anodic protection enables moisture-stable Mg3(Sb, Bi)2 for thermoelectric cooling
Source abstract
Abstract
Mg3(Sb, Bi)2 is the most promising candidate as a next-generation thermoelectric cooling material; however, its application is bottlenecked by poor moisture stability. We demonstrate a protection strategy for Mg3(Sb, Bi)2 by constructing anodic phases that are preferentially corroded to protect the cathodic material matrix, as enabled by the in situ formation of uniformly distributed multiscale anodic phases based on a large Pilling-Bedworth ratio, low equilibrium potential, high chemical inertness and rapid oxide/hydroxide coverage ability. Mg17Al12 preferentially corrodes and promotes the formation of a protective film, reducing the average corrosion rate of Mg3(Sb, Bi)2 by 92% to ~95 μm year-1 in air and 86% to ~0.36 μm h-1 in water, achieving excellent corrosion resistance. The cooling performance of the fabricated module is comparable with that of commercial bismuth telluride modules at 300 K, and exceeds them at 325 K and 350 K. Meanwhile, no performance degradation is observed after 28-day aging at 350 K and 70% relative humidity. Our study addresses the issues of moisture stability of Mg3(Sb, Bi)2 during storage, processing and application, and could be extended to other aqueous vapour-sensitive materials.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Advanced Thermoelectric Materials and Devices · Thermal Expansion and Ionic Conductivity · Thermal Radiation and Cooling Technologies
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (54)
Show source-provided references
1. Bian, L. et al. Observation of micro-droplets on metal surface in early atmospheric corrosion. Electrochem. Commun. 7, 1033–1038 (2005).10.1016/j.elecom.2005.06.016 ↗
2. Xu, N. et al. Laboratory observation of dew formation at an early stage of atmospheric corrosion of metals. Corros. Sci. 44, 163–170 (2002).10.1016/S0010-938X(01)00018-X ↗
3. Xu, C. et al. Device-level optimization of n-type Mg3(Sb, Bi)2-based thermoelectric modules toward applications: a perspective. Adv. Funct. Mater. 33, 2304173 (2023).10.1002/adfm.202304173 ↗
4. Yang, J. et al. Next-generation thermoelectric cooling modules based on high-performance Mg3(Bi,Sb)2 material. Joule 6, 193–204 (2022).10.1016/j.joule.2021.11.008 ↗
5. Li, J. W. et al. Wide-temperature-range thermoelectric n-type Mg3(Sb,Bi)2 with high average and peak zT values. Nat. Commun. 14, 7428 (2023).10.1038/s41467-023-43228-9 ↗
6. Mao, J. et al. High thermoelectric cooling performance of n-type Mg3Bi2-based materials. Science 365, 495–498 (2019).10.1126/science.aax7792 ↗
7. Zhao, P. et al. Plasticity in single-crystalline Mg3Bi2 thermoelecric material. Nature 631, 777–782 (2024).10.1038/s41586-024-07621-8 ↗
8. Mishra, P. et al. First-principles prediction of electrochemical polarization and mechanical behavior in Mg based intermetallics. Comput. Mater. Sci. 214, 111667 (2022).10.1016/j.commatsci.2022.111667 ↗
9. Luo, Z. et al. Theoretical analysis of the galvanic corrosion behavior of Mg-Ge binary alloy. J. Electrochem. Soc. 166, C421–C427 (2019).10.1149/2.1061913jes ↗
10. Wang, Y. et al. First-principles study of water decomposition and hydrogen evolution on MgZn2 Laves phase. Comput. Mater. Sci. 196, 110532 (2021).10.1016/j.commatsci.2021.110532 ↗
11. Zhu, Q. et al. Towards development of a high-strength stainless Mg alloy with Al-assisted growth of passive film. Nat. Commun. 13, 5838 (2022).10.1038/s41467-022-33480-w ↗
12. Liu, H. et al. Review of the atmospheric corrosion of magnesium alloys. J. Mater. Sci. Technol. 35, 2003–2016 (2019).10.1016/j.jmst.2019.05.001 ↗
13. Li, A. et al. Chemical stability and degradation mechanism of Mg3Sb2–xBix thermoelectrics towards room-temperature applications. Acta Mater. 239, 118301 (2022).10.1016/j.actamat.2022.118301 ↗
14. Song, G.-L. et al. Recently deepened insights regarding Mg corrosion and advanced engineering applications of Mg alloys. J. Magnes. Alloy. 11, 3948–3991 (2023).10.1016/j.jma.2023.08.012 ↗
15. Wu, X. et al. Revealing the chemical instability of Mg3Sb2–xBix-based thermoelectric materials. ACS Appl. Mater. Interfaces 15, 50216–50224 (2023).10.1021/acsami.3c12290 ↗
16. Choy, K. L. Chemical vapour deposition of coatings. Prog. Mater Sci. 48, 57–170 (2003).10.1016/S0079-6425(01)00009-3 ↗
17. Wu, X. et al. Interface and surface engineering realized high efficiency of 13% and improved thermal stability in Mg3Sb1.5Bi0.5-based thermoelectric generation devices. Adv. Energy Mater. 12, 2203039 (2022).10.1002/aenm.202203039 ↗
18. Ou, Y. X. et al. Recent advances and strategies for high-performance coatings. Prog. Mater Sci. 136, 101125 (2023).10.1016/j.pmatsci.2023.101125 ↗
19. Yoon, J. et al. Wet-style superhydrophobic antifogging coatings for optical sensors. Adv. Mater. 32, e2002710 (2020).10.1002/adma.202002710 ↗
20. Duarte, M. J. et al. Element-resolved corrosion analysis of stainless-type glass-forming steels. Science 341, 372–376 (2013).10.1126/science.1230081 ↗
21. Williams, D. E. et al. Passivity breakdown and pitting corrosion of binary alloys. Nature 350, 216–219 (1991).10.1038/350216a0 ↗
22. Sedriks, A. J. et al. Electrochemical behavior of Ti-Ni alloys in acidic chloride solutions. Corrosion 28, 137–142 (1972).10.5006/0010-9312-28.4.137 ↗
23. Tian, H. et al. Steel anti-corrosion strategy enables long-cycle Zn anode. Adv. Energy Mater. 13, 2202603 (2022).10.1002/aenm.202202603 ↗
24. Wu, Y. et al. State of the art and current trends on the metal corrosion and protection strategies in deep sea. J. Mater. Sci. Technol. 215, 192–213 (2025).10.1016/j.jmst.2024.07.026 ↗
25. Xu, C. et al. Pilling-Bedworth ratio for oxidation of alloys. Mater. Res. Innovations 3, 231–235 (2000).10.1007/s100190050008 ↗
26. Greenwood, N. N. et al. Chemistry of the Elements 2nd edn (Elsevier, 2012).
27. Dean, J. A. Lange’s Handbook of Chemistry 15th edn (McGraw-Hill, 1999).
28. Xie, L. et al. Screening strategy for developing thermoelectric interface materials. Science 382, 921–928 (2023).10.1126/science.adg8392 ↗
29. Yin, L. et al. CALPHAD accelerated design of advanced full-Zintl thermoelectric device. Nat. Commun. 15, 1468 (2024).10.1038/s41467-024-45869-w ↗
30. Tamaki, H. et al. Isotropic conduction network and defect chemistry in Mg3+δSb2-based layered Zintl compounds with high thermoelectric performance. Adv. Mater. 28, 10182–10187 (2016).10.1002/adma.201603955 ↗
31. Saal, J. E. et al. Materials design and discovery with high-throughput density functional theory: the Open Quantum Materials Database (OQMD). JOM 65, 1501–1509 (2013).10.1007/s11837-013-0755-4 ↗
32. Kirklin, S. et al. The Open Quantum Materials Database (OQMD): assessing the accuracy of DFT formation energies. npj Comput. Mater. 1, 15010 (2015).10.1038/npjcompumats.2015.10 ↗
33. Wang, S. et al. Electrochemical impedance spectroscopy. Nat. Rev. Methods Primers 1, 41 (2021).10.1038/s43586-021-00039-w ↗
34. Collins, L. et al. Towards nanoscale electrical measurements in liquid by advanced KPFM techniques: a review. Rep. Prog. Phys. 81, 086101 (2018).10.1088/1361-6633/aab560 ↗
35. Yan, Y. et al. Corrosion behavior of stainless steel-tungsten carbide joints brazed with AgCuX (X = In, Ti) alloys. Corros. Sci. 200, 110231 (2022).10.1016/j.corsci.2022.110231 ↗
36. Liu, J. et al. The special role of anodic second phases in the micro-galvanic corrosion of EW75 Mg alloy. Electrochim. Acta 189, 190–195 (2016).10.1016/j.electacta.2015.12.075 ↗
37. Song, Y. et al. Pitting corrosion of a rare earth Mg alloy GW93. J. Mater. Sci. Technol. 33, 954–960 (2017).10.1016/j.jmst.2017.01.014 ↗
38. Santamaria, M. et al. Initial surface film on magnesium metal: a characterization by X-ray photoelectron spectroscopy (XPS) and photocurrent spectroscopy (PCS). Electrochim. Acta 53, 1314–1324 (2007).10.1016/j.electacta.2007.03.019 ↗
39. Naumkin, A. V. et al. NIST X-ray Photoelectron Spectroscopy Database (National Institute of Standards and Technology, 2008).
40. Zhang, F. et al. Corrosion resistance of Mg-Al-LDH coating on magnesium alloy AZ31. Surf. Coat. Technol. 258, 1152–1158 (2014).10.1016/j.surfcoat.2014.07.017 ↗
41. Esmaily, M. et al. Fundamentals and advances in magnesium alloy corrosion. Prog. Mater Sci. 89, 92–193 (2017).10.1016/j.pmatsci.2017.04.011 ↗
42. Guo, L. et al. Layered double hydroxide coatings on magnesium alloys: a review. J. Mater. Sci. Technol. 34, 1455–1466 (2018).10.1016/j.jmst.2018.03.003 ↗
43. Song, G. Recent progress in corrosion and protection of magnesium alloys. Adv. Eng. Mater. 7, 563–586 (2005).10.1002/adem.200500013 ↗
44. Qu, N. et al. Interfacial design contributing to high conversion efficiency in Mg3(Sb, Bi)2/Bi2Te3 thermoelectric module with superior stability. Adv. Energy Mater. 14, 2302818 (2023).10.1002/aenm.202302818 ↗
45. Uhlig, H. H. & Revie, R. W. Corrosion and Corrosion Control 3rd edn (Wiley, 1985).
46. Chen, N. et al. Improved figure of merit (z) at low temperatures for superior thermoelectric cooling in Mg3(Bi,Sb)2. Nat. Commun. 14, 4932 (2023).10.1038/s41467-023-40648-5 ↗
47. Zhang, X. et al. High-performance MgAgSb/Mg3(Sb,Bi)2-based thermoelectrics with η = 12% at T ≤ 583K. Joule 8, 3324–3335 (2024).10.1016/j.joule.2024.08.013 ↗
48. Ma, X. et al. Elevating thermoelectric performance in the sub-ambient temperature range for electronic refrigeration. Innovation 6, 100864 (2025).
49. Liu, Z. et al. Maximizing the performance of n-type Mg3Bi2 based materials for room-temperature power generation and thermoelectric cooling. Nat. Commun. 13, 1120 (2022).10.1038/s41467-022-28798-4 ↗
50. Zhang, Q. et al. Enhancing Mg3(Bi, Sb)2 thermoelectric performance via ZrSb1–x modified grain-boundary. Mater. Today Phys. 54, 101733 (2025).10.1016/j.mtphys.2025.101733 ↗
51. Ying, P. et al. A robust thermoelectric module based on MgAgSb/Mg3(Sb,Bi)2 with a conversion efficiency of 8.5% and a maximum cooling of 72 K. Energy Environ. Sci. 15, 2557–2566 (2022).10.1039/D2EE00883A ↗
52. Liu, Y. et al. Mg compensating design in the melting-sintering method for high-performance Mg3(Bi, Sb)2 thermoelectric devices. Small 19, 2303840 (2023).10.1002/smll.202303840 ↗
53. Xu, W. et al. Amorphous carbon-modulated Mg3(Bi,Sb)2 and electron-poor CdSb for ultralow-cost Te-free refrigeration modules. Adv. Funct. Mater. 35, 2414194 (2024).10.1002/adfm.202414194 ↗
54. Xie, L. et al. Highly efficient thermoelectric cooling performance of ultrafine-grained and nanoporous materials. Mater. Today 65, 5–13 (2023).10.1016/j.mattod.2023.03.021 ↗