Chapter
1.6.2 Major Problems of Lead–Acid Batteries in HEV Applications
2 - Fundamentals of Lead–Acid Batteries
2.1 Thermodynamics of the Lead–Acid Battery
2.1.2 Lead Sulfate Electrode (Pb/PbSO4) Potential
2.1.3 Lead Dioxide Electrode (PbO2/PbSO4) Potential
2.1.4 Electromotive Force of the Lead–Acid Cell, ΔE
2.1.5 Brief Summary of the Lead Compounds Involved in the Manufacture and Operation of the Lead–Acid Cell
2.1.5.2 Lead Sulfate (PbSO4)
2.1.5.3 Monobasic Lead Sulfate, PbO·PbSO4 (1BS)
2.1.5.4 Tribasic Lead Sulfate, 3PbO·PbSO4·H2O (3BS)
2.1.5.5 Tetrabasic Lead Sulfate, 4PbO·PbSO4 (4BS)
2.1.5.6 Lead Dioxide (PbO2)
2.1.5.7 Red Lead (in USA) or Minium (in Europe), Pb3O4
2.1.6 The Pb/H2SO4/H2O System
2.1.7 E/pH Diagram for the Pb/H2SO4/H2O System
2.1.8 Effect of Temperature on the EMF of the Lead–Acid Cell
2.2 Electrode Systems Formed During Anodic Polarization of Pb in H2SO4 Solution
2.3 The Pb/PbSO4/H2SO4 Electrode
2.3.1 Electrode Processes on the Pb Surface
2.3.2 Elementary Processes of Anodic Oxidation of Pb and Formation of PbSO4 Crystal Layer
2.3.3 Processes of Alkalization of the Solution in the Pores of the PbSO4 Layer
2.3.4 The PbSO4 Layer as a Selective Semipermeable Membrane—Pb/PbO/PbSO4 Electrode Potential
2.4 H2/H+ Electrode on Pb Surface
2.5 The Pb/PbO/PbSO4 Electrode System
2.5.1 Mechanism of PbO Growth
2.5.2 Intermediate Lead Oxides
2.5.2.2 Electrical Conductivity
2.5.3 Photoelectrochemical Oxidation of Pb/PbO/PbSO4 to Pb/PbOn/PbSO4
2.5.4 Electrochemical Oxidation of Pb/PbO/PbSO4 Electrode to Pb/PbO2 Electrode
2.6 The Pb/PbO2/PbSO4 Electrode System
2.6.1 Physicochemical Properties of PbO2
2.6.1.3 Semiconductor Properties
2.7 Electrochemical Preparation of the Me/PbO2 Electrode
2.7.1 Preparation of α-PbO2 Layers
2.7.2 Preparation of β-PbO2
2.8 Electrochemical Behavior of the Pb/PbO2/H2SO4 Electrode
2.8.1 Equilibrium Potentials
2.8.2 Temperature Dependence
2.8.3 Adsorption of H2SO4
2.9 Hydration and Amorphization of Active-Mass PbO2 Particles and Impact on the Discharge Processes
2.9.1 Gel–Crystal Structure of PAM Particles
2.9.1.1 Surface Hydration of Lead Dioxide Particles
2.9.2 Equilibrium Between the Crystal and Gel Zones in the Particles and Agglomerates of PAM, and the Ions in the Solution
2.9.3 Proton–Electron Mechanism of Discharge of the Positive Active Mass
2.9.4 Processes During Anodic Polarization of Pb/PbO2/PbSO4 (O2/H2O) Electrode
2.10 The H2O/O2 Electrode System
2.10.1 Oxygen Overvoltage on Lead Dioxide
2.10.2 Oxygen Coverage of PbO2 and Diffusion into the Lead Dioxide Layer
2.10.3 Mechanism of Oxygen Evolution
2.11 Elementary Processes During Charge and Discharge of the Positive and Negative Electrodes in a Lead–Acid Cell
2.11.1 Elementary Processes During Cell Discharge
2.11.2 Elementary Processes During Cell Charge
2.11.3 General Scheme of the Reactions at the Two electrodes During Charge and Discharge
2.11.3.1 Discharge Reactions
2.11.3.2 Charge Reactions
2.11.4 Electric Current Transfer in the LeadAcid Cell
2.12 Anodic Corrosion of Lead and Lead Alloys in the Lead Dioxide Potential Region
2.12.1 Corrosion Layer Growth
2.12.2 Dependence of the Partial Currents of Lead Oxidation and Oxygen Evolution, as Well as of the Composition of the Anodic Laye ...
2.12.3 Mechanism of Anodic Corrosion of Lead Within the PbO2 Potential Region
2.12.4 Stability of α-PbO2 and β-PbO2
2.13 Introduction to the Lead–Acid Cell
2.13.1 Specific Energy of a Lead–Acid Cell
2.13.2 General Notes on Lead–Acid Cell Design
2.13.3 Technological Schemes for Battery Manufacture
2.13.3.1 Flat-Plate Batteries
2.13.3.2 Tubular-Plate Batteries
2.13.4 Electrode Structures in Lead–Acid Cells
2.13.5 Basic Considerations Related to the Technology of Manufacture of Positive Electrodes With Lead Dioxide-Active Mass
2.13.6 Basic Considerations Related to the Technology of Manufacture of Negative Electrodes With Lead-Active Mass
2 - Materials Used for Lead–Acid Battery Manufacture
3 - H2SO4 Electrolyte—An Active Material in the Lead–Acid Cell
3.1 H2SO4 Solutions Used as Electrolytes in the Battery Industry
3.2 Purity of H2SO4 Used in Lead–Acid Batteries
3.3 Dissociation of H2SO4
3.4 Electrical Conductivity of H2SO4 Solutions
3.5 Influence of Temperature on the Performance of Lead–Acid Batteries
3.5.1 Influence of Temperature on Water Loss in Lead–Acid Batteries
3.5.2 Behavior of H2SO4 Solutions at Low Temperatures
3.6 Dependence of the Electromotive Force of a Lead–Acid Cell on Electrolyte Concentration and Its Influence on Charge Voltage
3.7 Distribution of the Sulfuric Acid Solution in the Active Block of the Cell
3.8 Utilization of the Active Materials in the Lead–Acid Battery and Battery Performance
3.9 Correlation Between the Electrochemical Activity of PbO2/PbSO4 Electrode and H2SO4 Electrolyte Concentration
3.10 Correlation Between Solubility of PbSO4 Crystals and Electrolyte Concentration
3.11 Influence of H2SO4 Electrolyte Concentration on Battery Performance
3.12 Additives to Electrolyte
3.12.1 Inorganic Compounds
3.12.1.1 Phosphoric Acid, H3PO4
3.12.1.2 Other Inorganic Acids or Salts
3.12.2 Carbon Suspensions
3.13 Contaminants (Impurities) in Electrolyte Solution
3.14 Processes Causing Electrolyte Stratification and Influence of Electrolyte Stratification on Battery Performance
4 - Lead Alloys and Grids. Grid Design Principles
4.1 Battery Industry Requirements to Lead Alloys
4.2 Purity Specifications for Lead Used in the Battery Industry
4.3.2 Equilibrium Phase Diagram and Microstructure of the Lead–Antimony Alloy System
4.3.3 Properties of Pb–Sb Alloys With Different Antimony Contents
4.3.3.1 Castability and Melting Temperature of Pb–Sb Alloys
4.3.3.2 Hardness of Pb–Sb Alloys
4.3.3.3 Yield Strength, Ultimate Tensile Strength, and Elongation of Pb–Sb alloys
4.3.3.4 Creep Resistance of Pb–Sb Alloys
4.3.3.5 Corrosion Resistance of Pb–Sb Alloy
4.3.4 Additives to Pb–Sb Alloys
4.3.5 Effect of Antimony in the Grid Alloy on the Rate of Water Decomposition
4.3.5.1 The Oxygen Evolution Reaction
4.3.5.2 The Hydrogen Evolution Reaction
4.3.6 Mechanism of Grid Hot Cracking
4.3.7 Nucleants (Refiners)
4.3.7.1 Selenium (Se) and Sulfur (S)
4.3.8 Influence of Sb, As, and Bi on the Reversibility of the Lead Dioxide Active Mass Structure
4.3.9 Influence of Antimony on the Composition and Electrical Resistance of the Corrosion Layer Formed on Lead–Antimony Electrode ...
4.4.1 How Were Lead–Calcium Alloys Widely Adopted in the Battery Industry
4.4.2 Equilibrium Phase Diagram of the Lead–Calcium Alloy System
4.4.3 Mechanical Properties of Lead–Calcium Alloys
4.4.4 Aluminum Addition to Pb–Ca Alloys
4.5 Lead–Calcium–Tin Alloys
4.5.1 Microstructure of Pb–Ca–Sn Alloys
4.5.2 Mechanical Properties of Pb–Ca–Sn Alloys
4.5.3 Corrosion Resistance of Pb–Ca–Sn Alloys
4.5.4 Electrochemical Properties of Pb–Ca–Sn Alloys. Sn-Free Effect
4.5.4.1 Basic Conclusions About the Effects of Tin in Pb–Ca–Sn Alloys
4.5.5 Additives to Pb–Ca–Sn Alloys
4.7 Grid Design Principles
4.9 Continuous Plate Production Process
4.10 Tubular Positive Plates
4.11 Copper-Stretch-Metal Negative Grids
5.1 Physical Properties of Lead Oxide and Red Lead
5.2 Mechanism of Thermal Oxidation of Lead
5.3 Production of Leady Oxide
5.3.1 Barton Pot Method of Leady Oxide Production with Moderate Temperature Oxidation of Lead
5.3.2 Ball Mill Method of Leady Oxide Production with Low-Temperature Oxidation of Lead
5.3.3 Comparison of Barton Pot and Ball Mill Leady Oxides
5.3.4 Latest Advances in the Development of Barton Pot and Ball Mill Leady Oxide Processes
5.3.5 Production of Red Lead (Minium)
5.4 Characteristics of Leady Oxide
5.4.1 Purity of Lead for Lead Oxide Production
5.4.2 Crystal Modification of the Lead Oxide
5.4.3 Chemical Composition of Leady Oxide
5.4.4 Absorption of Water and Sulfuric Acid
5.4.5 Surface Area (Specific Surface)
5.4.6 Real Density, Poured (Apparent) Density, and Packed Density
5.4.7 Particle Size Distribution
5.4.8 Stability of Leady Oxide
5.4.9 Environmental and Health Hazard Issues Related to Leady Oxide Production
5.5 Influence of Leady Oxide Properties on Battery Performance Characteristics
5.5.1 Cells Produced with Leady Oxide
5.5.2 Cells Produced with Nano-Structured Lead Oxide
3 - Processes During Paste Preparation and Curing of the Plates
6 - Pastes and Grid Pasting
6.2.1 Thermodynamics of the PbO/H2SO4/H2O System: Phase Composition of the Paste as a Function of Solution pH
6.2.2 Phase Composition of the Paste as a Function of Paste Preparation Temperature
6.2.3 Thermal Effects During Paste Preparation
6.2.4 Tribasic Lead Sulfate Pastes, 3PbO·PbSO4·H2O (3BS)
6.2.4.1 Kinetics of 3BS Paste Preparation
6.2.4.2 Influence of H2SO4/PbO Ratio on Phase Composition and Crystal Morphology of the Paste
6.2.4.2.1 Phase Composition
6.2.4.2.2 Crystal Morphology of Pastes Prepared at Different H2SO4/LO Ratios
6.2.4.3 Effect of Expander Added to the Negative Paste
6.2.4.4 Effect of PbO Modification on the Rate of the Reaction of 3BS Formation
6.2.5 Tetrabasic Lead Sulfate Pastes, 4PbO·PbSO4 (4BS)
6.2.5.1 Methods for Preparation of 4PbO·PbSO4 (4BS) Pastes
6.2.5.2 Kinetics of 4BS Crystal Formation
6.2.5.3 Effect of Temperature on the Preparation of 4BS Pastes
6.2.5.4 Effect of H2SO4/LO Ratio on Phase Composition of the Paste
6.2.5.5 Effect of Expanders or Surface Active Materials on the Preparation of 4BS Pastes
6.2.5.6 Influence of PbO Modification on the Kinetics of 4BS Formation
6.2.6 Amorphous Components as Indispensable Constituents of the Paste
6.2.6.1 Reactions of Hydration and Carbonization of the Paste, and Oxidation of Pb
6.2.7 Cycle Life of Positive Plates as a Function of Phase Composition of the Paste
6.2.8 Technological Applicability of Basic Lead Sulfate Pastes in the Battery Industry
6.2.9 Pastes Prepared From Leady Oxide and Pb3O4
6.3 Technology of Paste Preparation
6.3.1 General Requirements to the Pastes
6.3.2.1 Liquid/Particle System
6.3.2.2 Paste Density and Parameters it Depends on
6.3.2.3 Paste Density Critical Values
6.3.2.4 Semi-suspension Technology for Preparation of 4BS Pastes
6.3.4 Technological Process and Equipment for Paste Preparation
6.3.4.1 Preparation of 3BS Pastes for Positive Plates
6.3.4.2 Preparation of 4BS Pastes for Positive Plates
6.3.4.3 Preparation of 3BS Pastes for Negative Plates
6.3.4.4 Technological Scheme for Paste Preparation and Grid Pasting
6.3.4.5 Paste Preparation Equipment
6.3.5 Manufacture of Positive Tubular Plates
6.3.5.1 Tubular Plate Filling
7 - Additives to the Pastes for Positive and Negative Battery Plates
7.1 Additives to the Pastes for Negative Plate Manufacture
7.1.1.2 Influence of the Organic Expander Component on the Processes of Nucleation and Growth of Pb and PbSO4 Crystals
7.1.1.2.1 Effect of Expander on the Electrochemical Processes
7.1.1.2.2 Impact of the Organic Expander Component on Pb and PbSO4 Crystal Morphology and Size
7.1.1.3 Mechanism of Action of the Organic Expander Component on the Charge and Discharge Processes
7.1.1.3.1 Discharge Processes
7.1.1.3.2 Charge Processes
7.1.1.4 Correlation Between Expander Structural Group Composition and Negative Battery Plate Performance
7.1.1.5 Influence of Grid Alloy Composition on Expander Efficiency
7.1.1.6 Impact of Hydrogen and Oxygen on Expander Stability
7.1.1.7 Influence of Temperature on Expander Stability During Battery Cycling
7.1.2.1 Types of Carbon Additives to the Negative Plates and Their Influence on the Structure of NAM
7.1.2.2 Parallel Mechanism of the Charge Reactions on Negative Plates Containing Carbons or Graphites
7.1.2.3 Influence of Type and Concentration of Carbon and Graphite Additives to NAM on the Cycle Life of Cells in HRPSoC Duty
7.1.3.1 Properties, Structure, and Influence of BaSO4 on PbSO4 Crystallization
7.1.3.2 Influence of BaSO4 on Negative Plate Performance
7.1.3.3 Expander Compositions for the Various Types of Batteries
7.1.4 Other Additives to the Negative Paste
7.1.4.1 Structural Stabilizers of the Lead Active Mass: Fibers, Dynel Flock, and Carboxymethylcellulose
7.1.4.2 Additives Creating Hydrophobic Channels in NAM and Accelerating the Rate of Oxygen Reduction at the Negative Plates of VRLAB
7.1.4.3 Inhibitors of Hydrogen Evolution at the Negative Plates
7.2 Additives to the Positive Paste
7.2.1 Additives Accelerating the Formation of the Positive Plates
7.2.2 Electroconductive Additives
7.2.2.1 Barium Plumbate (BaPbO3)
7.2.2.2 Magneli Phases of Titanium Oxide (Ti4O7)
7.2.2.3 Tin Dioxide (SnO2)-Coated Glass Flakes and Fibers
7.2.2.4 Carbon, Carbon Fibers, Isotropic Graphite, and Graphite Fibers
7.2.2.5 Conductive Polymers
7.2.2.6 Red Lead (RL), Pb3O4 (25–100wt% in the Paste)
7.2.2.7 Ozone (O3) Treatment of the Plates
7.2.3 Additives Improving the Capacity, Energy, Power Output, and Cycle Life of the Battery, When These Performance Characteristi ...
7.2.4 Additives to the Positive Pastes That Retard Sulfation of the Active Mass
7.2.4.1 Phosphoric Acid (H3PO4) and Lead Phosphate Salts
7.2.4.2 Sodium Sulfate (Na2SO4)
8 - Curing of Battery Plates
8.2.1 Formation of a Hard Porous Mass (Skeleton) in the Cured Paste
8.2.1.1 Changes in Phase Composition and Crystallinity of the Paste on Curing
8.2.1.2 Phase Composition of the Cured Paste as a Function of H2SO4/LO Ratio Used for Paste Preparation
8.2.1.3 Structure and Crystal Morphology of Cured 3BS and 4BS Pastes
8.2.1.4 Processes of Conversion of 3BS Pastes into 4BS Ones
8.2.1.5 Influence of Curing Conditions on the Size of 4BS Particles
8.2.1.6 Pore Volume, BET Surface Area, and Solid-Phase Density of Cured Pastes
8.2.2 Oxidation of Residual-Free Lead in the Paste
8.2.2.1 Rate of Oxidation as a Function of Moisture Content of the Paste
8.2.2.2 Rate of Oxidation of Free Pb in the Paste as a Function of Air Humidity and Temperature
8.2.2.3 Mechanisms of Pb Oxidation and Role of Water in These Processes
8.2.2.4 Mechanism of Pb Oxidation Through Chemical Reactions
8.2.2.5 Mechanism of Pb Oxidation in the Paste Through Electrochemical Micro-galvanic Elements
8.2.3 Corrosion of PbSnCa Grids During Plate Curing and Formation of Corrosion Layer
8.2.3.1 Segregation of Sn and Ca During Plate Curing and Its Effect on Grid Corrosion
8.2.3.2 Corrosion Layer and Its Interfaces With PbSnCa Grid and Paste
8.2.3.2.1 Corrosion Layer Structure
8.2.3.2.2 Oxygen Vacancies Mechanism of Grid Corrosion During Plate Curing
8.2.3.2.3 Bonding of Paste Crystals to the CL2 Layer
8.2.3.2.4 Formation of Hydrocarbonates at the Paste/Corrosion Layer Interface
8.2.3.2.5 Formation of Gas Bubbles at the Paste/CL2 Layer Interface
8.2.4 Processes During Plate Drying
8.2.4.1 Decrease in Moisture Content of the Paste on Drying
8.2.4.2 Paste Curing and Drying: Atmospherically Dependent Processes
8.2.4.3 Paste Adhesion and Cohesion Strengths
8.3 Technology of Plate Curing
8.3.2 Curing in a Curing Chamber
8.3.2.1 Curing Schedules for 3BS and 4BS Pastes
8.3.2.2 Plate-Curing Equipment
8.3.2.3 Methods to Accelerate the Plate-Curing Process
9 - Soaking of Cured Plates Before Formation
9.1 Technological Procedures Involved in the Formation of Lead–Acid Battery Plates
9.2 H2SO4 Electrolyte During Soaking and Formation
9.2.1 Concentration of H2SO4 Solution During Soaking and Formation
9.2.2 Electrolyte Filling Process for Container Formation of Flooded and VRLA Batteries
9.3 Processes During Soaking of 3BS-Cured Plates
9.3.1 Changes in Chemical and Phase Composition of the Paste and in H2SO4 Concentration During Soaking
9.3.2 Zonal Processes During Plate Soaking, Forming Different Sublayers Across the Plate Thickness
9.3.2.2 B—Intermediate Layer
9.3.2.3 C—Central Layer (Zone)
9.3.3 Changes in Structure of the Interface Cured Paste/Corrosion Layer/Grid During Plate Soaking
9.3.4 Mechanism of the Reactions That Proceed During Soaking of 3BS Pastes
9.3.5 Influence of Soaking Processes on Battery Cycle Life Performance
9.4 Soaking of 4BS-Cured Pastes
9.4.1 Sulfation Rates of 3BS and 4BS Pastes in H2SO4 Solution
9.4.2 Processes of Sulfation of 4BS Crystals During Soaking
9.4.3 Changes in Macro- and Microstructures of 4BS Pastes on Soaking
9.4.4 Structure of the Interface Paste/Corrosion Layer After Soaking of 4BS Plates
9.4.5 Porometric and BET Surface Measurements of Soaked 4BS Pastes
9.4.6 Differential Scanning Calorimetric (DSC) Measurements of Soaked Pastes Cured at 90°C
9.5 Influence of the Soaking Process on Battery Performance
10 - Formation of Positive Lead–Acid Battery Plates
10.1 Equilibrium Potentials of the Electrode Systems Formed During the Formation Process
10.2 Formation of Positive Active Mass (PAM) From 3BS-Cured Pastes
10.2.1 Influence of H2SO4 Concentration on the Reactions of PAM Formation From 3BS Pastes
10.2.2 Evolution of the Pore System in the Paste During Formation
10.2.3 Chemical and Electrochemical Reactions During Formation of Lead–Acid Battery Positive Plates
10.2.4 Influence of the Ratio H2SO4/LO on the Reactions of Formation of 3BS Pastes
10.3 Formation of Plates Prepared With 4BS-Cured Pastes
10.4 Mechanisms of the Crystallization Processes During Formation of Positive Plates With 4BS Paste
10.5 Structure of the Formed Interface Grid/Corrosion Layer/Active Mass
10.6 Influence of the H2SO4/LO Ratio on the Proportion Between β- and α-PbO2 in PAM and on Plate Capacity
10.7 Structure of the Positive Active Mass
10.7.1 Micro- and Macrostructures of PAM
10.7.1.1 Microstructure of PAM
10.7.1.2 Macrostructure of PAM
10.7.2 Transport and Reaction Pores in the Structure of PAM and Their Influence on Plate Capacity
10.7.3 Gel–Crystal Forms of PbO2 Particles
10.7.4 Electrochemical Reactions That Proceed in the Gel Zones of the PbO2 Active Mass
10.8 Influence of Grid-Alloying Additives on the Electrochemical Activity of PbO2 Binders
11 - Processes During Formation of Negative Battery Plates
11.1 Equilibrium Potentials of the Electrochemical Reactions of Formation
11.2 Reactions During Formation of Negative Plate
11.4 Structure of Negative Active Mass
11.4.1 Influence of the Two Stages of Formation on NAM Structure
11.4.2 Evolution of Pore Structure of Negative Plates During Formation
11.5 Effect of Expander on the Processes of Formation of NAM Structure and Factors Responsible for Expander Disintegration
11.5.1 Influence of Expander on the Processes of Plate Formation
11.5.2 Changes in NAM Structure on Cycling Limiting Battery Cycle Life
12 - Technology of Formation
12.1.1 Changes in Temperature, H2SO4 Concentration, and Open-Circuit Cell Voltage During Active Mass Formation
12.1.2 Technological Parameters of the Formation Process
12.2 Influence of Active Mass Structure on Plate Capacity
12.3 Initial Stages of Formation of Lead–Acid Batteries
12.3.1 Processes During the Initial Stage of Corrosion Layer Formation
12.3.2 Current and Voltage Algorithms for the Initial Stage of Formation
12.4 Formation of Positive- and Negative Active Materials From Cured Pastes
12.4.1 Distinction Between Formation and Charging of Lead–Acid Batteries
12.4.2 Formation Algorithms
12.4.2.1 Constant-Current Formation Algorithms
12.4.2.2 Multistep Formation Current Algorithms
12.4.3 Formation of the Active Mass Connecting Layer (AMCL)
12.4.4 Rest and Discharge Periods in the Formation Algorithms
12.5 Influence of PbO2 Crystal Modifications on the Capacity of Positive Plates. Formation Parameters That Affect the α/β-PbO2 P ...
12.5.1 Electrochemical Activity of α-PbO2 and β-PbO2
12.5.2 Influence of Formation Parameters on Its Efficiency and on the α-to β-PbO2 Ratio in PAM
12.5.2.1 Influence of Paste Density on Formation Efficiency
12.5.2.2 Influence of Formation Current Density on the α/β-PbO2 Ratio
12.5.2.3 Influence of Temperature on the Efficiency of Formation and on the α/β-PbO2 Ratio
12.6 Criteria Indicating End of Formation
12.7 Influence of Current-Collector Surface on Formation of PbSO4 Crystals at Grid/PAM Interface
12.8 Method for Shortening the Duration of the Formation Process
12.8.1 Accelerated Formation Through Electrolyte Recirculation
12.8.2 Conceptual Block Scheme of Electrolyte Recirculation Process Employed to Accelerate Formation
12.9 Identification of Defective Batteries After Formation
12.9.1 Methods for Detection of Defective Batteries
12.9.2 Determination of Battery Voltage Gradient (ΔV) on High Constant-Current Pulse Discharge
5 - Battery Storage and VRLA Batteries
13 - Processes After Formation of the Plates and During Battery Storage
13.1 State of Battery Plates After Formation
13.2 Dry-Charged Batteries
13.2.1 Processes That Occur in the Positive Plates During Drying. Thermopassivation
13.2.2 Methods for Drying Negative Plates After Formation
13.2.2.2 Drying in an Inert Gas Atmosphere
13.2.2.3 Contact Drying With Superheated Steam
13.2.2.4 Drying of Negative Plates Treated With Inhibitors of Lead Oxidation (Antioxidants)
13.2.3 Processes That Occur in the Negative Plates Between the Technological Procedures of Plate Formation and Drying
13.2.4 Inhibitors of Lead Oxidation
13.2.5 Quality-Control Monitoring During Manufacture of Dry-Charged Batteries
13.2.6 Processes During Storage of Dry-Charged Batteries
13.2.6.1 Processes That Occur in the Positive Plates
13.2.6.2 Processes That Occur in the Negative Plates
13.3 Wet-Charged Batteries
13.3.1 Processes That Occur During Storage of Wet-Charged Batteries
13.3.2 Influence of Sulfuric Acid Concentration on the Self-Discharge Processes of the Positive Plates of Wet-Charged Lead–Acid Ba ...
13.3.3 Influence of Additives to the Positive Grid Alloy on the Processes During Storage and on the Performance Parameters of Wet- ...
13.3.4 Processes That Occur in the Negative Plates During Storage of Wet-Charged Batteries
14 - Valve-Regulated Lead–Acid (VRLA) Batteries
14.1 Recombination of Hydrogen and Oxygen Into Water
14.2 Valve-Regulated Lead–Acid Batteries (VRLAB)
14.2.1 General Principles of VRLAB Design and Operation
14.2.2 Reactions That Proceed in VRLA Cells During Charge and COC Operation
14.2.3 Behavior of the Positive Plates in VRLABs During Charge and Oxygen Cycle Operation
14.2.4 AGM Separator and Transport Processes Between the Positive and Negative Plates
14.2.4.1 Structure and Functions of the AGM Separator
14.2.4.2 Gas Transport Through the AGM Separator
14.2.4.3 Pore System of the AGM Separator
14.2.4.4 Critical Gas Pressure for Electrolyte Displacement From the AGM Pores
14.2.4.5 AGM Separator Saturation and Electrical Resistance of the VRLA Cell
14.2.4.6 Correlation Between Cell Saturation With Electrolyte and Its Capacity and Electrical Characteristics
14.2.5 Charge Processes at the Negative Plates of VRLA Batteries and COC
14.2.5.1 Thermal Phenomena During Operation of the COC
14.2.5.2 Types of Currents Flowing Between the Positive and Negative Plates in a VRLA Cell
14.2.5.3 Mechanism of the Oxygen Reduction at the Negative Plates
14.2.5.3.1 Electrochemical Mechanism of O2 Reduction ()
14.2.5.3.2 Reduction of Oxygen With Formation of PbO as an Intermediate Product ()
15 - Lead–Carbon Electrodes
15.2 Carbon Used as Additive to the Negative Active Material
15.2.1 Mechanism of Action of Carbon Added to Negative Active Mass and Its Effect on the Processes in Lead–Acid Batteries and on T ...
15.2.2 Contribution of Carbon Additives to the Electrochemical Processes in Negative Active Mass of Lead–Acid Batteries
15.2.3 Periods of Predominating Activity of the Lead or Carbon Parts of the Negative Electrodes in Lead–Acid Batteries
15.2.4 Capacitive Processes of Charging and Discharging of the Interface Carbon-Doped Negative Active Mass/Electrolyte on Cycling ...
15.2.5 Electrochemical and Chemical Reactions of Anodic and Cathodic Polarization of the Negative Electrodes of Lead–Acid Batteries
15.2.6 Electrochemical and Capacitive Systems Operating in the Lead–Carbon Negative Plates of Lead–Acid Batteries
15.2.7 Influence of Carbon Additives on the Structure and Electrochemical Properties of the Negative Active Mass and on Battery Pe ...
15.2.8 Correlation Between Negative Active Mass–Specific Surface Area and Number of High-Rate Partial-State-of-Charge Cycles (Reve ...
15.2.9 Influence of Carbon on the Pore System of the Negative Active Mass of Lead–Acid Batteries
15.2.10 Influence of Carbon Particle Size on High-Rate Partial-State-of-Charge Cycling Performance of Cells With Carbon Blacks or A ...
15.2.11 Influence of Vaniseprse A and Carbons on the High-Rate Partial-State-of-Charge Cycling Performance of Cells With Carbon Bla ...
15.3 Enhancing the Performance of the Negative Plates of Lead–Acid Batteries by Combining With a Supercapacitor
15.3.2 Mechanism of the Processes That Take Place on the Carbon Supercapacitor Component of the Hybrid Lead–Carbon Electrode
15.3.3 Electrochemical Capacitors
15.4 Hydrogen Evolution on the Lead–Carbon Electrode
15.4.1 Hydrogen Overvoltage
15.4.2 Additives to the Negative Active Material Reducing Hydrogen Evolution on the Lead–Carbon Electrode
15.5 Sulfation of the Lead–Carbon Electrodes of Lead–Acid Batteries on High-Rate Partial-State-of-Charge Cycling
15.5.1 Effect of Polyaspartic Acid (DS) on the Recrystallization of PbSO4
15.5.1.1 Influence of DS Added to the Electrolyte on the Electrochemical Processes on a Pb/PbSO4 Electrode During Linear Sweep Volta ...
15.5.1.2 High-Rate Partial-State-of-Charge Cycling Behavior of Cells With DS and Different Carbon Additives in the Negative Active Mass
15.5.2 Effect of Benzyl Benzoate on the Recrystallization of PbSO4
15.5.2.1 Initial Capacity Tests at 10-h Discharge Rate of 4.6Ah Cells With Various Benzyl Benzoate Content in the Negative Plates
15.5.2.2 High-Rate Partial-State-of-Charge Cycling Tests at 10h Discharge Rate of 4.6Ah Cells With Various Benzyl Benzoate Content i ...
15.5.2.3 Initial C20 Capacity and High-Rate Partial-State-of-Charge Cycling Tests of 42Ah AGM Cells With Benzyl Benzoate Added to th ...
6 Calculation of the Active Materials in a Lead–Acid Cell
16 - Calculation of the Active Materials for Lead–Acid Cells
16.1 Theoretical Calculation of the Active Materials in Lead–Acid Batteries
16.1.1 Basic Units of Electricity and Equivalents for Electricity and Mass
16.1.2 Electrochemical Equivalent Weights of Active Materials in a Lead–Acid Cell per Ah of Electric Charge (Electricity)
16.1.2.1 Pb|PbSO4 Electrode
16.1.2.2 PbO2|PbSO4 Electrode
16.1.3 Calculation of the Weights of the Positive or Negative Active Materials in a Lead–Acid Cell
16.1.4 Exemplary Calculation of the Weights of the Positive- and Negative-Active Materials in a 50Ah Lead–Acid Cell at 50% Utiliza ...
16.1.5 Other Parameters Used for Calculating the Active Materials in a Lead–Acid Cell
16.1.6 Amount of H2SO4 in a Lead–Acid Cell
16.1.7 Correlation Between H2SO4 Amount and Cell Capacity
16.1.8 Capacity and Active Mass Utilization Coefficients for Various Types of Flooded 100Ah SLI Batteries
16.1.9 Examples for Calculating the Active Materials for Various Types of Lead–Acid Batteries
16.1.9.1 12V/60Ah SLI Flooded Battery
16.1.9.2 12V/180Ah VRLA AGM Battery for Telecommunication Applications
16.1.9.3 2V/210-Ah Flooded Traction Battery With Tubular Positive Plates
16.1.10 Electrochemical Equivalent Weights and Capacitive Equivalents for Different Battery Types
16.2 Examples for Calculating the Active Materials and the Energy Needed for the Different Technological Processes of Lead–Acid ...
16.2.1 An Exemplary Calculation of Paste Composition
16.2.1.1 Calculation of the Content of Solid Phases in the Cured Paste
16.2.2 Calculation of the Volumes of H2O and H2SO4 Solution Needed for Paste Preparation
16.2.3 Calculation of the Quantity of Electricity Needed for Formation of Cured Paste of a Definite Composition
16.2.3.2 δ and σ for 3PbO·PbSO4·H2O (3BS)
16.2.4 Calculation of the Amounts of Positive or Negative Active Materials in the Plates after the Formation Process
16.3 Measuring of Electrode Potentials
16.3.1 Open Circuit Voltage of a Lead–Acid Cell (Battery)
16.3.2 Reference Electrodes
16.3.3 Calculated Electrode Potentials of Pb|PbSO4 and PbO2|PbSO4 Electrodes versus the Above Four Types of Reference Electrodes
16.3.4 Diffusion Potential Between Cell Electrolyte and Reference Electrode Electrolyte
Appendix 1. Thermodynamic Data for Lead Compounds. H. Bode, Lead–Acid Batteries, John Wiles & Sons, Inc., New York, USA, 19 ...
Appendix 2. X-ray Powder Diffraction Data for Battery Phases Pb R.J. Hill, J. Power Sources 9 (1983) 55
Appendix 3. H2SO4 Concentrations in Relation to Different Relative Density (Specific Gravity), V.A. Rabinovich, Z.Y. Havin, ...
Lead-Acid Batteries: Science and Technology
：A Handbook of Lead-Acid Battery Technology and Its Influence on the Product
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