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Inhibiting effect of tin additives on the solid-phase conversion of PbSO4 to PbO2

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Abstract

Stannous sulfate is commonly used as an additive in the positive lead pastes of lead-acid batteries, but its real function and mechanism are still vague and need further study. The present work investigates the intrinsic effects of tin additives on the positive electrode performance under well-controlled experimental conditions. The tin additives are added in three ways: the SnSO4 dissolved in 4.5 M H2SO4 electrolyte, the metal Sn melted in metal Pb substrate, and the SnSO4 mixed in homemade industrial lead pastes. A series of evolutions are clearly revealed in structure, composition, and redox activity of the positive active materials with the content of Sn. Both the SnSO4 in the electrolyte and in the positive lead pastes have a significant inhibiting effect on the transformation between PbSO4 and PbO2, leading to a decrease in the charge/discharge capacities with increasing content of SnSO4. A similar but weaker inhibiting effect was also found for the Sn melted in the Pb-Sn alloys. The SnSO4 has a significant enhancement effect on the grain size of PbSO4/PbO2, which increases the resistance of the solid-phase transformation deep inside the grains during the charge/discharge. All these results do not support the use of SnSO4 in the positive pastes of lead-acid batteries.

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References

  1. Lopes PP, Stamenkovic VR (2020) Past, present, and future of lead-acid batteries. Science 369:923–924

    Article  CAS  PubMed  Google Scholar 

  2. Hu J, Yang F, Lai C, Wang H, Sun J, Zhou H, Ji S, Lei L (2022) Researches on a conductive polyaniline-acetylene black composite to suppress the hydrogen evolution reaction in lead-acid batteries. J Solid State Electrochem 26:1153–1161

    Article  CAS  Google Scholar 

  3. Yang J, Zhang C, Zhang H, Li F, Yang F, Ji S, Lei L (2020) Fabrication of PbSO4 negative electrode of lead-acid battery with high performance. J Solid State Electrochem 24:2555–2560

    Article  CAS  Google Scholar 

  4. Zan X, Zhang D (2022) Analysis on the optimal recycling path of Chinese lead-acid battery under the extended producer responsibility system. Sustainability 14:4950

    Article  CAS  Google Scholar 

  5. Varshney K, Varshney PK, Gautam K, Tanwar M, Chaudhary M (2020) Current trends and future perspectives in the recycling of spent lead acid batteries in India. Mater Today 26:592–602

    CAS  Google Scholar 

  6. Yang S, Li R, Cai X, Xue K, Yang B, Hu X, Dai C (2018) Enhanced cycle performance and lifetime estimation of lead-acid batteries. New J Chem 42:8900–8904

    Article  CAS  Google Scholar 

  7. Saoudi O, Matrakova M, Aleksandrova A, Zerroual L (2020) Electrochemical behavior of PbO2/PbSO4 electrode in the presence of surfactants in electrolyte. Arab J Chem 13:5326–5331

    Article  CAS  Google Scholar 

  8. Prengaman RD (2001) Challenges from corrosion-resistant grid alloys in lead acid battery manufacturing. J Power Sources 95:224–233

    Article  CAS  Google Scholar 

  9. Hao H (2018) A review of the positive electrode additives in lead-acid batteries. Int J Electrochem Sci 13:2329–2340

    Article  CAS  Google Scholar 

  10. Paglietti A (2016) Electrolyte additive concentration for maximum energy storage in lead-acid batteries. Batteries 2:36

    Article  Google Scholar 

  11. Wang Q, Liu J, Yang D, Yuan X, Li L, Zhu X, Zhang W, Hu Y, Sun X, Liang S, Hu J, Kumar RV, Yang J (2015) Stannous sulfate as an electrolyte additive for lead acid battery made from a novel ultrafine leady oxide. J Power Sources 285:485–492

    Article  CAS  Google Scholar 

  12. Hong B, Jiang L, Xue H, Liu F, Jia M, Li J, Liu Y (2014) Characterization of nano-lead-doped active carbon and its application in lead-acid battery. J Power Sources 270:332–341

    Article  CAS  Google Scholar 

  13. Deyab MA, Mohsen Q (2021) Controlling the corrosion and hydrogen gas liberation inside lead-acid battery via PANI/Cu-Pp/CNTs nanocomposite coating (in eng). Sci Rep 11:9507

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  14. Mandal S, Thangarasu S, Thong PT, Kim S-C, Shim J-Y, Jung H-Y (2021) Positive electrode active material development opportunities through carbon addition in the lead-acid batteries: a recent progress. J Power Sources 485:229336

    Article  CAS  Google Scholar 

  15. Marom R, Ziv B, Banerjee A, Cahana B, Luski S, Aurbach D (2015) Enhanced performance of starter lighting ignition type lead-acid batteries with carbon nanotubes as an additive to the active mass. J Power Sources 296:78–85

    Article  CAS  Google Scholar 

  16. Lach J, Wróbel K, Wróbel J, Podsadni P, Czerwiński A (2019) Applications of carbon in lead-acid batteries: a review. J Solid State Electrochem 23:693–705

    Article  CAS  Google Scholar 

  17. Broda B, Inzelt G (2020) Studying the effects of bismuth on the electrochemical properties of lead dioxide layers by using the in situ EQCM technique. J Solid State Electrochem 24:2733–2739

    Article  CAS  Google Scholar 

  18. Ponraj R, McAllister SD, Cheng IF, Edwards DB (2009) Investigation on electronically conductive additives to improve positive active material utilization in lead-acid batteries. J Power Sources 189:1199–1203

    Article  CAS  Google Scholar 

  19. Newell JD, Patankar SN, Edwards DB (2009) Porous microspheres as additives in lead–acid batteries. J Power Sources 188:292–295

    Article  CAS  Google Scholar 

  20. Wang L-F, Fang B-J, Lin Y-K, Chen J-S (2006) Investigation of silica additive for high-rate sealed lead-acid cells. Electrochim Acta 51:4135–4141

    Article  CAS  Google Scholar 

  21. Vangapally N, Gaffoor SA, Martha SK (2017) Na2EDTA chelating agent as an electrolyte additive for high performance lead-acid batteries. Electrochim Acta 258:1493–1501

    Article  CAS  Google Scholar 

  22. Yang B, Cai X, Li E, Yang S, Liu W, Dai C, Yin G (2019) Evaluation of the effect of additive group five elements on the properties of Pb-Ca-Sn-Al alloy as the positive grid for lead-acid batteries. J Solid State Electrochem 23:1715–1725

    Article  CAS  Google Scholar 

  23. Lang X, Wang D, Hu C, Tang S, Zhu J, Guo C (2014) The use of nanometer tetrabasic lead sulfate as positive active material additive for valve regulated lead-acid battery. J Power Sources 270:9–13

    Article  CAS  Google Scholar 

  24. Fan Z (2018) Tetrabasic lead sulphate micro-rods as positive active material for lead acid battery. Int J Electrochem Sci 13:6083–6097

    Article  CAS  Google Scholar 

  25. Wei G-L, Wang J-R (1994) Electrochemical behaviour of SnSO4 in sulfuric acid solution. J Power Sources 52:81–85

    Article  CAS  Google Scholar 

  26. Hariprakash B, Mane AU, Martha SK, Gaffoor SA, Shivashankar SA, Shukla AK (2004) Improved lead-acid cells employing tin oxide coated Dynel fibres with positive active-material. J Appl Electrochem 34:1039–1044

    Article  CAS  Google Scholar 

  27. Pavlov D, Dimitrov M, Petkova G, Giess H, Gnehm C (1995) The effect of selenium on the electrochemical behavior and corrosion of Pb-Sn alloys used in lead-acid batteries. J Electrochem Soc 142:2919–2927

    Article  CAS  Google Scholar 

  28. Peixoto LC, Osório WR, Garcia A (2010) The interrelation between mechanical properties, corrosion resistance and microstructure of Pb-Sn casting alloys for lead-acid battery components. J Power Sources 195:621–630

    Article  CAS  Google Scholar 

  29. Zhang Y, Zhou C-g, Yang J, Xue S-c, Gao H-l, Yan X-h, Huo Q-y, Wang S-w, Cao Y, Yan J, Gao K-z, Wang L-x (2022) Advances and challenges in improvement of the electrochemical performance for lead-acid batteries: a comprehensive review. J Power Sources 520:230800

    Article  CAS  Google Scholar 

  30. Broda B, Inzelt G (2020) Investigation of the electrochemical behaviour of lead dioxide in aqueous sulfuric acid solutions by using the in situ EQCM technique. J Solid State Electrochem 24:1–10

    Article  CAS  Google Scholar 

  31. Zhang B, Zhong J, Zhang B, Cheng Z (2011) Mechanism of formation of anodic excursion peaks on lead electrode in sulfuric acid. J Power Sources 196:5719–5724

    Article  CAS  Google Scholar 

  32. Zhang B, Zhong J, Li W, Dai Z, Zhang B, Cheng Z (2010) Transformation of inert PbSO4 deposit on the negative electrode of a lead-acid battery into its active state. J Power Sources 195:4338–4343

    Article  CAS  Google Scholar 

  33. Visscher W (1976) Cyclic voltammetry on lead electrodes in sulphuric acid solution. J Power Sources 1:257–266

    Article  Google Scholar 

  34. Zen-ichiro T, Kiyoshi K (1987) The oxidation of PbSO4 to PbO2 in sulfuric acid solution. B Chem Soc Jpn 60:1567–1572

    Article  Google Scholar 

  35. Tan Z, Wang Z, Zhang S, Bai S, Zhang D, Jin Y, Xing S (2021) Corrosion behavior of X80 pipeline steel local defect pits under static liquid film. Sci Rep 11:20755

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  36. Gao H, He J-B, Wang Y, Deng N (2012) Advantageous combination of solid carbon paste and a conducting polymer film as a support of platinum electrocatalyst for methanol fuel cell. J Power Sources 205:164–172

    Article  CAS  Google Scholar 

  37. Zhao M-J, Li E-M, Deng N, Hu Y, Li C-X, Li B, Li F, Guo Z-G, He J-B (2022) Indirect electrodeposition of a NiMo@Ni(OH)2MoOx composite catalyst for superior hydrogen production in acidic and alkaline electrolytes. Renew Energy 191:370–379

    Article  CAS  Google Scholar 

  38. Rocca E, Steinmetz J, Weber S (1999) Mechanism of formation of dense anodic films of PbO on lead and lead alloys in sulfuric acid: use of an 18O tracer. J Electrochem Soc 146:54–58

    Article  CAS  Google Scholar 

  39. He X-D, Xu F, Li F, Liu L, Wang Y, Deng N, Zhu Y-W, He J-B (2017) Composition-performance relationship of NixCuy nanoalloys as hydrogen evolution electrocatalyst. J Electroanal Chem 799:235–241

    Article  CAS  Google Scholar 

  40. Liu L, Zha D-W, Wang Y, He J-B (2014) A nitrogen- and sulfur-rich conductive polymer for electrocatalytic evolution of hydrogen in acidic electrolytes. Int J Hydrogen Energy 39:14712–14719

    Article  CAS  Google Scholar 

  41. Müller JT, Urban PM, Hölderich WF (1999) Impedance studies on direct methanol fuel cell anodes. J Power Sources 84:157–160

    Article  Google Scholar 

  42. Liu B, He J-B, Chen Y-J, Wang Y, Deng N (2013) Phytic acid-coated titanium as electrocatalyst of hydrogen evolution reaction in alkaline electrolyte. Int J Hydrogen Energy 38:3130–3136

    Article  CAS  Google Scholar 

  43. Danaee I, Jafarian M, Forouzandeh F, Gobal F, Mahjani MG (2009) Electrochemical impedance studies of methanol oxidation on GC/Ni and GC/NiCu electrode (in English). Int J Hydrogen Energy 34:859–869

    Article  CAS  Google Scholar 

  44. Bavykin DV, Friedrich JM, Walsh FC (2006) Protonated titanates and TiO2 nanostructured materials: synthesis, properties, and applications. Adv Mater 18:2807–2824

    Article  CAS  Google Scholar 

  45. Li Y, Yang X-Y, Feng Y, Yuan Z-Y, Su B-L (2012) One-dimensional metal oxide nanotubes, nanowires, nanoribbons, and nanorods: synthesis, characterizations, properties and applications. Crit Rev Solid State Mater Sci 37:1–74

    Article  Google Scholar 

  46. Osório WR, Peixoto LC, Garcia A (2009) Electrochemical corrosion of Pb-1wt% Sn and Pb-2.5wt% Sn alloys for lead-acid battery applications. J Power Sources 194:1120–1127

    Article  Google Scholar 

  47. He J-B, Lu D-Y, Jin G-P (2006) Potential dependence of cuprous/cupric duplex film growth on copper electrode in alkaline media. Appl Surf Sci 253:689–697

    Article  CAS  Google Scholar 

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Funding

This work was supported by the Open Funds of Anhui Province Key Laboratory of Green Manufacturing of Power Battery, Tianneng Battery Group, China (No. W2021JSFW0218).

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei, 230009, People’s Republic of China

    Er-Mei Li, Li Zhu, Bing Li, Fang Li, Ning Deng & Jian-Bo He

  2. Anhui Province Key Laboratory of Green Manufacturing of Power Battery, Tianneng, Jieshou, 236500, People’s Republic of China

    Chao-Xiong Li, Ling-Jun Shi, Bing Li, Fang Li & Jian-Bo He

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  1. Er-Mei Li
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Correspondence to Ning Deng or Jian-Bo He.

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Li, EM., Zhu, L., Li, CX. et al. Inhibiting effect of tin additives on the solid-phase conversion of PbSO4 to PbO2. J Solid State Electrochem 27, 2593–2606 (2023). https://doi.org/10.1007/s10008-023-05558-y

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