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A Lead Monoxide Precursor of High Surface-Area for Lead-Acid Battery Paste

A Lead Monoxide Precursor of High Surface-Area for Lead-Acid Battery Paste. R Vasant Kumar Department of Materials Science University of Cambridge, UK. Acknowledgements.

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A Lead Monoxide Precursor of High Surface-Area for Lead-Acid Battery Paste

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  1. A Lead Monoxide Precursor of High Surface-Area for Lead-Acid Battery Paste R Vasant Kumar Department of Materials Science University of Cambridge, UK

  2. Acknowledgements • Seref Sonmez, Vega Kotzeva, Jiakuan Yang, Lilia Sanchez, Richard Darby, Yingjun Liu, David Zou, of Department of Materials Science • Lei Wang, Nigel Williams of the Business School • Maggie Wilkinson & Zlatka Stoeva of Cambridge Enterprise

  3. A Schematic Cut-Away of Lead Battery

  4. Table 1 Range of Compositions from a dry lead battery paste

  5. Current Method - Pyrometallurgy *For 10,000 tpy plant Capital: $4-5M Energy: 14,000MWH *Independent Consultants

  6. Battery Manufacture • Lead is then chemically oxidised to PbO for the battery industry • PbO is electrochemically reduced to Pb and oxidised to PbO2 to make anode and cathode

  7. A new process for recycling lead battery waste Special Leaching/Crystallization Process Waste Battery Paste → → Lead Battery ↓ ↑ Combustion/ Calcination Process Manufacturing Lead Battery New Paste Patent: PCT/GB2007/ 004222; WO2008/056125 RV Kumar, S Sonmez and V Kotzeva

  8. A new process for recycling lead battery waste Paste Waste Battery → Pb Grid Heat Energy from paste recycling Kettle New lead Battery New Grid New Paste directly from paste recycling

  9. Green PB Recycling Process Spent Lead grid Leaching Combustion-Calcination Energy Metallic Lead Patent: PCT/GB2007/ 004222; WO2008/056125 RV Kumar, S Sonmez, V Kotzeva

  10. Leaching of battery paste PbO and PbO2 Ratio of Paste/ reagent

  11. pH vs time for varying paste/reagent ratio

  12. XRD Pattern of A: Standard Lead citrate; B: from PbO; C: from PbO2 and D: from PbSO4

  13. Lead organic crystallites of Lead citrate (A) from PbO and PbO2

  14. SEM images of Lead Citrate (B) from PbSO4

  15. Combustion-Calcination of Lead citrates in Air

  16. Wt loss and heat produced on decomposing Pb citrate (A)

  17. Wt loss and heat produced from lead citrate (B)

  18. Mixture of α and β PbO and metallic Pb – can be controlled to varying ratios

  19. Heat Produced • Combustion-calcination of lead citrates can generate thermal energy of 2 kJ/ g of lead battery paste • The Raceway Adiabatic Flame Temperature is over 1500K! • This energy is equivalent to 550 kWh/kg of paste!

  20. PbO morphology after combustion-calcination TEM SEM

  21. Agglomerated PbO Spongy PbO Skeletal PbO

  22. Additives during leaching to control PbO morphology Lead citrate PbO

  23. Addition of C-fibre to PbO precursor

  24. FEGSEM – Each fibre is coated with PbO

  25. Physical Properties of PbO • Free Pb: 0 to 20 % • Crystal structure: α/β ratio: 0.05 to 1 • Crystal size: 20 – 100 nm • Particle average size: 1 – 5 μm • Specific surface area (BET) m2/g: 2.4 to 5.5 • Acid absorption (mg H2SO4/ g oxide): 270 – 530

  26. Preliminary Electrochemical Testing • First discharge capacity in the 130 – 160 mAh/g of PbO • Increase in discharge capacity with no of cycles up to 8-10 cycles and then remained constant to 50 cycles • Further work is ongoing C B D E A A: PbO /PbSO4 reduction to Pb B: Pb oxidation to PbSO4 C: PbSO4 oxidation to PbO2 D: PbO2 reduction to PbSO4 E: PbSO4 reduction to Pb

  27. The Green PB Process 5000 MWh Energy available For 10,000 tpy plant Capital: $1-1.5 M Energy: 1750 MWH

  28. Conclusions • New method for directly recovering PbO from spent battery paste • Many control variables available to vary physical properties of PbO product • Promising preliminary results • Thank You

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