Nickel–cadmium battery


The nickel–cadmium battery is a type of rechargeable battery using nickel oxide hydroxide and metallic cadmium as electrodes. The abbreviation Ni–Cd is derived from the chemical symbols of nickel and cadmium : the abbreviation NiCad is a registered trademark of SAFT Corporation, although this brand name is commonly used to describe all Ni–Cd batteries.
Wet-cell nickel–cadmium batteries were invented in 1899. A Ni–Cd battery has a terminal voltage during discharge of around 1.2 volts which decreases little until nearly the end of discharge. The maximum electromotive force offered by a Ni–Cd cell is 1.3V. Ni–Cd batteries are made in a wide range of sizes and capacities, from portable sealed types interchangeable with carbon–zinc dry cells, to large ventilated cells used for standby power and motive power. Compared with other types of rechargeable cells they offer good cycle life and performance at low temperatures with a fair capacity but their significant advantage is the ability to deliver practically their full rated capacity at high discharge rates. However, the materials are more costly than that of the lead–acid battery, and the cells have high self-discharge rates.
Sealed Ni–Cd cells were at one time widely used in portable power tools, photography equipment, flashlights, emergency lighting, hobby RC, and portable electronic devices. The superior capacity of nickel–metal hydride batteries, and recent lower cost, has largely supplanted Ni–Cd use. Further, the environmental impact of the disposal of the toxic metal cadmium has contributed considerably to the reduction in their use. Within the European Union, Ni–Cd batteries can now only be supplied for replacement purposes or for certain types of new equipment such as medical devices.
Larger ventilated wet cell Ni–Cd batteries are used in emergency lighting, standby power, and uninterruptible power supplies and other applications.

History

The first Ni–Cd battery was created by Waldemar Jungner of Sweden in 1899. At that time, the only direct competitor was the lead–acid battery, which was less physically and chemically robust. With minor improvements to the first prototypes, energy density rapidly increased to about half of that of primary batteries, and significantly greater than lead–acid batteries. Jungner experimented with substituting iron for the cadmium in varying quantities, but found the iron formulations to be wanting. Jungner's work was largely unknown in the United States. Thomas Edison patented a nickel– or cobalt–cadmium battery in 1902, and adapted the battery design when he introduced the nickel–iron battery to the US two years after Jungner had built one. In 1906, Jungner established a factory close to Oskarshamn, Sweden, to produce flooded design Ni–Cd batteries.
In 1932, active materials were deposited inside a porous nickel-plated electrode and fifteen years later work began on a sealed nickel–cadmium battery.
The first production in the United States began in 1946. Up to this point, the batteries were "pocket type," constructed of nickel-plated steel pockets containing nickel and cadmium active materials. Around the middle of the twentieth century, sintered-plate Ni–Cd batteries became increasingly popular. Fusing nickel powder at a temperature well below its melting point using high pressures creates sintered plates. The plates thus formed are highly porous, about 80 percent by volume. Positive and negative plates are produced by soaking the nickel plates in nickel- and cadmium-active materials, respectively. Sintered plates are usually much thinner than the pocket type, resulting in greater surface area per volume and higher currents. In general, the greater amount of reactive material surface area in a battery, the lower its internal resistance.
Since the 2000s, all consumer Ni–Cd batteries use the jelly-roll configuration.

Characteristics

The maximum discharge rate for a Ni–Cd battery varies by size. For a common AA-size cell, the maximum discharge rate is approximately 1.8 amperes; for a D size battery the discharge rate can be as high as 3.5 amperes.
Model-aircraft or -boat builders often take much larger currents of up to a hundred amps or so from specially constructed Ni–Cd batteries, which are used to drive main motors. 5–6 minutes of model operation is easily achievable from quite small batteries, so a reasonably high power-to-weight figure is achieved, comparable to internal combustion motors, though of lesser duration. In this, however, they have been largely superseded by lithium polymer and lithium iron phosphate batteries, which can provide even higher energy densities.

Voltage

Ni–Cd cells have a nominal cell potential of 1.2 volts. This is lower than the 1.5 V of alkaline and zinc–carbon primary cells, and consequently they are not appropriate as a replacement in all applications. However, the 1.5 V of a primary alkaline cell refers to its initial, rather than average, voltage. Unlike alkaline and zinc–carbon primary cells, a Ni–Cd cell's terminal voltage only changes a little as it discharges. Because many electronic devices are designed to work with primary cells that may discharge to as low as 0.90 to 1.0 V per cell, the relatively steady 1.2 V of a Ni–Cd cell is enough to allow operation. Some would consider the near-constant voltage a drawback as it makes it difficult to detect the remaining chemical charge capacity of an operating cell.
Ni–Cd batteries used to replace 9 V batteries usually only have six cells, for a terminal voltage of 7.2 volts. While most pocket radios will operate satisfactorily at this voltage, some manufacturers such as Varta made 8.4 volt batteries with seven cells for more critical applications.

Charging

Ni–Cd batteries can be charged at several different rates, depending on how the cell was manufactured. The charge rate is measured based on the percentage of the amp-hour capacity the battery is fed as a steady current over the duration of the charge. Regardless of the charge speed, more energy must be supplied to the battery than its actual capacity, to account for energy loss during charging, with faster charges being more efficient. For example, an "overnight" charge, might consist of supplying a current equal to one tenth the ampere-hour rating for 14–16 hours; that is, a 100 mAh battery takes 10 mA for 14 hours, for a total of 140 mAh to charge at this rate. At the rapid-charge rate, done at 100% of the rated capacity of the battery in 1 hour, the battery holds roughly 80% of the charge, so a 100 mAh battery takes 125 mAh to charge. Some specialized batteries can be charged in as little as 10–15 minutes at a 4C or 6C charge rate, but this is very uncommon. It also greatly increases the risk of the cells overheating and venting due to an internal over-pressure condition: the cell's rate of temperature rise is governed by its internal resistance and the square of the charging rate. At a 4C rate, the amount of heat generated in the cell is sixteen times higher than the heat at the 1C rate. The downside to faster charging is the higher risk of overcharging, which can damage the battery. and the increased temperatures the cell has to endure.
The safe temperature range when in use is between −20 °C and 45 °C. During charging, the battery temperature typically stays low, around the same as the ambient temperature, but as the battery nears full charge the temperature will rise to 45–50 °C. Some battery chargers detect this temperature increase to cut off charging and prevent over-charging.
When not under load or charge, a Ni–Cd battery will self-discharge approximately 10% per month at 20 °C, ranging up to 20% per month at higher temperatures. It is possible to perform a trickle charge at current levels just high enough to offset this discharge rate; to keep a battery fully charged. However, if the battery is going to be stored unused for a long period of time, it should be discharged down to at most 40% of capacity, and stored in a cool, dry environment.

Overcharging

Sealed Ni–Cd cells consist of a pressure vessel that is supposed to contain any generation of oxygen and hydrogen gases until they can recombine back to water. Such generation typically occurs during rapid charge and discharge, and exceedingly at overcharge condition. If the pressure exceeds the limit of the safety valve, water in the form of gas is lost. Since the vessel is designed to contain an exact amount of electrolyte this loss will rapidly affect the capacity of the cell and its ability to receive and deliver current. To detect all conditions of overcharge demands great sophistication from the charging circuit and a cheap charger will eventually damage even the best quality cells.

Electrochemistry

A fully charged Ni–Cd cell contains:
  • a nickel oxide-hydroxide positive electrode plate
  • a cadmium negative electrode plate
  • a separator, and
  • an alkaline electrolyte.
Ni–Cd batteries usually have a metal case with a sealing plate equipped with a self-sealing safety valve. The positive and negative electrode plates, isolated from each other by the separator, are rolled in a spiral shape inside the case. This is known as the jelly-roll design and allows a Ni–Cd cell to deliver a much higher maximum current than an equivalent size alkaline cell. Alkaline cells have a bobbin construction where the cell casing is filled with electrolyte and contains a graphite rod which acts as the positive electrode. As a relatively small area of the electrode is in contact with the electrolyte, the internal resistance for an equivalent sized alkaline cell is higher which limits the maximum current that can be delivered.
The chemical reactions at the cadmium electrode during discharge are:
The reactions at the nickel oxide electrode are:
The net reaction during discharge is
During recharge, the reactions go from right to left. The alkaline electrolyte is not consumed in this reaction and therefore its specific gravity, unlike in lead–acid batteries, is not a guide to its state of charge.
When Jungner built the first Ni–Cd batteries, he used nickel oxide in the positive electrode, and iron and cadmium materials in the negative. It was not until later that pure cadmium metal and nickel hydroxide were used. Until about 1960, the chemical reaction was not completely understood. There were several speculations as to the reaction products. The debate was finally resolved by infrared spectroscopy, which revealed cadmium hydroxide and nickel hydroxide.
Another historically important variation on the basic Ni–Cd cell is the addition of lithium hydroxide to the potassium hydroxide electrolyte. This was believed to prolong the service life by making the cell more resistant to electrical abuse. The Ni–Cd battery in its modern form is extremely resistant to electrical abuse anyway, so this practice has been discontinued.