Application Of Tetrabasic Lead Sulphate In Lead Acid Batteries

Previous studies have found that tetrabasic lead sulphate(4PbO·PbSO4,4BS)can efficiently improve the cycle life and discharge capacity of the lead acid battery(LAB).Directly using 4BS as the raw materials for positive active material(PAM)can eliminate the traditional curing process and decrease the production cost of LAB,if 4BS can be prepared at low cost.In this paper we developed a fast and easy route to prepare 4BS at low cost,which is now being applied industrially.And we studied the electrochemical performance of 4BS as the raw materials for PAM.Then further studied the influence of the addition of Pb3O4,SnSO4 and Sb2O3 on the battery performance.Firstly,4BS with dimensions of about 10 ?m in length and 1 ?m in diameter was prepared.By grinding,we obtained pulverised 4BS articles with dimensions of 0.5 to 2?m.Then the original as-prepared 4BS and pulverised 4BS crystals in positive electrodes were used as PAM.The electrode use the original 4BS micro-rods can be more easily formatted than the one used the pulverised 4BS.After 50 cycles of 100%DOD at 100 mA·g-1,the discharge capacity of the original 4BS electrode is 97.4 mAh·g-1,which is nearly 2 times of the pulverised 4BS electrode(50.3 mAh·g-1).Considering of the excellent electrochemical performance of the original 4BS micro-rods electrode,the electrode was tested for 1000 cycles at current density of 100 mA·g-1.The results show that the original 4BS micro-rods electrode exhibits an excellent cycle performance,which has the capacity of 103 mAh·g-1 at 100 mA·g-1 in the end of 1000 cycles with above 90%of coulombic efficiency.Then,we further studied the addition of different ratios of Pb3O4,SnSO4 and Sb2O3 on the battery performance.We found that Pb3O4 can improve the formation efficiency,and adding 10%Pb3O4 can improve the discharge capacity to a large extent,which is 98.4 mAh·g-1 after 50 cycles.Then,we added different ratios of SnSO4 to the PAM in the presence of 10%Pb3O4.The results show that SnSO4 can reduce the discharge capacity after formation,but increasing the discharge capacity after stabilization.Adding 0.5%SnSO4 can improve the discharge capacity to a large extent,which is 105.5 mAh·g-1 after 50 cycles.After that we added different ratios of Sb2O3 to the PAM in the presence of 10%? Pb3O4.The results show that Sb2O3 can improve both the initial discharge capacity and the discharge capacity after stabilization.Adding 0.5%Sb2O3 can improve the discharge capacity to a large extent,which is 114.2 mAh·g-1 after 50 cycles.Lastly,we added 10%Pb3O4,0.5%SnSO4 and 0.5%Sb2O3 to the PAM and found that discharge capacity is 121.0 mAh·g-1 after 150 cycles.