LEAD ACID BATTERIES

1. General Characteristic

The lead-acid battery has been a successful article of commerce for over a

century. Its production and use continue to grow because of new applications for

battery power in energy storage, emergency power, and electric and hybrid

vehicles (including off-road vehicles) and because of the increased number of

vehicles for which it provides the energy for engine starting, vehicle lighting, and

engine ignition (SLI). This battery system is also used extensively in telephone

systems, power tools, communication devices, emergency lighting systems, and as

the power source for mining and material-handling equipment. The wide use of

the lead-acid battery in many designs, sizes, and system voltages is accounted for

by the low price and the ease of manufacture on a local geographic basis of this

battery system. The lead-acid battery is almost always the least expensive storage

battery for any application, while still providing good performance and life

characteristics.

There have been many improvements in lead-acid battery design and charger

system logic to make high-voltage batteries more uniform in performance.

Electric-vehicle batteries are typically 100 to 300 V systems. The lead-acid

battery has a high electrical turnaround efficiency, 75 to 80%, which makes the

system attractive for electric-vehicle and energy-storage use. Traditional vertical-

plate batteries are capable of energy densities greater than 40 Wh/ kg, and a

horizontal-plate design with higher energy and power densities have found use in

traction and fork lift applications. Modified lead-acid batteries are being
investigated for both electric and hybrid-drive vehicles. The worlds largest

energy-storage battery system was finished in late 1988. This 40-MWh battery,

located in Chino, Calif., uses individual industrial-size lead-acid cells in series and

parallel connection to make a 10-MW system delivering energy into the utility

grid at 2000 V and 8000 A for 4 hours. AC to DC conversion is built into the

system. This battery operated for more than a decade as a demonstration project.

At the other extreme, small individual lead-acid cells and batteries are now

available with quick connects for use in small electric appliances and electronics

applications. Many of these newer applications require low-maintenance or

maintenance-free designs. Thin film capacitor-like lead-acid batteries have

become commercially available in the past few years, for consumer and electronic

applications.

2. Chemistry Characteristic

The lead-acid battery uses lead dioxide as the active material of the positive

electrode and metallic lead, in a high-surface-area porous structure, as the

negative active material. The physical and chemical properties of these materials

are listed in Table 23.5.5 Typically, a charged positive electrode contains both -

PbO2 (orthorhombic) and -PbO2 (tetragonal). The equilibrium potential of the -

PbO2 is more positive than that of -PbO2 by 0.01 V. The form also has a larger,

more compact crystal morphology which is less active electrochemically and

slightly lower in capacity per unit weight; it does, however, promote longer cycle

life. Neither of the two forms is fully stoichiometric. Their composition can be

represented by PbOx, with x varying between 1.85 and 2.05. The introduction of

antimony, even at low concentrations, in the preparation or cycling of these

species leads to a considerable increase in their performance. The preparation of

the active material precursor consists of a series of mixing and curing operations

using leady lead oxide (PbO + Pb), sulfuric acid, and water. The ratios of the

reactants and curing conditions (temperature, humidity, and time) affect the

development of crystallinity and pore structure. The cured plate consists of lead

sulfate, lead oxide, and some residual lead (<5%). The positive active material,

which is formed electrochemically from the cured plate, is a major factor

influencing the performance and life of the lead-acid battery. In general the

negative, or lead, electrode controls cold-temperature performance (such as engine

starting).

As the cell discharges, both electrodes are converted to lead sulfate. The

process reverses on charge:

 The nominal voltage of the lead-acid cell is 2 V; the voltage on open circuit is a

direct function of the electrolyte concentration, ranging from 2.125 V for a cell

with 1.28 specific gravity electrolyte to 2.05 V with 1.21 specific gravity (see Sec.
23.2.2). The end or cutoff voltage on moderate-rate discharges is 1.75 V per cell,

but may range to as low as 1.0 V per cell at extremely high discharge rates at low

temperatures.

The selection of specific gravity used for the electrolyte depends on the

application and service requirements. The electrolyte concentration must be high

enough for good ionic conductivity and to fulfill electrochemical requirements,

but not so high as to cause separator deterioration or corrosion of other parts of

the cell, which would shorten life and increase self-discharge. The electrolyte

concentration is deliberately reduced in high-temperature climates. During

discharge, the specific gravity decreases in proportion to the Ampere-hours

discharged (Table 23.6). The specific gravity is thus a means for checking the

state of charge of the battery. On charge, the change in specific gravity should

similarly be proportional to the Ampere-hour charge accepted by the cell.

However, there is a lag because complete mixing of the electrolyte does not occur

until gassing commences near the end of the charge.

3. Advantage and Disadvantage

The overall advantages and disadvantages of the lead-acid battery, compared

with other systems, are listed in Table 23.1.