İyileştirilmiş Isıl İletkenliğe Sahip Cu, Cu/Ag ve Ag Kaplamalar Yoluyla LaNi₅ Metal Hidritlerinin Hidrojen Depolama Performansının Artırılması

Abstract

Bu çalışma, üç farklı yüzey kaplaması uygulandıktan sonra hidrojen emilimi sırasında LaNi₅ alaşımının termal ve kütle transfer davranışlarını incelemektedir. Metal hidrit reaktör içindeki ısı transferini artırmak ve performansını değerlendirmek için üç reaktör konfigürasyonu geliştirilmiştir: bir referans tasarım, merkezi bir ısı borusu içeren bir tasarım ve ısı dağıtımını iyileştirmek için kanatçıklı bir ısı borusu ile donatılmış gelişmiş bir tasarım. LaNi₅ tozları mekanik öğütme kullanılarak bir saat boyunca öğütüldü ve ardından bakır kaplı, bakır/gümüş çift katmanlı kaplamalı ve gümüş kaplı numuneler üretmek için kontrollü koşullar altında kaplandı. Bulgular, homojen ve kararlı bir Cu/Ag dupleks kaplamanın LaNi₅ tozlarına başarıyla uygulanabileceğini göstermektedir. Bu, metal hidritlerin termal davranışını iyileştirerek hidrojen depolama sistemlerinde ısı transferini artırma potansiyeli sunmaktadır. Kaplanmamış ve kaplanmış tozların termal iletkenliği deneysel olarak ölçülmüştür. Deneyler, daha yüksek çalışma basınçlarının gelişmiş hidrojen emilimi ile sonuçlandığını doğrulamıştır. Geliştirilmiş termal iletkenlik, hidrojen emilimini hızlandırmakla kalmadı, aynı zamanda yerel sıcaklık artışlarını da azaltarak reaktör genelinde daha homojen bir sıcaklık dağılımı sağladı. Bu değerler daha sonra hidrojen emilim sürecini simüle etmek için üç boyutlu bir modelde kullanıldı. Bu model, hidrojenin depolama kapasitesini ve çeşitli çalışma basınçlarında (3, 6, 9, 10, 12 ve 15 bar) zaman içindeki sıcaklık dağılımını değerlendirdi. Isı boruları ve kanatçıkların kullanımı, reaktör içindeki ısı transferini önemli ölçüde artırarak genel performansı iyileştirdi.

Keywords

• Hidrojen depolama
• Metal hidrit reaktör
• LaNi5 alaşımları
• Isı borusu
• toz kaplama

Enhancing the Hydrogen Storage Performance of LaNi5 Metal Hydrides via Cu, Cu/Ag and Ag Coatings with Improved Thermal Conductivity

Abstract

This study investigates the thermal and mass transfer behaviors of the LaNi5 alloy during hydrogen absorption after applying three different surface coatings. To enhance heat transfer within the metal hydride reactor and evaluate its performance, three reactor designs were developed: a reference design, a design incorporating a central heat pipe, and an advanced design equipped with a finned heat pipe to improve heat distribution. LaNi5 powders were ground for one hour using mechanical milling and then coated under controlled conditions to produce copper-coated, Cu/Ag double-layer-coated, and silver-coated samples. The findings demonstrate that a homogeneous and stable Cu/Ag duplex coating can be successfully applied to LaNi5 powders. This offers the potential to enhance heat transfer in hydrogen storage systems by improving the thermal behavior of metal hydrides. The thermal conductivity of uncoated and coated powders was measured experimentally. Experiments confirmed that higher operating pressures resulted in improved hydrogen absorption. Not only did enhanced thermal conductivity accelerate hydrogen absorption, but it also reduced local temperature spikes, promoting a more uniform temperature distribution throughout the reactor. These values were then used in a three-dimensional model to simulate the hydrogen absorption process. This model assessed the storage capacity of hydrogen and the temperature distribution over time at various operating pressures (3, 6, 9, 10, 12, and 15 bar). Using heat pipes and fins significantly enhanced heat transfer within the reactor, resulting in improved overall performance.

Keywords

• Hydrogen storage
• Metal hydride reactor
• LaNi5 alloys
• Heat pipe
• Coating powders

References

1. [1] Bishnoi, A., Pati, S., Sharma P., “Architectural design of metal hydrides to improve the hydrogen storage characteristics”, Journal of Power Sources, 608:234609, (2024). DOI: https://doi.org/10.1016/J.JPOWSOUR.2024.234609
2. [2] Ang, B.W., Choong, W.L., Ng, T.S., “Energy security: Definitions, dimensions and indexes”, Renewable and Sustainable Energy Reviews 42:1077–1093, (2015). DOI: https://doi.org/10.1016/J.RSER.2014.10.064
3. [3] Atalmis, G., Demiralp, M., Yelegen, N., Kaplan, Y., “The effect of copper coated metal hydride at different ratios on the reaction kinetics”, International Journal of Hydrogen Energy, 48:23067–76, (2023). DOI: https://doi.org/10.1016/J.IJHYDENE.2022.12.078
4. [4] Andersson, J., Grönkvist, S., “Large-scale storage of hydrogen”, International Journal of Hydrogen Energy, 44:11901–19, (2019). DOI: https://doi.org/10.1016/J.IJHYDENE.2019.03.063
5. [5] Nakagawa, T., Inomata, A., Aoki, H., Miura, T., “Numerical analysis of heat and mass transfer characteristics in the metal hydride bed”, International Journal of Hydrogen Energy, 25:339–50, (2000). DOI: https://doi.org/10.1016/S0360-3199(99)00036-1
6. [6] Souahlia, A., Dhaou, H., Askri, F., Mellouli, S., Jemni, A., Ben Nasrallah, S., “Experimental study and characterization of metal hydride containers”, International Journal of Hydrogen Energy, 36:4952–7, (2011). DOI: https://doi.org/10.1016/J.IJHYDENE.2011.01.074
7. [7] Hua, T.Q., Roh, H.S., Ahluwalia, R.K., “Performance assessment of 700-bar compressed hydrogen storage for light duty fuel cell vehicles”, International Journal of Hydrogen Energy, 42:25121–9, (2017). DOI: https://doi.org/10.1016/J.IJHYDENE.2017.08.123
8. [8] Demirci, U.B., “Ammonia borane, a material with exceptional properties for chemical hydrogen storage”, International Journal of Hydrogen Energy, 42:9978–10013, (2017). DOI: https://doi.org/10.1016/J.IJHYDENE.2017.01.154

9. [9] Schlapbach, L., Züttel, A., “Hydrogen-storage materials for mobile applications”, Nature, 414:353–8, (2001). DOI: 2001;414:353–8. https://doi.org/10.1038/35104634
10. [10] Baetcke, L., Kaltschmitt, M., Hydrogen storage for mobile application: Technologies and their assessment, Hydrogen Supply Chains: Design, Deployment and Operation, Academic Press, p. 167–206, (2018). DOI: https://doi.org/10.1016/B978-0-12-811197-0.00005-1
11. [11] Sandrock, G., “A panoramic overview of hydrogen storage alloys from a gas reaction point of view”, Journal of Alloys and Compounds, 293–295:877–88, (1999). DOI: https://doi.org/10.1016/S0925-8388(99)00384-9
12. [12] Züttel, A., “Materials for hydrogen storage”, Materials Today, 6:24–33, (2003). DOI: https://doi.org/10.1016/S1369-7021(03)00922-2
13. [13] Lototskyy, M.V., Yartys, V.A., Pollet, B.G., Bowman, R.C., “Metal hydride hydrogen compressors: A review”, International Journal of Hydrogen Energy, 39:5818–51, (2014). DOI: https://doi.org/10.1016/J.IJHYDENE.2014.01.158
14. [14] Broom, D.P., Hydrogen Storage Materials: The Characterisation of Their Storage Properties 1st Edition, vol. 27, Springer Verlag, (2011). DOI: https://doi.org/10.1007/978-0-85729-221-6/COVER
15. [15] Rusman, N.A.A., Dahari, M., “A review on the current progress of metal hydrides material for solid-state hydrogen storage applications”, International Journal of Hydrogen Energy, 41:12108–26, (2016). DOI: https://doi.org/10.1016/J.IJHYDENE.2016.05.244
16. [16] Modibane, K.D., Lototskyy, M., Davids, M.W., Williams, M., Hato, M.J., Molapo, K.M., “Influence of co-milling with palladium black on hydrogen sorption performance and poisoning tolerance of surface modified AB₅-type hydrogen storage alloy”, Journal of Alloys and Compounds, 750:523–9, (2018). DOI: https://doi.org/10.1016/J.JALLCOM.2018.04.003
17. [17] Sharma, V.K., Anil Kumar, E., “Effect of measurement parameters on thermodynamic properties of La-based metal hydrides”, International Journal of Hydrogen Energy, 39:5888–98, (2014). DOI: https://doi.org/10.1016/J.IJHYDENE.2014.01.174
18. [18] Georgiadis, M.C., Kikkinides, E.S., Makridis, S.S., Kouramas, K., Pistikopoulos, E.N., “Design and Optimization of Advanced Materials and Processes for Efficient Hydrogen Storage”, Computer Aided Chemical Engineering, 26:183–8, (2009). DOI: https://doi.org/10.1016/S1570-7946(09)70031-8
19. [19] Singh, A., Maiya, M.P., Srinivasa Murthy, S., “Experiments on solid state hydrogen storage device with a finned tube heat exchanger”, International Journal of Hydrogen Energy, 42:15226–35, (2017). DOI: https://doi.org/10.1016/j.ijhydene.2017.05.002
20. [20] Elhamshri, F.A.M., Kayfeci, M., “Enhancement of hydrogen charging in metal hydride-based storage systems using heat pipe”, International Journal of Hydrogen Energy, 18927–38, (2019). DOI: https://doi.org/10.1016/j.ijhydene.2018.10.040
21. [21] Karmakar, A., Mallik, A., Gupta, N., Sharma, P., “Studies on 10 kg alloy mass metal hydride based reactor for hydrogen storage”, International Journal of Hydrogen Energy, 46:5495–506, (2021). DOI: https://doi.org/10.1016/j.ijhydene.2020.11.091
22. [22] Sunku prasad, J., Muthukumar, P., “Experimental investigation on annular metal hydride reactor for medium to large-scale hydrogen storage applications”, Journal of Energy Storage, 44:103473, (2021). DOI: https://doi.org/10.1016/j.est.2021.103473
23. [23] Elhamshri, F., Kayfeci, M., Matik, U., Alous, S., “Thermofluidynamic modelling of hydrogen absorption in metal hydride beds by using multiphysics software”, International Journal of Hydrogen Energy, 45:34956–71, (2020). DOI: https://doi.org/10.1016/J.IJHYDENE.2020.04.041
24. [24] Chandra, S., Sharma, P., Muthukumar, P., Sarma V Tatiparti, S., “Experimental hydrogen sorption study on a LaNi5-based 5 kg reactor with novel conical fins and water tubes and its numerical scale-up through a modular approach”, International Journal of Hydrogen Energy, 48:37872–85, (2023). DOI: https://doi.org/10.1016/j.ijhydene.2022.08.098
25. [25] Chandra, S., Sharma, P., Muthukumar, P., Sarma V. Tatiparti, S., “Modeling and numerical simulation of a 5 kg LaNi5-based hydrogen storage reactor with internal conical fins”, International Journal of Hydrogen Energy, 45:8794–809, (2020). DOI: https://doi.org/10.1016/j.ijhydene.2020.01.115
26. [26] Chibani, A., Dehane, A., Nemdili, L., Merouani, S., “Upscaling of LaNi5-based metal hydride reactor for solid-state hydrogen storage: numerical simulation of the absorption–desorption cyclic processes”, Green Approach to Alternative Fuel for a Sustainable Future, 257–69, (2023). DOI: https://doi.org/10.1016/B978-0-12-824318-3.00030-8
27. [27] Dashbabu, D., Kumar, E.A., Jain, I.P., “Thermodynamic analysis of a metal hydride hydrogen compressor with aluminium substituted LaNi5 hydrides”, International Journal of Hydrogen Energy, 48:37886–97, (2023). DOI: https://doi.org/10.1016/j.ijhydene.2022.09.094
28. [28] Afzal, M., Sharma, P., “Design of a large-scale metal hydride based hydrogen storage reactor: Simulation and heat transfer optimization”, International Journal of Hydrogen Energy, 43:13356–72, (2018). DOI: https://doi.org/10.1016/j.ijhydene.2018.05.084
29. [29] Afzal, M., Sharma, P., “Design and computational analysis of a metal hydride hydrogen storage system with hexagonal honeycomb based heat transfer enhancements-part A”, International Journal of Hydrogen Energy, 46:13116–30, (2021). DOI: https://doi.org/10.1016/j.ijhydene.2021.01.135
30. [30] Liu, W., Tupe, J.A., Aguey-Zinsou, K.F., “Metal Hydride Storage Systems: Approaches to Improve Their Performances”, Particle and Particle Systems Characterization, 42(3), (2025). DOI: https://doi.org/10.1002/ppsc.202400163
31. [31] Mellouli, S., Dhaou, H., Askri, F., Jemni, A., Ben Nasrallah, S., “Hydrogen storage in metal hydride tanks equipped with metal foam heat exchanger”, International Journal of Hydrogen Energy, 34:9393–401, (2009). DOI: https://doi.org/10.1016/j.ijhydene.2009.09.043
32. [32] Chung, C.A., Yang, S.W., Yang, C.Y., Hsu, C.W., Chiu, P.Y., “Experimental study on the hydrogen charge and discharge rates of metal hydride tanks using heat pipes to enhance heat transfer”, Applied Energy, 103:581–7, (2013). DOI: https://doi.org/10.1016/j.apenergy.2012.10.024
33. [33] Dhaou, H., Souahlia, A., Mellouli, S., Askri, F., Jemni, A., Ben Nasrallah, S., “Experimental study of a metal hydride vessel based on a finned spiral heat exchanger”, International Journal of Hydrogen Energy, 35:1674–80, (2010). DOI: https://doi.org/10.1016/j.ijhydene.2009.11.094
34. [34] Dhaou, H., Ben Khedher, N., Mellouli, S., Souahlia, A., Askri, F., Jemni, A., et al., “Improvement of thermal performance of spiral heat exchanger on hydrogen storage by adding copper fins”, International Journal of Thermal Sciences, 50:2536–42, (2011). DOI: https://doi.org/10.1016/j.ijthermalsci.2011.05.016
35. [35] Freni, A., Cipitì, F., Cacciola, G., “Finite element-based simulation of a metal hydride-based hydrogen storage tank”, International Journal of Hydrogen Energy, 34:8574–82, (2009). DOI: https://doi.org/10.1016/j.ijhydene.2009.07.118
36. [36] Kayfeci̇, M., Bedi̇r, F., Kurt, H., “Experimental investigation of the effects of vessel design and hydrogen charge pressure on metal hydride-based hydrogen storage parameters”, Journal of Thermal Science and Technology, 34:83–90, (2014). DOI: https://dergipark.org.tr/en/download/article-file/400540
37. [37] Singh, A., Maiya, M.P., Murthy, S.S., “Effects of heat exchanger design on the performance of a solid state hydrogen storage device”, International Journal of Hydrogen Energy, 40:9733–46, (2015). DOI: https://doi.org/10.1016/j.ijhydene.2015.06.015
38. [38] Eisapour, A.H., Fung, A.S., Shafaghat, A., Khosravi, K., “Enhancing hydrogen storage efficiency in metal hydride tanks through conical heat exchangers and phase change material integration”, International Journal of Hydrogen Energy, 109:1090–107, (2025). DOI: https://doi.org/10.1016/j.ijhydene.2025.02.146
39. [39] Muthukumar, P., Singhal, A., Bansal, G.K., “Thermal modeling and performance analysis of industrial-scale metal hydride based hydrogen storage container”, International Journal of Hydrogen Energy, 37:14351–64, (2012). DOI: https://doi.org/10.1016/j.ijhydene.2012.07.010
40. [40] Anbarasu, S., Muthukumar, P., Mishra, S.C., “Thermal modeling of LmNi4.91Sn0.15 based solid state hydrogen storage device with embedded cooling tubes”, International Journal of Hydrogen Energy, 39:15549–62, (2014). DOI: https://doi.org/10.1016/j.ijhydene.2014.07.088
41. [41] Oi, T., Maki, K., Sakaki, Y., “Heat transfer characteristics of the metal hydride vessel based on the plate-fin type heat exchanger”, Journal of Power Sources, 125:52–61, (2004). DOI: https://doi.org/10.1016/S0378-7753(03)00822-X
42. [42] Atalmis, G., Toros, S., Timurkutluk, B., Kaplan, Y., “Effect of expanded natural graphite addition and copper coating on reaction kinetics and hydrogen storage characteristics of metal hydride reactors”, International Journal of Hydrogen Energy, 53:647–56, (2024). DOI: https://doi.org/10.1016/j.ijhydene.2023.12.147
43. [43] Atalmis, G., Toros, S., Timurkutluk, B., Kaplan, Y., “2D-axisymmetrical modeling and experimental study of hydrogen absorption in copper coated metal hydride”, International Journal of Hydrogen Energy, 48:38400–11, (2023). DOI: https://doi.org/10.1016/j.ijhydene.2023.06.091
44. [44] Kim, S.W., Kim, K.J., “Hydrogen storage with annular LaNi5 metal hydride pellets”, Advanced Materials Research, 875–877:1671–5, (2014). DOI: https://doi.org/10.4028/www.scientific.net/AMR.875-877.1671
45. [45] Kim, K.J., Feldman, K.T., Lloyd, G., Razani, A., Shanahan, K.L., “Performance of high power metal hydride reactors”, International Journal of Hydrogen Energy, 23:355–62, (1998). DOI: https://doi.org/10.1016/S0360-3199(97)00058-X
46. [46] Kim, K.J., Lloyd, G., Razani, A., Feldman, K.T., “Development of LaNi5/Cu/Sn metal hydride powder composites”, Powder Technology, 99:40–5, (1998). DOI: https://doi.org/10.1016/S0032-5910(98)00088-6
47. [47] Lee, M., Kim, K.J., Hopkins, R.R., Gawlik, K., “Thermal conductivity measurements of copper-coated metal hydrides (LaNi5, Ca0.6Mm0.4Ni5, and LaNi4.75Al0.25) for use in metal hydride hydrogen compression systems”, International Journal of Hydrogen Energy, 34:3185–90, (2009). DOI: https://doi.org/10.1016/j.ijhydene.2009.01.078
48. [48] Zhang, B., Wu, W., Yin, S., Li, S., Luo, Y., Bian, X., et al., “Process optimization of electroless copper plating and its influence on electrochemical properties of AB5-type hydrogen storage alloy”, Journal of Rare Earths, 28:922–6, (2010). DOI: https://doi.org/10.1016/S1002-0721(09)60221-0
49. [49] Ambrosio, R.C., Ticianelli, E.A., “Electrochemical and X-ray absorption spectroscopy studies of copper coatings on a hydrogen storage alloy”, Journal of Electroanalytical Chemistry, 574:251–60, (2005). DOI: https://doi.org/10.1016/j.jelechem.2004.08.006
50. [50] Kim, J.K., Park, I.S., Kim, K.J., Gawlik, K., “A hydrogen-compression system using porous metal hydride pellets of LaNi5-xAlₓ”, International Journal of Hydrogen Energy, 33:870–7, (2008). DOI: https://doi.org/10.1016/j.ijhydene.2007.10.027
51. [51] Deng, C., Shi, P., Zhang, S., “Effect of surface modification on the electrochemical performances of LaNi5 hydrogen storage alloy in Ni/MH batteries”, Materials Chemistry and Physics, 98:514–8, (2006). DOI: https://doi.org/10.1016/j.matchemphys.2005.09.083
52. [52] Romanov, I.A., Borzenko, V.I., Kazakov, A.N., “Influence of high thermal conductivity addition on PCT-isotherms of hydrogen storage alloy”, Journal of Physics: Conference Series, 1128:012105, (2018). DOI: https://iopscience.iop.org/article/10.1088/1742-6596/1128/1/012105
53. [53] Kukkapalli, V.K., Kim, S., Thomas, S.A., “Thermal Management Techniques in Metal Hydrides for Hydrogen Storage Applications: A Review”, Energies, 16:3444, (2023). DOI: https://doi.org/10.3390/en16083444
54. [54] Aliofkhazraei, M., Walsh, F.C., Zangari, G., Köçkar, H., Alper, M., Rizal, C., et al., “Development of electrodeposited multilayer coatings: A review of fabrication, microstructure, properties and applications”, Applied Surface Science Advances, 6, (2021). DOI: https://doi.org/10.1016/j.apsadv.2021.100141
55. [55] Cahill, D.G., Ford, W.K., Goodson, K.E., Mahan, G.D., Majumdar, A., Maris, H.J., et al., “Nanoscale thermal transport”, Journal of Applied Physics, 93:793–818, (2003). DOI: https://doi.org/10.1063/1.1524305
56. [56] Nasrallah, S Ben., Jemni, A., “Heat and mass transfer models in metal-hydrogen reactor”, International Journal Hydrogen Energy, 22:67–76, (1997). DOI: https://doi.org/10.1016/S0360-3199(96)00039-0
57. [57] Jemni, A., Nasrallah, S Ben., “Study of two-dimensional heat and mass transfer during absorption in a metal-hydrogen reactor”, International Journal of Hydrogen Energy, 20:43–52, (1995). DOI: https://doi.org/10.1016/0360-3199(93)E0007-8
58. [58] Elhamshri, F., “Experimental and numerical investigations of effect of a heat pipe in the metal hydride tank for the hydriding process”, Doctoral Thesis, Karabük University, Institute of Graduate Programs, (2019).
59. [59] Dimitrov, N., “Recent Advances in the Growth of Metals, Alloys, and Multilayers by Surface Limited Redox Replacement (SLRR) Based Approaches”, Electrochimica Acta, 209:599–622, (2016). DOI: https://doi.org/10.1016/j.electacta.2016.05.115