The Impact of Single Wall Carbon Nanotubes on Lead Acid Stop-Start Battery Performance

Abstract

Lead-acid batteries are widely used due to their abundant raw materials, reliable technology, and high rate recyclability. Advancing vehicle technologies and sustainability conditions have made stop-start features essential for battery charging acceptance, capacity, and cycle life. Due to their high conductivity, sulfating-inhibiting ion bonding structures, surface area, and porous features, carbon and carbon derivatives are used as additives for negative active materials. There are limited studies on their use as additives for positive active materials. This research aimed to investigate the effects of Single Walled Carbon Nanotubes (SWCNTs) used as additives in positive plates in enhanced flooded lead-acid batteries (EFBs) as electrochemical performance and plate structural properties of the battery and its industrial usability. SWCNT mixed with 0.4% N-methyl-2-pyrrolidone (NMP) was added to the positive active material with a wide range of ratios from 0.0005% to 0.1%. Lead oxide, polyester fiber, and diluted sulfuric acid solution were used in the preparation of the active material, and the plates were cured to create their crystal structures. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses showed that the addition of SWCNTs did not negatively affect the formation of crystal structures and the crystal structures were predominantly formed in 3BS crystal structures. 2V test cells were designed and manufactured. The electrical performance of the test cells was evaluated as capacity, impedance, and cycle life tests. It has been observed that cells with SWCNT can be charged at lower voltages during formation process, and their specific capacity and cycle life are increased as well. Cells with high SWCNT additive exhibited up to 55% higher capacity and 1.5 times longer cycle life compared to control samples. These improvements are explained by increased conductivity in the positive active material and decreased sulfating on the plate, which is consistent with the potential of SWCNT additive to enhance improved lead-acid battery performance.

Keywords

• Lead Acid Battery
• Additive
• Carbon Nanotube
• Active materials

Tek Duvarlı Karbon Nanotüpün Kurşun Asit Stop-Start Akü Performansına Etkisi

Öz

Kurşun-asit aküler hammaddesinin bol olması, güvenilir teknolojisi, geri dönüştürülebilirlik oranının yüksek olması nedeni ile yaygın olarak kullanılmaktadır. Gelişen araç teknolojileri ve çevresel sürdürülebilirlik şartları; Stop-Start özellikli akülerin sarj kabul kabiliyeti, kapasite ve çevrim ömrü özelliklerinin geliştirilmesini gerekli kılmıştır. Yüksek iletkenlik kabiliyetleri, sülfatlaşmayı engelleyici iyon bağ yapıları, yüzey alanı ve gözenekli yapıya katkıları nedeniyle karbon ve karbon türevleri çoğunlukla negatif aktif malzeme için katkı maddesi olarak kullanılmaktadır. Pozitif aktif malzeme katkısı olarak kullanımı için sınırlı sayıda çalışma bulunmaktadır. Bu araştırma, geliştirilmiş sulu kurşun-asit akü (EFB) içerisindeki pozitif plakalarda katkı maddesi olarak kullanılan Tek Duvarlı Karbon Nanotüplerin (SWCNT), akünün elektrokimyasal performansına ve plaka yapısal özelliklerine etkisini ve endüstriyel olarak kullanılabilirliğini incelemeyi amaçlamıştır. %0,4 oranında N-metil-2-pirolidon (NMP) ile karıştırılmış SWCNT 0,0005%-0,1% geniş bir oran aralığında pozitif aktif malzemeye eklenmiştir. Aktif malzeme hazırlanmasında kurşun oksit, polyester elyaf ve seyreltilmiş sülfürik asit çözeltisi kullanılmış ve plakalar kürleme işlemi uygulanarak kristal yapıları oluşturulmuştur. Taramalı elektron mikroskobu (SEM) ve X-ışını kırınımı (XRD) analizleri, SWCNT ilavesinin kristal yapıların oluşumunu olumsuz etkilemediğini, kristal yapıların ağırlıklı olarak 3BS kristal yapılarında şekillendiğini göstermiştir. 2V test hücreleri tasarlanmış ve üretilmiştir. Test hücrelerinin elektriksel performansları; kapasite, empedans ve çevrim ömrü testleri yapılarak sonuçlar irdelenmiştir. SWCNT katkısı olan hücrelerin, formasyon esnasında daha düşük voltajlarda şarj edilebildiği, özgül kapasite ve çevrim ömrünün de arttığı gözlemlenmiştir. Katkı oranı yüksek SWCNT içeren hücreler, kontrol örneklerine kıyasla %55'e kadar daha yüksek kapasite ve 1,5 kat daha fazla çevrim ömrü ortaya koymuştur. Bu gelişmeler, pozitif aktif malzemedeki iletkenliğin artması, plaka üzerindeki sülfatlaşmanın azalmasıyla açıklanmaktadır; Bu da SWCNT katkısının geliştirilmiş kurşun-asit akü performansını artırma potansiyeliyle tutarlılık göstermektedir.

Anahtar Kelimeler

• Kurşun Asit Akü
• Katkı malzemesi
• Karbon nanotüp
• Aktif malzemeler

References

1. [1] Presenter, Geoffrey May (2022, September). Lead Battery Market: By Application and Region. European Lead Battery Conference, Lyon, France.
2. [2] Lach, J.; Wróbel, K.; Wróbel, J.; Podsadni, P.; Czerwiński, A Applications of Carbon in Lead-Acid Batteries: A Review. J. Solid State Electrochem. 2019, 23, 693–705.
3. [3] Hu, H.Y.; Xie, N.; Wang, C.; Wu, F.; Pan, M.; Li, H.F.; Wu, P.; Wang, X.D.; Zeng, Z.; Deng, S.; Vinodgopal,K. et al. Enhancing the Performance of Motive Power Lead-Acid Batteries by High Surface Area Carbon Black Additives. Appl. Sci. 2019, 9, 186.
4. [4] Wang, L.; Zhang, H.; Zhang, W.; Cao, G.; Zhao, H.; Yang, Y. Enhancing Cycle Performance of Lead-Carbon Battery Anodes by Lead-Doped Porous Carbon Composite and Graphite Additives. Mater. Lett. 2017, 206, 113–116.
5. [5] Saravanan, M., Ganesan, M., & Ambalavanan, S. (2015). Enhanced electrochemical performance of a lead–acid battery by a surface modified negative grid with multiwall carbon nanotube coating. RSC advances, 5(33), 26081-26091.
6. [6] Mahajan, V.; Bharj, R.S.; Bharj, J. Role of Nano-Carbon Additives in Lead-Acid Batteries: A Review. Bull. Mater. Sci. 2019, 42, 21.
7. [7] Hao, H.; Chen, K.; Liu, H.; Wang, H.; Liu, J.; Yang, K.; Yan, H. A Review of the Positive Electrode Additives in Lead-Acid Batteries. Int. J. Electrochem. Sci. 2018, 13, 2329–2340.
8. [8] Ball, R.J.; Evans, R.; Thacker, E.L.; Stevens, R. Effect of Valve Regulated Lead/Acid Battery Positive Paste Carbon Fibre Additive. J. Mater. Sci. 2003, 38, 3013–3017.

9. [9] Logeshkumar, S.; Manoharan, R. Influence of Some Nanostructured Materials Additives on the Performance of Lead Acid Battery Negative Electrodes. Electrochim. Acta 2014, 144, 147–153.
10. [10] Blecua, M.; Fatas, E.; Ocon, P.; Gonzalo, B.; Merino, C.; de la Fuente, F.; Valenciano, J.; Trinidad, F. Graphitized Carbon Nanofibers: New Additive for the Negative Active Material of Lead Acid Batteries. Electrochim. Acta 2017, 257, 109–117.
11. [11] Moseley, P.T.; Rand, D.A.J.; Peters, K. Enhancing the Performance of Lead-Acid Batteries with Carbon—In Pursuit of an Understanding J. Power Sources 2015, 295, 268–274.
12. [12] Moseley, P.T.; Rand, D.A.J.; Davidson, A.; Monahov B. Understanding the Functions of Carbon in the Negative Active-Mass of the Lead–Acid Battery: A Review of Progress. J. Energy Storage 2018, 19, 272–290.
13. [13] Kumar, S. M., Arun, S., & Mayavan, S. (2019). Effect of carbon nanotubes with varying dimensions and properties on the performance of lead acid batteries operating under high rate partial state of charge conditions. Journal of Energy Storage, 24, 100806.
14. [14] Mandal, S., Thangarasu, S., Thong, P. T., 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. Journal of Power Sources, 485, 229336.
15. [15] Swogger, S. W., Everill, P., Dubey, D. P., & Sugumaran, N. (2014). Discrete carbon nanotubes increase lead acid battery charge acceptance and performance. Journal of power sources, 261, 55-63.
16. [16] Sugumaran, N., Everill, P., Swogger, S. W., & Dubey, D. P. (2015). Lead acid battery performance and cycle life increased through addition of discrete carbon nanotubes to both electrodes. Journal of Power Sources, 279, 281-293.
17. [17] Shapira, R., Nessim, G. D., Zimrin, T., & Aurbach, D. (2013). Towards promising electrochemical technology for load leveling applications: extending cycle life of lead acid batteries by the use of carbon nano-tubes (CNTs). Energy & Environmental Science, 6(2), 587-594.
18. [18] Saravanan, M., Sennu, P., Ganesan, M., & Ambalavanan, S. (2012). Multi-walled carbon nanotubes percolation network enhanced the performance of negative electrode for lead-acid battery. Journal of The Electrochemical Society, 160(1), A70.
19. [19] 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. Journal of Power Sources, 296, 78-85.
20. [20] Banerjee, A., Ziv, B., Levi, E., Shilina, Y., Luski, S., & Aurbach, D. (2016). Single-wall carbon nanotubes embedded in active masses for high-performance lead-acid batteries. Journal of The Electrochemical Society, 163(8), A1518.
21. [21] Banerjee, A., Ziv, B., Shilina, Y., Levi, E., Luski, S., & Aurbach, D. (2017). Single-wall carbon nanotube doping in lead-acid batteries: a new horizon. ACS applied materials & interfaces, 9(4), 3634-3643.
22. [22] Kumar, R., Kumari, S., Mathur, R. B., & Dhakate, S. R. (2015). Nanostructuring effect of multi-walled carbon nanotubes on electrochemical properties of carbon foam as constructive electrode for lead acid battery. Applied Nanoscience, 5, 53-61.
23. [23] Meyers, J. P., de Guzman, R. C., Swogger, S. W., McCarrell, C., McPherson, J., Guan, J., ... & Everill, P. (2020). Discrete carbon nanotubes promote resistance to corrosion in lead-acid batteries by altering the grid-active material interface. Journal of Energy Storage, 32, 101983.
24. [24] Hao, Z.; Xu, X.; Wang, H.; Liu, J.; Yan, H. Review on the Roles of Carbon Materials in Lead-Carbon Batteries. Ionics 2018, 24,951–965.