Nickel-metal hydride battery

A nickel-metal hydride battery, abbreviated NiMH, is a type of rechargeable battery similar to a nickel-cadmium (NiCd) battery but using a hydrogen-absorbing alloy for the negative electrode instead of cadmium. As in NiCd batteries, the positive electrode is nickel oxyhydroxide (NiOOH). A NiMH battery can have two to three times the capacity of an equivalent size NiCd. However, compared to the lithium-ion battery, the volumetric energy density is lower and self-discharge is higher.

Common penlight-size (AA) batteries have nominal charge capacities (C) ranging from 1100 mA·h to 2700 mA·h at 1.2 V, usually measured at a discharge rate of 0.2×C per hour. Useful discharge capacity is a decreasing function of the discharge rate, but up to a rate of around 1×C (full discharge in one hour), it does not differ significantly from the nominal capacity.

The specific energy density for NiMH material is approximately 70 W·h/kg (250 kJ/kg), with a volumetric energy density of about 300 W·h/L (360 MJ/m³).

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History

The first consumer grade NiMH batteries began to appear at the end of the 1980s. Positive electrode development was done by Dr. Masahiko Oshitani from Yuasa Company, who was the first to develop high-energy paste electrode technology. The association of this high-energy electrode with high-energy hydrid alloys for the negative electrode, discovered by Philips Laboratories and French CNRS labs in the 1970s, led to the new environmentally friendly high energy NiMH battery.

Applications

Applications of NiMH type batteries includes all-electric plug-in vehicles such as the Toyota RAV4-EV, GM EV1, HondaEV and Ford RangerEV, hybrid vehicles such as the Toyota Prius or Honda Insight/Civic and consumer electronics. The NiMH technology will also be used on the Alstom Citadis low floor tram ordered for Nice, France; as well as the humanoid prototype robot ASIMO designed by Honda. Standard NiMH batteries perform better with moderate drain devices such as digital cameras, flashlights, and other consumer electronics. Because NiCd batteries have lower internal resistance, they still have the edge in very high current drain applications such as cordless power tools.

Electrochemistry

The negative electrode reaction occurring in a NiMH battery is

The electrode is charged in the right direction of this equation and discharged in the left direction. On the positive electrode, nickel oxyhydroxide (NiOOH) is formed,

The "metal" M in the negative electrode of a NiMH battery is actually an intermetallic compound. Many different compounds have been developed for this application, but those in current use fall into two classes. The most common is AB₅, where A is a rare earth mixture of lanthanum, cerium, neodymium, praseodymium and B is nickel, cobalt, manganese, and/or aluminum. Very few batteries use higher-capacity negative material electrodes based on AB₂ compounds, where A is titanium and/or vanadium and B is zirconium or nickel, modified with chromium, cobalt, iron, and/or manganese, due to the reduced life performances [2]. Any of these compounds serves the same role, reversibly forming a mixture of metal hydride compounds.

When overcharged at low rates, oxygen produced at the positive electrode passes through the separator and recombines at the surface of the negative. Hydrogen evolution is suppressed and the charging energy is converted to heat. This process allows NiMH batteries to remain sealed in normal operation and to be maintenance-free.

NiMH batteries have an alkaline electrolyte, usually potassium hydroxide.

Charging

The charging voltage is 1.4-1.6 V/cell.[3] Duracell recommends "a maintenance charge of indefinite duration at C/300 rate". A fully charged cell measures 1.35-1.4 V (unloaded), and supplies a nominal average 1.2 V during discharge, down to about 1.0 V (further discharge may cause permanent damage).

Voltage Depression ("Memory Effect") from repeated partial discharge can occur, but is reversible through charge cycling.^[2]

When fast-charging, it is advisable to charge the NiMH batteries with a smart battery charger to avoid overcharging, which can damage batteries and cause dangerous conditions. Modern NiMH batteries contain catalysts to immediately deal with gases developed as a result of over-charging without being harmed (2 H₂ + O₂ ---catalyst → 2 H₂O). However, this only works with overcharging currents of up to C/10 h (nominal capacity divided by 10 hours). As a result of this reaction, the batteries will heat up considerably, marking the end of the charging process. Some quick chargers have a fan to keep the batteries cool.

A method for very rapid charging called In-Cell Charge Control involves an internal pressure switch in the cell, which disconnects the charging current in the event of overpressure.

Some equipment manufacturers consider that NiMH can be safely charged in simple fixed (low) less current chargers with or without timers, and that permanent overcharging is permissible with currents up to 'C'/10 h. In fact, this is what happens in cheap cordless phone base stations and the cheapest battery chargers. Although this may be safe, it may not be good for the health of the battery. According to the Panasonic NiMH charging manual (link below), permanent trickle charging (small current overcharging) can cause battery deterioration and the trickle charge rate should be limited to between 0.033×C per hour and 0.05×C per hour for a maximum of 20 hours to avoid damaging the batteries.

Long-term maintenance charge of NiMH batteries needs to be by low duty cycle pulses of high current rather than continuous low current in order to preserve battery health.

Brand new batteries, or batteries which have been unused for some time, need "reforming" to reach their full capacity. For this reason new batteries may need several charge/discharge cycles before they operate to their advertised capacity.^{[citation needed]}

Discharging

Care must also be taken during discharge to ensure that one or more cells in a series-connected battery pack, like the common arrangement of four AA cells in series in a digital camera, do not become completely discharged and go into polarity reversal. Cells are never absolutely identical, and inevitably one will be completely discharged before the others. When this happens, the "good" cells will start to "drive" the discharged cell in reverse, which can cause permanent damage to that cell. Some cameras, GPS receivers and PDAs detect the safe end-of-discharge voltage of the series cells and shut themselves down, but devices like flashlights and some toys do not. Once noticeable dimming or slowing of the device is noticed, it should be turned off immediately to avoid polarity reversal. A single cell driving a load won't suffer from polarity reversal, because there are no other cells to reverse-charge it when it becomes discharged.

Self-discharge

NiMH historically had a somewhat higher self-discharge rate (equivalent to internal leakage) than NiCd in the past. However, this is no longer the case. The self-discharge is 5-10% on the first day, and stabilizes around 0.5-1% per day at room temperature. ^{[3] [4] [5] [6] [7]} This is not a problem in the short term, but makes them unsuitable for many light-duty uses, such as clocks, remote controls or safety devices, where the battery would normally be expected to last many months or years. The rate is strongly affected by the temperature at which the batteries are stored with cooler storage temperatures leading to slower discharge rate and longer battery life. The highest capacity cells on the market (> 2700mAh) are reported to have the highest self-discharge rates.

Low Self Discharge Batteries

Main article: Low self-discharge NiMH battery

A new type of nickel-metal hydride battery was introduced in 2006 that reduces self-discharge and, therefore, lengthens shelf life. By using a new separator, manufacturers claim the batteries retain 70 to 85% of their capacity after one year when stored at 20 degrees Celsius (68F). These cells are marketed as "ready-to-use" or "pre-charged" rechargeables. Besides the longer shelf life, they are otherwise similar to normal NiMH batteries of equivalent capacity and can be charged in typical NiMH chargers.

Some brands that are currently available on the market (Nov 2007) are Accupower Acculoop, Ansmann MaxE range, Duracell Pre-charged, Gold Peak ReCyko, Kodak Pre Charged, Nexcell EnergyOn, Panasonic R2, Rayovac Hybrid, GE/Sanyo Eneloop, Sony CycleEnergy, Titanium Power Enduro, Uniross Hybrio, Vapextech Instant and VARTA Ready2use. As there are only three manufacturers of this new type of cell (Sanyo, Panasonic, Yuasa-Delta) most of these brands are rebranded OEMs.

Low self discharge batteries appear only to be available in AA and AAA sizes and have less capacity than standard NiMH batteries. The highest capacity low self discharge batteries have 2000-2100mAh and 800mAh capacities for AA and AAA batteries, respectively, compared to 2800mAh and 1000mAh for standard AA and AAA batteries.

Environment

NiMH batteries are less detrimental to the environment than NiCd batteries containing cadmium which is poisonous.

Battery recycling programs exist to take care of end-of-life batteries.

Most Nickel is recycled, due to the relatively easy retrieval of the metal from scrap, and most is used in corrosion-resistant alloys such as stainless steel and Monel. Use in batteries constitutes a tiny fraction of the available Nickel supplies, so there's no problem expanding use of these batteries by several orders of magnitude for transportation applications.

Comparison with other battery types

NiMH batteries and chargers are readily available in retail stores in the common sizes AAA and AA. Adapter sleeves are available to use the more common AA size in C and D applications. The sizes C and D batteries are somewhat available, but are often just an AA core hidden in an outer shell, with a rating of about 2500 mAh, much less than ordinary alkaline C and D batteries. Real NiMH C and D batteries are expensive (and the chargers are uncommon); they should be rated at least 5000 mAh for C and 10000 mAh for D sizes.

NiMH batteries are not expensive, and the voltage and performance is similar to standard alkaline batteries in those sizes; they can be substituted for most purposes. The ability to recharge hundreds of times can save a lot of money and resources.

They are often used in digital cameras and work well in this application. Applications that require frequent replacement of the battery, such as toys or video game controllers, also benefit from use of rechargeable batteries. With the development of low self-discharge NiMHs (see section above), many occasional-use and very low power applications are now candidates for NiMH rechargeables.

NiMH batteries are particularly advantageous for high current drain applications, due in large part to their low internal resistance. Alkaline batteries, which might have approximately 3000 mA·h capacity at low current demand (200 mA), will have less than 1000 mA·h capacity with a 1000 mA load. Digital cameras with LCDs and flashlights can draw over 1000 mA, quickly depleting alkaline batteries after a few shots. NiMH can handle these current levels and maintain their full capacity.

Sometimes, voltage-sensitive devices won't perform well because the voltage of NiMH batteries is lower than fresh disposable batteries at equivalent sizes, particularly at light loads. Even though the nominal NiMH voltage is lower, it sustains for the length of the discharge cycle, since the low internal resistance allows NiMH cells to deliver a near-constant voltage until they are almost completely discharged. Alkaline discharge voltage droops more towards the end of the discharge cycle.

Lithium ion batteries are more compact than nickel-metal hydride batteries.^[8]

Patent encumbrance of NiMH batteries

In 1994, General Motors acquired a controlling interest in Ovonics's battery development and manufacturing, including patents controlling the manufacturing of large nickel metal hydride (NiMH) batteries. In 2001, Texaco purchased GM's share in GM Ovonics. A few months later, Chevron acquired Texaco. In 2003, Texaco Ovonics Battery Systems was restructured into Cobasys, a 50/50 joint venture between Chevron and Energy Conversion Devices (ECD) Ovonics.^[9] Chevron's influence over Cobasys extends beyond a strict 50/50 joint venture. Chevron holds a 19.99% interest in ECD Ovonics.^[10] Chevron also maintains veto power over any sale or licensing of NiMH technology.^[11] In addition, Chevron maintains the right to seize all of Cobasys' intellectual property rights in the event that ECD Ovonics does not fulfill its contractual obligations.^[11] On September 10, 2007, Chevron filed a legal claim that ECD Ovonics has not fulfilled its obligations. ECD Ovonics disputes this claim.^[12] NiMH patent expires in 2015.

In her book, Plug-in Hybrids: The Cars that Will Recharge America, published in February 2007, Sherry Boschert argues that large-format NiMH batteries are commercially viable but that Cobasys refuses to sell or license them to small companies or individuals. Boschert reveals that Cobasys accepts only very large orders for these batteries. When Boschert conducted her research, major auto makers showed little interest in large orders for large-format NiMH batteries. However, Toyota employees complained about the difficulty in getting smaller orders of large format NiMH batteries to service the existing 825 RAV-4EVs. Since no other companies were willing to make large orders, Cobasys was not manufacturing nor licensing any large format NiMH battery technology for automotive purposes. Boschert concludes that "it's possible that Cobasys (Chevron) is squelching all access to large NiMH batteries through its control of patent licenses in order to remove a competitor to gasoline. Or it's possible that Cobasys simply wants the market for itself and is waiting for a major automaker to start producing plug-in hybrids or electric vehicles." ^[13]

However, recently-signed Cobasys contracts demonstrate that the company is willing to use its NiMH technology in the automotive industry, specifically for use with hybrid electric vehicles. In December 2006, Cobasys and General Motors announced that they had signed a contract under which Cobasys provides NiMH batteries for the Saturn Aura hybrid sedan.^[14] In March 2007, GM announced that it would use Cobasys NiMH batteries in the 2008 Chevrolet Malibu hybrid as well. Cobasys remains unwilling to sell NiMH batteries in smaller quantities to individuals interested in building or retrofitting their own PHEVs.

Saft offers a NHE NiMH Module Has capacities of 100Ah and 200Ah.

Tianjin peace Gulf Power Group Co. offers NiMH in there HP-280QNF line of 40Ah , 80Ah , and 100Ah.

References

Bibliography

• "Bipolar Nickel Metal Hydride Battery" by Martin G. Klein, Michael Eskra, Robert Plivelich and Paula Ralston