Lead-Acid Batteries: Science and Technology

1. Invention and Development of the Lead–Acid Battery 1.1. A Prelude1.2. Gaston Planté – The Inventor of the Lead–Acid Battery1.3. What Pains Had the Lead–Acid Battery to Go Through1.4. The Lead–Acid Battery in the Twentieth Century – Second Stage in its Development1.5. Applications of Lead–Acid Batteries1.6. Challenges Calling for a New Stage in the Development of the Lead–Acid Battery2. Fundamentals of Lead–Acid Batteries 2.1. Thermodynamics of the Lead–Acid Battery2.2. Electrode Systems Formed During Anodic Polarization of Pb in H2SO4 Solution2.3. The Pb/PbSO4/H2SO4 Electrode2.4. H2/H+ Electrode on Pb Surface2.5. The Pb/PbO/PbSO4 Electrode System2.6. The Pb/PbO2/PbSO4 Electrode System2.7. Electrochemical Preparation of the Me/PbO2 Electrode2.8. Electrochemical Behaviour of the Pb/PbO2/H2SO4 Electrode2.9. Hydration and Amorphization of Active Mass PbO2 Particles and Impact on the Discharge Processes2.10. The H2O/O2 Electrode System2.11. Anodic Corrosion of Lead and Lead Alloys in the Lead Dioxide Potential Region2.12. The Lead–Acid Cell3. H2SO4 Electrolyte – An Active Material in the Lead–Acid Cell 3.1. H2SO4 Solutions Used as Electrolytes in the Battery Industry3.2. Purity of H2SO4 Used in Lead–Acid Batteries3.3. Dissociation of H2SO43.4. Electrical Conductivity of H2SO4 Solutions3.5. Dependence of the Electromotive Force of a Lead–Acid Cell on Electrolyte Concentration and Its Influence on Charge Voltage3.6. Correlation Between H2SO4 Amount and Cell Capacity3.7. Utilization of the Active Materials in the Lead–Acid Battery and Battery Performance3.8. Correlation Between the Electrochemical Activity of PbO2/PbSO4 Electrode and H2SO4 Electrolyte Concentration3.9. Correlation Between Solubility of PbSO4 Crystals and Electrolyte Concentration3.10. Influence of H2SO4 Electrolyte Concentration on Battery Performance3.11. Additives to Electrolyte3.12. Contaminants (Impurities) in Electrolyte Solution3.13. Influence of Electrolyte Stratification on Battery Performance4. Lead Alloys and Grids. Grid Design Principles 4.1. Battery Industry Requirements to Lead Alloys4.2. Purity Specifications for Lead Used in the Battery Industry4.3. Lead–Antimony Alloys4.4. Lead–Calcium Alloys4.5. Lead–Calcium–Tin Alloys4.6. Lead–Tin Alloys4.7. Grid Design Principles4.8. Grid/Spine Casting4.9. Continuous Plate Production Process4.10. Tubular Positive Plates4.11. Copper-Stretch-Metal Negative Grids5. Leady Oxide 5.1. Physical Properties of Lead Oxide and Red Lead5.2. Mechanism of Thermal Oxidation of Lead5.3. Production of Leady Oxide5.4. Characteristics of Leady Oxide5.5. Influence of Leady Oxide Properties on Battery Performance Characteristics6. Pastes and Grid Pasting 6.1. Introduction6.2. Fundamentals6.3. Technology of Paste Preparation7. Additives to the Pastes for Positive and Negative Battery Plates 7.1. Additives to the Pastes for Negative Plate Manufacture7.2. Additives to the Positive Paste8. Curing of Battery Plates 8.1. Introduction8.2. Fundamentals8.3. Technology of Plate Curing9. Soaking of Cured Plates Before Formation 9.1. Technological Procedures Involved in the Formation of Lead–Acid Battery Plates9.2. H2SO4 Electrolyte During Soaking and Formation9.3. Processes During Soaking of 3BS Cured Plates9.4. Soaking of 4BS Cured Pastes9.5. Influence of the Soaking Process on Battery Performance10. Formation of Positive Lead–Acid Battery Plates 10.1. Equilibrium Potentials of the Electrode Systems Formed During the Formation Process10.2. Formation of PAM from 3BS-Cured Pastes10.3. Formation of Plates Prepared with 4BS Cured Pastes10.4. Mechanisms of the Crystallization Processes During Formation of Positive Plates with 4BS Paste10.5. Structure of the Formed Interface Grid/Corrosion Layer/Active Mass [14]10.6. Influence of the H2SO4/LO Ratio on the Proportion Between β- and α-PbO2 in PAM and on Plate Capacity10.7. Structure of the Positive Active Mass10.8. Influence of Grid Alloying Additives on the Electrochemical Activity of PbO2 Binders11. Processes During Formation of Negative Battery Plates 11.1. Equilibrium Potentials of the Electrochemical Reactions of Formation11.2. Reactions During Formation of Negative Plate11.3. Zonal Processes11.4. Structure of Negative Active Mass11.5. Effect of Expander on the Processes of Formation of NAM Structure and Factors Responsible for Expander Disintegration12. Technology of Formation 12.1. Introduction12.2. Influence of Active Mass Structure on Plate Capacity12.3. Initial Stages of Formation of Lead–Acid Batteries12.4. Formation of Positive and Negative Active Materials from Cured Pastes12.5. Influence of PbO2 Crystal Modifications on the Capacity of Positive Plates. Formation Parameters that Affect the α/β-PbO2 Proportion12.6. Criteria Indicating End of Formation12.7. Influence of Current-Collector Surface on Formation of PbSO4 Crystals at Grid/PAM Interface12.8. Method for Shortening the Duration of the Formation Process13. Processes After Formation of the Plates and During Battery Storage 13.1. State of Battery Plates After Formation13.2. Dry-Charged Batteries13.2.7. Summary13.3. Wet-Charged Batteries14. Methods to Restore the Water Decomposed During Charge and Overcharge of Lead–Acid Batteries. VRLA Batteries 14.1. Recombination of Hydrogen and Oxygen into Water Using Catalytic Plugs14.2. Recombination of Hydrogen and Oxygen to Water on Auxiliary Catalytic Electrodes14.3. Valve-Regulated Lead–Acid Batteries (VRLAB)15. Calculation of the Active Materials for Lead–Acid Cells 15.1. Basic Units of Electricity and Equivalents for Electricity and Mass15.2. Electrochemical Equivalent Weights of Active Materials in a Lead–Acid Cell per Ah of Electric Charge (Electricity)15.3. Parameters Accounting for the Degree of Active Material Utilization During Current Generation and Correlation Between These Parameters15.4. Amount of H2SO4 in a Lead–Acid Cell15.5. An Example for Calculating the Active Materials in a 50Ah SLI Cell at ηPAM = 50% and ηNAM = 45%15.6. An Exemplary Calculation of Paste Composition15.7. Measuring of Electrode Potentials