The high-power Lithium-ion Battery

The widely used cobalt-based lithium-ion has drawbacks; it offers a relatively low discharge current. A high load would overheat the pack and its safety would be jeopardized. The safety circuit of the cobalt-based battery is typically limited to a charge and discharge rate of about 1C. This means that a 2400mAh 18650 cell can only be charged and discharged with a maximum current of 2.4A. Another downside is the increase of the internal resistance that occurs with cycling and aging. After 2-3 years of use, the pack often becomes unserviceable due to a large voltage drop under load that is caused by high internal resistance. Figure 1 illustrates the crystalline structure of cobalt oxide.

Figure 1: Cathode crystalline of lithium cobalt oxide has 'layered' structures. The lithium ions are shown bound to the cobalt oxide. During discharge, the lithium ions move from the cathode to the anode. The flow reverses on charge.

In 1996, scientists succeeded in using lithium manganese oxide as a cathode material. This substance forms a three-dimensional spinel structure that improves the ion flow between the electrodes. High ion flow lowers the internal resistance and increases loading capability. The resistance stays low with cycling, however, the battery does age and the overall service life is similar to that of cobalt. Spinel has an inherently high thermal stability and needs less safety circuitry than a cobalt system.Low internal cell resistance is the key to high rate capability. This characteristic benefits fast-charging and high-current discharging. A spinel-based lithium-ion in an 18650 cell can be discharged at 20-30A with marginal heat build-up. Short one-second load pulses of twice the specified current are permissible. Some heat build-up cannot be prevented and the cell temperature should not exceed 80°C.

Figure 2: Cathode crystalline of lithium manganese oxide has a 'three-dimensional framework structure'. This spinel structure, which is usually composed of diamond shapes connected into a lattice, appears after initial formation. This system provides high conductivity but lower energy density.

The spinel battery also has weaknesses. One of the most significant drawbacks is the lower capacity compared to the cobalt-based system. Spinel provides roughly 1200mAh in an 18650 package, about half that of the cobalt equivalent. In spite of this, spinel still provides an energy density that is about 50% higher than that of a nickel-based equivalent.

Figure 3: Format of 18650 cell. The dimensionsof this commonly used cell are: 18mm in diameter and 650mm in length.

Types of lithium-ion batteries
   Lithium-ion has not yet reached full maturity and the technology is continually improving. The anode in today's cells is made up of a graphite mixture and the cathode is a combination of lithium and other choice metals. It should be noted that all materials in a battery have a theoretical energy density. With lithium-ion, the anode is well optimized and little improvements can be gained in terms of design changes. The cathode, however, shows promise for further enhancements. Battery research is therefore focusing on the cathode material. Another part that has potential is the electrolyte. The electrolyte serves as a reaction medium between the anode and the cathode.

   The battery industry is making incremental capacity gains of 8-10% per year. This trend is expected to continue. This, however, is a far cry from Moore's Law that specifies a doubling of transistors on a chip every 18 to 24 months. Translating this increase to a battery would mean a doubling of capacity every two years. Instead of two years, lithium-ion has doubled its energy capacity in 10 years.
Today's lithium-ion comes in many "flavours" and the differences in the composition are mostly related to the cathode material. Table 1 below summarizes the most commonly used lithium-ion on the market today. For simplicity, we summarize the chemistries into four groupings, which are Cobalt, Manganese, NCM and Phosphate.

   The cobalt-based lithium-ion appeared first in 1991, introduced by Sony. This battery chemistry gained quick acceptance because of its high energy density. Possibly due to lower energy density, spinel-based lithium-ion had a slower start. When introduced in 1996, the world demanded longer runtime above anything else. With the need for high current rate on many portable devices, spinel has now moved to the frontline and is in hot demand. The requirements are so great that manufacturers producing these batteries are unable to meet the demand. This is one of the reasons why so little advertising is done to promote this product. E-One Moli Energy (Canada) is a leading manufacturer of the spinel lithium-ion in cylindrical form. They are specializing in the 18650 and 26700 cell formats. Other major players of spinel-based lithium-ion are Sanyo, Panasonic and Sony.

   Sony is focusing on the nickel-cobalt manganese (NCM) version. The cathode incorporates cobalt, nickel and manganese in the crystal structure that forms a multi-metal oxide material to which lithium is added. The manufacturer offers a range of different products within this battery family, catering to users that either needs high energy density or high load capability. It should be noted that these two attributes could not be combined in one and the same package; there is a compromise between the two. Note that the NCM charges to 4.10V/cell, 100mV lower than cobalt and spinel. Charging this battery chemistry to 4.20V/cell would provide higher capacities but the cycle life would be cut short. Instead of the customary 800 cycles achieved in a laboratory environment, the cycle count would be reduced to about 300.

   The newest addition to the lithium-ion family is the A123 System in which nano-phosphate materials are added in the cathode. Although the manufacturer has not officially announced what metal is being used, it is widely believed to be iron. They claim to have the highest energy density of a commercially available lithium-ion battery. The cell can be continuously discharged to 100% depth-of-discharge at 35C and endures discharge pulses as high as 100C. The phosphate-based system has a nominal voltage of about 3.25V/cell. The charge limit is 3.60V. This is far lower than the customary 4.20V/cell of the cobalt-based lithium-ion. Because of these lower voltages, the A123 System will need be charged with a special charger. Due to the anticipated strong demand, this cell is expected to be in short supply. A123 Systems was founded in 2001, the company is privately held and the major shareholders include Motorola, Qualcomm and MIT.

Confusion with voltages
   For the last 10 years or so, the nominal voltage of lithium-ion was known to be 3.60V/cell. This was a rather handy figure because it made up for three nickel-based batteries (1.2V/cell) connected in series. Using the higher cell voltages for lithium-ion reflects in better watt/hours readings on paper and poses a marketing advantage, however, the equipment manufacturer will continue assuming the cell to be 3.60V.
The nominal voltage of a lithium-ion battery is calculated by taking a fully charged battery of about 4.20V, fully discharging it to about 3.00V at a rate of 0.5C while measuring the average voltage.

   Because of the lower internal resistance, the average voltage of a spinel system will be higher than that of the cobalt-based equivalent. Pure spinel has the lowest internal resistance and the nominal cell voltage is 3.80V. The exception again is the phosphate-based lithium-ion. This system deviates the furthest from the conventional lithium-ion system.

(From author Isidor Buchmann )
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